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CN103183628B - Pyrrolidine-2,4-dione compound comprising substituted phenylhydrazine, and preparation method and application thereof - Google Patents

Pyrrolidine-2,4-dione compound comprising substituted phenylhydrazine, and preparation method and application thereof Download PDF

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CN103183628B
CN103183628B CN201110453110.XA CN201110453110A CN103183628B CN 103183628 B CN103183628 B CN 103183628B CN 201110453110 A CN201110453110 A CN 201110453110A CN 103183628 B CN103183628 B CN 103183628B
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pyrrolidine
dione
hydrazino
ethylidene
arnhnh
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CN103183628A (en
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杨春龙
王先锋
冯玲玲
王洋
陈敏
胡颖
王思思
褚海彬
王军军
何睿
黄霂
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Nanjing Agricultural University
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Abstract

本发明属于杀菌剂领域，公开了一种含取代苯肼的吡咯烷-2，4-二酮类化合物、制备方法及应用。该化合物结构如式(I)所示：本发明涉及的化合物和组合物制备工艺方法简单，杀菌效果突出，具有广阔的应用前景。The invention belongs to the field of fungicides, and discloses a pyrrolidine-2,4-dione compound containing a substituted phenylhydrazine, a preparation method and an application. This compound structure is shown in formula (I): The compound and composition involved in the invention have simple preparation process, outstanding bactericidal effect and broad application prospect.

Description

一种含取代苯肼的吡咯烷-2,4-二酮类化合物、制备方法及应用Pyrrolidine-2,4-dione compound containing substituted phenylhydrazine, preparation method and application

技术领域 technical field

本发明属于杀菌剂领域，具体涉及一种含取代苯肼的吡咯烷-2，4-二酮类化合物、制备方法及应用。 The invention belongs to the field of fungicides, and in particular relates to a pyrrolidine-2,4-dione compound containing a substituted phenylhydrazine, a preparation method and an application.

背景技术 Background technique

Tetramic acids类化合物具有广泛的生物活性，如抗癌、杀菌、除草、抗病毒等活性，同时还具有毒性低、易降解、环境相容性好等良好特性，是发现和筛选药物先导化合物的重要来源，已被科学家应用于研究和开发新型绿色生态型农药。专利US5045560描述了一类3-取代苯基吡咯烷-2，4-二酮类化合物，具有杀虫和杀螨活性。US5504057描述了一类3-(2，4-二甲基苯基)吡咯烷-2，4-二酮类化合物，具有除草和杀虫活性。US6472419描述了另一类3-取代苯基吡咯烷-2，4-二酮类化合物，可以防治节肢动物。CN03821634.5描述了一类5-取代螺环吡咯烷-2，4-二酮类化合物，可以防治害虫。专利CN200510013206.9、CN201010232595.5、CN201010202871.3、CN201010576398.5先后分别描述了3-芳酰基吡咯烷-2，4-二酮类化合物、3-取代环丙甲酰基吡咯烷-2，4-二酮类化合物、3-酰基吡咯烷-2，4-二酮缩氨基脲类化合物、3-酰基-5-取代甲基吡咯烷-2，4-二酮类化合物，均具有除草活性。 Tetramic acids compounds have a wide range of biological activities, such as anticancer, bactericidal, herbicidal, antiviral, etc., and also have good characteristics such as low toxicity, easy degradation, and good environmental compatibility. They are important for the discovery and screening of drug lead compounds. Source, has been used by scientists to research and develop new green ecological pesticides. Patent US5045560 describes a class of 3-substituted phenylpyrrolidine-2,4-dione compounds with insecticidal and acaricidal activities. US5504057 describes a class of 3-(2,4-dimethylphenyl)pyrrolidine-2,4-diones with herbicidal and insecticidal activity. US6472419 describes another class of 3-substituted phenylpyrrolidine-2,4-dione compounds, which can control arthropods. CN03821634.5 describes a class of 5-substituted spirocyclic pyrrolidine-2,4-dione compounds, which can control pests. Patents CN200510013206.9, CN201010232595.5, CN201010202871.3, and CN201010576398.5 respectively describe 3-aroylpyrrolidine-2,4-dione compounds, 3-substituted cyclopropamoylpyrrolidine-2,4- Diketone compounds, 3-acylpyrrolidine-2,4-diketone semicarbazone compounds, and 3-acyl-5-substituted methylpyrrolidine-2,4-dione compounds all have herbicidal activity.

发明内容 Contents of the invention

本发明的目的在于，提供一种含取代苯肼的吡咯烷-2，4-二酮类化合物。 The object of the present invention is to provide a pyrrolidine-2,4-dione compound containing a substituted phenylhydrazine.

本发明的另一目的在于提供含该类取代苯肼的吡咯烷-2，4-二酮类化合物的制备方法。 Another object of the present invention is to provide a method for preparing pyrrolidine-2,4-dione compounds containing such substituted phenylhydrazines.

本发明的另一个目的在于提供上述化合物的用途。 Another object of the present invention is to provide the use of the above compound.

本发明的第一方面提供了一种具有通式(I)所示结构的含取代苯肼的吡咯烷-2，4-二酮类化合物、或其异构体、或农药学上可接受的盐及其金属配合物。 The first aspect of the present invention provides a substituted phenylhydrazine-containing pyrrolidine-2,4-dione compound having a structure represented by general formula (I), or an isomer thereof, or a pesticide acceptable Salts and their metal complexes.

其中， in,

R1选自氢、取代或未取代的直链或支链的C1-12烷基、C3-8环烷基、C2-12烯基、C4-8环烯基、C2-12炔基、C4-8环炔基、C1-12酰基、C5-12芳基、C5-12芳基甲酰基、C6-19芳基烷基、杂环基，所述的取代基团选自：-R’、-X、-OR’、-SR’、-N(R’)2、-COR’、-COOR’、-CON(R’)2、-NO2、-CN，其中X表示卤素，R’代表氢、未取代或卤素、N、O、S的原子取代的C1-12烷基；所述的杂环基为环系统中的一个或多个碳原子被选自N、O、S的杂原子取代的C3-8环烷基、C4-8环烯基、C4-8环炔基、C5-12芳基、C5-12芳基甲酰基、C6-19芳基烷基； R 1 is selected from hydrogen, substituted or unsubstituted linear or branched C 1-12 alkyl, C 3-8 cycloalkyl, C 2-12 alkenyl, C 4-8 cycloalkenyl, C 2- 12 alkynyl, C 4-8 cycloalkynyl, C 1-12 acyl, C 5-12 aryl, C 5-12 arylformyl, C 6-19 arylalkyl, heterocyclyl, said The substituent group is selected from: -R', -X, -OR', -SR', -N(R') 2 , -COR', -COOR', -CON(R') 2 , -NO 2 , - CN, wherein X represents halogen, R' represents hydrogen, unsubstituted or halogen, N, O, S atoms substituted C 1-12 alkyl; the heterocyclic group is one or more carbon atoms in the ring system C 3-8 cycloalkyl, C 4-8 cycloalkenyl, C 4-8 cycloalkynyl, C 5-12 aryl, C 5-12 aryl substituted by heteroatoms selected from N , O, S Formyl, C 6-19 arylalkyl;

R2选自氢、取代或未取代的直链或支链的C1-12烷基、C3-8环烷基、C2-12烯基、C4-8环烯基、C2-12炔基、C4-8环炔基，其所述的取代基团选自：-R’、-X、-OR’、-SR’、-N(R’)2、-COR’、-COOR’、-CON(R’)2、-NO2、-CN，其中X表示卤素，R’代表氢、未取代或卤素、N、O、S的原子取代的C1-12烷基； R 2 is selected from hydrogen, substituted or unsubstituted linear or branched C 1-12 alkyl, C 3-8 cycloalkyl, C 2-12 alkenyl, C 4-8 cycloalkenyl, C 2- 12 alkynyl, C 4-8 cycloalkynyl, the substituents are selected from: -R', -X, -OR', -SR', -N(R') 2 , -COR', - COOR', -CON(R') 2 , -NO 2 , -CN, wherein X represents halogen, and R' represents hydrogen, unsubstituted or C 1-12 alkyl substituted by atoms of halogen, N, O, and S;

R3选自氢、取代或未取代的直链或支链的C1-12烷基、C3-8环烷基、C2-12烯基、C4-8环烯基、C2-12炔基、C4-8环炔基、C1-12酰基、C5-12芳基、C5-12芳基甲酰基、C6-19芳基烷基、杂环基，所述的取代基团选自：-R’、-X、-OR’、-SR’、-N(R’)2、-COR’、-COOR’、-CON(R’)2、-NO2、-CN，其中X表示卤素，R’代表氢、未取代或卤素、N、O、S的原子取代的C1-12烷基；所述的杂环基为环系统中的一个或多个碳原子被选自N、O、S的杂原子取代的C3-8环烷基、C4-8环烯基、C4-8环炔基、C5-12芳基、C5-12芳基甲酰基、C6-19芳基烷基； R 3 is selected from hydrogen, substituted or unsubstituted linear or branched C 1-12 alkyl, C 3-8 cycloalkyl, C 2-12 alkenyl, C 4-8 cycloalkenyl, C 2- 12 alkynyl, C 4-8 cycloalkynyl, C 1-12 acyl, C 5-12 aryl, C 5-12 arylformyl, C 6-19 arylalkyl, heterocyclyl, said The substituent group is selected from: -R', -X, -OR', -SR', -N(R') 2 , -COR', -COOR', -CON(R') 2 , -NO 2 , - CN, wherein X represents halogen, R' represents hydrogen, unsubstituted or halogen, N, O, S atoms substituted C 1-12 alkyl; the heterocyclic group is one or more carbon atoms in the ring system C 3-8 cycloalkyl, C 4-8 cycloalkenyl, C 4-8 cycloalkynyl, C 5-12 aryl, C 5-12 aryl substituted by heteroatoms selected from N , O, S Formyl, C 6-19 arylalkyl;

R4选自氢、取代或未取代的直链或支链的C1-12烷基、C2-12烯基、C2-12炔基，所述的取代基团选自：-R’、-X、-OR’、-SR’、-N(R’)2、-COR’、-COOR’、-CON(R’)2、-NO2、-CN，其中X表示卤素，R’代表氢、未取代或卤素、N、O、S的原子取代的C1-12烷基； R 4 is selected from hydrogen, substituted or unsubstituted linear or branched C 1-12 alkyl, C 2-12 alkenyl, C 2-12 alkynyl, and the substituent group is selected from: -R' , -X, -OR', -SR', -N(R') 2 , -COR', -COOR', -CON(R') 2 , -NO 2 , -CN, where X represents a halogen, R' C 1-12 alkyl representing hydrogen, unsubstituted or halogen, N, O, S atoms substituted;

Y(n)中，n＝1-5取代，Y(n)选自下列的一个或多个基团：-R、-X、-OR’、-SR’、SO2NR’2、-COR’、-COOR’、-CON(R’)2、-CN、未取代或卤素取代的C2-12烯基、未取代或卤素取代的C2-12炔基、-N(R”)2，其中X表示卤素；R代表未取代或卤素、O、S的原子取代的C1-12烷基；R’代表氢、未取代或卤素、N、 O、S的原子取代的C1-12烷基；R”代表氢、未取代或卤素取代的C1-6烷基。 In Y(n), n=1-5 substitutions, Y(n) is selected from one or more of the following groups: -R, -X, -OR', -SR', SO 2 NR' 2 , -COR ', -COOR', -CON(R') 2 , -CN, unsubstituted or halogen-substituted C 2-12 alkenyl, unsubstituted or halogen-substituted C 2-12 alkynyl, -N(R") 2 , wherein X represents halogen; R represents unsubstituted or halogen, O, S atoms substituted C 1-12 alkyl; R' represents hydrogen, unsubstituted or halogen, N, O, S atoms substituted C 1-12 Alkyl; R" represents hydrogen, unsubstituted or halogen substituted C 1-6 alkyl.

本发明的第二个方面提供了制备本发明的含取代苯肼的吡咯烷-2，4-二酮类化合物(I)的方法，该方法包括下述步骤A或B中的至少一种： A second aspect of the present invention provides a method for preparing the substituted phenylhydrazine-containing pyrrolidine-2,4-dione compound (I) of the present invention, the method comprising at least one of the following steps A or B:

A.用吡咯烷-2，4-二酮(II)与取代苯肼(III)按照下述反应路线进行制备： A. Use pyrrolidine-2,4-dione (II) and substituted phenylhydrazine (III) to prepare according to the following reaction scheme:

B.用吡咯烷-2，4-二酮(II)与取代苯肼的盐(IV)在加碱的条件下按照下述反应路线进行制备： B. Use the salt (IV) of pyrrolidine-2,4-diketone (II) and substituted phenylhydrazine to prepare according to the following reaction scheme under the condition of adding alkali:

其中在上述各结构式中： Wherein in each above-mentioned structural formula:

R1至R4、Y(n)均具有如前所述的含义； R 1 to R 4 , Y (n) all have the meanings as described above;

R5根据下列方式选择：R2选自氢时，R5选自直链或支链的C1-12烷基，优先选自甲基或乙基，进一步优先选自乙基；R2不选自氢时，R5选自氢。 R is selected according to the following manner: when R is selected from hydrogen, R is selected from linear or branched C 1-12 alkyl, preferably from methyl or ethyl, and further preferably from ethyl; R is not When selected from hydrogen, R is selected from hydrogen.

酸选自无机酸、有机酸或者酸式盐，优选HCl、HBr、H2SO4、HNO3、H2CO3、H3PO4、HClO、H2C2O2、苯磺酸、对甲基苯磺酸；进一步优先选自HCl。 The acid is selected from inorganic acids, organic acids or acid salts, preferably HCl, HBr, H 2 SO 4 , HNO 3 , H 2 CO 3 , H 3 PO 4 , HClO, H 2 C 2 O 2 , benzenesulfonic acid, p- Toluenesulfonic acid; further preferably selected from HCl.

碱选自无机碱或有机碱，优选碱金属或者碱土金属的氢氧化物、氨类、胺类、铵类、醇盐、乙酸盐、碳酸盐、碳酸氢盐，进一步优选NaOH、KOH、NH3、NH4OH、Na2CO3、NaHCO3、K2CO3、KHCO3、(CH3)3N、(C2H5)3N、(CH3)2NH、(C2H5)2NH、CH3NH2、C2H5NH2、CH3ONa、C2H5ONa、吡啶、CH3COONa、(CH3)4NOH。 The base is selected from inorganic bases or organic bases, preferably alkali metal or alkaline earth metal hydroxides, ammonia, amines, ammonium, alkoxides, acetates, carbonates, bicarbonates, more preferably NaOH, KOH, NH 3 , NH 4 OH, Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , KHCO 3 , (CH 3 ) 3 N, (C 2 H 5 ) 3 N, (CH 3 ) 2 NH, (C 2 H 5 ) 2 NH, CH 3 NH 2 , C 2 H 5 NH 2 , CH 3 ONa, C 2 H 5 ONa, Pyridine, CH 3 COONa, (CH 3 ) 4 NOH.

上述取代苯肼(III)和取代苯肼的盐(IV)采用市售产品。 The above-mentioned substituted phenylhydrazine (III) and the salt (IV) of substituted phenylhydrazine adopt commercially available products.

上述吡咯烷-2，4-二酮(II)根据结构差异分别采用以下步骤C、D、E的方法进行合成： The above-mentioned pyrrolidine-2,4-dione (II) is synthesized by the following steps C, D, and E respectively according to structural differences:

C.R2选自氢时，吡咯烷-2，4-二酮(II-1)按照下述反应路线进行制备： When CR 2 is selected from hydrogen, pyrrolidine-2,4-dione (II-1) is prepared according to the following reaction scheme:

上述化合物(V)按照下述两种反应路线之一进行制备： Above-mentioned compound (V) is prepared according to one of following two kinds of reaction schemes:

化合物(V)的第一种反应路线： The first reaction scheme of compound (V):

化合物(V)的第二种反应路线： The second reaction scheme of compound (V):

方法D.R2选自CH3时，吡咯烷-2，4-二酮(II-2)按照下述反应路线进行制备： When method DR 2 is selected from CH 3 , pyrrolidine-2,4-dione (II-2) is prepared according to the following reaction scheme:

方法E.R2选自除H和CH3以外的其他基团时，吡咯烷-2，4-二酮(II-3)按照下述两种反应路线之一进行制备： Method When ER 2 is selected from other groups except H and CH 3 , pyrrolidine-2,4-dione (II-3) is prepared according to one of the following two reaction schemes:

吡咯烷-2，4-二酮(II-3)的第一种反应路线： The first reaction scheme of pyrrolidine-2,4-dione (II-3):

吡咯烷-2，4-二酮(II-3)的第二种反应路线： The second reaction scheme of pyrrolidine-2,4-dione (II-3):

其中在上述各结构式中： Wherein in each above-mentioned structural formula:

R1至R5均具有如前所述的含义； R 1 to R 5 all have the meanings as previously described;

R6选自直链或支链的C1-12烷基，优选甲基或乙基；R7选自甲基或乙基。 R 6 is selected from linear or branched C 1-12 alkyl, preferably methyl or ethyl; R 7 is selected from methyl or ethyl.

本发明的第三个方面涉及本发明的含取代苯肼的吡咯烷-2，4-二酮类化合物或其混合物在防治植物有害真菌中的应用。 The third aspect of the present invention relates to the use of the substituted phenylhydrazine-containing pyrrolidine-2,4-dione compound or the mixture thereof in the control of plant harmful fungi.

本发明的第四个方面涉及包括本发明的含取代苯肼的吡咯烷-2，4-二酮类化合物的一种组合物。 A fourth aspect of the present invention relates to a composition comprising a substituted phenylhydrazine-containing pyrrolidine-2,4-dione compound of the present invention.

本发明的第五个方面涉及所述的组合物在防治植物有害真菌中的应用。 The fifth aspect of the present invention relates to the use of the composition in controlling plant harmful fungi.

本发明的第六个方面涉及一种防治有害真菌的方法，将本发明的含取代苯肼的吡咯烷-2，4-二酮类化合物用于所述的真菌及其生境。 The sixth aspect of the present invention relates to a method for controlling harmful fungi, using the substituted phenylhydrazine-containing pyrrolidine-2,4-dione compounds of the present invention for the fungi and their habitats.

一般性定义general definition

本发明中，所述的取代可为单取代或多取代的基团，在多取代时，各个取代基可相同或不相同。 In the present invention, the substituents may be monosubstituted or polysubstituted groups, and in the case of polysubstituted, each substituent may be the same or different.

除非另有定义，术语卤素(X)选自氟、氯、溴、碘，其中优选氟、氯、溴。 Unless otherwise defined, the term halogen (X) is selected from fluorine, chlorine, bromine, iodine, wherein fluorine, chlorine, bromine are preferred.

基团-X表示选自氟、氯、溴、碘的卤素原子，其中优选氟、氯、溴。 The group -X represents a halogen atom selected from fluorine, chlorine, bromine and iodine, among which fluorine, chlorine and bromine are preferred.

卤代烷基可为一卤代烷基或多卤代烷基，如选自CF3、CCl3、CHF2、CHCl2、CH2Cl、CF3CH2、CHF2CF2、 CF3CF2、(CF3)2CF、CF3CCl2。 The haloalkyl group can be a monohaloalkyl group or a polyhaloalkyl group, such as being selected from CF 3 , CCl 3 , CHF 2 , CHCl 2 , CH 2 Cl, CF 3 CH 2 , CHF 2 CF 2 , CF 3 CF 2 , (CF 3 ) 2 CF, CF 3 CCl 2 .

本发明中，除非另有定义，烷基基团表示选自直链、支链的饱和烃基基团。同时，本发明中取代的烷基基团表示本发明所述的烷基可任选被选自下列的一个或多个基团取代：-R’、-X、-OR’、-SR’、-N(R’)2、-COR’、-COOR’、-CON(R’)2、-NO2、-CN，其中R’代表氢或C1-12烷基，优选C1-8烷基，特别优选C1-6烷基，所述烷基可以被一个或多个选自卤素、N、O、S的原子取代； In the present invention, unless otherwise defined, the alkyl group means a saturated hydrocarbon group selected from straight chain and branched chain. At the same time, the substituted alkyl group in the present invention means that the alkyl group described in the present invention can be optionally substituted by one or more groups selected from the following groups: -R', -X, -OR', -SR', -N(R') 2 , -COR', -COOR', -CON(R') 2 , -NO 2 , -CN, wherein R' represents hydrogen or C 1-12 alkyl, preferably C 1-8 alkane A group, particularly preferably a C 1-6 alkyl group, which may be substituted by one or more atoms selected from halogen, N, O, S;

除非另有定义，“烷基可以被一个或多个选自卤素、N、O、S的原子取代”或“卤素、N、O、S的原子取代的C1-12烷基”是指烷基中的氢原子被一个或多个卤素原子取代，或烷基中的氢原子或碳原子被一个或多个选自N、O、S的原子取代； Unless otherwise defined, "alkyl may be substituted by one or more atoms selected from halogen, N, O, S" or "C 1-12 alkyl substituted by atoms of halogen, N, O, S" means an alkyl The hydrogen atom in the group is replaced by one or more halogen atoms, or the hydrogen atom or carbon atom in the alkyl group is replaced by one or more atoms selected from N, O and S;

定义“C1-12烷基”包括本发明中对烷基定义的最宽泛的范围。具体来说，这一定义包括如下含义：CH3-、C2H5-、n-C3H7-、i-C3H7-、n-C4H9-、i-C4H9-、sec-C4H9-、t-C4H9-、n-C5H11-、i-C5H11-、sec-C5H11-、2-CH3-C4H8、1-C2H5-C3H6-、1，2-(CH3)2-C3H5-、n-C6H13-、sec-C6H13-、i-C6H13-、1，2-(CH3)2-C4H7-、n-C7H15-、3，3-(CH3)2-C5H9-、n-C8H17-、n-C9H19-、n-C10H21-、n-C11H23-、n-C12H25-。 The definition "C 1-12 alkyl" includes the broadest range defined for alkyl in the present invention. Specifically, this definition includes the following meanings: CH 3 -, C 2 H 5 -, nC 3 H 7 -, iC 3 H 7 -, nC 4 H 9 -, iC 4 H 9 -, sec-C 4 H 9 -, tC 4 H 9 -, nC 5 H 11 -, iC 5 H 11 -, sec-C 5 H 11 -, 2-CH 3 -C 4 H 8 , 1-C 2 H 5 -C 3 H 6 -, 1,2-(CH 3 ) 2 -C 3 H 5 -, nC 6 H 13 -, sec-C 6 H 13 -, iC 6 H 13 -, 1,2-(CH 3 ) 2 -C 4 H 7 -, nC 7 H 15 -, 3,3-(CH 3 ) 2 -C 5 H 9 -, nC 8 H 17 -, nC 9 H 19 -, nC 10 H 21 -, nC 11 H 23 -, nC 12 H 25 -.

本发明中，除非另有定义，烯基基团表示含有至少一个单不饱和度(双键)的直链或支链的烃基基团。同时，本发明中取代的烯基基团表示本发明所述的烯基基团可任选被选自下列的一个或多个基团取代：-R’、-X、-OR’、-SR’、-N(R’)2、-COR’、-COOR’、-CON(R’)2、-NO2、-CN，其中R’代表氢或C1-12烷基，优选C1-8烷基，特别优选C1-6烷基，所述烷基可以被一个或多个选自卤素、N、O、S的原子取代； In the present invention, unless defined otherwise, an alkenyl group denotes a straight-chain or branched hydrocarbon group containing at least one monounsaturation (double bond). At the same time, the substituted alkenyl group in the present invention means that the alkenyl group described in the present invention can be optionally substituted by one or more groups selected from the following groups: -R', -X, -OR', -SR ', -N(R') 2 , -COR', -COOR', -CON(R') 2 , -NO 2 , -CN, wherein R' represents hydrogen or C 1-12 alkyl, preferably C 1- 8 Alkyl, particularly preferably C 1-6 alkyl, said alkyl can be substituted by one or more atoms selected from halogen, N, O, S;

定义“C2-12烯基”包括本发明中对烯基定义的最宽泛的范围。具体来说，这一定义包括如下含义：CH2＝CH-、CH3CH＝CH-、CH2＝CHCH2-、CH2＝C(CH3)-、CH3CH2CH＝CH-、CH 3CH＝CHCH2-、CH2＝CHCH2CH2-、CH3(CH2)2CH＝CH-、CH3CH2CH＝CHCH2-、CH3CH＝CHCH2CH2-、CH2＝CH(CH2)2CH2-、CH3(CH2)3CH＝CH-、CH3CH2CH＝CHCH2CH2-、CH2＝CH(CH2)4CH2-、CH3(CH2)3CH＝CHCH2CH2-、CH3CH2CH＝CH(CH2)3CH2-、CH3(CH2)5CH＝CHCH2-、CH3(CH2)4CH＝CHCH2CH2-、CH 3(CH2)2CH＝CH(CH2)4CH2-、CH3(CH2)2CH＝CH(CH2)4CH2-、 CH3(CH2)3CH2＝CH(CH2)4CH2-、CH 3(CH2)2CH＝CH(CH2)5CH2-、CH3CH＝CH(CH2)7CH2-、CH3(CH2)3CH＝CH(CH2)4CH2-、CH3(CH2)5CH＝CH(CH2)2CH2-、CH3(CH2)4CH＝CH(CH2)4CH2-、CH3(CH2)2CH＝CH(CH2)6CH2-、CH2＝CH(CH2)9CH2-、CH3(CH2)9CH＝CH-、CH2＝CHCH＝CH-、CH3CH＝CHCH＝CH-、CH3(CH2)4CH＝CHCH＝CH-。 The definition "C 2-12 alkenyl" includes the broadest range defined for alkenyl in the present invention. Specifically, this definition includes the following meanings: CH 2 =CH-, CH 3 CH=CH-, CH 2 =CHCH 2 -, CH 2 =C(CH 3 )-, CH 3 CH 2 CH=CH-, CH 3 CH=CHCH 2 -, CH 2 =CHCH 2 CH 2 -, CH 3 (CH 2 ) 2 CH=CH-, CH 3 CH 2 CH=CHCH 2 -, CH 3 CH=CHCH 2 CH 2 -, CH 2 =CH(CH 2 ) 2 CH 2 -, CH 3 (CH 2 ) 3 CH=CH-, CH 3 CH 2 CH=CHCH 2 CH 2 -, CH 2 =CH(CH 2 ) 4 CH 2 -, CH 3 (CH 2 ) 3 CH=CHCH 2 CH 2 -, CH 3 CH 2 CH=CH(CH 2 ) 3 CH 2 -, CH 3 (CH 2 ) 5 CH=CHCH 2 -, CH 3 (CH 2 ) 4 CH=CHCH 2 CH 2 -, CH 3 (CH 2 ) 2 CH=CH(CH 2 ) 4 CH 2 -, CH 3 (CH 2 ) 2 CH=CH( CH 2 ) 4 CH 2 -, CH 3 (CH 2 ) 3 CH 2 =CH(CH 2 ) 4 CH 2 -, CH 3 (CH 2 ) 2 CH=CH(CH 2 ) 5 CH 2 -, CH 3 CH=CH(CH 2 ) 7 CH 2 -, CH 3 (CH 2 ) 3 CH=CH(CH 2 ) 4 CH 2 -, CH 3 (CH 2 ) 5 CH=CH(CH 2 ) 2 CH 2 -, CH 3 (CH 2 ) 4 CH=CH(CH 2 ) 4 CH 2 -, CH 3 (CH 2 ) 2 CH=CH(CH 2 ) 6 CH 2 -, CH 2 =CH(CH 2 ) 9 CH 2 -, CH 3 (CH 2 ) 9 CH=CH-, CH 2 =CHCH=CH-, CH 3 CH=CHCH=CH-, CH 3 (CH 2 ) 4 CH=CHCH=CH-.

本发明中，除非另有定义，炔基基团表示含有至少一个双不饱和度(叁键)的直链或支链烃基基团。同时，本发明中取代的炔基基团表示本发明所述的炔基基团可被任选自下列的一个或多个基团取代：-R’、-X、-OR’、-SR’、-N(R’)2、-COR’、-COOR’、-CON(R’)2、-NO2、-CN，其中R’代表氢或C1-12烷基，优选C1-8烷基，特别优选C1-6烷基，所述烷基可以被一个或多个选自卤素、N、O、S的原子取代； In the present invention, unless otherwise defined, an alkynyl group denotes a straight-chain or branched hydrocarbon group containing at least one double unsaturation (triple bond). At the same time, the substituted alkynyl group in the present invention means that the alkynyl group described in the present invention can be substituted by one or more groups optionally selected from the following groups: -R', -X, -OR', -SR' , -N(R') 2 , -COR', -COOR', -CON(R') 2 , -NO 2 , -CN, wherein R' represents hydrogen or C 1-12 alkyl, preferably C 1-8 Alkyl, particularly preferably C 1-6 alkyl, said alkyl can be substituted by one or more atoms selected from halogen, N, O, S;

定义“C2-12炔基”包括本发明中对炔基定义的最宽泛的范围。具体来说，这一定义包括如下含义：CH≡C-、CH3C≡C-、CH≡CCH2-、CH3CH2C≡C-、CH3C≡CCH2CH2-。 The definition "C 2-12 alkynyl" includes the broadest range defined for alkynyl in the present invention. Specifically, this definition includes the following meanings: CH≡C-, CH 3 C≡C-, CH≡CCH 2 -, CH 3 CH 2 C≡C-, CH 3 C≡CCH 2 CH 2 -.

本发明中，除非另有定义，酰基基团表示选自直链、支链含有至少一个甲酰基(-CO或者-C＝O)的基团，所述基团可任选含有一个、两个或者多个单不饱和度或者双不饱和度。同时，本发明中取代的酰基基团表示本发明所述的酰基基团可任选被选自下列的一个或多个基团取代：-R’、-X、-OR’、-SR’、-N(R’)2、-COR’、-COOR’、-CON(R’)2、-NO2、-CN，其中R’代表氢或C1-12烷基，优选C1-8烷基，特别优选C1-6烷基，所述烷基可以被一个或多个选自卤素、N、O、S的原子取代； In the present invention, unless otherwise defined, an acyl group means a group selected from linear and branched chains containing at least one formyl group (-CO or -C=O), and the group may optionally contain one or two or multiple monounsaturations or double unsaturations. At the same time, the substituted acyl group in the present invention means that the acyl group described in the present invention can be optionally substituted by one or more groups selected from the following groups: -R', -X, -OR', -SR', -N(R') 2 , -COR', -COOR', -CON(R') 2 , -NO 2 , -CN, wherein R' represents hydrogen or C 1-12 alkyl, preferably C 1-8 alkane A group, particularly preferably a C 1-6 alkyl group, which may be substituted by one or more atoms selected from halogen, N, O, S;

定义“C1-12酰基”包括本发明中对酰基定义的最宽泛的范围。具体来说，这一定义包括如下含义：HCO-、CH3CO-、C2H5CO-、n-C3H7CO-、i-C3H7CO-、n-C4H9CO-、i-C4H9CO-、sec-C4H9CO-、t-C4H9CO-、n-C5H11CO-、i-C5H11CO-、sec-C5H11CO-、n-C6H13CO-、1，2-(CH3)2-C4H7CO-、n-C7H15CO-、3，3-(CH3)2-C5H9CO-、n-C8H17CO-、n-C9H19CO-、n-C10H21CO-、n-C11H23CO-、CH2＝CHCO-、CH3CH＝CHCO-、CH 3COCH2-、CH 3CH2COCH2-、CH3COCH2CH2-。 The definition "C 1-12 acyl" includes the broadest definition of acyl in the present invention. Specifically, this definition includes the following meanings: HCO-, CH 3 CO-, C 2 H 5 CO-, nC 3 H 7 CO-, iC 3 H 7 CO-, nC 4 H 9 CO-, iC 4 H 9 CO-, sec-C 4 H 9 CO-, tC 4 H 9 CO-, nC 5 H 11 CO-, iC 5 H 11 CO-, sec-C 5 H 11 CO-, nC 6 H 13 CO-, 1,2-(CH 3 ) 2 -C 4 H 7 CO-, nC 7 H 15 CO-, 3,3-(CH 3 ) 2 -C 5 H 9 CO-, nC 8 H 17 CO-, nC 9 H 19 CO-, nC 10 H 21 CO-, nC 11 H 23 CO-, CH 2 =CHCO-, CH 3 CH=CHCO-, CH 3 COCH 2 -, CH 3 CH 2 COCH 2 -, CH 3 COCH 2 CH2- .

本发明中，除非另有定义，芳基基团表示芳香烃基团。同时，本发明中取代的芳基基团表示本发明所述的芳基基团可任选被选自下列的一个或多个基团取代：-R’、-X、-OR’、-SR’、-N(R’)2、-COR’、-COOR’、-CON(R’)2、-NO2、-CN，其中R’代表氢或C1-12烷基，优选C1-8烷基，特别优选C1-6烷基，所述烷基 可以被一个或多个选自卤素、N、O、S的原子取代； In the present invention, unless otherwise defined, an aryl group means an aromatic hydrocarbon group. At the same time, the substituted aryl group in the present invention means that the aryl group described in the present invention can be optionally substituted by one or more groups selected from the following groups: -R', -X, -OR', -SR ', -N(R') 2 , -COR', -COOR', -CON(R') 2 , -NO 2 , -CN, wherein R' represents hydrogen or C 1-12 alkyl, preferably C 1- 8 alkyl, particularly preferably C 1-6 alkyl, said alkyl can be substituted by one or more atoms selected from halogen, N, O, S;

定义“C5-12芳基”包括本发明中对含有5至12个原子的芳基定义的最宽泛的范围。具体来说，这一定义包括如下含义：苯基、萘基、环戊二烯基、环庚三烯基、环辛四烯基。 The definition "C 5-12 aryl" includes the broadest range defined herein for aryl groups containing 5 to 12 atoms. Specifically, this definition includes the following meanings: phenyl, naphthyl, cyclopentadienyl, cycloheptatrienyl, cyclooctatetraenyl.

本发明中，除非另有定义，芳基烷基基团表示被芳基取代的烷基基团，所述芳基烷基基团可具有C1-7亚烷基链，所述的亚烷基链可选自直链、支链的基团，可任选含有一个、两个或者多个单不饱和度或者双不饱和度。同时，本发明取代的芳基烷基基团表示本发明所述的芳基烷基基团可任选被选自下列的一个或多个基团取代：-R’、-X、-OR’、-SR’、-N(R’)2、-COR’、-COOR’、-CON(R’)2、-NO2、-CN，其中R’代表氢或C1-12烷基，优选C1-8烷基，特别优选C1-6烷基，所述烷基可以被一个或多个选自卤素、N、O、S的原子取代； In the present invention, unless otherwise defined, an arylalkyl group represents an alkyl group substituted by an aryl group, and the arylalkyl group may have a C 1-7 alkylene chain, and the alkylene The base chain can be selected from linear and branched groups, and can optionally contain one, two or more monounsaturations or double unsaturations. At the same time, the substituted arylalkyl group of the present invention means that the arylalkyl group described in the present invention can be optionally substituted by one or more groups selected from the following groups: -R', -X, -OR' , -SR', -N(R') 2 , -COR', -COOR', -CON(R') 2 , -NO 2 , -CN, wherein R' represents hydrogen or C 1-12 alkyl, preferably C 1-8 alkyl, particularly preferably C 1-6 alkyl, said alkyl can be substituted by one or more atoms selected from halogen, N, O, S;

定义“C6-19芳基烷基”包括本发明中对芳基和亚烷基链总共含有6至19个碳原子的芳基烷基基团定义的最宽泛的范围。具体来说，这一定义优选包括如下含义：苯甲基、萘甲基、环戊二烯甲基、苯乙基。 The definition "C 6-19 arylalkyl" includes the broadest range defined herein for arylalkyl groups having a total of 6 to 19 carbon atoms in the aryl and alkylene chains. In particular, this definition preferably includes the following meanings: benzyl, naphthylmethyl, cyclopentadienylmethyl, phenethyl.

本发明中，除非另有定义，杂环基为环系统中的一个或多个碳原子被选自N、O、S的杂原子取代的C3-8环烷基、C4-8环烯基、C4-8环炔基、C5-12芳基、C5-12芳基甲酰基、C6-19芳基烷基。 In the present invention, unless otherwise defined, a heterocyclic group is a C 3-8 cycloalkyl, a C 4-8 cycloalkene in which one or more carbon atoms in the ring system are replaced by a heteroatom selected from N, O, and S Base, C 4-8 cycloalkynyl, C 5-12 aryl, C 5-12 arylformyl, C 6-19 arylalkyl.

本发明中，所述的含取代苯肼的吡咯烷2，4二酮类化合物(I)可以以可能的含有不同异构体的混合物的形式存在，也可以以可能的其中一种异构体的形式单独存在，所述的异构体包括几何异构体，如Z式与E式、光学异构体，如R型与S型，及互变异构体，如酮式与烯醇式。本发明公开的和要求保护的异构体形式包括几何异构体，如Z式与E式、光学异构体，如R型与S型，及互变异构体，如酮式与烯醇式，以及含任意比例的所述异构体的混合物。 In the present invention, the pyrrolidine 2,4 diketone compound (I) containing substituted phenylhydrazines may exist in the form of a mixture of possible isomers, or in the form of one of the possible isomers The form exists alone, and the isomers include geometric isomers, such as Z-form and E-form, optical isomers, such as R-form and S-form, and tautomers, such as keto-form and enol-form . The isomeric forms disclosed and claimed in the present invention include geometric isomers, such as Z and E, optical isomers, such as R and S, and tautomers, such as keto and enol formula, and mixtures containing said isomers in any proportion.

本发明中，所述的含取代苯肼的吡咯烷-2，4-二酮类化合物的几何异构体，可以指顺式或反式异构体，或者Z式或E式异构体，可以用下述的通式(I-1)与(I-2)表示，其中哪一个是顺式或反式异构体，或者Z式或E式异构体，因R2基团的不同而确定： In the present invention, the geometric isomers of pyrrolidine-2,4-dione compounds containing substituted phenylhydrazines may refer to cis or trans isomers, or Z or E isomers, It can be represented by the following general formulas (I-1) and (I-2), which one is cis or trans isomer, or Z or E isomer, due to the difference of R2 groups And OK:

本发明中，所述的含取代苯肼的吡咯烷-2，4-二酮类化合物的光学异构体，如R型与S型，是指基团R3与R4不相同时产生的立体异构体，其中所述的通式(I-1)的立体异构体可以用下述的通式(I-3)与(I-4)表示，所述的通式(I-2)也可产生两种相应的立体异构体，其中哪一个是R型或S型，因基团R3与R4的不同而确定： In the present invention, the optical isomers of pyrrolidine-2,4-dione compounds containing substituted phenylhydrazines, such as R-type and S-type, refer to those produced when the groups R3 and R4 are different Stereoisomers, wherein the stereoisomers of the general formula (I-1) can be represented by the following general formulas (I-3) and (I-4), the general formula (I-2 ) can also produce two corresponding stereoisomers, which one is R-type or S-type, depending on the difference between the groups R3 and R4 :

本发明中，所述的含取代苯肼的吡咯烷-2，4-二酮类化合物的互变异构体，是由酮式与烯醇式互变引起的，是吡咯烷-2，4-二酮类化合物所共同具有的一种常见现象(J.Chem.Soc.，Perkin Trans.1，1998，2443-2449；结构化学，2004，23：952-956.)，如下述的通式(I-5)、(I-6)与上述通式(I-3)为互变异构体，上述通式(I-4)也存在相应的互变异构体： In the present invention, the tautomers of pyrrolidine-2,4-dione compounds containing substituted phenylhydrazines are caused by the interconversion of keto and enol forms, and are pyrrolidine-2,4 - a common phenomenon (J.Chem.Soc., Perkin Trans.1, 1998, 2443-2449; Structural Chemistry, 2004, 23: 952-956.) shared by diketone compounds, such as the following general formula (I-5), (I-6) and above-mentioned general formula (I-3) are tautomers, and above-mentioned general formula (I-4) also has corresponding tautomers:

本发明的一种具有通式(I)所示结构的含取代苯肼的吡咯烷-2，4-二酮类化合物、或其顺反异构体、光学异构体、互变异构体，或农药学上可接受的盐及其金属配合物。 A substituted phenylhydrazine-containing pyrrolidine-2,4-dione compound having a structure represented by general formula (I), or its cis-trans isomers, optical isomers, and tautomers of the present invention , or pesticide acceptable salts and metal complexes thereof.

在式(I)中，所述各个基团具有如下所述的优选定义，下述的优选定义也同样适用于制备该化合物的所有中间体： In formula (I), each group has the preferred definitions as described below, and the following preferred definitions are also applicable to all intermediates for the preparation of the compound:

R1选自氢、取代或未取代的直链或支链的C1-6烷基、C3-6环烷基、C2-6烯基、C5-6环烯基、C2-3炔基、C1-4酰基、苯基、苯甲酰基、苯甲基、杂环基，所述的取代基团选自：-R’、-X、-OR’、-SR’、-N(R’)2、-NO2，其中X表示卤素，R’代表氢、未取代或被一个或多个选自F、Cl、Br的卤素原子取代的C1-4烷基；所述的杂环基为环系统中的一个或多个碳原子被选自N、O、S的杂原子取代的C3-6环烷基、C5-6环烯基、苯基、苯甲酰基、苯甲基； R 1 is selected from hydrogen, substituted or unsubstituted linear or branched C 1-6 alkyl, C 3-6 cycloalkyl, C 2-6 alkenyl, C 5-6 cycloalkenyl, C 2- 3 alkynyl, C 1-4 acyl, phenyl, benzoyl, benzyl, heterocyclyl, the substituent group is selected from: -R', -X, -OR', -SR', - N(R') 2 , -NO 2 , wherein X represents halogen, R' represents hydrogen, C 1-4 alkyl unsubstituted or substituted by one or more halogen atoms selected from F, Cl, Br; said The heterocyclic group is C 3-6 cycloalkyl, C 5-6 cycloalkenyl, phenyl, benzoyl in which one or more carbon atoms in the ring system are replaced by heteroatoms selected from N, O, and S , Benzyl;

R2选自氢、取代或未取代的直链或支链的C1-6烷基、C3-6环烷基、C2-6烯基、C5-6环烯基、C2-3炔基，所述的取代基团选自：-R’、-X，其中X表示卤素，R’代表氢或C1-4烷基； R 2 is selected from hydrogen, substituted or unsubstituted linear or branched C 1-6 alkyl, C 3-6 cycloalkyl, C 2-6 alkenyl, C 5-6 cycloalkenyl, C 2- 3 alkynyl, the substituent group is selected from: -R', -X, wherein X represents halogen, R' represents hydrogen or C 1-4 alkyl;

R3选自氢、取代或未取代的直链或支链的C1-8烷基、C5-6环烷基、C2-6烯基、C2-6酰基、苯基、苯甲酰基、苯甲基，所述的取代基团选自：-R’、-X、-OR’、-SR’、-N(R’)2、-NO2，其中X表示卤素，R’代表氢、未取代或被一个或多个选自F、Cl、Br的卤素原子取代的C1-4烷基； R 3 is selected from hydrogen, substituted or unsubstituted linear or branched C 1-8 alkyl, C 5-6 cycloalkyl, C 2-6 alkenyl, C 2-6 acyl, phenyl, benzyl Acyl, benzyl, the substituents are selected from: -R', -X, -OR', -SR', -N(R') 2 , -NO 2 , where X represents halogen, and R' represents Hydrogen, unsubstituted or C 1-4 alkyl substituted by one or more halogen atoms selected from F, Cl, Br;

R4选自氢、直链或支链的C1-6烷基； R 4 is selected from hydrogen, straight chain or branched C 1-6 alkyl;

Y(n)中，n＝1-3取代，Y(n)选自下列的一个、两个或三个基团：-R、-X、-OR’、-SR’、SO2NR’2、C2-5烯基、C2-3炔基、-N(R”)2，其中X表示卤素；R代表未取代或被一个或多个选自F、Cl、O、S的原子取代的C1-6烷基；R’代表氢、未取代或被一个或多个选自F、Cl、N、O、S的原子取代的C1-6烷基；R”代表氢或C1-4烷基。 In Y(n), n=1-3 substitution, Y(n) is selected from one, two or three of the following groups: -R, -X, -OR', -SR', SO 2 NR' 2 , C 2-5 alkenyl, C 2-3 alkynyl, -N(R") 2 , where X represents halogen; R represents unsubstituted or substituted by one or more atoms selected from F, Cl, O, S C 1-6 alkyl; R' represents hydrogen, unsubstituted or C 1-6 alkyl substituted by one or more atoms selected from F, Cl, N, O, S; R" represents hydrogen or C 1 -4 alkyl.

在式(I)中，所述各个基团具有如下所述的进一步优选定义，下述的进一步优选定义也同样适用于制备该化合物的所有中间体： In formula (I), each group has a further preferred definition as described below, and the following further preferred definition is also applicable to all intermediates for the preparation of the compound:

R1选自氢、取代或未取代的直链或支链的C1-6烷基、C3-6环烷基、C2-4酰基、苯基、苯甲基，所述的取代基团选自：-R’、-X、-OR’，其中X表示卤素，R’代表氢、未取代或被一个或多个F或Cl取代的C1-3 烷基； R 1 is selected from hydrogen, substituted or unsubstituted linear or branched C 1-6 alkyl, C 3-6 cycloalkyl, C 2-4 acyl, phenyl, benzyl, the substituent The group is selected from: -R', -X, -OR', wherein X represents halogen, R' represents hydrogen, unsubstituted or C 1-3 alkyl substituted by one or more F or Cl;

R2选自氢、直链或支链的C1-4烷基； R 2 is selected from hydrogen, linear or branched C 1-4 alkyl;

R3选自氢、取代或未取代的直链或支链的C1-6烷基、C5-6环烷基、苯基、苯甲基，所述的取代基团选自：-R’、-X、-OR’，其中X表示卤素，R’代表氢、未取代或被一个或多个F或Cl取代的C1-3烷基； R 3 is selected from hydrogen, substituted or unsubstituted linear or branched C 1-6 alkyl, C 5-6 cycloalkyl, phenyl, benzyl, and the substituting group is selected from: -R ', -X, -OR', wherein X represents halogen, R' represents hydrogen, unsubstituted or C 1-3 alkyl substituted by one or more F or Cl;

R4选自氢、直链或支链的C1-4烷基； R 4 is selected from hydrogen, straight chain or branched C 1-4 alkyl;

Y(n)中，n＝1-2取代，Y(n)选自下列的一个或两个基团：-R、-X、-OR’、SO2NR’2，其中X表示卤素，R代表未取代或被一个或多个F或Cl取代的C1-5烷基，R’代表氢、未取代或被一个或多个F或Cl取代的C1-3烷基。 In Y(n), n=1-2 substitution, Y(n) is selected from one or two of the following groups: -R, -X, -OR', SO 2 NR' 2 , where X represents halogen, R represents C 1-5 alkyl unsubstituted or substituted by one or more F or Cl, R' represents hydrogen, C 1-3 alkyl unsubstituted or substituted by one or more F or Cl.

在式(I)中，所述各个基团具有如下所述的更进一步优选定义，下述的优选定义也同意适用于所有的中间体： In formula (I), the respective groups have further preferred definitions as described below, which also agree to apply to all intermediates:

R1选自氢、甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、异戊基、仲戊基、2-甲基丁基、1-乙基丙基、己基、仲己基、异己基、环丙烷基、环丁烷基、环戊烷基、环己烷基、甲酰基、乙酰基、丙酰基、丁酰基、苯基、4-氯苯基、3-氯苯基、2-氯苯基、2-氟苯基、3-氟苯基、4-氟苯基、2-溴苯基、3-溴苯基、4-溴苯基、2-甲基苯基、3-甲基苯基、4-甲基苯基、4-三氟甲基苯基、2，4-二甲基苯基、2，4-二氯苯基、苄基、4-氯苄基或4-羟基苄基； R is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, 2-methylbutyl base, 1-ethylpropyl, hexyl, sec-hexyl, isohexyl, cyclopropanyl, cyclobutanyl, cyclopentyl, cyclohexane, formyl, acetyl, propionyl, butyryl, phenyl , 4-chlorophenyl, 3-chlorophenyl, 2-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-bromophenyl, 3-bromophenyl, 4 -Bromophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 2,4-dimethylphenyl, 2,4-di Chlorophenyl, benzyl, 4-chlorobenzyl or 4-hydroxybenzyl;

R2选自氢、甲基、乙基或丙基； R is selected from hydrogen, methyl, ethyl or propyl;

R3选自氢、甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、异戊基、仲戊基、2-甲基丁基、1-乙基丙基、己基、仲己基、异己基、环丙烷基、环丁烷基、环戊烷基、环己烷基、苯基、4-氯苯基、3-氯苯基、2-氯苯基、2-氟苯基、3-氟苯基、4-氟苯基、2-溴苯基、3-溴苯基、4-溴苯基、2-甲基苯基、3-甲基苯基、4-甲基苯基、4-三氟甲基苯基、2，4-二甲基苯基、2，4-二氯苯基、苄基、4-氯苄基或4-羟基苄基； R is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, 2-methylbutyl base, 1-ethylpropyl, hexyl, sec-hexyl, isohexyl, cyclopropanyl, cyclobutanyl, cyclopentyl, cyclohexyl, phenyl, 4-chlorophenyl, 3-chlorophenyl , 2-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 2,4-dimethylphenyl, 2,4-dichlorophenyl, benzyl, 4-chlorobenzyl or 4-hydroxybenzyl;

R4选自氢、甲基、乙基或丙基； R is selected from hydrogen, methyl, ethyl or propyl;

Y(n)中，n＝1-2取代，Y(n)选自下列的一个或两个基团：氟、氯、溴、碘、甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、三氟甲基、五氟乙基、七氟异丙基、甲氧基、乙氧基、丙氧基、异丙氧基、三氟甲氧基、氨基磺酰基。 In Y(n), n=1-2 is substituted, and Y(n) is selected from one or two of the following groups: fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl Base, isobutyl, sec-butyl, tert-butyl, trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, methoxy, ethoxy, propoxy, isopropoxy, trifluoromethyl Oxygen, aminosulfonyl.

在式(I)中，所述各个基团具有如下所述的特别优选定义： In formula (I), the individual radicals have particularly preferred definitions as described below:

5-仲丁基-3-(1-(2-(4-甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-仲丁基-3-(1-(2-(4-三氟甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-仲丁基-3-(1-(2-(3，4-二甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-仲丁基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-仲丁基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-仲丁基-3-(1-(2-(2-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-仲丁基-3-(1-(2-(2，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-仲丁基-3-(1-(2-(3，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-仲丁基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-仲丁基-3-(1-(2-(3-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、3-(1-(2-(2-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、3-(1-(2-(3-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、3-(1-(2-(2，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、3-(1-(2-(4-甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、3-(1-(2-(4-甲氧基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、3-(1-(2-(3，4-二甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、3-(1-(2-(4-氨基磺酰基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-异丙基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-异丙基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-异丙基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-丁基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-异丁基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-异丁基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-异丁基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-己 基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-苯甲基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-苯甲基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-苯甲基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-异丙基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-异丙基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-异丙基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-仲丁基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-仲丁基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-仲丁基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-叔丁基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-叔丁基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-叔丁基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-苯基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-苯基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-苯基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-(4-甲基苯基)-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-(4-甲基苯基)-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-(4-甲基苯基)-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-(4-氯苯基)-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-(4-氯苯基)-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-(4-氯苯基)-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-乙酰基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-甲基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-甲基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-甲基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-甲基-3-(1-(2-(2-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-甲基-3-(1-(2-(3-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-甲基-3-(1-(2-(2，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-甲基-3-(1-(2-(4-甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-甲基-3-(1-(2-(4-甲氧基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-甲基-3-(1-(2-(3，4-二甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-甲基-3-(1-(2-(4-氨基磺酰基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-环己烷基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-环丙烷基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-环丙烷基 -3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1-苄基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5，5-二甲基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5，5-二甲基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5，5-二甲基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5，5-二甲基-3-(1-(2-(2-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5，5-二甲基-3-(1-(2-(3-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5，5-二甲基-3-(1-(2-(2，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5，5-二甲基-3-(1-(2-(4-甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5，5-二甲基-3-(1-(2-(3，4-二甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5，5-二甲基-3-(1-(2-(4-氨基磺酰基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-乙基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-乙基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-乙基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-乙基-3-(1-(2-(2-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-乙基-3-(1-(2-(3-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-乙基-3-(1-(2-(2，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-乙基-3-(1-(2-(4-甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-乙基-3-(1-(2-(3，4-二甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-乙基-3-(1-(2-(4-氨基磺酰基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-苄基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-苄基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-苄基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-苄基-3-(1-(2-(2-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-苄基-3-(1-(2-(3-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-苄基-3-(1-(2-(2，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-苄基-3-(1-(2-(4-甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-苄基-3-(1-(2-(3，4-二甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、5-甲基-5-苄基-3-(1-(2-(4-氨基磺酰基苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1，5-二甲基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1，5-二甲基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1，5-二甲基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1，5，5-三甲基-3-(1-(2-(4-氟苯基)肼基)亚乙基) 吡咯烷-2，4-二酮、1，5，5-三甲基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮、1，5，5-三甲基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮、3-(1-(2-(4-氟苯基)肼基)亚甲基)吡咯烷-2，4-二酮、3-(1-(2-(4-氯苯基)肼基)亚甲基)吡咯烷-2，4-二酮、3-(1-(2-(4-溴苯基)肼基)亚甲基)吡咯烷-2，4-二酮、3-(1-(2-(4-氟苯基)肼基)亚丙基)吡咯烷-2，4-二酮、3-(1-(2-(4-氯苯基)肼基)亚丙基)吡咯烷-2，4-二酮、3-(1-(2-(4-溴苯基)肼基)亚丙基)吡咯烷-2，4-二酮、3-(1-(2-(4-氟苯基)肼基)亚丁基)吡咯烷-2，4-二酮、3-(1-(2-(4-氯苯基)肼基)亚丁基)吡咯烷-2，4-二酮、3-(1-(2-(4-溴苯基)肼基)亚丁基)吡咯烷-2，4-二酮。 5-sec-butyl-3-(1-(2-(4-methylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-sec-butyl-3-(1- (2-(4-trifluoromethylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-sec-butyl-3-(1-(2-(3,4-di Methylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-sec-butyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene) Pyrrolidine-2,4-dione, 5-sec-butyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5- sec-butyl-3-(1-(2-(2-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-sec-butyl-3-(1-(2- (2,4-dichlorophenyl)hydrazino)ethylene)pyrrolidine-2,4-dione, 5-sec-butyl-3-(1-(2-(3,4-dichlorophenyl )hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-sec-butyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2 , 4-diketone, 5-sec-butyl-3-(1-(2-(3-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 3-(1-( 2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine -2,4-dione, 3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 3-(1-(2-(2 -Fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 3-(1-(2-(3-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4 -diketone, 3-(1-(2-(2,4-dichlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 3-(1-(2-(4- Methylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 3-(1-(2-(4-methoxyphenyl)hydrazino)ethylidene)pyrrolidine-2 , 4-diketone, 3-(1-(2-(3,4-dimethylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 3-(1-(2- (4-aminosulfonylphenyl)hydrazino)ethylene)pyrrolidine-2,4-dione, 5-methyl-3-(1-(2-(4-fluorophenyl)hydrazino) Ethyl)pyrrolidine-2,4-dione, 5-methyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-methyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-isopropyl-3-(1-(2 -(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-isopropyl-3-(1-(2-(4-chlorophenyl)hydrazino)idene Ethyl)pyrrolidine-2,4-dione, 5-isopropyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione , 5-butyl-3-(1-(2-(4-chlorophenyl)hydrazine Base) ethylidene) pyrrolidine-2,4-dione, 5-isobutyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4 -Diketone, 5-isobutyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-isobutyl-3- (1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-hexyl-3-(1-(2-(4-chlorophenyl) Hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-benzyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2, 4-diketone, 5-benzyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-benzyl-3 -(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-isopropyl-3-(1-(2-(4-fluorobenzene Base) hydrazino) ethylene) pyrrolidine-2,4-dione, 1-isopropyl-3-(1-(2-(4-chlorophenyl) hydrazino) ethylidene) pyrrolidine- 2,4-dione, 1-isopropyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-sec-butyl -3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-sec-butyl-3-(1-(2-(4- Chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-sec-butyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrole Alkane-2,4-dione, 1-tert-butyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-tert Butyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-tert-butyl-3-(1-(2-( 4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-phenyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene) Pyrrolidine-2,4-dione, 1-phenyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-benzene Base-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-(4-methylphenyl)-3-(1- (2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-(4-methylphenyl)-3-(1-(2-(4-chloro Phenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-(4-methylphenyl)-3-(1-(2-(4-bromophenyl)hydrazino)pyrrolidine Ethyl)pyrrolidine-2,4-dione, 1-(4-chlorophenyl)-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2, 4-diketone, 1-(4-chlorophenyl)-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-( 4-Chlorophenyl)-3-(1-(2-(4-bromophenyl)hydrazino ) Ethylene) pyrrolidine-2,4-dione, 1-acetyl-3-(1-(2-(4-chlorophenyl)hydrazino) ethylidene)pyrrolidine-2,4-two Ketone, 1-methyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-methyl-3-(1-( 2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-methyl-3-(1-(2-(4-bromophenyl)hydrazino) Ethyl)pyrrolidine-2,4-dione, 1-methyl-3-(1-(2-(2-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-methyl-3-(1-(2-(3-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-methyl-3-(1-(2- (2,4-dichlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-methyl-3-(1-(2-(4-methylphenyl)hydrazino ) Ethylene) pyrrolidine-2,4-dione, 1-methyl-3-(1-(2-(4-methoxyphenyl)hydrazino) ethylidene)pyrrolidine-2,4 -Diketone, 1-methyl-3-(1-(2-(3,4-dimethylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-methyl- 3-(1-(2-(4-aminosulfonylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-cyclohexane-3-(1-(2-( 4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1-cyclopropanyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylene ) pyrrolidine-2,4-dione, 1-cyclopropanyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1 -Benzyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5,5-dimethyl-3-(1-( 2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5,5-dimethyl-3-(1-(2-(4-chlorophenyl)hydrazine Base) ethylidene) pyrrolidine-2,4-dione, 5,5-dimethyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2 , 4-diketone, 5,5-dimethyl-3-(1-(2-(2-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5,5- Dimethyl-3-(1-(2-(3-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5,5-dimethyl-3-(1-( 2-(2,4-dichlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5,5-dimethyl-3-(1-(2-(4-methyl Phenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5,5-dimethyl-3-(1-(2-(3,4-dimethylphenyl)hydrazino) Ethylene)pyrrolidine-2,4-dione, 5,5-dimethyl-3-(1-(2-(4-aminosulfonylphenyl)hydrazino)ethylidene)pyrrolidine-2 , 4-diketone, 5-methyl-5-ethyl-3 -(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-methyl-5-ethyl-3-(1-(2-( 4-Chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-methyl-5-ethyl-3-(1-(2-(4-bromophenyl)hydrazino ) Ethylene) pyrrolidine-2,4-dione, 5-methyl-5-ethyl-3-(1-(2-(2-fluorophenyl) hydrazino) ethylidene) pyrrolidine- 2,4-dione, 5-methyl-5-ethyl-3-(1-(2-(3-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5 -Methyl-5-ethyl-3-(1-(2-(2,4-dichlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-methyl-5 -Ethyl-3-(1-(2-(4-methylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-methyl-5-ethyl-3-( 1-(2-(3,4-Dimethylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-methyl-5-ethyl-3-(1-(2 -(4-aminosulfonylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-methyl-5-benzyl-3-(1-(2-(4-fluorobenzene Base) hydrazino) ethylene) pyrrolidine-2,4-dione, 5-methyl-5-benzyl-3-(1-(2-(4-chlorophenyl) hydrazino) ethylene ) pyrrolidine-2,4-dione, 5-methyl-5-benzyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4- Diketone, 5-methyl-5-benzyl-3-(1-(2-(2-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-methyl- 5-benzyl-3-(1-(2-(3-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-methyl-5-benzyl-3-( 1-(2-(2,4-dichlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-methyl-5-benzyl-3-(1-(2- (4-methylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-methyl-5-benzyl-3-(1-(2-(3,4-dimethyl ylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 5-methyl-5-benzyl-3-(1-(2-(4-aminosulfonylphenyl)hydrazino ) Ethylene)pyrrolidine-2,4-dione, 1,5-dimethyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2, 4-diketone, 1,5-dimethyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1,5-di Methyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1,5,5-trimethyl-3-(1- (2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 1,5,5-trimethyl-3-(1-(2-(4-chlorobenzene base) hydrazino) ethylidene) pyrrolidine-2,4-dione, 1,5 , 5-trimethyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione, 3-(1-(2-(4- Fluorophenyl)hydrazino)methylene)pyrrolidine-2,4-dione, 3-(1-(2-(4-chlorophenyl)hydrazino)methylene)pyrrolidine-2,4- Diketone, 3-(1-(2-(4-bromophenyl)hydrazino)methylene)pyrrolidine-2,4-dione, 3-(1-(2-(4-fluorophenyl) Hydrazino) propylene) pyrrolidine-2,4-dione, 3-(1-(2-(4-chlorophenyl) hydrazino) propylene) pyrrolidine-2,4-dione, 3 -(1-(2-(4-bromophenyl)hydrazino)propylene)pyrrolidine-2,4-dione, 3-(1-(2-(4-fluorophenyl)hydrazino)butylene Base) pyrrolidine-2,4-dione, 3-(1-(2-(4-chlorophenyl)hydrazino)butylene)pyrrolidine-2,4-dione, 3-(1-(2 -(4-bromophenyl)hydrazino)butylene)pyrrolidine-2,4-dione.

本发明的一种具有通式(I)所示结构的含取代苯肼的吡咯烷-2，4-二酮类化合物、或其顺反异构体、光学异构体、互变异构体，当取代基不同时，可表现出酸性或者碱性的性质，可与酸或者碱形成盐，或者与金属盐形成配合物。 A substituted phenylhydrazine-containing pyrrolidine-2,4-dione compound having a structure represented by general formula (I), or its cis-trans isomers, optical isomers, and tautomers of the present invention , when the substituents are different, it can exhibit acidic or basic properties, and can form salts with acids or bases, or form complexes with metal salts.

本发明的化合物结构中带有氨基及其他能够产生碱性性质的基团时，可以与酸反应形成盐。 When the compounds of the present invention have amino groups and other groups capable of producing basic properties, they can react with acids to form salts.

酸选自合适的无机酸、有机酸或者酸式盐，如HCl、HBr、HF、Hl、H2SO4、HNO3、HNO2、H2CO3、H3PO4、H3PO3、HClO、HClO4、H2C2O2、HCOOH、CH3COOH、ClCH2COOH、CCl3COOH、CF3COOH、苯甲酸、甲磺酸、苯磺酸、对甲基苯磺酸、NaHSO4、KHSO4，等。 The acid is selected from suitable inorganic acids, organic acids or acid salts, such as HCl, HBr, HF, Hl, H 2 SO 4 , HNO 3 , HNO 2 , H 2 CO 3 , H 3 PO 4 , H 3 PO 3 , HClO, HClO 4 , H 2 C 2 O 2 , HCOOH, CH 3 COOH, ClCH 2 COOH, CCl 3 COOH, CF 3 COOH, Benzoic acid, Methanesulfonic acid, Benzenesulfonic acid, p-Toluenesulfonic acid, NaHSO 4 , KHSO 4 , etc.

本发明的化合物结构中带有羟基、羧基及其他能够产生酸性性质的基团时，可以与碱反应形成盐。 When the compounds of the present invention have hydroxyl groups, carboxyl groups and other groups capable of producing acidic properties, they can react with bases to form salts.

碱选自合适的无机碱或有机碱，包括碱金属或者碱土金属的氢氧化物、氨类、胺类、铵类、醇盐、乙酸盐、碳酸盐、碳酸氢盐，如NaOH、KOH、NH3、NH4OH、Na2CO3、NaHCO3、K2CO3、KHCO3、(CH3)3N、(C2H 5)3N、(CH3)2NH、(C2H5)2NH、CH3NH2、C2H5NH2、CH3ONa、C2H5ONa、吡啶、CH3COONa、(CH3)4NOH，等。 The base is selected from suitable inorganic bases or organic bases, including hydroxides of alkali metals or alkaline earth metals, ammonia, amines, ammoniums, alkoxides, acetates, carbonates, bicarbonates, such as NaOH, KOH , NH 3 , NH 4 OH, Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , KHCO 3 , (CH 3 ) 3 N, (C 2 H 5 ) 3 N, (CH 3 ) 2 NH, (C 2 H 5 ) 2 NH, CH 3 NH 2 , C 2 H 5 NH 2 , CH 3 ONa, C 2 H 5 ONa, pyridine, CH 3 COONa, (CH 3 ) 4 NOH, and the like.

本发明的化合物可以与合适的金属盐反应形成金属配合物。 The compounds of the present invention can be reacted with suitable metal salts to form metal complexes.

合适的金属盐是指由金属离子与阴离子构成的盐，也可包括结晶溶剂分子。其中合适的金属离子选自Zn2+、Cu2+、Cu+、Co2+、Ni2+、Mn2+、Fe3+、Fe2+、Mg2+、Sn2+、Ca2+、Pt2+、Cr2+、Al3+、、Ru3+、Pd2+、Rh3+、Ti3+、Ti4+，优选Zn2+、Cu2+、Mn2+；合适的阴离子选自Cl-、Br-、F-、I-、NO3 -、NO2 -、CO3 2-、HCO3 -、SO4 2-、SO3 2-、HSO3 -、PO4 3-、PO3 2-、CH3COO-、HCOO-、CN-、SCN-、NCS -、ClO-、ClO4 -、C2O4 2-，优选Cl-、SO4 2-；结晶溶剂分子可选自H2O、NH3、DMF、DMSO、CH3OH、 C2H5OH、C3H7OH、CH3COOH、CH3COCH3、吡啶，形成的配合物可包含上述结晶溶剂分子。 Suitable metal salts are salts composed of metal ions and anions, which may also include crystallization solvent molecules. Wherein suitable metal ions are selected from Zn 2+ , Cu 2+ , Cu + , Co 2+ , Ni 2+ , Mn 2+ , Fe 3+ , Fe 2+ , Mg 2+ , Sn 2+ , Ca 2+ , Pt 2+ , Cr 2+ , Al 3+ , Ru 3+ , Pd 2+ , Rh 3+ , Ti 3+ , Ti 4+ , preferably Zn 2+ , Cu 2+ , Mn 2+ ; From Cl - , Br - , F - , I - , NO 3 - , NO 2 - , CO 3 2- , HCO 3 - , SO 4 2- , SO 3 2- , HSO 3 - , PO 4 3- , PO 3 2- , CH 3 COO - , HCOO - , CN - , SCN - , NCS - , ClO - , ClO 4 - , C 2 O 4 2- , preferably Cl - , SO 4 2- ; crystallization solvent molecules can be selected from H 2 O, NH 3 , DMF, DMSO, CH 3 OH, C 2 H 5 OH, C 3 H 7 OH, CH 3 COOH, CH 3 COCH 3 , pyridine, the complexes formed may contain the above crystallization solvent molecules.

用上述方式得到的盐或者配合物也具有抑制真菌活性。 The salts or complexes obtained in the above manner also have antifungal activity.

本发明的含取代苯肼的吡咯烷-2，4-二酮类化合物的制备Preparation of pyrrolidine-2,4-dione compounds containing substituted phenylhydrazines of the present invention

本发明的含取代苯肼的吡咯烷-2，4-二酮类化合物(I)可以通过下述的方法A或B制备： The pyrrolidine-2,4-diketone compound (I) containing substituted phenylhydrazine of the present invention can be prepared by the following method A or B:

方法A： Method A:

在本发明的一个实施方案中，用吡咯烷-2，4-二酮(II)与取代苯肼(III)按照下述反应路线进行化学反应，可制备含取代苯肼的吡咯烷-2，4-二酮类化合物(I)： In one embodiment of the present invention, pyrrolidine-2 containing substituted phenylhydrazine can be prepared by chemically reacting with pyrrolidine-2,4-dione (II) and substituted phenylhydrazine (III) according to the following reaction scheme, 4-diketone compound (I):

吡咯烷-2，4-二酮(II)与取代苯肼(III)的反应在常温下即可进行，如有必要，也可加热或者降温，优选在常温下进行。 The reaction between pyrrolidine-2,4-dione (II) and substituted phenylhydrazine (III) can be carried out at normal temperature, and can be heated or lowered if necessary, preferably at normal temperature.

上述反应可不加催化剂，也可加入酸促进反应的进行，所述的酸包括无机酸、有机酸或者酸式盐，优选选自：HCl、HBr、H2SO4、甲磺酸、苯磺酸、对甲基苯磺酸。 The above reaction can be carried out without adding a catalyst, and an acid can also be added to promote the reaction. The acid includes inorganic acid, organic acid or acid salt, preferably selected from: HCl, HBr, H 2 SO 4 , methanesulfonic acid, benzenesulfonic acid , p-toluenesulfonic acid.

上述反应可以在无溶剂条件下进行，也可以在溶剂中进行，优选在溶剂中进行，所述的溶剂选自常用的惰性溶剂，优选的溶剂包括：醇类，如甲醇、乙醇、异丙醇；醚类，如乙醚、二异丙醚、四氢呋喃；腈类，如乙腈、丙腈；酰胺类，如N，N-二甲基甲酰胺、N，N-二甲基乙酰胺；酯类，如乙酸乙酯、乙酸甲酯；卤代烃类，如二氯甲烷、三氯甲烷、四氯化碳、二氯乙烷；砜类，如二甲基亚砜；或者他们的混合物。 The above reaction can be carried out under solvent-free conditions or in a solvent, preferably in a solvent. The solvent is selected from common inert solvents. Preferred solvents include: alcohols, such as methanol, ethanol, isopropanol ; Ethers, such as diethyl ether, diisopropyl ether, tetrahydrofuran; Nitriles, such as acetonitrile, propionitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide; Esters, Such as ethyl acetate, methyl acetate; halogenated hydrocarbons, such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane; sulfones, such as dimethyl sulfoxide; or their mixtures.

方法B： Method B:

在本发明的另一个实施方案中，用吡咯烷-2，4-二酮(II)与取代苯肼的盐(IV)在加碱的条件下按照下述反应路线进行化学反应，可制备含取代苯肼的吡咯烷-2，4-二酮类化合物(I)： In another embodiment of the present invention, use the salt (IV) of pyrrolidine-2,4-dione (II) and substituted phenylhydrazine to carry out the chemical reaction according to the following reaction scheme under the condition of adding alkali, and the compound containing Pyrrolidine-2,4-dione compounds (I) substituted with phenylhydrazine:

吡咯烷-2，4-二酮(II)与取代苯肼的盐(IV)的反应采用的温度、溶剂参照方法(A)进行选择。 The temperature and solvent used in the reaction of pyrrolidine-2,4-dione (II) with the salt of substituted phenylhydrazine (IV) are selected with reference to method (A).

上述反应在加入碱的条件下进行，合适的碱选自无机碱或有机碱，选自碱金属或者碱土金属的氢氧化物、氨类、胺类、铵类、醇盐、乙酸盐、碳酸盐、碳酸氢盐，优选选自NaOH、KOH、NH3、NH4OH、Na2CO3、NaHCO3、K2CO3、KHCO3、(CH3)3N、(C2H5)3N、(CH3)2NH、(C2H5)2NH、CH3NH2、C2H5NH2、CH3ONa、C2H5ONa、吡啶、CH3COONa、(CH3)4NOH。 The above-mentioned reaction is carried out under the condition of adding a base, and the suitable base is selected from inorganic bases or organic bases, and is selected from alkali metal or alkaline earth metal hydroxides, ammonia, amines, ammonium, alkoxide, acetate, carbon NaOH, KOH, NH 3 , NH 4 OH, Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , KHCO 3 , (CH 3 ) 3 N, (C 2 H 5 ) 3 N, (CH 3 ) 2 NH, (C 2 H 5 ) 2 NH, CH 3 NH 2 , C 2 H 5 NH 2 , CH 3 ONa, C 2 H 5 ONa, pyridine, CH 3 COONa, (CH 3 ) 4 NOH.

上述取代苯肼(III)和取代苯肼的盐(IV)采用市售产品。 The above-mentioned substituted phenylhydrazine (III) and the salt (IV) of substituted phenylhydrazine adopt commercially available products.

吡咯烷-2，4-二酮(II)根据结构的不同分别采用以下步骤C、D、E的方法进行合成： Pyrrolidine-2,4-dione (II) adopts the method of following steps C, D, E to synthesize respectively according to the difference of structure:

方法C.R2选自氢时，吡咯烷-2，4-二酮(II-1)按照下述反应路线进行制备： When method CR 2 is selected from hydrogen, pyrrolidine-2,4-dione (II-1) is prepared according to the following reaction scheme:

化合物(V)与(R5O)3CH可以在无溶剂条件下进行，也可以在溶剂中进行。在无溶剂条件下进行时，通过加热溶解化合物(V)，反应完成后，选择合适的惰性溶剂萃取，经过洗涤、干燥，可得产物II-1。在溶剂中进行时，溶剂选自常用的惰性溶剂，加热促进反应，反应完成后，冷却，过滤，即得产物II-1。 The compound (V) and (R 5 O) 3 CH can be carried out without a solvent or in a solvent. When carried out under solvent-free conditions, the compound (V) is dissolved by heating. After the reaction is completed, an appropriate inert solvent is selected for extraction, washed and dried to obtain the product II-1. When carried out in a solvent, the solvent is selected from commonly used inert solvents, and the reaction is accelerated by heating. After the reaction is completed, it is cooled and filtered to obtain the product II-1.

上述化合物(V)按照下述两种反应路线之一进行制备： Above-mentioned compound (V) is prepared according to one of following two kinds of reaction schemes:

化合物(V)的第一种反应路线： The first reaction scheme of compound (V):

化合物(V)的第二种反应路线： The second reaction scheme of compound (V):

化合物(V)的合成方法参照文献(Synlett.2009，15：2487-2491.)介绍的方法进行。 The synthesis method of compound (V) was carried out according to the method introduced in the literature (Synlett. 2009, 15: 2487-2491.).

方法D.R2选自CH3时，吡咯烷-2，4-二酮(II-2)按照下述反应路线进行制备： When method DR 2 is selected from CH 3 , pyrrolidine-2,4-dione (II-2) is prepared according to the following reaction scheme:

吡咯烷-2，4-二酮(II-2)的合成方法参照文献(Bull Korean Chem.Soc.2010，31：2467-2472.)介绍的方法进行。 The synthesis method of pyrrolidine-2,4-dione (II-2) is carried out according to the method introduced in the literature (Bull Korean Chem. Soc. 2010, 31: 2467-2472.).

方法E.R2选自除H和CH3以外的其他基团时，吡咯烷-2，4-二酮(II-3)按照下述两种反应路线之一进行制备： Method When ER 2 is selected from other groups except H and CH 3 , pyrrolidine-2,4-dione (II-3) is prepared according to one of the following two reaction schemes:

吡咯烷-2，4-二酮(II-3)的第一种反应路线： The first reaction scheme of pyrrolidine-2,4-dione (II-3):

吡咯烷-2，4-二酮(II-3)的第二种反应路线： The second reaction scheme of pyrrolidine-2,4-dione (II-3):

吡咯烷-2，4-二酮(II-3)的第一种反应路线的合成方法参照文献(有机化学，2010，30(8)：1207-1211.)介绍的方法进行，吡咯烷-2，4-二酮(II-3)的第二种反应路线的合成方法参照文献(Tetrahedron，2005，61：2301-2307.)介绍的方法进行，化合物(V)的合成方法参照如前所述的方法进行。 The synthetic method of the first reaction route of pyrrolidine-2,4-dione (II-3) is carried out with reference to the method introduced in the literature (Organic Chemistry, 2010, 30(8):1207-1211.), pyrrolidine-2 , the synthetic method of the second reaction route of 4-diketone (II-3) is carried out with reference to the method introduced in literature (Tetrahedron, 2005, 61: 2301-2307.), and the synthetic method of compound (V) is carried out with reference to the aforementioned method is carried out.

其中在上述各结构式中： Wherein in each above-mentioned structural formula:

所述的惰性溶剂具有如前所述的含义； Described inert solvent has the implication as mentioned above;

R1至R5均具有如前所述的含义； R 1 to R 5 all have the meanings as previously described;

R6选自直链或支链的C1-12烷基，优选甲基或乙基；R7选自甲基或乙基。 R 6 is selected from linear or branched C 1-12 alkyl, preferably methyl or ethyl; R 7 is selected from methyl or ethyl.

在本发明的制备含取代苯肼的吡咯烷-2，4-二酮类化合物(I)的过程中，采用常规的磁力或者机械搅拌，监控反应完成的方法采用常规的簿层层析或者色谱法，纯化过程中采用常规的冷却、蒸馏、洗涤、萃取、结晶、过滤及干燥方法。 In the process of preparing pyrrolidine-2,4-diketone compound (I) containing substituted phenylhydrazine in the present invention, conventional magnetic or mechanical stirring is used, and the method for monitoring the completion of the reaction adopts conventional thin-layer chromatography or chromatography In the purification process, conventional cooling, distillation, washing, extraction, crystallization, filtration and drying methods are used.

防治有害真菌Control harmful fungi

本发明的含取代苯肼的吡咯烷-2，4-二酮类化合物具有十分显著的抑制和杀灭真菌的活性，可在植物保护中用于防治植物有害真菌。 The substituted phenylhydrazine-containing pyrrolidine-2,4-dione compound of the present invention has very significant activity of inhibiting and killing fungi, and can be used in plant protection to prevent and control plant harmful fungi.

本发明的含取代苯肼的吡咯烷-2，4-二酮类化合物可以在植物保护中用于防治植物上鞭毛菌(Mastigomycotina)、接合菌(Zygomycotina)、子囊菌(Ascomycotian)、担子菌(Basidiomycontina)和半知菌(Deute romycotina)。 Pyrrolidine-2,4-diketone compounds containing substituted phenylhydrazines of the present invention can be used in plant protection to prevent and treat flagellate (Mastigomycotina), zygomycotina (Zygomycotina), ascomycota (Ascomycotian), basidiomycetes ( Basidiomycontina) and Deute romycotina.

以下列举本发明可以防治的作物上发生的属于上述所列真菌的一些病原菌，但它不应视为是对本发明的任何限制： List some pathogenic bacteria belonging to the fungi listed above that occur on the crops that the present invention can control, but it should not be considered as any limitation of the present invention:

防治麦类作物真菌病害，所述病原菌如： Prevention and treatment of fungal diseases of wheat crops, the pathogenic bacteria such as:

镰孢属，如禾谷镰孢菌Fusarium graminearum，引起小麦赤霉病； Fusarium spp., such as Fusarium graminearum, which causes head blight of wheat;

丝核菌属，如禾谷丝核菌Rhizoctonia cereadis、茄丝核菌Rhizoctonia solani，引起小麦纹枯病； Rhizoctonia, such as Rhizoctonia cereadis and Rhizoctonia solani, cause wheat sheath blight;

粉孢属，如串珠粉状孢菌Oidium monilioides，引起小麦白粉病； Powdery mildew species such as Oidium monilioides, which cause wheat powdery mildew;

柄锈菌属，如条形柄锈菌Puccinia striiformis，引起小麦条锈病、隐匿柄锈菌Puccinia recondita，引起小麦叶锈病、禾柄锈菌Puccinia graminis，引起小麦秆锈病； Puccinia striiformis, which causes wheat stripe rust, Puccinia recondita, which causes wheat leaf rust, and Puccinia graminis, which causes wheat stem rust;

黑粉菌属，如小麦散黑粉菌Ustilago tritici、裸黑粉菌Ustilago nuda引起小麦散黑穗病； Smut, such as Ustilago tritici and Ustilago nuda, cause wheat loose smut;

腥黑粉菌属，如小麦网腥黑粉菌Tilletia caries、小麦光腥黑粉菌Tilletia foetida引起小麦腥黑穗病； Tilletia spp., such as Tilletia caries and Tilletia foetida, cause wheat smut;

角担菌属，如禾谷角担菌Ceratobasidium graminearum，引起小麦纹枯病； Ceratobasidium species, such as Ceratobasidium graminearum, which causes wheat sheath blight;

赤霉属，如玉粟黍赤霉菌Gibberella zeae，引起小麦赤霉病； Gibberella, such as Gibberella zeae, which causes wheat head blight;

布氏白粉菌属，如禾布氏白粉菌Blumeria graminis，引起小麦白粉病； Brucella spp., such as Blumeria graminis, which causes wheat powdery mildew;

顶囊壳属，如禾顶囊壳菌Gaeumannomyces graminis，引起小麦全蚀病； Acrocysts, such as Gaeumannomyces graminis, cause take-all in wheat;

防治水稻作物真菌病害，所述病原菌如： Prevention and treatment of rice crop fungal diseases, the pathogenic bacteria such as:

梨孢属，如灰梨孢菌Pyricularia grisea，引起稻瘟病； Pyricularia spp., such as Pyricularia grisea, which cause rice blast;

丝核菌属，如茄丝核菌Rhizoctonia solani，引起水稻纹枯病； Rhizoctonia species, such as Rhizoctonia solani, cause rice sheath blight;

绿核菌属，如绿核菌Ustilaginoidae virens，引起稻胡麻斑病； Sclerotinia spp., such as Ustilaginoidae virens, cause flax spot in rice;

腥黑粉菌属，如狼尾草腥黑粉菌Tilletia barchayama，引起稻粒黑粉病； Tilletia species, such as Tilletia barchayama, cause rice smut;

亡革菌属，如瓜亡革菌Thanatephorus cucumeris，引起水稻纹枯病； Cleatherum spp., such as Thanatephorus cucumeris, cause rice sheath blight;

麦角菌属，如稻麦角菌菌Claviceps oryzae-sativae，引起稻胡麻斑病； Ergot fungi, such as Claviceps oryzae-sativae, cause flax spot in rice;

防治棉花作物真菌病害，所述病原菌如： Prevention and treatment of fungal diseases of cotton crops, the pathogenic bacteria such as:

镰孢属，如尖镰孢菌Fusarium oxysporum，引起棉花枯萎病； Fusarium spp., such as Fusarium oxysporum, which causes cotton wilt;

轮枝孢属，如大丽轮枝孢菌Verticillium dahliae、黑白轮枝孢菌Verticillium albo-atrum，引起棉花黄萎病； Verticillium spp., such as Verticillium dahliae and Verticillium albo-atrum, cause cotton verticillium wilt;

疫霉属，如苎麻疫霉菌Phytophthora boehmeriae，引起棉铃疫病； Phytophthora, such as Phytophthora boehmeriae, which causes cotton boll blight;

防治油料作物真菌病害，所述病原菌如： Prevention and treatment of fungal diseases of oil crops, the pathogenic bacteria such as:

核盘菌属，如核盘菌Sclerotinia sclerotiorum，引起油菜菌核病； Sclerotinia, such as Sclerotinia sclerotiorum, which causes Sclerotinia sclerotiorum;

防治杂粮作物真菌病害，所述病原菌如： Prevention and treatment of fungal diseases of miscellaneous grain crops, the pathogenic bacteria such as:

双极蠕孢属，如玉粟黍双极蠕孢菌Bipolaris maydis，引起玉米小斑病； Bipolaris spp., such as Bipolaris maydis, which causes small spot in maize;

蠕孢属，如大斑病凸脐蠕孢菌Exserohilum turcicum，引起玉米大斑病； Helminthospora, such as Exserohilum turcicum, which causes maize leaf spot;

散黑粉菌属，如玉米散黑粉菌Ustilago maydis，引起玉米瘤黑粉病； Ustilago smut, such as Ustilago maydis, causes maize tumor smut;

轴黑粉菌属，如丝轴黑粉菌Sphacelotheca reiliana，引起玉米丝黑穗病； smut, such as Sphacelotheca reiliana, which causes corn head smut;

长喙壳属，如甘薯长喙壳菌Ceratocystis fimbriata，引起甘薯黑斑病； Ceratocystis fimbriata, such as Ceratocystis fimbriata, cause sweet potato black spot;

旋孢腔菌属，如异旋孢腔菌Cochliobolus heterostrophus，引起玉米小斑病； Cochliobolus heterostrophus, such as Cochliobolus heterostrophus, cause small spot of corn;

毛球腔菌属，如大斑病毛球腔菌Setosphaeria turcica，引起玉米大斑病； Trichophaeria, such as Setosphaeria turcica, which causes maize leaf spot;

防治烟草作物真菌病害，所述病原菌如： Prevention and treatment of fungal diseases of tobacco crops, the pathogenic bacteria such as:

链格孢属，如链格孢菌Alternaria alternate，引起烟草赤星病； Alternaria species, such as Alternaria alternate, which cause tobacco spot disease;

防治果树作物真菌病害，所述病原菌如： Prevention and treatment of fruit tree crop fungal diseases, the pathogenic bacteria such as:

小穴壳属，如簇小穴壳菌Dothiorella gregaria，引起苹果、梨轮纹病； Dothiorella gregaria, such as Dothiorella gregaria, cause ring spot of apples and pears;

黑星孢属，如苹果壳囊菌Fusicladium virescens，引起梨黑星病； Scab species such as Fusicladium virescens, which cause pear scab;

炭疽菌属，如胶孢炭疽菌Colletotrium gloeosporioides，引起苹果炭疽病； Anthracnose species, such as Colletotrium gloeosporioides, which cause apple anthracnose;

壳囊孢属，如苹果壳囊菌Cytospora mandshurica，引起苹果腐烂病； Ascospora, such as Cytospora mandshurica, cause apple rot;

胶锈菌属，如亚洲胶锈菌Gymnosporangium asiaticum，引起梨锈病； Gymnosporangium asiaticum, such as Gymnosporangium asiaticum, which causes pear rust;

小丛壳属，如围小丛壳菌Glomerella cingulata，引起苹果炭疽病； cingulata, such as Glomerella cingulata, cause apple anthracnose;

黑腐皮壳属，如苹果黑腐皮壳菌Valsa mali，引起苹果腐烂病； Black rot fungus, such as the apple black rot fungus Valsa mali, causes apple rot;

黑星菌属，如纳雪黑星菌Venturia nashicola，引起梨黑星病； Scab species such as Venturia nashicola, which cause pear scab;

葡萄座腔菌属，如贝伦格葡萄座腔菌Botryosphaeria berengeriana，引起苹果、梨轮纹病； Botryosphaeria berengeriana, such as Botryosphaeria berengeriana, cause ring spot of apples and pears;

单轴霉属，如葡萄生单轴霉菌Plasmopara viticola，引起葡萄霜霉病； Plasmopara spp., such as Plasmopara viticola, which cause grape downy mildew;

疫霉属，如烟草疫霉菌Phytophthora nicotianae，引起烟草黑胫病； Phytophthora, such as Phytophthora nicotianae, which causes tobacco black shank;

防治蔬菜作物真菌病害，所述病原菌如： Prevention and treatment of vegetable crop fungal diseases, the pathogenic bacteria such as:

葡萄孢属，如灰葡萄孢菌Botrytis cinerea，引起茄科蔬菜灰霉病，如辣椒灰霉病、茄子灰霉病； Botrytis, such as Botrytis cinerea, which causes gray mold of solanaceous vegetables, such as pepper gray mold and eggplant gray mold;

镰孢属，如尖镰孢菌Fusarium oxysporum，引起瓜类枯萎病； Fusarium spp., such as Fusarium oxysporum, which causes blight of melons;

链格孢属，如茄链格孢菌Alternaria solani，引起番茄早疫病； Alternaria species, such as Alternaria solani, cause tomato early blight;

褐孢属，如褐孢霉菌Fulvia fulva，引起番茄叶霉病； Brown spores, such as Fulvia fulva, cause tomato leaf mold;

轮枝孢属，如大丽轮枝孢菌Verticillium dahliae，引起茄黄萎病； Verticillium spp., such as Verticillium dahliae, which cause Verticillium dahliae;

霜霉属，如寄生霜霉菌Peronospora parasitica，引起蔬菜霜霉病； Peronospora, such as Peronospora parasitica, causes vegetable downy mildew;

疫霉属，如辣椒疫霉菌Phytophthora capsici，引起辣椒疫病、掘氏疫霉菌Phytophthora drechsleri，引起黄瓜疫病； Phytophthora, such as Phytophthora capsici, which causes blight of peppers, and Phytophthora drechsleri, which causes blight of cucumbers;

炭疽菌属，如辣椒刺盘孢Colletotrichum capsici，引起辣椒炭疽病。 Anthracnose species, such as Colletotrichum capsici, cause pepper anthracnose.

在本发明中，有害真菌的含义应该理解为植物致病真菌。本发明的化合物在处理后可以保护植物抵御上述病原菌的侵染与危害。 In the present invention, harmful fungi are to be understood as meaning phytopathogenic fungi. The compound of the present invention can protect plants against the infection and damage of the above-mentioned pathogenic bacteria after treatment.

本发明的化合物在用于防治植物病害时，对植物安全，可用于植物的任何生长阶段、植株的任何部位，及种子处理、土壤处理。植物的生长阶段和部位可以理解为植物的种子、果实、根、茎、枝、叶、花，包括植株的地上部位、地下部位。种子处理可以理解为对种子进行包含本发明的化合物的处理，如熏蒸、浸泡、包衣。土壤处理可以理解为将本发明的化合物施入土壤中，用于防治植物病害。 When the compound of the present invention is used for preventing and controlling plant diseases, it is safe for plants, and can be used for any growth stage of plants, any part of plants, and seed treatment and soil treatment. The growth stages and parts of plants can be understood as seeds, fruits, roots, stems, branches, leaves and flowers of plants, including aboveground parts and underground parts of plants. Seed treatment can be understood as the treatment of seeds comprising the compound of the present invention, such as fumigation, soaking, coating. Soil treatment can be understood as the application of the compounds according to the invention to the soil for the control of plant diseases.

本发明的化合物对植物或者其部位进行处理的方法采用常规的农药施药方法，可直接处理于植物，也可对其生境、环境或者储存区进行处理，所述的常规的农药施药方法，选自如喷雾、喷粉、浸泡、熏蒸、泼浇、涂抹、缓释、烟化、雾化。 The method for treating plants or their parts with the compound of the present invention adopts conventional pesticide application methods, which can directly treat plants, or treat their habitats, environments or storage areas. The conventional pesticide application methods, Selected from eg spraying, dusting, soaking, fumigation, pouring, smearing, slow release, fuming, atomizing.

本发明的化合物特别适合于用于防治麦类作物真菌病害，如：小麦赤霉病、小麦纹枯病、小麦锈病及小麦白粉病，防治蔬菜作物真菌病害，如蔬菜灰霉病、蔬菜霜霉病、辣椒炭疽病，防治果树作物真菌病害，如苹果腐烂病、葡萄霜霉病，防治水稻作物真菌病害，如稻瘟病、水稻纹枯病。 The compound of the present invention is particularly suitable for preventing and treating fungal diseases of wheat crops, such as: wheat scab, wheat sheath blight, wheat rust and wheat powdery mildew, and preventing and controlling fungal diseases of vegetable crops, such as vegetable gray mold and vegetable downy mildew Pepper anthracnose, control fungal diseases of fruit tree crops, such as apple rot, grape downy mildew, and control fungal diseases of rice crops, such as rice blast and rice sheath blight.

本发明的化合物通过有效防治作物真菌病害，降低收获的农产品中的真菌毒素的含量，能够提高作物品质与产量，且具有低毒性、低残留、容易降解而不造成对环境的污染等特性。 The compound of the present invention can effectively prevent and treat fungal diseases of crops, reduce the content of mycotoxins in harvested agricultural products, improve crop quality and yield, and has the characteristics of low toxicity, low residue, easy degradation without causing environmental pollution, and the like.

剂型dosage form

本发明涉及包括本发明的含取代苯肼的吡咯烷-2，4-二酮类化合物的一种用于防治有害真菌的组合物。 The present invention relates to a composition for controlling harmful fungi comprising the substituted phenylhydrazine-containing pyrrolidine-2,4-dione compounds of the present invention.

根据本发明的含取代苯肼的吡咯烷-2，4-二酮类化合物的各自物理与化学性质及防治有害真菌的方法上的具体需要，制备含本发明的化合物的合适的剂型，所述的合适的剂型任选选自：粉剂、可分散性粉剂、可湿性粉剂、可溶性粉剂、悬浮剂、粒剂、缓释剂、烟雾剂、熏蒸剂、乳剂、油剂、水剂、泡沫剂、微胶囊剂、泡腾剂、包衣剂。 According to the specific needs of the respective physical and chemical properties of the pyrrolidine-2,4-diketone compounds containing substituted phenylhydrazines of the present invention and the method for preventing and controlling harmful fungi, a suitable dosage form containing the compound of the present invention is prepared, the described A suitable dosage form is optionally selected from: powder, dispersible powder, wettable powder, soluble powder, suspension, granule, sustained release agent, aerosol, fumigant, emulsion, oil, water, foam, Microcapsules, effervescent agents, coating agents.

上述剂型采用已知的方法进行制备，如将本发明的化合物与填充物均匀混合，所述的填充物任选选自下列一种或者多种：水、有机溶剂、液化气、固体填料、乳化剂、分散剂、发泡剂、稳定剂、粘着剂、着色剂。合适的水，如软水、去离子水、蒸馏水、纯净水、自来水。合适的有机溶剂：烃类，如甲苯、二甲苯、石油醚、液体石蜡、重油；卤代烃类，如三氯甲烷、氯苯；醇类，如甲醇、乙醇、乙二醇、高级脂肪醇；酮类，如丙酮、丁酮、环己酮；醚类，如乙二醇醚、聚乙二醇、二氧六环；酰胺类，如N，N-二甲基甲酰胺；砜类，如二甲基亚砜。合适的液化气，如氟利昂、丙烷、丁烷。合适的固体填料，如粘土、滑石粉、石灰石、白炭黑、高岭土、硅藻土、硅胶、尿素、锯屑、炉渣粉。合适的乳化剂，如非离子型的脂肪酸、多元醇、聚乙二醇醚；阴离子型的烷基苯磺酸钙盐、烷基聚氧乙烯醚磷酸盐；阳离子型的烷基季铵盐、吡啶季铵盐。合适的分散剂，如萘磺酸甲醛缩合物钠盐、甲酚甲醛缩合物磺酸钠盐、木质素磺酸钠。合适的发泡剂，如阴离子型的烷基萘磺酸盐、苯乙基酚聚氧乙烯醚硫酸盐；非离子型的茶皂素。合适的稳定剂，如磷酸酯环氧乙烷加成物、环氧化脂肪酸酯。合适的粘着剂，如阿拉伯胶、羧甲基纤维素、聚乙烯醇、聚乙二醇醚、聚乙烯吡咯烷酮、尿素。合适的着色剂，如普鲁斯蓝、钴盐、偶氮染料。 The above-mentioned dosage form is prepared by a known method, such as uniformly mixing the compound of the present invention with a filler, and the filler is optionally selected from one or more of the following: water, organic solvent, liquefied gas, solid filler, emulsified Agents, dispersants, foaming agents, stabilizers, adhesives, colorants. Suitable water, such as soft water, deionized water, distilled water, purified water, tap water. Suitable organic solvents: hydrocarbons, such as toluene, xylene, petroleum ether, liquid paraffin, heavy oil; halogenated hydrocarbons, such as chloroform, chlorobenzene; alcohols, such as methanol, ethanol, ethylene glycol, higher aliphatic alcohols ; Ketones, such as acetone, butanone, cyclohexanone; Ethers, such as glycol ether, polyethylene glycol, dioxane; Amides, such as N, N-dimethylformamide; Sulfones, Such as dimethyl sulfoxide. Suitable liquefied gas such as freon, propane, butane. Suitable solid fillers such as clay, talc, limestone, silica, kaolin, diatomaceous earth, silica gel, urea, sawdust, slag powder. Suitable emulsifiers, such as non-ionic fatty acids, polyols, polyethylene glycol ethers; anionic calcium salts of alkylbenzene sulfonates, alkyl polyoxyethylene ether phosphates; cationic alkyl quaternary ammonium salts, Pyridinium quaternary ammonium salt. Suitable dispersants, such as naphthalene sulfonic acid formaldehyde condensate sodium salt, cresol formaldehyde condensate sulfonic acid sodium salt, sodium lignosulfonate. Suitable foaming agents, such as anionic alkyl naphthalene sulfonate, phenethylphenol polyoxyethylene ether sulfate; nonionic tea saponin. Suitable stabilizers such as phosphate ester ethylene oxide adducts, epoxidized fatty acid esters. Suitable binders, such as gum arabic, carboxymethylcellulose, polyvinyl alcohol, polyethylene glycol ethers, polyvinylpyrrolidone, urea. Suitable colorants such as Prussian blue, cobalt salts, azo dyes.

上述剂型中，本发明的化合物的质量百分含量在0.1％-99.9％之间，优选0.25％-95％之间。 In the above dosage form, the mass percentage of the compound of the present invention is between 0.1% and 99.9%, preferably between 0.25% and 95%.

上述剂型在本发明所述的方法中可用于防治植物有害真菌，优选用于防治麦类作物真菌病害、水稻作物真菌病害、棉花作物真菌病害、油料作物真菌病害、杂粮作物真菌病害、烟草作物真菌病害、果树作物真菌病害、蔬菜作物真菌病害。 The above dosage form can be used to prevent and control plant harmful fungi in the method of the present invention, preferably for preventing and treating fungal diseases of wheat crops, rice crops, cotton crops, oil crops, miscellaneous grains and tobacco crops. Diseases, fungal diseases of fruit tree crops, fungal diseases of vegetable crops.

与已知杀菌剂、杀虫剂、杀螨剂、杀线虫剂、除草剂的混合物Mixture with known fungicides, insecticides, acaricides, nematicides, herbicides

本发明的含取代苯肼的吡咯烷-2，4-二酮类化合物可以自身单独使用，或者以其剂型形式使用，或者其与选自下列一种或者多种的已知的杀真菌剂、杀细菌剂、抗病毒剂、杀虫剂、杀螨剂、杀线虫剂、除草剂、生长调节剂、肥料、安全剂混合后使用，以便起到如提高防治效果、扩大防治靶标谱、防止抗药性产生、提高安全性的作用。 The substituted phenylhydrazine-containing pyrrolidine-2,4-dione compound of the present invention can be used alone or in its dosage form, or it can be used together with one or more known fungicides selected from the following, Bactericides, antiviral agents, insecticides, acaricides, nematocides, herbicides, growth regulators, fertilizers, and safeners are mixed and used in order to improve the control effect, expand the control target spectrum, and prevent antibiotics. The effect of medicinal properties and improving safety.

本发明的化合物可以以其自身、以其剂型形式、以其混合物形式，或者以其制备的使用形式使用，如使用其制备的粉剂、可分散性粉剂、可湿性粉剂、可溶性粉剂、悬浮剂、粒剂、缓释剂、烟雾剂、熏蒸剂、乳剂、油剂、水剂、泡沫剂、微胶囊剂、泡腾剂、包衣剂。可采用常规的农药施药方法，如喷雾、喷粉、浸泡、熏蒸、泼浇、涂抹、缓释、烟化、雾化、撒播、发泡等。或者进行种子处理和土壤处理。种子处理可以理解为对植物的种子采用常规使用的方法进行处理，如熏蒸、浸泡、包衣，用于防治植物病害。土壤处理可以理解为将本发明的化合物施入土壤中，用于防治植物病害。 The compound of the present invention can be used by itself, in the form of its dosage form, in the form of its mixture, or in the use form prepared by it, such as powder, dispersible powder, wettable powder, soluble powder, suspension, Granules, sustained-release agents, aerosol agents, fumigants, emulsions, oil agents, water agents, foam agents, microcapsules, effervescent agents, and coating agents. Conventional pesticide application methods can be used, such as spraying, dusting, soaking, fumigation, pouring, smearing, slow release, fuming, atomization, broadcasting, foaming, etc. Or do seed treatment and soil treatment. Seed treatment can be understood as the treatment of plant seeds by conventional methods, such as fumigation, soaking, and coating, to prevent and control plant diseases. Soil treatment can be understood as the application of the compounds according to the invention to the soil for the control of plant diseases.

在使用本发明的含取代苯肼的吡咯烷-2，4-二酮类化合物或者其组合物作为杀真菌剂防治植物真菌病害时，根据使用形式、植物种类、作用对象、施用方法等的不同，施用剂量可在一定范围内选择。如施用 于植物部位时，本发明的化合物的施用剂量控制在0.5-20000g/ha，优先选择5-5000g/ha；进行种子处理时，本发明的化合物的施用剂量控制在0.001-100g/kg种子，优先选择0.01-10g/kg种子；进行土壤处理时，本发明的化合物的施用剂量控制在0.5-20000g/ha，优先选择5-5000g/ha。 When using the substituted phenylhydrazine-containing pyrrolidine-2,4-dione compound of the present invention or its composition as a fungicide to prevent and treat plant fungal diseases, depending on the form of use, plant species, object of action, application method, etc. , The dosage can be selected within a certain range. When applied to plant parts, the application dose of the compound of the present invention is controlled at 0.5-20000g/ha, preferably 5-5000g/ha; when seed treatment is performed, the application dose of the compound of the present invention is controlled at 0.001-100g/kg seed , preferably 0.01-10g/kg seeds; when soil treatment is carried out, the application dose of the compound of the present invention is controlled at 0.5-20000g/ha, preferably 5-5000g/ha.

有益效果：  Beneficial effect:

1、本发明在吡咯烷-2，4-二酮3号位的侧链上引入取代苯肼结构单元，得到如式(I)所示的新型含取代苯肼的吡咯烷-2，4-二酮类化合物，令人惊奇的是这类化合物表现出意想不到的十分显著的杀真菌活性，杀菌谱广，且与产生了抗药性的杀菌剂无交互抗性，可以为农业生产中植物保护提供有效服务。 1. The present invention introduces a substituted phenylhydrazine structural unit on the side chain at position 3 of pyrrolidine-2,4-dione to obtain a novel pyrrolidine-2,4-dione containing substituted phenylhydrazine as shown in formula (I). Diketone compounds, what is surprising is that these compounds exhibit unexpected very significant fungicidal activity, a wide bactericidal spectrum, and no cross-resistance with fungicides that have produced resistance, and can be used for plant protection in agricultural production. Provide effective service.

2、本发明专利所述的含取代苯肼的吡咯烷-2，4-二酮类化合物的制备方法是以吡咯烷-2，4-二酮与取代苯肼或者取代苯肼的盐反应。本合成方法采用的原料易得，对设备要求简单，操作十分简便。所述的制备方法具有独特性和可行性。 2. The preparation method of pyrrolidine-2,4-dione compounds containing substituted phenylhydrazines described in the patent of the present invention is to react pyrrolidine-2,4-dione with substituted phenylhydrazines or salts of substituted phenylhydrazines. The raw materials used in the synthesis method are easy to obtain, the equipment requirements are simple, and the operation is very convenient. The preparation method is unique and feasible.

3、本发明专利所述的含取代苯肼的吡咯烷-2，4-二酮类化合物出人意料地对植物病原真菌具有十分显著的杀菌活性，其中有些化合物的杀菌效果甚至超过部分商品化的杀菌剂，这种含取代苯肼的吡咯烷-2，4-二酮类化合物对植物病原真菌具有突出的杀菌活性从未有过报道。 3. The pyrrolidine-2,4-dione compounds containing substituted phenylhydrazines described in the patent of the present invention unexpectedly have very significant bactericidal activity against phytopathogenic fungi, and the bactericidal effect of some compounds even exceeds that of some commercialized bactericidal It has never been reported that this pyrrolidine-2,4-dione compound containing substituted phenylhydrazine has outstanding fungicidal activity against plant pathogenic fungi.

4、本发明专利所述的含取代苯肼的吡咯烷-2，4-二酮类化合物对已经使得植物病原真菌产生了抗药性的杀菌剂没有交互抗性。所述的化合物可以作为杀菌剂用于农业生产中的植物保护，特别是可以替代产生了抗药性的杀菌剂。 4. The pyrrolidine-2,4-dione compounds containing substituted phenylhydrazines described in the patent of the present invention have no cross-resistance to fungicides that have made plant pathogenic fungi resistant. The compound can be used as a fungicide for plant protection in agricultural production, especially as a substitute for a fungicide that has produced drug resistance.

5、本发明专利涉及的技术方案在农药创制中的杀菌剂领域，是一个显著的科技进步，具有广阔的应用前景，其推广应用将为农业生产作出重大贡献，具有显著的实质性特点。 5. The technical solution involved in the patent of the present invention is a remarkable scientific and technological progress in the field of fungicides in the creation of pesticides, and has broad application prospects. Its popularization and application will make a major contribution to agricultural production and has significant substantive features.

具体实施方式 Detailed ways

本发明的实质性特点可从下述实施例得以体现，但它不应视为是对本发明的任何限制。 The substantive features of the present invention can be realized from the following examples, but it should not be regarded as any limitation to the present invention.

制备实施例Preparation Example

实施例1：5-仲丁基-3-(1-(2-(4-甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(H-6)的制备Example 1: Preparation of 5-sec-butyl-3-(1-(2-(4-methylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (H-6)

在125mL三口烧瓶中加入L-异亮氨酸甲酯0.05mol(7.25g)，甲醇14mL，于冷阱中冷却，搅拌，滴加双乙烯酮0.05mol(4.2g)，滴加时温度不超过-5℃，滴毕，于室温下搅拌10h。减压脱去溶剂。向所得产物中加入12mL苯，12mL甲醇钠溶液(1.15g金属钠，10mL甲醇)，搅拌，回流反应4 h。冷却，加水溶解，水层用20％的盐酸酸化至pH＝2-3，用乙醚萃取，合并有机相，用饱和食盐水洗涤，无水Na2SO4干燥，减压脱去溶剂，得红色油状物，加入等体积的乙醇重结晶，抽滤，得7.3g 3-(1-羟基亚乙基)-5-仲丁基吡咯烷-2，4-二酮： Add 0.05 mol (7.25 g) of L-isoleucine methyl ester and 14 mL of methanol into a 125 mL three-necked flask, cool in a cold trap, stir, add 0.05 mol (4.2 g) of diketene dropwise, and the temperature does not exceed -5 ℃, dropwise completed, stirred at room temperature for 10h. The solvent was removed under reduced pressure. Add 12mL of benzene and 12mL of sodium methoxide solution (1.15g of sodium metal, 10mL of methanol) to the resulting product, stir, and reflux for 4 h. Cool, add water to dissolve, acidify the aqueous layer with 20% hydrochloric acid to pH=2-3, extract with ether, combine the organic phases, wash with saturated brine, dry over anhydrous Na 2 SO 4 , remove the solvent under reduced pressure to obtain a red color The oil was recrystallized by adding an equal volume of ethanol, and suction filtered to obtain 7.3 g of 3-(1-hydroxyethylidene)-5-sec-butylpyrrolidine-2,4-dione:

淡黄色固体；收率74％；mp 61.1-62.9℃；1H NMR(400MHz，CDCl3)δ：12.67(br，1H，OH)，6.82，6.58(d，d，J＝22.6Hz，J＝17.2Hz，75/25，1H，NH)，4.06-4.80(m，1H，CHNH)，2.53，2.48(s，s，25/75，3H，CH3COH)，2.07-1.92(m，1H，CH3CH)，1.52-1.17(m，2H，CH3CH2)，1.04-0.80(m，6H，CH3CH2(CH3)CH)；EI-MS，m/z(％)：197[M+]. Pale yellow solid; yield 74%; mp 61.1-62.9°C; 1 H NMR (400MHz, CDCl 3 ) δ: 12.67 (br, 1H, OH), 6.82, 6.58 (d, d, J=22.6Hz, J= 17.2Hz, 75/25, 1H, NH), 4.06-4.80(m, 1H, CHNH), 2.53, 2.48(s, s, 25/75, 3H, CH 3 COH), 2.07-1.92(m, 1H, CH 3 CH), 1.52-1.17 (m, 2H, CH 3 CH 2 ), 1.04-0.80 (m, 6H, CH 3 CH 2 (CH 3 ) CH); EI-MS, m/z (%): 197 [M + ].

在125mL三口烧瓶中加入乙醇20mL，3-(1-羟基亚乙基)-5-仲丁基吡咯烷-2，4-二酮10mmol(2.0g)，及等摩尔量的4-甲基苯肼1.3g，磁力搅拌，加热，回流反应，采用TLC(展开剂：乙酸乙酯∶石油醚∶乙酸＝10∶10∶1，V/V/V)监控反应进程。反应结束后，冷却，减压脱去溶剂，加入5mL水，用乙酸乙酯萃取，合并有机相，用无水硫酸镁干燥，减压脱去溶剂，用适量乙酸乙酯/石油醚(1∶1V/V)于0℃以下环境中结晶，有固体析出，抽滤，水洗，干燥，得1.65g 5-仲丁基-3-(1-(2-(4-甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(H-6)： In a 125mL three-necked flask, add 20mL of ethanol, 10mmol (2.0g) of 3-(1-hydroxyethylidene)-5-sec-butylpyrrolidine-2,4-dione, and an equimolar amount of 4-methylbenzene Hydrazine 1.3 g, magnetic stirring, heating, reflux reaction, using TLC (developer: ethyl acetate: petroleum ether: acetic acid = 10:10:1, V/V/V) to monitor the reaction progress. After the reaction, cool, remove the solvent under reduced pressure, add 5 mL of water, extract with ethyl acetate, combine the organic phases, dry with anhydrous magnesium sulfate, remove the solvent under reduced pressure, and use an appropriate amount of ethyl acetate/petroleum ether (1: 1V/V) crystallized in an environment below 0°C, solids were precipitated, filtered with suction, washed with water, and dried to obtain 1.65g of 5-sec-butyl-3-(1-(2-(4-methylphenyl)hydrazine ) Ethylene) pyrrolidine-2,4-dione (H-6):

灰白色粉末；收率55％；mp 141.3-143.2℃；1H NMR(400MHz，CDCl3)δ：11.89，11.42(s，s，50/50，1H，ArNHNH)，7.09(d，J＝8.2Hz，2H，ArH)，6.69(d，J＝7.9Hz，2H，ArH)，5.74(br，1H，ArNHNH)，5.45(br，1H，NH)，3.86-3.73(m，1H，CHNH)，2.64(s，3H，CH3CNH)，2.29(s，3H，ArCH3)，2.05-1.90(m，1H，CH3CH)，1.48-1.19(m，2H，CH3CH2)，1.01-0.79(m，6H，CH3CH2(CH3)CH)；EI-MS，m/z(％)：301[M+]. Off-white powder; yield 55%; mp 141.3-143.2°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.89, 11.42 (s, s, 50/50, 1H, ArNHNH), 7.09 (d, J=8.2Hz , 2H, ArH), 6.69 (d, J=7.9Hz, 2H, ArH), 5.74 (br, 1H, ArNHNH), 5.45 (br, 1H, NH), 3.86-3.73 (m, 1H, CHNH), 2.64 (s, 3H, CH 3 CNH), 2.29 (s, 3H, ArCH 3 ), 2.05-1.90 (m, 1H, CH 3 CH ), 1.48-1.19 (m, 2H, CH 3 CH 2 ), 1.01-0.79 (m, 6H, CH 3 CH 2 (CH 3 ) CH); EI-MS, m/z (%): 301 [M + ].

采用实施例1的方法，制备了下述H系列化合物：  Adopt the method for embodiment 1, prepared following H series compound:

5-仲丁基-3-(1-(2-(4-三氟甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(H-7)： 5-sec-butyl-3-(1-(2-(4-trifluoromethylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (H-7):

黄褐色粉末；收率86％；mp 176.3-177.5℃；1H NMR(400MHz，CDCl3)δ：1H NMR(400MHz，CDCl3)δ：11.89，11.47(s，s，45/55，1H，ArNHNH)，7.53(d，J＝8.1Hz，2H，ArH)，6.84(d，J＝8.6Hz，2H，ArH)，6.18，6.12(s，s，45/55，1H，ArNHNH)，5.03-5.50(m，1H，NH)，3.88-3.75(m，1H，CHNH)，2.64，2.60(s，s，45/55，3H，CH3CNH)，2.09-1.89(m，1H，CH3CH)，1.47-1.19(m，2H，CH3CH2)，0.99-0.79(m，6H，CH3CH2(CH3)CH)；EI-MS，m/z(％)：355[M+]). Yellow-brown powder; yield 86%; mp 176.3-177.5°C; 1 H NMR (400MHz, CDCl 3 ) δ: 1 H NMR (400 MHz, CDCl 3 ) δ: 11.89, 11.47 (s, s, 45/55, 1H , ArNHNH), 7.53 (d, J=8.1Hz, 2H, ArH), 6.84 (d, J=8.6Hz, 2H, ArH), 6.18, 6.12 (s, s, 45/55, 1H, ArNHNH), 5.03 -5.50 (m, 1H, NH), 3.88-3.75 (m, 1H, CHNH), 2.64, 2.60 (s, s, 45/55, 3H, CH 3 CNH), 2.09-1.89 (m, 1H, CH 3 CH), 1.47-1.19 (m, 2H, CH 3 CH 2 ), 0.99-0.79 (m, 6H, CH 3 CH 2 (CH 3 ) CH); EI-MS, m/z (%): 355 [M + ]).

5-仲丁基-3-(1-(2-(3，4-二甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(H-8)： 5-sec-butyl-3-(1-(2-(3,4-dimethylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (H-8):

灰白色粉末；收率44％；mp 128.5-129.6℃；1H NMR(400MHz，CDCl3)δ：11.85，11.39(s，s，48/52，1H，ArNHNH)，7.03(d，J＝8.0Hz，1H，ArH)，6.64-6.46(m，2H，ArH)，5.88-5.41(m，2H，ArNHNH+NH)，3.85-3.73(m，1H，CHNH)，2.65，2.63(s，s，48/52，3H，CH3CNH)，2.22(s，3H，ArCH3)，2.19(s，3H，ArCH3)，2.06-1.88(m，1H，CH3CH)，1.45-1.19(m，2H，CH3CH2)，1.01-0.79(m，6H，CH3CH2(CH3)CH)；EI-MS，m/z(％)：315[M+]. Off-white powder; yield 44%; mp 128.5-129.6°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.85, 11.39 (s, s, 48/52, 1H, ArNHNH), 7.03 (d, J=8.0Hz , 1H, ArH), 6.64-6.46(m, 2H, ArH), 5.88-5.41(m, 2H, ArNHNH+NH), 3.85-3.73(m, 1H, CHNH), 2.65, 2.63(s, s, 48 /52, 3H, CH 3 CNH), 2.22 (s, 3H, ArCH 3 ), 2.19 (s, 3H, ArCH 3 ), 2.06-1.88 (m, 1H, CH 3 CH), 1.45-1.19 (m, 2H , CH 3 CH 2 ), 1.01-0.79 (m, 6H, CH 3 CH 2 (CH 3 ) CH); EI-MS, m/z (%): 315 [M + ].

5-仲丁基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(H-9)： 5-sec-butyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (H-9):

5S，6S    5R，6S 5S, 6S 5R, 6S

灰白色粉末；收率65％；mp 81.7-83.5℃；1H NMR(400MHz，CDCl3)δ：11.91，11.43(s，s，52/48，1H，ArNHNH)，6.99(t，J＝8.6Hz，2H，ArH)，6.75(dd，J＝7.9Hz，J＝4.3Hz，2H，ArH)，5.82(br，1H，ArNHNH)，5.55(br，1H，NH)，3.89-3.71(m，1H，CHNH)，2.64(s，3H，CH3CNH)，2.06-1.89(m，1H，CH3CH)，1.46-1.17(m，2H，CH3CH2)，1.01-0.79(m，6H，CH3CH2(CH3)CH)；EI-MS，m/z(％)：305[M+]. Off-white powder; yield 65%; mp 81.7-83.5°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.91, 11.43 (s, s, 52/48, 1H, ArNHNH), 6.99(t, J=8.6Hz , 2H, ArH), 6.75(dd, J=7.9Hz, J=4.3Hz, 2H, ArH), 5.82(br, 1H, ArNHNH), 5.55(br, 1H, NH), 3.89-3.71(m, 1H , CHNH), 2.64 (s, 3H, CH 3 CNH), 2.06-1.89 (m, 1H, CH 3 CH), 1.46-1.17 (m, 2H, CH 3 CH 2 ), 1.01-0.79 (m, 6H, CH 3 CH 2 (CH 3 ) CH); EI-MS, m/z (%): 305 [M + ].

5-仲丁基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(H-10)： 5-sec-butyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (H-10):

白色粉末；收率51％；mp 141.9-142.8℃；1H NMR(400MHz，CDCl3)δ：11.90，11.42(s，s，53/47，1H，ArNHNH)，7.24(d，J＝8.8Hz，2H，ArH)，6.72(d，J＝8.7Hz，2H，ArH)，5.91(br，1H，ArNHNH)，5.49(br，1H，NH)，3.92-3.69(m，1H，CHNH)，2.62(s，3H，CH3CNH)，2.05-1.91(m，1H，CH3CH)，1.46-1.22(m，2H，CH3CH2)，1.01-0.79(m，6H，CH3CH2(CH3)CH)；EI-MS，m/z(％)：321[M+]. White powder; yield 51%; mp 141.9-142.8°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.90, 11.42 (s, s, 53/47, 1H, ArNHNH), 7.24 (d, J=8.8Hz , 2H, ArH), 6.72 (d, J=8.7Hz, 2H, ArH), 5.91 (br, 1H, ArNHNH), 5.49 (br, 1H, NH), 3.92-3.69 (m, 1H, CHNH), 2.62 (s, 3H, CH 3 CNH), 2.05-1.91 (m, 1H, CH 3 CH ), 1.46-1.22 (m, 2H, CH 3 CH 2 ), 1.01-0.79 (m, 6H, CH 3 CH 2 ( CH 3 )CH); EI-MS, m/z (%): 321 [M + ].

5-仲丁基-3-(1-(2-(2-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(H-11)： 5-sec-butyl-3-(1-(2-(2-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (H-11):

黄褐色粉末；收率85％；mp 144.2-146.2℃；1H NMR(400MHz，CDCl3)δ：11.87，11.39(s，s，44/56，1H，ArNHNH)，7.18-6.88(m，3H，ArH)，6.70(t，J＝8.4Hz，1H，ArH)，5.73(d，J＝5.1Hz，1H，ArNHNH)，5.48(br，1H，NH)，3.86-3.70(m，1H，CHNH)，2.65，2.61(s，s，56/44，3H，CH3CNH)， 2.06-1.88(m，1H，CH3CH)，1.46-1.19(m，2H，CH3CH2)，1.01-0.79(m，6H，CH3CH2(CH3)CH)；EI-MS，m/z(％)：321[M+]. Yellow-brown powder; yield 85%; mp 144.2-146.2°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.87, 11.39 (s, s, 44/56, 1H, ArNHNH), 7.18-6.88 (m, 3H , ArH), 6.70(t, J=8.4Hz, 1H, ArH), 5.73(d, J=5.1Hz, 1H, ArNHNH), 5.48(br, 1H, NH), 3.86-3.70(m, 1H, CHNH ), 2.65, 2.61 (s, s, 56/44, 3H, CH 3 CNH), 2.06-1.88 (m, 1H, CH 3 CH), 1.46-1.19 (m, 2H, CH 3 CH 2 ), 1.01- 0.79 (m, 6H, CH 3 CH 2 (CH 3 ) CH); EI-MS, m/z (%): 321 [M + ].

5-仲丁基-3-(1-(2-(2，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(H-12)： 5-sec-butyl-3-(1-(2-(2,4-dichlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (H-12):

白色粉末；收率67％；mp 171.6-172.9℃；1H NMR(400MHz，CDCl3)δ：11.85，11.41(s，s，46/54，1H，ArNHNH)，7.35(s，1H，ArH)，7.19(dd，J＝8.7Hz，J＝2.1Hz，1H，ArH)，6.72(dd，J＝17.4Hz，J＝8.5Hz，1H，ArH)，6.35(d，J＝25.2Hz，1H，ArNHNH)，5.95-5.54(m，1H，NH)，3.88-3.73(m，1H，CHNH)，2.64，2.61(s，s，46/54，3H，CH3CNH)，2.07-1.88(m，1H，CH3CH)，1.46-1.20(m，2H，CH3CH2)，1.01-0.79(m，6H，CH3CH2(CH3)CH)；EI-MS，m/z(％)：355[M+-H]. White powder; yield 67%; mp 171.6-172.9°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.85, 11.41 (s, s, 46/54, 1H, ArNHNH), 7.35 (s, 1H, ArH) , 7.19(dd, J=8.7Hz, J=2.1Hz, 1H, ArH), 6.72(dd, J=17.4Hz, J=8.5Hz, 1H, ArH), 6.35(d, J=25.2Hz, 1H, ArNHNH), 5.95-5.54 (m, 1H, NH), 3.88-3.73 (m, 1H, CHNH), 2.64, 2.61 (s, s, 46/54, 3H, CH 3 CNH), 2.07-1.88 (m, 1H, CH 3 CH ), 1.46-1.20 (m, 2H, CH 3 CH 2 ), 1.01-0.79 (m, 6H, CH 3 CH 2 (CH 3 )CH); EI-MS, m/z (%) : 355[M + -H].

5-仲丁基-3-(1-(2-(3，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(H-13)： 5-sec-butyl-3-(1-(2-(3,4-dichlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (H-13):

灰白色粉末；收率54％；mp 156.3-158.2℃；1H NMR(400MHz，CDCl3)δ：11.84，11.41(s，s，46/54，1H，ArNHNH)，7.32(d，J＝8.7Hz，1H，ArH)，6.88(s，1H，ArH)，6.64(d，J＝8.1Hz，1H，ArH)，6.10(d，J＝29.4Hz，1H，ArNHNH)，5.79-5.55(m，1H，NH)，3.89-3.70(m，1H，CHNH)，2.61，2.59(s，s，46/54，3H，CH3CNH)，2.07-1.89(m，1H，CH3CH)，1.47-1.21(m，2H，CH3CH2)，1.01-0.79(m，6H，CH3CH2(CH3)CH)；EI-MS，m/z(％)：355[M+-H]. Off-white powder; yield 54%; mp 156.3-158.2°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.84, 11.41 (s, s, 46/54, 1H, ArNHNH), 7.32 (d, J=8.7Hz , 1H, ArH), 6.88(s, 1H, ArH), 6.64(d, J=8.1Hz, 1H, ArH), 6.10(d, J=29.4Hz, 1H, ArNHNH), 5.79-5.55(m, 1H , NH), 3.89-3.70 (m, 1H, CHNH), 2.61, 2.59 (s, s, 46/54, 3H, CH 3 CNH), 2.07-1.89 (m, 1H, CH 3 CH), 1.47-1.21 (m, 2H, CH 3 CH 2 ), 1.01-0.79 (m, 6H, CH 3 CH 2 (CH 3 ) CH); EI-MS, m/z(%): 355[M + -H].

5-仲丁基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(H-14)： 5-sec-butyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (H-14):

白色粉末；收率68％；mp 150.4-152.7℃；1H NMR(400MHz，CDCl3)δ：11.88，11.41(s，s，51/49，1H，ArNHNH)，7.38(d，J＝8.7Hz，2H，ArH)，6.67(d，J＝8.6Hz，2H，ArH)，5.92(br，1H，ArNHNH)，5.53(br，1H，NH)，3.91-3.70(m，1H，CHNH)，2.62(s，3H，CH3CNH)，2.06-1.90(m，1H，CH3CH)，1.45-1.19(m，2H，CH3CH2)，1.01-0.79(m，6H，CH3CH2(CH3)CH)；EI-MS，m/z(％)：367[M++H]. White powder; yield 68%; mp 150.4-152.7°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.88, 11.41 (s, s, 51/49, 1H, ArNHNH), 7.38 (d, J=8.7Hz , 2H, ArH), 6.67 (d, J=8.6Hz, 2H, ArH), 5.92 (br, 1H, ArNHNH), 5.53 (br, 1H, NH), 3.91-3.70 (m, 1H, CHNH), 2.62 (s, 3H, CH 3 CNH), 2.06-1.90 (m, 1H, CH 3 CH ), 1.45-1.19 (m, 2H, CH 3 CH 2 ), 1.01-0.79 (m, 6H, CH 3 CH 2 ( CH 3 )CH); EI-MS, m/z(%): 367[M + +H].

5-仲丁基-3-(1-(2-(3-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(H-15) 5-sec-butyl-3-(1-(2-(3-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (H-15)

白色粉末；收率66％；mp 128.7-130.5℃；1H NMR(400MHz，CDCl3)δ：11.87，11.41(s，s，50/50，1H，ArNHNH)，7.16-7.08(m，2H，ArH)，6.93(s，1H，ArH)，6.71(d，J＝7.4Hz，1H，ArH)，5.98(br，1H，ArNHNH)，5.52(br，1H，NH)，3.90-3.71(m，1H，CHNH)，2.62(s，3H，CH3CNH)，2.06-1.89(m，1H，CH3CH)，1.46-1.20(m，2H，CH3CH2)，1.01-0.80(m，6H，CH3CH2(CH3)CH)；EI-MS，m/z(％)：367[M++H]. White powder; yield 66%; mp 128.7-130.5°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.87, 11.41 (s, s, 50/50, 1H, ArNHNH), 7.16-7.08 (m, 2H, ArH), 6.93(s, 1H, ArH), 6.71(d, J=7.4Hz, 1H, ArH), 5.98(br, 1H, ArNHNH), 5.52(br, 1H, NH), 3.90-3.71(m, 1H, CHNH), 2.62 (s, 3H, CH 3 CNH), 2.06-1.89 (m, 1H, CH 3 CH), 1.46-1.20 (m, 2H, CH 3 CH 2 ), 1.01-0.80 (m, 6H , CH 3 CH 2 (CH 3 )CH); EI-MS, m/z (%): 367 [M + +H].

实施例2：3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(K-2)的制备Example 2: Preparation of 3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (K-2)

在250mL三口烧瓶中加入甘氨酸甲酯盐酸盐22.5g，50mL新制的甲醇钠溶液(4.1g金属钠，50mL甲醇)，常温下搅拌反应1h，有白色固体生成。抽滤，将所得滤液于冰浴中冷却，搅拌，滴加双乙烯酮15.0g。滴加时控制温度不超过0℃，滴加完毕，室温下搅拌反应10h，减压脱去溶剂。向所得产物中 加入50mL苯，50mL甲醇钠溶液(4.1g金属钠，50mL甲醇)。搅拌，回流反应3h，有大量白色固体生成。冷却，抽滤，将所得的固体加水溶解，用20％的盐酸酸化至pH＝2-3。静置冷却，有白色固体析出，抽滤，干燥，17.5g 3-(1-羟基亚乙基)吡咯烷-2，4-二酮： Add 22.5 g of glycine methyl ester hydrochloride and 50 mL of freshly prepared sodium methoxide solution (4.1 g of metallic sodium, 50 mL of methanol) into a 250 mL three-neck flask, stir and react at room temperature for 1 h, and a white solid is formed. After suction filtration, the resulting filtrate was cooled in an ice bath, stirred, and 15.0 g of diketene was added dropwise. During the dropwise addition, the temperature was controlled not to exceed 0°C. After the dropwise addition was completed, the reaction was stirred at room temperature for 10 h, and the solvent was removed under reduced pressure. Add 50 mL of benzene, 50 mL of sodium methoxide solution (4.1 g of metallic sodium, 50 mL of methanol) to the resulting product. Stir and reflux for 3h, a large amount of white solid is generated. Cool, filter with suction, dissolve the resulting solid in water, and acidify to pH=2-3 with 20% hydrochloric acid. Standing and cooling, a white solid precipitated out, suction filtered and dried, 17.5g 3-(1-hydroxyethylidene)pyrrolidine-2,4-dione:

白色固体；收率70％；mp 155.2-156.6℃；1H NMR(400MHz，CDCl3)δ：12.49(br，1H，OH)，6.73(s，1H，NH)，3.85，3.93(s，s，2H，NCH2)，2.46(s，3H，CH3)；EI-MS，m/z(％)：141[M+]. White solid; yield 70%; mp 155.2-156.6°C; 1 H NMR (400 MHz, CDCl 3 ) δ: 12.49 (br, 1H, OH), 6.73 (s, 1H, NH), 3.85, 3.93 (s, s , 2H, NCH 2 ), 2.46 (s, 3H, CH 3 ); EI-MS, m/z (%): 141 [M + ].

在50mL三口烧瓶中加入乙醇15mL，3-(1-羟基亚乙基)吡咯烷-2，4-二酮7.1mmol(1.00g)，对氯苯肼盐酸盐7.1mmol(1.27g)，滴加含1.2倍量三乙胺8.5mmol(0.86g)的乙醇溶液5m L，待溶液完全澄清后，加热回流，搅拌，采用TLC(展开剂：乙酸乙酯∶石油醚∶乙酸＝10∶10∶1，V/V/V)监控反应进程。反应结束后，冷却，有固体析出，抽滤，水洗，用乙醇洗涤，干燥，得1.26g 3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(K-2)： Add 15 mL of ethanol, 7.1 mmol (1.00 g) of 3-(1-hydroxyethylidene) pyrrolidine-2,4-dione, and 7.1 mmol (1.27 g) of p-chlorophenylhydrazine hydrochloride into a 50 mL three-necked flask, drop Add 5mL of ethanol solution containing 8.5mmol (0.86g) of 1.2 times the amount of triethylamine. After the solution is completely clarified, heat to reflux, stir, and use TLC (developing solvent: ethyl acetate:petroleum ether:acetic acid=10:10: 1, V/V/V) to monitor the progress of the reaction. After the reaction was completed, cooled, solids were precipitated, suction filtered, washed with water, washed with ethanol, and dried to obtain 1.26g 3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2 , 4-diketone (K-2):

白色粉末；收率67％；mp 177.9-179.3℃；1H NMR(400MHz，DMSO-d6)δ：E(61％)：11.45(s，1H，ArNHNH)，8.45(s，1H，ArNHNH)，7.70(s，1H，NH)，7.28(d，J＝8.8Hz，2H，ArH)，6.73(d，J＝8.8Hz，2H，ArH)，3.60(s，2H，CH2NH)，2.44(s，3H，CH3CNH)；Z(39％)：11.64(s，1H，ArNHNH)，8.51(s，1H，ArNHNH)，7.41(s，1H，NH)，7.28(d，J＝8.8Hz，2H，ArH)，6.73(d，J＝8.8Hz，2H，ArH)，3.64(s，2H，CH2NH)，2.48(s，3H，CH3CNH)；EI-MS，m/z(％)：265[M+]. White powder; yield 67%; mp 177.9-179.3°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (61%): 11.45 (s, 1H, ArNHNH), 8.45 (s, 1H, ArNHNH) , 7.70 (s, 1H, NH), 7.28 (d, J=8.8Hz, 2H, ArH), 6.73 (d, J=8.8Hz, 2H, ArH), 3.60 (s, 2H, CH2NH ), 2.44 (s, 3H, CH 3 CNH); Z (39%): 11.64 (s, 1H, ArNHNH), 8.51 (s, 1H, ArNHNH), 7.41 (s, 1H, NH), 7.28 (d, J=8.8 Hz, 2H, ArH), 6.73 (d, J=8.8Hz, 2H, ArH), 3.64 (s, 2H, CH 2 NH), 2.48 (s, 3H, CH 3 CNH); EI-MS, m/z (%): 265[M + ].

采用实施例2的方法，制备了下述K系列和N系列化合物：  Adopt the method for embodiment 2, prepared following K series and N series compound:

3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(K-1)： 3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (K-1):

Z                       E  Z E

黄褐色粉末；收率65％；mp 167.2-168.7℃；1H NMR(400MHz，DMSO-d6)δ：E(63％)：11.47(s，1H，ArNHNH)，8.25(s，1H，ArNHNH)，7.67(s，1H，NH)，7.09(t，J＝8.8Hz，2H，ArH)，6.74(dd，J＝8.9Hz，J＝4.5Hz，2H，ArH)，3.59(s，2H，CH2NH)，2.46(s，3H，CH3CNH)；Z(37％)：11.68(s，1H，ArNHNH)，8.31(s，1H，ArNHNH)，7.39(s，1H，NH)，7.09(t，J＝8.8Hz，2H，ArH)，6.74(dd，J＝8.9Hz，J＝4.5Hz，ArH)，3.64(s，2H，CH2NH)，2.50(s，3H，CH3CNH)；EI-MS，m/z(％)：249[M+]. Yellow-brown powder; yield 65%; mp 167.2-168.7°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (63%): 11.47(s, 1H, ArNHNH), 8.25(s, 1H, ArNHNH ), 7.67(s, 1H, NH), 7.09(t, J=8.8Hz, 2H, ArH), 6.74(dd, J=8.9Hz, J=4.5Hz, 2H, ArH), 3.59(s, 2H, CH 2 NH), 2.46 (s, 3H, CH 3 CNH); Z (37%): 11.68 (s, 1H, ArNHNH), 8.31 (s, 1H, ArNHNH), 7.39 (s, 1H, NH), 7.09 (t, J=8.8Hz, 2H, ArH), 6.74(dd, J=8.9Hz, J=4.5Hz, ArH), 3.64(s, 2H, CH2NH ), 2.50(s, 3H, CH3CNH ); EI-MS, m/z (%): 249 [M + ].

3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(K-3)： 3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (K-3):

灰白色粉末；收率60％；mp 293.2-295.1℃；1H NMR(400MHz，DMSO-d6)δ：E(61％)：11.44(s，1H，ArNHNH)，8.45(s，1H，ArNHNH)，7.67(s，1H，NH)，7.40(d，J＝8.8Hz，2H，ArH)，6.68(d，J＝8.8Hz，2H，ArH)，3.59(s，2H，CH2NH)，2.44(s，3H，CH3CNH)；Z(39％)：11.63(s，1H，ArNHNH)，8.50(s，1H，ArNHNH)，7.42(s，1H，NH)，7.40(d，J＝8.8Hz，2H，ArH)，6.68(d，J＝8.8Hz，2H，ArH)，3.64(s，2H，CH2NH)，2.48(s，3H，CH3CNH)；EI-MS，m/z(％)：311[M++H]. Off-white powder; yield 60%; mp 293.2-295.1°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (61%): 11.44(s, 1H, ArNHNH), 8.45(s, 1H, ArNHNH) , 7.67 (s, 1H, NH), 7.40 (d, J=8.8Hz, 2H, ArH), 6.68 (d, J=8.8Hz, 2H, ArH), 3.59 (s, 2H, CH 2 NH), 2.44 (s, 3H, CH 3 CNH); Z (39%): 11.63 (s, 1H, ArNHNH), 8.50 (s, 1H, ArNHNH), 7.42 (s, 1H, NH), 7.40 (d, J=8.8 Hz, 2H, ArH), 6.68 (d, J=8.8Hz, 2H, ArH), 3.64 (s, 2H, CH 2 NH), 2.48 (s, 3H, CH 3 CNH); EI-MS, m/z (%): 311[M + +H].

3-(1-(2-(2-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(K-4)： 3-(1-(2-(2-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (K-4):

白色粉末；收率54％；mp 200.8-201.6℃；1H NMR(400MHz，DMSO-d6)δ：E(64％)：11.44(s，1H，ArNHNH)，8.34(s，1H，ArNHNH)，7.69(s，1H，NH)，7.21-6.75(m，4H，ArH)，3.60(s，2H，CH2NH)，2.47(s，3H，CH3)；Z(36％)：11.63(s，1H，ArNHNH)，8.39(s，1H，ArNHNH)，7.40(s，1H，NH)，7.21-6.75(m，4H，ArH)，3.65(s，2H，CH2NH)，2.51(s，3H，CH3)；EI-MS，m/z(％)：249[M+]. White powder; yield 54%; mp 200.8-201.6°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (64%): 11.44(s, 1H, ArNHNH), 8.34(s, 1H, ArNHNH) , 7.69 (s, 1H, NH), 7.21-6.75 (m, 4H, ArH), 3.60 (s, 2H, CH 2 NH), 2.47 (s, 3H, CH 3 ); Z (36%): 11.63 ( s, 1H, ArNHNH), 8.39(s, 1H, ArNHNH) , 7.40(s, 1H, NH), 7.21-6.75(m, 4H, ArH), 3.65(s, 2H, CH2NH), 2.51(s , 3H, CH 3 ); EI-MS, m/z (%): 249[M + ].

3-(1-(2-(3-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(K-5)： 3-(1-(2-(3-Chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (K-5):

白色粉末；收率59％；mp 202.0-203.0℃；1H NMR(400MHz，DMSO-d6)δ：E(63％)：11.44(s，1H，ArNHNH)，8.53(s，1H，ArNHNH)，7.68(s，1H，NH)，7.28-6.67(m，4H，ArH)，3.60(s，2H，CH2NH)，2.44(s，3H，CH3)；Z(37％)：11.62(s，1H，ArNHNH)，8.59(s，1H，ArNHNH)，7.39(s，1H，NH)，7.28-6.67(m，4H，ArH)，3.65(s，2H，CH2NH)，2.48(s，3H，CH3)；EI-MS，m/z(％)：265[M+]. White powder; yield 59%; mp 202.0-203.0°C; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (63%): 11.44(s, 1H, ArNHNH), 8.53(s, 1H, ArNHNH) , 7.68 (s, 1H, NH), 7.28-6.67 (m, 4H, ArH), 3.60 (s, 2H, CH 2 NH), 2.44 (s, 3H, CH 3 ); Z (37%): 11.62 ( s, 1H, ArNHNH), 8.59 (s, 1H, ArNHNH), 7.39 (s, 1H, NH), 7.28-6.67 (m, 4H, ArH), 3.65 (s, 2H, CH 2 NH), 2.48 (s , 3H, CH 3 ); EI-MS, m/z (%): 265[M + ].

3-(1-(2-(2，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(K-6)： 3-(1-(2-(2,4-dichlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (K-6):

浅绿色粉末；收率49％；mp 216.0-217.0℃；1H NMR(400MHz，DMSO-d6)δ：E(64％)：11.43(s，1H，ArNHNH)，8.32(s，1H，ArNHNH)，7.70(s，1H，NH)，7.53-6.72(m，3H，ArH)，3.61(s，2H，CH2NH)，2.42(s，3H，CH3)；Z(36％)：11.58(s，1H，ArNHNH)，8.35(s，1H，ArNHNH)，7.42(s，1H，NH)，7.53-6.72(m，3H，ArH)，3.65(s，2H，CH2NH)，2.47(s，3H，CH3)；EI-MS，m/z(％)：300[M+]. Light green powder; yield 49%; mp 216.0-217.0°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (64%): 11.43(s, 1H, ArNHNH), 8.32(s, 1H, ArNHNH ), 7.70 (s, 1H, NH), 7.53-6.72 (m, 3H, ArH), 3.61 (s, 2H, CH 2 NH), 2.42 (s, 3H, CH 3 ); Z (36%): 11.58 (s, 1H, ArNHNH), 8.35 (s, 1H, ArNHNH), 7.42 (s, 1H, NH), 7.53-6.72 (m, 3H, ArH), 3.65 (s, 2H, CH 2 NH), 2.47 ( s, 3H, CH 3 ); EI-MS, m/z (%): 300 [M + ].

3-(1-(2-(4-甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(K-7)： 3-(1-(2-(4-methylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (K-7):

白色粉末；收率44％；mp 197.0-197.8℃；1H NMR(400MHz，DMSO-d6)δ：E(64％)：11.47(s，1H，ArNHNH)，8.14(s，1H，ArNHNH)，7.63(s，1H，NH)，7.07-6.63(m，4H，ArH)，3.58(s，2H，CH2NH)， 2.46(s，3H，CH3)，2.21(s，3H，ArCH3)；Z(36％)：11.70(s，1H，ArNHNH)，8.20(s，1H，ArNHNH)，7.35(s，1H，NH)，7.07-6.63(m，4H，ArH)，3.63(s，2H，CH2NH)，2.50(s，3H，CH3)，2.21(s，3H，ArCH3)；EI-MS，m/z(％)：245[M+]. White powder; yield 44%; mp 197.0-197.8°C; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (64%): 11.47(s, 1H, ArNHNH), 8.14(s, 1H, ArNHNH) , 7.63(s, 1H, NH), 7.07-6.63(m, 4H, ArH), 3.58(s, 2H, CH 2 NH), 2.46(s, 3H, CH 3 ), 2.21(s, 3H, ArCH 3 ); Z (36%): 11.70 (s, 1H, ArNHNH), 8.20 (s, 1H, ArNHNH), 7.35 (s, 1H, NH), 7.07-6.63 (m, 4H, ArH), 3.63 (s, 2H, CH 2 NH), 2.50(s, 3H, CH 3 ), 2.21(s, 3H, ArCH 3 ); EI-MS, m/z(%): 245[M + ].

3-(1-(2-(4-甲氧基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(K-8)： 3-(1-(2-(4-methoxyphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (K-8):

白色粉末；收率33％；mp 157.5-159.0℃；1H NMR(400MHz，DMSO-d6)δ：E(63％)：11.47(s，1H，ArNHNH)，7.98(s，1H，ArNHNH)，7.61(s，1H，NH)，6.87-6.69(m，4H，ArH)，3.69(s，3H，OCH3)，3.58(s，2H，CH2NH)，2.48(s，3H，CH3)；Z(37％)：11.71(s，1H，ArNHNH)，8.04(s，1H，ArNHNH)，7.33(s，1H，NH)，6.87-6.69(m，4H，ArH)，3.63(s，3H，OCH3)，3.63(s，2H，CH2NH)，2.51(s，3H，CH3)；EI-MS，m/z(％)：261[M+]. White powder; yield 33%; mp 157.5-159.0°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (63%): 11.47 (s, 1H, ArNHNH), 7.98 (s, 1H, ArNHNH) , 7.61 (s, 1H, NH), 6.87-6.69 (m, 4H, ArH), 3.69 (s, 3H, OCH 3 ), 3.58 (s, 2H, CH 2 NH), 2.48 (s, 3H, CH 3 ); Z (37%): 11.71 (s, 1H, ArNHNH), 8.04 (s, 1H, ArNHNH), 7.33 (s, 1H, NH), 6.87-6.69 (m, 4H, ArH), 3.63 (s, 3H, OCH 3 ), 3.63(s, 2H, CH 2 NH), 2.51(s, 3H, CH 3 ); EI-MS, m/z(%): 261[M + ].

3-(1-(2-(3，4-二甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(K-9)： 3-(1-(2-(3,4-dimethylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (K-9):

白色粉末；收率41％；mp180.4-182.1℃；1H NMR(400MHz，DMSO-d6)δ：E(63％)：11.46(s，1H，ArNHNH)，8.05(s，1H，ArNHNH)，7.61(s，1H，NH)，7.01-6.44(m，3H，ArH)，3.58(s，2H，CH2NH)，2.46(s，3H，CH3CNHN)，2.16(s，3H，ArCH3)，2.12((s，3H，ArCH3)；Z(37％)：11.69(s，1H，ArNHNH)，8.12(s，1H，ArNHNH)，7.33(s，1H，NH)，7.01-6.44(m，3H，ArH)，3.63(s，2H，CH2NH)，2.49(s，3H，CH3CNHN)，2.16(s，3H，ArCH3)，2.12((s，3H，ArCH3)；EI-MS，m/z(％)：259[M+]. White powder; yield 41%; mp180.4-182.1°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (63%): 11.46(s, 1H, ArNHNH), 8.05(s, 1H, ArNHNH ), 7.61(s, 1H, NH), 7.01-6.44(m, 3H, ArH), 3.58(s, 2H, CH 2 NH), 2.46(s, 3H, CH 3 CNHN), 2.16(s, 3H, ArCH 3 ), 2.12 ((s, 3H, ArCH 3 ); Z (37%): 11.69 (s, 1H, ArNHNH), 8.12 (s, 1H, ArNHNH), 7.33 (s, 1H, NH), 7.01- 6.44(m, 3H, ArH), 3.63(s, 2H, CH 2 NH), 2.49(s, 3H, CH 3 CNHN), 2.16(s, 3H, ArCH 3 ), 2.12((s, 3H, ArCH 3 ); EI-MS, m/z (%): 259 [M + ].

3-(1-(2-(4-氨基磺酰基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(K-10)： 3-(1-(2-(4-aminosulfonylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (K-10):

白色粉末；收率81％；mp 233.4-234.5℃；1H NMR(400MHz，DMSO-d6)δ：E(62％)：11.48(s，1H，ArNHNH)，8.84(s，1H，ArNHNH)，7.70(s，1H，NH)，7.69-6.67(m，2H，ArH)，7.11(s，2H，NH2)，7.82-6.79(m，2H，ArH)，3.61(s，2H，CH2NH)，2.43(s，3H，CH3CNHN)；Z(38％)：11.65(s，1H，ArNHNH)，8.89(s，1H，ArNHNH)，7.69-6.67(m，2H，ArH)，7.42(s，1H，NH)，7.11(s，2H，NH2)，7.82-6.79(m，2H，ArH)，3.65(s，2H，CH2NH)，2.47(s，3H，CH3CNHN)；EI-MS，m/z(％)：338[M+]. White powder; yield 81%; mp 233.4-234.5°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (62%): 11.48(s, 1H, ArNHNH), 8.84(s, 1H, ArNHNH) , 7.70 (s, 1H, NH), 7.69-6.67 (m, 2H, ArH), 7.11 (s, 2H, NH 2 ), 7.82-6.79 (m, 2H, ArH), 3.61 (s, 2H, CH 2 NH), 2.43 (s, 3H, CH 3 CNHN); Z (38%): 11.65 (s, 1H, ArNHNH), 8.89 (s, 1H, ArNHNH), 7.69-6.67 (m, 2H, ArH), 7.42 (s, 1H, NH), 7.11 (s, 2H, NH 2 ), 7.82-6.79 (m, 2H, ArH), 3.65 (s, 2H, CH 2 NH), 2.47 (s, 3H, CH 3 CNHN) ; EI-MS, m/z (%): 338 [M + ].

5-甲基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-10)： 5-methyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-10):

黄色粉末；收率33％；mp 197.2-198.7℃；1H NMR(400MHz，DMSO-d6)δ：E(64％)：11.49(s，1H，ArNHNH)，8.25(s，1H，ArNHNH)，7.82(s，1H，NH)，7.10(t，J＝8.5Hz，2H，ArH)，6.75(dd，J＝8.5Hz，J＝4.4Hz，2H，ArH)，3.66(q，J＝6.6Hz，1H，CHNH)，2.46(s，3H，CH3CNH)，1.16(t，J＝6.4Hz，3H，CH3CH)；Z(36％)：11.63(s，1H，ArNHNH)，8.30(s，1H，ArNHNH)，7.54(s，1H，NH)，7.10(t，J＝8.5Hz，2H，ArH)，6.75(dd，J＝8.5Hz，J＝4.4Hz，2H，ArH)，3.73(q，J＝6.6Hz，1H，CHNH)，2.50(s，3H，CH3CNH)，1.06(t，J＝7.0Hz，3H，CH3CH)；EI-MS，m/z(％)：263[M+]. Yellow powder; yield 33%; mp 197.2-198.7°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (64%): 11.49 (s, 1H, ArNHNH), 8.25 (s, 1H, ArNHNH) , 7.82(s, 1H, NH), 7.10(t, J=8.5Hz, 2H, ArH), 6.75(dd, J=8.5Hz, J=4.4Hz, 2H, ArH), 3.66(q, J=6.6 Hz, 1H, CHNH), 2.46 (s, 3H, CH3CNH ), 1.16 (t, J = 6.4Hz, 3H, CH3CH) ; Z (36%): 11.63 (s, 1H, ArNHNH), 8.30 (s, 1H, ArNHNH), 7.54 (s, 1H, NH), 7.10 (t, J=8.5Hz, 2H, ArH), 6.75 (dd, J=8.5Hz, J=4.4Hz, 2H, ArH), 3.73(q, J=6.6Hz, 1H, CHNH), 2.50(s, 3H, CH3CNH ), 1.06(t, J=7.0Hz, 3H, CH3CH ); EI-MS, m/z (% ): 263[M + ].

5-甲基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-11)： 5-methyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-11):

浅黄色粉末；收率73％；mp 191.9-193.1℃；1H NMR(400MHz，DMSO-d6)δ：E(60％)：11.47(s， 1H，ArNHNH)，8.44(s，1H，ArNHNH)，7.84(s，1H，NH)，7.28(d，J＝8.7Hz，2H，ArH)，6.73(d，J＝8.8Hz，2H，ArH)，3.66(q，J＝6.8Hz，1H，CHNH)，2.43(s，3H，CH3CNH)，1.16(t，J＝6.9Hz，3H，CH3CH)；Z(40％)：11.59(s，1H，ArNHNH)，8.49(s，1H，ArNHNH)，7.56(s，1H，NH)，7.28(d，J＝8.7Hz，2H，ArH)，6.73(d，J＝8.8Hz，2H，ArH)，3.73(q，J＝6.8Hz，1H，CHNH)，2.47(s，3H，CH3CNH)，1.06(t，J＝7.0Hz，3H，CH3CH)；EI-MS，m/z(％)：279[M+]. Pale yellow powder; yield 73%; mp 191.9-193.1°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (60%): 11.47(s, 1H, ArNHNH), 8.44(s, 1H, ArNHNH ), 7.84 (s, 1H, NH), 7.28 (d, J=8.7Hz, 2H, ArH), 6.73 (d, J=8.8Hz, 2H, ArH), 3.66 (q, J=6.8Hz, 1H, CHNH), 2.43(s, 3H , CH3CNH ), 1.16(t, J=6.9Hz, 3H, CH3CH); Z(40%): 11.59(s, 1H, ArNHNH), 8.49(s, 1H , ArNHNH), 7.56(s, 1H, NH), 7.28(d, J=8.7Hz, 2H, ArH), 6.73(d, J=8.8Hz, 2H, ArH), 3.73(q, J=6.8Hz, 1H, CHNH), 2.47(s, 3H, CH 3 CNH), 1.06(t, J=7.0Hz, 3H, CH 3 CH); EI-MS, m/z(%): 279[M + ].

5-甲基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-12)： 5-Methyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-12):

黄色粉末；收率54％；mp 179.3-180.2℃；1H NMR(400MHz，DMSO-d6)δ：E(62％)：11.46(s，1H，ArNHNH)，8.46(s，1H，ArNHNH)，7.85(s，1H，NH)，7.41(d，J＝8.7Hz，2H，ArH)，6.69(d，J＝8.7Hz，2H，ArH)，3.67(q，J＝6.8Hz，1H，CHNH)，2.43(s，3H，CH3CNH)，1.17(t，J＝6.9Hz，3H，CH3CH)；Z(38％)：11.58(s，1H，ArNHNH)，8.51(s，1H，ArNHNH)，7.56(s，1H，NH)，7.41(d，J＝8.7Hz，2H，ArH)，6.69(d，J＝8.7Hz，2H，ArH)，3.74(q，J＝6.7Hz，1H，CHNH)，2.48(s，3H，CH3CNH)，1.06(t，J＝7.0Hz，3H，CH3CH)；EI-MS，m/z(％)：325[M++H]. Yellow powder; yield 54%; mp 179.3-180.2°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (62%): 11.46 (s, 1H, ArNHNH), 8.46 (s, 1H, ArNHNH) , 7.85(s, 1H, NH), 7.41(d, J=8.7Hz, 2H, ArH), 6.69(d, J=8.7Hz, 2H, ArH), 3.67(q, J=6.8Hz, 1H, CHNH ), 2.43 (s, 3H, CH 3 CNH), 1.17 (t, J=6.9Hz, 3H, CH 3 CH); Z (38%): 11.58 (s, 1H, ArNHNH), 8.51 (s, 1H, ArNHNH), 7.56(s, 1H, NH), 7.41(d, J=8.7Hz, 2H, ArH), 6.69(d, J=8.7Hz, 2H, ArH), 3.74(q, J=6.7Hz, 1H , CHNH), 2.48 (s, 3H, CH 3 CNH), 1.06 (t, J=7.0Hz, 3H, CH 3 CH); EI-MS, m/z (%): 325 [M + +H].

5-异丙基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-13)： 5-isopropyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-13):

白色粉末；收率30％；mp 127.8-129.1℃；1H NMR(400MHz，CDCl3)δ：11.87，11.43(s，s，38/62，Z/E，1H，ArNHNH)，6.98(t，J＝8.4Hz，2H，ArH)，6.77-6.72(m，2H，ArH)，5.89(s，1H，ArNHNH)，5.66(s，1H，NH)，3.70(s，1H，CHNH)，2.65，2.62(s，s，38/62，Z/E，3H，CH3CNH)，2.21 (br，1H，CHNH)，1.03(d，J＝7.0Hz，3H，CH3)，0.85(d，J＝6.7Hz，3H，CH3)；EI-MS，m/z(％)：291[M+]. White powder; yield 30%; mp 127.8-129.1°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.87, 11.43 (s, s, 38/62, Z/E, 1H, ArNHNH), 6.98(t, J=8.4Hz, 2H, ArH), 6.77-6.72(m, 2H, ArH), 5.89(s, 1H, ArNHNH), 5.66(s, 1H, NH), 3.70(s, 1H, CHNH), 2.65, 2.62 (s, s, 38/62, Z/E, 3H, CH 3 CNH), 2.21 (br, 1H, CHNH), 1.03 (d, J=7.0Hz, 3H, CH 3 ), 0.85 (d, J =6.7Hz, 3H, CH 3 ); EI-MS, m/z (%): 291 [M + ].

5-异丙基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-14)： 5-isopropyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-14):

白色粉末；收率41％；mp 161.0-162.8℃；1H NMR(400MHz，CDCl3)δ：11.87，11.42(s，s，48/52，Z/E，1H，ArNHNH)，7.24(d，J＝8.6Hz，2H，ArH)，6.72(d，J＝8.1Hz，1H，ArH)，5.99(br，1H，ArNHNH)，5.67(br，1H，NH)，3.71(s，1H，CHNH)，2.61(s，3H，CH3CNH)，2.22(br，1H，CHNH)，1.03(d，J＝7.0Hz，3H，CH3)，0.85(d，J＝6.7Hz，3H，CH3)；EI-MS，m/z(％)：307[M+]. White powder; yield 41%; mp 161.0-162.8°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.87, 11.42 (s, s, 48/52, Z/E, 1H, ArNHNH), 7.24(d, J=8.6Hz, 2H, ArH), 6.72(d, J=8.1Hz, 1H, ArH), 5.99(br, 1H, ArNHNH), 5.67(br, 1H, NH), 3.71(s, 1H, CHNH) , 2.61 (s, 3H, CH 3 CNH), 2.22 (br, 1H, CHNH), 1.03 (d, J=7.0Hz, 3H, CH 3 ), 0.85 (d, J=6.7Hz, 3H, CH 3 ) ; EI-MS, m/z (%): 307 [M + ].

5-异丙基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-15)： 5-isopropyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-15):

白色粉末；收率29％；mp 150.6-152.2℃；1H NMR(400MHz，CDCl3)δ：11.86，11.39(s，s，48/52，Z/E，1H，ArNHNH)，7.38(d，J＝8.3Hz，2H，ArH)，6.67(d，J＝7.5Hz，2H，ArH)，5.92(br，1H，ArNHNH)，5.60(br，1H，NH)，3.72(s，1H，CHNH)，2.60(s，3H，CH3CNH)，2.22(br，1H，CHNH)，1.03(d，J＝6.9Hz，3H，CH3)，0.85(d，J＝6.7Hz，3H，CH3)；EI-MS，m/z(％)：353[M++H]. White powder; yield 29%; mp 150.6-152.2°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.86, 11.39 (s, s, 48/52, Z/E, 1H, ArNHNH), 7.38(d, J=8.3Hz, 2H, ArH), 6.67(d, J=7.5Hz, 2H, ArH), 5.92(br, 1H, ArNHNH), 5.60(br, 1H, NH), 3.72(s, 1H, CHNH) , 2.60 (s, 3H, CH 3 CNH), 2.22 (br, 1H, CHNH), 1.03 (d, J=6.9Hz, 3H, CH 3 ), 0.85 (d, J=6.7Hz, 3H, CH 3 ) ; EI-MS, m/z (%): 353 [M + +H].

5-丁基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-16)： 5-Butyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-16):

白色粉末；收率77％；mp 120.1-121.5℃；1H NMR(400MHz，CDCl3)δ：11.80，11.41(s，s，39/61，Z/E，1H，ArNHNH)，7.23(dd，J＝8.0Hz，J＝5.7Hz，2H，ArH)，6.71(d，2H，J＝6.9Hz，ArH)，5.96(s，1H，ArNHNH)，5.77(s，1H，NH)，3.80-3.71(m，1H，CHNH)，2.62，2.59(s，s，39/61，Z/E，3H，CH3CNH)，1.89-1.78，(m，2H，CH3CH2CH2CH2)，1.63-1.50，(m，2H，CH3CH2CH2CH2)，1.42-1.24，(m，2H，CH3CH2CH2CH2)，0.91(t，J＝6.5Hz，3H，CH3CH2CH2CH2)；EI-MS，m/z(％)：321[M+]. White powder; yield 77%; mp 120.1-121.5°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.80, 11.41 (s, s, 39/61, Z/E, 1H, ArNHNH), 7.23 (dd, J=8.0Hz, J=5.7Hz, 2H, ArH), 6.71(d, 2H, J=6.9Hz, ArH), 5.96(s, 1H, ArNHNH), 5.77(s, 1H, NH), 3.80-3.71 (m, 1H, CHNH), 2.62, 2.59 (s, s, 39/61, Z/E, 3H, CH 3 CNH), 1.89-1.78, (m, 2H, CH 3 CH 2 CH 2 CH 2 ), 1.63-1.50, (m, 2H, CH 3 CH 2 CH 2 CH 2 ), 1.42-1.24, (m, 2H, CH 3 CH 2 CH 2 CH 2 ), 0.91 (t, J=6.5Hz, 3H, CH 3 CH 2 CH 2 CH 2 ); EI-MS, m/z (%): 321 [M + ].

5-异丁基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-17)： 5-isobutyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-17):

灰白色粉末；收率79％；mp 91.6-92.9℃；1H NMR(400MHz，CDCl3)δ：11.84，11.45(s，s，52/48，Z/E，1H，ArNHNH)，6.99(t，J＝8.1Hz，2H，ArH)，6.76(dd，J＝7.8Hz，J＝3.8Hz，2H，ArH)，5.89(br，1H，ArNHNH)，5.67(s，1H，NH)，3.84(s，1H，CHNH)，2.64(s，3H，CH3CNH)，1.76(s，2H，(CH3)2CHCH2)，1.50-1.33(m，1H，(CH3)2CHCH2)，0.97(t，J＝4.6Hz，6H，(CH3)2CHCH2)；EI-MS，m/z(％)：305[M+]. Off-white powder; yield 79%; mp 91.6-92.9°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.84, 11.45 (s, s, 52/48, Z/E, 1H, ArNHNH), 6.99(t, J=8.1Hz, 2H, ArH), 6.76(dd, J=7.8Hz, J=3.8Hz, 2H, ArH), 5.89(br, 1H, ArNHNH), 5.67(s, 1H, NH), 3.84(s , 1H, CHNH), 2.64 (s, 3H, CH 3 CNH), 1.76 (s, 2H, (CH 3 ) 2 CHCH 2 ), 1.50-1.33 (m, 1H, (CH 3 ) 2 CHCH 2 ), 0.97 (t, J=4.6Hz, 6H, (CH 3 ) 2 CHCH 2 ); EI-MS, m/z(%): 305[M + ].

5-异丁基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-18)： 5-isobutyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-18):

灰白色粉末；收率72％；mp 149.2-150.5℃；1H NMR(400MHz，CDCl3)δ：11.82，11.45(s，s，49/51，Z/E，1H，ArNHNH)，7.24(d，J＝8.7Hz，2H，ArH)，6.72(d，J＝8.8Hz，2H，ArH)，5.97(br，1H，ArNHNH)，5.69(s，1H，NH)，3.82(s，1H，CHNH)，2.61(s，3H，CH3CNH)，1.76(s，2H，(CH3)2CHCH2)， 1.44-1.38(m，1H，(CH3)2CHCH2)，0.97(dd，J＝6.0Hz，J＝4.9Hz，6H，(CH3)2CHCH2)；EI-MS，m/z(％)：321[M+]. Off-white powder; yield 72%; mp 149.2-150.5°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.82, 11.45 (s, s, 49/51, Z/E, 1H, ArNHNH), 7.24(d, J=8.7Hz, 2H, ArH), 6.72(d, J=8.8Hz, 2H, ArH), 5.97(br, 1H, ArNHNH), 5.69(s, 1H, NH), 3.82(s, 1H, CHNH) , 2.61 (s, 3H, CH 3 CNH), 1.76 (s, 2H, (CH 3 ) 2 CHCH 2 ), 1.44-1.38 (m, 1H, (CH 3 ) 2 CHCH 2 ), 0.97 (dd, J= 6.0Hz, J=4.9Hz, 6H, (CH 3 ) 2 CHCH 2 ); EI-MS, m/z(%): 321[M + ].

5-异丁基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-19)： 5-isobutyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-19):

白色粉末；收率39％；mp 155.4-156.3℃；1H NMR(400MHz，CDCl3)δ：11.82，11.44(s，s，49/51，Z/E，1H，ArNHNH)，7.38(d，J＝8.7Hz，2H，ArH)，6.67(d，J＝8.8Hz，2H，ArH)，5.97(br，1H，ArNHNH)，5.66(s，1H，NH)，3.81(s，1H，CHNH)，2.61(s，3H，CH3CNH)，1.76(s，2H，(CH3)2CHCH2)，1.46-1.39(m，1H，(CH3)2CHCH2)，0.96(dd，J＝6.0Hz，J＝5.0Hz，6H，(CH3)2CHCH2)；EI-MS，m/z(％)：367[M++H]. White powder; yield 39%; mp 155.4-156.3°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.82, 11.44 (s, s, 49/51, Z/E, 1H, ArNHNH), 7.38(d, J=8.7Hz, 2H, ArH), 6.67(d, J=8.8Hz, 2H, ArH), 5.97(br, 1H, ArNHNH), 5.66(s, 1H, NH), 3.81(s, 1H, CHNH) , 2.61 (s, 3H, CH 3 CNH), 1.76 (s, 2H, (CH 3 ) 2 CHCH 2 ), 1.46-1.39 (m, 1H, (CH 3 ) 2 CHCH 2 ), 0.96 (dd, J= 6.0Hz, J=5.0Hz, 6H, (CH 3 ) 2 CHCH 2 ); EI-MS, m/z(%): 367[M + +H].

5-己基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-20)： 5-hexyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-20):

白色粉末；收率82％；mp 136.7-138.3℃；1H NMR(400MHz，CDCl3)δ：11.80，11.41(s，s，47/53，Z/E，1H，ArNHNH)，7.23(dd，J＝8.3Hz，J＝5.8Hz，2H，ArH)，6.71(dd，2H，J＝8.6Hz，J＝2.0Hz，ArH)，5.92(s，1H，ArNHNH)，5.74(s，1H，NH)，3.80-3.71(m，1H，CHNH)，2.62，2.59(s，s，47/53，3H，Z/E，CH3CNH)，1.90-1.77，(m，2H，CH3(CH2)3CH2CH2)，1.61-1.50，(m，2H，CH3(CH2)3CH2CH2)，1.39-1.20，(m，6H，CH3(CH2)3CH2CH2)，0.88(t，J  ＝6.6Hz，3H，CH3(CH2)3CH2CH2)；EI-MS，m/z(％)：349[M+]. White powder; yield 82%; mp 136.7-138.3°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.80, 11.41 (s, s, 47/53, Z/E, 1H, ArNHNH), 7.23 (dd, J=8.3Hz, J=5.8Hz, 2H, ArH), 6.71(dd, 2H, J=8.6Hz, J=2.0Hz, ArH), 5.92(s, 1H, ArNHNH), 5.74(s, 1H, NH ), 3.80-3.71 (m, 1H, CHNH), 2.62, 2.59 (s, s, 47/53, 3H, Z/E, CH 3 CNH), 1.90-1.77, (m, 2H, CH 3 (CH 2 ) 3 CH 2 CH 2 ), 1.61-1.50, (m, 2H, CH 3 (CH 2 ) 3 CH 2 CH 2 ), 1.39-1.20, (m, 6H, CH 3 (CH 2 ) 3 CH 2 CH 2 ), 0.88 (t, J = 6.6Hz, 3H, CH 3 (CH 2 ) 3 CH 2 CH 2 ); EI-MS, m/z (%): 349 [M + ].

5-苯甲基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-21)： 5-Benzyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-21):

白色粉末；收率79％；mp 186.1-186.5℃；1H NMR(400MHz，DMSO-d6)δ：E(62％)：11.31(s，1H，ArNHNH)，8.19(s，1H，ArNHNH)，7.80(s，1H，NH)，7.27-7.05(m，7H，ArH)，6.64(td，J＝9.2Hz，J＝4.5Hz，2H，ArH)，3.92(t，J＝5.1Hz，1H，CHNH)，2.97-2.80(m，2H，ArCH2)，2.39(s，3H，CH3CNH)；Z(38％)：11.61(s，1H，ArNHNH)，8.29(s，1H，ArNHNH)，7.52(s，1H，NH)，7.27-7.05(m，7H，ArH)，6.67-6.62(m，2H，ArH)，4.02(t，J＝5.0Hz，1H，CHNH)，2.97-2.80(m，2H，ArCH2)，2.37(s，3H，CH3CNH)；EI-MS，m/z(％)：329[M+]. White powder; yield 79%; mp 186.1-186.5°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (62%): 11.31 (s, 1H, ArNHNH), 8.19 (s, 1H, ArNHNH) , 7.80(s, 1H, NH), 7.27-7.05(m, 7H, ArH), 6.64(td, J=9.2Hz, J=4.5Hz, 2H, ArH), 3.92(t, J=5.1Hz, 1H , CHNH), 2.97-2.80 (m, 2H, ArCH 2 ), 2.39 (s, 3H, CH 3 CNH); Z (38%): 11.61 (s, 1H, ArNHNH), 8.29 (s, 1H, ArNHNH) , 7.52(s, 1H, NH), 7.27-7.05(m, 7H, ArH), 6.67-6.62(m, 2H, ArH), 4.02(t, J=5.0Hz, 1H, CHNH), 2.97-2.80( m, 2H, ArCH 2 ), 2.37 (s, 3H, CH 3 CNH); EI-MS, m/z (%): 329 [M + ].

5-苯甲基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-22)： 5-Benzyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-22):

白色粉末；收率90％；mp 196.7-197.7℃；1H NMR(400MHz，DMSO-d6)δ：E(60％)：11.30(s，1H，ArNHNH)，8.39(s，1H，ArNHNH)，7.82(s，1H，NH)，7.31-7.17(m，7H，ArH)，6.64(t，J＝8.8Hz，2H，ArH)，3.93(t，J＝5.2Hz，1H，CHNH)，2.97-2.80(m，2H，ArCH2)，2.38(s，3H，CH3CNH)；Z(40％)：11.58(s，1H，ArNHNH)，8.50(s，1H，ArNHNH)，7.54(s，1H，NH)，7.34-7.12(m，7H，ArH)，6.64(t，J＝8.8Hz，2H，ArH)，4.02(t，J＝5.0Hz，1H，CHNH)，2.97-2.80(m，2H，ArCH2)，2.35(s，3H，CH3CNH)；EI-MS，m/z(％)：355[M+]. White powder; yield 90%; mp 196.7-197.7°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (60%): 11.30 (s, 1H, ArNHNH), 8.39 (s, 1H, ArNHNH) , 7.82(s, 1H, NH), 7.31-7.17(m, 7H, ArH), 6.64(t, J=8.8Hz, 2H, ArH), 3.93(t, J=5.2Hz, 1H, CHNH), 2.97 -2.80 (m, 2H, ArCH 2 ), 2.38 (s, 3H, CH 3 CNH); Z (40%): 11.58 (s, 1H, ArNHNH), 8.50 (s, 1H, ArNHNH), 7.54 (s, 1H, NH), 7.34-7.12(m, 7H, ArH), 6.64(t, J=8.8Hz, 2H, ArH), 4.02(t, J=5.0Hz, 1H, CHNH), 2.97-2.80(m, 2H, ArCH 2 ), 2.35 (s, 3H, CH 3 CNH); EI-MS, m/z (%): 355 [M + ].

5-苯甲基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-23)： 5-Benzyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-23):

Z                      E  Z E

白色粉末；收率88％；mp 193.8-194.1℃；1H NMR(400MHz，DMSO-d6)δ：E(58％)：11.29(s，1H，ArNHNH)，8.40(s，1H，ArNHNH)，7.82(s，1H，NH)，7.42-7.17(m，7H，ArH)，6.59(t，J＝8.7Hz，2H，ArH)，3.93(t，J＝5.1Hz，1H，CHNH)，2.97-2.80(m，2H，ArCH2)，2.37(s，3H，CH3CNH)；Z(42％)：11.57(s，1H，ArNHNH)，8.50(s，1H，ArNHNH)，7.54(s，1H，NH)，7.42-7.17(m，7H，ArH)，6.59(t，J＝8.7Hz，2H，ArH)，4.02(t，J＝5.0Hz，1H，CHNH)，2.97-2.80(m，2H，ArCH2)，2.35(s，3H，CH3CNH)；EI-MS，m/z(％)：401[M++H]. White powder; yield 88%; mp 193.8-194.1°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (58%): 11.29 (s, 1H, ArNHNH), 8.40 (s, 1H, ArNHNH) , 7.82(s, 1H, NH), 7.42-7.17(m, 7H, ArH), 6.59(t, J=8.7Hz, 2H, ArH), 3.93(t, J=5.1Hz, 1H, CHNH), 2.97 -2.80 (m, 2H, ArCH 2 ), 2.37 (s, 3H, CH 3 CNH); Z (42%): 11.57 (s, 1H, ArNHNH), 8.50 (s, 1H, ArNHNH), 7.54 (s, 1H, NH), 7.42-7.17(m, 7H, ArH), 6.59(t, J=8.7Hz, 2H, ArH), 4.02(t, J=5.0Hz, 1H, CHNH), 2.97-2.80(m, 2H, ArCH 2 ), 2.35(s, 3H, CH 3 CNH); EI-MS, m/z(%): 401[M + +H].

1-异丙基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-24)： 1-isopropyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-24):

浅黄色晶体；收率39％；mp 150.9-151.0℃；1H NMR(400MHz，CDCl3)δ：11.66(s，1H，ArNHNH)，7.37(d，J＝8.6Hz，2H，ArH)，6.68(d，J＝8.7Hz，2H，ArH)，6.02(s，1H，ArNHNH)，4.53(s，1H，CH(CH3)2)，3.67(s，2H，CH2N)，2.61(s，3H，CH3CNH)，1.18(d，J＝6.8Hz，6H，CH(CH3)2)；EI-MS，m/z(％)：291[M+]. Pale yellow crystals; yield 39%; mp 150.9-151.0°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.66 (s, 1H, ArNHNH), 7.37 (d, J=8.6Hz, 2H, ArH), 6.68 (d, J=8.7Hz, 2H, ArH), 6.02(s, 1H, ArNHNH), 4.53(s, 1H, CH( CH3 ) 2 ), 3.67(s, 2H, CH2N ), 2.61(s , 3H, CH 3 CNH), 1.18 (d, J=6.8Hz, 6H, CH(CH 3 ) 2 ); EI-MS, m/z(%): 291[M + ].

1-异丙基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-25)： 1-isopropyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-25):

无色晶体；收率58％；mp 163.6-164.0℃；1H NMR(400MHz，CDCl3)δ：11.63(s，1H，ArNHNH)，7.23(d，J＝8.7Hz，2H，ArH)，6.73(d，J＝8.7Hz，2H，ArH)，5.98(s，1H，ArNHNH)，4.53(s，1H，CH(CH3)2)，3.66(s，2H，CH2N)，2.61(s，3H，CH3CNH)，1.18(d，J＝6.8Hz，6H，CH(CH3)2)；EI-MS，m/z(％)：307[M+]). Colorless crystals; yield 58%; mp 163.6-164.0°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.63 (s, 1H, ArNHNH), 7.23 (d, J=8.7Hz, 2H, ArH), 6.73 (d, J=8.7Hz, 2H, ArH), 5.98(s, 1H, ArNHNH), 4.53(s, 1H, CH( CH3 ) 2 ), 3.66(s, 2H, CH2N ), 2.61(s , 3H, CH 3 CNH), 1.18 (d, J=6.8Hz, 6H, CH(CH 3 ) 2 ); EI-MS, m/z(%): 307[M + ]).

1-异丙基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-26)： 1-isopropyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-26):

无色晶体；收率82％；mp 166.2-166.6℃；1H NMR(400MHz，CDCl3)δ：11.69(s，1H，ArNHNH)，6.98(t，J＝8.5Hz，2H，ArH)，6.76(dd，J＝8.7Hz，J＝4.2Hz，2H，ArH)，5.91(s，1H，ArNHNH)，4.53(s，1H，CH(CH3)2)，3.67(s，2H，CH2N)，2.63(s，3H，CH3CNH)，1.18(d，J＝6.8Hz，6H，CH(CH3)2)；EI-MS，m/z(％)：353[M++H]. Colorless crystals; yield 82%; mp 166.2-166.6°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.69 (s, 1H, ArNHNH), 6.98 (t, J=8.5Hz, 2H, ArH), 6.76 (dd, J=8.7Hz, J=4.2Hz, 2H, ArH), 5.91(s, 1H, ArNHNH), 4.53(s, 1H, CH( CH3 ) 2 ), 3.67(s, 2H, CH2N ), 2.63 (s, 3H, CH 3 CNH), 1.18 (d, J=6.8Hz, 6H, CH(CH 3 ) 2 ); EI-MS, m/z (%): 353 [M + +H] .

1-仲丁基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-27)： 1-sec-butyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-27):

白色粉末；收率83％；mp 158.3-159.1℃；1H NMR(400MHz，CDCl3)δ：11.72(s，1H，ArNHNH)，6.99(t，J＝8.6Hz，2H，ArH)，6.76(dd，J＝8.8Hz，J＝4.3Hz，2H，ArH)，5.89(s，1H，ArNHNH)，4.27(s，1H，CH(CH3)CH2CH3)，3.64(q，J＝17.4Hz，2H，CH2N)，2.64(s，3H，CH3CNH)，1.56-1.45(m，2H，CH(CH3)CH2CH3)，1.16(d，J＝6.8Hz，3H，CH(CH3)CH2CH3)，0.88(t，J＝7.4Hz，3H，CH(CH3)CH2CH3)；EI-MS，m/z(％)：305[M+]. White powder; yield 83%; mp 158.3-159.1°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.72 (s, 1H, ArNHNH), 6.99 (t, J=8.6Hz, 2H, ArH), 6.76( dd, J=8.8Hz, J=4.3Hz, 2H, ArH), 5.89(s, 1H, ArNHNH ) , 4.27(s, 1H, CH( CH3 ) CH2CH3 ), 3.64(q, J=17.4 Hz, 2H, CH 2 N), 2.64 (s, 3H, CH 3 CNH), 1.56-1.45 (m, 2H, CH(CH 3 )CH 2 CH 3 ), 1.16 (d, J=6.8Hz, 3H, CH(CH 3 )CH 2 CH 3 ), 0.88 (t, J=7.4Hz, 3H, CH(CH 3 )CH 2 CH 3 ); EI-MS, m/z(%): 305[M + ].

1-仲丁基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-28)： 1-sec-butyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-28):

白色粉末；收率54％；mp 178.7-179.1℃；1H NMR(400MHz，CDCl3)δ：11.71(s，1H，ArNHNH)，7.24(d，J＝8.8Hz，2H，ArH)，6.74(d，J＝7.3Hz，2H，ArH)，5.98(s，1H，ArNHNH)，4.27(s，1H，CH(CH3)CH2CH3)，3.64(q，J＝17.5Hz，2H，CH2N)，2.62(s，3H，CH3CNH)，1.54-1.47(m，2H，CH(CH3)CH2CH3)，1.16(d，J＝6.7Hz，3H，CH(CH3)CH2CH3)，0.89(t，J＝7.3Hz，3H，CH(CH3)CH2CH3)；EI-MS，m/z(％)：321[M+]. White powder; yield 54%; mp 178.7-179.1°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.71 (s, 1H, ArNHNH), 7.24 (d, J=8.8Hz, 2H, ArH), 6.74( d, J = 7.3Hz , 2H, ArH), 5.98 (s, 1H, ArNHNH), 4.27 (s, 1H, CH( CH3 ) CH2CH3 ), 3.64 (q, J = 17.5Hz, 2H, CH 2 N), 2.62 (s, 3H, CH 3 CNH), 1.54-1.47 (m, 2H, CH(CH 3 )CH 2 CH 3 ), 1.16 (d, J=6.7Hz, 3H, CH(CH 3 ) CH 2 CH 3 ), 0.89 (t, J=7.3Hz, 3H, CH(CH 3 )CH 2 CH 3 ); EI-MS, m/z(%): 321[M + ].

1-仲丁基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-29)： 1-sec-butyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-29):

白色粉末；收率89％；mp 168.3-169.2℃；1H NMR(400MHz，CDCl3)δ：11.70(s，1H，ArNHNH)，7.37(d，J＝8.7Hz，2H，ArH)，6.69(d，J＝8.4Hz，2H，ArH)，5.98(s，1H，ArNHNH)，4.27(s，1H，CH(CH3)CH2CH3)，3.64(q，J＝17.4Hz，2H，CH2N)，2.61(s，3H，CH3CNH)，1.54-1.45(m，2H，CH(CH3)CH2CH3)，1.16(d，J＝6.7Hz，3H，CH(CH3)CH2CH3)，0.88(t，J＝7.3Hz，3H，CH(CH3)CH2CH3)；EI-MS，m/z(％)：367[M++H]). White powder; yield 89%; mp 168.3-169.2°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.70 (s, 1H, ArNHNH), 7.37 (d, J=8.7Hz, 2H, ArH), 6.69( d, J = 8.4Hz , 2H, ArH), 5.98 (s, 1H, ArNHNH), 4.27 (s, 1H, CH( CH3 ) CH2CH3 ), 3.64 (q, J = 17.4Hz, 2H, CH 2 N), 2.61 (s, 3H, CH 3 CNH), 1.54-1.45 (m, 2H, CH(CH 3 )CH 2 CH 3 ), 1.16 (d, J=6.7Hz, 3H, CH(CH 3 ) CH 2 CH 3 ), 0.88 (t, J=7.3Hz, 3H, CH(CH 3 )CH 2 CH 3 ); EI-MS, m/z(%): 367[M + +H]).

1-叔丁基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-30)： 1-tert-butyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-30):

黄色粉末；收率52％；mp 124.7-126.4℃；1H NMR(400MHz，CDCl3)δ：11.72(s，1H，ArNHNH)，6.98(t，J＝8.4Hz，2H，ArH)，6.75(d，J＝8.3Hz，2H，ArH)，5.67(s，1H，ArNHNH)，3.74(s，2H，CH2N)，2.59(s，3H，CH3CNH)，1.44(s，9H)；EI-MS，m/z(％)：305[M+]. Yellow powder; yield 52%; mp 124.7-126.4°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.72 (s, 1H, ArNHNH), 6.98 (t, J=8.4Hz, 2H, ArH), 6.75( d, J=8.3Hz, 2H, ArH ) , 5.67(s, 1H, ArNHNH), 3.74(s, 2H, CH2N), 2.59(s, 3H, CH3CNH ), 1.44(s, 9H); EI-MS, m/z(%): 305[M + ].

1-叔丁基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-31)： 1-tert-butyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-31):

黄色粉末；收率67％；mp 146.2-147.8℃；1H NMR(400MHz，CDCl3)δ：11.76(s，1H，ArNHNH)，7.23(d，J＝8.8Hz，2H，ArH)，6.72(d，J＝8.7Hz，2H，ArH)，5.86(s，1H，ArNHNH)，3.77(s，2H，CH2N)，2.59(s，3H，CH3CNH)，1.45(s，9H)；EI-MS，m/z(％)：321[M+]. Yellow powder; yield 67%; mp 146.2-147.8°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.76 (s, 1H, ArNHNH), 7.23 (d, J=8.8Hz, 2H, ArH), 6.72( d, J=8.7Hz, 2H, ArH ), 5.86(s, 1H, ArNHNH), 3.77(s, 2H, CH2N), 2.59(s, 3H, CH3CNH ), 1.45(s, 9H); EI-MS, m/z (%): 321 [M + ].

1-叔丁基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-32)： 1-tert-butyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-32):

无色晶体；收率70％；mp 135.6-136.9℃；1H NMR(400MHz，CDCl3)δ：11.97(s，1H，ArNHNH)，7.38(d，J＝8.8Hz，2H，ArH)，6.69(d，J＝8.6Hz，2H，ArH)，6.09(s，1H，ArNHNH)，3.82(s，2H，CH2N)，2.60(s，3H，CH3CNH)，1.45(s，9H)；EI-MS，m/z(％)：367[M++H]. Colorless crystals; yield 70%; mp 135.6-136.9°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.97 (s, 1H, ArNHNH), 7.38 (d, J=8.8Hz, 2H, ArH), 6.69 (d, J=8.6Hz, 2H, ArH), 6.09(s, 1H, ArNHNH), 3.82(s, 2H, CH2N ), 2.60(s, 3H, CH3CNH ), 1.45(s, 9H) ; EI-MS, m/z (%): 367 [M + +H].

1-苯基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-33)： 1-phenyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-33):

白色粉末；收率35％；mp 168.3-170.1℃；1H NMR(400MHz，CDCl3)δ：11.84(s，1H，ArNHNH)，7.66(d，J＝8.1Hz，2H，ArH)，7.37(t，J＝8.0Hz，2H，ArH)，7.12(t，J＝7.4Hz，1H，ArH)，7.00(t，J＝8.6Hz，2H，ArH)，6.76(dd，J＝8.9Hz，J＝4.3Hz，2H，ArH)，5.92(s，1H，ArNHNH)，4.17(s，2H，CH2N)，2.71(s，3H，CH3CNH)；EI-MS，m/z(％)：325[M+]. White powder; yield 35%; mp 168.3-170.1°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.84 (s, 1H, ArNHNH), 7.66 (d, J=8.1Hz, 2H, ArH), 7.37( t, J=8.0Hz, 2H, ArH), 7.12(t, J=7.4Hz, 1H, ArH), 7.00(t, J=8.6Hz, 2H, ArH), 6.76(dd, J=8.9Hz, J =4.3Hz, 2H, ArH), 5.92(s, 1H, ArNHNH), 4.17(s, 2H, CH2N ), 2.71(s, 3H, CH3CNH ); EI-MS, m/z(%) : 325[M + ].

1-苯基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-34)： 1-phenyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-34):

白色粉末；收率27％；mp 159.4-160.3℃；1H NMR(400MHz，CDCl3)δ：11.78(s，1H，ArNHNH)，7.66(d，J＝8.1Hz，2H，ArH)，7.38(t，J＝8.0Hz，2H，ArH)，7.25(d，J＝8.8Hz，2H，ArH)，7.13(t，J＝7.4Hz，1H，ArH)，6.73(d，J＝8.8Hz，2H，ArH)，5.95(s，1H，ArNHNH)，4.16(s，2H，CH2N)，2.69(s，3H，CH3CNH)；EI-MS，m/z(％)：341[M+]. White powder; yield 27%; mp 159.4-160.3°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.78 (s, 1H, ArNHNH), 7.66 (d, J=8.1Hz, 2H, ArH), 7.38( t, J=8.0Hz, 2H, ArH), 7.25(d, J=8.8Hz, 2H, ArH), 7.13(t, J=7.4Hz, 1H, ArH), 6.73(d, J=8.8Hz, 2H , ArH), 5.95 (s, 1H, ArNHNH), 4.16 (s, 2H, CH 2 N), 2.69 (s, 3H, CH 3 CNH); EI-MS, m/z (%): 341 [M + ].

1-苯基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-35)： 1-phenyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-35):

白色粉末；收率27％；mp 189.3-190.7℃；1H NMR(400MHz，CDCl3)δ：11.83(s，1H，ArNHNH)，7.66(d，J＝8.0Hz，2H，ArH)，7.41-7.36(m，4H，ArH)，7.13(t，J＝7.4Hz，1H，ArH)，6.70(d，J＝8.9Hz，2H，ArH)，5.93(s，1H，ArNHNH)，4.18(s，2H，CH2N)，2.70(s，3H，CH3CNH)；EI-MS，m/z(％)：387[M++H]. White powder; yield 27%; mp 189.3-190.7°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.83 (s, 1H, ArNHNH), 7.66 (d, J=8.0Hz, 2H, ArH), 7.41- 7.36(m, 4H, ArH), 7.13(t, J=7.4Hz, 1H, ArH), 6.70(d, J=8.9Hz, 2H, ArH), 5.93(s, 1H, ArNHNH), 4.18(s, 2H, CH 2 N), 2.70(s, 3H, CH 3 CNH); EI-MS, m/z(%): 387[M + +H].

1-(4-甲基苯基)-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-36)： 1-(4-methylphenyl)-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-36):

白色粉末；收率30％；mp 156.4-156.8℃；1H NMR(400MHz，CDCl3)δ：11.77(s，1H，ArNHNH)，7.52(d，J＝8.2Hz，2H，ArH)，7.38(d，J＝8.7Hz，2H，ArH)，7.17(d，J＝8.2Hz，2H，ArH)，6.67(d，J＝8.7Hz，2H，ArH)，6.01(s，1H，ArNHNH)，4.14(s，2H，CH2N)，2.67(s，3H，CH3CNH)，2.33(s，3H，ArCH3)；EI-MS，m/z(％)：339[M+]. White powder; yield 30%; mp 156.4-156.8°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.77 (s, 1H, ArNHNH), 7.52 (d, J=8.2Hz, 2H, ArH), 7.38( d, J = 8.7Hz, 2H, ArH), 7.17 (d, J = 8.2Hz, 2H, ArH), 6.67 (d, J = 8.7Hz, 2H, ArH), 6.01 (s, 1H, ArNHNH), 4.14 (s, 2H, CH 2 N), 2.67 (s, 3H, CH 3 CNH), 2.33 (s, 3H, ArCH 3 ); EI-MS, m/z (%): 339 [M + ].

1-(4-甲基苯基)-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-37)： 1-(4-methylphenyl)-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-37):

灰白色粉末；收率77％；mp 150.2-151.2℃；1H NMR(400MHz，CDCl3)δ：11.76(s，1H，ArNHNH)，7.52(d，J＝8.4Hz，2H，ArH)，7.23(d，J＝8.6Hz，2H，ArH)，7.17(d，J＝8.4Hz，2H，ArH)，6.71(d，J＝8.0Hz，2H，ArH)，5.98(s，1H，ArNHNH)，4.13(s，2H，CH2N)，2.67(s，3H，CH3CNH)，2.33(s，3H，ArCH3)；EI-MS，m/z(％)：355[M+]. Off-white powder; yield 77%; mp 150.2-151.2°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.76 (s, 1H, ArNHNH), 7.52 (d, J=8.4Hz, 2H, ArH), 7.23( d, J = 8.6Hz, 2H, ArH), 7.17 (d, J = 8.4Hz, 2H, ArH), 6.71 (d, J = 8.0Hz, 2H, ArH), 5.98 (s, 1H, ArNHNH), 4.13 (s, 2H, CH 2 N), 2.67 (s, 3H, CH 3 CNH), 2.33 (s, 3H, ArCH 3 ); EI-MS, m/z (%): 355 [M + ].

1-(4-甲基苯基)-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-38)： 1-(4-methylphenyl)-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-38):

灰白色粉末；收率71％；mp 145.4-146.1℃；1H NMR(400MHz，CDCl3)δ：11.76(s，1H， ArNHNH)，7.52(d，J＝8.4Hz，2H，ArH)，7.23(d，J＝8.6Hz，2H，ArH)，7.17(d，J＝8.4Hz，2H，ArH)，6.71(d，J＝8.0Hz，2H，ArH)，5.98(s，1H，ArNHNH)，4.13(s，2H，CH2N)，2.67(s，3H，CH3CNH)，2.33(s，3H，ArCH3)；EI-MS，m/z(％)：401[M++H]. Off-white powder; yield 71%; mp 145.4-146.1°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.76 (s, 1H, ArNHNH), 7.52 (d, J=8.4Hz, 2H, ArH), 7.23( d, J = 8.6Hz, 2H, ArH), 7.17 (d, J = 8.4Hz, 2H, ArH), 6.71 (d, J = 8.0Hz, 2H, ArH), 5.98 (s, 1H, ArNHNH), 4.13 (s, 2H, CH 2 N), 2.67 (s, 3H, CH 3 CNH), 2.33 (s, 3H, ArCH 3 ); EI-MS, m/z(%): 401[M + +H].

1-(4-氯苯基)-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-39)： 1-(4-chlorophenyl)-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-39):

浅黄色粉末；收率85％；mp 182.3-184.1℃；1H NMR(400MHz，CDCl3)δ：11.71(s，1H，ArNHNH)，7.63(d，J＝8.8Hz，2H，ArH)，7.40(d，J＝8.8Hz，2H，ArH)，7.33(d，J＝9.0Hz，2H，ArH)，6.70(d，J＝8.8Hz，2H，ArH)，5.88(s，1H，ArNHNH)，4.13(s，2H，CH2N)，2.70(s，3H，CH3CNH)；EI-MS，m/z(％)：359[M+]. Pale yellow powder; yield 85%; mp 182.3-184.1°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.71 (s, 1H, ArNHNH), 7.63 (d, J=8.8Hz, 2H, ArH), 7.40 (d, J = 8.8Hz, 2H, ArH), 7.33 (d, J = 9.0Hz, 2H, ArH), 6.70 (d, J = 8.8Hz, 2H, ArH), 5.88 (s, 1H, ArNHNH), 4.13 (s, 2H, CH 2 N), 2.70 (s, 3H, CH 3 CNH); EI-MS, m/z (%): 359 [M + ].

1-(4-氯苯基)-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-40)： 1-(4-chlorophenyl)-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-40):

灰白色粉末；收率60％；mp 175.3-176.2℃；1H NMR(400MHz，CDCl3)δ：11.74(s，1H，ArNHNH)，7.62(d，J＝8.8Hz，2H，ArH)，7.33(d，J＝8.9Hz，2H，ArH)，7.26(d，J＝8.7Hz，2H，ArH)，6.75(d，J＝8.8Hz，2H，ArH)，5.89(s，1H，ArNHNH)，4.13(s，2H，CH2N)，2.70(s，3H，CH3CNH)；EI-MS，m/z(％)：375[M+-H]. Off-white powder; yield 60%; mp 175.3-176.2°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.74 (s, 1H, ArNHNH), 7.62 (d, J=8.8Hz, 2H, ArH), 7.33( d, J = 8.9Hz, 2H, ArH), 7.26 (d, J = 8.7Hz, 2H, ArH), 6.75 (d, J = 8.8Hz, 2H, ArH), 5.89 (s, 1H, ArNHNH), 4.13 (s, 2H, CH 2 N), 2.70 (s, 3H, CH 3 CNH); EI-MS, m/z(%): 375[M + -H].

1-(4-氯苯基)-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-41)： 1-(4-chlorophenyl)-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-41):

黄色粉末；收率40％；mp 178.3-179.7℃；1H NMR(400MHz，CDCl3)δ：11.76(s，1H，ArNHNH)，7.63(d，J＝8.5Hz，2H，ArH)，7.33(d，J＝8.4Hz，2H，ArH)，7.01(t，J＝8.2Hz，2H，ArH)，6.78(d， J＝7.9Hz，2H，ArH)，5.81(s，1H，ArNHNH)，4.13(s，2H，CH2N)，2.72(s，3H，CH3CNH)；EI-MS，m/z(％)：421[M++H]. Yellow powder; yield 40%; mp 178.3-179.7°C; 1 H NMR (400MHz, CDCl 3 ) δ: 11.76 (s, 1H, ArNHNH), 7.63 (d, J=8.5Hz, 2H, ArH), 7.33( d, J=8.4Hz, 2H, ArH), 7.01(t, J=8.2Hz, 2H, ArH), 6.78(d, J=7.9Hz, 2H, ArH), 5.81(s, 1H, ArNHNH), 4.13 (s, 2H, CH 2 N), 2.72 (s, 3H, CH 3 CNH); EI-MS, m/z(%): 421[M + +H].

1-乙酰基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-42)： 1-Acetyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-42):

无色粘稠液体；收率51％；1H NMR(400MHz，DMSO-d6)δ：11.32(s，1H，ArNHNH)，8.37(s，1H，ArNHNH)，7.34-6.62(m，4H，ArH)，3.69(s，2H，CH2NH)，2.48(s，3H，CH3CNHN)，2.09(s，3H，COCH3)；EI-MS，m/z(％)：307[M+]. Colorless viscous liquid; yield 51%; 1 H NMR (400MHz, DMSO-d 6 ) δ: 11.32 (s, 1H, ArNHNH), 8.37 (s, 1H, ArNHNH), 7.34-6.62 (m, 4H, ArH), 3.69 (s, 2H, CH 2 NH), 2.48 (s, 3H, CH 3 CNHN), 2.09 (s, 3H, COCH 3 ); EI-MS, m/z (%): 307 [M + ].

1-甲基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-45)： 1-methyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-45):

白色粉末；收率44％；mp 153.6-154.7℃；1H NMR(400MHz，DMSO-d6)δ：E(63％)：11.33(s，1H，ArNHNH)，8.25(s，1H，ArNHNH)，7.11-6.72(m，4H，ArH)，3.66(s，2H，CH2NH)，2.85(s，3H，NCH3)，2.45(s，3H，CH3CNHN)；Z(37％)：11.57(s，1H，ArNHNH)，8.29(s，1H，ArNHNH)，7.11-6.72(m，4H，ArH)，3.71(s，2H，CH2NH)，2.84(s，3H，NCH3)，2.49(s，3H，CH3CNHN)；EI-MS，m/z(％)：263[M+]. White powder; yield 44%; mp 153.6-154.7°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (63%): 11.33 (s, 1H, ArNHNH), 8.25 (s, 1H, ArNHNH) , 7.11-6.72 (m, 4H, ArH), 3.66 (s, 2H, CH 2 NH), 2.85 (s, 3H, NCH 3 ), 2.45 (s, 3H, CH 3 CNHN); Z (37%): 11.57 (s, 1H, ArNHNH), 8.29 (s, 1H, ArNHNH), 7.11-6.72 (m, 4H, ArH), 3.71 (s, 2H, CH 2 NH), 2.84 (s, 3H, NCH 3 ), 2.49 (s, 3H, CH 3 CNHN); EI-MS, m/z (%): 263 [M + ].

1-甲基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-46)： 1-methyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-46):

白色粉末；收率34％；mp 133.0-133.7℃；1H NMR(400MHz，DMSO-d6)δ：E(63％)：11.32(s，1H，ArNHNH)，8.44(s，1H，ArNHNH)，7.30-6.71(m，4H，ArH)，3.67(s，2H，CH2NH)，2.85(s，3H，NCH3)，2.43(s，3H，CH3CNHN)；Z(37％)：11.54(s，1H，ArNHNH)，8.48(s，1H，ArNHNH)，7.30-6.71(m，4H，ArH)，3.72(s，2H，CH2NH)，2.84(s，3H，NCH3)，2.48(s，3H，CH3CNHN)；EI-MS，m/z(％)：279[M+]. White powder; yield 34%; mp 133.0-133.7°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (63%): 11.32 (s, 1H, ArNHNH), 8.44 (s, 1H, ArNHNH) , 7.30-6.71 (m, 4H, ArH), 3.67 (s, 2H, CH 2 NH), 2.85 (s, 3H, NCH 3 ), 2.43 (s, 3H, CH 3 CNHN); Z (37%): 11.54(s, 1H, ArNHNH), 8.48(s, 1H, ArNHNH), 7.30-6.71(m, 4H, ArH), 3.72(s, 2H, CH2NH ), 2.84(s, 3H, NCH3 ), 2.48 (s, 3H, CH 3 CNHN); EI-MS, m/z (%): 279 [M + ].

1-甲基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-47)： 1-methyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-47):

白色粉末；收率54％；mp 146.0-146.7℃；1H NMR(400MHz，DMSO-d6)δ：E(61％)：11.31(s，1H，ArNHNH)，8.46(s，1H，ArNHNH)，7.41-6.66(m，4H，ArH)，3.67(s，2H，CH2NH)，2.85(s，3H，NCH3)，2.43(s，3H，CH3CNHN)；Z(39％)：11.53(s，1H，ArNHNH)，8.50(s，1H，ArNHNH)，7.41-6.66(m，4H，ArH)，3.72(s，2H，CH2NH)，2.84(s，3H，NCH3)，2.47(s，3H，CH2CNHN)；EI-MS，m/z(％)：325[M++H]. White powder; yield 54%; mp 146.0-146.7°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (61%): 11.31 (s, 1H, ArNHNH), 8.46 (s, 1H, ArNHNH) , 7.41-6.66 (m, 4H, ArH), 3.67 (s, 2H, CH 2 NH), 2.85 (s, 3H, NCH 3 ), 2.43 (s, 3H, CH 3 CNHN); Z (39%): 11.53 (s, 1H, ArNHNH), 8.50 (s, 1H, ArNHNH), 7.41-6.66 (m, 4H, ArH), 3.72 (s, 2H, CH 2 NH), 2.84 (s, 3H, NCH 3 ), 2.47(s, 3H, CH 2 CNHN); EI-MS, m/z(%): 325[M + +H].

1-甲基-3-(1-(2-(2-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-48)： 1-Methyl-3-(1-(2-(2-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-48):

白色粉末；收率44％；mp 194.0-194.8℃；1H NMR(400MHz，DMSO-d6)δ：E(62％)：11.31(s，1H，ArNHNH)，8.34(s，1H，ArNHNH)，7.21-6.73(m，4H，ArH)，3.68(s，2H，CH2NH)，2.85(s，3H，NCH3)，2.46(s，3H，CH3CNHN)；Z(38％)：11.52(s，1H，ArNHNH)，8.37(s，1H，ArNHNH)，7.21-6.73(m，4H，ArH)，3.72(s，2H，CH2NH)，2.85(s，3H，NCH3)，2.51(s，3H，CH3CNHN)；EI-MS，m/z(％)：263[M+]. White powder; yield 44%; mp 194.0-194.8°C; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (62%): 11.31(s, 1H, ArNHNH), 8.34(s, 1H, ArNHNH) , 7.21-6.73 (m, 4H, ArH), 3.68 (s, 2H, CH 2 NH), 2.85 (s, 3H, NCH 3 ), 2.46 (s, 3H, CH 3 CNHN); Z (38%): 11.52 (s, 1H, ArNHNH), 8.37 (s, 1H, ArNHNH), 7.21-6.73 (m, 4H, ArH), 3.72 (s, 2H, CH 2 NH), 2.85 (s, 3H, NCH 3 ), 2.51 (s, 3H, CH 3 CNHN); EI-MS, m/z (%): 263 [M + ].

1-甲基-3-(1-(2-(3-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-49)： 1-methyl-3-(1-(2-(3-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-49):

白色粉末；收率55％；mp 175.0-175.8℃；1H NMR(400MHz，DMSO-d6)δ：E(62％)：11.31(s，1H，ArNHNH)，8.54(s，1H，ArNHNH)，7.27-6.66(m，4H，ArH)，3.67(s，2H，CH2NH)，2.85(s，3H，NCH3)，2.44(s，3H，CH3CNHN)；Z(38％)：11.52(s，1H，ArNHNH)，8.58(s，1H，ArNHNH)，7.27-6.66(m，4H， ArH)，3.72(s，2H，CH2NH)，2.84(s，3H，NCH3)，2.48(s，3H，CH3CNHN)；EI-MS，m/z(％)：279[M+]. White powder; yield 55%; mp 175.0-175.8°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (62%): 11.31(s, 1H, ArNHNH), 8.54(s, 1H, ArNHNH) , 7.27-6.66 (m, 4H, ArH), 3.67 (s, 2H, CH 2 NH), 2.85 (s, 3H, NCH 3 ), 2.44 (s, 3H, CH 3 CNHN); Z (38%): 11.52 (s, 1H, ArNHNH), 8.58 (s, 1H, ArNHNH), 7.27-6.66 (m, 4H, ArH), 3.72 (s, 2H, CH 2 NH), 2.84 (s, 3H, NCH 3 ), 2.48 (s, 3H, CH 3 CNHN); EI-MS, m/z (%): 279 [M + ].

1-甲基-3-(1-(2-(2，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-50)： 1-methyl-3-(1-(2-(2,4-dichlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-50):

白色粉末；收率49％；mp 189.9-190.4℃；1H NMR(400MHz，DMSO-d6)δ：E(63％)：11.30(s，1H，ArNHNH)，8.33(s，1H，ArNHNH)，7.53-6.71(m，3H，ArH)，3.69(s，2H，CH2NH)，2.86(s，3H，NCH3)，2.41(s，3H，CH3CNHN)；Z(37％)：11.49(s，1H，ArNHNH)，8.34(s，1H，ArNHNH)，7.53-6.71(m，3H，ArH)，3.73(s，2H，CH2NH)，2.85(s，3H，NCH3)，2.46(s，3H，CH3CNHN)；EI-MS，m/z(％)：314[M+]. White powder; yield 49%; mp 189.9-190.4°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (63%): 11.30 (s, 1H, ArNHNH), 8.33 (s, 1H, ArNHNH) , 7.53-6.71 (m, 3H, ArH), 3.69 (s, 2H, CH 2 NH), 2.86 (s, 3H, NCH 3 ), 2.41 (s, 3H, CH 3 CNHN); Z (37%): 11.49 (s, 1H, ArNHNH), 8.34 (s, 1H, ArNHNH), 7.53-6.71 (m, 3H, ArH), 3.73 (s, 2H, CH 2 NH), 2.85 (s, 3H, NCH 3 ), 2.46 (s, 3H, CH 3 CNHN); EI-MS, m/z (%): 314 [M + ].

1-甲基-3-(1-(2-(4-甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-51)： 1-Methyl-3-(1-(2-(4-methylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-51):

米黄色粉末；收率43％；mp 139.0-139.8℃；1H NMR(400MHz，DMSO-d6)δ：E(62％)：11.33(s，1H，ArNHNH)，8.14(s，1H，ArNHNH)，7.06-6.62(m，4H，ArH)，3.66(s，2H，CH2NH)，2.84(s，3H，NCH3)，2.45(s，3H，CH3CNHN)，2.21(s，3H，ArCH3)；Z(38％)：11.59(s，1H，ArNHNH)，8.19(s，1H，ArNHNH)，7.06-6.62(m，4H，ArH)，3.71(s，2H，CH2NH)，2.84(s，3H，NCH3)，2.49(s，3H，CH3CNHN)，2.21(s，3H，ArCH3)；EI-MS，m/z(％)：259[M+]. Beige powder; yield 43%; mp 139.0-139.8°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (62%): 11.33(s, 1H, ArNHNH), 8.14(s, 1H, ArNHNH ), 7.06-6.62 (m, 4H, ArH), 3.66 (s, 2H, CH 2 NH), 2.84 (s, 3H, NCH 3 ), 2.45 (s, 3H, CH 3 CNHN), 2.21 (s, 3H , ArCH 3 ); Z (38%): 11.59 (s, 1H, ArNHNH), 8.19 (s, 1H, ArNHNH), 7.06-6.62 (m, 4H, ArH), 3.71 (s, 2H, CH 2 NH) , 2.84 (s, 3H, NCH 3 ), 2.49 (s, 3H, CH 3 CNHN), 2.21 (s, 3H, ArCH 3 ); EI-MS, m/z (%): 259 [M + ].

1-甲基-3-(1-(2-(4-甲氧基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-52)： 1-Methyl-3-(1-(2-(4-methoxyphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-52):

褐色粉末；收率45％；mp 114.1-115.5℃；1H NMR(400MHz，DMSO-d6)δ：E(62％)：11.33(s，1H， ArNHNH)，7.98(s，1H，ArNHNH)，6.87-6.68(m，4H，ArH)，3.68(s，3H，OCH3)，3.65(s，2H，CH2NH)，2.84(s，3H，NCH3)，2.47(s，3H，CH3CNHN)；Z(38％)：11.60(s，1H，ArNHNH)，8.03(s，1H，ArNHNH)，6.87-6.68(m，4H，ArH)，3.70(s，2H，CH2NH)，3.68(s，3H，OCH3)，2.84(s，3H，NCH3)，2.51(s，3H，CH3CNHN)；EI-MS，m/z(％)：275[M+]. Brown powder; yield 45%; mp 114.1-115.5°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (62%): 11.33 (s, 1H, ArNHNH), 7.98 (s, 1H, ArNHNH) , 6.87-6.68 (m, 4H, ArH), 3.68 (s, 3H, OCH 3 ), 3.65 (s, 2H, CH 2 NH), 2.84 (s, 3H, NCH 3 ), 2.47 (s, 3H, CH 3 CNHN); Z (38%): 11.60 (s, 1H, ArNHNH), 8.03 (s, 1H, ArNHNH), 6.87-6.68 (m, 4H, ArH), 3.70 (s, 2H, CH 2 NH), 3.68 (s, 3H, OCH 3 ), 2.84 (s, 3H, NCH 3 ), 2.51 (s, 3H, CH 3 CNHN); EI-MS, m/z (%): 275 [M + ].

1-甲基-3-(1-(2-(3，4-二甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-53)： 1-methyl-3-(1-(2-(3,4-dimethylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-53):

浅黄色粉末；收率33％；mp 115.3-116.1℃；1H NMR(400MHz，DMSO-d6)δ：E(62％)：11.32(s，1H，ArNHNH)，8.06(s，1H，ArNHNH)，7.61(s，1H，NH)，7.00-6.43(m，3H，ArH)，3.65(s，2H，CH2NH)，2.84(s，3H，NCH3)，2.45(s，3H，CH3CNHN)，2.15(s，3H，ArCH3)，2.12((s，3H，ArCH3)；Z(38％)：11.59(s，1H，ArNHNH)，8.11(s，1H，ArNHNH)，7.33(s，1H，NH)，7.00-6.43(m，3H，ArH)，3.71(s，2H，CH2NH)，2.84(s，3H，NCH3)，2.49(s，3H，CH3CNHN)，2.15(s，3H，ArCH3)，2.12((s，3H，ArCH3)；EI-MS，m/z(％)：273[M+]. Pale yellow powder; yield 33%; mp 115.3-116.1°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (62%): 11.32(s, 1H, ArNHNH), 8.06(s, 1H, ArNHNH ), 7.61(s, 1H, NH), 7.00-6.43(m, 3H, ArH), 3.65(s, 2H, CH 2 NH), 2.84(s, 3H, NCH 3 ), 2.45(s, 3H, CH 3 CNHN), 2.15 (s, 3H, ArCH 3 ), 2.12 ((s, 3H, ArCH 3 ); Z (38%): 11.59 (s, 1H, ArNHNH), 8.11 (s, 1H, ArNHNH), 7.33 (s, 1H, NH), 7.00-6.43 (m, 3H, ArH), 3.71 (s, 2H, CH 2 NH), 2.84 (s, 3H, NCH 3 ), 2.49 (s, 3H, CH 3 CNHN) , 2.15(s, 3H, ArCH 3 ), 2.12((s, 3H, ArCH 3 ); EI-MS, m/z(%): 273[M + ].

1-甲基-3-(1-(2-(4-氨基磺酰基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-56)： 1-Methyl-3-(1-(2-(4-aminosulfonylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-56):

白色粉末；收率76％；mp 215.2-215.9℃；1H NMR(400MHz，DMSO-d6)δ：E(60％)：11.35(s，1H，ArNHNH)，8.85(s，1H，ArNHNH)，7.69-6.66(m，2H，ArH)，7.13(s，2H，NH2)，7.81-6.78(m，2H，ArH)，3.69(s，2H，CH2NH)，2.86(s，3H，NCH3)，2.42(s，3H，CH3CNHN)；Z(40％)：11.54(s，1H，ArNHNH)，8.89(s，1H，ArNHNH)，7.69-6.66(m，2H，ArH)，7.13(s，2H，NH2)，7.81-6.78(m，2H， ArH)，3.73(s，2H，CH2NH)，2.85(s，3H，NCH3)，2.47(s，3H，CH3CNHN)；EI-MS，m/z(％)：338[M+]. White powder; yield 76%; mp 215.2-215.9°C; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (60%): 11.35 (s, 1H, ArNHNH), 8.85 (s, 1H, ArNHNH) , 7.69-6.66(m, 2H, ArH), 7.13(s, 2H, NH 2 ), 7.81-6.78(m, 2H, ArH), 3.69(s, 2H, CH 2 NH), 2.86(s, 3H, NCH 3 ), 2.42 (s, 3H, CH 3 CNHN); Z (40%): 11.54 (s, 1H, ArNHNH), 8.89 (s, 1H, ArNHNH), 7.69-6.66 (m, 2H, ArH), 7.13 (s, 2H, NH 2 ), 7.81-6.78 (m, 2H, ArH), 3.73 (s, 2H, CH 2 NH), 2.85 (s, 3H, NCH 3 ), 2.47 (s, 3H, CH 3 CNHN); EI-MS, m/z (%): 338 [M + ].

1-环己烷基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-57)： 1-cyclohexyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-57):

无色粘稠液体；收率65％；1H NMR(400MHz，DMSO-d6)δ：E(64％)：11.43(s，1H，ArNHNH)，8.46(s，1H，ArNHNH)，7.32-6.70(m，4H，ArH)，3.66(s，2H，CH2NH)，3.12-3.10(m，1H，NCH)，2.45(s，3H，CH3CNHN)，1.05-1.28(m，10H，(CH2)5；Z(36％)：11.57(s，1H，ArNHNH)，8.51(s，1H，ArNHNH)，7.32-6.70(m，4H，ArH)，3.70(s，2H，CH2NH)，3.12-3.10(m，1H，NCH)，2.49(s，3H，CH3CNHN)，1.05-1.28(m，10H，(CH2)5)；EI-MS，m/z(％)：331[M+]. Colorless viscous liquid; yield 65%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (64%): 11.43 (s, 1H, ArNHNH), 8.46 (s, 1H, ArNHNH), 7.32- 6.70(m, 4H, ArH), 3.66(s, 2H, CH 2 NH), 3.12-3.10(m, 1H, NCH), 2.45(s, 3H, CH 3 CNHN), 1.05-1.28(m, 10H, (CH 2 ) 5 ; Z (36%): 11.57 (s, 1H, ArNHNH), 8.51 (s, 1H, ArNHNH), 7.32-6.70 (m, 4H, ArH), 3.70 (s, 2H, CH 2 NH ), 3.12-3.10 (m, 1H, NCH), 2.49 (s, 3H, CH 3 CNHN), 1.05-1.28 (m, 10H, (CH 2 ) 5 ); EI-MS, m/z (%): 331[M + ].

1-环丙烷基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-58)： 1-Cyclopropanyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-58):

无色粘稠液体；收率72％；1H NMR(400MHz，DMSO-d6)δ：E(63％)：11.36(s，1H，ArNHNH)，8.45(s，1H，ArNHNH)，7.29-6.69(m，4H，ArH)，3.65(s，2H，CH2NH)，3.02-2.95(m，1H，NCH)，2.44(s，3H，CH3CNHN)，1.01-1.22(m，4H，(CH2)2)；Z(37％)：11.57(s，1H，ArNHNH)，8.49(s，1H，ArNHNH)，7.29-6.69(m，4H，ArH)，3.69(s，2H，CH2NH)，3.02-2.95(m，1H，NCH)，2.48(s，3H，CH3CNHN)，1.01-1.22(m，4H，(CH2)2)；EI-MS，m/z(％)：305[M+]. Colorless viscous liquid; yield 72%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (63%): 11.36 (s, 1H, ArNHNH), 8.45 (s, 1H, ArNHNH), 7.29- 6.69(m, 4H, ArH), 3.65(s, 2H, CH 2 NH), 3.02-2.95(m, 1H, NCH), 2.44(s, 3H, CH 3 CNHN), 1.01-1.22(m, 4H, (CH 2 ) 2 ); Z (37%): 11.57 (s, 1H, ArNHNH), 8.49 (s, 1H, ArNHNH), 7.29-6.69 (m, 4H, ArH), 3.69 (s, 2H, CH 2 NH), 3.02-2.95(m, 1H, NCH), 2.48(s, 3H, CH 3 CNHN), 1.01-1.22(m, 4H, (CH 2 ) 2 ); EI-MS, m/z(%) : 305[M + ].

1-环丙烷基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-59)： 1-Cyclopropanyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-59):

浅黄色粘稠液体；收率80％；1H NMR(400MHz，DMSO-d6)δ：E(62％)：11.33(s，1H，ArNHNH)，8.46(s，1H，ArNHNH)，7.38-6.67(m，4H，ArH)，3.66(s，2H，CH2NH)，3.03-2.93(m，1H，NCH)，2.43(s，3H，CH3CNHN)，1.00-1.21(m，4H，(CH2)2)；Z(38％)：11.54(s，1H，ArNHNH)，8.50(s，1H，ArNHNH)，7.38-6.67(m，4H，ArH)，3.71(s，2H，CH2NH)，3.03-2.93(m，1H，NCH)，2.47(s，3H，CH3CNHN)，1.00-1.21(m，4H，(CH2)2)；EI-MS，m/z(％)：351[M++1]. Pale yellow viscous liquid; yield 80%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (62%): 11.33 (s, 1H, ArNHNH), 8.46 (s, 1H, ArNHNH), 7.38- 6.67(m, 4H, ArH), 3.66(s, 2H, CH 2 NH), 3.03-2.93(m, 1H, NCH), 2.43(s, 3H, CH 3 CNHN), 1.00-1.21(m, 4H, (CH 2 ) 2 ); Z (38%): 11.54 (s, 1H, ArNHNH), 8.50 (s, 1H, ArNHNH), 7.38-6.67 (m, 4H, ArH), 3.71 (s, 2H, CH 2 NH), 3.03-2.93 (m, 1H, NCH), 2.47 (s, 3H, CH 3 CNHN), 1.00-1.21 (m, 4H, (CH 2 ) 2 ); EI-MS, m/z (%) :351[M ++ 1].

1-苄基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-60)： 1-Benzyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-60):

无色粘稠液体；收率78％；1H NMR(400MHz，DMSO-d6)δ：E(63％)：11.31(s，1H，ArNHNH)，8.34(s，1H，ArNHNH)，7.38-6.79(m，9H，ArH)，4.32(s，2H，CH2NH)，3.71(s，2H，NCH2)，2.41(s，3H，CH3CNHN)；Z(37％)：11.51(s，1H，ArNHNH)，8.42(s，1H，ArNHNH)，7.38-6.79(m，9H，ArH)，4.32(s，2H，CH2NH)，3.71(s，2H，NCH2)，2.50(s，3H，CH3CNHN)；EI-MS，m/z(％)：355[M+]. Colorless viscous liquid; yield 78%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (63%): 11.31 (s, 1H, ArNHNH), 8.34 (s, 1H, ArNHNH), 7.38- 6.79 (m, 9H, ArH), 4.32 (s, 2H, CH 2 NH), 3.71 (s, 2H, NCH 2 ), 2.41 (s, 3H, CH 3 CNHN); Z (37%): 11.51 (s , 1H, ArNHNH), 8.42(s, 1H, ArNHNH), 7.38-6.79(m, 9H, ArH), 4.32(s, 2H, CH 2 NH), 3.71(s, 2H, NCH 2 ), 2.50(s , 3H, CH 3 CNHN); EI-MS, m/z (%): 355[M + ].

5，5-二甲基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-61)： 5,5-Dimethyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-61):

白色粉末；收率66％；mp 198.2℃(分解)；1H NMR(400MHz，DMSO-d6)δ：E(68％)：11.53(s，1H， ArNHNH)，8.23(s，1H，ArNHNH)，7.86(s，1H，NH)，7.13-6.74(m，4H，ArH)，2.46(s，3H，CH3CNHN)，1.16(s，6H，2CH3)；Z(32％)：11.57(s，1H，ArNHNH)，8.27(s，1H，ArNHNH)，7.57(s，1H，NH)，7.13-6.74(m，4H，ArH)，2.51(s，3H，CH3CNHN)，1.19(s，6H，2CH3)；EI-MS，m/z(％)：277[M+]. White powder; yield 66%; mp 198.2°C (decomposition); 1 H NMR (400MHz, DMSO-d 6 ) δ: E (68%): 11.53(s, 1H, ArNHNH), 8.23(s, 1H, ArNHNH ), 7.86 (s, 1H, NH), 7.13-6.74 (m, 4H, ArH), 2.46 (s, 3H, CH 3 CNHN), 1.16 (s, 6H, 2CH 3 ); Z (32%): 11.57 (s, 1H, ArNHNH), 8.27 (s, 1H, ArNHNH), 7.57 (s, 1H, NH), 7.13-6.74 (m, 4H, ArH), 2.51 (s, 3H, CH 3 CNHN), 1.19 ( s, 6H, 2CH 3 ); EI-MS, m/z (%): 277 [M + ].

5，5-二甲基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-62)： 5,5-Dimethyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-62):

白色粉末；收率36％；mp 193.6-193.9℃；1H NMR(400MHz，DMSO-d6)δ：E(68％)：11.52(s，1H，ArNHNH)，8.42(s，1H，ArNHNH)，7.88(s，1H，NH)，7.29(d，J＝8.8Hz，2H，ArH)，6.75(d，J＝8.8Hz，2H，ArH)，2.44(s，3H，CH3CNHN)，1.16(s，6H，2CH3)；Z(32％)：11.54(s，1H，ArNHNH)，8.46(s，1H，ArNHNH)，7.59(s，1H，NH)；7.29(d，J＝8.8Hz，2H，ArH)，6.75(d，J＝8.8Hz，2H，ArH)，2.49(s，3H，CH3CNHN)，1.19(s，6H，2CH3)；EI-MS，m/z(％)：293[M+]. White powder; yield 36%; mp 193.6-193.9°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (68%): 11.52 (s, 1H, ArNHNH), 8.42 (s, 1H, ArNHNH) , 7.88 (s, 1H, NH), 7.29 (d, J=8.8Hz, 2H, ArH), 6.75 (d, J=8.8Hz, 2H, ArH), 2.44 (s, 3H, CH 3 CNHN), 1.16 (s, 6H, 2CH 3 ); Z (32%): 11.54 (s, 1H, ArNHNH), 8.46 (s, 1H, ArNHNH), 7.59 (s, 1H, NH); 7.29 (d, J=8.8Hz , 2H, ArH), 6.75 (d, J=8.8Hz, 2H, ArH), 2.49 (s, 3H, CH 3 CNHN), 1.19 (s, 6H, 2CH 3 ); EI-MS, m/z (% ): 293[M + ].

5，5-二甲基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-63)： 5,5-Dimethyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-63):

白色粉末；收率45％；mp 185.0-185.5℃；1H NMR(400MHz，DMSO-d6)δ：E(67％)：11.50(s，1H，ArNHNH)，8.43(s，1H，ArNHNH)，7.87(s，1H，NH)，7.41-6.68(m，4H，ArH)，2.43(s，3H，CH3CNHN)，1.15(s，6H，2CH3)；Z(33％)：11.52(s，1H，ArNHNH)，8.47(s，1H，ArNHNH)，7.57(s，1H，NH)，7.41-6.68(m，4H，ArH)，2.48(s，3H，CH3CNHN)，1.18(s，6H，2CH3)；EI-MS，m/z(％)：339[M++H]. White powder; yield 45%; mp 185.0-185.5°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (67%): 11.50(s, 1H, ArNHNH), 8.43(s, 1H, ArNHNH) , 7.87 (s, 1H, NH), 7.41-6.68 (m, 4H, ArH), 2.43 (s, 3H, CH 3 CNHN), 1.15 (s, 6H, 2CH 3 ); Z (33%): 11.52 ( s, 1H, ArNHNH), 8.47(s, 1H, ArNHNH), 7.57(s, 1H, NH), 7.41-6.68(m, 4H, ArH), 2.48(s, 3H, CH 3 CNHN), 1.18(s , 6H, 2CH 3 ); EI-MS, m/z (%): 339[M + +H].

5，5-二甲基-3-(1-(2-(2-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-64)： 5,5-Dimethyl-3-(1-(2-(2-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-64):

白色粉末；收率49％；mp 190.0-190.6℃；1H NMR(400MHz，DMSO-d6)δ：E(69％)：11.51(s，1H，ArNHNH)，8.32(s，1H，ArNHNH)，7.89(s，1H，NH)，7.22-6.77(m，4H，ArH)，2.47(s，3H，CH3CNHN)，1.17(s，6H，2CH3)；Z(31％)：11.52(s，1H，ArNHNH)，8.35(s，1H，ArNHNH)，7.60(s，1H，NH)，7.22-6.77(m，4H，ArH)，2.52(s，3H，CH3CNHN)，1.20(s，6H，2CH3)；EI-MS，m/z(％)：277[M+]. White powder; yield 49%; mp 190.0-190.6°C; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (69%): 11.51(s, 1H, ArNHNH), 8.32(s, 1H, ArNHNH) , 7.89 (s, 1H, NH), 7.22-6.77 (m, 4H, ArH), 2.47 (s, 3H, CH 3 CNHN), 1.17 (s, 6H, 2CH 3 ); Z (31%): 11.52 ( s, 1H, ArNHNH), 8.35(s, 1H, ArNHNH), 7.60(s, 1H, NH), 7.22-6.77(m, 4H, ArH), 2.52(s, 3H, CH 3 CNHN), 1.20(s , 6H, 2CH 3 ); EI-MS, m/z (%): 277[M + ].

5，5-二甲基-3-(1-(2-(3-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-65)： 5,5-Dimethyl-3-(1-(2-(3-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-65):

白色粉末；收率61％；mp 191.0-191.7℃；1H NMR(400MHz，DMSO-d6)δ：E(67％)：11.51(s，1H，ArNHNH)，8.53(s，1H，ArNHNH)，7.89(s，1H，NH)，7.29-6.68(m，4H，ArH)，2.44(s，3H，CH3CNHN)，1.17(s，6H，2CH3)；Z(33％)：11.52(s，1H，ArNHNH)，8.56(s，1H，ArNHNH)，7.60(s，1H，NH)，7.29-6.68(m，4H，ArH)，2.49(s，3H，CH3CNHN)，1.20(s，6H，2CH3)；EI-MS，m/z(％)：293[M+]. White powder; yield 61%; mp 191.0-191.7°C; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (67%): 11.51(s, 1H, ArNHNH), 8.53(s, 1H, ArNHNH) , 7.89 (s, 1H, NH), 7.29-6.68 (m, 4H, ArH), 2.44 (s, 3H, CH 3 CNHN), 1.17 (s, 6H, 2CH 3 ); Z (33%): 11.52 ( s, 1H, ArNHNH), 8.56(s, 1H, ArNHNH), 7.60(s, 1H, NH), 7.29-6.68(m, 4H, ArH), 2.49(s, 3H, CH 3 CNHN), 1.20(s , 6H, 2CH 3 ); EI-MS, m/z (%): 293[M + ].

5，5-二甲基-3-(1-(2-(2，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-66)： 5,5-Dimethyl-3-(1-(2-(2,4-dichlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-66):

浅绿色粉末；收率57％；mp 205.7-206.0℃；1H NMR(400MHz，DMSO-d6)δ：E(65％)：11.50(s，1H，ArNHNH)，8.30(s，1H，ArNHNH)，7.92(s，1H，NH)，7.54-6.75(m，3H，ArH)，2.42(s，3H， CH3CNHN)，1.17(s，6H，2CH3)；Z(35％)：11.48(s，1H，ArNHNH)，8.32(s，1H，ArNHNH)，7.63(s，1H，NH)，7.54-6.75(m，3H，ArH)，2.48(s，3H，CH3CNHN)，1.20(s，6H，2CH3)；EI-MS，m/z(％)：328[M+]. Light green powder; yield 57%; mp 205.7-206.0°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (65%): 11.50(s, 1H, ArNHNH), 8.30(s, 1H, ArNHNH ), 7.92 (s, 1H, NH), 7.54-6.75 (m, 3H, ArH), 2.42 (s, 3H, CH 3 CNHN), 1.17 (s, 6H, 2CH 3 ); Z (35%): 11.48 (s, 1H, ArNHNH), 8.32 (s, 1H, ArNHNH), 7.63 (s, 1H, NH), 7.54-6.75 (m, 3H, ArH), 2.48 (s, 3H, CH 3 CNHN), 1.20 ( s, 6H, 2CH 3 ); EI-MS, m/z (%): 328 [M + ].

5，5-二甲基-3-(1-(2-(4-甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-67)： 5,5-Dimethyl-3-(1-(2-(4-methylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-67):

白色粉末；收率46％；mp 178.7-180.6℃；1H NMR(400MHz，DMSO-d6)δ：E(67％)：11.52(s，1H，ArNHNH)，8.10(s，1H，ArNHNH)，7.82(s，1H，NH)，7.07-6.63(m，4H，ArH)，2.45(s，3H，CH3CNHN)，2.21(s，3H，ArCH3)，1.15(s，6H，2CH3)；Z(33％)：11.58(s，1H，ArNHNH)，8.15(s，1H，ArNHNH)，7.52(s，1H，NH)，7.07-6.63(m，4H，ArH)，2.50(s，3H，CH3CNHN)，2.21(s，3H，ArCH3)，1.18(s，6H，2CH3)；EI-MS，m/z(％)：273[M+]. White powder; yield 46%; mp 178.7-180.6°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (67%): 11.52(s, 1H, ArNHNH), 8.10(s, 1H, ArNHNH) , 7.82(s, 1H, NH), 7.07-6.63(m, 4H, ArH), 2.45(s, 3H, CH 3 CNHN), 2.21(s, 3H, ArCH 3 ), 1.15(s, 6H, 2CH 3 ); Z (33%): 11.58 (s, 1H, ArNHNH), 8.15 (s, 1H, ArNHNH), 7.52 (s, 1H, NH), 7.07-6.63 (m, 4H, ArH), 2.50 (s, 3H, CH 3 CNHN), 2.21 (s, 3H, ArCH 3 ), 1.18 (s, 6H, 2CH 3 ); EI-MS, m/z (%): 273 [M + ].

5，5-二甲基-3-(1-(2-(3，4-二甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-68)： 5,5-Dimethyl-3-(1-(2-(3,4-dimethylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-68):

白色粉末；收率72％；mp 167.6-168.0℃；1H NMR(400MHz，DMSO-d6)δ：E(66％)：11.52(s，1H，ArNHNH)，8.05(s，1H，ArNHNH)，7.82(s，1H，NH)，7.02-6.45(m，3H，ArH)，2.46(s，3H，CH3CNHN)，2.17(s，3H，ArCH3)，2.13((s，3H，ArCH3)，1.16(s，6H，2CH3)；Z(34％)：11.58(s，1H，ArNHNH)，8.09(s，1H，ArNHNH)，7.54(s，1H，NH)，7.02-6.45(m，3H，ArH)，2.50(s，3H，CH3CNHN)，2.17(s，3H，ArCH3)，2.13((s，3H，ArCH3)，1.19(s，6H，2CH3)；EI-MS，m/z(％)：287[M+]. White powder; yield 72%; mp 167.6-168.0°C; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (66%): 11.52(s, 1H, ArNHNH), 8.05(s, 1H, ArNHNH) , 7.82(s, 1H, NH), 7.02-6.45(m, 3H, ArH), 2.46(s, 3H, CH 3 CNHN), 2.17(s, 3H, ArCH 3 ), 2.13((s, 3H, ArCH 3 ), 1.16 (s, 6H, 2CH 3 ); Z (34%): 11.58 (s, 1H, ArNHNH), 8.09 (s, 1H, ArNHNH), 7.54 (s, 1H, NH), 7.02-6.45 ( m, 3H, ArH), 2.50(s, 3H, CH3CNHN ), 2.17(s, 3H, ArCH3 ), 2.13((s, 3H, ArCH3 ), 1.19(s, 6H, 2CH3 ); EI -MS, m/z(%): 287[M + ].

5，5-二甲基-3-(1-(2-(4-氨基磺酰基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-71)： 5,5-Dimethyl-3-(1-(2-(4-aminosulfonylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-71):

白色粉末；收率75％；mp 266.1-267.1℃；1H NMR(400MHz，DMSO-d6)δ：E(68％)：11.55(s，1H，ArNHNH)，8.86(s，1H，ArNHNH)，7.91(s，1H，NH)，7.70-6.68(m，2H，ArH)，7.13(s，2H，NH2)，7.83-6.81(m，2H，ArH)，2.43(s，3H，CH3CNHN)，1.17(s，6H，2CH3)；Z(32％)：11.54(s，1H，ArNHNH)，8.83(s，1H，ArNHNH)，7.62(s，1H，NH)，7.70-6.68(m，2H，ArH)，7.13(s，2H，NH2)，7.83-6.81(m，2H，ArH)，2.48(s，3H，CH3CNHN)，1.21(s，6H，2CH3)；EI-MS，m/z(％)：338[M+]. White powder; yield 75%; mp 266.1-267.1°C; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (68%): 11.55 (s, 1H, ArNHNH), 8.86 (s, 1H, ArNHNH) , 7.91(s, 1H, NH), 7.70-6.68(m, 2H, ArH), 7.13(s, 2H, NH 2 ), 7.83-6.81(m, 2H, ArH), 2.43(s, 3H, CH 3 CNHN), 1.17 (s, 6H, 2CH 3 ); Z (32%): 11.54 (s, 1H, ArNHNH), 8.83 (s, 1H, ArNHNH), 7.62 (s, 1H, NH), 7.70-6.68 ( m, 2H, ArH), 7.13 (s, 2H, NH 2 ), 7.83-6.81 (m, 2H, ArH), 2.48 (s, 3H, CH 3 CNHN), 1.21 (s, 6H, 2CH 3 ); EI -MS, m/z(%): 338[M + ].

5-甲基-5-乙基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-75)： 5-Methyl-5-ethyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-75):

浅黄色粉末；收率34％；mp 162.8℃(分解)；1H NMR(400MHz，DMSO-d6)δ：E(65％)：11.51(s，1H，ArNHNH)，8.21(s，1H，ArNHNH)，7.78(s，1H，NH)，7.13-6.72(m，4H，ArH)，2.46(s，3H，CH3CNHN)，1.60-1.42(m，2H，CH2)，1.13(s，3H，CH3)，0.74(t，J＝7.4Hz，3H，CH3)；Z(35％)：11.61(s，1H，ArNHNH)，8.26(s，1H，ArNHNH)，7.48(s，1H，NH)，7.13-6.72(m，4H，ArH)，2.51(s，3H，CH3CNHN)，1.60-1.42(m，2H，CH2)，1.16(s，3H，CH3)，0.74(t，J＝7.4Hz，3H，CH3)；EI-MS，m/z(％)：291[M+]. Pale yellow powder; yield 34%; mp 162.8°C (decomposition); 1 H NMR (400MHz, DMSO-d 6 )δ: E (65%): 11.51(s, 1H, ArNHNH), 8.21(s, 1H, ArNHNH), 7.78 (s, 1H, NH), 7.13-6.72 (m, 4H, ArH), 2.46 (s, 3H, CH 3 CNHN), 1.60-1.42 (m, 2H, CH 2 ), 1.13 (s, 3H, CH 3 ), 0.74 (t, J=7.4Hz, 3H, CH 3 ); Z (35%): 11.61 (s, 1H, ArNHNH), 8.26 (s, 1H, ArNHNH), 7.48 (s, 1H , NH), 7.13-6.72 (m, 4H, ArH), 2.51 (s, 3H, CH 3 CNHN), 1.60-1.42 (m, 2H, CH 2 ), 1.16 (s, 3H, CH 3 ), 0.74 ( t, J=7.4Hz, 3H, CH 3 ); EI-MS, m/z (%): 291 [M + ].

5-甲基-5-乙基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-76)： 5-Methyl-5-ethyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-76):

浅粉色粉末；收率42％；mp 175.3-175.6℃；1H NMR(400MHz，DMSO-d6)δ：E(64％)：11.50(s，1H，ArNHNH)，8.40(s，1H，ArNHNH)，7.80(s，1H，NH)，7.30-6.72(m，4H，ArH)，2.44(s，3H，CH3CNHN)，1.58-1.46(m，2H，CH2)，1.13(s，3H，CH3)，0.74(t，J＝7.4Hz，3H，CH3)；Z(36％)：11.58(s，1H，ArNHNH)，8.46(s，1H，ArNHNH)，7.51(s，1H，NH)，7.30-6.72(m，4H，ArH)，2.49(s，3H，CH3CNHN)，1.58-1.46(m，2H，CH2)，1.17(s，3H，CH3)，0.74(t，J＝7.2Hz，3H，CH3)；EI-MS，m/z(％)：307[M+]. Light pink powder; yield 42%; mp 175.3-175.6°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (64%): 11.50(s, 1H, ArNHNH), 8.40(s, 1H, ArNHNH ), 7.80(s, 1H, NH), 7.30-6.72(m, 4H, ArH), 2.44(s, 3H, CH 3 CNHN), 1.58-1.46(m, 2H, CH 2 ), 1.13(s, 3H , CH 3 ), 0.74 (t, J=7.4Hz, 3H, CH 3 ); Z (36%): 11.58 (s, 1H, ArNHNH), 8.46 (s, 1H, ArNHNH), 7.51 (s, 1H, NH), 7.30-6.72 (m, 4H, ArH), 2.49 (s, 3H, CH 3 CNHN), 1.58-1.46 (m, 2H, CH 2 ), 1.17 (s, 3H, CH 3 ), 0.74 (t , J=7.2Hz, 3H, CH 3 ); EI-MS, m/z (%): 307[M + ].

5-甲基-5-乙基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-77)： 5-Methyl-5-ethyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-77):

浅粉色粉末；收率49％；mp 186.4-186.7℃；1H NMR(400MHz，DMSO-d6)δ：E(64％)：11.49(s，1H，ArNHNH)，8.41(s，1H，ArNHNH)，7.80(s，1H，NH)，7.42-6.68(m，4H，ArH)，2.44(s，3H，CH3CNHN)，1.56-1.46(m，2H，CH2)，1.13(s，3H，CH3)，0.74(t，J＝7.4Hz，3H，CH3)；Z(36％)：11.49(s，1H，ArNHNH)，8.47(s，1H，ArNHNH)，7.51(s，1H，NH)，7.42-6.68(m，4H，ArH)，2.49(s，3H，CH3CNHN)，1.56-1.46(m，2H，CH2)，1.16(s，3H，CH3)，0.74(t，J＝7.4Hz，3H，CH3)；EI-MS，m/z(％)：353[M++H]. Light pink powder; yield 49%; mp 186.4-186.7°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (64%): 11.49(s, 1H, ArNHNH), 8.41(s, 1H, ArNHNH ), 7.80(s, 1H, NH), 7.42-6.68(m, 4H, ArH), 2.44(s, 3H, CH 3 CNHN), 1.56-1.46(m, 2H, CH 2 ), 1.13(s, 3H , CH 3 ), 0.74 (t, J=7.4Hz, 3H, CH 3 ); Z (36%): 11.49 (s, 1H, ArNHNH), 8.47 (s, 1H, ArNHNH), 7.51 (s, 1H, NH), 7.42-6.68 (m, 4H, ArH), 2.49 (s, 3H, CH 3 CNHN), 1.56-1.46 (m, 2H, CH 2 ), 1.16 (s, 3H, CH 3 ), 0.74 (t , J=7.4Hz, 3H, CH 3 ); EI-MS, m/z (%): 353[M + +H].

5-甲基-5-乙基-3-(1-(2-(2-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-78)： 5-Methyl-5-ethyl-3-(1-(2-(2-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-78):

浅黄色粉末；收率62％；mp 178.9-180.6℃；1H NMR(400MHz，DMSO-d6)δ：E(62％)：11.48(s，1H，ArNHNH)，8.29(s，1H，ArNHNH)，7.80(s，1H，NH)，7.20-6.72(m，4H，ArH)，2.46(s，3H， CH3CNHN)，1.60-1.42(m，2H，CH2)，1.12(s，3H，CH3)，0.74(t，J＝7.4Hz，3H，CH3)；Z(38％)：11.55(s，1H，ArNHNH)，8.33(s，1H，ArNHNH)，7.50(s，1H，NH)，7.20-6.72(m，4H，ArH)，2.51(s，3H，CH3CNHN)，1.60-1.42(m，2H，CH2)，1.16(s，3H，CH3)，0.74(t，J＝7.4Hz，3H，CH3)；EI-MS，m/z(％)：291[M+]. Pale yellow powder; yield 62%; mp 178.9-180.6°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (62%): 11.48(s, 1H, ArNHNH), 8.29(s, 1H, ArNHNH ), 7.80(s, 1H, NH), 7.20-6.72(m, 4H, ArH), 2.46(s, 3H, CH 3 CNHN), 1.60-1.42(m, 2H, CH 2 ), 1.12(s, 3H , CH 3 ), 0.74 (t, J=7.4Hz, 3H, CH 3 ); Z (38%): 11.55 (s, 1H, ArNHNH), 8.33 (s, 1H, ArNHNH), 7.50 (s, 1H, NH), 7.20-6.72 (m, 4H, ArH), 2.51 (s, 3H, CH 3 CNHN), 1.60-1.42 (m, 2H, CH 2 ), 1.16 (s, 3H, CH 3 ), 0.74 (t , J=7.4Hz, 3H, CH 3 ); EI-MS, m/z (%): 291[M + ].

5-甲基-5-乙基-3-(1-(2-(3-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-79)： 5-Methyl-5-ethyl-3-(1-(2-(3-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-79):

浅黄色粉末；收率53％；mp 172.8-176.5℃；1H NMR(400MHz，DMSO-d6)δ：E(66％)：11.48(s，1H，ArNHNH)，8.49(s，1H，ArNHNH)，7.81(s，1H，NH)，7.28-6.65(m，4H，ArH)，2.44(s，3H，CH3CNHN)，1.60-1.42(m，2H，CH2)，1.13(s，3H，CH3)，0.74(t，J＝7.2Hz，3H，CH3)；Z(34％)：11.54(s，1H，ArNHNH)，8.55(s，1H，ArNHNH)，7.51(s，1H，NH)，7.28-6.65(m，4H，ArH)，2.48(s，3H，CH3CNHN)，1.60-1.42(m，2H，CH2)，1.16(s，3H，CH3)，0.74(t，J＝7.2Hz，3H，CH3)；EI-MS，m/z(％)：307[M+]. Pale yellow powder; yield 53%; mp 172.8-176.5°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (66%): 11.48(s, 1H, ArNHNH), 8.49(s, 1H, ArNHNH ), 7.81(s, 1H, NH), 7.28-6.65(m, 4H, ArH), 2.44(s, 3H, CH 3 CNHN), 1.60-1.42(m, 2H, CH 2 ), 1.13(s, 3H , CH 3 ), 0.74 (t, J=7.2Hz, 3H, CH 3 ); Z (34%): 11.54 (s, 1H, ArNHNH), 8.55 (s, 1H, ArNHNH), 7.51 (s, 1H, NH), 7.28-6.65 (m, 4H, ArH), 2.48 (s, 3H, CH 3 CNHN), 1.60-1.42 (m, 2H, CH 2 ), 1.16 (s, 3H, CH 3 ), 0.74 (t , J=7.2Hz, 3H, CH 3 ); EI-MS, m/z (%): 307[M + ].

5-甲基-5-乙基-3-(1-(2-(2，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-80)： 5-Methyl-5-ethyl-3-(1-(2-(2,4-dichlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-80):

白色粉末；收率56％；mp 199.8-201.0℃；1H NMR(400MHz，DMSO-d6)δ：E(66％)：11.49(s，1H，ArNHNH)，8.28(s，1H，ArNHNH)，7.84(s，1H，NH)，7.54-6.71(m，3H，ArH)，2.42(s，3H，CH3CNHN)，1.61-1.43(m，2H，CH2)，1.14(s，3H，CH3)，0.77-0.73(m，3H，CH3)；Z(34％)：11.51(s， 1H，ArNHNH)，8.32(s，1H，ArNHNH)，7.55(s，1H，NH)，7.54-6.71(m，3H，ArH)，2.48(s，3H，CH3CNHN)，1.61-1.43(m，2H，CH2)，1.17(s，3H，CH3)，0.77-0.73(m，3H，CH3)；EI-MS，m/z(％)：342[M+]. White powder; yield 56%; mp 199.8-201.0°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (66%): 11.49 (s, 1H, ArNHNH), 8.28 (s, 1H, ArNHNH) , 7.84(s, 1H, NH), 7.54-6.71(m, 3H, ArH), 2.42(s, 3H, CH 3 CNHN), 1.61-1.43(m, 2H, CH 2 ), 1.14(s, 3H, CH 3 ), 0.77-0.73 (m, 3H, CH 3 ); Z (34%): 11.51 (s, 1H, ArNHNH), 8.32 (s, 1H, ArNHNH), 7.55 (s, 1H, NH), 7.54 -6.71(m, 3H, ArH), 2.48(s, 3H, CH 3 CNHN), 1.61-1.43(m, 2H, CH 2 ), 1.17(s, 3H, CH 3 ), 0.77-0.73(m, 3H , CH 3 ); EI-MS, m/z (%): 342[M + ].

5-甲基-5-乙基-3-(1-(2-(4-甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-81)： 5-Methyl-5-ethyl-3-(1-(2-(4-methylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-81):

浅黄色粉末；收率32％；mp 160.4-160.8℃；1H NMR(400MHz，DMSO-d6)δ：E(66％)：11.51(s，1H，ArNHNH)，8.10(s，1H，ArNHNH)，7.75(s，1H，NH)，7.08-6.62(m，4H，ArH)，2.46(s，3H，CH3CNHN)，2.22(s，3H，PhCH3)，1.57-1.46(m，2H，CH2)，1.13(s，3H，CH3)，0.74(t，J＝7.4Hz，3H，CH3)；Z(34％)：11.63(s，1H，ArNHNH)，8.16(s，1H，ArNHNH)，7.46(s，1H，NH)，7.08-6.62(m，4H，ArH)，2.50(s，3H，CH3CH3CNHN)，2.22(s，3H，PhCH3)，1.57-1.46(m，2H，CH2)，1.17(s，3H，CH3)，0.75(t，J＝7.4Hz，3H，CH3)；EI-MS，m/z(％)：287[M+]. Pale yellow powder; yield 32%; mp 160.4-160.8°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (66%): 11.51(s, 1H, ArNHNH), 8.10(s, 1H, ArNHNH ), 7.75 (s, 1H, NH), 7.08-6.62 (m, 4H, ArH), 2.46 (s, 3H, CH 3 CNHN), 2.22 (s, 3H, PhCH 3 ), 1.57-1.46 (m, 2H , CH 2 ), 1.13 (s, 3H, CH 3 ), 0.74 (t, J=7.4Hz, 3H, CH 3 ); Z (34%): 11.63 (s, 1H, ArNHNH), 8.16 (s, 1H , ArNHNH), 7.46 (s, 1H, NH), 7.08-6.62 (m, 4H, ArH), 2.50 (s, 3H, CH 3 CH 3 CNHN), 2.22 (s, 3H, PhCH 3 ), 1.57-1.46 (m, 2H, CH 2 ), 1.17 (s, 3H, CH 3 ), 0.75 (t, J=7.4Hz, 3H, CH 3 ); EI-MS, m/z (%): 287 [M + ] .

5-甲基-5-乙基-3-(1-(2-(3，4-二甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-82)： 5-methyl-5-ethyl-3-(1-(2-(3,4-dimethylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-82) :

浅粉色粉末；收率66％；mp 156.5-157.3℃；1H NMR(400MHz，DMSO-d6)δ：E(64％)：11.50(s，1H，ArNHNH)，8.02(s，1H，ArNHNH)，7.74(s，1H，NH)，7.02-6.43(m，3H，ArH)，2.46(s，3H，CH3CNHN)，2.17(s，3H，ArCH3)，2.13((s，3H，ArCH3)，1.62-1.42(m，2H，CH2)，1.13(s，3H，CH3)，0.74(t，J＝7.4Hz，3H，CH3)；Z(36％)：11.61(s，1H，ArNHNH)，8.09(s，1H，ArNHNH)，7.46(s，1H，NH)，7.02-6.43(m，3H，ArH)，2.50(s，3H，CH3CNHN)，2.17(s，3H，ArCH3)，2.13((s，3H，ArCH3)， 1.62-1.42(m，2H，CH2)，1.17(s，3H，CH3)，0.75(t，J＝7.4Hz，3H，CH3)；EI-MS，m/z(％)：301[M+]. Light pink powder; yield 66%; mp 156.5-157.3°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (64%): 11.50(s, 1H, ArNHNH), 8.02(s, 1H, ArNHNH ), 7.74(s, 1H, NH), 7.02-6.43(m, 3H, ArH), 2.46(s, 3H, CH 3 CNHN), 2.17(s, 3H, ArCH 3 ), 2.13((s, 3H, ArCH 3 ), 1.62-1.42 (m, 2H, CH 2 ), 1.13 (s, 3H, CH 3 ), 0.74 (t, J=7.4Hz, 3H, CH 3 ); Z (36%): 11.61 (s , 1H, ArNHNH), 8.09(s, 1H, ArNHNH), 7.46(s, 1H, NH), 7.02-6.43(m, 3H, ArH), 2.50(s, 3H, CH 3 CNHN), 2.17(s, 3H, ArCH 3 ), 2.13((s, 3H, ArCH 3 ), 1.62-1.42(m, 2H, CH 2 ), 1.17(s, 3H, CH 3 ), 0.75(t, J=7.4Hz, 3H, CH 3 ); EI-MS, m/z (%): 301 [M + ].

5-甲基-5-乙基-3-(1-(2-(4-氨基磺酰基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-85)： 5-Methyl-5-ethyl-3-(1-(2-(4-aminosulfonylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-85):

白色粉末；收率58％；mp 224.7-227.9℃；1H NMR(400MHz，DMSO-d6)δ：E(65％)：11.52(s，1H，ArNHNH)，8.85(s，1H，ArNHNH)，7.83(s，1H，NH)，7.69-6.67(m，2H，ArH)，7.11(s，2H，NH2)，7.82-6.78(m，2H，ArH)，2.42(s，3H，CH3CNHN)，1.60-1.42(m，2H，CH2)，1.13(s，3H，CH3)，0.75(t，J＝7.8Hz，3H，CH3)；Z(35％)：11.56(s，1H，ArNHNH)，8.80(s，1H，ArNHNH)，7.54(s，1H，NH)，7.69-6.67(m，2H，ArH)，7.11(s，2H，NH2)，7.82-6.78(m，2H，ArH)，2.47(s，3H，CH3CNHN)，1.60-1.42(m，2H，CH2)，1.17(s，3H，CH3)，0.75(t，J＝7.8Hz，3H，CH3)；EI-MS，m/z(％)：352[M+]. White powder; yield 58%; mp 224.7-227.9°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (65%): 11.52 (s, 1H, ArNHNH), 8.85 (s, 1H, ArNHNH) , 7.83 (s, 1H, NH), 7.69-6.67 (m, 2H, ArH), 7.11 (s, 2H, NH 2 ), 7.82-6.78 (m, 2H, ArH), 2.42 (s, 3H, CH 3 CNHN), 1.60-1.42 (m, 2H, CH 2 ), 1.13 (s, 3H, CH 3 ), 0.75 (t, J=7.8Hz, 3H, CH 3 ); Z (35%): 11.56 (s, 1H, ArNHNH), 8.80(s, 1H, ArNHNH), 7.54(s, 1H, NH), 7.69-6.67(m, 2H, ArH), 7.11(s, 2H, NH 2 ), 7.82-6.78(m, 2H, ArH), 2.47(s, 3H, CH 3 CNHN), 1.60-1.42(m, 2H, CH 2 ), 1.17(s, 3H, CH 3 ), 0.75(t, J=7.8Hz, 3H, CH 3 ); EI-MS, m/z (%): 352 [M + ].

5-甲基-5-苄基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-88)： 5-Methyl-5-benzyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-88):

浅黄色粉末；收率53％；mp 174.4℃(分解)；1H NMR(400MHz，DMSO-d6)δ：E(67％)：11.20(s，1H，ArNHNH)，8.12(s，1H，ArNHNH)，7.82(s，1H，NH)，7.23-6.52(m，9H，ArH)，2.95-2.66(m，2H，CH2)，2.33(s，3H，CH3CNHN)，1.25(s，3H，CH3)；Z(33％)：11.50(s，1H，ArNHNH)，8.25(s，1H，ArNHNH)，7.55(s，1H，NH)，7.23-6.52(m，9H，ArH)，2.95-2.66(m，2H，CH2)，2.28(s，3H，CH3CNHN)，1.28(s，3H，CH3)；EI-MS，m/z(％)：353[M+]. Pale yellow powder; yield 53%; mp 174.4°C (decomposition); 1 H NMR (400MHz, DMSO-d 6 )δ: E (67%): 11.20(s, 1H, ArNHNH), 8.12(s, 1H, ArNHNH), 7.82(s, 1H, NH), 7.23-6.52(m, 9H, ArH), 2.95-2.66(m, 2H, CH 2 ), 2.33(s, 3H, CH 3 CNHN), 1.25(s, 3H, CH 3 ); Z (33%): 11.50 (s, 1H, ArNHNH), 8.25 (s, 1H, ArNHNH), 7.55 (s, 1H, NH), 7.23-6.52 (m, 9H, ArH), 2.95-2.66 (m, 2H, CH 2 ), 2.28 (s, 3H, CH 3 CNHN), 1.28 (s, 3H, CH 3 ); EI-MS, m/z (%): 353 [M + ].

5-甲基-5-苄基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-89)： 5-Methyl-5-benzyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-89):

浅粉色粉末；收率32％；mp 185.4-185.7℃；1H NMR(400MHz，DMSO-d6)δ：E(66％)：11.19(s，1H，ArNHNH)，8.31(s，1H，ArNHNH)，7.84(s，1H，NH)，7.32-6.52(m，9H，ArH)，2.95-2.67(m，2H，CH2)，2.31(s，3H，CH3CNHN)，1.25(s，3H，CH3)；Z(34％)：11.47(s，1H，ArNHNH)，8.44(s，1H，ArNHNH)，7.57(s，1H，NH)，7.32-6.52(m，9H，ArH)，2.95-2.67(m，2H，CH2)，2.26(s，3H，CH3CNHN)，1.29(s，3H，CH3)；EI-MS，m/z(％)：369[M+]. Light pink powder; yield 32%; mp 185.4-185.7°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (66%): 11.19(s, 1H, ArNHNH), 8.31(s, 1H, ArNHNH ), 7.84(s, 1H, NH), 7.32-6.52(m, 9H, ArH), 2.95-2.67(m, 2H, CH 2 ), 2.31(s, 3H, CH 3 CNHN), 1.25(s, 3H , CH 3 ); Z (34%): 11.47 (s, 1H, ArNHNH), 8.44 (s, 1H, ArNHNH), 7.57 (s, 1H, NH), 7.32-6.52 (m, 9H, ArH), 2.95 -2.67 (m, 2H, CH 2 ), 2.26 (s, 3H, CH 3 CNHN), 1.29 (s, 3H, CH 3 ); EI-MS, m/z (%): 369 [M + ].

5-甲基-5-苄基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-90)： 5-Methyl-5-benzyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-90):

浅粉色粉末；收率36％；mp 166.3-166.9℃；1H NMR(400MHz，DMSO-d6)δ：E(66％)：11.19(s，1H，ArNHNH)，8.32(s，1H，ArNHNH)，7.84(s，1H，NH)，7.43-6.48(m，9H，ArH)，2.95-2.66(m，2H，CH2)，2.30(s，3H，CH3CNHN)，1.25(s，3H，CH3)；Z(34％)：11.46(s，1H，ArNHNH)，8.46(s，1H，ArNHNH)，7.57(s，1H，NH)，7.43-6.48(m，9H，ArH)，2.95-2.66(m，2H，CH2)，2.26(s，3H，CH3CNHN)，1.29(s，3H，CH3)；EI-MS，m/z(％)：415[M++H]. Light pink powder; yield 36%; mp 166.3-166.9°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (66%): 11.19(s, 1H, ArNHNH), 8.32(s, 1H, ArNHNH ), 7.84(s, 1H, NH), 7.43-6.48(m, 9H, ArH), 2.95-2.66(m, 2H, CH 2 ), 2.30(s, 3H, CH 3 CNHN), 1.25(s, 3H , CH 3 ); Z (34%): 11.46 (s, 1H, ArNHNH), 8.46 (s, 1H, ArNHNH), 7.57 (s, 1H, NH), 7.43-6.48 (m, 9H, ArH), 2.95 -2.66 (m, 2H, CH 2 ), 2.26 (s, 3H, CH 3 CNHN), 1.29 (s, 3H, CH 3 ); EI-MS, m/z (%): 415 [M + +H] .

5-甲基-5-苄基-3-(1-(2-(2-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-91)： 5-Methyl-5-benzyl-3-(1-(2-(2-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-91):

白色粉末；收率42％；mp 153.9-154.3℃；1H NMR(400MHz，DMSO-d6)δ：E(67％)：11.18(s，1H， ArNHNH)，8.20(s，1H，ArNHNH)，7.84(s，1H，NH)，7.24-6.39(m，9H，ArH)，2.95-2.66(m，2H，CH2)，2.32(s，3H，CH3CNHN)，1.24(s，3H，CH3)；Z(33％)：11.44(s，1H，ArNHNH)，8.33(s，1H，ArNHNH)，7.57(s，1H，NH)，7.24-6.39(m，9H，ArH)，2.95-2.66(m，2H，CH2)，2.28(s，3H，CH3CNHN)，1.28(s，3H，CH3)；EI-MS，m/z(％)：353[M+]. White powder; yield 42%; mp 153.9-154.3°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (67%): 11.18 (s, 1H, ArNHNH), 8.20 (s, 1H, ArNHNH) , 7.84(s, 1H, NH), 7.24-6.39(m, 9H, ArH), 2.95-2.66(m, 2H, CH 2 ), 2.32(s, 3H, CH 3 CNHN), 1.24(s, 3H, CH 3 ); Z (33%): 11.44 (s, 1H, ArNHNH), 8.33 (s, 1H, ArNHNH), 7.57 (s, 1H, NH), 7.24-6.39 (m, 9H, ArH), 2.95- 2.66 (m, 2H, CH 2 ), 2.28 (s, 3H, CH 3 CNHN), 1.28 (s, 3H, CH 3 ); EI-MS, m/z (%): 353 [M + ].

5-甲基-5-苄基-3-(1-(2-(3-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-92)： 5-Methyl-5-benzyl-3-(1-(2-(3-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-92):

白色粉末；收率39％；mp 124.3-126.6℃；1H NMR(400MHz，DMSO-d6)δ：E(66％)：11.17(s，1H，ArNHNH)，8.42(s，1H，ArNHNH)，7.84(s，1H，NH)，7.29-6.45(m，9H，ArH)，2.95-2.66(m，2H，CH2)，2.30(s，3H，CH3CNHN)，1.24(s，3H，CH3)；Z(34％)：11.45(s，1H，ArNHNH)，8.55(s，1H，ArNHNH)，7.57(s，1H，NH)，7.29-6.45(m，9H，ArH)，2.95-2.66(m，2H，CH2)，2.25(s，3H，CH3CNHN)，1.28(s，3H，CH3)；EI-MS，m/z(％)：369[M+]. White powder; yield 39%; mp 124.3-126.6°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (66%): 11.17 (s, 1H, ArNHNH), 8.42 (s, 1H, ArNHNH) , 7.84(s, 1H, NH), 7.29-6.45(m, 9H, ArH), 2.95-2.66(m, 2H, CH 2 ), 2.30(s, 3H, CH 3 CNHN), 1.24(s, 3H, CH 3 ); Z (34%): 11.45 (s, 1H, ArNHNH), 8.55 (s, 1H, ArNHNH), 7.57 (s, 1H, NH), 7.29-6.45 (m, 9H, ArH), 2.95- 2.66 (m, 2H, CH 2 ), 2.25 (s, 3H, CH 3 CNHN), 1.28 (s, 3H, CH 3 ); EI-MS, m/z (%): 369 [M + ].

5-甲基-5-苄基-3-(1-(2-(2，4-二氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-93)： 5-Methyl-5-benzyl-3-(1-(2-(2,4-dichlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-93):

白色粉末；收率47％；mp 180.8-181.4℃；1H NMR(400MHz，DMSO-d6)δ：E(68％)：11.18(s，1H，ArNHNH)，8.20(s，1H，ArNHNH)，7.88(s，1H，NH)，7.53-6.39(m，8H，ArH)，2.94-2.66(m，2H，CH2)，2.28(s，3H，CH3CNHN)，1.24(s，3H，CH3)；Z(32％)：11.41(s，1H，ArNHNH)，8.30(s，1H，ArNHNH)，7.60(s，1H，NH)，7.53-6.39(m，8H，ArH)，2.94-2.66(m，2H，CH2)，2.25(s，3H，CH3CNHN)，1.28(s，3H，CH3)；EI-MS，m/z(％)：404[M+]. White powder; yield 47%; mp 180.8-181.4°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (68%): 11.18 (s, 1H, ArNHNH), 8.20 (s, 1H, ArNHNH) , 7.88(s, 1H, NH), 7.53-6.39(m, 8H, ArH), 2.94-2.66(m, 2H, CH 2 ), 2.28(s, 3H, CH 3 CNHN), 1.24(s, 3H, CH 3 ); Z (32%): 11.41 (s, 1H, ArNHNH), 8.30 (s, 1H, ArNHNH), 7.60 (s, 1H, NH), 7.53-6.39 (m, 8H, ArH), 2.94- 2.66 (m, 2H, CH 2 ), 2.25 (s, 3H, CH 3 CNHN), 1.28 (s, 3H, CH 3 ); EI-MS, m/z (%): 404 [M + ].

5-甲基-5-苄基-3-(1-(2-(4-甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-94)： 5-Methyl-5-benzyl-3-(1-(2-(4-methylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-94):

白色粉末；收率46％；mp 197.3-198.8℃；1H NMR(400MHz，DMSO-d6)δ：E(66％)：11.19(s，1H，ArNHNH)，7.99(s，1H，ArNHNH)，7.78(s，1H，NH)，7.22-6.01(m，9H，ArH)，2.94-2.65(m，2H，CH2)，2.31(s，3H，CH3CNHN)，2.20(s，1H，ArCH3)，1.23(s，3H，CH3)；Z(34％)：11.51(s，1H，ArNHNH)，8.13(s，1H，ArNHNH)，7.51(s，1H，NH)，7.22-6.01(m，9H，ArH)，2.94-2.65(m，2H，CH2)，2.26(s，3H，CH3CNHN)，2.23(s，1H，ArCH3)，1.27(s，3H，CH3)；EI-MS，m/z(％)：349[M+]. White powder; yield 46%; mp 197.3-198.8°C; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (66%): 11.19 (s, 1H, ArNHNH), 7.99 (s, 1H, ArNHNH) , 7.78(s, 1H, NH), 7.22-6.01(m, 9H, ArH), 2.94-2.65(m, 2H, CH 2 ), 2.31(s, 3H, CH 3 CNHN), 2.20(s, 1H, ArCH 3 ), 1.23 (s, 3H, CH 3 ); Z (34%): 11.51 (s, 1H, ArNHNH), 8.13 (s, 1H, ArNHNH), 7.51 (s, 1H, NH), 7.22-6.01 (m, 9H, ArH), 2.94-2.65 (m, 2H, CH 2 ), 2.26 (s, 3H, CH 3 CNHN), 2.23 (s, 1H, ArCH 3 ), 1.27 (s, 3H, CH 3 ) ; EI-MS, m/z (%): 349 [M + ].

5-甲基-5-苄基-3-(1-(2-(3，4-二甲基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-95)： 5-Methyl-5-benzyl-3-(1-(2-(3,4-dimethylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-95) :

浅粉色粉末；收率39％；mp 175.2-175.5℃；1H NMR(400MHz，DMSO-d6)δ：E(65％)：11.19(s，1H，ArNHNH)，7.92(s，1H，ArNHNH)，7.77(s，1H，NH)，7.23-6.22(m，8H，ArH)，2.94-2.65(m，2H，CH2)，2.32(s，3H，CH3CNHN)，2.11(s，1H，ArCH3)，2.13(s，1H，ArCH3)，1.23(s，3H，CH 3)；Z(35％)：11.51(s，1H，ArNHNH)，8.06(s，1H，ArNHNH)，7.51(s，1H，NH)，7.23-6.22(m，8H，ArH)，2.94-2.65(m，2H，CH2)，2.27(s，3H，CH3CNHN)，2.17(s，1H，ArCH3)，2.13(s，1H，ArCH3)，1.27(s，3H，CH3)；EI-MS，m/z(％)：363[M+]. Light pink powder; yield 39%; mp 175.2-175.5°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (65%): 11.19(s, 1H, ArNHNH), 7.92(s, 1H, ArNHNH ), 7.77(s, 1H, NH), 7.23-6.22(m, 8H, ArH), 2.94-2.65(m, 2H, CH 2 ), 2.32(s, 3H, CH 3 CNHN), 2.11(s, 1H , ArCH 3 ), 2.13 (s, 1H, ArCH 3 ), 1.23 (s, 3H, CH 3 ); Z (35%): 11.51 (s, 1H, ArNHNH), 8.06 (s, 1H, ArNHNH), 7.51 (s, 1H, NH), 7.23-6.22 (m, 8H, ArH), 2.94-2.65 (m, 2H, CH 2 ), 2.27 (s, 3H, CH 3 CNHN), 2.17 (s, 1H, ArCH 3 ), 2.13(s, 1H, ArCH 3 ), 1.27(s, 3H, CH 3 ); EI-MS, m/z(%): 363[M + ].

5-甲基-5-苄基-3-(1-(2-(4-氨基磺酰基苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-98)： 5-Methyl-5-benzyl-3-(1-(2-(4-aminosulfonylphenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-98):

浅黄色粉末；收率47％；mp 235.7-237.5℃；1H NMR(400MHz，DMSO-d6)δ：E(67％)：11.21(s，1H，ArNHNH)，8.72(s，1H，ArNHNH)，7.88(s，1H，NH)，7.69-6.57(m，11H，ArH+NH2)，2.95-2.67(m，2H，CH2)，2.28(s，3H，CH3CNHN)，1.25(s，3H，CH3)；Z(33％)：11.46(s，1H，ArNHNH)，8.85(s，1H，ArNHNH)，7.60(s，1H，NH)，7.69-6.57(m，11H，ArH+NH2)，2.95-2.67(m，2H，CH2)，2.24(s，3H，CH3CNHN)，1.29(s，3H，CH3)；EI-MS，m/z(％)：414[M+]. Pale yellow powder; yield 47%; mp 235.7-237.5°C; 1 H NMR (400MHz, DMSO-d 6 )δ: E (67%): 11.21(s, 1H, ArNHNH), 8.72(s, 1H, ArNHNH ), 7.88 (s, 1H, NH), 7.69-6.57 (m, 11H, ArH+NH 2 ), 2.95-2.67 (m, 2H, CH 2 ), 2.28 (s, 3H, CH 3 CNHN), 1.25 ( s, 3H, CH 3 ); Z (33%): 11.46 (s, 1H, ArNHNH), 8.85 (s, 1H, ArNHNH), 7.60 (s, 1H, NH), 7.69-6.57 (m, 11H, ArH +NH 2 ), 2.95-2.67 (m, 2H, CH 2 ), 2.24 (s, 3H, CH 3 CNHN), 1.29 (s, 3H, CH 3 ); EI-MS, m/z (%): 414 [M + ].

1，5-二甲基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-102)： 1,5-Dimethyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-102):

浅黄色粘稠液体；收率77％；1H NMR(400MHz，DMSO-d6)δ：E(68％)：11.49(s，1H，ArNHNH)，8.24(s，1H，ArNHNH)，7.12-6.73(m，4H，ArH)，3.76-3.65(m，1H，CHN)，2.86(s，3H，NCH3)，2.47(s，3H，CH3CNH)，1.13-1.07(m，3H，CH3)；Z(32％)：11.58(s，1H，ArNHNH)，8.28(s，1H，ArNHNH)，7.12-6.73(m，4H，ArH)，3.76-3.65(m，1H，CHN)，2.85(s，3H，NCH3)，2.52(s，3H，CH3CNH)，1.13-1.07(m，3H，CH3)；EI-MS，m/z(％)：277[M+]. Pale yellow viscous liquid; yield 77%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (68%): 11.49 (s, 1H, ArNHNH), 8.24 (s, 1H, ArNHNH), 7.12- 6.73 (m, 4H, ArH), 3.76-3.65 (m, 1H, CHN), 2.86 (s, 3H, NCH 3 ), 2.47 (s, 3H, CH 3 CNH), 1.13-1.07 (m, 3H, CH 3 ); Z (32%): 11.58 (s, 1H, ArNHNH), 8.28 (s, 1H, ArNHNH), 7.12-6.73 (m, 4H, ArH), 3.76-3.65 (m, 1H, CHN), 2.85 (s, 3H, NCH 3 ), 2.52 (s, 3H, CH 3 CNH), 1.13-1.07 (m, 3H, CH 3 ); EI-MS, m/z(%): 277[M + ].

1，5-二甲基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-103)： 1,5-Dimethyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-103):

无色粘稠液体；收率82％；1H NMR(400MHz，DMSO-d6)δ：E(66％)：11.41(s，1H，ArNHNH)，8.44(s，1H，ArNHNH)，7.30-6.71(m，4H，ArH)，3.73-3.67(m，1H，CHN)，2.87(s，3H，NCH3)，2.43(s，3H，CH3CNH)，1.17-1.11(m，3H，CH3)；Z(34％)：11.57(s，1H，ArNHNH)，8.48(s，1H，ArNHNH)，7.30-6.71(m，4H，ArH)，3.73-3.67(m，1H，CHN)，2.85(s，3H，NCH3)，2.48(s，3H，CH3CNH)，1.17-1.11(m，3H，CH3)；EI-MS，m/z(％)：293[M+]. Colorless viscous liquid; yield 82%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (66%): 11.41 (s, 1H, ArNHNH), 8.44 (s, 1H, ArNHNH), 7.30- 6.71 (m, 4H, ArH), 3.73-3.67 (m, 1H, CHN), 2.87 (s, 3H, NCH 3 ), 2.43 (s, 3H, CH 3 CNH), 1.17-1.11 (m, 3H, CH 3 ); Z (34%): 11.57 (s, 1H, ArNHNH), 8.48 (s, 1H, ArNHNH), 7.30-6.71 (m, 4H, ArH), 3.73-3.67 (m, 1H, CHN), 2.85 (s, 3H, NCH 3 ), 2.48 (s, 3H, CH 3 CNH), 1.17-1.11 (m, 3H, CH 3 ); EI-MS, m/z (%): 293 [M + ].

1，5-二甲基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-104)： 1,5-Dimethyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-104):

黄色粘稠液体；收率79％；1H NMR(400MHz，DMSO-d6)δ：E(62％)：11.41(s，1H，ArNHNH)，8.46(s，1H，ArNHNH)，7.41-6.70(m，4H，ArH)，3.73-3.67(m，1H，CHN)，2.86(s，3H，NCH3)，2.43(s，3H，CH3CNH)，1.16(t，J＝6.9Hz，3H，CH3CH)；Z(38％)：11.57(s，1H，ArNHNH)，8.51(s，1H，ArNHNH)，7.41-6.70(m，4H，ArH)，3.73-3.67(m，H，CHN)，2.85(s，3H，NCH3)，2.47(s，3H，CH3CNH)，1.09(t，J＝7.0Hz，3H，CH3CH)；EI-MS，m/z(％)：339[M++H]. Yellow viscous liquid; yield 79%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (62%): 11.41 (s, 1H, ArNHNH), 8.46 (s, 1H, ArNHNH), 7.41-6.70 (m, 4H, ArH), 3.73-3.67 (m, 1H, CHN), 2.86 (s, 3H, NCH 3 ), 2.43 (s, 3H, CH 3 CNH), 1.16 (t, J=6.9Hz, 3H , CH 3 CH); Z (38%): 11.57 (s, 1H, ArNHNH), 8.51 (s, 1H, ArNHNH), 7.41-6.70 (m, 4H, ArH), 3.73-3.67 (m, H, CHN ), 2.85 (s, 3H, NCH 3 ), 2.47 (s, 3H, CH 3 CNH), 1.09 (t, J=7.0 Hz, 3H, CH 3 CH ); EI-MS, m/z (%): 339[M + +H].

1，5，5-三甲基-3-(1-(2-(4-氟苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-105)： 1,5,5-Trimethyl-3-(1-(2-(4-fluorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-105):

浅黄色粘稠液体；收率72％；1H NMR(400MHz，DMSO-d6)δ：E(68％)：11.43(s，1H，ArNHNH)，8.22(s，1H，ArNHNH)，7.15-6.77(m，4H，ArH)，2.84(s，3H，NCH3)；2.47(s，3H，CH3CNH)，1.17(s，6H，2CH3)；Z(32％)：11.47(s，1H，ArNHNH)，8.26(s，1H，ArNHNH)，7.15-6.77(m，4H，ArH)，2.84(s，3H，NCH3)；2.50(s，3H，CH3CNH)，1.20(s，6H，2CH3)；EI-MS，m/z(％)：291[M+]. Pale yellow viscous liquid; yield 72%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (68%): 11.43 (s, 1H, ArNHNH), 8.22 (s, 1H, ArNHNH), 7.15- 6.77 (m, 4H, ArH), 2.84 (s, 3H, NCH 3 ); 2.47 (s, 3H, CH 3 CNH), 1.17 (s, 6H, 2CH 3 ); Z (32%): 11.47 (s, 1H, ArNHNH), 8.26(s, 1H, ArNHNH), 7.15-6.77(m, 4H, ArH), 2.84(s, 3H, NCH 3 ); 2.50(s, 3H, CH 3 CNH), 1.20(s, 6H, 2CH 3 ); EI-MS, m/z (%): 291 [M + ].

1，5，5-三甲基-3-(1-(2-(4-氯苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-106)： 1,5,5-Trimethyl-3-(1-(2-(4-chlorophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-106):

黄色粘稠液体；收率82％；1H NMR(400MHz，DMSO-d6)δ：E(63％)：11.42(s，1H，ArNHNH)，8.43(s，1H，ArNHNH)，7.33-6.75(m，4H，ArH)，2.85(s，3H，NCH3)，2.45(s，3H，CH3CNH)，1.11(s，6H， 2CH3)；Z(37％)：11.54(s，1H，ArNHNH)，8.47(s，1H，ArNHNH)，7.33-6.75(m，4H，ArH)，2.84(s，3H，NCH3)，2.51(s，3H，CH3CNH)，1.14(s，6H，2CH3)；EI-MS，m/z(％)：307[M+]. Yellow viscous liquid; yield 82%; 1 H NMR (400 MHz, DMSO-d 6 ) δ: E (63%): 11.42 (s, 1H, ArNHNH), 8.43 (s, 1H, ArNHNH), 7.33-6.75 (m, 4H, ArH), 2.85 (s, 3H, NCH 3 ), 2.45 (s, 3H, CH 3 CNH), 1.11 (s, 6H, 2CH 3 ); Z (37%): 11.54 (s, 1H , ArNHNH), 8.47(s, 1H, ArNHNH), 7.33-6.75(m, 4H, ArH), 2.84(s, 3H, NCH 3 ), 2.51(s, 3H, CH 3 CNH), 1.14(s, 6H , 2CH 3 ); EI-MS, m/z (%): 307[M + ].

1，5，5-三甲基-3-(1-(2-(4-溴苯基)肼基)亚乙基)吡咯烷-2，4-二酮(N-107)： 1,5,5-Trimethyl-3-(1-(2-(4-bromophenyl)hydrazino)ethylidene)pyrrolidine-2,4-dione (N-107):

黄色粘稠液体；收率79％；1H NMR(400MHz，DMSO-d6)δ：E(66％)：11.40(s，1H，ArNHNH)，8.45(s，1H，ArNHNH)，7.87(s，1H，NH)，7.41-6.67(m，4H，ArH)，2.85(s，3H，NCH3)，2.43(s，3H，CH3CNH)，1.12(s，6H，2CH3)；Z(34％)：11.52(s，1H，ArNHNH)，8.48(s，1H，ArNHNH)，7.57(s，1H，NH)，7.41-6.67(m，4H，ArH)，2.84(s，3H，NCH3)，2.48(s，3H，CH3CNH)，1.16(s，6H，2CH3)；EI-MS，m/z(％)：353[M++H]. Yellow viscous liquid; yield 79%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (66%): 11.40(s, 1H, ArNHNH), 8.45(s, 1H, ArNHNH), 7.87(s , 1H, NH), 7.41-6.67 (m, 4H, ArH), 2.85 (s, 3H, NCH 3 ), 2.43 (s, 3H, CH 3 CNH), 1.12 (s, 6H, 2CH 3 ); Z( 34%): 11.52 (s, 1H, ArNHNH), 8.48 (s, 1H, ArNHNH), 7.57 (s, 1H, NH), 7.41-6.67 (m, 4H, ArH), 2.84 (s, 3H, NCH3 ), 2.48(s, 3H, CH 3 CNH), 1.16(s, 6H, 2CH 3 ); EI-MS, m/z(%): 353[M + +H].

实施例3：3-(2-(4-氟苯基)肼基亚甲基)吡咯烷-2，4-二酮(Q-1)的制备Example 3: Preparation of 3-(2-(4-fluorophenyl)hydrazinomethylene)pyrrolidine-2,4-dione (Q-1)

参照文献(Synlett.2009，15：2487-2491.)介绍的方法合成吡咯烷-2，4-二酮。 Pyrrolidine-2,4-dione was synthesized by referring to the method introduced in the literature (Synlett.2009, 15:2487-2491.).

在250mL三口烧瓶中加入吡咯烷-2，4-二酮9.9g和原甲酸三乙酯37g，80℃下搅拌反应2h，减压蒸去剩余的原甲酸三乙酯，残余物用乙醇重结晶，抽滤，干燥，得10.4g 3-乙氧基亚甲基吡咯烷-2，4-二酮白色固体，收率67％。 Add 9.9 g of pyrrolidine-2,4-dione and 37 g of triethyl orthoformate into a 250 mL three-necked flask, stir and react at 80°C for 2 hours, evaporate the remaining triethyl orthoformate under reduced pressure, and recrystallize the residue with ethanol , filtered with suction, and dried to obtain 10.4g of 3-ethoxymethylenepyrrolidine-2,4-dione as a white solid with a yield of 67%.

在50mL三口烧瓶中加入乙醇15mL，3-乙氧基亚甲基吡咯烷-2，4-二酮7.1mmol(1.10g)，对氟苯肼盐酸盐7.1mmol(1.15g)，滴加含1.2倍量三乙胺8.5mmol(0.86g)的乙醇溶液5mL，待溶液完全澄清后，加热回流，搅拌，采用TLC(展开剂：乙酸乙酯∶石油醚∶乙酸＝10∶10∶1，V/V/V)监控反应进程。反应结束后，减压蒸去溶剂，冷却，用乙醚萃取，水洗，取乙醚层，干燥，蒸去溶剂得1.17g 3-(2-(4-氟苯基)肼基亚甲基)吡咯烷-2，4-二酮(Q-1)： Add 15mL of ethanol, 7.1mmol (1.10g) of 3-ethoxymethylenepyrrolidine-2,4-dione, 7.1mmol (1.15g) of p-fluorophenylhydrazine hydrochloride in a 50mL three-necked flask, and dropwise add 1.2 times the amount of triethylamine 8.5mmol (0.86g) ethanol solution 5mL, after the solution is completely clear, heat to reflux, stir, use TLC (developing solvent: ethyl acetate: petroleum ether: acetic acid = 10: 10: 1, V /V/V) to monitor the progress of the reaction. After the reaction, the solvent was evaporated under reduced pressure, cooled, extracted with ether, washed with water, the ether layer was taken, dried, and the solvent was evaporated to obtain 1.17g 3-(2-(4-fluorophenyl)hydrazinomethylene)pyrrolidine -2,4-Diketone (Q-1):

浅褐色粘稠液体；收率70％；1H NMR(400MHz，DMSO-d6)δ：11.30(s，1H，ArNHNH)，8.22(s，1H，ArNHNH)，7.78(s，1H，NH)，7.52(s，1H，＝CH)，7.16-6.65(m，4H，ArH)，3.58(s，2H，CH2NH)；EI-MS，m/z(％)：235[M+]. Light brown viscous liquid; yield 70%; 1 H NMR (400MHz, DMSO-d 6 ) δ: 11.30 (s, 1H, ArNHNH), 8.22 (s, 1H, ArNHNH), 7.78 (s, 1H, NH) , 7.52 (s, 1H, =CH), 7.16-6.65 (m, 4H, ArH), 3.58 (s, 2H, CH 2 NH); EI-MS, m/z (%): 235 [M + ].

采用实施例3的方法，制备了下述Q系列化合物：  Adopt the method for embodiment 3, prepared following Q series compound:

3-(1-(2-(4-氯苯基)肼基)亚甲基)吡咯烷-2，4-二酮(Q-2)： 3-(1-(2-(4-chlorophenyl)hydrazino)methylene)pyrrolidine-2,4-dione (Q-2):

黄色粘稠液体；收率79％；1H NMR(400MHz，DMSO-d6)δ：11.34(s，1H，ArNHNH)，8.35(s，1H，ArNHNH)，7.75(s，1H，NH)，7.55(s，1H，＝CH)，7.26-6.69(m，4H，ArH)，3.57(s，2H，CH2NH)；EI-MS，m/z(％)：251[M+]. Yellow viscous liquid; yield 79%; 1 H NMR (400 MHz, DMSO-d 6 ) δ: 11.34 (s, 1H, ArNHNH), 8.35 (s, 1H, ArNHNH), 7.75 (s, 1H, NH), 7.55 (s, 1H, =CH), 7.26-6.69 (m, 4H, ArH), 3.57 (s, 2H, CH 2 NH); EI-MS, m/z (%): 251 [M + ].

3-(1-(2-(4-溴苯基)肼基)亚甲基)吡咯烷-2，4-二酮(Q-3)： 3-(1-(2-(4-bromophenyl)hydrazino)methylene)pyrrolidine-2,4-dione (Q-3):

黄色粘稠液体；收率71％；1H NMR(400MHz，DMSO-d6)δ：11.32(s，1H，ArNHNH)，8.32(s，1H，ArNHNH)，7.65(s，1H，NH)，7.56(s，1H，＝CH)，7.36-6.68(m，4H，ArH)，3.58(s，2H，CH2NH)；EI-MS，m/z(％)：297[M++H]. Yellow viscous liquid; yield 71%; 1 H NMR (400 MHz, DMSO-d 6 ) δ: 11.32 (s, 1H, ArNHNH), 8.32 (s, 1H, ArNHNH), 7.65 (s, 1H, NH), 7.56 (s, 1H, =CH), 7.36-6.68 (m, 4H, ArH), 3.58 (s, 2H, CH 2 NH); EI-MS, m/z (%): 297 [M + +H] .

实施例4：3-(1-(2-(4-氟苯基)肼基)亚丙基)吡咯烷-2，4-二酮(S-1)的制备Example 4: Preparation of 3-(1-(2-(4-fluorophenyl)hydrazino)propylene)pyrrolidine-2,4-dione (S-1)

参照文献(Synlett.2009，15：2487-2491.)介绍的方法合成吡咯烷-2，4-二酮。 Pyrrolidine-2,4-dione was synthesized by referring to the method introduced in the literature (Synlett.2009, 15:2487-2491.).

参照文献(Tetrahed ron，2005，61：2301-2307.)介绍的方法合成3-(1-羟基亚丙基)吡咯烷-2，4-二 酮。 3-(1-hydroxypropylene) pyrrolidine-2,4-dione was synthesized according to the method introduced in literature (Tetrahedron, 2005, 2005, 61:2301-2307.).

在50mL三口烧瓶中加入乙醇15mL、3-(1-羟基亚丙基)吡咯烷-2，4-二酮7.1mmol(1.10g)和对氟苯肼盐酸盐7.1mmol(1.15g)，滴加含1.2倍量三乙胺8.5mmol(0.86g)的乙醇溶液5m L，待溶液完全澄清后，加热回流，搅拌，采用TLC(展开剂：乙酸乙酯∶石油醚∶乙酸＝10∶10∶1，V/V/V)监控反应进程。反应结束后，减压蒸去溶剂，冷却，用乙醚萃取，水洗，取乙醚层，干燥，蒸去溶剂得1.28g 3-(1-(2-(4-氟苯基)肼基)亚丙基)吡咯烷-2，4-二酮(S-1)： Add 15 mL of ethanol, 7.1 mmol (1.10 g) of 3-(1-hydroxypropylene) pyrrolidine-2,4-dione and 7.1 mmol (1.15 g) of p-fluorophenylhydrazine hydrochloride into a 50 mL three-necked flask, drop Add 5mL of ethanol solution containing 8.5mmol (0.86g) of 1.2 times the amount of triethylamine. After the solution is completely clarified, heat to reflux, stir, and use TLC (developing solvent: ethyl acetate:petroleum ether:acetic acid=10:10: 1, V/V/V) to monitor the progress of the reaction. After the reaction, the solvent was evaporated under reduced pressure, cooled, extracted with ether, washed with water, the ether layer was taken, dried, and the solvent was evaporated to obtain 1.28g of 3-(1-(2-(4-fluorophenyl)hydrazino)propylene Base) pyrrolidine-2,4-dione (S-1):

浅黄色粘稠液体；收率69％；1H NMR(400MHz，DMSO-d6)δ：E(66％)：11.52(s，1H，ArNHNH)，8.31(s，1H，ArNHNH)，7.69(s，1H，NH)，7.21-6.72(m，4H，ArH)，3.59(s，2H，CH2NH)，2.59-2.52(m，3H，CH2CH3)；0.91(t，J＝7.4Hz，3H，CH2CH3)；Z(34％)：11.69(s，1H，ArNHNH)，8.38(s，1H，ArNHNH)，7.43(s，1H，NH)，7.21-6.72(m，4H，ArH)，3.64(s，2H，CH2NH)，2.59-2.52(m，3H，CH2CH3)；0.91(t，J＝7.4Hz，3H，CH2CH3)；EI-MS，m/z(％)：263[M+]. Pale yellow viscous liquid; yield 69%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (66%): 11.52 (s, 1H, ArNHNH), 8.31 (s, 1H, ArNHNH), 7.69 ( s, 1H, NH), 7.21-6.72 (m, 4H, ArH), 3.59 (s, 2H, CH 2 NH), 2.59-2.52 (m, 3H, CH 2 CH 3 ); 0.91 (t, J=7.4 Hz, 3H, CH 2 CH 3 ); Z (34%): 11.69 (s, 1H, ArNHNH), 8.38 (s, 1H, ArNHNH), 7.43 (s, 1H, NH), 7.21-6.72 (m, 4H , ArH), 3.64 (s, 2H, CH 2 NH), 2.59-2.52 (m, 3H, CH 2 CH 3 ); 0.91 (t, J=7.4Hz, 3H, CH 2 CH 3 ); EI-MS, m/z(%): 263[M + ].

采用实施例4的方法，制备了下述S系列和U系列化合物：  Adopt the method for embodiment 4, prepared following S series and U series compound:

3-(1-(2-(4-氯苯基)肼基)亚丙基)吡咯烷-2，4-二酮(S-2)： 3-(1-(2-(4-chlorophenyl)hydrazino)propylene)pyrrolidine-2,4-dione (S-2):

浅黄色粘稠液体；收率78％；1H NMR(400MHz，DMSO-d6)δ：E(64％)：11.54(s，1H，ArNHNH)，8.47(s，1H，ArNHNH)，7.72(s，1H，NH)，7.31-6.73(m，4H，ArH)，3.61(s，2H，CH2NH)，2.58-2.53(m，3H，CH2CH3)；0.90(t，J＝7.4Hz，3H，CH2CH3)；Z(36％)：11.70(s，1H，ArNHNH)，8.52(s，1H， ArNHNH)，7.44(s，1H，NH)，7.31-6.73(m，4H，ArH)，3.64(s，2H，CH2NH)，2.58-2.53(m，3H，CH2CH3)；0.90(t，J＝7.4Hz，3H，CH2CH3)；EI-MS，m/z(％)：279[M+]. Pale yellow viscous liquid; yield 78%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (64%): 11.54 (s, 1H, ArNHNH), 8.47 (s, 1H, ArNHNH), 7.72 ( s, 1H, NH), 7.31-6.73 (m, 4H, ArH), 3.61 (s, 2H, CH 2 NH), 2.58-2.53 (m, 3H, CH 2 CH 3 ); 0.90 (t, J=7.4 Hz, 3H, CH 2 CH 3 ); Z (36%): 11.70 (s, 1H, ArNHNH), 8.52 (s, 1H, ArNHNH), 7.44 (s, 1H, NH), 7.31-6.73 (m, 4H , ArH), 3.64 (s, 2H, CH 2 NH), 2.58-2.53 (m, 3H, CH 2 CH 3 ); 0.90 (t, J=7.4Hz, 3H, CH 2 CH 3 ); EI-MS, m/z(%): 279[M + ].

3-(1-(2-(4-溴苯基)肼基)亚丙基)吡咯烷-2，4-二酮(S-3)： 3-(1-(2-(4-bromophenyl)hydrazino)propylene)pyrrolidine-2,4-dione (S-3):

浅黄色粘稠液体；收率70％；1H NMR(400MHz，DMSO-d6)δ：E(63％)：11.54(s，1H，ArNHNH)，8.51(s，1H，ArNHNH)，7.69(s，1H，NH)，7.43-6.66(m，4H，ArH)，3.60(s，2H，CH2NH)，2.57-2.53(m，3H，CH2CH3)；0.90(t，J＝7.4Hz，3H，CH2CH3)；Z(37％)：11.69(s，1H，ArNHNH)，8.55(s，1H，ArNHNH)，7.43(s，1H，NH)，7.43-6.66(m，4H，ArH)，3.67(s，2H，CH2NH)，2.57-2.53(m，3H，CH2CH3)；0.90(t，J＝7.4Hz，3H，CH2CH3)；EI-MS，m/z(％)：325[M++H]. Pale yellow viscous liquid; yield 70%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (63%): 11.54(s, 1H, ArNHNH), 8.51(s, 1H, ArNHNH), 7.69( s, 1H, NH), 7.43-6.66 (m, 4H, ArH), 3.60 (s, 2H, CH 2 NH), 2.57-2.53 (m, 3H, CH 2 CH 3 ); 0.90 (t, J=7.4 Hz, 3H, CH 2 CH 3 ); Z (37%): 11.69 (s, 1H, ArNHNH), 8.55 (s, 1H, ArNHNH), 7.43 (s, 1H, NH), 7.43-6.66 (m, 4H , ArH), 3.67 (s, 2H, CH 2 NH), 2.57-2.53 (m, 3H, CH 2 CH 3 ); 0.90 (t, J=7.4Hz, 3H, CH 2 CH 3 ); EI-MS, m/z(%): 325[M + +H].

3-(1-(2-(4-氟苯基)肼基)亚丁基)吡咯烷-2，4-二酮(U-1)： 3-(1-(2-(4-fluorophenyl)hydrazino)butylene)pyrrolidine-2,4-dione (U-1):

黄色粘稠液体；收率69％；1H NMR(400MHz，DMSO-d6)δ：E(65％)：11.50(s，1H，ArNHNH)，8.33(s，1H，ArNHNH)，7.71(s，1H，NH)，7.27-6.70(m，4H，ArH)，3.63(s，2H，CH2NH)，2.60-2.54(m，3H，CH2CH2CH3)，1.61-1.50，(m，2H，CH3CH2CH2)；0.85(t，J＝7.4Hz，3H，CH2CH3)；Z(35％)：11.71(s，1H，ArNHNH)，8.42(s，1H，ArNHNH)，7.27-6.70(m，4H，ArH)，3.66(s，2H，CH2NH)，2.60-2.54(m，3H，CH2CH2CH3)，1.61-1.50，(m，2H，CH3CH2CH2)；0.85(t，J＝7.4Hz，3H，CH2CH3)；EI-MS，m/z(％)：277[M+]. Yellow viscous liquid; yield 69%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (65%): 11.50(s, 1H, ArNHNH), 8.33(s, 1H, ArNHNH), 7.71(s , 1H, NH), 7.27-6.70 (m, 4H, ArH), 3.63 (s, 2H, CH 2 NH), 2.60-2.54 (m, 3H, CH 2 CH 2 CH 3 ), 1.61-1.50, (m , 2H, CH 3 CH 2 CH 2 ); 0.85 (t, J=7.4Hz, 3H, CH 2 CH 3 ); Z (35%): 11.71 (s, 1H, ArNHNH), 8.42 (s, 1H, ArNHNH ), 7.27-6.70 (m, 4H, ArH), 3.66 (s, 2H, CH 2 NH), 2.60-2.54 (m, 3H, CH 2 CH 2 CH 3 ), 1.61-1.50, (m, 2H, CH 3 CH 2 CH 2 ); 0.85 (t, J=7.4Hz, 3H, CH 2 CH 3 ); EI-MS, m/z(%): 277[M + ].

3-(1-(2-(4-氯苯基)肼基)亚丁基)吡咯烷-2，4-二酮(U-2)： 3-(1-(2-(4-chlorophenyl)hydrazino)butylene)pyrrolidine-2,4-dione (U-2):

黄色粘稠液体；收率82％；1H NMR(400MHz，DMSO-d6)δ：E(64％)：11.51(s，1H，ArNHNH)，8.48(s，1H，ArNHNH)，7.71(s，1H，NH)，7.30-6.71(m，4H，ArH)，3.63(s，2H，CH2NH)，2.61-2.52(m，3H，CH2CH2CH3)，1.60-1.58，(m，2H，CH3CH2CH2)；0.83(t，J＝7.4Hz，3H，CH2CH3)；Z(36％)：11.72(s，1H，ArNHNH)，8.53(s，1H，ArNHNH)，7.42(s，1H，NH)，7.30-6.71(m，4H，ArH)，3.65(s，2H，CH2NH)，2.61-2.52(m，3H，CH2CH2CH3)，1.60-1.58，(m，2H，CH3CH2CH2)；0.83(t，J＝7.4Hz，3H，CH2CH3)；EI-MS，m/z(％)：293[M+]. Yellow viscous liquid; yield 82%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (64%): 11.51(s, 1H, ArNHNH), 8.48(s, 1H, ArNHNH), 7.71(s , 1H, NH), 7.30-6.71 (m, 4H, ArH), 3.63 (s, 2H, CH 2 NH), 2.61-2.52 (m, 3H, CH 2 CH 2 CH 3 ), 1.60-1.58, (m , 2H, CH 3 CH 2 CH 2 ); 0.83 (t, J=7.4Hz, 3H, CH 2 CH 3 ); Z (36%): 11.72 (s, 1H, ArNHNH), 8.53 (s, 1H, ArNHNH ), 7.42 (s, 1H, NH), 7.30-6.71 (m, 4H, ArH), 3.65 (s, 2H, CH 2 NH), 2.61-2.52 (m, 3H, CH 2 CH 2 CH 3 ), 1.60 -1.58, (m, 2H, CH 3 CH 2 CH 2 ); 0.83 (t, J=7.4Hz, 3H, CH 2 CH 3 ); EI-MS, m/z(%): 293[M + ].

3-(1-(2-(4-溴苯基)肼基)亚丁基)吡咯烷-2，4-二酮(U-3)： 3-(1-(2-(4-bromophenyl)hydrazino)butylene)pyrrolidine-2,4-dione (U-3):

黄色粘稠液体；收率77％；1H NMR(400MHz，DMSO-d6)δ：E(64％)：11.53(s，1H，ArNHNH)，8.53(s，1H，ArNHNH)，7.70(s，1H，NH)，7.45-6.62(m，4H，ArH)，3.61(s，2H，CH2NH)，2.60-2.52(m，3H，CH2CH2CH3)，1.61-1.57，(m，2H，CH3CH2CH2)；0.85(t，J＝7.4Hz，3H，CH2CH3)；Z(36％)：11.74(s，1H，ArNHNH)，8.58(s，1H，ArNHNH)，7.44(s，1H，NH)，7.45-6.62(m，4H，ArH)，3.66(s，2H，CH2NH)，2.60-2.52(m，3H，CH2CH2CH3)，1.61-1.57，(m，2H，CH3CH2CH2)；0.85(t，J＝7.4Hz，3H，CH2CH3)；EI-MS，m/z(％)：339[M++H].. Yellow viscous liquid; yield 77%; 1 H NMR (400MHz, DMSO-d 6 ) δ: E (64%): 11.53(s, 1H, ArNHNH), 8.53(s, 1H, ArNHNH), 7.70(s , 1H, NH), 7.45-6.62 (m, 4H, ArH), 3.61 (s, 2H, CH 2 NH), 2.60-2.52 (m, 3H, CH 2 CH 2 CH 3 ), 1.61-1.57, (m , 2H, CH 3 CH 2 CH 2 ); 0.85 (t, J=7.4Hz, 3H, CH 2 CH 3 ); Z (36%): 11.74 (s, 1H, ArNHNH), 8.58 (s, 1H, ArNHNH ), 7.44 (s, 1H, NH), 7.45-6.62 (m, 4H, ArH), 3.66 (s, 2H, CH 2 NH), 2.60-2.52 (m, 3H, CH 2 CH 2 CH 3 ), 1.61 -1.57, (m, 2H, CH 3 CH 2 CH 2 ); 0.85 (t, J=7.4Hz, 3H, CH 2 CH 3 ); EI-MS, m/z(%): 339 [M + +H ]..

用途实施例Example of use

实施例5：本发明的化合物对真菌的杀菌活性Embodiment 5: the bactericidal activity of compound of the present invention to fungus

采用菌丝生长速率法进行杀菌活性评价，以小麦赤霉病菌(Fusarium graminearum)、蔬菜灰霉病菌(Botrytis cinerea)、小麦纹枯病菌(Rhizoctonia cerealis)和辣椒炭疽病菌(Colletotrichum capsici)为测定对象。 Bactericidal activity was evaluated by mycelium growth rate method, with Fusarium graminearum, Botrytis cinerea, Rhizoctonia cerealis and Colletotrichum capsici as the test objects .

准确称取一定量的目标化合物溶于甲醇中制得一定浓度的母液，准确吸取母液0.5mL，加入到99.5mL灭过菌的PSA培养基中(溶剂浓度小于1.0％)，摇匀，制成浓度为100mg/L的带药培养基，将其倒入直径9cm的培养皿中。以加入等量溶剂制成的培养基为空白对照。用打孔器(内径0.5cm)将生长正常的菌落打孔制取菌饼，用接种棒将菌饼接入上述培养基平板中央，于25℃下培养箱中倒置培养。待对照培养基上的菌落直径长至平板的2/3时测量其直径，每个菌落直径按十字交叉法测量2次，计算其平均值(单位：cm)。各浓度及空白对照均设三个重复。计算抑制百分率。再采用二倍稀释法制备至少6个合适的浓度梯度培养基平板，按上述方法培养，测量菌落直径，计算EC50值。试验结果如下表所示： Accurately weigh a certain amount of the target compound and dissolve it in methanol to obtain a certain concentration of mother liquor, accurately draw 0.5mL of the mother liquor, add it to 99.5mL of sterilized PSA medium (solvent concentration is less than 1.0%), shake well, and prepare The drug-carrying medium with a concentration of 100 mg/L is poured into a petri dish with a diameter of 9 cm. The culture medium prepared by adding an equal amount of solvent was used as the blank control. Use a puncher (0.5 cm inner diameter) to punch holes in the normal-growing colony to obtain a bacterial cake, insert the bacterial cake into the center of the above-mentioned medium plate with an inoculation stick, and culture it upside down in an incubator at 25°C. When the colony diameter on the control medium grows to 2/3 of the plate, measure its diameter, measure the diameter of each colony twice by the cross method, and calculate the average value (unit: cm). Three replicates were set up for each concentration and blank control. Calculate percent inhibition. Then prepare at least 6 appropriate concentration gradient culture medium plates by the double dilution method, cultivate them according to the above method, measure the colony diameter, and calculate the EC 50 value. The test results are shown in the table below:

*：F.graminearum抗多菌灵品系。 * : F. graminearum carbendazim-resistant strain.

在本测定中，本发明的化合物H-9、H-10、H-14、K-1、K-2、K-3、N-11、N-12、N-14、N-16、N-18、N-19、N-20、N-23～N-29、N-31对F.graminearum的EC50值小于1μg/mL，其中K-1、K-2、K-3、N-25、N-26与多菌灵相当，H-9、H-10对F.graminearum抗多菌灵品系的EC50值与敏感品系基本一致，说明本发明的化合物与多菌灵没有交互抗性。 In this assay, compounds H-9, H-10, H-14, K-1, K-2, K-3, N-11, N-12, N-14, N-16, N -18, N-19, N-20, N-23～N-29, N-31 have an EC 50 value of less than 1 μg/mL for F. graminearum, among which K-1, K-2, K-3, N- 25. N-26 is equivalent to carbendazim, and the EC 50 values of H-9 and H-10 to the carbendazim-resistant strain of F. graminearum are basically consistent with the sensitive strain, indicating that the compound of the present invention has no cross-resistance to carbendazim .

本发明的化合物H-10、K-2、N-10、N-11、N-12、N-14、N-15、N-16、N-18、N-20、N-25对B.cinerea的EC50值小于1μg/mL。 Compounds H-10, K-2, N-10, N-11, N-12, N-14, N-15, N-16, N-18, N-20, N-25 of the present invention are to B. The EC 50 value of cinerea is less than 1 μg/mL.

本发明的化合物H-7、H-9、H-10、H-12～H-15、K-1、K-2、K-3、N-10、N-11、N-12、N-14～N-20、N-22、N-23、N-25、N-26、N-28、N-29、N-31～N-41对R.cerealis的EC50值小于1μg/mL，其中K-3与己唑醇相当，H-7、H-10、H-12、H-14、K-2、N-11、N-12、N-14、N-15、N-18、N-25、N-26、N-28、N-29、N-34、N-35、N-37、N-38优于氟酰胺。 Compounds of the present invention H-7, H-9, H-10, H-12～H-15, K-1, K-2, K-3, N-10, N-11, N-12, N- The EC 50 value of 14～N-20, N-22, N-23, N-25, N-26, N-28, N-29, N-31～N-41 to R.cerealis is less than 1 μg/mL, Among them, K-3 is equivalent to hexaconazole, H-7, H-10, H-12, H-14, K-2, N-11, N-12, N-14, N-15, N-18, N-25, N-26, N-28, N-29, N-34, N-35, N-37, N-38 are better than fluoroamides.

本发明的化合物H-10、H-14、K-1、K-2、K-3、N-11、N-16、N-18、N-20、N-22、N-23、N-25、N-26、N-28、N-29、N-31、N-35对C.capsicis的EC50值小于1μg/mL，其中K-3与嘧菌酯相当。 Compounds of the present invention H-10, H-14, K-1, K-2, K-3, N-11, N-16, N-18, N-20, N-22, N-23, N- 25. The EC 50 values of N-26, N-28, N-29, N-31 and N-35 against C. capsicis are less than 1 μg/mL, among which K-3 is equivalent to azoxystrobin.

实施例6：本发明的化合物对镰孢属菌种的防治效果Embodiment 6: the control effect of compound of the present invention to Fusarium species

分别称取5mg本发明的化合物H-9、H-10、H-14、K-1、K-2、K-3、N-11、N-12、N-14、N-16、N-18、N-19、N-20、N-23～N-29、N-31，溶于0.5mL丙酮，加入4.5mL 0.1％吐温80溶液，摇匀，配制成1000μg/mL溶液。以多菌灵为对照药剂，用0.1N HCl配制成5000μg/mL的多菌 灵母液，再用0.1％吐温80溶液稀释成1000μg/mL溶液。空白对照用0.5mL丙酮和4.5mL 0.1％吐温80溶液配制。 Weigh 5mg of the compounds of the present invention H-9, H-10, H-14, K-1, K-2, K-3, N-11, N-12, N-14, N-16, N- 18. N-19, N-20, N-23~N-29, N-31, dissolved in 0.5mL of acetone, added 4.5mL of 0.1% Tween 80 solution, shake well, to prepare a 1000μg/mL solution. With carbendazim as the control agent, 5000 μg/mL carbendazim mother solution was prepared with 0.1N HCl, and then diluted with 0.1% Tween 80 solution to 1000 μg/mL solution. The blank control was prepared with 0.5mL acetone and 4.5mL 0.1% Tween 80 solution.

将小麦种子在水中浸泡1小时，放置于培养箱中，于25℃催芽24小时，种植于塑料盆钵中，每盆种植20粒种子，于25℃培养，生长至3叶期时喷施上述配制的溶液，每盆喷施2.5mL，设3次重复，24小时后针刺小麦叶片，接种小麦赤霉病菌Fusarium graminearum的菌丝块，于25℃下培养3天，测量病斑长度，计算防治效果。 Soak wheat seeds in water for 1 hour, place them in an incubator, accelerate germination at 25°C for 24 hours, plant them in plastic pots, plant 20 seeds in each pot, cultivate them at 25°C, and spray the above-mentioned seeds when they grow to the 3-leaf stage The prepared solution was sprayed with 2.5mL per pot, and repeated 3 times. After 24 hours, the wheat leaves were needled, inoculated with the mycelium block of Fusarium graminearum, and cultured at 25°C for 3 days. The length of the lesion was measured and calculated. Control effect.

试验结果表明，在1000μg/mL浓度下，本发明的化合物K-1、K-2、K-3、N-25、N-26的防治效果为100％，H-9、H-10、H-14、N-11、N-12、N-14、N-16、N-18、N-19、N-20、N-23、N-24、N-27、N-28、N-29、N-31的防治效果在60.7-99.0％之间，对照药剂多菌灵为100％。 The test results show that at a concentration of 1000 μg/mL, the control effects of compounds K-1, K-2, K-3, N-25, and N-26 of the present invention are 100%, and H-9, H-10, and H -14, N-11, N-12, N-14, N-16, N-18, N-19, N-20, N-23, N-24, N-27, N-28, N-29 , The control effect of N-31 is between 60.7-99.0%, and the control drug carbendazim is 100%.

实施例7：本发明的化合物对葡萄孢属菌种的防治效果Embodiment 7: the control effect of compound of the present invention to Botrytis species

分别称取5mg本发明的化合物H-10、K-2、N-10、N-11、N-12、N-14、N-15、N-16、N-18、N-20、N-25，溶于0.5mL丙酮，加入4.5mL 0.1％吐温80溶液，摇匀，配制成1000μg/mL溶液。以速克灵为对照药剂，用0.1N HCl配制成5000μg/mL的速克灵母液，再用0.1％吐温80溶液稀释成1000μg/mL溶液。空白对照用0.5mL丙酮和4.5mL 0.1％吐温80溶液配制。 Weigh 5mg of the compounds of the present invention H-10, K-2, N-10, N-11, N-12, N-14, N-15, N-16, N-18, N-20, N- 25. Dissolve in 0.5mL acetone, add 4.5mL 0.1% Tween 80 solution, shake well, and prepare a 1000μg/mL solution. Using sacralin as the control drug, 5000 μg/mL sacralin mother solution was prepared with 0.1N HCl, and then diluted with 0.1% Tween 80 solution to 1000 μg/mL solution. The blank control was prepared with 0.5mL acetone and 4.5mL 0.1% Tween 80 solution.

将辣椒种子在水中浸泡1小时，放置于培养箱中，于25℃催芽24小时，种植于塑料盆钵中，每盆种植20粒种子，于25℃培养，生长至3叶期时喷施上述配制的溶液，每盆喷施2.5mL，设3次重复，24小时后针刺辣椒叶片，接种蔬菜灰霉病菌Botrytis cinerea的菌丝块，于25℃下培养3天，测量病斑长度，计算防治效果。 Soak pepper seeds in water for 1 hour, place them in an incubator, germinate them at 25°C for 24 hours, plant them in plastic pots, plant 20 seeds in each pot, cultivate them at 25°C, and spray the above-mentioned seeds when they grow to the 3-leaf stage The prepared solution was sprayed with 2.5mL per pot, and repeated 3 times. After 24 hours, the pepper leaves were needled, and the mycelium block of Botrytis cinerea was inoculated, cultivated at 25°C for 3 days, and the lesion length was measured. Calculate Control effect.

试验结果表明，在1000μg/mL浓度下，本发明的化合物K-2、N-11、N-14的防治效果为100％，H-10、N-10、N-12、N-15、N-16、N-18、N-20、N-25的防治效果在52.7-96.9％之间，对照药剂速克灵为100％。 Test result shows, under 1000 μ g/mL concentration, the control effect of compound K-2, N-11, N-14 of the present invention is 100%, H-10, N-10, N-12, N-15, N -16, N-18, N-20, and N-25 have a control effect of 52.7-96.9%, and the control drug saccharin is 100%.

实施例8：本发明的化合物对丝核菌属菌种的防治效果Embodiment 8: the control effect of compound of the present invention to Rhizoctonia species

分别称取5mg本发明的化合物H-7、H-9、H-10、H-12～H-15、K-1、K-2、K-3、N-10、N-11、N-12、N-14～N-20、N-22、N-23、N-25、N-26、N-28、N-29、N-31～N-41，溶于0.5mL丙酮，加入4.5mL 0.1％吐温80溶液，摇匀，配制成1000μg/mL溶液。以氟酰胺为对照药剂，用0.1N HCl配制成5000μg/mL的氟酰胺母液，再用0.1％吐温80溶液稀释成1000μg/mL溶液。空白对照用0.5mL丙酮和4.5mL 0.1％吐温80溶液配制。 Weigh 5mg of the compounds of the present invention H-7, H-9, H-10, H-12～H-15, K-1, K-2, K-3, N-10, N-11, N- 12. N-14～N-20, N-22, N-23, N-25, N-26, N-28, N-29, N-31～N-41, dissolve in 0.5mL acetone, add 4.5 mL 0.1% Tween 80 solution, shake well, and prepare 1000μg/mL solution. Fluoramide was used as a control agent, and 5000 μg/mL fluamide mother solution was prepared with 0.1N HCl, and then diluted with 0.1% Tween 80 solution to a 1000 μg/mL solution. The blank control was prepared with 0.5mL acetone and 4.5mL 0.1% Tween 80 solution.

将小麦种子在水中浸泡1小时，放置于培养箱中，于25℃催芽24小时，种植于塑料盆钵中，每盆种植20粒种子，于25℃培养，生长至3叶期时喷施上述配制的溶液，每盆喷施2.5mL，设3次重复，24小时后针刺小麦叶片，接种小麦纹枯病菌Rhizoctonia cereadis的菌丝块，于25℃下培养3天，测量病斑长度，计算防治效果。 Soak wheat seeds in water for 1 hour, place them in an incubator, accelerate germination at 25°C for 24 hours, plant them in plastic pots, plant 20 seeds in each pot, cultivate them at 25°C, and spray the above-mentioned seeds when they grow to the 3-leaf stage The prepared solution was sprayed with 2.5mL in each pot, and repeated 3 times. After 24 hours, the wheat leaves were needled, and the mycelia block of Rhizoctonia cereadis was inoculated, cultivated at 25°C for 3 days, and the length of the lesion was measured. Calculate the control effect.

试验结果表明，在1000μg/mL浓度下，本发明的化合物H-7、H-10、H-12、H-14、K-2、K-3、N-11、N-12、N-14、N-15、N-18、N-25、N-26、N-28、N-29、N-34、N-35的防治效果为100％，H-9、H-13、H-15、K-1、N-10、N-16、N-17、N-19、N-20、N-22、N-23、N-31～N-33、N-36～N-41的防治效果在77.7-98.3％之间，对照药剂氟酰胺为100％。 Test result shows, under 1000 μ g/mL concentration, compound H-7, H-10, H-12, H-14, K-2, K-3, N-11, N-12, N-14 of the present invention , N-15, N-18, N-25, N-26, N-28, N-29, N-34, N-35 have a control effect of 100%, H-9, H-13, H-15 , K-1, N-10, N-16, N-17, N-19, N-20, N-22, N-23, N-31～N-33, N-36～N-41 The effect is between 77.7-98.3%, and the contrast drug flunamide is 100%.

实施例9：本发明的化合物对炭疽菌属菌种的防治效果Embodiment 9: the compound of the present invention is to the control effect of anthracnose bacteria

分别称取5mg本发明的化合物H-10、H-14、K-1、K-2、K-3、N-11、N-16、N-18、N-20、N-22、N-23、N-25、N-26、N-28、N-29、N-31、N-35，溶于0.5mL丙酮，加入4.5mL 0.1％吐温80溶液，摇匀，配制成1000μg/mL溶液。以嘧菌酯为对照药剂，用0.1N HCl配制成5000μg/mL的嘧菌酯母液，再用0.1％吐温80溶液稀释成1000μg/mL溶液。空白对照用0.5mL丙酮和4.5mL 0.1％吐温80溶液配制。 Weigh 5mg of the compounds of the present invention H-10, H-14, K-1, K-2, K-3, N-11, N-16, N-18, N-20, N-22, N- 23. N-25, N-26, N-28, N-29, N-31, N-35, dissolve in 0.5mL acetone, add 4.5mL 0.1% Tween 80 solution, shake well, and make 1000μg/mL solution. Taking azoxystrobin as the control drug, azoxystrobin mother solution of 5000 μg/mL was prepared with 0.1N HCl, and then diluted with 0.1% Tween 80 solution to a 1000 μg/mL solution. The blank control was prepared with 0.5mL acetone and 4.5mL 0.1% Tween 80 solution.

将辣椒种子在水中浸泡1小时，放置于培养箱中，于25℃催芽24小时，种植于塑料盆钵中，每盆种植20粒种子，于25℃培养，生长至3叶期时喷施上述配制的溶液，每盆喷施2.5mL，设3次重复，24小时后针刺辣椒叶片，接种辣椒炭疽病菌Colletotrichum capsici的菌丝块，于25℃下培养3天，测量病斑长度，计算防治效果。 Soak pepper seeds in water for 1 hour, place them in an incubator, germinate them at 25°C for 24 hours, plant them in plastic pots, plant 20 seeds in each pot, cultivate them at 25°C, and spray the above-mentioned seeds when they grow to the 3-leaf stage The prepared solution was sprayed with 2.5mL per pot, and repeated 3 times. After 24 hours, the pepper leaves were needled, inoculated with the mycelium block of the pepper anthracnose pathogen Colletotrichum capsici, and cultured at 25°C for 3 days. The length of the lesion was measured, and the control method was calculated. Effect.

试验结果表明，在1000μg/mL浓度下，本发明的化合物K-2、K-3、N-31、N-35的防治效果为100％，H-10、H-14、K-1、N-11、N-16、N-18、N-20、N-22、N-23、N-25、N-26、N-28、N-29的防治效果在50.1-98.5％之间，对照药剂嘧菌酯为100％。 The test results show that, at a concentration of 1000 μg/mL, the control effect of compounds K-2, K-3, N-31, N-35 of the present invention is 100%, and H-10, H-14, K-1, N-35 -11, N-16, N-18, N-20, N-22, N-23, N-25, N-26, N-28, N-29 have control effects between 50.1-98.5%, compared with The drug azoxystrobin is 100%.

Claims (7)

1. Pyrrolidine-2, 4-dione compounds containing substituted phenylhydrazine of formula (I) or an agriculturally pharmaceutically acceptable salt thereof,
characterized in that it is selected from any one of the following compounds:
5-sec-butyl-3- (1- (2- (4-methylphenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-sec-butyl-3- (1- (2- (4-trifluoromethylphenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-sec-butyl-3- (1- (2- (3, 4-dimethylphenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-sec-butyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-sec-butyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-sec-butyl-3- (1- (2- (2, 4-dichlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-sec-butyl-3- (1- (2- (3, 4-dichlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-sec-butyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-sec-butyl-3- (1- (2- (3-bromophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-chlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-fluorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-bromophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 3- (1- (2- (2-fluorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 3- (1- (2- (3-chlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 3- (1- (2- (2, 4-dichlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-methylphenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-methoxyphenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 3- (1- (2- (3, 4-dimethylphenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-aminosulfonylphenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 4-dione, 5-methyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-isopropyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-isopropyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-isopropyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-butyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-isobutyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-isobutyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-isobutyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-hexyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-benzyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-benzyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-benzyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-isopropyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-isopropyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-isopropyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-sec-butyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-sec-butyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-sec-butyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-tert-butyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-tert-butyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-tert-butyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-phenyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 1-phenyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 1-phenyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 1- (4-methylphenyl) -3- (1- (2- (4-fluorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 1- (4-methylphenyl) -3- (1- (2- (4-chlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 1- (4-methylphenyl) -3- (1- (2- (4-bromophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 1- (4-chlorophenyl) -3- (1- (2- (4-fluorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 4-dione, 1- (4-chlorophenyl) -3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1- (4-chlorophenyl) -3- (1- (2- (4-bromophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-acetyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-methyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-methyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-methyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-methyl-3- (1- (2- (2-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-methyl-3- (1- (2- (3-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-methyl-3- (1- (2- (2, 4-dichlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-methyl-3- (1- (2- (4-methylphenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-methyl-3- (1- (2- (4-methoxyphenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-methyl-3- (1- (2- (3, 4-dimethylphenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-methyl-3- (1- (2- (4-aminosulfonylphenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-cyclohexane-3- (1- (2- (4-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-cyclopropylalkyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-cyclopropylalkyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1-benzyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-dimethyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-dimethyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-dimethyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-dimethyl-3- (1- (2- (2-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-dimethyl-3- (1- (2- (2-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-dimethyl-3- (1- (2- (3-chlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-dimethyl-3- (1- (2- (2, 4-dichlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-dimethyl-3- (1- (2- (4-methylphenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-dimethyl-3- (1- (2- (3, 4-dimethylphenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-dimethyl-3- (1- (2- (4-aminosulfonylphenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-ethyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-ethyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-ethyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-ethyl-3- (1- (2- (2-fluorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-ethyl-3- (1- (2- (3-chlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-ethyl-3- (1- (2- (2, 4-dichlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-ethyl-3- (1- (2- (4-methylphenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-ethyl-3- (1- (2- (3, 4-dimethylphenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-ethyl-3- (1- (2- (4-aminosulfonylphenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-benzyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-benzyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-benzyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-benzyl-3- (1- (2- (2-fluorophenyl) hydrazino) ethylene) pyrrolidine-2, 4-dione, 5-methyl-5-benzyl-3- (1- (2- (3-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-methyl-5-benzyl-3- (1- (2- (2, 4-dichlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-methyl-5-benzyl-3- (1- (2- (4-methylphenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-methyl-5-benzyl-3- (1- (2- (3, 4-dimethylphenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 5-methyl-5-benzyl-3- (1- (2- (4-aminosulfonylphenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1, 5-dimethyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1, 5-dimethyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1, 5-dimethyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1,5, 5-trimethyl-3- (1- (2- (4-fluorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1,5, 5-trimethyl-3- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 1,5, 5-trimethyl-3- (1- (2- (4-bromophenyl) hydrazino) ethylidene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-fluorophenyl) hydrazino) methylene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-chlorophenyl) hydrazino) methylene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-bromophenyl) hydrazino) methylene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-fluorophenyl) hydrazino) propylidene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-chlorophenyl) hydrazino) propylidene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-bromophenyl) hydrazino) propylidene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-fluorophenyl) hydrazino) butylidene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-chlorophenyl) hydrazino) butylidene) pyrrolidine-2, 4-dione, 3- (1- (2- (4-bromophenyl) hydrazino) butylidene) pyrrolidine-2, 4-dione.
2. A composition comprising at least one substituted phenylhydrazine-containing pyrrolidine-2, 4-dione compound according to claim 1 or an agriculturally pharmaceutically acceptable salt thereof.
3. The use of pyrrolidine-2, 4-diones containing substituted phenylhydrazine according to claim 1 or of an agriculturally acceptable salt thereof for controlling harmful fungi in plants.
4. The use according to claim 3, characterized in that the substituted phenylhydrazine-containing pyrrolidine-2, 4-dione compound according to claim 1 or an agriculturally pharmaceutically acceptable salt thereof is used for controlling fungal diseases of wheat crops, rice crops, cotton crops, oil crops, coarse cereal crops, tobacco crops, fruit crops and vegetables.
5. Use of the composition according to claim 2 for controlling plant-harmful fungi.
6. The use according to claim 5, characterized in that the composition according to claim 2 is used for controlling fungal diseases of wheat crops, rice crops, cotton crops, oil crops, coarse cereal crops, tobacco crops, fruit crops and vegetables.
7. A method for controlling phytopathogenic fungi, characterized in that substituted phenylhydrazine-containing pyrrolidine-2, 4-diones according to claim 1 or an agriculturally acceptable salt thereof is applied to the fungi and their habitat.
CN201110453110.XA 2011-12-30 2011-12-30 Pyrrolidine-2,4-dione compound comprising substituted phenylhydrazine, and preparation method and application thereof Expired - Fee Related CN103183628B (en)

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