CN103145700A - 2-(2-benzyl hydrazono)-4-(benzofuran-5-yl) thiazole and preparation method and application thereof - Google Patents
2-(2-benzyl hydrazono)-4-(benzofuran-5-yl) thiazole and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to 2-(2-benzyl hydrazono)-4-(benzofuran-5-yl) thiazole as shown in the chemical structural formula I and salt thereof, wherein R and R1 are selected from H, C1-C2 alkyl, C3-C4 straight chain alkyl or branch chain alkyl; X1-X5 are selected from hydrogen, C1-C2 alkyl, hydroxyl, methoxyl, ethoxyl, trifluoromethyl, fluorine, chlorine, bromine and nitryl; thiosemicarbazone is reacted with 2-holo-1-(7-methoxyl-2, 2-dimethyl-2, 3-dihydrobenzofuran-5-yl) alkyl ketone, and is neutralized to prepare 2-(2-benzyl hydrazono)-4-(2,2-dimethly-2, 3-dihydrobenzofuran-5-yl) thiazole. The compound is applied to preparing bactericide.
Description
Technical field
The present invention relates to class new compound and its preparation method and application, specifically 2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and preparation method thereof and as the application of sterilant.
Background technology
Benzofuranol (chemical name 2,2-dimethyl-2,3-Dihydrobenzofuranes phenol) is the important intermediate of producing carbofuran, pacifying well the large-tonnage carbamates chemicals for agriculture such as prestige and benfuracarb.Therefore the carbamate chemicals for agriculture activity is high, be widely used, but toxicity is larger, needs that exploitation toxicity is lower, activity substitute products preferably, with the demand of satisfying the market.As everyone knows, the exploitation of a new varieties of pesticides needed for 8～10 years, add that present new varieties of pesticides registration required data and project are many, required expense reaches multi-billion dollar, therefore world's novel pesticide initiative company transfers to part energy with existing intermediate and develops pesticide new variety, be intended to shorten the construction cycle, reduce development cost.The effect such as antiviral, antibiotic and desinsection that thiazole compound has.Chinese patent has been described non-carbamate chemicals for agriculture or other functional compounds based on the benzofuranol research and development, and following table is listed in the preparation and application of particular compound in:
Table is based on the application patent of benzofuranol
Summary of the invention
The object of the present invention is to provide the 2-shown in the chemical structural formula I (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and salt thereof.
Ⅰ
Wherein, R is selected from: H, C
1~ C
2Alkyl, C
3~ C
4Straight chained alkyl or branched-chain alkyl; R
1Be selected from: H, C
1~ C
2Alkyl, C
3~ C
4Straight chained alkyl or branched-chain alkyl; X
1, X
5Be selected from: hydrogen, C
1~ C
2Alkyl, hydroxyl, methoxyl group, oxyethyl group, trifluoromethyl, fluorine, chlorine, bromine, nitro; X
2, X
4Be selected from: hydrogen, C
1~ C
2Alkyl, hydroxyl, methoxyl group, oxyethyl group, trifluoromethyl, fluorine, chlorine, bromine, nitro; X
3Be selected from: hydrogen, C
1~ C
2Alkyl, hydroxyl, methoxyl group, oxyethyl group, trifluoromethyl, fluorine, chlorine, bromine or nitro; Its salt is selected from hydrochloride, hydrobromate, nitrate, vitriol or phosphoric acid salt.
The object of the invention is to also provide 2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) preparation method of thiazole, its preparation comprises the steps:
2-halogen-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) reaction of alkyl ketone and thiosemicarbazone makes 2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole halogen acid salt (I .HX); 2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole halogen acid salt obtains 2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole through neutralization; Preparation is undertaken by following reaction formula:
Ⅰ.HX
Ⅰ.HX Ⅰ
In reaction formula, X is selected from: chlorine or bromine; R is selected from: H, C
1~ C
2Alkyl, C
3~ C
4Straight chained alkyl or branched-chain alkyl; R
1Be selected from: H, C
1~ C
2Alkyl, C
3~ C
4Straight chained alkyl or branched-chain alkyl; X
1, X
5Be selected from: hydrogen, C
1~ C
2Alkyl, hydroxyl, methoxyl group, oxyethyl group, trifluoromethyl, fluorine, chlorine, bromine, nitro; X
2, X
4Be selected from: hydrogen, C
1~ C
2Alkyl, hydroxyl, methoxyl group, oxyethyl group, trifluoromethyl, fluorine, chlorine, bromine, nitro; X
3Be selected from: hydrogen, C
1~ C
2Alkyl, hydroxyl, methoxyl group, oxyethyl group, trifluoromethyl, fluorine, chlorine, bromine or nitro; Its salt is selected from hydrochloride, hydrobromate, nitrate, vitriol or phosphoric acid salt.
the 2-that the object of the invention is to also provide (2-benzyl hydrazono-)-4-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or its salt are 2-[2-(2, 5-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole, 2-[2-(2, 3-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole, 2-[2-(3, 4-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole, 5-methyl-2-[2-(2, 3-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or 2-[2-(3, 4-benzyl dichloride hydrazono-)]-4-(7-oxyethyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or 2-[2-(2, 4-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt:
the 2-that the object of the invention is to also provide (2-benzyl hydrazono-)-4-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or its salt are 2-[2-(2-benzyl chloride hydrazono-s)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or 2-[2-(3-benzyl chloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or 2-[2-(4-fluorine benzyl hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt, 2-[2-(4-benzyl chloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt:
the 2-that the object of the invention is to also provide (2-benzyl hydrazono-)-4-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or its salt are 2-[2-(4-methoxybenzyl hydrazono-s)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or 2-[2-(4-methoxybenzyl hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or 2-[2-(4-methyl benzyl hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt, 2-[2-(2-methoxybenzyl hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt:
the 2-that the object of the invention is to also provide (2-benzyl hydrazono-)-4-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or its salt are 5-methyl-2-[2-(4-nitrobenzyl hydrazono-s)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or 2-[2-(2-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt, 2-[2-(3-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt, 2-[2-(4-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt:
The 2-that the object of the invention is to also provide (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) salt of thiazole is 2-[2-(2-hydroxyl-5-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt or 2-[2-(2-hydroxyl-4-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt:
The 2-that the object of the invention is to also provide (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole or its salt are 2-[2-(2-hydroxyl benzyl hydrazono-s)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole, 2-[2-(4-hydroxyl benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole or its hydrobromate:
the 2-that the object of the invention is to also provide (2-benzyl hydrazono-)-4-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or its salt are 2-[2-(2-hydroxyl-3-chloro-5-bromobenzyl hydrazono-s)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or 2-[2-(2-hydroxyl-3, 5-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt, 2-[2-(2-hydroxyl-3, 5-cyclite hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt, 2-[2-(2-hydroxyl-3, 5-diiodo-benzyl hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt:
The 2-that the object of the present invention is to provide (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole or its salt have good fungicidal activity, can use in the preparation sterilant.
The present invention compared with prior art has following advantage:
1. the present invention has prepared a class 2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole first.
2. find first that 2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and salt thereof have fungicidal activity, can be used for preparing sterilant.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1
The preparation of 2-bromo-1-(7-oxyethyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone (C1)
C1
4.66 g 1-(7-oxyethyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 80 mL ethanol, stirring and refluxing adds 8.96 g cupric bromides, reaction 2 h, reacting liquor while hot is filtered, and revolves to steam to reclaim solvent, acetic acid ethyl dissolution, weak acid scrubbing filters, washing, separatory, drying, underpressure distillation gets crude product, and ethyl alcohol recrystallization gets white solid C1; Yield 72.0%, 98 ~ 100 ℃ of m.p..
Embodiment 2
The preparation of 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone (C2)
C2
4.38 g 1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 80 mL ethanol, stirring and refluxing adds 8.96 g cupric bromides, reaction 2 h, reacting liquor while hot is filtered, and revolves to steam to reclaim solvent, acetic acid ethyl dissolution, weak acid scrubbing filters, washing, separatory, drying, underpressure distillation gets crude product, and ethyl alcohol recrystallization gets white solid C2; Yield 50.0%, 90 ~ 91 ℃ of m.p..
Embodiment 3
The preparation of 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) acetone (C3)
C3
9.37 g 1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) acetone, 120 mL ethanol stirring and refluxing add 18.02 g(0.08 mol in batches) cupric bromide, react 2 h, reacting liquor while hot is filtered, and revolves the steaming solvent, acetic acid ethyl dissolution, weak acid scrubbing, filter, filtrate is through washing, separatory, underpressure distillation gets crude product, and ethyl alcohol recrystallization gets white solid C3; Yield 97.8%, 85 ~ 87 ℃ of m.p..
Embodiment 4
2-[2-(4-fluorine benzyl hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.46 g thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip the ethanolic soln of 0.62 g p-Fluorobenzenecarboxaldehyde, reaction 1 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(4-fluorine benzyl hydrazono-) thioamides; Yield 96.4%, 195 ~ 197 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.20 g2-(4-fluorine benzyl hydrazono-) thioamides, 15 mL ethanol reflux, the TLC monitoring reaction, react 0.2 h, the cooling solid of separating out of reaction solution filters, dry, ethyl alcohol recrystallization gets 2-[2-(4-fluorine benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 64.9%, 200 ~ 201 ℃ of m.p..
1H NMR(CDCl
3，400 MHz) δ：1.54(s，6H，2×CH
3)，3.09(s，2H，CH
2)，3.98(s，3H，CH
3)，6.57(s，1H，thiazole 5-H)，7.12~7.17(m，4H，C
6H
2，C
6H
4 2,6-H)，7.70(q，J = 8.8Hz，J = 5.2Hz，2H，C
6H
4 3,5-H)，8.17(s，1H，N=CH）。
2-[2-(4-fluorine benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt obtains 2-[2-(4-fluorine benzyl hydrazono-) with ammonia neutralization]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 5
2-[2-(4-benzyl chloride hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.46 g thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip the ethanolic soln of 0.70 g 4-chloro-benzaldehyde, reaction 5.0 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(4-benzyl chloride hydrazono-) thioamides; Yield 87.9%, 209 ~ 211 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.21 g 2-(4-benzyl chloride hydrazono-) thioamides, 15 mL ethanol reflux, the TLC monitoring reaction, react 1.0 h, the cooling solid of separating out of reaction solution filters, dry, ethyl alcohol recrystallization gets 2-[2-(4-benzyl chloride hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 56.2%, 217 ~ 219 ℃ of m.p..
1H NMR(CDCl
3，400 MHz) δ：1.55(s，6H，2×CH
3)，3.09(s，2H，CH
2)，3.99(s，3H，CH
3)，6.56(s，1H，thiazole 5-H)，7.14(s，2H，C
6H
2)，7.43(d，J = 8.8Hz，2H，C
6H
4 2,6-H)，7.65(d，J = 8.8Hz，2H，C
6H
4 3,5-H)，8.23(s，1H，N=CH）。
2-[2-(4-benzyl chloride hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt obtains 2-[2-(4-benzyl chloride hydrazono-) with ammonia neutralization]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 6
2-[2-(2,4-benzyl dichloride hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.46 g thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip the ethanolic soln of 0.88 g 2,4 dichloro benzene formaldehyde, reaction 2.0 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(2,4-benzyl dichloride hydrazono-) thioamides; Yield 72.6%, 238 ~ 240 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.25 g 2-(2,4-benzyl dichloride hydrazono-) thioamides, 15 mL ethanol reflux, the TLC monitoring reaction, react 1.0 h, the cooling solid of separating out of reaction solution filters drying, ethyl alcohol recrystallization gets 2-[2-(2,4-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 73.7%, 227 ~ 228 ℃ of m.p..
1H NMR(DMSO-d
6，400 MHz) δ：1.43(s，6H，2×CH
3)，3.03(s，2H，CH
2)，3.79(s，3H，CH
3)，7.17(s，1H，thiazole 5-H)，7.30(s，2H，C
6H
2)，7.51(dd，J = 8.4Hz，J = 2.0Hz，1H，C
6H
3 5-H)，7.69(d，J = 2.0Hz，1H，C
6H
3 3-H)，7.91(d，J = 8.4Hz，1H，C
6H
3 6-H)，8.32(s，1H，N=CH)，12.45(brs，1H，NH）。
2-[2-(2,4-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt obtains 2-[2-(2 with ammonia neutralization, 4-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 7
2-[2-(4-methyl benzyl hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.46 g thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip the ethanolic soln of 0.60 g4-tolyl aldehyde, reaction 2.0 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(4-methyl benzyl hydrazono-) thioamides B4; Yield 80.8%, 166 ~ 168 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.19 g 2-(4-methyl benzyl hydrazono-) thioamides (B4), 15 mL ethanol reflux, the TLC monitoring reaction, react 0.3 h, the cooling solid of separating out of reaction solution filters, dry, ethyl alcohol recrystallization gets 2-[2-(4-methyl benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 67.4%, 221 ~ 223 ℃ of m.p..
1H NMR(DMSO-d
6，400 MHz) δ：1.43(s，6H，2×CH
3)，2.33(s，3H，CH
3)，3.03(s，2H，CH
2)，3.79(s，3H，CH
3)，7.11(s，1H，thiazole 5-H)，7.25(d，J = 8.0Hz，2H，C
6H
4 3,5-H)，7.29(s，2H，C
6H
2)，7.54(d，J = 8.0Hz，2H，C
6H
4 2,6-H)，7.99(s，1H，N=CH)，12.07(brs，1H，NH）。
2-[2-(4-methyl benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt obtains 2-[2-(4-methyl benzyl hydrazono-) with ammonia neutralization]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 8
2-[2-(2-methoxybenzyl hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.46 g thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip the ethanolic soln of 0.68 g Benzaldehyde,2-methoxy, reaction 4.0 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(2-methoxybenzyl hydrazono-) thioamides B5; Yield 84.2%, 215 ~ 216 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.21 g 2-(2-methoxybenzyl hydrazono-) thioamides (B5), 15 mL ethanol reflux, the TLC monitoring reaction, react 0.3 h, the cooling solid of separating out of reaction solution filters, dry, ethyl alcohol recrystallization gets 2-[2-(2-methoxybenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 73.5%, 224 ~ 226 ℃ of m.p..
1H NMR(DMSO-d
6，400 MHz) δ：1.43(s，6H，2×CH
3)，3.03(s，2H，CH
2)，3.79(s，3H，CH
3)，3.85(s，3H，CH
3)，7.01(t，J = 7.2Hz，1H，C
6H
4 5-H)，7.09(d，J = 8.0Hz，1H，C
6H
4 3-H)，7.10(s，1H，thiazole 5-H)，7.29(s，2H，C
6H
2)，7.37(td，J = 7.2Hz，J = 1.6Hz，1H，C
6H
4 4-H)，7.78(dd，J = 8.0Hz，J = 1.6Hz，1H，C
6H
4 6-H)，8.34(s，1H，N=CH）。
2-[2-(2-methoxybenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt (obtain 2-[2-(2-methoxybenzyl hydrazono-) with ammonia neutralization]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 9
2-[2-(2-nitrobenzyl hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.46 g thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip the ethanolic soln of 0.76 g 2-nitrobenzaldehyde, reaction 5.0 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(2-nitrobenzyl hydrazono-) thioamides B6; Yield 96.4%, 246 ~ 247 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.22 g 2-(2-nitrobenzyl hydrazono-) thioamides (B6), 15 mL ethanol reflux, the TLC monitoring reaction, react 0.3 h, the cooling solid of separating out of reaction solution filters, dry, ethyl alcohol recrystallization gets 2-[2-(2-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 85.4%, 221 ~ 223 ℃ of m.p..
1H NMR(DMSO-d
6，400 MHz) δ：1.43(s，6H，2×CH
3)，3.04(s，2H，CH
2)，3.79(s，3H，CH
3)，7.19(s，1H，thiazole 5-H)，7.30(s，2H，C
6H
2)，7.61(t，J = 7.2Hz，1H，C
6H
4 5-H)，7.79(t，J = 7.6Hz，1H，C
6H
4 4-H)，8.04(d，J = 8.0Hz，2H，C
6H
4 3,6-H)，8.41(s，1H，N=CH)，12.54(brs，1H，NH）。
2-[2-(2-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt obtains 2-[2-(2-nitrobenzyl hydrazono-) with ammonia neutralization]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 10
2-[2-(3-nitrobenzyl hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.46 g thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip the ethanolic soln of 0.76 g3-nitrobenzaldehyde, reaction 2.0 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(3-nitrobenzyl hydrazono-) thioamides B7; Yield 89.3%, 231 ~ 232 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.22 g 2-(3-nitrobenzyl hydrazono-) thioamides (B7), 15 mL ethanol reflux, the TLC monitoring reaction, react 0.3 h, the cooling solid of separating out of reaction solution filters, dry, ethyl alcohol recrystallization gets 2-[2-(3-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 83.3%, 238 ~ 240 ℃ of m.p..
1H NMR(DMSO-d
6，400 MHz) δ：1.43(s，6H，2×CH
3)，3.04(s，2H，CH
2)，3.80(s，3H，CH
3)，7.18(s，1H，thiazole 5-H)，7.31(s，2H，C
6H
2)，7.73(t，J = 8.0Hz，1H，C
6H
4 5-H)，8.09(d，J = 8.0Hz，1H，C
6H
4 6-H)，8.14(s，1H，C
6H
4 2-H)，8.20(dd，J = 8.4Hz，J = 1.6Hz，1H，C
6H
4 4-H)，8.47(s，1H，N=CH)，12.47(brs，1H，NH）。
2-[2-(3-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt obtains 2-[2-(3-nitrobenzyl hydrazono-) with ammonia neutralization]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 11
2-[2-(4-nitrobenzyl hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.46 g thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip the ethanolic soln of 0.76 g4-nitrobenzaldehyde, reaction 4.0 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(4-nitrobenzyl hydrazono-) thioamides B8; Yield 98.2%, 238 ~ 239 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.22 g 2-(4-nitrobenzyl hydrazono-) thioamides (B8), 15 mL ethanol reflux, the TLC monitoring reaction, react 0.2 h, the cooling solid of separating out of reaction solution filters, dry, ethyl alcohol recrystallization gets 2-[2-(4-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 85.4%, 223 ~ 225 ℃ of m.p..
1H NMR(CDCl
3，400 MHz) δ：1.55(s，6H，2×CH
3)，3.10(s，2H，CH
2)，3.99(s，3H，CH
3)，6.63(s，1H，thiazole 5-H)， 7.15(s，2H，C
6H
2)，7.88(d，J = 8.8Hz，2H，C
6H
4 2,6-H)，8.31(d，J = 8.8Hz，2H，C
6H
4 3,5-H)，8.31(s，1H，N=CH）。
2-[2-(4-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt obtains 2-[2-(4-nitrobenzyl hydrazono-) with ammonia neutralization]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 12
2-[2-(2-hydroxyl-5-nitrobenzyl hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.46 g thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip the ethanolic soln of 0.84 g 2-hydroxyl-5-nitrobenzaldehyde, reaction 2.0 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(2-hydroxyl-5-nitrobenzyl hydrazono-) thioamides B9; Yield 95.8%, 243 ~ 244 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.24 g 2-(2-hydroxyl-5-nitrobenzyl hydrazono-) thioamides (B9), 15 mL ethanol reflux, the TLC monitoring reaction, react 1.0 h, the cooling solid of separating out of reaction solution filters, dry, ethyl alcohol recrystallization gets 2-[2-(2-hydroxyl-5-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 84.1%, 237 ~ 238 ℃ of m.p..
1H NMR(CDCl
3，400 MHz) δ：1.55(s，6H，2×CH
3)，3.10(s，2H，CH
2)，3.99(s，3H，CH
3)，6.64(s，1H，thiazole 5-H)，7.13~7.17(m，3H，C
6H
2，C
6H
3 3-H)，8.28~8.33(m，2H，C
6H
3 4,6-H)，8.57(s，1H，N=CH)，10.09(s，1H，OH)，13.68(brs，1H，NH)，14.05(brs，1H，HBr）。
2-[2-(2-hydroxyl-5-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt obtains 2-[2-(2-hydroxyl-5-nitrobenzyl hydrazono-) with ammonia neutralization]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 13
2-[2-(2-hydroxyl benzyl hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.46 g thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip the ethanolic soln of 0.61 g Benzaldehyde,2-hydroxy, reaction 4.0 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(2-hydroxyl benzyl hydrazono-) thioamides B10; Yield 94.4%, 222 ~ 224 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.20 g 2-(2-hydroxyl benzyl hydrazono-) thioamides (B10), 15 mL ethanol reflux, the TLC monitoring reaction, react 0.2 h, the cooling solid of separating out of reaction solution filters, dry, ethyl alcohol recrystallization gets 2-[2-(2-hydroxyl benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 54.1%, 203 ~ 205 ℃ of m.p..
1H NMR(DMSO-d
6，400 MHz) δ：1.43(s，6H，2×CH
3)，3.03(s，2H，CH
2)，3.79(s，3H，CH
3)，6.88(t，J = 7.2Hz，1H，C
6H
4 5-H)，6.90(d，J = 8.4Hz，1H，C
6H
4 3-H)，7.11(s，1H，thiazole 5-H)，7.22(td，J = 8.4Hz，J = 1.6Hz，1H，C
6H
4 4-H)，7.29(s，2H，C
6H
2)，7.61(d，J = 7.2Hz，1H，C
6H
4 6-H)，8.30(s，1H，N=CH)，10.09(brs，1H，OH)，12.11(brs，1H，NH)。
2-[2-(2-hydroxyl benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt obtains 2-[2-(2-hydroxyl benzyl hydrazono-) with ammonia neutralization]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 14
2-[2-(4-hydroxyl benzyl hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.46 g thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip the ethanolic soln of 0.61 g4-hydroxy benzaldehyde, reaction 2.0 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(4-hydroxyl benzyl hydrazono-) thioamides B11; Yield 89.2%, 225 ~ 227 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.20 g 2-(4-hydroxyl benzyl hydrazono-) thioamides (B11), 15 mL ethanol reflux, the TLC monitoring reaction, react 0.3 h, the cooling solid of separating out of reaction solution filters, dry, ethyl alcohol recrystallization gets 2-[2-(4-hydroxyl benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 52.0%, 233 ~ 234 ℃ of m.p..
1H NMR(DMSO-d
6，400 MHz) δ：1.42(s，6H，2×CH
3)，3.03(s，2H，CH
2)，3.79(s，3H，CH
3)，6.82(d，J = 8.8Hz，2H，C
6H
4 3,5-H)，7.08(s，1H，thiazole 5-H)，7.28，7.29(2×s，2H，C
6H
2)，7.48(d，J = 8.8Hz，2H，C
6H
4 2,6-H)，7.93(s，1H，N=CH)，9.86(brs，1H，OH)，11.94(brs，1H，NH）。
2-[2-(4-hydroxyl benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt obtains 2-[2-(4-hydroxyl benzyl hydrazono-) with ammonia neutralization]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 15
2-[2-(2-hydroxyl-3,5-benzyl dichloride hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.46 g thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip 0.96 g 2-hydroxyl-3, the ethanolic soln of 5-dichlorobenzaldehyde, reaction 5.0 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(2-hydroxyl-3,5-benzyl dichloride hydrazono-) thioamides B12; Yield 68.2%, 242 ~ 244 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.26 g 2-(2-hydroxyl-3,5-benzyl dichloride hydrazono-) thioamides (B12), 15 mL ethanol, reflux, the TLC monitoring reaction, react 0.3 h, the cooling solid of separating out of reaction solution filters drying, ethyl alcohol recrystallization gets 2-[2-(2-hydroxyl-3,5-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 80.7%, 257 ~ 259 ℃ of m.p..
1H NMR(CDCl
3，400 MHz) δ：1.55(s，6H，2×CH
3)，3.10(s，2H，CH
2)，3.99(s，3H，CH
3)，6.62(s，1H，thiazole 5-H)，7.13，7.14(2×s，2H，C
6H
2)，7.31(d，J = 2.4Hz，1H，C
6H
2 6-H)，7.49(d，J = 2.4Hz，1H，C
6H
2 4-H)，8.46(s，1H，N=CH)，9.48(s，1H，OH）。
2-[2-(2-hydroxyl-3,5-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt obtains 2-[2-(2-hydroxyl-3 with ammonia neutralization, 5-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 16
2-[2-(2-hydroxyl-3,5-cyclite hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.46 g thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip 1.40 g 2-hydroxyls-3, the ethanolic soln of 5-dibromo benzaldehyde, reaction 2.0 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(2-hydroxyl-3,5-cyclite hydrazono-) thioamides B13; Yield 90.1%, 237 ~ 238 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.35 g 2-(2-hydroxyl-3,5-cyclite hydrazono-) thioamides (B13), 15 mL ethanol, reflux, the TLC monitoring reaction, react 0.2 h, the cooling solid of separating out of reaction solution filters drying, ethyl alcohol recrystallization gets 2-[2-(2-hydroxyl-3,5-cyclite hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 83.4%, 263 ~ 265 ℃ of m.p..
1H NMR(CDCl
3，400 MHz) δ：1.55(s，6H，2×CH
3)，3.10(s，2H，CH
2)，3.98(s，3H，CH
3)，6.63(s，1H，thiazole 5-H)，7.12，7.14(2×s，2H，C
6H
2)，7.47(d，J = 2.0Hz，1H，C
6H
2 6-H)，7.78(d，J = 2.0Hz，1H，C
6H
2 4-H)，8.41(s，1H，N=CH)，9.66(s，1H，OH）。
2-[2-(2-hydroxyl-3,5-cyclite hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt obtains 2-[2-(2-hydroxyl-3 with ammonia neutralization, 5-cyclite hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 17
2-[2-(2-hydroxyl-3,5-diiodo-benzyl hydrazono-)]-preparation of 4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and hydrobromate thereof
0.18 g(2 mmol) thiosemicarbazide, 20 mL alcohol-waters (1: 3) reflux, and slowly drip 0.75 g(2 mmol) 2-hydroxyl-3, the ethanolic soln of 5-diiodo-benzene formaldehyde, reaction 2.0 h.The cooling solid of separating out of reaction solution filters, drying, and ethyl alcohol recrystallization gets 2-(2-hydroxyl-3,5-diiodo-benzyl hydrazono-) thioamides B14; Yield 81.7%, 210 ~ 211 ℃ of m.p..
0.30 g 2-bromo-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 0.45 g 2-(2-hydroxyl-3,5-diiodo-benzyl hydrazono-) thioamides (B14), 15 mL ethanol, reflux, the TLC monitoring reaction, react 1.0 h, the cooling solid of separating out of reaction solution filters drying, ethyl alcohol recrystallization gets 2-[2-(2-hydroxyl-3,5-diiodo-benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt; Yield 79.3%, 237 ~ 239 ℃ of m.p..
1H NMR(CDCl
3，400 MHz) δ：1.55(s，6H，2×CH
3)，3.10(s，2H，CH
2)，3.98(s，3H，CH
3)，6.62(s，1H，thiazole 5-H)，7.11，7.13(2×s，2H，C
6H
2)，7.61(d，J = 2.0Hz，1H，C
6H
2 6-H)，8.13(d，J = 2.0Hz，1H，C
6H
2 4-H)，8.33(s，1H，N=CH)，10.08(s，1H，OH）。
2-[2-(2-hydroxyl-3,5-diiodo-benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt obtains 2-[2-(2-hydroxyl-3 with ammonia neutralization, 5-diiodo-benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole.
Embodiment 18
The fungicidal activity of 2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole is measured
1 test objective
At indoor measurement new compound under for examination concentration to the virulence of various pathogenic bacterias, its fungicidal activity of preliminary assessment.
2 test conditionss
2.1 for the examination target
Sclerotinia sclerotiorum (Sclerotonia sclerotiorum); Bacterial classification all is kept in refrigerator (4-8 ℃), is inoculated in culture dish from the test tube slant in 2-3 days before test, cultivates to be for experiment under optimal temperature.Experiment is potato agar substratum (PDA) with substratum.
Wheat powdery mildew (Blumeria graminis) is preserved spore with stem and leaf of Wheat and is for experiment.
2.2 culture condition
Culture condition for target after examination target and test is 25 ± 5 ℃ of temperature, relative humidity 65 ± 5%
2.3 plant and instrument
Beaker, transfer pipet, graduated cylinder, culture dish, high-pressure sterilizing pot, constant temperature biochemical cultivation case etc.
3 test design
3.1 test medicine
2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and salt thereof.
3.2 experimental concentration
Stripped drug concentration is established 25mg/L, and Broad Bean Leaves method drug concentration is established 500mg/L.
3.3 medicament preparation
Former medicine: take aequum with ten thousand/electronic balance; Solvent: DMF (DMF), 0.2%; Emulsifying agent: Tween 80,0.1%;
General sieve is measured: accurately take the 0.0500g sample, with the 0.20mLDMF dissolving, add the sterilized water 98.8ml that contains 0.1% Tween80 emulsifying agent, stir, be mixed with 500mg/L concentration solution for standby.
4 test methods
With reference to " pesticide bioactivity is estimated SOP ".
Sclerotinia sclerotiorum: with reference to giving birth to the accurate method NY/T1156.2-2006 of mark, adopt the pastille medium therapy: get each 500mg/L compound liquid 2mL, add in the PDA of the 38mL that is cooled to 45 ℃, making final concentration is the pastille culture medium flat plate of 25mg/L.Then get 6.5mm diameter mycelia piece from cultured test germ colony edge, move on the pastille substratum, every processing repeats for 4 times.Be disposed, the constant temperature biochemical cultivation case that is placed in 28 ℃ is cultivated, and measures colony diameter after 4 days, calculates growth inhibition ratio.
Wheat powdery mildew: adopt pot-culture method with reference to giving birth to the accurate method NY/T1156.4-2006 of mark; select seedling to grow to the susceptible variety stem and leaf of Wheat of 2 leaves ~ 3 leaf phases; with spray method with 500mg/L compound medicine liquid spray on stem and leaf of Wheat; naturally dry; the fresh spore of Powdery Mildew that the morbidity wheat leaf blade produced in upper 24 hour is evenly shaken off to be inoculated on stem and leaf of Wheat, and every processing is no less than 3 basins, every basin 10 strains; the protectiveness test is inoculation in 24 hours after chemicals treatment, then puts under suitable condition and cultivates.According to blank incidence classification investigation, calculate prevention effect.
5 fungicidal activity evaluations
After processing, routine observation records incidence and the mycelial growth situation of blade, plant, according to disease index and hyphal diameter, calculates preventive effect and inhibiting rate.
In formula: P represents prevention effect, D
0Expression blank scab diameter, D
1The scab diameter is processed in expression
2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) the general sieve result of thiazole fungicidal activity is: outstanding compound 2-[2-(2,4-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) inhibiting rate of thiazole hydrobromide salt pair Sclerotinia sclerotiorum (25 mg/L) and wheat powdery mildew (500mg/L) is respectively 72.5% and 80.0%.
The demonstration of active testing result, 2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and salt thereof have good fungicidal activity, can be used for preparing sterilant.
Claims (10)
1. the 2-shown in the chemical structural formula I (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole or its salt:
Wherein, R is selected from: H, C
1~ C
2Alkyl, C
3~ C
4Straight chained alkyl or branched-chain alkyl; R
1Be selected from: H, C
1~ C
2Alkyl, C
3~ C
4Straight chained alkyl or branched-chain alkyl; X
1, X
5Be selected from: hydrogen, C
1~ C
2Alkyl, hydroxyl, methoxyl group, oxyethyl group, trifluoromethyl, fluorine, chlorine, bromine, nitro; X
2, X
4Be selected from: hydrogen, C
1~ C
2Alkyl, hydroxyl, methoxyl group, oxyethyl group, trifluoromethyl, fluorine, chlorine, bromine, nitro; X
3Be selected from: hydrogen, C
1~ C
2Alkyl, hydroxyl, methoxyl group, oxyethyl group, trifluoromethyl, fluorine, chlorine, bromine or nitro; Its salt is selected from hydrochloride, hydrobromate, nitrate, vitriol or phosphoric acid salt.
2. the described 2-of claim 1 (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole or its salt, described compound is 2-[2-(2, 5-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole, 2-[2-(2, 3-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole, 2-[2-(3, 4-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole, 5-methyl-2-[2-(2, 3-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole, 2-[2-(3, 4-benzyl dichloride hydrazono-)]-4-(7-oxyethyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole or 2-[2-(2, 4-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt:
3. the described 2-of claim 1 (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole or its salt; described compound is 2-[2-(2-benzyl chloride hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole, 2-[2-(3-benzyl chloride hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole, 2-[2-(4-fluorine benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt or 2-[2-(4-benzyl chloride hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt:
4. the described 2-of claim 1 (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole or its salt; described compound is 2-[2-(4-methoxybenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole, 2-[2-(4-methoxybenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole, 2-[2-(4-methyl benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt or 2-[2-(2-methoxybenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt:
5. the described 2-of claim 1 (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole or its salt; described compound is 5-methyl-2-[2-(4-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole, 2-[2-(2-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt, 2-[2-(3-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt or 2-[2-(4-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt:
6. the described 2-of claim 1 (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) salt of thiazole is 2-[2-(2-hydroxyl-5-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt or 2-[2-(2-hydroxyl-4-nitrobenzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt:
7. the described 2-of claim 1 (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole or its salt; Described compound is 2-[2-(2-hydroxyl benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole, 2-[2-(4-hydroxyl benzyl hydrazono-)]-4-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole or its hydrobromate:
8. the described 2-of claim 1 (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole or its salt, described compound is 2-[2-(2-hydroxyl-3-chloro-5-bromobenzyl hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole, 2-[2-(2-hydroxyl-3, 5-benzyl dichloride hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt, 2-[2-(2-hydroxyl-3, 5-cyclite hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt or 2-[2-(2-hydroxyl-3, 5-diiodo-benzyl hydrazono-)]-4-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-yl) thiazole hydrobromide salt:
9. the preparation method of the described 2-of any one (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole and salt thereof in claim 1 ~ 8; The preparation that it is characterized in that it comprises the steps:
2-halogen-1-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) reaction of alkyl ketone and thiosemicarbazone makes 2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole halogen acid salt (I .HX); 2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole halogen acid salt obtains 2-(2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole (I) through neutralization; Preparation is undertaken by following reaction formula:
R, R in formula
1, X
1~ X
5Definition as claimed in claim 1; X is selected from: Cl or Br.
10. the described 2-of any one (2-benzyl hydrazono-)-4-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-yl) thiazole or its salt application in the preparation sterilant in claim 1,2 or 3 ~ 8.
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| CN103342703A (en) * | 2013-07-22 | 2013-10-09 | 湖南大学 | N-[4-(benzofuran-5-yl)thiazole-2-yl] amide as well as preparation method and application for same |
| CN104026137A (en) * | 2014-06-19 | 2014-09-10 | 湖南海利株洲精细化工有限公司 | Application of N-[4-(benzofuran-5-radical) thiazole-2-radical] fatty acid amide as insecticide |
| CN104387373A (en) * | 2014-10-27 | 2015-03-04 | 湖南大学 | 1-(7-propoxy benzofuran-5-group)-3-(2-methoxyl phenyl)-2-(1,2,4-triazole-1- group)acrylketone |
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