JPH05105672A - Isoxazoline derivative, its production and agricultural and horticultural germicide - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as an agricultural and horticultural germicide, especially against downy mildew of grape, late blight of tomato and blast of rice plant. CONSTITUTION:A compound expressed by formula I [R<1> is H, 1-6C alkyl or 1-6C alkoxy; (n) is 0-2; A is 1-6C alkyl, 3-6C cycloalkyl, 2-6C alkenyl, etc., substitutive with (substituted)phenyll, e.g. 3-(4-bromophenylthio)-5-cyano-2- isoxazoline. The compound expressed by formula I is obtained by reacting a compound expressed by formula II (X is halogen) with a mercaptan derivative expressed by the formula AaSH (Aa is 1-6C alkyl, 3-6C cycloalkyl, 6-membered aromatic heterocyclic ring, etc.). The compound expressed by formula II is obtained by reacting an acrylonitrile derivative expressed by formula III with an oxime derivative expressed by formula IV.

Description

Detailed Description of the Invention

[0001]

[Object of the Invention]

[0002]

TECHNICAL FIELD The present invention relates to a novel isoxazoline derivative having excellent bactericidal activity, an agricultural and horticultural fungicide containing the isoxazoline derivative, and a method for producing the isoxazoline derivative.

[0003]

2. Description of the Related Art A compound having a phenylsulfonyl group at the 3-position of an isoxazoline ring (bretin of
The Chemical Society of Japan, 57
Vol. 2531, 1975), but has a benzyl group at the 5-position, which is different from the compound of the present invention. Further, the document does not describe any agro-horticultural fungicide activity of these compounds.

[0004]

The object of the present invention is tomato late blight (Phytophtora infestans), which often causes serious damage to agricultural and horticultural crops among mold diseases of plants.
The aim is to develop a new fungicide capable of controlling a downy mildew (Plasmopara viticola) and a rice blast (Piricularia oryzae) with a low dose.

[0005]

[Constitution of the invention]

[0006]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have conducted diligent research and found that the novel isoxazoline derivative effectively controls the mold disease of the above plants. .. That is, the present invention provides (1) the general formula

[0007]

[Chemical 15]

It is to provide a compound represented by:

[Wherein R ¹ represents a hydrogen atom; a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkoxy group, n is 0,
1 or 2, A is a C ₁ -C ₆ alkyl group; C ₃
-C ₆ cycloalkyl group; selected from the substituent group A the following group wherein the same or different 1 to 3 of a substituent may be substituted in a phenyl group C ₂ -C ₆ alkenyl group A C ₂ -C ₆ alkynyl group selected from the following substituent group A and optionally substituted with a phenyl group which may have the same or different 1 to 3 substituents; Group B, selected from the same or different 1 to 6
Aralkyl groups which may have 4 substituents (the substituents are the same or differently substituted with an alkylene moiety or an aryl moiety); the same or different substituents selected from the following substituent group C group An aryl group which may have 1 to 5 substituents; 1 nitrogen atom which may be selected from the following substituent group A group and which may have the same or different 1 to 3 substituents
Alternatively, a 6-membered aromatic heterocyclic group containing two is shown. ] The isoxazoline derivative represented by these.

[Substituent group A] Halogen atom; C ₁ -C ₄ alkyl group; C ₁ -C ₄ alkoxy group [Substituent group B] Halogen atom; C ₁ -C ₂ halogenated alkyl group; C ₁
-C ₄ alkyl radical; C ₂ -C ₅ alkanoyloxy group;
C ₁ -C ₄ alkoxy group, a hydroxyl group, a cyano group [substituent group C] a halogen atom; C ₁ -C ₂ halogenated alkyl group; C ₁
-C ₄ alkyl radical; C ₂ -C ₅ alkanoylamino group;
Selected from the substituent group A group described above; C ₁ -C ₄ alkylsulfonyl group; C ₁ -C ₄ alkylthio group; C ₁ -C ₄ alkoxy groups; C ₂ -C ₅ alkoxycarbonyl group; a cyano group; a nitro group A benzyl group which may have 1 to 3 substituents which are the same or different on the ring; which has 1 to 3 substituents which are the same or different and which are selected from the above-mentioned substituent group A group Good phenoxy group (2) The present invention also provides an agricultural and horticultural fungicide containing an isoxazoline derivative having the above formula (I) as an active ingredient.

(3) The present invention also has the general formula

[0012]

[Chemical 16]

(Wherein R ¹ is as defined above, X is a halogen atom).

(3) The present invention also provides _a process for producing the isoxazoline intermediate (II) of the above formula (I) and the formula (I _a ),
It is an object of the present invention to provide a method for producing an isoxazoline derivative having the formula ( _Ib ), the formula ( _Ic1 ) and the formula ( _Ic2 ). That is, (3-1) general formula

[0015]

[Chemical 17]

(Wherein R ¹ is the same as above) and an acrylonitrile derivative represented by the general formula

[0017]

[Chemical 18]

[Wherein X is a halogen atom] a general formula characterized by reacting with an oxime derivative

[0019]

[Chemical 19]

A process for producing an isoxazoline derivative represented by the formula (wherein R ¹ and X are the same as above).

(3-2) General formula

[0022]

[Chemical 20]

(Wherein A _a is the same as above) and a mercaptan derivative represented by the general formula

[0024]

[Chemical 21]

(Wherein X is a halogen atom) a general formula characterized by reacting with an isoxazoline derivative

[0026]

[Chemical formula 22]

(In the formula, R ¹ and A _a are the same as above.)
The manufacturing method of the isoxazoline derivative shown by these.

(3-3) General formula

[0029]

[Chemical formula 23]

(Wherein R ¹ is the same as above) and an acrylonitrile derivative represented by the general formula

[0031]

[Chemical formula 24]

(Wherein A _b is the same as A _a above) and a mercapto oxime derivative represented by the formula is reacted.

[0033]

[Chemical 25]

(In the formula, R ¹ and A _b are the same as above.)
The manufacturing method of the isoxazoline derivative shown by these.

(3-4) General formula

[0036]

[Chemical formula 26]

(Wherein R ¹ and A are the same as above), the isoxazoline derivative is treated with an oxidizing agent to give a compound of the general formula

[0038]

[Chemical 27]

(Wherein R ¹ and A are the same as above) or the general formula

[0040]

[Chemical 28]

A process for producing an isoxazoline derivative represented by the formula (wherein R ¹ and A are the same as above).

It relates to

The present invention will be described in detail below.

In the above general formula (I), when R ¹ and A are C ₁ -C ₆ alkyl groups, they are linear or branched alkyl groups having 1 to 6 carbon atoms, for example, Methyl, ethyl, propyl, i-propyl, butyl, i-
Butyl, s-butyl, t-butyl, pentyl, i-pentyl, neo-pentyl, hexyl or i-hexyl.

In the above general formula (I), R ¹ is C _1-
When it is a C ₆ alkoxy group, it represents a linear or branched alkoxy group having 1 to 6 carbon atoms, and examples thereof include methoxy, ethoxy, propoxy, i-propoxy, butoxy, i-butoxy and sec-butoxy. , T-butoxy, pentoxy, i-pentoxy, neo-pentoxy, hexyloxy or i-hexyloxy.

In the above general formula (I), A is C ₃ -C
When it is a _6- cycloalkyl group, it represents a cycloalkyl group having 3 to 6 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

In the above general formula (I), A is selected from the group A of substituent groups, and C ₂ -C may be substituted with a phenyl group which may have the same or different 1 to 3 substituents.
₆ alkenyl C ₂ -C ₆ alkenyl group when a group of 2 to 6 carbon atoms straight chain or branched C ₂ -C ₆
An alkenyl group, for example, vinyl, 2-propenyl (allyl), 2-butenyl, 2-methyl-2-butenyl, 2-pentenyl group, and 2-hexenyl.

[0048] In the above general formula (I), A is selected from the substituent group A group the same or different 1 to 3 optionally C ₂ -C be substituted with also a phenyl group having a substituent
₆ alkynyl C ₂ -C ₆ alkynyl group when a group of 2 to 6 carbon atoms straight chain or branched C ₂ -C ₆
An alkynyl group, for example, propargyl, 2-butynyl, 2-pentynyl, 2-hexynyl.

In the above general formula (I), when A is an aralkyl group which is selected from the substituent group B and may have the same or different 1 to 6 substituents, the aralkyl group is a methyl group, An aralkyl group in which a linear alkyl group having 1 to 3 carbon atoms such as an ethyl group or a propyl group is substituted with an aryl group such as a phenyl group or a naphthyl group,
For example, benzyl, phenylethyl, phenylpropyl, naphthylmethyl. In the above general formula (I), A is selected from the substituent group C and is the same or different 1
The aryl group, which is an aryl group which may have 5 to 5 substituents, is an aryl group having 6 to 10 carbon atoms, and is, for example, phenyl or naphthyl.

In the above general formula (I), an aromatic heterocyclic group in which A is an aromatic heterocyclic group selected from the group A of substituents and optionally having the same or different 1 to 3 substituents The cyclic group is a 6-membered aromatic heterocyclic group containing 1 or 2 nitrogen atoms, for example, 2-, 3-, 4-pyridyl, 2
-Pyrimidyl, 2-pyridazyl or 2-pyrazyl.

[0051] In the above formula (I), A is a substituted selected from group A group the same or different 1 to 3 of a substituent may be substituted in a phenyl group C ₂ -
A group A substituent when it is a C ₆ alkenyl group is, for example, a halogen atom such as fluorine, chlorine, bromine or iodine, for example, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, s-butyl, a linear or branched alkyl group having 1 to 4 carbon atoms such as t-butyl, or, for example, methoxy, ethoxy, propoxy, i-propoxy, butoxy, i-butoxy, sec-butoxy, t-
It is a linear or branched alkoxy group having 1 to 4 carbon atoms such as butoxy.

In the above general formula (I), A is selected from the group A of substituent groups, and C ₂ -C which may be substituted with a phenyl group which may have the same or different 1 to 3 substituents.
When it is a ₆ alkynyl group, the group A substituent is the above-mentioned C _2-
It is the same as those exemplified for the substituent group A in the case where the phenyl group substituted on the C ₆ alkenyl group further has a substituent.

In the above general formula (I), when A is an aralkyl group which is selected from the substituent group B and may have the same or different 1 to 6 substituents, the group B substituent is A halogen atom such as fluorine, chlorine, bromine or iodine; a halogenated alkyl group having 1 or 2 carbon atoms such as trifluoromethyl, trichloromethyl, tribromomethyl, trichloroethyl, trifluoroethyl; For example, methyl, ethyl, propyl, i-
A linear or branched alkyl group having 1 to 4 carbon atoms such as propyl, butyl, i-butyl, s-butyl, t-butyl; for example, acetoxy, propionyloxy,
Butyryloxy, i- butyryloxy, Valerio oxy, i- Valerio oxy, C ₂ -C ₅ alkanoyloxy group such as pivaloyloxy; for example, methoxy,
Ethoxy, propoxy, i-propoxy, butoxy, i
-A straight or branched chain alkoxy group having 1 to 4 carbon atoms such as butoxy, sec-butoxy, t-butoxy;
Hydroxyl group: a cyano group, and when these substituents are present, they are substituted with an alkylene group or an aryl group in the aralkyl group.

In the above general formula (I), when A is an aryl group which is selected from the substituent group C and may have the same or different 1 to 5 substituents, the group C substituent is For example, a halogen atom such as fluorine, chlorine, bromine or iodine; for example, a halogenated alkyl group having 1 or 2 carbon atoms such as trifluoromethyl, trichloromethyl, tribromomethyl, trichloroethyl, trifluoroethyl; , Methyl, ethyl, propyl, i-propyl, butyl, i-butyl, s-butyl, t-butyl, straight-chain or branched alkyl groups having 1 to 4 carbon atoms; acetylamino, propionylamino , Butyrylamino, i-butyrylamino, valerylamino, i-
2 carbon atoms such as valerylamino and pivaloylamino
To 5 straight or branched chain alkanoylamino groups; for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, i-propylsulfonyl, butylsulfonyl, i-butylsulfonyl, s-butylsulfonyl, t-butylsulfonyl. A linear or branched alkylsulfonyl group having 1 to 4 carbon atoms;
Methylthio, ethylthio, propylthio, i-propylthio, butylthio, i-butylthio, s-butylthio,
a linear or branched alkylthio group having 1 to 4 carbon atoms such as t-butylthio; for example, methoxy, ethoxy, propoxy, i-propoxy, butoxy, i-butoxy, sec-butoxy, t-butoxy Such carbon number 1
To 4 straight or branched chain alkoxy groups; such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, i-propoxycarbonyl, butoxycarbonyl, i-butoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl. Carbon number 2
To 5 linear or branched alkoxycarbonyl groups; cyano group; nitro group; selected from the group A of substituent groups, and may have 1 to 3 substituents which are the same or different from each other on the ring. Benzyl group: a phenoxy group selected from Substituent Group A and having the same or different 1 to 3 substituents.

In the above general formula (I), when A is an aryl group which is selected from the substituent group C and may have the same or different 1 to 5 substituents, the group C substituent is benzyl. When the benzyl group further has 1 to 3 substituents which are the same or different on the ring, the substituent is, for example, a halogen atom such as fluorine, chlorine, bromine or iodine; , Methyl, ethyl, propyl,
i-propyl, butyl, i-butyl, s-butyl, t-
A linear or branched alkyl group having 1 to 4 carbon atoms such as butyl; for example, methoxy, ethoxy, propoxy, i-propoxy, butoxy, i-butoxy, sec-
It is a linear or branched alkoxy group having 1 to 4 carbon atoms such as butoxy and t-butoxy.

In the above general formula (I), when A is an aryl group which is selected from the substituent group C and may have the same or different 1 to 5 substituents, the group C substituent is A phenoxy group, and when the phenoxy group further has the same or different 1 to 3 substituents on the ring, the substituent is, for example, a halogen atom such as fluorine, chlorine, bromine or iodine; For example, a linear or branched alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, i-propyl, butyl, i-butyl, s-butyl, t-butyl; for example, methoxy, Ethoxy,
It is a linear or branched alkoxy group having 1 to 4 carbon atoms such as propoxy, i-propoxy, butoxy, i-butoxy, sec-butoxy and t-butoxy.

In the above general formula (I), A is a 6-membered fragrance selected from the group A of substituents and containing 1 or 2 nitrogen atoms which may have the same or different 1 to 3 substituents. The group A substituent when it is a group heterocyclic group is the above C ₂ -C
₆ It is the same as those exemplified for the substituent group A group when the phenyl group substituted on the ₆ alkenyl group further has a substituent.

Further preferred compounds in the above general formula (I) are (1) R ¹ is 1. A compound which is a hydrogen atom, 2. 3. A linear or branched alkyl group having 1 to 3 carbon atoms, for example, a compound such as methyl, ethyl, propyl or i-propyl, 3. A straight chain or branched chain alkoxy group having 1 to 3 carbon atoms, for example, methoxy, ethoxy, propoxy, i-
Compounds such as propoxy, (2) compounds where n is 2, (3) A is 1. Halogen atom such as fluorine, chlorine, bromine; alkyl group having 1 or 4 carbon atoms such as methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl, tert-butyl; methoxy, ethoxy An alkoxy group having 1 or 2 carbon atoms such as; a halogenated alkyl group having 1 carbon atom such as trifluoromethyl; a nitro group; 1 to 3 substituents such as a cyano group which are the same or different. Optionally a phenyl, an aryl group such as naphthyl,
For example, phenyl, 2-, 3-, 4-fluorophenyl, 3,4-dichlorophenyl, 3-fluoro-4-chlorophenyl, 2,4,6-tribromophenyl, 2
-, 3-, 4-methylphenyl, 4-methylthiophenyl, 2-, 3-, 4-methoxyphenyl, 3-trifluoromethylphenyl, 4-nitrophenyl, 4-cyanophenyl, 3-trifluoromethyl-4 -Fluorophenyl, 1-naphthyl, 2-naphthyl, 4-bromo-1-
Compounds such as naphthyl, 1-bromo-2-naphthyl, 2. Halogen atom such as fluorine, chlorine and bromine; alkyl group having 1 or 2 carbon atoms such as methyl and ethyl;
Acetoxy group; alkoxy group having 1 or 2 carbon atoms such as methoxy and ethoxy; halogenated alkyl group having 1 carbon atom such as trifluoromethyl; nitro group; alkylene group or aryl moiety having substitution such as cyano group An aralkyl group such as benzyl and 2-phenethyl which may be the same or different and may be substituted by 1 to 3 groups, for example, benzyl, 2-, 3-, 4-fluorobenzyl, 3,4-
Dichlorobenzyl, 3,5-dibromobenzyl, 2-,
3-, 4-methylbenzyl, 2-, 3-, 4-methoxybenzyl, 3-trifluoromethylbenzyl, 4-nitrobenzyl, α-acetoxy-2-bromobenzyl, α
-Compounds such as cyano-2-bromobenzyl, 3-trifluoromethylbenzyl, 2-phenethyl, 3. 4. A linear or branched alkyl group having 1 to 4 carbon atoms, for example, a compound such as methyl, ethyl, propyl, i-propyl, butyl, i-butyl, s-butyl or t-butyl, 4. Halogen atom such as fluorine, chlorine, bromine; Nitrogen in which substituents such as alkyl group having 1 or 2 carbon atoms such as methyl and ethyl may be the same or different and may be substituted by 1 or 2 2-3 containing 1 or 2 atoms
6-membered aromatic heterocyclic group such as-, 4-pyridyl or 2-pyrimidyl, for example, 2-, 3-, 4-pyridyl,
Or a compound such as 2-pyrimidyl or 4,6-dimethyl-2-pyrimidyl.

Specific examples of the compounds represented by formula (I) are shown in Table 1.

[0060]

[Table 1]

[0061]

[Chemical 29]

───────────────────────────────── Compound No. No R ¹ n A A Substituent * 1 ─ ──────────────────────────────── 1H 0 Me 2 H 0 Et 3 H 0 Vi 2-Ph 4 H 0 Pr 5 H 0 i Pr 6 H 0 c Pr 7 H 0 All 8 H 0 Prg 9 H 0 Prg 3-Ph 10 H 0 Bu 11 H 0 i Bu 12 H 0 s Bu 13 H 0 t Bu 14 H 0 c Bu 15 H 0 2-Bun 16 H 0 2-Butn 17 H 0 Pn 18 H 0 i Pn 19 H 0 n Pn 20 H 0 c Pn 21 H 0 2-Pen 22 H 0 2-Pntn 23 H 0 Hx 24 H 0 i Hx 25 H 0 c Hx 26 H 0 2-Hex 27 H 0 2-Hexn 28 H 0 Ph 29 H 0 Ph 2-Me 30 H 0 Ph 3-Me 31 H 0 Ph 4-Me 32 H 0 Ph 3- Et 33 H 0 Ph 4-Et 34 H 0 Ph 3- i Pr 35 H 0 Ph 4- i Pr 36 H 0 Ph 3- s Bu 37 H 0 Ph 4- s Bu 38 H 0 Ph 3- t Bu 39 H 0 Ph 4- t B u 40 H 0 Ph 2-OMe 41 H 0 Ph 3-OMe 42 H 0 Ph 4-OMe 43 H 0 Ph 3,4- (OMe) ₂ 44 H 0 Ph 3, 5- (OMe) ₂ 45 H 0 Ph 4-OEt 46 H 0 Ph 4-OPr 47 H 0 Ph 4-OPh 48 H 0 Ph 2-Bz 49 H 0 Ph 3-NHAc 50 H 0 Ph 4-NHAc 51 H 0 Ph 3-CN 52 H 0 Ph 4 -CN 53 H 0 Ph 3-NO ₂ 54 H 0 Ph 4-NO ₂ 55 H 0 Ph 2-CF ₃ 56 H 0 Ph 3-CF ₃ 57 H 0 Ph 4-CF ₃ 58 H 0 Ph 3-SMe 59 H 0 Ph 4-SMe 60 H 0 Ph 2-Br 61 H 0 Ph 3-Br 62 H 0 Ph 4-Br 63 H 0 Ph 2-Cl 64 H 0 Ph 3-Cl 65 H 0 Ph 4-Cl 66 H 0 Ph 2-F 67 H 0 Ph 3-F 68 H 0 Ph 4-F 69 H 0 Ph 2, 4-F ₂ 70 H 0 Ph 3, 4-F ₂ 71 H 0 Ph 3, 5-F ₂ 72 H 0 Ph 2-CO ₂ Me 73 H 0 Ph 3-CO ₂ Me 74 H 0 Ph 4-CO ₂ Me 75 H 0 Ph 2-CO ₂ Et 76 H 0 Ph 3-CO ₂ Et 77 H 0 Ph 4- CO ₂ Et 78 H 0 Ph _2, 3- (Me) ₂ 79 H 0 Ph 3, 4- (Me) ₂ 80 H 0 Ph 3, 5- (Me) ₂ 81 H 0 Ph 2-Me, 4-NO ₂ 82 H 0 Ph 3-Me, 4-Br 83 H 0 Ph 2-Me, 4-Cl 84 H 0 Ph 2-Me, 5-Cl 85 H 0 Ph 3-F, 4-Me 86 H 0 Ph 2- F, 5-Me 87 H 0 Ph ₂ , 5- (Br) ₂ 88 H 0 Ph 3, 4- (Br) ₂ 89 H 0 Ph 3, 5- (Br) ₂ 90 H 0 Ph _2, 4- ( Br) ₂ 91 H 0 Ph _{2, 4,} 6- (Br) ₃ 92 H 0 Ph _2, 4- (Cl) ₂ 93 H 0 Ph _2, 5- (Cl) ₂ 94 H 0 Ph _2, 6- ( Cl) ₂ 95 H 0 Ph 3, 4- (Cl) ₂ 96 H 0 Ph 3, 5- (Cl) ₂ 97 H 0 Ph 2, 4, 6- (Cl) ₃ 98 H 0 Ph 2-Cl, 4 -Br 99 H 0 Ph 2-F, 4-Br 100 H 0 Ph 3-Cl, 4-F 101 H 0 Ph 2-F, 4-Cl 102 H 0 Ph 2-CF ₃ , 4-Br 103 H 0 Ph 3-CF ₃ , 4-Br 104 H 0 Ph 3-CF ₃ , 4-F 105 H 0 Ph 3-Cl, 4-NO ₂ 106 H 0 Ph 3-Cl, 4-Me 107 H 0 Ph 3- NO ₂ , 4-Cl 108 H 0 Ph 3-Me, 5-Cl 109 H 0 Ph 3-Cl, 4-OMe 110 H 0 1-Np 111 H 0 1-Np 4-Br 112 H 0 2-Np 113 H 0 2-Np 4-Br 114 H 0 Bz 115 H 0 Bz 2-Me 116 H Bz 3-Me 117 H 0 Bz 4-Me 118 H 0 Bz 3,4- (Me) 2 119 H 0 Bz 3,5- (Me) 2 120 H 0 Bz 4-Et 121 H 0 Bz 2-F 122 H 0 Bz 3-F 123 H 0 Bz 4-F 124 H 0 Bz 2-Br 125 H 0 Bz 3-Br 126 H 0 Bz 4-Br 127 H 0 Bz _2, 4- (Br) ₂ 128 H 0 Bz 3, 4- (Br) ₂ 129 H 0 Bz 3, 5- (Br) ₂ 130 H 0 Bz 2-Cl 131 H 0 Bz 3-Cl 132 H 0 Bz 4-Cl 133 H 0 Bz 2-OMe 134 H 0 Bz 3-OMe 135 H 0 Bz 4-OMe 136 H 0 Bz 3, 4- (OMe) ₂ 137 H 0 Bz 4-OEt 138 H 0 Bz 4-OPr 139 H 0 Bz 3-CF ₃ 140 H 0 Bz 4-CF ₃ 141 H 0 Bz 2-Br, α-OAc 142 H 0 Bz 2-Br, α-CN 143 H 0 2-Pyr 144 H 0 2-Pyr 5-Cl 145 H 0 2-Pyr 5-Br 146 H 0 2-Pyr 6-Me 147 H 0 2-Pyr 5-CF ₃ 148 H 0 3-Pyr 149 H 0 4-Pyr 150 H 0 2-Pym 151 H 0 2-Pym 4-Me 152 H 0 2 -Pym 4, 6- (Me) ₂ 153 H 0 3-Pyzn 154 H 0 3-Pyzn 4, 5- (Me) ₂ 155 H 0 2-Pyz 3-Me 156 H 0 2-Pyz 3, 5-Cl ₂ 157 H 0 Phety 158 H 0 Phety 4-Cl 159 H 0 Phety α , Β- (OH) ₂ 160 H 0 Phety α, β- (OAc) ₂ 161 H 1 Ph 162 H 1 Ph 2-Br 163 H 1 Ph 3-Br 164 H 1 Ph ₂ , 4- (Cl) ₂ 165 H 1 Ph 2, 4, 6- (Br) ₃ 166 H 1 Bz 2-Br 167 H 1 Bz 3-Br 168 H 1 Bz 2-Br, α-CN 169 H 2 Me 170 H 2 Et 171 H 2 Vi 2-Ph 172 H 2 Pr 173 H 2 i Pr 174 H 2 c Pr 175 H 2 All 176 H 2 Prg 177 H 2 Prg 3-Ph 178 H 2 Bu 179 H 2 i Bu 180 H 2 s Bu 181 H 2 t Bu 182 H 2 c Bu 183 H 2 2-Bun 184 H 2 2-Butn 185 H 2 Pn 186 H 2 i Pn 187 H 2 n Pn 188 H 2 c Pn 189 H 2 2-Pen 190 H 2 2-Pntn 191 H 2 Hx 192 H 2 i Hx 193 H 2 c Hx 194 H 2 2-Hex 195 H 2 2-Hexn 96 H 2 Ph 197 H 2 Ph 2-Me 198 H 2 Ph 3-Me 199 H 2 Ph 4-Me 200 H 2 Ph 3-Et 201 H 2 Ph 4-Et 202 H 2 Ph 3- i Pr 203 H 2 Ph 4- i Pr 204 H 2 Ph 3- s Bu 205 H 2 Ph 4- s Bu 206 H 2 Ph 3- t Bu 207 H 2 Ph 4- t Bu 208 H 2 Ph 2-OMe 209 H 2 Ph 3- OMe 210 H 2 Ph 4-OMe 211 H 2 Ph 3, 4- (OMe) ₂ 212 H 2 Ph 3, 5- (OMe) ₂ 213 H 2 Ph 4-OEt 214 H 2 Ph 4-OPr 215 H 2 Ph 4-OPh 216 H 2 Ph 2-Bz 217 H 2 Ph 3-NHAc 218 H 2 Ph 4-NHAc 219 H 2 Ph 3-CN 220 H 2 Ph 4-CN 221 H 2 Ph 3-NO ₂ 222 H 2 Ph 4-NO ₂ 223 H 2 Ph 2-CF ₃ 224 H 2 Ph 3-CF ₃ 225 H 2 Ph 4-CF ₃ 226 H 2 Ph 3-SO ₂ Me 227 H 2 Ph 4-SO ₂ Me 228 H 2 Ph 2-Br 229 H 2 Ph 3-Br 230 H 2 Ph 4-Br 231 H 2 Ph 2-Cl 232 H 2 Ph 3-Cl 233 H 2 Ph 4-Cl 234 H 2 Ph 2-F 23 5 H 2 Ph 3-F 236 H 2 Ph 4-F 237 H 2 Ph 2, 4-F ₂ 238 H 2 Ph 3, 4-F ₂ 239 H 2 Ph 3, 5-F ₂ 240 H 2 Ph 2- CO ₂ Me 241 H 2 Ph 3-CO ₂ Me 242 H 2 Ph 4-CO ₂ Me 243 H 2 Ph 2-CO ₂ Et 244 H 2 Ph 3-CO ₂ Et 245 H 2 Ph 4-CO ₂ Et 246 H 2 Ph 2, 3- (Me) ₂ 247 H 2 Ph 3, 4- (Me) ₂ 248 H 2 Ph 3, 5- (Me) ₂ 249 H 2 Ph 2-Me, 4-NO ₂ 250 H 2 Ph 3-Me, 4-Br 251 H 2 Ph 2-Me, 4-Cl 252 H 2 Ph 2-Me, 5-Cl 253 H 2 Ph 3-F, 4-Me 254 H 2 Ph 2-F, 5- Me 255 H 2 Ph 2, 5- (Br) ₂ 256 H 2 Ph 3, 4- (Br) ₂ 257 H 2 Ph 3, 5- (Br) ₂ 258 H 2 Ph 2, 4- (Br) ₂ 259 _{H 2 Ph 2,4,6- (Br) 3} 260 H 2 Ph 2,4- (Cl) 2 261 H 2 Ph 2,5- (Cl) 2 262 H 2 Ph 2,6- (Cl) 2 263 H 2 Ph 3, 4- (Cl) ₂ 264 H 2 Ph 3, 5- (Cl) ₂ 265 H 2 Ph 2, 4, 6- (Cl) ₃ 266 H 2 Ph 2-Cl, 4-Br 267 H 2 Ph 2-F, 4-Br 268 H 2 Ph 3-Cl, 4-F 269 H 2 Ph 2-F, 4-Cl 270 H 2 Ph 2-CF ₃ , 4-Br 271 H 2 Ph 3-CF ₃ , 4-Br 272 H 2 Ph 3-CF ₃ , 4-F 273 H 2 Ph 3-Cl, 4-NO ₂ 274 H 2 Ph 3-Cl, 4-OMe 275 H 2 Ph 3-Cl, 4-Me 276 H 2 Ph 3-NO ₂ , 4-Cl 277 H 2 Ph 3-Me, 5-Cl 278 H 2 2-Pyr 279 H 2 2-Pyr 5-Cl 280 H 2 2-Pyr 5-Br 281 H 2 2 -Pyr 6-Me 282 H 2 2-Pyr 5-CF ₃ 283 H 2 3-Pyr 284 H 2 4-Pyr 285 H 2 2-Pym 286 H 2 2-Pym 4-Me 287 H 2 2-Pym 4, 6- (Me) ₂ 288 H 2 3-Pyzn 289 H 2 3-Pyzn 4, 5- (Me) ₂ 290 H 2 2-Pyz 3-Me 291 H 2 2-Pyz 3, 5-Cl ₂ 292 H 2 1-Np 293 H 2 1-Np 4-Br 294 H 2 2-Np 295 H 2 2-Np 4-Br 296 H 2 Bz 297 H 2 Bz 2-Me 298 H 2 Bz 3-Me 299 H 2 Bz 4 -Me 300 H 2 Bz 3,4- (Me ) 2 301 H 2 Bz 3,5- (Me) 2 302 H 2 Bz 4-Et 303 H Bz 2-F 304 H 2 Bz 3-F 305 H 2 Bz 4-F 306 H 2 Bz 2-Br 307 H 2 Bz 3-Br 308 H 2 Bz 4-Br 309 H 2 Bz 2,4-Br 2 310 H 2 Bz 3, 4-Br ₂ 311 H 2 Bz 3, 5-Br ₂ 312 H 2 Bz 2-Cl 313 H 2 Bz 3-Cl 314 H 2 Bz 4-Cl 315 H 2 Bz 2-OMe 316 H 2 Bz 3-OMe 317 H 2 Bz 4-OMe 318 H 2 Bz 3, 4- (OMe) ₂ 319 H 2 Bz 4-OEt 320 H 2 Bz 4-OPr 321 H 2 Bz 3-CF ₃ 322 H 2 Bz 4 -CF ₃ 323 H 2 Bz 2-Br, α-OAc 324 H 2 Bz 2-Br, α-CN 325 H 2 Phety 326 H 2 Phety 4-Cl 327 H 2 Phety α, β- (OH) ₂ 328 H 2 Phety α, β- (OAc) ₂ 329 Me 0 Me 330 Me 0 Et 331 Me 0 Vi 2-Ph 332 Me 0 Pr 333 Me 0 i Pr 334 Me 0 c Pr 335 Me 0 All 336 Me 0 Prg 337 Me 0 Prg 2-Ph 338 Me 0 Bu 339 Me 0 i Bu 340 Me 0 s Bu 341 Me 0 c Bu 342 Me 0 2-Bun 43 Me 0 2-Butn 344 Me 0 Pn 345 Me 0 i Pn 346 Me 0 n Pn 347 Me 0 c Pn 348 Me 0 2-Pen 349 Me 0 2-Pntn 350 Me 0 Hx 351 Me 0 i Hx 352 Me 0 c Hx 353 Me 0 2-Hex 354 Me 0 2-Hexn 355 Me 0 Ph 356 Me 0 Ph 2-Me 357 Me 0 Ph 3-Me 358 Me 0 Ph 4-Me 359 Me 0 Ph 3-Et 360 Me 0 Ph 4 -Et 361 Me 0 Ph 3- i Pr 362 Me 0 Ph 4- i Pr 363 Me 0 Ph 3- s Bu 364 Me 0 Ph 4- s Bu 365 Me 0 Ph 3- t Bu 366 Me 0 Ph 4- t Bu 367 Me 0 Ph 2-OMe 368 Me 0 Ph 3-OMe 369 Me 0 Ph 4-OMe 370 Me 0 Ph 3, 4- (OMe) ₂ 371 Me 0 Ph 3, 5- (OMe) ₂ 372 Me 0 Ph 4 -OEt 373 Me 0 Ph 4-OPr 374 Me 0 Ph 4-OPh 375 Me 0 Ph 2-Bz 376 Me 0 Ph 3-NHAc 377 Me 0 Ph 4-NHAc 378 Me 0 Ph 3-CN 379 Me 0 Ph 4- CN 380 Me 0 Ph 3-NO 2 381 Me 0 Ph 4-NO 2 382 Me _{Ph 2-CF 3 383 Me 0} Ph 3-CF 3 384 Me 0 Ph 4-CF 3 385 Me 0 Ph 3-SMe 386 Me 0 Ph 4-SMe 387 Me 0 Ph 2-Br 388 Me 0 Ph 3-Br 389 Me 0 Ph 4-Br 390 Me 0 Ph 2-Cl 391 Me 0 Ph 3-Cl 392 Me 0 Ph 4-Cl 393 Me 0 Ph 2-F 394 Me 0 Ph 3-F 395 Me 0 Ph 4-F 396 Me 0 Ph 2, 4-F ₂ 397 Me 0 Ph 3, 4-F ₂ 398 Me 0 Ph 3, 5-F ₂ 399 Me 0 Ph 2-CO ₂ Me 400 Me 0 Ph 3-CO ₂ Me 401 Me 0 Ph 4-CO ₂ Me 402 Me 0 Ph 2-CO ₂ Et 403 Me 0 Ph 3-CO ₂ Et 404 Me 0 Ph 4-CO ₂ Et 405 Me 0 Ph ₂ , 3- (Me) ₂ 406 Me 0 Ph 3, _{4- (Me) 2 407 Me 0} Ph 3,5- (Me) 2 408 Me 0 Ph 2-Me, 4-NO 2 409 Me 0 Ph 3-Me, 4-Br 410 Me 0 Ph 2-Me, 5 -Cl 411 Me 0 Ph 3-Cl, 4-OMe 412 Me 0 Ph 2-F, 5-Me 413 Me 0 Ph 2-Me, 4-Cl 414 Me 0 Ph 3-F, 4-Me 415 Me 0 Ph 2-Cl, 4-Br 416 Me 0 Ph 2-F, 4-Br 17 Me 0 Ph 3-Cl, 4-F 418 Me 0 Ph 2-F, 4-Cl 419 Me 0 Ph 2,4- (Br) 2 420 Me 0 Ph 2,5- (Br) 2 421 Me 0 Ph 3, 4- (Br) ₂ 422 Me 0 Ph 3, 5- (Br) ₂ 423 Me 0 Ph _{2, 4,} 6- (Br) ₃ 424 Me 0 Ph _3, 4- (Cl) ₂ 425 Me 0 Ph _2, 4- (Cl) ₂ 426 Me 0 Ph _2, 5- (Cl) ₂ 427 Me 0 Ph _2, 6- (Cl) ₂ 428 Me 0 Ph 3, 5- (Cl) ₂ 429 Me 0 Ph 2, 4, 6- (Cl) ₃ 430 Me 0 Ph 2-CF ₃ , 4-Br 431 Me 0 Ph 3-CF ₃ , 4-Br 432 Me 0 Ph 3-CF ₃ , 4-F 433 Me 0 Ph 3- Cl, 4-Me 434 Me 0 Ph 3-NO ₂ , 4-Cl 435 Me 0 Ph 3-Cl, 4-NO ₂ 436 Me 0 Ph 3-Me, 5-Cl 437 Me 0 1-Np 438 Me 0 1 -Np 4-Br 439 Me 0 2-Np 440 Me 0 2-Np 4-Br 441 Me 0 Bz 442 Me 0 Bz 2-Me 443 Me 0 Bz 3-Me 444 Me 0 Bz 4-Me 445 Me 0 Bz 3 _{, 4- (Me) 2 446 Me} 0 Bz 3,5- (Me) 2 447 Me 0 Bz 4-Et 448 Me 0 Bz 2-OMe 449 Me 0 Bz 3- OMe 450 Me 0 Bz 4-OMe 451 Me 0 Bz _3, 4- (OMe) ₂ 452 Me 0 Bz 4-OEt 453 Me 0 Bz 4-OPr 454 Me 0 Bz 2-CF ₃ 455 Me 0 Bz 3-CF ₃ 456 Me 0 Bz 4-CF ₃ 457 Me 0 Bz 2-F 458 Me 0 Bz 3-F 459 Me 0 Bz 4-F 460 Me 0 Bz 2-Br 461 Me 0 Bz 3-Br 462 Me 0 Bz 4-Br 463 Me 0 Bz 2, 4-Br ₂ 464 Me 0 Bz 3, 4-Br ₂ 465 Me 0 Bz 3, 5-Br ₂ 466 Me 0 Bz 2-Cl 467 Me 0 Bz 3-Cl 468 Me 0 Bz 4- Cl 469 Me 1 Bz 470 Me 1 Bz 2-Br 471 Me 1 Bz 3-Br 472 Me 1 Bz _2, 4- (Cl) ₂ 473 Me 1 Bz _2, 4, 6- (Br) ₃ 474 Me 1 Bz 475 Me 1 Bz 2-Br 476 Me 1 Bz 3-Br 477 Me 1 Bz _2, 4- (Cl) ₂ 478 Me 1 Bz _2, 4, 6- (Br) ₃ 479 Me 2 Me 480 Me 2 Et 481 Me 2 Vi 2-Ph 482 Me 2 Pr 483 Me 2 i Pr 484 Me 2 c Pr 485 Me 2 All 486 Me 2 Prg 487 Me 2 Prg 2-Ph 488 M e 2 Bu 489 Me 2 i Bu 490 Me 2 s Bu 491 Me 2 c Bu 492 Me 2 Pn 493 Me 2 i Pn 494 Me 2 n Pn 495 Me 2 c Pn 496 Me 2 2-Pen 497 Me 2 2-Pntn 498 Me 2 Hx 499 Me 2 i Hx 500 Me 2 c Hx 501 Me 2 2-Hex 502 Me 2 2-Hexn 503 Me 2 Ph 504 Me 2 Ph 2-Me 505 Me 2 Ph 3-Me 506 Me 2 Ph 4-Me 507 Me 2 Ph 3-Et 508 Me 2 Ph 4-Et 509 Me 2 Ph 3- i Pr 510 Me 2 Ph 4- i Pr 511 Me 2 Ph 3- s Bu 512 Me 2 Ph 4- s Bu 513 Me 2 Ph 3- t Bu 514 Me 2 Ph 4- t Bu 515 Me 2 Ph 2-OMe 516 Me 2 Ph 3-OMe 517 Me 2 Ph 4-OMe 518 Me 2 Ph 3, 4- (OMe) ₂ 519 Me 2 Ph 3 , 5- (OMe) ₂ 520 Me 2 Ph 3-OEt 521 Me 2 Ph 4-OEt 522 Me 2 Ph 3-OPr 523 Me 2 Ph 4-OPr 524 Me 2 Ph 4-OPh 525 Me 2 Ph 2-Bz 526 Me 2 Ph 3-NHAc 527 Me 2 Ph 4-NHAc 528 Me 2 Ph 3-CN 529 Me 2 Ph 4-CN 530 Me 2 Ph 3-NO ₂ 531 Me 2 Ph 4-NO ₂ 532 Me 2 Ph 2-CF ₃ 533 Me 2 Ph 3-CF ₃ 534 Me 2 Ph 4- CF ₃ 535 Me 2 Ph 3-SO ₂ Me 536 Me 2 Ph 4-SO ₂ Me 537 Me 2 Ph 2-Br 538 Me 2 Ph 3-Br 539 Me 2 Ph 4-Br 540 Me 2 Ph 2-Cl 541 Me 2 Ph 3-Cl 542 Me 2 Ph 4-Cl 543 Me 2 Ph 2-F 544 Me 2 Ph 3-F 545 Me 2 Ph 4-F 546 Me 2 Ph 2, 4-F ₂ 547 Me 2 Ph 3, 4 -F ₂ 548 Me 2 Ph 3, 5-F ₂ 549 Me 2 Ph 2-CO ₂ Me 550 Me 2 Ph 3-CO ₂ Me 551 Me 2 Ph 4-CO ₂ Me 552 Me 2 Ph 2-CO ₂ Et 553 Me 2 Ph 3-CO ₂ Et 554 Me 2 Ph 4-CO ₂ Et 555 Me 2 Ph _2, 3- (Me) ₂ 556 Me 2 Ph 3, 4- (Me) ₂ 557 Me 2 Ph 3, 5- ( Me) ₂ 558 Me 2 Ph 2-Me, 4-NO ₂ 559 Me 2 Ph 3-Me, 4-Br 560 Me 2 Ph 2-Me, 5-Cl 561 Me 2 Ph 3-Cl, 4-OMe 562 Me 2 Ph 2-F, 5-Me 563 Me Ph 2-Me, 4-Cl 564 Me 2 Ph 2-Cl, 4-Br 565 Me 2 Ph 2-F, 4-Br 566 Me 2 Ph 3-Cl, 4-F 567 Me 2 Ph 2-F, 4 -Cl 568 Me 2 Ph 3-F, 4-Me 569 Me 2 Ph 2, 4- (Br) ₂ 570 Me 2 Ph 2, 5- (Br) ₂ 571 Me 2 Ph 3, 4- (Br) ₂ 572 Me 2 Ph 3, 5- (Br) ₂ 573 Me 2 Ph 2, 4, 6- (Br) ₃ 574 Me 2 Ph _3, 4- (Cl) ₂ 575 Me 2 Ph 2, 4- (Cl) ₂ 576 Me 2 Ph 2, 5- (Cl) ₂ 577 Me 2 Ph 2, 6- (Cl) ₂ 578 Me 2 Ph 3, 5- (Cl) ₂ 579 Me 2 Ph 2, 4, 6- (Cl) ₃ 580 Me 2 Ph 2-CF ₃ , 4-Br 581 Me 2 Ph 3-CF ₃ , 4-Br 582 Me 2 Ph 3-CF ₃ , 4-F 583 Me 2 Ph 3-Cl, 4-Me 584 Me 2 Ph 3-NO ₂ , 4-Cl 585 Me 2 Ph 3-Cl, 4-NO ₂ 586 Me 2 Ph 3-Me, 5-Cl 587 Me 2 2-Np 588 Me 2 2-Np 4-Br 589 Me 2 Bz 590 Me 2 Bz 2-Me 591 Me 2 Bz 3-Me 592 Me 2 Bz 4-Me 593 Me 2 Bz 3,4- (Me) 2 594 Me 2 Bz 3,5- (Me) 2 59 Me 2 Bz 4-Et 696 Me 2 Bz 2-OMe 697 Me 2 Bz 3-OMe 698 Me 2 Bz 4-OMe 699 Me 2 Bz 3,4- (OMe) 2 600 Me 2 Bz 4-OEt 601 Me 2 Bz 4-OPr 602 Me 2 Bz 2-CF ₃ 603 Me 2 Bz 3-CF ₃ 604 Me 2 Bz 4-CF ₃ 605 Me 2 Bz 2-F 606 Me 2 Bz 3-F 607 Me 2 Bz 4-F 608 Me 2 Bz 2-Br 609 Me 2 Bz 3-Br 610 Me 2 Bz 4-Br 611 Me 2 Bz 2-Cl 612 Me 2 Bz 3-Cl 613 Me 2 Bz 4-Cl 614 Me 2 Bz 2, 4-Br ₂ 615 Me 2 Bz 3, 4-Br ₂ 616 Me 2 Bz 3, 5-Br ₂ 617 Et 0 i Pr 618 Et 0 Bu 619 Et 0 Pn 620 Et 0 Hx 621 Et 0 Ph 622 Et 0 Ph 4-NO ₂ 623 Et 0 Ph 3-Br 624 Et 0 Ph 4-Br 625 Et 0 Ph 3, 4- (Br) ₂ 626 Et 0 Ph 3, 5- (Cl) ₂ 627 Et 0 Ph 3-Cl 628 Et 2 i Pr 629 Et 2 Bu 630 Et 2 Pn 631 Et 2 Hx 632 Et 2 Ph 633 Et 2 Ph 4-NO ₂ 634 Et 2 Ph 3-Br 635 Et 2 Ph 4-Br 636 Et 2 Ph 3, 4- (Br) ₂ 637 Et 2 Ph 3, 5- (Cl) ₂ 638 Et 2 Ph 3-Cl 639 i Pr 0 Bu 640 i Pr 0 Ph 641 i Pr 0 Ph 4-NO ₂ 642 i Pr 0 Ph 3-Br 643 i Pr 0 Ph 4-Br 644 i Pr 0 Ph 3, 4- (Br) ₂ 645 i Pr 0 Ph 3, 5- (Cl) ₂ 646 i Pr 0 Ph 3-Cl 647 i Pr 2 Bu 648 i Pr 2 Ph 649 i Pr 2 Ph 4-NO ₂ 650 i Pr 2 Ph 3-Br 651 i Pr 2 Ph 4-Br 652 i Pr 2 Ph 3, 4 -(Br) ₂ 653 i Pr 2 Ph 3, 5- (Cl) ₂ 654 i Pr 2 Ph 3-Cl 655 Bu 0 Bu 656 Bu 0 Ph 657 Bu 0 Ph 4-NO ₂ 658 Bu 0 Ph 3-Br 659 Bu 0 Ph 4-Br 660 Bu 0 Ph 3, 4- (Br) ₂ 661 Bu 0 Ph 3, 5- (Cl) ₂ 662 Bu 0 Ph 3-Cl 663 Bu 2 Bu 664 Bu 2 Ph 665 Bu 2 Ph 4 -NO ₂ 666 Bu 2 Ph 3-Br 667 Bu 2 Ph 4-Br 668 Bu 2 Ph 3, 4- (Br) ₂ 669 Bu 2 Ph 3, 5- (Cl) ₂ 670 Bu 2 Ph 3-Cl 671 Pn 0 Bu 672 Pn 0 Ph 673 Pn 0 Ph 4-NO ₂ 674 Pn 0 Ph 4-Br 675 Pn 2 Bu 676 Pn 2 Ph 677 Pn 2 Ph 4-NO ₂ 678 Pn 2 Ph 4-Br 679 Hx 0 Bu 680 Hx 0 Ph 681 Hx 0 Ph 4-NO ₂ 682 Hx 0 Ph 4-Br 683 Hx 2 Bu 684 Hx 2 Ph 685 Hx 2 Ph 4-NO ₂ 686 Hx 2 Ph 4-Br 687 OMe 0 Bu 688 OMe 0 Ph 689 OMe 0 Ph 4-NO ₂ 690 OMe 0 Ph 3-Br 691 OMe 0 Ph 4-Br 692 OMe 0 Ph 3-CF ₃ , 4-Br 693 OMe 0 Ph ₃ , 4- (Br) ₂ 694 OMe 0 Ph 3, 5- (Cl) ₂ 695 OMe 0 Ph 3-Cl 696 OMe 2 Bu 697 OMe 2 Ph 698 OMe 2 Ph 4-NO ₂ 699 OMe 2 Ph 3-Br 700 OMe 2 Ph 4-Br 701 OMe 2 Ph 3-CF ₃ , 4-Br 702 OMe 2 Ph 3, 4- (Br) ₂ 703 OMe 2 Ph 3, 5- (Cl) ₂ 704 OMe 2 Ph 3-Cl 705 OEt 0 Bu 706 OEt 0 Ph 707 OEt 0 Ph 4-NO ₂ 708 OEt 0 Ph 3-Br 709 OEt 0 Ph 4-Br 710 OEt 0 Ph 3, 5- (Cl) ₂ 711 OEt 0 Ph 3, 4- (Br) ₂ 712 OEt 0 Ph 3-Cl 713 OEt 2 Bu 714 OEt 2 Ph 715 OEt 2 Ph 4-NO ₂ 716 OEt 2 Ph 3-Br 717 OEt 2 Ph 4-Br 718 OEt 2 Ph 3, 5- (Cl) ₂ 719 OEt 2 Ph 3, 4- (Br) ₂ 720 OEt 2 Ph 3-Cl 711 O i Pr 0 Bu 722 O i Pr 0 Ph 723 O i Pr 0 Ph 4-NO ₂ 724 O i Pr 0 Ph 3-Br 725 O i Pr 0 Ph 4-Br 726 O i Pr 0 Ph 3, 5- (Cl) ₂ 727 O i Pr 0 Ph 3, 4- (Br) ₂ 728 O i Pr 0 Ph 3-Cl 729 O i Pr 2 Bu 730 O i Pr 2 Ph 731 O i Pr 2 Ph 4-NO ₂ 732 O i Pr 2 Ph 3-Br 733 O i Pr 2 Ph 4-Br 734 O i Pr 2 Ph 3, 5- (Cl) ₂ 735 O i Pr 2 Ph 3, 4- (Br) ₂ 736 O i Pr 2 Ph 3-Cl 737 OBu 0 Bu 738 OBu 0 Ph 739 OBu 0 Ph 4-NO ₂ 740 OBu 0 Ph 3-Br 741 OBu 0 Ph 4-Br 742 OBu 0 Ph 3,5- (Cl) ₂ 743 OBu 0 Ph 3,4- (Br) ₂ 744 OBu 0 Ph 3- Cl 745 OBu 2 B u 746 OBu 2 Ph 747 OBu 2 Ph 4-NO ₂ 748 OBu 2 Ph 3-Br 749 OBu 2 Ph 4-Br 740 OBu 2 Ph 3, 5- (Cl) ₂ 741 OBu 2 Ph 3, 4- (Br) ₂ 752 OBu 2 Ph 3-Cl 753 OPn 0 Bu 754 OPn 0 Ph 755 OPn 0 Ph 4-NO ₂ 756 OPn 0 Ph 3-Br 757 OPn 0 Ph 4-Br 758 OPn 0 Ph 3, 5- (Cl) ₂ 759 OPn 2 Bu 760 OPn 2 Ph 761 OPn 2 Ph 4-NO ₂ 762 OPn 2 Ph 3-Br 763 OPn 2 Ph 4-Br 764 OPn 2 Ph 3, 5- (Cl) ₂ 765 OHx 0 Bu 766 OHx 0 Ph 767 OHx 0 Ph 4-Br 768 OHx 0 Ph 3, 5- (Cl) ₂ 769 OHx 0 Ph 3, 4- (Br) ₂ 770 OHx 0 Ph 3-Cl 771 OHx 2 Bu 772 OHx 2 Ph 773 OHx 2 Ph 4-Br 774 OHx 2 Ph 3, 5- (Cl) ₂ 775 OHx 2 Ph 3, 4- (Br) ₂ 776 OHx 2 Ph 3-Cl ──────────────── ────────────────── In the table above, the abbreviations refer to the following groups or symbols. It is. Me ・ ・ ・ ・ Methyl OMe ・ ・ ・ Methoxy Et ・ ・ ・ ・ Ethyl OEt ・ ・ ・ Ethoxy Vi ・ ・ ・ ・ Vinyl Pr ・ ・ ・ Propyl OPr ・ ・ ・ ・ Propoxy All ・ ・ ・ ・Allyl Prg ・ ・ ・ ・ Propargyl Bu ・ ・ ・ ・ Butyl OBu ・ ・ ・ ・ Butoxy Bun ・ ・ ・ ・ Butenyl Butn ・ ・ ・ Butynyl Pn ・ ・ ・ ・ Pentyl Pen ・ ・ ・ ・ Pentenyl Pntn ・ ・ ・ ・ Pentynyl Hx ・・ ・ ・ Hexyl Hex ・ ・ ・ ・ Hexenyl Hexn ・ ・ ・ Hexynyl Phety ・ ・ ・ Phenethyl Ac ・ ・ ・ ・ Acetyl Bz ・ ・ ・ ・ Benzyl OBz ・ ・ ・ Benzyloxy Ph ・ ・ ・ ・ Phenyl OPh ・ ・ ・・ Phenoxy Np ・ ・ ・ ・ Naphthyl Pyr ・ ・ ・ ・ Pyridyl Pyzn ・ ・ ・ ・ Pyridazinyl Pyz ・ ・ ・ ・ Pyrazinyl Pym ・ ・ ・ ・ Pyrimidinyl i・ ・ ・ ・ ・ ・ Iso s・ ・ ・ ・ Secondary t・ ・ ・ ・ Tasha Lee n ···· Ne c · · · · cyclo * 1: represents a substituent on the main groups A, numerals substitution positions on the A, alpha, beta is a substituted position on the alkylene in aralkyl groups.

Of the above compounds, compound numbers 196, 198, 199, 200 and 20 are preferably used against epidemics.
1, 206, 207, 209, 210, 211, 21
9, 220, 221, 222, 223, 224, 22
5, 228, 229, 230, 232, 233, 23
4, 235, 236, 237, 238, 239, 24
7, 248, 250, 252, 253, 254, 25
7, 260, 263, 264, 267, 268, 26
9, 271, 272, 277, 292, 294, 29
5, 296, 303, 304, 306, 307, 30
8, 309, 310, 311, 313, 314, 31
7, 318, 319, 320, 481, 487, 50
3, 506, 516, 517, 518, 520, 52
1, 528, 530, 532, 533, 538, 53
9, 541, 542, 543, 544, 549, 55
1, 558, 562, 580, 584, 591, 60
6, 607, 609, 613, 614, 615, 61
6, 648, 652, 664, 697, 700 or 7
Compound No. 17 and more preferably Compound No. 19
8, 199, 201, 209, 210, 222, 22
8, 229, 230, 232, 233, 235, 25
0, 263, 264, 269, 271, 272, 29
4, 308, 538, 539, 541, 580 or 6
It is 13.

Of the above-mentioned compounds, compound Nos. 197, 198, 199 and 2 are preferred for grape downy mildew.
00, 201, 202, 203, 204, 205, 20
6, 207, 219, 220, 221, 222, 22
8, 229, 230, 234, 235, 236, 23
7, 238, 239, 248, 250, 252, 25
3, 254, 256, 263, 264, 267, 26
8, 269, 270, 271, 272, 277, 30
6, 307, 309, 310, 311, 313, 31
7, 318, 319, 320, 481, 487, 50
3, 506, 509, 512, 513, 533, 53
8, 539, 541, 542, 543, 544, 54
6, 547, 548, 565, 566, 567, 56
8, 574, 578, 580, 587, 591, 61
4, 615, 616, 633, 634 or 703, more preferably Compound No. 199, 22
2, 229, 230, 250, 271, 533 or 5
41.

Of the above-mentioned compounds, the compound Nos. 178, 196, 198 and 2 are suitable for rice blast disease.
20, 221, 222, 223, 224, 225, 23
1, 232, 233, 235, 256, 260, 26
4, 272, 296, 488, 489, 492, 49
3, 498, 499, 503, 510, 512, 51
3, 514, 515, 516, 520, 521, 53
3, 540, 541, 542, 543, 544, 54
5, 546, 547, 548, 557, 563, 56
6, 571, 578, 580, 581, 582, 58
3, 586, 591, 629, 633, 637, 64
7, 653, 663 or 696, more preferably compound numbers 178, 198, 220, 22.
2, 224, 235, 256, 264, 515, 54
0, 541, 542 or 581.

The compounds of general formula (I) of the present invention are
It is manufactured by the following method.

[0067]

[Chemical 30]

[0068]

[Chemical 31]

[0069]

[Chemical 32]

[0070]

[Chemical 33]

[0071]

[Chemical 34]

[0072]

[Chemical 35]

[0073]

[Chemical 36]

In the above formula, R ¹ , A and X have the same meanings as described above. A _a is C out of the groups defined by A
₁ -C ₆ alkyl group, C ₃ -C ₆ cycloalkyl group, selected from the aforementioned substituent group A group the same or different 1 to 3
Number of a substituent may be substituted in a phenyl group a C ₂ -C ₆ alkenyl group, selected from the aforementioned substituent group A group have the same or different 1 to 3 substituents A C ₂ -C ₆ alkynyl group which may be substituted with a phenyl group, which does not have a substituent in the alkylene part, but which is selected from the aforementioned substituent group B in the aryl group part, and which is the same or different from 1 to 4 An aralkyl group that may have a substituent, selected from the above-mentioned substituent group C group, an aryl group that may have the same or different 1 to 5 substituents, selected from the above-mentioned substituent group A group, A 6-membered aromatic heterocyclic group containing 1 or 2 nitrogen atoms which may have the same or different 1 to 3 substituents is shown.

A _b is the same as A _a .

A _d is the same as A _a .

A _e is the expression

[0078]

[Chemical 37]

A group having: (wherein R ² is a hydrogen atom, C ₁
A -C ₅ alkyl group, an aryl group moiety selected from the above-mentioned substituent group B group, which may have the same or different 1 to 4 substituents, a benzyl group selected from the above-mentioned substituent group B group,
The aryl group which may have the same or different 1 to 4 substituents is shown. ) Is shown.

A _e1 is an expression

[0081]

[Chemical 38]

(In the formula, R ² has the same meaning as described above, and R ³ represents a C ₁ -C ₄ alkyl group, a C ₁ trihaloalkyl group, or a phenyl group).

A _f is the same as A _e .

A _f1 is an expression

[0085]

[Chemical Formula 39]

(Wherein R ² and X have the same meanings as described above). A _f2 is an expression

[0087]

[Chemical 40]

A group having the formula (in the formula, R ² has the same meaning as described above). A _g is the formula

[0089]

[Chemical 41]

A group having: (R ⁴ represents a group selected from the above-mentioned substituent group A group, and k represents 0, 1, 2 or 3.)
Indicates.

A _g1 is the formula

[0092]

[Chemical 42]

A group having R ⁴ and k (R ⁴ and k have the same meanings as described above). A process formula (I), R ¹ is a hydrogen atom, C ₁ -C ₆ alkyl or C ₁
Represents a —C ₆ alkoxy group, n is 0, and A is a group A _a
A method of producing _a compound (I _a ) having

The step A1 is a step for producing a compound having the general formula (II), wherein the compound having the general formula (III) is reacted with the compound having the general formula (IV) in the presence of a base in an inert solvent. It is achieved by

The compound of the compound (III) is, for example, the compound of the bulletin of the chemical society of
It is a compound described in Japan, vol. 42, page 3207, 1969. In addition, the compound (IV) is, for example,
Bichs Anna-Len Hemmy, pp. 985, 19
It is a compound described in 1989.

The inert solvent used is, for example, ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethyl ether, dioxane and tetrahydrofuran, halogenated compounds such as methylene chloride, chloroform, carbon tetrachloride and dichloroethane. Hydrocarbons, benzene, aromatic hydrocarbons such as toluene, ethyl acetate, acetic acid esters such as butyl acetate, nitriles such as acetonitrile, water or a mixed solvent with water, preferably, Hydrous ethers (particularly water-ethylene glycol dimethyl ether).

The base used is, for example, an alkali metal hydrogen carbonate such as sodium hydrogen carbonate or potassium hydrogen carbonate, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, calcium hydroxide or magnesium hydroxide. Alkaline earth metal hydroxides, alkali metal carbonates such as sodium carbonate, potassium carbonate, alkali metal acetates such as sodium acetate, potassium acetate,
Alkali metal fluorinated salts such as sodium fluoride and potassium fluoride, tertiary lower alkylamines such as triethylamine, ethyldiisopropylamine and tributylamine, 1,8-diazabicyclo [5.4.0] undecane-7
May be a tertiary cycloaliphatic amine such as -ene (DBU), 1,4-diazabicyclo [2.2.2] octane (DABCO), preferably with an alkali metal hydrogen carbonate (especially sodium hydrogen carbonate) is there.

The reaction temperature and the reaction time vary depending on the starting compounds (III, IV), the solvent and the kind of the base, but the reaction temperature is usually 0 ° C. to 150 ° C.
C-60C), and the reaction time is usually 30 minutes to 15 hours (preferably 1 to 5 hours).

After completion of the reaction, the target compound of this reaction is collected from the reaction mixture according to a conventional method. For example, water is added to the reaction mixture, or the reaction mixture from which insoluble matter has been removed is washed with an alkali such as sodium hydrogen carbonate or sodium hydroxide, and then extracted with a water-immiscible organic solvent such as ethyl acetate to obtain anhydrous sulfuric acid. It can be obtained by distilling off the solvent after drying with magnesium or the like. If necessary, it can be purified by recrystallization, column chromatography and the like.

The step A2 is a step for producing a compound having the general formula (I _a ), and is carried out in an inert solvent in the general formula (V _a ).
This is accomplished by reacting a mercaptan having ## STR4 ## with a base to give the corresponding mercaptide, which is reacted with compound (II).

The inert solvent used is, for example, ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and dichloroethane, aromatic hydrocarbons such as benzene and toluene. Hydrogen, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-
Amides such as pyrrolidinone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, alcohols such as t-butanol, acetone, ketones such as 2-butanone, nitriles such as acetonitrile, dimethyl sulfoxide Such sulfoxides can be used, preferably ethers (particularly tetrahydrofuran).

The base used is, for example, an alkali metal hydride such as sodium hydride, potassium hydride or lithium hydride, an alkali metal alkoxide such as sodium methoxide, sodium ethoxide or potassium t-butoxide, sodium. Amides, alkali metal amides such as lithium isopropylamide, tertiary lower alkylamines such as triethylamine, ethyldiisopropylamine and tributylamine, 1,8-diazabicyclo [5.4.0] undecane-7-ene (DBU), 1, It can be a tertiary cycloaliphatic amine such as 4-diazabicyclo [2.2.2] octane (DABCO), preferably an alkali metal hydride, especially sodium hydride.

The reaction temperature and reaction time are as follows:
The reaction temperature is usually 0 ° C. to 60 ° C. (preferably 0 ° C. to room temperature), and the reaction time is usually 5 minutes to 3 hours (preferably, depending on the type of the solvent and the base, at the stage of producing the mercaptide. 10 minutes to 1 hour). In the reaction step of mercaptide and compound (II), the reaction temperature is usually 15 to 120 ° C. (preferably room temperature to 80 ° C.).
C.) and the reaction time is usually 30 minutes to 5 hours (preferably 1 hour to 2 hours).

After completion of the reaction, the target compound of this reaction is collected from the reaction mixture according to a conventional method. For example, when the alkali metal hydride is excessively left in the reaction mixture, alcohols are added and decomposed, water is added to the reaction mixture, and the mixture is extracted with a water-immiscible organic solvent such as ethyl acetate,
It can be obtained by drying over anhydrous magnesium sulfate or the like and then distilling off the solvent. If necessary, conventional methods such as
It can be further purified by recrystallization, column chromatography and the like.

Step B in the general formula (I), R ¹ represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkoxy group, n is 0 and A has a group _Ab . It is a method for producing the compound (I _b ).

The step B1 is a step for producing the compound (VI), in which a mercaptan having the general formula (V _b ) is reacted with a base in an inert solvent to obtain a corresponding mercaptide,
This is achieved by reacting with general formula (IV).

The inert solvent used is, for example, ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and dichloroethane, aromatic carbons such as benzene and toluene. Hydrogen, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-
Amides such as pyrrolidinone, alcohols such as methanol, ethanol, propanol, i-propanol, butanol, i-butanol, t-butanol, ketones such as acetone, 2-butanone, nitriles such as acetonitrile, It may be a sulfoxide such as dimethyl sulfoxide, preferably an ether (particularly tetrahydrofuran).

Examples of the base used include alkali metal hydrides such as sodium hydride, potassium hydride and lithium hydride, alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, sodium. Amides, alkali metal amides such as lithium isopropylamide, tertiary lower alkylamines such as triethylamine, ethyldiisopropylamine and tributylamine, 1, 8-diazabicyclo [5.4.0] undecane-7-ene (DBU), 1, 4-
It can be a tertiary cycloaliphatic amine such as diazabicyclo [2.2.2] octane (DABCO), preferably an alkali metal hydride, especially sodium hydride.

The reaction temperature and reaction time are as follows:
Although it depends on the type of the solvent and the base, the reaction temperature is usually 0 ° C. to 60 ° C. (preferably 0 ° C. to room temperature) and the reaction time is 5 minutes to 3 hours (preferably 10 minutes) at the stage of obtaining the mercaptide. To 1 hour), and in the reaction step of the mercaptide and the compound (III), the reaction temperature is usually −60.
℃ to 50 ℃ (preferably -50 ℃ to 0 ℃),
The reaction time is usually 1 hour to 5 hours (preferably 1 hour to 3 hours).

After completion of the reaction, the target compound of this reaction is collected from the reaction mixture according to a conventional method. For example, when an alkali metal hydride is excessively left in the reaction mixture, alcohols are added to decompose it, water is added to the reaction mixture and acidified with a mineral acid, and then a water-immiscible organic solvent such as ethyl acetate. It can be obtained by distilling the solvent after extraction with, dried over anhydrous magnesium sulfate and the like. If necessary, it can be further purified by a conventional method such as recrystallization or column chromatography.

The step B2 is a step for producing the compound (I _b ) in which the compound having the general formula (VI) is converted to the compound having the general formula (III) in the presence of a desulfurizing agent and a base in an inert solvent. It is achieved by reacting.

The inert solvent used is, for example, ethers such as tetrahydrofuran, dioxane and diethyl ether, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and dichloroethane, benzene and toluene. Aromatic hydrocarbons, alcohols such as methanol, ethanol, t-butanol, amides such as N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidinone, and acetonitrile. Nitriles, water or a mixed solvent of water or water and the organic solvent, preferably,
Hydrous ethers (water-diethyl ether).

The desulfurizing agent used may preferably be a silver salt such as silver nitrate, silver carbonate, silver acetate, silver trifluoroacetate or silver oxide, cupric chloride, copper oxide or acetic acid, with preference Is a silver salt (particularly silver nitrate).

The base used is, for example, an alkali metal carbonate such as sodium carbonate or potassium carbonate, an alkali metal hydrogen carbonate such as sodium hydrogen carbonate or potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide or hydroxide. It may be an alkali metal hydroxide such as lithium, an alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide, an alkali metal acetate such as sodium acetate or potassium acetate, and preferably an alkali metal Carbonate (particularly potassium carbonate).

The reaction temperature and the reaction time are as follows:
It depends on the type of solvent and base, but it is usually 0 ℃ to 15 ℃.
It is 0 ° C. (preferably 20 ° C. to 40 ° C.), usually 30 hours to 10 days (preferably 2 days to 7 days).

After completion of the reaction, the target compound of this reaction is collected from the reaction mixture according to a conventional method. For example, it can be obtained by extracting the reaction mixture with a water-immiscible organic solvent such as diethyl ether or ethyl acetate, drying with anhydrous magnesium sulfate or the like, and distilling the solvent off. If necessary, it can be further purified by a conventional method such as recrystallization or column chromatography.

[0117] Step C in the general formula (I), R ¹ represents a hydrogen atom, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy group, n is 1, A is the same as described above A compound having a group (I _c1 ) or R ¹ is a hydrogen atom, C ₁
A method for producing a compound (I _c2 ) having a -C ₆ alkyl group or a C ₁ -C ₆ alkoxy group, n being 2, and A having the same group as described above.

The step C1 is performed by using the compound (I _c1 ) or (I _c1 ).
_In the step of producing _c2 ), it is achieved by carrying out an oxidation reaction of the compound having the general formula (I _c ) in the presence of an oxidizing agent in an inert solvent.

The inert solvent used is, for example, methylene chloride, chloroform, carbon tetrachloride, halogenated hydrocarbons such as dichloroethane, tetrahydrofuran, dioxane, ethers such as diethyl ether, acetone, 2-butanone. Ketones such as, methanol, ethanol, alcohols such as t-butanol, N,
N-dimethylacetamide, N, N-dimethylformamide, amides such as N-methyl-2-pyrrolidinone, nitriles such as acetonitrile, acetic acid, water or a mixed solvent of water and the above organic solvent may be preferable. Has
Halogenated hydrocarbons (particularly methylene chloride).

The oxidizing agent used can be, for example, m-chloroperbenzoic acid, performic acid, peracids such as peracetic acid, hydrogen peroxide, potassium permanganate, sodium periodate,
Preferred are peracids (particularly m-chloroperbenzoic acid).

The reaction temperature and reaction time are as follows:
When the target compound is the compound (I _c1 ), the reaction temperature is usually −20 ° C. to 50 (preferably −5 ° C. to 10 ° C.), and the reaction time is, though it varies depending on the type of the solvent, the oxidizing agent and the target compound. It is usually 10 minutes to 5 hours (preferably 30 minutes to 2 hours), and when the target compound is compound (I _c2 ), the reaction temperature is usually 0 ° C to 100 ° C (preferably 10 ° C to 5 ° C).
0 ° C.), the reaction time is usually 5 hours to 7 days (preferably,
10 hours to 4 days).

After completion of the reaction, the target compound of this reaction is collected from the reaction mixture according to a conventional method. For example, it can be obtained by extracting the reaction mixture with a water-immiscible organic solvent such as diethyl ether or ethyl acetate, drying with anhydrous magnesium sulfate or the like, and distilling the solvent off. If necessary, it can be further purified by a conventional method such as recrystallization or column chromatography.

Method D is the formula (I) wherein R ¹ represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkoxy group, n is 0 and A has a group _Ad . This is a method for producing the compound (I _d ).

The step D1 is a step for producing the compound (I _d ), in which an excess (2 to 5 times the molar amount) of the mercaptan having the general formula (V _d ) is reacted with a base in an inert solvent,
This is achieved by obtaining the corresponding mercaptide, which is reacted with a compound having the general formula (I _c2 ).

The inert solvent used is, for example, ethers such as tetrahydrofuran, dioxane and diethyl ether, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and dichloroethane, acetone and 2-butanone. Ketones such as, methanol,
Alcohols such as ethanol and t-butanol,
It may be an amide such as N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidinone, a nitrile such as acetonitrile, preferably an ether (particularly tetrahydrofuran). ..

The base used is, for example, an alkali metal hydride such as sodium hydride, potassium hydride or lithium hydride, an alkali metal alkoxide such as sodium methoxide, sodium ethoxide or potassium t-butoxide, sodium. Amides, alkali metal amides such as lithium isopropylamide, tertiary lower alkylamines such as triethylamine, ethyldiisopropylamine and tributylamine, 1, 8-diazabicyclo [5.4.0] undecane-7-ene (DBU), 1, 4-
It can be a tertiary cycloaliphatic amine such as diazabicyclo [2.2.2] octane (DABCO), preferably an alkali metal hydride, especially lithium hydride.

The reaction temperature and reaction time are as follows:
The reaction temperature is usually 0 ° C. to 60 ° C. (preferably 0 ° C. to room temperature) and the reaction time is usually 5 minutes to 3 hours (preferably, at the stage of obtaining mercaptide, although it varies depending on the type of solvent and base. 10 minutes to 1 hour). In the reaction step of mercaptide and compound (VIII), the reaction temperature is usually 15 to 100 ° C (preferably 25 ° C to 50 ° C).
C.) and the reaction time is usually 30 minutes to 10 hours (preferably 1 hour to 3 hours).

After completion of the reaction, the target compound of this reaction is collected from the reaction mixture according to a conventional method. For example, when the alkali metal hydride is excessively left in the reaction mixture, alcohols are added to decompose it, water is added to the reaction mixture, and the mixture is extracted with a water-immiscible organic solvent such as diethyl ether or ethyl acetate. And dried over anhydrous magnesium sulfate,
It can be obtained by distilling off the solvent. If necessary, it can be further purified by a conventional method such as recrystallization or column chromatography.

In the step E, in the general formula (I), R ¹ represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkoxy group, n is 0, A is a group A _e1 . A method for producing the compound (I _e1 ) having

The step E1 is a step of producing a compound having the general formula (I _e1 ), which is a so-called pomerer by reacting a compound having the general formula (I _e ) with an acid anhydride having the general formula (VII). Achieved by reaction.

Examples of the acid anhydride (VII) include C ₂ -C ₅
An acid anhydride having an alkanoyl group, a C ₂ trihaloalkanoyl group or a benzoyl group, which may be, for example, acetic anhydride, trifluoroacetic anhydride, trichloroacetic anhydride, propionic anhydride or benzoic anhydride, preferably acetic anhydride. Is.

In this step, the above-mentioned acid anhydride is also used as a solvent, but in the case of a small amount or a solid, an inert solvent is used.

Examples of the inert solvent used include ethers such as tetrahydrofuran, dioxane and ether, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and dichloroethane, benzene, toluene and xylene. Can be aromatic hydrocarbons such as
Aromatic hydrocarbons (particularly xylene) are preferred.

The reaction temperature is usually 50 ° C. to 150 ° C. (preferably 80 ° C. to 120 ° C.), and the reaction time is generally 12 hours to 48 hours (preferably 20 hours to 30 hours).

After completion of the reaction, the target compound of this reaction is collected from the reaction mixture according to a conventional method. For example, it is obtained by adding water to the reaction mixture, extracting with a water-immiscible organic solvent such as ethyl acetate, washing with an aqueous solution of sodium hydrogen carbonate, drying with anhydrous magnesium sulfate, etc., and then distilling the solvent off. You can If necessary, it can be further purified by a conventional method such as column chromatography.

In the step F, in the general formula (I), R ¹ represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkoxy group, n is 0, A is a group A _f1 . A method for producing the compound (I _f1 ) having the group or the compound (I _f2 ) having the group A _f2 .

Step F1 is a step for producing a compound having the general formula (I _f1 ) and is accomplished by treating the compound having the general formula (I _f ) with a halogenating agent in an inert solvent.

Examples of the solvent used include aromatic hydrocarbons such as benzene and toluene, methylene chloride, chloroform, carbon tetrachloride, halogenated hydrocarbons such as dichloroethane, tetrahydrofuran and i-propyl ether. , Ethers such as dioxane and ether, preferably halogenated hydrocarbons (especially,
Methylene chloride).

The halogenating agent used is bromine,
It may be NBS, phosphorus pentabromide, chlorine, NCS phosphorus pentachloride, sulfuryl chloride, preferably sulfuryl chloride.

The reaction is preferably carried out in two steps. That is, the reaction temperature in the first step is usually -50 ° C to 10 ° C (preferably -30 ° C to -10 ° C),
The reaction time is usually 5 minutes to 2 hours (preferably 10 minutes to 1 hour), and the reaction temperature in the second step is usually 20 ° C to 100 ° C (preferably 30 ° C to 80 ° C). The reaction time is usually 1 hour to 48 hours (preferably 10 hours to 24 hours). After completion of the reaction, the target compound of this reaction is used in the next step without isolation.

The step F2 is a step for producing a compound having the general formula (I _f2 ) and is achieved by treating the compound having the general formula (I _f1 ) with a _cyanating agent in an inert solvent.

The cyanating agent used is, for example,
It may be a trialkylsilyl cyanide such as trimethylsilyl cyanide, triethylsilyl cyanide, an alkali metal cyanide such as sodium cyanide, potassium cyanide, preferably trimethylsilyl cyanide.

The reaction temperature is usually 5 ° C. to 100 ° C. (preferably 15 ° C. to 50 ° C.), and the reaction time is usually 1 hour to 48 hours (preferably 10 hours to 24 hours).

After completion of the reaction, the target compound of this reaction is collected from the reaction mixture by a conventional method. For example, it is obtained by adding water to the reaction mixture, extracting with a water-immiscible organic solvent such as methylene chloride or ethyl acetate, washing with saturated brine, drying with anhydrous magnesium sulfate, etc., and distilling the solvent off. You can If necessary, it can be further purified by a conventional method such as column chromatography.

In the step G, in the general formula (I), R ¹ represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkoxy group, n is 0, and A has a group _{Ag 1} . This is a method for producing the compound (I _g1 ).

Step G1 is a step for producing a compound having the general formula (I _g1 ) and is accomplished by reacting the compound having the general formula (I _g ) with an oxidizing agent in an inert solvent.

The oxidant used can be, for example, sodium permanganate, potassium permanganate, osmium tetroxide, selenium dioxide, preferably osmium tetroxide.

The inert solvent used is, for example, ethers such as tetrahydrofuran, dioxane and ether, tertiary amines such as triethylamine and pyridin, aromatic hydrocarbons such as benzene and toluene, acetone. , Ketones such as 2-butanone, alcohols such as t-butanol, methylene chloride, chloroform, carbon tetrachloride, halogenated hydrocarbons such as dichloroethane, nitriles such as acetonitrile, ethyl acetate, butyl acetate. And an ether (particularly ethyl ether) is preferable.

The reaction temperature is usually 0 ° C to 100 ° C (preferably 10 ° C to 50 ° C), and the reaction time is usually 30.
Minutes to 48 hours (preferably 1 hour to 20 hours). After completion of the reaction, the produced osmium ester is led to the target diol compound by a conversion method into various diols, for example, an oxidative decomposition method, a reductive decomposition method or a transesterification method, and is collected according to a conventional method. For example, it can be obtained by adding water to the reaction mixture, extracting with a water-immiscible organic solvent such as ethyl acetate, washing with saturated brine, drying with anhydrous magnesium sulfate, etc., and distilling the solvent off. it can. If necessary, it can be further purified by a conventional method such as column chromatography.

The acylated product of (I _g1 ) can be derived by acylating the hydroxyl group of the product (I _g1 ) of this reaction.

[0151]

INDUSTRIAL APPLICABILITY The isoxazoline derivative of the present invention represented by the general formula (I) is particularly useful as an agricultural and horticultural fungicide, and is effective against plant diseases caused by tomato late blight, downy mildew and rice blast. On the other hand, it shows an excellent control effect. Next, examples of control tests of these tomato late blight, downy mildew and rice blast are shown.

Test Method a. Tomato epidemic control test Tomato seedlings were sprayed with a test drug solution containing 300 ppm of the compound, and 24 hours later, Phytophthora infes
The spore suspension of tans) was spray-inoculated and the disease was caused in a humid chamber at 20 ° C. The efficacy evaluation was described as "3" when the diseased area was 0%, "2" when it was 10% or less, "1" when it was 50% or less, and "0" when it was 51% or more.

B. Grape downy mildew control test Grape seedlings were sprayed with a test drug solution containing 300 ppm of the compound, and 24 hours later, grape downy mildew (Plasmopara vitic)
ola) spore suspension was spray-inoculated and diseased in a humid chamber at 20 ° C.

The efficacy evaluation is the same as the tomato epidemic control test.

C. Rice blast control test 300 compounds were added to rice seedlings (cultivar Kofu, 3.0 leaf stage)
Disperse the test chemical solution adjusted to ppm (20 ml per 2 pots)
After 24 hours, a conidial suspension of blast fungus (Piricularia oryzae) was sprayed and inoculated, and the disease was caused in a humid chamber at 20 ° C.

The efficacy evaluation is the same as the tomato epidemic control test.

The results of controlling the plant diseases of the compounds of formula (I) are shown in Table 2.

[0158]

[Table 2] Control activity against tomato epidemic, downy mildew and rice blast ───────────────────────────────── -Compound No. Tomato Epidemic disease, downy mildew disease, rice blast disease (* 2) ───────────────────────────────── 178 1-3 196 3 -3 197 1 3 2 198 3 3 3 3 199 3 3 2 201 3 3 3 1 202 1 3 1 203 3 1 3 2 2 205 2 3 2 207 3 3 2 209 3 -2 210 3 -2 219 3 3 2 220 3 3 3 3 222 3 3 3 224 3-3 3 228 3 3 1 229 3 3 2 230 3 3 2 2 231 1-3 3 232 3-3 233 3-3 3 234 3 3 2 235 3 3 3 236 3 3 2 2 247 3 -1 248 3 3 2 250 3 3 2 252 3 3 2 2 253 3 3 2 256 256 2 3 3 257 3 1 1 260 3-3 3 263 3 3 2 2264 3 3 3 267 3 3 2 268 3 3 2 269 3 2 270 2 3 2 271 3 3 3 1 272 3 3 3 294 3 -2 296 3 -3 306 3 3 3 1 307 3 3 1 1 308 3 -2 313 3 3 2 3 314 3 2 2 317 3 3 3 2 503 3 3 3 506 3 3 2 509 1 3 1 1 510 1 -3 512 512 1 3 3 514 1 1 3 515 1 2 3 516 3 1 3 3 517 3 3 1 1 533 3 3 3 3 5 38 3 3 2 539 3 1 3 5 2 3 3 542 3 3 3 543 3 3 3 544 3 3 3 545 2 2 3 556 2 3 2 557 2 1 3 562 3 -1 563 1 3 565 1 3 1 1 566 2 3 3 3 567 1 3 1 1 574 1 3 2 578 2 3 3 580 3 3 3 581 2 1 3 582 2 2 3 587 1 3 2 613 3 1 2 700 3-1 703 2 3 1 ────────────────────────────────── * 2: If no control test was performed- And Since the compound of the present invention has a long residual effect and an excellent preventive effect as well as an excellent therapeutic effect, it is possible to control diseases by treatment after infection. When using, as in the case of conventional pesticide formulations, along with auxiliary agents, emulsions, powders,
It can be formulated into various forms such as a wettable powder, a liquid formulation, a granule, a dry flowable formulation, a flowable formulation and a suspension formulation, and can be put to practical use. In the actual use of these preparations, they can be used as they are or diluted with a diluent such as water to a predetermined concentration and used. Examples of the auxiliary agent include a carrier, an emulsifying agent, a suspending agent, a dispersing agent, a spreading agent, a penetrating agent, a wetting agent, a thickener, a stabilizer, and the like,
It may be added as needed. The carrier is divided into solid carrier and liquid carrier, and the solid carrier includes starch, sugar, cellulose powder, cyclodextrin, activated carbon, soybean flour, wheat flour, chaff flour, wood flour, fish meal, milk powder and other animal and plant powders. , Talc, kaolin, bentonite, organic bentonite, calcium carbonate, calcium sulfate, sodium bicarbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, silica, mineral powder such as sulfur powder, and the like, the liquid carrier, Water, animal and vegetable oils such as soybean oil and cottonseed oil, alcohols such as ethyl alcohol and ethylene glycol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and tetrahydrofuran, aliphatic hydrocarbons such as kerosene, kerosene and liquid paraffin. , Xylene, trimethylbenzene Aromatic hydrocarbons such as tetramethylbenzene, cyclohexane, solvent naphtha, halogenated hydrocarbons such as chloroform and chlorobenzene, acid amides such as dimethylformamide, ethyl acetate, esters such as glycerin ester of fatty acids, acetonitrile, etc. Nitriles, sulfur-containing compounds such as dimethylsulfoxide, N-methylpyrrolidone, N, N-dimethylformamide and the like.

A suitable compounding weight ratio of the compound of the present invention to the adjuvant is generally 0.05: 99.95 to 90:10, preferably 0.2:
99.8 to 80:20. The concentration of the compound of the present invention varies depending on the target crop, method of use, formulation form, application amount, etc. and cannot be specified unconditionally, but in the case of foliar treatment, it is usually 0.1 to 10,000 ppm, preferably 1 to 10,000 ppm per active ingredient. 2,
It is 000 ppm. For soil treatment, usually 10-100,000g
/ ha, preferably 200 to 20,000 g / ha.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited thereto.

[0161]

【Example】

Example 1 (Method A) 3- (4-bromophenylthio) -5-cyano-2-i
Soxazoline (Compound No. 62) (a) Dissolve 5 g of 3-chloro-5-cyano-2- isoxazoringlyoxylic acid aldoxime in 55 ml of ethylene glycol dimethyl ether, add 14.99 g of N-chlorosuccinimide, and add 5 at 80 ° C. Heated and stirred for 1 minute. After cooling to room temperature, acrylonitrile 22.2m
1, 22.5 g of sodium hydrogen carbonate and 1.1 ml of water were added, and the mixture was stirred at room temperature for 2 hours and a half. The insoluble material was filtered off, and after concentration, the residue was dissolved in ethyl acetate and washed with 2N sodium hydroxide and then brine. After drying, the solvent was distilled off under reduced pressure to give 3-chloro-5-cyano-2-
4.39 g of isoxazoline as an oil (yield 5
9.9%).

NMR (CDCl ₃ , δppm, J = Hz) 5.38 (1H, dd, J = 10.
9,6.5); 3.64 (1H, dd, J = 17.3,10.9); 3.49 (1H, dd, J = 17.3,
6.5) (b) 3- (4-bromophenylthio) -5-cyano-
2-isoxazoline 60% sodium hydride 26.48 g was suspended in dry tetrahydrofuran 50 ml, while 4-bromothiophenol 12.51 g was dried in tetrahydrofuran 20 m.
The solution dissolved in 1 was added dropwise under ice cooling. After stirring at room temperature for 10 minutes, a solution of 5.76 g of 3-chloro-5-cyano-2-isoxazoline in 15 ml of dry tetrahydrofuran was added dropwise, and the mixture was further stirred for 2 hours. After diluting with water,
It was extracted with ethyl acetate. The extract was washed with 1N sodium hydroxide and then with saline, and dried. After the solvent was distilled off, the residue was subjected to silica gel column chromatography (eluate;
Hexane: ethyl acetate = 5: 1), melting point 57-
9.01 g of the title compound having a temperature of 61 ° C. (yield 72.1
%)Obtained.

NMR (CDCl ₃ , δppm, J = Hz) 7.44-7.59 (4H, m);
5.26 (1H, dd, J = 10.5,5.6); 3.44 (1H, dd, J = 16.5,10.5); 3.3
2 (1H, dd, J = 16.5,5.6) Example 2 (method B) 3-phenylthio-5-cyano-2-isoxazoline
(Compound No. 28) (a) Diphenylthioaldoxime 60% NaH 2.26 g was dried with tetrahydrofuran 15
A suspension of 0 ml of thiophenol and 8.0 ml of thiophenol dissolved in 7 ml of dry tetrahydrofuran was added, and the mixture was further stirred for 30 minutes. The obtained reaction solution was added dropwise to a solution of 4.58 g of dibromoaldoxime in 40 ml of dry tetrahydrofuran at -40 ° C. After stirring at the same temperature for 2 hours, 30 ml of water was added, acidified with 1N hydrochloric acid, and extracted with dichloromethane. After washing with saline,
It was dried and concentrated. The residue was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 2: 1) to obtain 4.49 g (yield 76.1%) of diphenylthioaldoxime having a melting point of 117 to 122 ° C.

NMR (CDCl ₃ , δppm, J = Hz) 8.44 (1H, s); 7.1-7.
44 (10H, m) (b) 3-phenylthio-5-cyano-2-isooxa
Zolin silver nitrate 164mg and potassium carbonate 67mg in water 10ml
Ether solution of 264 ml of acrylonitrile and 210 mg of diphenylthioaldoxime.
ml was added. After stirring at room temperature for 4 days, it was extracted with ether. The extract was washed with water, dried and concentrated, and the obtained residue was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 5: 1) to give the title compound as an oil (n _D
^23.6 (1.5885) as 147 mg (yield 89.4)
%)Obtained.

NMR (CDCl ₃ , δppm, J = Hz) 7.55-7.66 (5H, m);
7.38-7.48 (3H, m); 5.22 (1H, dd, J = 10.5,5.6); 3.41 (1H, dd,
J = 16.5,10.5); 3.28 (1H, dd, J = 16.5,5.6) Example 3 (method C-1) 3- (2-bromobenzylsulfinyl) -5-cyano
2-isoxazoline (Compound No. 166) 472 mg of 3- (2-bromobenzylthio) -5-cyano-2-isoxazoline was dissolved in 5 ml of dichloromethane, 323 mg of metachloroperbenzoic acid was added, and the mixture was stirred at 0 ° C. for 1 hour. .. After adding the sodium sulfite aqueous solution,
Extract with dichloromethane, wash with 1N sodium hydroxide then brine. After drying and concentrating, the resulting crude crystals were purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 3: 1) to obtain 330 mg (yield 66.3%) of the title compound as an oil. ..

NMR (CDCl3, δppm, J = Hz) 7.67-7.71 (1H, m);
7.25-7.44 (3H, m); 5.37 (1H, dd, J = 11.7,5.9); 4.59 (2H, d, J
= 1.7); 3.75 (1H, dd, J = 17.8,11.7); 3.41 (1H, dd, J = 17.8,5.
9) Example 4 (method C-2) 3-phenylsulfonyl-5-cyano-2-isooxa
Zoline (Compound No. 196) 124 mg of 3-phenylthio-5-cyano-2-isoxazoline was dissolved in 8 ml of dichloromethane, 314 mg of metachloroperbenzoic acid was added, and the mixture was stirred at room temperature for 24 hours. The mixture was poured into an aqueous solution of sodium hydrogen carbonate and extracted with dichloromethane. The crude crystals obtained by washing with water, drying, and concentrating are purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 2: 1) and have a melting point of 141-1.
139 mg of the title compound having 44.5 ° C. (yield 9
6.7%) was obtained.

NMR (CDCl ₃ , δppm, J = Hz) 8.00-8.11 (2H, m);
7.76-7.83 (1H, m); 7.62-7.69 (2H, m); 5.42 (1H, dd, J = 10.9,
7.3); 3.67-3.87 (2H, m) Example 5 (method D) 3- (4-methoxyphenylthio) -5-cyano-2-
19 mg of lithium hydride and 180 ml of p-methoxythiophenol were added to dry tetrahydrofuran of isoxazoline (Compound No. 42) . After stirring at room temperature for 10 minutes, 125 mg of 3-phenylsulfonyl-5-cyano-2-isoxazoline was added, and the mixture was further stirred for 2 hours. After adding 50 ml of water, the mixture was extracted with ether. The extract was washed with water, dried, and concentrated. Purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 4: 1) to give the title compound as an oil, 115 m.
g (yield 93%) was obtained.

NMR (CDCl ₃ , δppm, J = Hz) 7.49-7.54 (2H, m);
6.91-6.97 (2H, m); 5.20 (1H, dd, J = 10.5,5.6); 3.83 (3H, s);
3.37 (1H, dd, J = 16.9,10.5); 3.27 (1H, dd, J = 16.9,5.6) Example 6 (Method E) 3- (2-Bromo-α-acetoxybenzylthio) -5
-Cyano-2- isoxazoline (Compound No. 141) 3- (2-Bromobenzylsulfinyl) -5-cyano-2-isoxazoline 213 mg and acetic anhydride 0.42
The ml was heated at 100 ° C. for 25 hours. After adding water,
It was extracted with ethyl acetate, and the extract was washed with an aqueous sodium hydrogen carbonate solution. The residue obtained after drying and concentration was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 6: 1) to obtain 52 mg (yield 21.4%) of the title compound as an oil.

NMR (CDCl ₃ , δppm, J = Hz) 7.14-7.61 (4H, m);
5.26 (1H, dd, J = 9.9,5.8); 4.43 (1H, d, J = 1.6); 3.48 (1H, dd,
J = 16.4,9.9); 3.34 (1H, dd, J = 16.4,5.8); 2.16 (3H, d, J = 4.
3) Example 7 (Method F) 3- (2-bromo-α-cyanobenzylthio) -5-si
Ano 2- Isooki oxazoline (Compound No. 142) 3- (2-bromobenzyl) -5-cyano-2-isoxazoline 263mg of 1,2-dichloroethane 5
Dissolve in ml and sulphuryl chloride 0.0 at -30 ° C.
7 ml was added. After stirring at 60 ° C for 2 hours, cooling to room temperature, adding 0.59 ml of chlorotrimethyl cyanide,
Stir for 15 hours. Add water and extract with dichloromethane,
After drying and concentration, the residue was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 5: 1) to give 68 mg of the title compound having a melting point of 58-60 ° C.
(Yield 24%) was obtained.

NMR (CDCl ₃ , δppm, J = Hz) 7.22-7.87 (4H, m);
7.08-7.04 (1H, m); 5.29-5.41 (1H, m); 3.40-3.68 (2H, m) The physical properties of major derivatives are described below.

[0171]

[Table 3] Production method and physical properties of isoxazoline derivative ──────────────────────────────────── Compound physical property NMR (CDCL3, No. (melting point: ℃) Manufacturing method δppm, J = Hz) ───────────────────────────────── ─── 5 Oil D5.22 (1H, dd, J = 10.1,5.2); 3.87-3.72 (1H, m); 3.46 (1H, dd, J = 16.1,10.1); 3.3 4 (1H, dd, J) = 16.1,5.2); 1.45 (3H, d, J = 6.8); 1.43 (3H, d, J = 6.8) 10 oil B 5.24 (1H, dd, J = 10.1,5.2); 3.47 (1H, dd, J = 16.5,10.1); 3.35 (1H, dd, J = 16.5,5.2); 3.09 (2H, t, J = 7.3); 1.78-1.6 7 (2H, m); 1.59-1.36 (2H, m ); 0.94 (3H, t, J = 7.3) 28 oil B 7.55-7.66 (2H, m); 7.38-7.48 (3H, m); 5.22 (1H, dd, J = 10.5,5.6); 3.41 (1H , dd, J = 16.5,10.5); 3.28 (1H, dd, J = 16.5,5.6) 29 oil D 7.21-7.60 (4H, m); 5.22 (1H, dd, J = 10.5,5.2); 3.39 ( 1H, dd, J = 16.5, 10.5); 3.25 (1H, dd, J = 16.5,5.2); 2.50 (3H, s) 30 oil D 7.23-7.49 (4H, m); 5.22 (1H, dd, J) = 10.5,5.6); 3.40 (1H, dd, J = 16.5, 10.5); 3.28 (1H, dd, J = 16.5,5.6); 2.38 (3H, s) 31 oil D 7.46-7.50 (2H, m); 7.21-7.24 (2H, m); 5.21 (1H, dd, J = 10.5, 5.6); 3.38 (1H, dd, J = 16.9,10.5); 3.26 (1H, dd, J = 16.9,5.6); 2.38 (3H, s) 33 oil D 7.48-7.53 (2H, m); 7.24- 7.27 (2H, m); 5.21 (1H, dd, J = 10.5,5.6); 3.39 (1H, dd, J = 16.9,10.5); 3.27 (1H, dd, J = 16.9,5.6); 2.68 (2H, q, J = 7.7); 1.25 (3H, t, J = 7.7) 34 oil D 7.27-7.43 (4H, m); 5.22 (1H, dd, J = 10.5,5.6); 3.40 (1H, dd, J = 16.9, 10.5); 3.26 (1H, dd, J = 16.9,5.6); 2.93 (1H, septet, J = 6.9); 1.26 (6H, d, J = 6.9) 35 oil D 7.05-7.57 (4H, m); 5.21 (1H, dd, J = 10.5,5.6); 3.40 (1H, dd, J = 16.9, 10.5); 3.27 (1H, dd, J = 16.9,5.6); 2.93 (1H, septet, J = 7.3); 1.25 (6H, d, J = 7.3) 37 oil D 7.21-7.52 (4H, m); 5.21 (1H, dd, J = 10.5,5.6); 3.40 (1H, dd, J = 16.5, 10.5 ); 3.26 (1H, dd, J = 16.5,5.6); 2.61 (1H, dt, J = 7.3,6.9); 1.59 (2H, q, J = 7.3,); 1.23 (3H, d, J = 6.9) ; 0.82 (3H, t, J = 7.3) 39 70-71 D 40 oil D 7.55-7.58 (1H, m); 7.41-7.47 (1H, m); 6.96-7.02 (2H, m); 5.20 (1H , dd, J = 10.5,5.2); 3.92 (3H, s); 3.36 (1H, dd, J = 16.5,10.5); 3.24 (1H, dd, J = 16.5, 5.2) 41 oil D 7.30-7.36 (1H, t, J = 8.1); 6.95-7.18 (3H, m); 5.23 (1H, dd, J = 10.5,5.6); 3.83 (3H, s); 3.41 (1H, dd, J = 16.5, 10.5); 3.30 (1H, dd, J = 16.5,5.6) 42 oil D 7.49-7.54 (2H, m); 6.91-6.97 (2H, m); 5.20 (1H, dd, J = 10.5, 5.6); 3.83 (3H, s); 3.37 (1H, dd, J = 16.9,10.5); 3.27 (1H, dd, J = 16.9,5.6) 47 oil D 6.91-7.56 (9H, m); 5.23 ( 1H, dd, J = 10.5,5.6); 3.43 (1H, dd, J = 16.5, 10.5); 3.29 (1H, dd, J = 16.5,5.6) 48 oil D 7.14-7.63 (9H, m); 5.00 (1H, dd, J = 8.5,8.1); 4.24 (1H, d, J = 15.3); 4.21 (1H, d, J = 15.3); 2.99 (2H, d, J = 8.46) 49 112-113 D 50 Oil D 10.17 (1H, br); 7.53-7.69 (4H, m); 5.68 (1H, dd, J = 10.5,4.8); 3.55 (1H, dd, J = 16.9,10.5); 3.32-3.40 (1H , m); 2.06 (3H, s) 51 oil D 7.26-7.91 (4H, m); 5.31 (1H, dd, J = 10.5,5.6); 3.43 (1H, dd, J = 16.5, 10.5); 3.39 (1H, dd, J = 16.5,5.6) 52 oil D 7.40-7.74 (4H, m); 5.32 (1H, dd, J = 10.5,5.6); 3.43 (1H, dd, J = 16.5, 10.5); 3.39 (1H, dd, J = 16.5,5.6) 54 oil D 7.75-8.29 (4H, m); 5.33 (1H, dd, J = 10.5,5.6); 3.55 (1H, dd, J = 16.9, 10.5) 3.42 (1H, dd, J = 16.9,5.6) 56 oil D 7.51-7.86 (4H, m); 5.29 (1H, dd, J = 10.5,5.6); 3.47 (1H, dd, J = 16.5, 10.5); 3.37 (1H, dd, J = 16.5,5.6) 58 oil A 7.31-7.42 (4H, m) 5.24 (1H, dd, J = 10.5,5.6); 3.42 (1H, dd, J = 16.9, 10.5); 3.29 (1H, dd, J = 16.9,5.6); 2.50 (3H, s) 60 Oil D 7.65-7.74 (2H, m); 7.28-7.45 (2H, m); 5.26 (1H, dd, J = 10.5,5.6); 3.40 (1H, dd, J = 16.5,10.5); 3.32 (1H, dd, J = 16.5,5.6) 61 oil D 7.75-7.76 (1H, m); 7.52-7.60 (2H, m); 7.28-7.33 (1H, m); 5.27 (1H, dd, J = 10.5,5.6); 3.45 (1H, dd, J = 16.5, 10.5); 3.34 (1H, dd, J = 16.5,5.6) 62 51-61 D 63 oil D 7.30-7.73 (4H, m); 5.26 (1H, dd, J = 10.5,5.6); 3.44 (1H, dd, J = 16.9, 10.5); 3.33 (1H, dd, J = 16.9,5.6) 64 oil D 7.34-7.61 (4H, m); 5.26 (1H, dd, J = 10.5,5.6); 3.44 (1H, dd, J = 16.9, 10.5); 3.35 (1H, dd, J = 16.9,5.6) 65 71-73 D 66 oil D 7.17-7.64 (4H, m); 5.26 (1H, dd, J = 10.5,5.6); 3.47 (1H, dd, J = 16.9, 10.5); 3.32 (1H, dd, J = 16.9,5.6) 67 Oil D 7.09-7.45 (4H, m) 5.27 (1H, dd, J = 10.5,5.6); 3.46 (1H, dd, J = 16.9, 10.5); 3.32 (1H, dd, J = 16.9,5.6) 68 oil D 7.56-7.63 (2H, m) ); 7.17-7.09 (2H, m); 5.25 (1H, dd, J = 1 0.5,5.6); 3.43 (1H, dd, J = 16.9,10.5); 3.31 (1H, dd, J = 16.9, = 16.9,5.6) 78 Oil D 7.09-7.46 (3H, m); 5.21 (1H, dd, J = 10.5,5.2); 3.38 (1H, dd, J = 16.9, 10.5); 3.23 (1H, dd, J = 16.9,5.2); 2.44 (3H, s); 2.33 (3H, s) 79 oily Material A 7.14-7.33 (3H, m); 5.19 (1H, dd, J = 10.3,5.9); 3.38 (1H, dd, J = 16.8, 10.3); 3.23 (1H, dd, J = 16.8,5.9); 2.26 (6H, s) 80 oil D 7.19 (1H, s); 7.05 (1H, s); 5.21 (1H, dd, J = 10.5,5.6); 3.40 (1H, dd, J = 16.9,10.5); 3.27 (1H, dd, J = 16.9, 5.6); 2.33 (6H, s) 81 oil D 7.50-8.49 (3H, m); 5.32 (1H, dd, J = 10.5,5.6); 3.55 (1H, dd , J = 16.5, 10.5); 3.39 (1H, dd, J = 16.5,5.6); 2.61 (3H, s) 82 oil D 7.24-7.59 (3H, m); 5.25 (1H, dd, J = 10.5, 5.6); 3.44 (1H, dd, J = 16.9, 10.5); 3.30 (1H, dd, J = 16.9,5.6); 2.41 (3H, s) 83 oil A 7.20-7.53 (3H, m); 5.24 ( 1H, dd, J = 10.5,5.2); 3.42 (1H, dd, J = 16.5, 10.5); 3.27 (1H, dd, J = 16.5,5.2); 2.47 (3H, s) 84 61-64 D 85 oil Product D 7.21-7.28 (3H, m); 5.24 (1H, dd, J = 10.5,5.6); 3.43 (1H, dd, J = 16.9, 10.5); 3.29 (1H, dd, J = 16.9,5.6); 2.30 (3H, s) 87 Oil A 7.84 (1H, d, J = 2.3); 7.54 (1H, d, J = 8.5) ; 7.39 (1H, dd, J = 8.5,2.3); 5.27 (1H, dd, J = 10.3,5.7); 3.47 (1H, dd, J = 16.6,10.3); 3.32 (1H, dd, J = 16.6, 5.7) 88 oil A 7.34-7.87 (3H, m); 5.29 (1H, dd, J = 10.3,5.7); 3.49 (1H, dd, J = 16.6, 10.3); 3.34 (1H, dd, J = 16.6 , 5.7) 89 Oil A 7.69-7.75 (3H, m); 5.41 (1H, dd, J = 10.3,5.9); 3.50 (1H, dd, J = 16.7, 10.3); 3.36 (1H, dd, J = 16.7,5.9) 90 Oil A 7.49-7.89 (3H, m); 5.29 (1H, dd, J = 10.3,5.5); 3.48 (1H, dd, J = 16.8, 10.3); 3.33 (1H, dd, J = 16.8,5.5) 91 oil A 7.86 (2H, s); 5.31 (1H, dd, J = 7.7, 4.6); 3.39 (2H, dd, J = 7.7,4.6) 92 oil D 7.65 (1H, d) , J = 8.5); 7.56 (1H, d, J = 2.4); 7.32 (1H, dd, J = 8.5,2.4); 5.28 (1H, dd, J = 10.5,5.6); 3.47 (1H, dd, J = 16.5,10.5); 3.34 (1H, dd, J = 16.5,5.6) 93 74-75 A 94 oil D 7.31-7.49 (3H, m); 5.27 (1H, dd, J = 10.5,5.6); 3.47 (1H, dd, J = 16.5, 10.5); 3.32 (1H, dd, J = 16.5,5.6) 95 oil D 7.41-7.73 (3H, m); 5.26 (1H, dd, J = 10.5,5.3); 3.48 (1H, dd, J = 16.5, 10.5); 3.34 (1H, dd, J = 16.5,5.3) 96 oil A 7.42-7.50 (3H, m); 5.30 (1H, dd, J = 10.5,5.6) ; 3.50 (1H, dd, J = 16.5, 10.5); 3.36 (1H, dd, J = 16.5,5.6) 9 Oil A 7.71 (1H, d, J = 2.1); 7.58 (1H, d, J = 8.3); 7.47 (1H, dd, J = 8.3,2.1); 5.29 (1H, dd, J = 10.2,5.3) ; 3.49 (1H, dd, J = 16.4,10.2); 3.33 (1H, dd, J = 16.4,5.3) 99 oil D 7.30-7.75 (3H, m); 5.28 (1H, dd, J = 10.5,5.6 ); 3.49 (1H, dd, J = 16.5, 10.5); 3.35 (1H, dd, J = 16.5,5.6) 101 oil D 7.20-7.58 (3H, m); 5.28 (1H, dd, J = 10.5, 5.2); 3.49 (1H, dd, J = 16.5, 10.5); 3.35 (1H, dd, J = 16.5,5.2) 102 oil A 7.60-7.90 (3H, m); 5.31 (1H, dd, J = 10.3 , 5.6); 3.52 (1H, dd, J = 16.6, 10.3); 3.37 (1H, dd, J = 16.6,5.6) 103 Oil A 7.60-7.90 (3H, m); 5.31 (1H, dd, J = 10.3,5.7); 3.52 (1H, dd, J = 16.7, 10.3); 3.37 (1H, dd, J = 16.7,5.7) 104 oil D 7.79-7.88 (2H, m); 7.28 (1H, d, J = 7.7); 5.30 (1H, dd, J = 10.5,5.6); 3.51 (1H, dd, J = 16.5,10.5); 3.39 (1H, dd, J = 16.5,5.6) 109 Oil A 7.61 (1H, d, J = 2.4); 7.48 (1H, dd, J = 8.5,2.4); 6.96 (1H, d, J = 8.5); 5.24 (1H, dd, J = 10.5,5.6); 3.94 (3H, s) ; 3.43 (1H, dd, J = 16.5,10.5); 3.29 (1H, dd, J = 16.5,5.6) 112 69-72 D 114 48-52.5 D 115 oil A 7.14-7.34 (4H, m); 5.25 (1H, dd, J = 10.1,5.7); 4.33 (2H, s); 3.47 (1H, dd, J = 16.4,10.1); 3.33 (1H, dd, J = 16.4, 5.7); 2.38 (3H, s) 116 oil A 7.08-7.24 (4H, m); 5.24 ( 1H, dd, J = 10.1,5.7); 4.26 (2H, s); 3.46 (1H, dd, J = 16.4,10.1); 3.32 (1H, dd, J = 16.4,5.7); 2.33 (3H, s) 124 82-86 A 125 oil A 7.17-7.55 (4H, m); 5.27 (1H, dd, J = 10.2,5.8); 4.27 (2H, d, J = 2.0); 3.48 (1H, dd, J = 16.5,10.2); 3.35 (1H, dd, J = 16.5,5.9) 126 oil A 7.41-7,47 (2H, m); 7.22-7.27 (2H, m); 5.24 (1H, dd, J = 10.1 , 5.7); 4.23 (2H, s); 3.45 (1H, dd, J = 16.4,10.1); 3.31 (1H, dd, J = 16.4,5.6) 130 Oil A 7.47-7.52 (1H, m); 7.37 -7.43 (1H, m); 7.21-7.31 (2H, m); 5.26 (1H, dd, J = 10.1,5.2); 4.42 (2H, d, J = 2.4); 3.47 (1H, dd, J = 16.5 , 10.1); 3.34 (1H, dd, J = 16.5,5.2) 131 Oil A 7.37 (1H, s); 7.26-7.30 (1H, m); 5.27 (1H, dd, J = 10.5,5.2); 4.27 (2H, d, J = 3.6); 3.48 (1H, dd, J = 16.5,10.5); 3.35 (1H, dd, J = 16.5,5.2) 132 oil A 7.31 (4H, s); 5.26 (1H, dd, J = 10.1, 5.2); 4.26 (2H, d, J = 1.6); 3.46 (1H, dd, J = 16.5,10.1); 3.34 (1H, dd, J = 16.5,5.2) 134 Oil A 7.22 -7.28 (1H, m); 6.91-6.97 (2H, m); 6.82-6.86 (1H, m); 5.25 (1H, dd , J = 10.5,5.6); 4.29 (2H, s); 3.81 (3H, s); 3.47 (1H, dd, J = 16.5,10.5); 3.34 (1H, dd, J = 16.5,5.6) 135 oil A 7.26-7.31 (2H, m); 6.84-6.88 (2H, m); 5.25 (1H, dd, J = 10.1,5.2); 4.27 (2H, s); 3.80 (3H, s); 3.46 (1H, dd, J = 16.5, 10.1); 3.33 (1H, dd, J = 16.5,5.2) 139 Oil A 7.39-7.64 (4H, m); 5.27 (1H, dd, J = 10.1,5.2); 4.34 (2H , d, J = 3.6); 3.48 (1H, dd, J = 16.5,10.1); 3.35 (1H, dd, J = 16.5,5.2) 141 Oil E 7.14-7.61 (4H, m); 5.26 (1H, dd, J = 9.9,5.8); 4.43 (1H, d, J = 1.6); 3.48 (1H, dd, J = 16.4,9.9); 3.34 (1H, dd, J = 16.4,5.8); 2.16 (3H, d, J = 4.3) 142 58-60 F 143 Oil A 8.50-8.52 (1H, m); 7.62-7.71 (1H, m); 7.45-7.50 (1H, m); 7.17-7.23 (1H, m) 5.32 (1H, dd, J = 10.4,6.4); 3.75 (1H, dd, J = 16.8,10.4); 3.62 (1H, dd, J = 16.8,6.4) 148 Oil A 7.24-8.80 (4H, m) ); 5.29 (1H, dd, J = 10.4,5.8); 3.51 (1H, dd, J = 16.6, 10.4); 3.35 (1H, dd, J = 16.6,5.8) 149 Oil A 8.62 (2H, dd, J = 3.1,1.6); 7.51 (2H, dd, J = 3.1,1.6); 5.32 (1H, dd, J = 10.3, 5.9); 3.54 (1H, dd, J = 16.9,10.3); 3.40 (1H, dd, J = 16.9,5.9) 150 94-97 D 152 109-112 D 157 Material A 7.21-7.36 (5H, m); 5.26 (1H, dd, J = 10.2,5.5); 3.48 (1H, dd, J = 16.4, 10.2); 3.35 (2H, t, J = 7.3); 3.33 (1H, dd, J = 16.4, 5.5); 3.07 (2H, t, J = 7.3) 161 Oil C-1 7.57-7.73 (5H, m); 5.18-5.32 (1H, m); 3.69-3.81 ( 1H, m); 3.00-3.19 (1H, m) 162 107-111.5 C-1 163 Oil C-1 7.85-7.90 (1H, m); 7.70-7.77 (1H, m); 7.44-7.63 (2H, m); 5.22-5.35 (1H, m); 3.72-3.82 (1H, m); 3.04-3.22 (1H, m) 164 110-111 C-1 165 101-102 C-1 166 Oil C-1 7.67 -7.71 (1H, m); 7.25-7.44 (3H, m); 5.37 (1H, dd, J = 11.7,5.9); 4.59 (2H, d, J = 1.7); 3.75 (1H, dd, J = 17.8 , 11.7); 3.41 (1H, dd, J = 17.8,5.9) 167 oil C-1 7.25-7.61 (4H, m); 5.17-5.36 (1H, m); 4.14-4.39 (2H, m); 3.50 -3.69 (1H, m); 2.91-3.08 (1H, m) 168 Oil C-1 7.30-7.79 (4H, m); 6.44-6.52 (1H, m); 5.24-5.45 (1H, m); 3.57 -3.83 (2H, m) 173 66-70.5 C-2 178 oil C-2 5.44 (1H, dd, J = 10.5,7.7); 3.70-3.88 (2H, m); 3.48-3.66 (2H, m) ; 1.86-1.97 (2H, m); 1.44-1.65 (2H, m); 0.99 (3H, t, J = 7.3) 196 141-144.5 C-2 97 81-83 C-2 198 99-100.5 C-2 199 125-126 C-2 201 99.5-102 C-2 202 119-120 C-2 203 Oil C-2.47-7.98 (4H, m); 5.41 (1H, dd, J = 10.9,7.3); 3.81 (1H, dd, J = 17.3, 10.9); 3.71 (1H, dd, J = 17.3,7.3); 3.04 (1H, septet, J = 6.9); 1.30 (6H, d, J = 6.9) 205 oil C-2 7.42-7.94 (4H, m); 5.41 (1H, dd, J = 10.9,7.3); 3.81 (1H, dd, J = 17.3, 10.9) 3.71 (1H, dd, J = 17.3,7.3); 2.75 (2H, sextet, J = 6.9); 1.64 (2H, quintet, J = 7.3); 1.28 (3H, t, J = 6.9); 0.84 (3H , t, J = 7.3) 207 oil C-2 7.62-7.95 (4H, m); 5.41 (1H, dd, J = 1.11.3,7.7); 3.81 (1H, dd, J = 17.7, 11.3); 3.71 ( 1H, dd, J = 17.7,7.7); 1.37 (9H, s) 208 oil C-2 8.03-8.06 (1H, m); 7.67-7.73 (1H, m); 7.08-7.21 (2H, m); 5.45 (1H, dd, J = 10.9,6.5); 4.00 (3H, s); 3.87 (1H, dd, J = 17.3,10.9); 3.79 (1H, dd, J = 17.3, 6.5) 209 89-91.5 C -2 210 133.5-136 C-2 215 136-137 C-2 216 108-109 C-2 217 56-57 C-2 218 195-196 C-2 219 161-162 C-2 220 176- 177 C-2 222 153-155 C-2 224 77-79 C-2 226 116-117 C-2 228 115-120.5 C-2 229 132-133 C-2 230 130-139 C-2 231 106-110 C-2 232 121-126 C-2 233 111-117.5 C-2 234 132-133 C-2 235 121-122 C-2 236 129-130 C-2 246 78-79 C-2 247 96-97 C -2 248 117-118 C-2 249 84-85 C-2 250 108-109 C-2 251 149-153 C-2 252 115-117 C-2 253 113-114 C-2 255 119-121 C- 2 256 129-130 C-2 257 191-192 C-2 258 183-184 C-2 259 125-126 C-2 260 130-136 C-2 261 103-105 C-2 262 Oil C-2 7.29 -7.57 (3H, m); 5.50 (1H, dd, J = 10.5,7.3); 3.93 (1H, dd, J = 17.3, 10.5); 3.85 (1H, dd, J = 17.3,7.3) 263 120-121 C-2 264 163-166 C-2 266 168-169 C-2 267 116-117 C-2 2 8 79-80 C-2 269 113-114 C-2 270 79-80 C-2 271 90-92 C-2 272 76-80 C-2 278 84-86 C-2 294 130-133 C-2 296 107-110 C-2 297 89-90 C-2 298 46-51 C-2 299 82-87 C-2 306 92-93 C-2 307 96-99 C-2 308 113-114 C-2 312 Oil Product C-2 7.29-7.52 (4H, m); 5.35 (1H, dd, J = 11.5,7.0); 4.83 (2H, s); 3.59 (1H, dd, J = 17.6,11.4); 3.39 (1H, dd, J = 17.6, 7.0) 313 104-105 C-2 314 89-96 C-2 316 112-112.5 C-2 317 89-92 C-2 321 Oil C-2 7.45-7.67 (4H, m) ; 5.40 (1H, dd, J = 11.3,6.9); 4.73 (2H, s); 3.64 (1H, dd, J = 17.7,11.3); 3.51 (1H, dd, J = 17.7, 6.9) 325 87.5-88 C-28 355 oil B 7.54-7.61 (2H, m); 7.38-7.47 (3H, m); 3.22 (2H, ABq, J = 16.5); 1.80 (3H, s) 356 oil A 7.15-7.58 (4H, m); 3.18 (2H, ABq, J = 16.9); 2.49 (3H, s); 1.80 (3H, s) 357 oil A 7.13-7.35 (4H, m); 3.17 (2H, ABq, J = 18.3); 2.35 (3 H, s); 1.79 (3H, s) 358 oil A 7.10-7.50 (4H, m); 3.15 (2H, ABq, J = 18.3); 2.38 (3H, s); 1.79 (3H, s) 360 oil Material A 7.46 (2H, dd, J = 6.4,1.9); 7.21 (2H, dd, J = 6.4,1.9); 3.15 (2H, ABq, J = 16.8); 2.65 (2H, q, J = 7.6); 1.76 (3H, s); 1.20 (3H, t, J = 7.6) 361 Oil A 7.26-7.50 (4H, m); 3.21 (2H, ABq, J = 16.9); 2.93 (1H, septet, J = 6.9 ); 1.80 (3H, s); 1.26 (6H, d, J = 6.9) 362 oil A 7.01-7.51 (4H, m); 3.29 (2H, ABq, J = 16.9); 2.93 (1H, septet, J = 6.9); 1.79 (3H, s); 1.25 (6H, d, J = 6.9) 364 45-46 A 366 oil A 7.40-7.52 (4H, m); 3.22 (2H, ABq, J = 16.9); 1.80 (3H, s); 1.32 (9H, s) 367 Oil A 6.95-7.56 (4H, m); 3.92 (3H, s); 3.17 (2H, ABq, J = 16.9); 1.79 (3H, s) 368 oil A 6.94-7.35 (4H, m); 3.83 (3H, s); 3.23 (2H, ABq, J = 16.9); 1.81 (3H, s) 369 60-61 A 374 oil A 7.00-7.56 ( 9H, m); 3.24 (2H, ABq, J = 16.
5); 1.81 (3H, s) 375 oil A 7.51-7.62 (9H, m); 4.21 (2H, d, J = 3.6); 2.87 (2H, ABq, J = 16.9); 1.67 (3H, s) 377 98-99 A 383 oil A 7.54-7.85 (4H, m); 3.29 (2H, ABq, J = 16.9); 1.84 (3H, s) 374 oil A 7.26-7.41 (4H, m); 3.22 (2H, ABq, J = 16.9); 2.45 (3H, s); 1.81 (3H, s) 387 68-68.5 A 388 oil A 7.27-7.75 (4H, m); 3.26 (2H, ABq, J = 16.9); 1.83 (3H, s) 389 74-75 A 390 oil A 7.29-7.71 (4H, m); 3.25 (2H, ABq, J = 16.9); 1.82 (3H, s) 391 oil A 7.33- 7.60 (4H, m); 3.27 (2H, ABq, J = 16.9); 1.83 (3H, s) 392 oil A 7.37-7.54 (4H, m); 3.24 (2H, ABq, J = 16.9); 1.82 ( 3H, s) 393 oil A 7.09-7.68 (4H, m); 3.27 (2H, ABq, J = 16.9); 1.81 (3H, s) 394 oil A 7.10-7.45 (4H, m); 3.26 (2H) , ABq, J = 16.5); 1.83 (3H, s) 395 oil A 7.08-7.62 (4H, m); 3.24 (2H, ABq, J = 16.5); 1.81 (3H, s) 405 oil A 7.09- 7.40 (3H, m); 3.15 (2H, ABq, J = 16.7); 2.42 (3H, s); 2.31 (3H, s); 1.77 (3H, s) 406 Oil A 7.12-7.32 (3H, m) ; 3.17 (2H, ABq, J = 16.
8); 2.25 (6H, s); 1.77 (3H, s) 407 Oil A 7.16 (2H, bs); 7.02 (1H, bs); 3.18 (2
H, ABq, J = 16.9); 2.30 (6H, s); 1.77 (3H, s) 409 Oil A 7.22-7.57 (3H, m); 3.22 (2H, ABq, J = 16.8); 2.39 (3H, s); 1.79 (3H, s) 410 oil A 7.56 (1H, d, J = 2.2); 7.21-7.33 (2H, m); 3.20 (2H, ABq, J = 16.9); 2.43 (3H, s) ; 1.79 (3H, s) 411 107-108 A 412 Oil Ph A 7.36-7.40 (2H, m); 7.21-7.24 (2H, m); 7.06 (1H, t, J = 8.5); 3.26 (2H, ABq, J = 16.9); 2.34 (3H, s); 1.81 (3H, s) 413 57-58 A 415 87-88 A 416 Oil A 7.32-7.50 (3H, m); 3.26 (2H, ABq, J = 16.8,); 1.80 (3H, s) 417 oil A 7.65 (1H, dd, J = 6.8,2.3); 7.46 (1H, d dd, J = 8.6,6.8,2.3); 7.14-7.23 (1H, m); 3.25 (2H, ABq, J = 16.7); 1.82 (3H, S) 418 oil A 7.16-7.57 (3H, m); 3.27 (2H, ABq, J = 16.8,); 1.80 (3H, S) ) 419 oil A 7.45-7.85 (3H, m); 3.25 (2H, ABq, J = 16.8,); 1.81 (3H, S) 420 92-93 A 421 oil A 7.36-7.85 (3H, m); 3.28 (2H, ABq, J = 16.8); 1.84 (3H, s) 422 oil A 7.68-7.73 (3H, m); 3.30 (2H, ABq, J = 16.8); 1.85 (3H, s) 424 oil A 7.37-7.68 (3H, m); 3.26 (2H, ABq, J = 16.8); 1.81 (3H, s) 425 8 1-82 A 426 78-79 A 428 Oil A 7.48 (2H, d, J = 2.0); 7.42 (1H, t, J = 2.0); 3.29 (2H, ABq, J = 16.5); 1.84 (3H, s) 430 oil A 7.59-7.89 (3H, m); 3.32 (2H, ABq, J = 16.8); 1.85 (3H, s) 431 oil A 7.59-7.89 (3H, m); 3.32 (2H, ABq , J = 16.8); 1.85 (3H, s) 432 oil A 7.75-7.85 (2H, m); 7.25 (1H, t, J = 8.4); 3.28 (2H, ABq, J = 16.8); 1.82 (3H , s) 437 oil A 7.43-8.11 (7H, m); 3.24 (2H, ABq, J = 16.5); 1.79 (3H, s) 438 oil A 7.67-8.04 (6H, m); 3.09 (2H, m) ABq, J = 16.5); 1.73 (3H, s) 441 Oil A 7.31-7.39 (5H, m); 4.30 (2H, s); 3.29 (2H, ABq, J = 16.5); 1.83 (3H, s) 444 Oil A 7.13-7.28 (4H, m); 4.27 (2H, s); 3.28 (2H, ABq, J = 16.4); 2.34 (3H, s); 1.83 (3H, s) 450 65-66 A 455 Oil A 7.43-8.28 (4H, m); 4.33 (2H, dd, J = 16.1,13.3); 3.29 (2H, ABq, J = 16.52); 1.84 (3H, s) 462 Oil A 7.23-7.49 ( 4H, m); 4.23 (2H, s); 3.28 (2H, A
Bq, J = 16.5); 1.83 (3H, s) 466 oil A 7.21-7.52 (4H, m); 4.40 (2H, dd, J = 15.7,12.9); 3.29 (2H, ABq, J = 16.5); 1.83 (3H, s) 468 oil A 7.27-7.32 (4H, m); 4.25 (2H, s); 3.29 (2H, ABq, J = 16.5); 1.84 (3H, s) 503 83- 86 C-2 504 84-85 C-2 505 77-78 C-2 506 83-84 C-2 508 57-58 C-2 509 102-103 C-2 510 84-85 C-2 512 80-81 C-2 514 95-96 C-2 515 67-68 C-2 516 67-68 C-2 517 126-127 C-2 524 131-132 C-2 525 Oil C-2 7.09-8.15 (9H, m); 4.42 (2H, s); 3.41 (2H, ABq, J = 17.6); 1.74 (3H, s) 527 114-115 C-2 533 74-75.5 C-2 535 98-100 C-2 537 94 -95 C-2 538 104-106.5 C-2 539 102-103 C-2 540 93-94 C-2 541 99-101.5 C-2 542 94.5-95 C-2 543 73-74 C-2 544 102- 103 C-2 545 89-90 C -2 555 101-102 C-2 556 101-102 C-2 557 104-105 C-2 559 106-107 C-2 560 120-122 C-2 561 118-119 C-2 562 78-80.5 C- 2 563 77-78 C-2 564 98-98.5 C-2 565 120-121 C-2 566 102.5-103 C-2 567 105-106 C-2 569 103-104 C-2 570 172-174 C-2 571 122-124 C-2 572 158-159 C-2 574 136-137 C-2 575 77-78 C-2 576 127-128 C-2 578 119-122 C-2 580 81-82 C-2 581 82-84 C-2 582 107-109 C-2 587 109-110 C-2 588 142-143 C-2 589 112-113 C-2 592 97-98 C-2 598 79-80 C-2 603 100 -101 C-2 610 126-127 C-2 611 97-100 C-2 613 108-110 C-2 689 Oil A 8.27 (2H, d, J = 9.1); 7.75 (2H, d, J = 9.1) ); 3.60 (3H, s); 3.50 (2H, ABq, J = 17.6) 691 oily A 7.56 (2H, d, J = 8.6); 7.44 (2H, d, J = 8.6); 3.57 (3H, s); 3.41 (2H, ABq, J = 17.5) 692 Oil A 7.87 (1H, d, J = 2.2); 7.78 (1H, d, J = 6.3); 7.61 (1H, dd, J = 6.3.2.2); 3.58 (3H, s); 3.47 (2H, ABq, J = 17.4) 693 Oil A 7.84 (1H, d, J = 2.2); 7.77 (1H, d, J = 8.3); 7.38 (1H, dd, J = 8.3.2.2); 3.58 (3H, s); 3.44 (2H, ABq, J = 17.3) 694 oil A 7.42-7.48 (3H, m); 3.59 (3H, s); 3.45 (2H, ABq, J = 17.5) 698 89-91 C-2 700 97-99 C-2 701 oil C -8.27 (1H, d, J = 2.0); 8.01 (2H, d, J = 2.0); 3.82 (2H, ABq, J = 18.5); 3.63 (3H, s) 702 120-122 C-2 703 64 -65 C-2

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuhiko Kondo 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga In-house (72) Inventor Hakata Ota 1041 Yasu-cho Yasu-cho, Yasu-gun, Shiga (72) In-house (72) Inventor Shigehiro Kato 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga In-house (72) Inventor Shinichi Tanaka 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga Prefecture In-house

Claims (7)

[Claims] 1. A general formula: [Wherein, R ¹ represents a hydrogen atom; a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkoxy group, n represents 0, 1 or 2, and A represents a C ₁ -C ₆ alkyl group; C _3- C ₆ cycloalkyl group; C ₂ -C ₆ alkenyl selected from the following substituent group A group and optionally substituted with a phenyl group which may have the same or different 1 to 3 substituents Group; a C ₂ -C ₆ alkynyl group selected from the following substituent group A group and optionally substituted with a phenyl group which may have the same or different 1 to 3 substituents; Base group B
An aralkyl group selected from the group and optionally having 1 to 6 substituents which are the same or different (when the substituent is present, it is substituted with an alkylene moiety or an aryl moiety);
An aryl group selected from the following substituent group C group and optionally having 1 to 5 same or different substituents; the same or different 1 to 3 selected from the following substituent group A group
6-membered aromatic heterocyclic group containing 1 or 2 nitrogen atoms, which may have 1 substituent. ] The isoxazoline derivative represented by these. [Substituent Group A] halogen atom; C ₁ -C ₄ alkyl group; C ₁ -C ₄ alkoxy group [substituent group B] a halogen atom; C ₁ -C ₂ halogenated alkyl group; C ₁
-C ₄ alkyl radical; C ₂ -C ₅ alkanoyloxy group;
C ₁ -C ₄ alkoxy group, a hydroxyl group, a cyano group [substituent group C] a halogen atom; C ₁ -C ₂ halogenated alkyl group; C ₁
-C ₄ alkyl radical; C ₂ -C ₅ alkanoylamino group;
Selected from the substituent group A group described above; C ₁ -C ₄ alkylsulfonyl group; C ₁ -C ₄ alkylthio group; C ₁ -C ₄ alkoxy groups; C ₂ -C ₅ alkoxycarbonyl group; a cyano group; a nitro group A benzyl group which may have 1 to 3 substituents which are the same or different on the ring; which has 1 to 3 substituents which are the same or different and which are selected from the above-mentioned substituent group A group Good phenoxy group 2. An agricultural and horticultural fungicide containing the isoxazoline derivative of claim 1 as an active ingredient. 3. A general formula: (In the formula, R ¹ is the same as above. X is a halogen atom.) An isoxazoline derivative. 4. A general formula: (Wherein R ¹ is the same as above) and the acrylonitrile derivative represented by the general formula: (Wherein, X is the same as above), and is reacted with an oxime derivative represented by the general formula: (In the formula, R ¹ and X are the same as above.) A method for producing an isoxazoline derivative. 5. A general formula: (In the formula, A _a is a group defined by A and is selected from a C ₁ -C ₆ alkyl group, a C ₃ -C ₆ cycloalkyl group, and the above-mentioned substituent group A group, and the same or different 1 to 3 C ₂ -C which may be substituted with a phenyl group which may have a substituent
₆ alkenyl group, C ₂ -C ₆ alkynyl group selected from the above-mentioned substituent group A group, optionally substituted with phenyl group which may have the same or different 1 to 3 substituents, substituted on alkylene moiety An aralkyl group which does not have a group but which may have 1 to 4 substituents which are the same or different and are selected from the above-mentioned substituent group B group in the aryl group portion, and the aforementioned substituent group C
An aryl group selected from the group, which may have the same or different 1 to 5 substituents, and an aryl group selected from the aforementioned substituent group A, which may have the same or different 1 to 3 substituents A 6-membered aromatic heterocyclic group containing 1 or 2 nitrogen atoms is shown. ) And the general formula: (Wherein X is a halogen atom) is reacted with an isoxazoline derivative represented by the general formula: (In the formula, R ¹ and A _a are the same as above.) A method for producing an isoxazoline derivative. 6. A general formula: (Wherein R ¹ is the same as above) and the acrylonitrile derivative represented by the general formula: (Wherein A _b is the same as A _a above) and a mercaptooxime derivative represented by the general formula: (In the formula, R ¹ and A _b are the same as above.) A method for producing an isoxazoline derivative. 7. A general formula: (Wherein R ¹ and A are the same as above) by treating the isoxazoline derivative with an oxidizing agent. (Wherein R ¹ and A are the same as above) or the general formula: (In the formula, R ¹ and A are the same as above.) A method for producing an isoxazoline derivative.