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CN1216885C - Heterocycle substd. condensed heterocyclic derivs. with bioactivity - Google Patents

Heterocycle substd. condensed heterocyclic derivs. with bioactivity Download PDF

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Publication number
CN1216885C
CN1216885C CN 02139609 CN02139609A CN1216885C CN 1216885 C CN1216885 C CN 1216885C CN 02139609 CN02139609 CN 02139609 CN 02139609 A CN02139609 A CN 02139609A CN 1216885 C CN1216885 C CN 1216885C
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och
compound
chf
hnc
triazole
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CN1401648A (en
Inventor
侯仲轲
王晓光
任叶果
雷满香
臧开保
张立杰
黄明智
柳爱平
刘光辉
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Hunan Research Institute of Chemical Industry
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Hunan Research Institute of Chemical Industry
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Priority to CN 02139609 priority Critical patent/CN1216885C/en
Publication of CN1401648A publication Critical patent/CN1401648A/en
Priority to PCT/CN2003/000500 priority patent/WO2004024724A1/en
Priority to AU2003297067A priority patent/AU2003297067A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention discloses a heterocyclic substituted condensed heterocycle derivative (showed in the general formula (I)) and a preparing method thereof. A compound of the present invention has good herbicidal activity, the preventing effect on some broadleaf ruderal is at least 95% in the application at low dose of 18.75 ga. i/ha, and the compound is harmless to crops, such as wheat, corn, paddy rice, soybeans, etc. Meanwhile, some compounds have good bacteriostatic action for various fungal diseases, such as pestilence mildew and downy mildew.

Description

A kind of fused heterocyclic derivative of heterocyclic substituted of biologically active
Technical field: the fused heterocyclic derivative and preparation method thereof that the present invention relates to a kind of heterocyclic substituted of biologically active.
Background technology: we know 1,2,4, and 5-four substituted benzene compounds are a kind of proporphyrinogen oxidase inhibitors, have weeding activity.Wherein fused heterocycle four substituted benzene compounds have more biological activity, existing many abroad patent reports.For example: EP420194, USP5084084, USP5127935, USP5322835, USP6323154, DE3922107, JP03,47180, the compound of having reported following general formula such as USP5232898, WO96/28442 and WO0130782 has weeding activity:
Het is 2,4-(1H, 3H) pyrimidine dione, 1,3,4-thiadiazolidine ketone, 1,2,4-Triazolinones, pyrazoles, Evil (miaow) oxazolidinedione, phthalimide etc.
Wherein following compounds (flumioxazin) has good weeding activity (20-50ga.i/ha), commercialization (Sumisoya).
flumioxazin
Though above-mentioned various replacement fused heterocyclic derivative has weeding activity in various degree, the selective herbicidal effect to broadleaved herb that has is relatively poor, when being used for paddy rice, wheat, corn, Soybean and Other Crops weeding, can cause certain injury to crop itself; The bud pre-treatment that is only applicable to crop that has, relatively poor to weeds preventive effect in vegetative period; The interior suction conduction that also has is relatively poor, and is relatively poor to the elder weed preventive effect.
Summary of the invention: the purpose of this invention is to provide fused heterocyclic derivative of a kind of heterocyclic substituted and preparation method thereof.
Compound of the present invention is represented with general structure (I):
Figure C0213960900091
Wherein: n=0,1; X is carbon, nitrogen; Y, Z are oxygen or sulphur;
R is hydrogen, alkyl, thiazolinyl, alkynyl, alkynyl halide, alkyl carbonyl, carbalkoxy, alkanamine carbonyl, alkylsulfonyl, cyano group, amino;
R 1Be hydrogen, halogen, cyano group, nitro, amino, alkyl, alkoxyl group, alkylthio;
Het is 2,4-(1H, 3H) during pyrimidine (two) ketone structural formula of compound with general formula (II) expression; Be 1,3, structural formula of compound is represented with general formula (III) during 4-thiadiazolidine ketone; Be 1,2, structural formula of compound is represented with general formula (IV) during the 4-Triazolinones; Structural formula of compound is represented with logical formula V during for the phthaloyl cyclic imide; Structural formula of compound is represented with general formula (VI) during for the non-annularity phthalimide;
In the formula (II): n, X, Y, Z, R, R 1Same as above.
R 2=hydrogen, alkyl, thiazolinyl, alkynyl, alkoxyl group, alkylthio, alkyl carbonyl, carbalkoxy, cyano group, amino, cyano group; Better be alkyl and amino;
R 3=hydrogen, halogen, cyano group, amino, carboxyl, hydroxyl, alkyl, alkoxyl group, carbalkoxy, formyl radical, formamyl, oximido methyl, alkylsulfonyl; Better be amino;
Figure C0213960900101
In the formula (III): n, X, Y, Z, R, R 1Ditto described.
Figure C0213960900102
In the formula (IV): n, X, Y, Z, R, R 1Same as above.
R 4=hydrogen, alkyl, thiazolinyl, alkynyl, alkoxyl group, carbalkoxy, alkanamine carbonyl, alkyl sulphonyl, triazolyl, triazole methylene radical, triazole alkylsulfonyl; Better be alkyl, alkynyl, alkanamine carbonyl;
R 5=hydrogen, alkyl, thiazolinyl, alkynyl, halogen; It better is alkyl;
In the formula V: n, X, Y, Z, R, R 1Same as above.
In the formula (VI): n, X, Y, Z, R, R 1Same as above.
R 6=hydrogen, alkyl, alkyl carbonyl, alkene carbonyl, alkynes carbonyl, aryl carbonyl; Better be alkyl carbonyl, aryl carbonyl;
R 7=hydroxyl, alkoxyl group, alkylthio, alkylamino radical; Better be alkoxyl group, alkylamino radical;
Measure through biological screening, the fused heterocyclic derivative of finding the heterocyclic substituted of general formula of the present invention (I) has extraordinary biological activity, weeding activity is better than the conventional weedicide of use at present, when the low dosage of 18.75ga.i/ha is used, broadleaf weeds there is good preventive effect greater than 95%, to corn, wheat, soybean and rice safety.Formula (IV) compounds also has good fungicidal activity, under 100ppm concentration, to germ has greater than 90% protection and result of treatment such as downy mildew, epidemic disease be mould.
The present invention is prepared by the following method.
The preparation method of compound among 1 the present invention (II) is as follows:
Figure C0213960900111
Intermediate (A) adds corresponding substituted-amino chain acid ester in appropriate solvent, be heated to 30～150 ℃, and stirring reaction 1～12h obtains (D).Wherein solvent is an acetate preferably; Mol ratio is 1: 1 preferably; Preferable temperature is the solvent refluxing temperature; The more excellent reaction times is 3h.
Compound (D) adds acid binding agent in appropriate solvent and halide reaction obtains (II).Wherein solvent is DMF preferably; Acid binding agent is K preferably 2CO 3Mol ratio is (D) preferably: halogenide: K 2CO 3=1: 2: 3; 25 ℃ of preferable temperature; More excellent reaction times 24h.
Compound (D) adds ammoniation agent and obtains (II) in above-mentioned solvent and acid binding agent system.Wherein ammoniation agent is a 1-amino oxygen base-2 preferably, the 4-dinitrobenzene.
The preparation method of compound among 2 the present invention (III) is as follows:
Figure C0213960900121
Intermediate (A) obtains (H) with the thiophosgene processing in appropriate solvent.Better condition is: in toluene with excessive one times thiophosgene reflux 4h.
Compound (H) mixes with hexahydro-pyridazine in appropriate solvent, and stirring at room reaction 1～24h in the presence of suitable acid binding agent, adds 20% excessive phosgene toluene or thiophosgene and handles then, obtains general formula (III) compound.Wherein, better solvent is a methylene dichloride; Better mol ratio (H): hexahydro-pyridazine=1: 1; Stirring at room 12h; More excellent acid binding agent is a pyridine.
The preparation method of compound among 3 the present invention (IV) is as follows:
Figure C0213960900131
Intermediate (A) makes hydrazine (K) through diazotization, reduction, and good conditions is: use NaNO under 0 ℃ 2Diazotization, SnCl 2/ HCl reduction.
Compound (K) handles with aldehyde, sodium isothiocyanate and clorox successively that better condition is in the trimethyl carbinol that contains 12% water when obtaining (L) and wherein handling with aldehyde in appropriate solvent, use equimolar aldehyde, and stirring at room is reacted 4h; The more excellent condition of handling with sodium isothiocyanate is in same system, uses equimolar sodium isothiocyanate, stirring at room 4h; The more excellent condition of handling with clorox is to handle stirring at room 18h with 6% aqueous sodium hypochlorite solution of twice.
Compound (L) adds acid binding agent in appropriate solvent, handle obtaining general formula (IV) compound with corresponding halides.Better condition is in acetone, uses K 2CO 3Make acid binding agent, handle reflux 12h with equimolar bromide.
When R is thiazolinyl and alkynyl in the compound (IV), in the presence of appropriate solvent and catalyzer, can obtain the general formula that R is iodine thiazolinyl and iodine alkynyl (IV) compound with the processing of N-iodo succimide.Wherein solvent is an acetone preferably, and catalyzer is AgNO preferably 3
The preparation method of compound among 4 the present invention (V) is as follows:
Intermediate (A) is in appropriate solvent, and with 3,4,5, the 6-Tetra Hydro Phthalic Anhydride is handled and obtained (V), is logical formula V compound.Better condition is: in glacial acetic acid, and with equimolar 3,4,5,6-Tetra Hydro Phthalic Anhydride reflux 4h.
The preparation method of compound among 5 the present invention (VI) is as follows:
With 2,3,4, handle and obtain (O) by the 5-Tetra Hydro Phthalic Anhydride in appropriate solvent for intermediate (A), and esterification/amidation obtains (P) then, and last acidylate obtains general formula (VI) compound.Preparation (O) better condition is in acetone, stirring at room 24h; The better condition of esterification is to use H 2SO 4Make catalyzer, reflux, azeotropic dehydration; The better condition of acidylate is in the presence of catalyzer DMAP, reacts with carboxylic acid halides.
According to above-mentioned preparation method, synthesized the fused heterocyclic derivative of a series of heterocyclic substituted of the present invention, specifically see Table 1 to table 5.
Figure C0213960900151
Table 1
No n X Y Z R R1 R2 R3
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H H H H CH 3 CH 3 CH 3 CH 3 NH 2 NH 2 NH 2 NH 2 H H H H CH 3 CH 3 CH 3 CH 3 NH 2 NH 2 NH 2 NH 2 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3) CF 3) CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3) CF 3)
25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1 1 1 1 1 1 1 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H H H H H CH 3 CH 3 CH 3 CH 3 NH 2 NH 2 NH 2 NH 2 H H H H CH 3 CH 3 CH 3 CH 3 NH 2 NH 2 NH 2 NH 2 H H H H CH 3 CH 3 CH 3 CH 3 NH 2 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3) CF 3) CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3) CF 3) CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3
58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl NH 2 NH 2 NH 2 H H H H CH 3 CH 3 CH 3 CH 3 NH 2 NH 2 NH 2 NH 2 H H H H CH 3 CH 3 CH 3 CH 3 NH 2 NH 2 NH 2 NH 2 H H H H CH 3 CH 3 CF 3 CF 3) CF 3) CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3) CF 3) CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3) CF 3) CF 3 CF 3 CF 3 CF 3 CF 3 CF 3
91 92 93 94 95 96 1 1 1 1 1 1 C C C C C C O O O O O O O O O O O O CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH F CN H Cl F CN CH 3 CH 3 NH 2 NH 2 NH 2 NH 2 CF 3 CF 3 CF 3 CF 3 CF 3) CF 3)
Table 2
No. n X Y Z R R1
97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 C C C C C C C C C C C C C C C C C C C C C C C C O O O O 0 O O O O O O O O O O O O O O O S S S S O O O O O O O O O O O O O O O O S S S S O O O O H H H H CH 3 CH 3 CH 3 CH 3 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH H CH 3 CH 2C≡CI CH 2C≡CH H CH 3 CH 2C≡CI CH 2C≡CH H Cl F CN H Cl F CN H Cl F CN H Cl F CN F F F F F F F F
121 122 123 124 0 0 0 0 N N N N O O O O O O O O H CH 3 CH 2C≡CI CH 2C≡CH F F F F
125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 C C C C C C C C C C C C C C C C C C C C C C C C N N N N O O O O O O O O O O O O O O O O O O O O S S S S O O O O O O O O O O O O O O O O O O O O S S S S O O O O O O O O H H H H CH 3 CH 3 CH 3 CH 3 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH H CH 3 CH 2C≡CI CH 2C≡CH H CH 3 CH 2C≡CI CH 2C≡CH H CH 3 CH 2C≡CI CH 2C≡CH H Cl F CN H Cl F CN H Cl F CN H Cl F CN F F F F F F F F F F F F
Figure C0213960900211
Table 3
No. N X Y Z R R1 R4 R5
153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O H H H H H H H H H H H H H H H H H H H H H H H H CH 3 CH 3 H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡Cl CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C ≡ CI 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl CHF2 CHF 2 CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3
179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 198 199 200 201 202 203 204 205 206 207 208 209 210 211 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C ≡ CI 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl CHF2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3
212 213 214 215 216 217 218 219 220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C ≡ CI 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl CHF2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C ≡ CI 1.2.4-triazole alkylsulfonyl 1.2.4-triazole alkylsulfonyl 1.2.4-triazole alkylsulfonyl 1.2.4-triazole alkylsulfonyl CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3
245 246 247 248 249 250 251 252 253 254 255 256 257 258 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273 274 275 276 277 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 C C C C C C C C C N N N C C C C C C C C C C C C C C C C C C C C C O O O O O O O S S O O O O O O O O O O O O O O O O O O O O O O O O O O O O S S S O O O O S O O O O O O O O O O O O O O O O O O O O O CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH NH 2 CH 3 CH 2C≡CH NH 2 CH 2C≡CH CH 3 CH 2C≡CH H H H H H H H H H H H H H H H H H H H H H H Cl F CN F F F F F F F F H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H 1.2.4-triazole alkylsulfonyl 1.2.4-triazole alkylsulfonyl 1 2.4-triazole alkylsulfonyl 1.2.4-triazole alkylsulfonyl CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C ≡ CI 1.2.4-triazole alkylsulfonyl 1.2.4-triazole alkylsulfonyl 1.2.4-triazole alkylsulfonyl 1.2.4-triazole alkylsulfonyl 1.2.4-triazole alkylsulfonyl C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n
278 279 280 281 282 283 284 285 286 287 288 289 290 291 292 293 294 295 296 297 298 299 300 301 302 303 304 305 306 307 308 309 310 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O H H H CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl 1.2.4-triazole alkylsulfonyl 1.2.4-triazole alkylsulfonyl 1.2.4-triazole alkylsulfonyl CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C ≡ CI 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1 2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl CHF2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n
311 312 313 314 315 316 317 318 319 320 321 322 323 324 325 326 327 328 329 330 331 332 333 334 335 336 337 338 339 340 341 342 343 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 NH 2 CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CHF 2 CHF 2 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C ≡ CI 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1 2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.3.4-triazole sulfonyl CHF2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n
344 345 346 347 348 349 350 351 352 353 354 355 356 357 358 359 360 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 C C C C C C C C C C C C C C N N N O O O O O O O O O O O O S S O O O O O O O O O O O O S S S O O O O S CH 2C≡CI CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH NH 2 CH 3 CH 2C≡CH NH 2 CH 2C≡CH CH 3 CH 2C≡CH CN H Cl F CN H Cl F CN F F F F F F F F CH 2C ≡ CI 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl 1.2.4-triazole sulfonyl CHF2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 C 3H 7-n CH 3 CH 3 CH 3 CH 3 C 3H 7-n C 3H 7-n C 3H 7-n C 3H 7-n CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3
Figure C0213960900281
Table 4
No. n X Y Z R R1
361 362 363 364 365 366 367 368 369 370 371 372 373 374 375 376 377 378 379 380 381 382 383 384 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 C C C C C C C C C C C C C C C C C C C C C N N N O O O O O O O O O O O O O O O O O O O S S O O O O O O O O O O O O O O O O O O O S S S O O O O S H H H H CH 3 CH 3 CH 3 CH 3 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 3 CH 2C≡CH CH 2C≡CH CH 3 CH 2C≡CH CH 3 CH 2C≡CH H Cl F CN H Cl F CN H Cl F CN H Cl F CN F F F F F F F F
385 386 387 388 389 390 391 392 393 394 395 396 397 398 399 400 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O H H H H CH 3 CH 3 CH 3 CH 3 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH H Cl F CN H Cl F CN H Cl F CN H Cl F CN
Figure C0213960900301
Table 5
No. n X Y Z R R1 R6 R7
401 402 403 404 405 406 407 408 409 410 411 412 413 414 415 416 417 418 419 420 421 422 423 424 425 426 0 O 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O H H H H H H H H H H H H CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 2C≡CI CH 2C≡CI H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i OCH 3 OCH 3
427 428 429 430 431 432 433 434 435 436 437 438 439 440 441 442 443 444 445 446 447 448 449 450 451 452 453 454 455 456 457 458 459 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 O 0 0 0 0 0 0 0 0 0 0 0 0 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH H H H H H H H H H H H F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i
460 461 462 463 464 465 466 467 468 469 470 471 472 473 474 475 476 477 478 479 480 481 481 483 484 485 486 487 488 489 490 491 492 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O H CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO HNC 3H 7-i OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3
493 494 495 496 0 0 0 0 C C C C O O O O O O O O CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH H Cl F CN 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i
497 498 499 500 501 502 503 504 505 506 507 508 509 510 511 512 513 514 515 516 517 518 519 520 521 522 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O H H H H H H H H H H H H CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 2C≡CI CH 2C≡CI H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i OCH 3 OCH 3
523 524 525 526 527 528 529 530 531 532 533 534 535 536 537 538 539 540 541 542 543 544 545 546 547 548 549 550 551 552 553 554 555 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH H H H H H H H H H H H F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO C 2H 5CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i
556 557 558 559 560 561 562 563 564 565 566 567 568 569 570 571 572 573 574 575 576 577 578 579 580 581 582 583 584 585 586 587 588 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O H CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CI CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN H Cl F CN 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO HNC 3H 7-i OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i OCH 3 OCH 3 OCH 3 OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3 OCH 2CH 2OCH 3
589 590 591 592 1 1 1 1 C C C C O O O O O O O O CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH H Cl F CN 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO 3-F-C 6H 4CO HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i HNC 3H 7-i
Embodiment:
Below in conjunction with preparation and Application Example, the present invention will be further described:
Embodiment one: prepare weedicide 3-of the present invention (5-fluoro-3-propargyl-1,3-benzoxazolone-6-yl)-6-Trifluoromethyl-1 ,-methyl-2,4 (1H, 3H) pyrimidine dione (NO.43).
Chemical equation:
Get the amino benzoxazolone 2.06g of 3-propargyl-5-fluoro-6-, (N, N dimethylamine carbonyl) amido 4,4,4-trifluoromethyl butenoic acid ethyl 2.54g, glacial acetic acid 20ml is heated to backflow in reaction flask, stirring reaction 2h.Cooling is poured in the 200ml frozen water, separates out solid, filters washing, the dry intermediate that gets.This intermediate is dissolved among the 20mlDMF, adds 2,76gK 2CO 3With 2.13g methyl iodide, stirring at room 12h.Be poured into then in the 20ml frozen water and filter out solid, washing, drying, the post branch obtains (NO.43) 2.53g, yield 66%.
NMR:3.02 (m, 1H, pyrimidine ring H) 3.47 (S, 3H, N-CH 3) 4.75 (d, 2H, CH 2) 6.37 (S, 1H, C ≡ CH) 7.34 (d, 2H, phenyl ring H)
Can prepare 3-(5-fluoro-3-methyl isophthalic acid, 3-benzoxazolone-6-yl)-6-Trifluoromethyl-1-methyl-2,4 (1H, 3H) pyrimidine dione (NO.19) and similar compound thereof with method.
Embodiment two: prepare weedicide 9-of the present invention (5-fluoro-3-propargyl-1,3-benzoxazolone-6-yl)-8-sulphur-1,6-diaza-bicyclo [4,3,0] nonanone (NO.111)
Reaction formula:
Get the amino benzoxazolone 2.06g of 3-propargyl-5-fluoro-6-, be dissolved in the 20ml toluene, slowly add the 2.30g thiophosgene, reflux 2h.N is used in cooling 2Catch up with most residual air, precipitation gets the sulphur isocyanic ester.
In another reaction flask, add the 0.86g hexahydro-pyridazine and be dissolved in the 10ml dehydrated alcohol, below 10 degree, slowly slowly add above-mentioned sulphur isocyanic ester and be dissolved in the 15ml methylene dichloride, dropwise stirring at room 4h.With methylene dichloride dilution, washing, drying, precipitation, residual thing are dissolved in the 20ml ethylene dichloride, slowly drip 20% phosgene toluene 10ml under the room temperature.Stirring at room 12h then.Add the ethylene dichloride dilution, washing, drying, precipitation, the post branch obtains NO.111 2.42g, yield 68%.
NMR：1.76(m，4H) 2.32(m，4H) 4.70(d，2H) 6.39(S，1H) 7.35(d，2H)
Embodiment three: prepare weedicide N-of the present invention (5-fluoro-3-propargyl-1,3-benzoxazolone-6-yl) hexamethylene-1-alkene-1,2-dicarboximide (NO.375).
Reaction formula:
Figure C0213960900381
Get the amino benzoxazolone 2.06g of 3-propargyl-5-fluoro-6-, be dissolved in the 20ml glacial acetic acid, add 1.67g3,4,5,6-Tetra Hydro Phthalic Anhydride, reflux 4h then.Cooling is poured in the 200ml frozen water, filters out solid, washing, and drying, precipitation gets (NO.375) 3.00g, yield 88%.
NMR：3.68(m，4H) 3.79(m，4H) 4.72(d，2H) 6.31(S，1H) 7.30(d，2H)
Embodiment four: prepare sterilant 1-of the present invention (5-fluoro-3-iodine propargyl-1,3-benzoxazolone-6-yl)-3-n-propyl-4-iodine proyl Triazolinones (NO.239).
Reaction formula:
Figure C0213960900382
Get 3-propargyl-5-Fu benzoxazolone hydrazine 2.21g, be dissolved in the 40ml trimethyl carbinol: in the mixed solvent of water=88: 12, slowly drip the 0.72g butyraldehyde-n below 10 degree, then stirring at room 2h.Then in reaction flask, slowly add the soup compound that 0.97gNaSCN is dissolved in 2ml water, after adding, stirring at room 4h.Then in reaction, slowly drip the 20ml 6%NaClO aqueous solution, dropwise, stirring at room reaction 12h.Be poured in the 500ml frozen water, separate out solid, filter, washing, drying, precipitation, residual thing are dissolved in the 20ml acetone, add 4.5gN-iodo succimide, 0.2g AgNO 3, stirring at room 24h.Filter, precipitation, the post branch obtains (NO.239) 2.18g, yield 34%.
NMR：0.98(m，3H) 1.21(m，2H) 2.06(m，2H) 4.70(d，2H) 7.32(d，2H)
Application Example
Example one: potted plant weeding test
(1) reagent
Accurately take by weighing sample, after the The suitable solvent dissolving, add small amounts of emulsifiers, adding distil water is settled to 10ml and adopts suitable spraying machine sprinkling again, and reduced unit's area dose is 18.75ga.i/ha.
(2) examination material
Dicotyledonously select lamb's-quarters (Chenopodium album), piemarker (Abutilon theophrast) i, recessed amaranth (Amaranthus ascedense) for use, unifacial leaf is selected lady's-grass (Digitaria sanguinalis), barnyard grass grass (Echinochloa crus-galli), Herba Setariae Viridis (Setaria viridis) for use.
(3) cultivation of examination material plant
At sectional area 64cm 2The plastic tub alms bowl in quantitative dress soil, flatten, water permeable, choose full seed, lady's-grass of the same size, barnyard grass grass, Herba Setariae Viridis, piemarker, lamb's-quarters, recessed amaranth seed, divide single, double cotyledon plant to divide the pot culture kind, respectively account for 1/3 of alms bowl area, cover thick fine earth of 1cm and trickle, place hot-house culture.Treat that unifacial leaf examination material grows to 1 heart stage of 1 leaf, dicotyledonous examination material grows to 2 leaf periods, carry out seedling with soup after the cauline leaf spraying handle, soil treatment before the seedling is carried out in the sowing of examination material next day.Put back to the greenhouse subsequently.
(4) test
Range estimation overground part growing state calculates growth inhibition ratio after 15 days, growth inhibition ratio (%)=100 (contrast plant height-processing plant height)/contrast plant height.Carry out the weeding activity classification according to growth inhibition ratio: A level growth inhibition ratio＞90% B level growth inhibition ratio, 75～90% C level growth inhibition ratios, 50～75% D level growth inhibition ratios are less than 50%.
Part of compounds of the present invention such as compound N O.43 19 111 375 etc. respectively with the amount of application of 18.75gai./ha to potted plant examination material plant bud after cauline leaf handle, suppress the virulence effect and see Table 11.
Table 11: potted plant weeding test
Recessed amaranth of sample lady's-grass barnyard grass grass Herba Setariae Viridis lamb's-quarters piemarker
NO.43 D D D C B A
19 D D D A A A
111 D D D B B A
375 D D D C B B
As table 11 as can be known: four compounds of test all have certain preventive effect to broadleaf weeds under the low dosage of 18.75ga.i/ha, wherein O.19 compound N has good preventive effect to broadleaf weeds under the low dosage of 18.75ga.i/ha.But it is invalid to gramineous weeds under the low dosage of 18.75ga.i/ha.
Example two: crop safety test.
Choose full seed, paddy rice Oryza sativa of the same size, wheat Triticum aestivum, corn Zea mays, Chinese sorghum sorghum vulgare, soybean Glycine max and rape Brassicacampestris seed, use 0.1%HgCl 2Sterilization 5min, the back leaches and puts into little porcelain dish (putting wetting thieving paper) at 25 ℃ of growth chamber vernalization 24h with the distilled water 12h that soaks seed, and gets 10 in the consistent seed of size and bud length, is sowed at 64cm 2Quantitatively in the plastic tub alms bowl of dress soil, cover thick fine earth of 1cm and trickle, place hot-house culture.Treat that unifacial leaf examination material grows to 1 heart stage of 1 leaf, dicotyledonous examination material grows to 2 leaf periods, with 150,75,37.5,18.75,9.375, the 4.6875ga.i./ha soup carry out seedling after the cauline leaf spraying handle, the examination material is sowed and is carried out the preceding soil treatment of seedling next day, be contrast with spraying solvent and clear water respectively, twice repetition, handle the examination material and place hot-house culture, observe the crop symptom of being injured behind the 15d, range estimation overground part growth inhibition ratio.Growth inhibition ratio (%)=100 (contrast plant height-processing plant height)/contrast plant height is according to growth inhibition ratio estimation crop 1C ' 10Value, and in conjunction with weeds IC 90Value is pressed IC ' 10/ IC 90Calculate selectivity index (Z), safety grades standard: A: Z＞4 B, 2＜Z＜4 C Z＜2 can be considered safety more than the B level.
Compound of the present invention (NO.19) the results are shown in Table 12 to the safety experiment of crop
Table 12: safety experiment
Sample dose ga.i/ha rice and wheat rape corn jowar soybean
150 C A C A C C
75 C A C A C C
NO.19 37.5 B A C A C B
18.75 A A C A C A
9.375 A A C A C A
4.6875 A A B A C A
As table 12 as seen: compound N O.19 under the high dosage of 150ga.i/ha to wheat and corn safety.18.75ga.i/ha than under the low dosage to paddy rice and soybean safety.But to rape and jowar even also dangerous under the low dosage of 4.6875ga.i/ha.
Example three: bactericidal assay.
At greenhouse pot culture plant examination material, it is standby to grow to the certain period.The former medicinal a certain amount of DMF dissolving of testing compound is diluted with water to finite concentration.Spray pesticide is contrast with the examination material that sprays clear water to plant examination material, and after the spray medicine finished, it is In Shade air-dry that plant is tried material, carries out the disease inoculation after 24 hours.After the inoculation, plant is tried in the incubator that material is placed on fixed temperature and humidity, made infecting continuing of pathogenic bacteria.After inoculating a couple of days, when contrast is fully fallen ill, carry out the incidence survey of disease.The fungicidal activity grade is as follows: the A level: bacteriostasis rate＞90%; B level: bacteriostasis rate 75～90%; C level: bacteriostasis rate 50～75%; The D level: bacteriostasis rate is less than 50%.
Part of compounds of the present invention such as compound N O.239 with 100ppm concentration to potted plant examination material plant bud after cauline leaf handle, fungistatic effect sees Table 13.
Table 13: bacteriostatic experiment
The mould tomato late blight of sample Phytophthora nicotianae Phytophthora capsici cucumber epidemic disease potato late blight grape downy mildew
NO.239 A A A A A A
As shown in Table 13: new compound NO.239 has a bacteriostatic action preferably to various fungal diseases such as Yimeishuang cream against mould are mould.

Claims (4)

  1. The fused heterocyclic derivative of 1 one kinds of heterocyclic substituted is characterized in that it has following general structure (I)
    Figure C021396090002C1
    Het is:
    Figure C021396090002C2
    N=0; X is a carbon; Y, Z are oxygen;
    R is hydrogen, alkyl, thiazolinyl, alkynyl, alkynyl halide;
    R 1Be halogen;
    R 4=hydrogen, alkynyl;
    R 5=alkyl;
    Working as Het in its formula of (I) is:
    Figure C021396090003C1
    The time gained compound with general formula (III) expression:
    Figure C021396090003C2
    When Het is:
    The time gained compound with general formula (IV) expression:
    Figure C021396090003C4
    When Het is:
    The time gained compound represent with logical formula V:
  2. The preparation method of the fused heterocyclic derivative of 2 heterocyclic substituted according to claim 1 is characterized in that obtaining with following synthetic route;
    The reaction scheme of general formula (III) compound is:
    Intermediate (A) obtains (H) with excessive one times thiophosgene reflux 4h in toluene solvant; Compound (H) mixes with hexahydro-pyridazine in dichloromethane solvent, mol ratio (H): hexahydro-pyridazine=1: 1, stirring at room reaction 1～24h, in the presence of suitable acid binding agent pyridine, add 20% excessive phosgene toluene or thiophosgene and handle then, obtain general formula (III) compound;
    The reaction scheme of general formula (IV) compound is:
    Figure C021396090005C2
    Intermediate (A) makes hydrazine (K) through diazotization, reduction; Compound (K) uses equimolar aldehyde in the trimethyl carbinol that contains 12% water, stirring at room reaction 4h; Add equimolar sodium isothiocyanate stirring at room 4h again; 6% of the usefulness twice aqueous sodium hypochlorite solution is handled again, and stirring at room 18h obtains compound (L); Compound (L) adds acid binding agent K in acetone solvent 2CO 3, handling with equimolar bromide, reflux 12h obtains general formula (IV) compound;
    The reaction scheme of logical formula V compound is:
    Figure C021396090006C1
    Intermediate (A) is in the glacial acetic acid solvent, and with equimolar 3,4,5,6-Tetra Hydro Phthalic Anhydride reflux 4h obtains logical formula V compound.
  3. 3 one kinds of fused heterocyclic compounds, its structural formula is as follows:
  4. 4 fused heterocyclic derivatives according to claim 1 and 3 described heterocyclic substituted is characterized in that having weeding activity, under the dosage of 18.75ga.i/ha, and to preventive effect 〉=95% of broadleaf weeds, and to wheat, corn, paddy rice, soybean crops safety; Simultaneously, downy mildew mould by fungus-caused epidemic disease there are protection and therapeutic action.
CN 02139609 2002-09-13 2002-09-13 Heterocycle substd. condensed heterocyclic derivs. with bioactivity Expired - Fee Related CN1216885C (en)

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US4790868A (en) * 1986-03-17 1988-12-13 Ppg Industries, Inc. Herbicidally active substituted phenoxy or phenylthio benzoxazolone (or benzthiazolone) compounds
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