CN101407503A - 2-(4-aryl thiazole-2-yl)-3-alkyloxy acrylonitrile compounds and uses thereof - Google Patents

2-(4-aryl thiazole-2-yl)-3-alkyloxy acrylonitrile compounds and uses thereof Download PDF

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CN101407503A
CN101407503A CNA2008101624882A CN200810162488A CN101407503A CN 101407503 A CN101407503 A CN 101407503A CN A2008101624882 A CNA2008101624882 A CN A2008101624882A CN 200810162488 A CN200810162488 A CN 200810162488A CN 101407503 A CN101407503 A CN 101407503A
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thiazole
oxyl
aryl
acrylonitrile compound
difluorophenyl
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沈德隆
杨鹏
谭成侠
翁建全
曹耀艳
刘会君
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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Abstract

The invention relates to a 2-(4-aryl thiazole-2-based)-3-alkoxide acrylonitrile compound, the structure of which is as shown in formula (I), wherein, R stands for alkyl of C1 to C10 or aryl of C6 to C10. The invention also relates to a preparing method of the compound and the application thereof as weedicide in killing plant anthracnose pathogen; the compound inherits the advantages of high efficiency, low toxicity, safety and being environmental friendly of acrylonitrile compounds and adds new applicable substance for developing new pesticides.

Description

2-(4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound and application
(1) technical field
The present invention relates to a kind of 2-(4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound and synthetic method and application.
(2) background technology
Thiazole compound has important status in agricultural chemicals, but 2-(4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound is used in agricultural chemicals seldom.Because that the 2-thiazolyl acrylonitrile compounds shows is efficient, the advantage of low toxicity and structure diversity, therefore has boundless research and development prospect.The present invention replaces 3 hydrogen with-oxyl, and obtains a series of 2-(4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound.
(3) summary of the invention
The technical problem to be solved in the present invention be to provide a kind of 2-(4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound of biologically active and synthetic method thereof with and use.
The structure of 2-of the present invention (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound is suc as formula shown in (I)
Figure A20081016248800051
Wherein R is C 1～C 10Alkyl, C 6-C 10Aryl.
2-of the present invention (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound is preferably: structural formula
(I) R is n-propyl, sec.-propyl, normal-butyl, isobutyl-, propenyl, n-hexyl, n-octyl, phenyl in.
2-of the present invention (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound synthetic method is: suc as formula the 2-cyanogen methyl-4-(2 shown in (II), the 6-difluorophenyl) chloro-formic ester shown in thiazole and the formula (III) is in organic solvent, under the acid binding agent effect, carry out nucleophilic substitution reaction in 0～100 ℃ and got reaction solution in 1～20 hour, the reaction solution aftertreatment gets 2-(4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound;
Figure A20081016248800052
R is C in the formula (III) 1～C 10Alkyl, C 6-C 10Phenyl.
Recommending described 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and the amount of substance ratio that feeds intake suc as formula chloro-formic ester shown in (III) and acid binding agent among the present invention is 1: 1～1.5: 1～2.4.
Recommend described volume of organic solvent consumption to count 4～45ml/g by 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole quality.
Organic solvent of the present invention is protic solvent and non-protonic solvent, is preferably tetrahydrofuran (THF), ethyl acetate, methylene dichloride, toluene or 1, the 4-dioxane.
Described acid binding agent is sodium hydroxide, potassium hydroxide, triethylamine, pyridine, alkaline carbonate or alkali metal hydrocarbonate, and described alkaline carbonate typically refers to: yellow soda ash or salt of wormwood.Alkali metal hydrocarbonate typically refers to sodium bicarbonate or saleratus.
Aftertreatment of the present invention is: reaction finishes, and reacting liquid filtering, filter cake chloroform recrystallization gets described 2-(4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound.
Comparatively concrete, described method is carried out according to following steps: in organic solvent, the 2-cyanogen methyl-4-(2 that adds metering successively, the 6-difluorophenyl) thiazole, chloro-formic ester and acid binding agent, 2-cyanogen methyl-4-(2, the 6-difluorophenyl) ratio of the amount of substance of thiazole, chloro-formic ester and acid binding agent is 1: 1～1.3: 1～1.5, under 40-100 ℃ of temperature nucleophilic substitution reaction takes place, reaction times 1-12 hour.Reaction finishes after-filtration, and filter cake chloroform recrystallization gets described 2-(4-aryl thiazole-2-yl)-3-hydroxyl oxygen base acrylonitrile compound.
The present invention recommends 2-cyanogen methyl-4-(2, the 6-difluorophenyl) the thiazole synthetic method is: with 2-cyano-thioacetamide and 2-bromo-2 ', 6 '-difluoro acetophenone stirring at room 9h, add strong aqua, the ratio of the amount of substance of the ammonia in described 2-cyano-thioacetamide, 2-bromo-2 ', 6 '-difluoro acetophenone and the strong aqua is 1: 1: 1.Reaction finishes after-filtration, uses re-crystallizing in ethyl acetate, gets white, needle-shaped crystals and is 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole.
2-of the present invention (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound can be used as weedicide and uses:
With monocotyledon weed barnyard grass grass Echinochloa crus-galli, recessed amaranth Amaranthusascedense of dicotyledons carries out the weeding activity test to institute's synthetic 2-thiazolyl acrylonitrile compounds and finds,
Formula (I) compound that the middle R of structural formula (I) is n-hexyl, phenyl is as follows:
Figure A20081016248800061
Compound shown in formula (a) or the formula (b) all reaches more than 80% the inhibition activity of recessed weeds root such as amaranth Amaranthusascedense of dicotyledons under 100ppm.
2-of the present invention (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound is as the application of bactericide:
Adopt toxic potato agar substratum (PDA) method that the synthetic compound has been carried out cotton-wilt fusarium (Fusarium oxysporium), fusarium graminearum (Gibberella zeae), ring rot of apple bacterium (Dothiorella gregaria), the fungicidal activity of cotton anthracnose bacterium (Colletotrichum gossypii) and botrytis cinerea pers (Botrytis cinereapers) is measured, and adopts the toxic potato agar substratum of excised leaf (PDA) method that the fungicidal activity that the synthetic compound has carried out Rhizoctonia solani Kuhn (Rhizoctonia solani) is measured.The result shows that R is that formula (I) compound of n-hexyl, phenyl reaches more than 80% the inhibiting rate of cotton anthracnose bacterium (Colletotrichum gossypii) under 100ppm.
The invention has the beneficial effects as follows 2-(4-aryl thiazole-2-the yl)-3--oxyl acrylonitrile compound that has found a class new, this compound can be used as weedicide, bactericide is used, and this compounds has been followed, and acrylonitrile compound is efficient, low toxicity, safety and environment amenable advantage, for the exploitation of novel pesticide has increased new applicable material.
(4) embodiment
Below in conjunction with specific embodiment the present invention is further specified, but protection scope of the present invention is not limited to this.
Embodiment 1
With 4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 2.40g (30mmol) pyridine joins in the 20mL tetrahydrofuran (THF), drips 2.94g (24mmol) chloroformic acid n-propyl, and 40min drips complete, 66 ℃ are reacted 12h down then, reaction is finished, and filters filter cake chloroform recrystallization, get black solid 2-[4-(2, the 6-difluorophenyl)-the 2-thiazolyl]-3-hydroxyl-3-positive propoxy vinyl cyanide 2.70g, fusing point 162-166 ℃, yield is 42%.
This compound 1H NMR and IR are as described below,
1H NMR(CDCl 3)δ：1.00-1.02(t，J＝10.0Hz，3H，CH 3)，1.72-1.79(m，2H，CH 3 CH 2 )，4.19-4.21(t，J＝10.0，2H， CH 2 -O)，7.07-7.13(m，3H，thiazole&Ar- CH-CH- CH)，7.41-7.44(t，J＝15.00，H，Ar-CH- CH-CH)，12.79(H，OH)
IR(KBr，cm -1)3310，3179，2967，2196，1646，1623，1528，1472，1258，789，728
Embodiment 2
4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 1.13g (28mmol) sodium hydroxide are joined 25mL 1, the 4-dioxane, drip 3.19g (26mmol) isopropyl chlorocarbonate, 40min drips complete, and 100 ℃ are reacted 6h down then, and reaction is finished, filter, filter cake chloroform recrystallization gets brown solid 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxyl-3-isopropoxy vinyl cyanide 2.52g, fusing point 173-176 ℃, yield is 40%.
This compound 1H NMR and IR are as described below,
1H NMR(CDCl 3)δ：31-1.33(d，J＝10.0Hz，6H，CH 3)，5.10-5.15(m，H，CH)，7.06-7.10(m，3H，Ar- CH-CH- CH&thiazole)，7.39-7.42(t，J＝15.0，H，Ar-CH- CH-CH)，1 2.80(H，OH)
IR(KBr，cm -1)v：3266，3176，2991，2192，1638，1526，1476，1363，1258，1110
Embodiment 3
With 4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 3.18g (30mmol) yellow soda ash joins in the 20mL methylene dichloride, drips 3.28g (24mmol) butyl chloroformate, and 40min drips complete, 40 ℃ are reacted 12h down then, reaction is finished, and filters filter cake chloroform recrystallization, obtain brown solid 2-[4-(2, the 6-difluorophenyl)-the 2-thiazolyl]-3-hydroxyl-3-n-butoxy vinyl cyanide 2.81g, fusing point 168-173 ℃, yield is 43%.
This compound 1H NMR and IR are as described below,
1H NMR(CDCl 3)δ：0.95-0.98(t，J＝15.0Hz，3H，CH 3)，1.44-4.18(m，2H，CH 3- CH 2 )，1.68-1.74(m，2H，CH 3-CH 2- CH 2 -)，4.23-4.25(t，J＝10.0Hz，2H，CH 2-O)，7.08-7.13(m，3H，Ar- CH-CH- CH&thiazole)，7.41-7.43(t，J＝10.0，H，Ar-CH- CH-CH)，12.79(H，OH)
IR(KBr，cm -1)v：3448，3177，2959，2196，1646，1623，1528，1472，1256，1159，790，768
Embodiment 4
With 4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 1.60g (20mmol) pyridine joins in the 20mL methylene dichloride, drips 2.73g (20mmol) isobutyl chlorocarbonate again, and 40min drips complete, 40 ℃ of following reaction response 12h then, reaction is finished, and filters filter cake chloroform recrystallization, obtain brown solid 2-[4-(2, the 6-difluorophenyl)-the 2-thiazolyl]-3-hydroxyl-3-isobutoxy vinyl cyanide 2.68g, fusing point 152-155 ℃, yield is 40%.
This compound 1H NMR and IR are as described below,
1H NMR(CDCl 3)δ：0.99-1.00(d，J＝5.0Hz，6H，CH 3)，2.00-2.08(m，H，CH)，4.01-4.02(d，2H，CH 2)，7.08-7.14(m，3H，Ar- CH-CH- CH&thiazole)，7.40-7.42(t，J＝10.0，H，Ar-CH- CH-CH)，12.79(H，OH)
IR(KBr，cm -1)v：3447，3168，2966，2888，2196，1645，1560，1335，1258
Embodiment 5
With 4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 1.46g (26mmol) potassium hydroxide joins in the 20mL ethyl acetate, drips 2.65g (22mmo1) chloroformic acid propylene ester, and 40min drips complete, 77 ℃ are reacted 8h down then, reaction is finished, and filters filter cake chloroform recrystallization, obtain black solid 2-[4-(2, the 6-difluorophenyl)-the 2-thiazolyl]-3-hydroxyl-3-propenyloxy group vinyl cyanide 2.90g, fusing point 128-132 ℃, yield is 46%.
This compound 1H NMR and IR are as described below,
1H NMR(CDCl 3)δ：4.63-4.65(d，J＝10.0Hz，2H，O-CH 2)，5.24-5.25(d，J＝10.0Hz，2H，＝CH 2)，5.89-5.95(t，H，CH)，7.08-7.14(m，3H，thiazole&Ar- CH-CH- CH)，7.42-7.44(t，J＝10.00，H，Ar-CH- CH-CH)，12.70(H，OH)；
IR(KBr，cm -1)v：3320，3179，2967，2196，1646，1623，1528，1000，910
Embodiment 6
Tetrahydrofuran (THF) changes toluene into, and other is operated with embodiment 1, gets black solid 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxyl-3-positive propoxy vinyl cyanide 2.70g, yield is 36%.
Embodiment 7
Change organic solvent into 200mL 1, the 4-dioxane, temperature is 100 ℃, other are operated with embodiment 1, get black solid 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxyl-3-positive propoxy vinyl cyanide 2.70g, fusing point 162-166 ℃, yield is 45%.
Embodiment 8
With 4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 3.04g (30mmol) triethylamine joins in the 20mL tetrahydrofuran (THF), drips the just own ester of 3.95g (24mmol) chloroformic acid, and 40min drips complete, 66 ℃ are reacted 12h down then, reaction is finished, and filters filter cake chloroform recrystallization, get brown solid 2-[4-(2, the 6-difluorophenyl)-the 2-thiazolyl]-the positive hexyloxy vinyl cyanide of 3-hydroxyl-3-2.79g, fusing point 145-148 ℃, yield is 38%.
This compound 1H NMR and IR are as described below,
1H NMR(CDCl 3)δ：0.89-0.92(t，J＝15.0Hz，3H，CH 3)，1.31-1.34(m，6H，CH 3( CH 2 ) 3)，1.71-1.74(t，J＝15.0Hz，2H，O-CH 2- CH 2)，4.21-4.24(t，J＝15.0Hz，2H，- CH 2-O)，7.08-7.13(m，3H，Ar- CH-CH- CH&thiazole)，7.41-7.44(t，J＝15.0Hz，H，Ar-CH- CH-CH)，12.79(H，OH)
IR(KBr，cm -1)v：3448，2956，2195，1646，1624，1528，1472，1287，728
Embodiment 9
With 4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 3.04g (30mmol) triethylamine joins in the 20mL tetrahydrofuran (THF), drips 4.62g (24mmol) octyl chloroformate, and 40min drips complete, 66 ℃ are reacted 12h down then, reaction is finished, and filters filter cake chloroform recrystallization, get garnet solid 2-[4-(2, the 6-difluorophenyl)-the 2-thiazolyl]-3-hydroxyl-3-n-octyloxy vinyl cyanide 2.80g, fusing point 139-143 ℃, yield is 35%.
This compound 1H NMR and IR are as described below,
1H NMR(CDCl 3)δ：0.87-0.89(t，J＝10.0Hz，3H，CH 3)，1.27-1.40(m，10H，CH 3( CH 2 ) 5)，1.69-1.72(m，2H，O-CH 2- CH 2)，4.20-4.22(t，J＝10.0Hz，3H，- CH 2-O)，7.07-7.12(m，3H，Ar- CH-CH- CH&thiazole)，7.39-7.42(t，J＝15.0Hz，H，Ar-CH- CH-CH)，12.78(H，OH)
IR(KBr，cm -1)v：3440，3159，2966，2196，1646，1623，1528，1472，1286，729
Embodiment 10
With 4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 3.05g (30mmol) triethylamine joins in the 20mL tetrahydrofuran (THF), drips 3.76g (24mmol) phenyl chloroformate, and 40min drips complete, 66 ℃ are reacted 12h down then, reaction is finished, and filters filter cake chloroform recrystallization, get brown solid 2-[4-(2, the 6-difluorophenyl)-the 2-thiazolyl]-3-hydroxyl-3-phenoxy group vinyl cyanide 2.90g, fusing point 200-203 ℃, yield is 40%.
This compound 1H NMR and IR are as described below,
1H NMR(CDCl 3)δ：7.06-7.08(d，J＝10.0Hz，2H，Ph- CH-CH-CH-CH-CH- CH)，7.17-7.25(m，4H，Ar- CH- CH- CH&Ph-(CH) 2- CH-(CH) 2)，7.38-7.41(m，3H，Ph-CH- CH-CH-CH- CH-CH&thiazole)
IR(KBr，cm -1)v：3447，3174，3068，2196，1660，1628，1527，1493，1288
Embodiment 11
Temperature is 0 ℃, and the reaction times is 20h, and other reactants, consumption and processing parameter get black solid 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl all with embodiment 1]-3-hydroxyl-3-positive propoxy vinyl cyanide 0.20g, yield is 3%.
Embodiment 12
Solvent is a toluene, and temperature is 100 ℃, and the reaction times is 1h, and other are operated with embodiment 1, gets black solid 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxyl-3-positive propoxy vinyl cyanide 0.76g, yield is 11%.
Embodiment 13
With 4.72g (20mmol) 20mmol 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 1.96g (48mmol) sodium hydroxide joins 50mL 1, the 4-dioxane, drip 3.68g (30mmol) isopropyl chlorocarbonate, other operations are with embodiment 2, get brown solid 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxyl-3-isopropoxy vinyl cyanide 2.52g, yield is 47%.
Table 1 is the data of reaction conditions and the product of embodiment 1～10
Table 1 each embodiment reaction conditions and product
Embodiment Reactant (1) the amount (mmol) Reactant (2) the amount (mmol) Acid binding agent the amount (mmol) Organic solvent the amount (mL) Temperature (℃) Time (h) Yield The product molecular formula
1 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol The chloroformic acid n-propyl 24 mmol Triethylamine 30mmol Tetrahydrofuran (THF) 20mL 66 12 42 ％ C 15H 12F 2N 2O 2S
2 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Isopropyl chlorocarbonate 26 mmol Sodium hydroxide 28mmol 1, the 4-dioxane 25mL 100 6 40 ％ C 15H 12F 2N 2O 2S
3 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Butyl chloroformate 24 mmol Yellow soda ash 30mmol Methylene dichloride 20mL 40 12 43 ％ C 16H 14F 2N 2O 2S
4 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Isobutyl chlorocarbonate 20 mmol Pyridine 20mmol Methylene dichloride 20mL 40 12 40 ％ C 16H 14F 2N 2O 2S
5 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Chloroformic acid propylene ester 22 mmol Potassium hydroxide 26mmol Ethyl acetate 20mL 77 8 46 ％ C 15H 10F 2N 2O 2S
6 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol The chloroformic acid n-propyl 24 mmol Triethylamine 30mmol Toluene 20mL 66 12 36 ％ C 15H 12F 2N 2O 2S
7 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol The chloroformic acid n-propyl 24 mmol Triethylamine 30mmol 1, the 4-dioxane 200mL 100 12 45 ％ C 15H 12F 2N 2O 2S
8 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol The just own ester of chloroformic acid 24 mmol Triethylamine 30mmol Tetrahydrofuran (THF) 20mL 66 12 38 ％ C 18H 18F 2N 2O 2S
9 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Octyl chloroformate 24mmol Triethylamine 30mmol Tetrahydrofuran (THF) 20mL 66 12 35 ％ C 20H 22F 2N 2O 2S
10 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Phenyl chloroformate 24mmol Triethylamine 30mmol Tetrahydrofuran (THF) 20mL 66 12 40 ％ C 18H 10F 2N 2O 2S
11 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol The chloroformic acid n-propyl 24 mmol Triethylamine 30mmol Tetrahydrofuran (THF) 20mL 0 20 3％ C 15H 12F 2N 2O 2S
12 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol The chloroformic acid n-propyl 24 mmol Triethylamine 30mmol Toluene 20mL 100 1 11 ％ C 15H 12F 2N 2O 2S
13 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Isopropyl chlorocarbonate 30 mmol Sodium hydroxide 48mmol 1, the 4-dioxane 50mL 100 6 47 ％ C 15H 12F 2N 2O 2S
The embodiment of the invention 1 ~ 13 each product structure formula is as follows:
Figure A20081016248800141
Figure A20081016248800151
Figure A20081016248800161
The test of embodiment 14 weeding activity
1 specimen
Embodiment 4,5,8,9,10 makes 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxyl-3--oxyl acrylonitrile compound.
2 screening methods
2.1 screening target: unifacial leaf barnyard grass grass Echinochloa crus-galli seed, dicotyledonous recessed amaranth Amaranthusascedense seed
2.2 schedule of operation
2.2.1 accurately take by weighing sample, add a little tween-80 emulsification with DMF dissolving back, add the distilled water of low-grade fever again, compound concentration is the sample solution of 100ppm;
2.2.2 measure the soup 9mL of 100ppm, place the culture dish of diameter 9cm, each culture dish adds two of the filter paper that diameter is 9cm, puts into 15-20 grain test plant seed then;
2.2.3 culture dish is put into growth cabinet to be cultivated, culture temperature is 25 ℃, cultivate after three days, add 8h illumination (adding light application time can according to circumstances control) every day, the root of the 10 strain plants that " Invest, Then Investigate " growth in 5 days is the most luxuriant is long and stem is long and the seed development situation, and root length, the stem of measuring every seed are long, ask its weighted mean, long with the root of blank again, stem appearance compares, and calculates effect, and drug effect is estimated.
3 method of calculation
According to investigation result, calculate the preventive effect of each compound as follows to weeds:
Effect (%)=100 (blank-processing)/blank
The result be on the occasion of, illustrate that drug effect has restraining effect; The result is a negative value, illustrates to have the growth of promotion effect.
Gained the results are shown in Table 2.
Table 2 contains 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxyl-3--oxyl acrylonitrile compound is to the restraining effect of grass
Figure A20081016248800171
Carry out the weeding activity classification according to preventive effect: A level preventive effect＞90 %B level preventive effects, 75～90% C level preventive effects, 50～75% D level preventive effects, 25～50% E level preventive effect＜25%
The screening of embodiment 15 fungicidal activities
1 for the examination bacterial classification
Cotton-wilt fusarium (Fusarium oxysporium), fusarium graminearum (Gibberella zeae), ring rot of apple bacterium (Dothiorella gregaria), cotton anthracnose bacterium (Colletotrichum gossypii), botrytis cinerea pers (Botrytis cinereapers), Rhizoctonia solani Kuhn (Rhizoctonia solani).Above bacterial classification all is kept in the refrigerator (4-8 ℃), is inoculated in the culture dish from the test tube slant in 2-3 days before the test, is for experiment after cultivating.Experiment is potato agar substratum (PDA) with substratum.Fusarium graminearum is preserved spore with stem and leaf of Wheat and is for experiment.
2 measuring methods
Accurately take by weighing an amount of embodiment 1～5 and 8～10 and make compound, elder generation is with the DMF dissolving and add a small amount of tween-80 emulsification, is diluted to 100ppm with clear water.Concrete grammar is as follows:
Fusarium graminearum, ring rot of apple bacterium and botrytis cinerea pers: adopt toxic medium therapy, general sieve concentration is 100ppm.
Rhizoctonia solani Kuhn: adopt the excised leaf culture method, general sieve concentration is 100ppm.
Cotton-wilt fusarium and cotton anthracnose bacterium: adopt pot-culture method, general sieve concentration is 100ppm.
3 fungicidal activity evaluations
Handle incidence and the mycelial growth situation of back routine observation record blade, plant,, calculate preventive effect and inhibiting rate according to disease index and hyphal diameter.The fungicidal activity grade standard is divided: A level-preventive effect (inhibiting rate) 〉=95%, B level-70%≤preventive effect (inhibiting rate)＜95%, C level-50%≤preventive effect (inhibiting rate)＜70%, D level-preventive effect (inhibiting rate)＜50%.
4 The selection result
The result is as shown in table 4:
Table 4 contains 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-test of the fungicidal activity of 3-hydroxyl-3--oxyl acrylonitrile compound
Figure A20081016248800181

Claims (10)

1. a structure is suc as formula the 2-shown in (I) (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound,
Wherein R is C 1～C 10Alkyl or C 6～C 10Aryl.
2. 2-as claimed in claim 1 (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound is characterized in that described R is n-hexyl or phenyl.
3. synthetic method for preparing 2-as claimed in claim 1 (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound, it is characterized in that described synthetic method is: suc as formula the 2-cyanogen methyl-4-(2 shown in (II), the 6-difluorophenyl) chloro-formic ester shown in thiazole and the formula (III) in organic solvent under the acid binding agent effect, carry out nucleophilic substitution reaction in 0～100 ℃ and got reaction solution in 1～20 hour, the reaction solution aftertreatment gets 2-(4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound, and R is C in the formula (III) 1～C 10Alkyl or C 6～C 10Aryl;
Figure A2008101624880002C2
4. 2-as claimed in claim 3 (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound is characterized in that described organic solvent is tetrahydrofuran (THF), ethyl acetate, methylene dichloride, toluene or 1, the 4-dioxane.
5. the preparation method of 2-as claimed in claim 3 (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound is characterized in that described acid binding agent is sodium hydroxide, potassium hydroxide, triethylamine, pyridine, alkaline carbonate, alkali metal hydrocarbonate.
6. as the preparation method of the described 2-of one of claim 3～5 (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound, the amount of substance ratio that feeds intake that it is characterized in that chloro-formic ester shown in (2, the 6-difluorophenyl) thiazole of the 2-cyanogen methyl-4-shown in the formula (II) and the formula (III) and acid binding agent is 1: 1～1.5: 1～2.4.
7. as the described 2-of one of claim 3～5 (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound, it is characterized in that described volume of organic solvent consumption counts 4～45ml/g by 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole quality.
8. 2-as claimed in claim 3 (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound, it is characterized in that described reaction solution post-processing step is: reaction solution, filter, filter cake chloroform recrystallization gets described 2-(4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound.
9. the described 2-of claim 1 (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound is as herbicide applications.
10. the described 2-of claim 1 (4-aryl thiazole-2-yl)-3--oxyl acrylonitrile compound is as killing the application that removes the plant anthrax bacteria.
CNA2008101624882A 2008-11-14 2008-11-14 2-(4-aryl thiazole-2-yl)-3-alkyloxy acrylonitrile compounds and uses thereof Pending CN101407503A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101906079A (en) * 2010-07-23 2010-12-08 浙江工业大学 Thiazolyl acrylonitrile ester compound, preparation method and application thereof
CN108605949A (en) * 2018-06-19 2018-10-02 浙江工业大学 A kind of application of the class diphenyl ethene compounds as fungicide containing thiazole ring
CN108863977A (en) * 2018-06-19 2018-11-23 浙江工业大学 The class diphenyl ethene compounds and its synthetic method of a kind of thiazole ring containing bromo and application

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101906079A (en) * 2010-07-23 2010-12-08 浙江工业大学 Thiazolyl acrylonitrile ester compound, preparation method and application thereof
CN101906079B (en) * 2010-07-23 2012-07-18 浙江工业大学 Thiazolyl acrylonitrile ester compound, preparation method and application thereof
CN108605949A (en) * 2018-06-19 2018-10-02 浙江工业大学 A kind of application of the class diphenyl ethene compounds as fungicide containing thiazole ring
CN108863977A (en) * 2018-06-19 2018-11-23 浙江工业大学 The class diphenyl ethene compounds and its synthetic method of a kind of thiazole ring containing bromo and application
CN108605949B (en) * 2018-06-19 2020-12-15 浙江工业大学 Application of stilbene compound containing thiazole ring as bactericide

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