CN101215269B - 2-thiazolylacrylonitrile compounds and its synthetic method and application - Google Patents

2-thiazolylacrylonitrile compounds and its synthetic method and application Download PDF

Info

Publication number
CN101215269B
CN101215269B CN2007103072463A CN200710307246A CN101215269B CN 101215269 B CN101215269 B CN 101215269B CN 2007103072463 A CN2007103072463 A CN 2007103072463A CN 200710307246 A CN200710307246 A CN 200710307246A CN 101215269 B CN101215269 B CN 101215269B
Authority
CN
China
Prior art keywords
thiazolyl
acrylonitrile compounds
difluorophenyl
formula
thiazole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2007103072463A
Other languages
Chinese (zh)
Other versions
CN101215269A (en
Inventor
沈德隆
杨鹏
谭成侠
翁建全
曹耀艳
刘会君
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN2007103072463A priority Critical patent/CN101215269B/en
Publication of CN101215269A publication Critical patent/CN101215269A/en
Application granted granted Critical
Publication of CN101215269B publication Critical patent/CN101215269B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a 2-thiazolyl acrylonitriles coumpound, a synthesis process and an application. The structure of 2-thiazolyl acrylonitriles is showed as formula (I), wherein R is C1-C10 alkyl,C1-C5 halogenated alkyl, C3-C6 cycloalkyl, phenyl, benzyl or p-nitro phenyl. The synthesis process of the invention comprises conducting nucleophilic substitution towards2- cyanide-4-(2, 6-difluorophenyl) thiazole showed as formula (II) and acyl chloride showed in formula (III) in protonic solvent or nonprotonic solvent for 1-20h with 0-100 DEG C under the effect of acid binding agent to obtain reaction solution, and treating reaction solution to obtain 2-thiazolyl acrylonitriles compound. The 2-thiazolyl acrylonitriles compound can be used as herbicide, pesticide and pesticide, and adds newmatters for the screening of herbicide, pesticide and pesticide.

Description

A kind of 2-thiazolyl acrylonitrile compounds and synthetic method and application
Technical field
The present invention relates to a kind of 2-thiazolyl acrylonitrile compounds and synthetic method and application.
Background technology
Thiazole compound has important status in agricultural chemicals, but the 2-thiazolyl acrylonitrile compounds is used in agricultural chemicals seldom.Because that the 2-thiazolyl acrylonitrile compounds shows is efficient, low toxicity and diversity structure, thereby has boundless research and development prospect.The present invention replaces 3 hydrogen with alkane and aromatic ring, and obtains a series of 2-thiazolyl acrylonitrile compounds.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of 2-thiazolyl acrylonitrile compounds of biologically active and synthetic method thereof with and use.
The structure of 2-thiazolyl acrylonitrile compounds of the present invention is suc as formula shown in (I)
Figure G2007103072463D00011
Wherein R is C 1～C 10Alkyl, C 1～C 5Haloalkyl, C 3～C 6Cycloalkyl, phenyl, benzyl or p-nitrophenyl.
2-thiazolyl acrylonitrile compounds of the present invention is preferably: R is chloro methyl, methyl, ethyl, phenyl, benzyl, p-nitrophenyl or cycloalkyl in the structural formula (I).
2-thiazolyl acrylonitrile compounds synthetic method of the present invention is: suc as formula the 2-cyanogen methyl-4-(2 shown in (II), the 6-difluorophenyl) acyl chlorides shown in thiazole and the formula (III) in protic or non-proton 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 the 2-thiazolyl acrylonitrile compounds;
R is C in the formula (III) 1～～C 10Alkyl, C 1～C 5Haloalkyl, C 3～C 6Cycloalkyl, phenyl, benzyl or p-nitrophenyl.
Recommending described 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and the amount of substance ratio that feeds intake suc as formula acyl chlorides shown in (III) and acid binding agent among the present invention is 1: 1～1.5: 1～2.4.
Recommending described volume of organic solvent consumption is 4～45 times (ml/g) of 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, alkaline carbonate, alkali metal hydrocarbonate, triethylamine or pyridine.
Aftertreatment of the present invention is: reaction finishes, and filters, and filter cake chloroform recrystallization gets described 2-thiazolyl acrylonitrile compounds.
2-cyanogen methyl-4-(2 of the present invention, the 6-difluorophenyl) the thiazole synthetic method is: with 2-cyano-thioacetamide and 2-bromo-2 ', 6 '-difluoro acetophenone stirring at room 9h, add ammoniacal liquor, filter, re-crystallizing in ethyl acetate gets white, needle-shaped crystals and is 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole.
2-thiazolyl acrylonitrile compounds of the present invention is as herbicide applications:
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, R is that formula (I) compound of methyl or phenyl reaches respectively more than 80% and 90% the inhibition activity of weeds such as monocotyledon weed barnyard grass grass Echinochloa crus-galli and recessed amaranth Amaranthus of dicotyledons ascedense under 100ppm.
2-thiazolyl acrylonitrile compounds of the present invention is as the application of sterilant:
Adopt pickling process the synthetic compound to be carried out the insecticidal activity assay of black bean aphid (Aphis fabae) and two-spotted spider mite (Tetranychus urticae).The result shows, R is that formula (I) compound of phenyl reaches 95% at 250ppm following formula (I) compound to the insecticidal activity of black bean aphid (Aphis fabae).
2-thiazolyl acrylonitrile compounds of the present invention 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 chloro methyl reaches more than 85% the inhibiting rate of botrytis cinerea pers (Botrytis cinereapers) under 100ppm.
The invention has the beneficial effects as follows the 2-thiazolyl acrylonitrile compounds that has found a class new, this compound can be used as weedicide, sterilant, bactericide application, 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.
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 3.05g (30mmol) triethylamine joins in the 20mL tetrahydrofuran (THF), drips 2.76g (24mmol) chloroacetyl chloride, and 40min drips complete, 66 ℃ are reacted 12h down then, reaction is finished, and filters filter cake chloroform recrystallization, the light green crystal 2-[4-(2, the 6-difluorophenyl)-the 2-thiazolyl]-3-hydroxyl-3-chloromethyl propylene nitrile 4.40g, fusing point 193-195 ℃, yield is 70%.
This compound 1HNMR and IR are as described below,
1HNMR(CDCl 3)δ＝4.43(H，s，CH 2Cl)，7.09～7.13(2H，m，Ar- CH-CH- CH)，7.40(H，s，Triazole)，7.42～7.50(H，m，Ar-CH- CH-CH)，14.67(H，OH)
IR(KBr，cm -1)3378，3155，2201，1524，1610～1450，1233，783，727
Embodiment 2
4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 1.13g (28mmol) sodium hydroxide are joined 25mL1, the 4-dioxane, drip 2.10g (26mmol) Acetyl Chloride 98Min., 40min drips complete, and 100 ℃ are reacted 6h down then, and reaction is finished, filter, filter cake chloroform recrystallization gets white plates crystal 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxy-3-methyl vinyl cyanide 4.36g, fusing point 197-198 ℃, yield is 78%.
This compound 1H NMR and IR are as described below,
1HNMR(CDCl 3)δ＝2.41(3H，s，CH 3)，7.05～7.09(2H，m，Ar- CH-CH- CH)，7.36～7.46(2H，m，Ar-CH- CH-CH&Triazole)
IR(KBr，cm -1)3453，3179，2191，1513，1610～1450，1378，1246，790，712
Embodiment 3
With 4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 3.22g (30mmol) yellow soda ash joins in the 20mL methylene dichloride, drips 2.27g (24mmol) propionyl chloride, and 40min drips complete, 40 ℃ are reacted 12h down then, reaction is finished, and filters filter cake chloroform recrystallization, obtain light green solid 2-[4-(2, the 6-difluorophenyl)-the 2-thiazolyl]-3-hydroxyl-3-ethyl acrylonitrile 4.21g, fusing point 172-174 ℃, yield is 72%.This compound 1HNMR and IR are as described below,
1HNMR(CDCl 3)δ＝1.25～1.28(3H，t，CH 3)，2.70～2.75(2H，m，CH 2)，7.05～7.09(2H，t，Ar- CH-CH- CH)，7.37～7.41(2H，m，Ar-CH- CH-CH&Triazole)，14.67(H，OH)
IR(KBr，cm -1)3450，3161，2194，1513，1620～1480，1459，1237，997
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, is dripping 2.90g (20mmol) Benzoyl chloride, 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-phenyl vinyl cyanide 4.20g, fusing point 210-211 ℃, yield is 61%.
This compound 1HNMR and IR are as described below,
1HNMR(CDCl 3)δ＝7.07～7.11(2H，t，Ar- CH-CH- CH)，7.38～7.42(H，m，Ar-CH- CH-CH)，7.47～7.54(4H，m，Ph-CH- CH- CH- CH-CH-&Triazole)，7.98～8.00(2H，d，Ph- CH-CH-CH-CH- CH-)，15.60(H，OH)
IR(KBr，cm -1)3424，3128，2195，1629～1466，1233，789
Embodiment 5
With 4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 1.47g (26mmol) potassium hydroxide joins in the 20mL ethyl acetate, drips 3.40g (22mmol) Butyltriphenylphosphonium chloride, and 40min drips complete, 77 ℃ are reacted 8h down then, reaction is finished, and filters filter cake chloroform recrystallization, obtain light green solid 2-[4-(2, the 6-difluorophenyl)-the 2-thiazolyl]-3-hydroxyl-3-p-methylphenyl vinyl cyanide 4.18g, fusing point 207-209 ℃, yield is 59%.
This compound 1HNMR and IR are as described below,
1HNMR(CDCl 3)δ＝2.42(3H，s，CH 3)，7.07～7.11(2H，t，Ar- CH-CH- CH)，7.28～7.31(2H，d，Ar- CH-C- CH)，7.38～7.42(H，m，Ar-CH- CH-CH)，7.50(H，s，Triazole)，7.91～7.93(2H，d，Ar- CH-C- CH)，15.57(H，OH)
IR(KBr，cm -1)3450，3149，2198，1630～1501，1005，797
Embodiment 6
Tetrahydrofuran (THF) changes toluene into, and other is operated with embodiment 1, gets light green crystal 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxyl-3-chloromethyl propylene nitrile 4.20g, and yield is 67%.
Embodiment 7
Change organic solvent into 200mL1, the 4-dioxane, temperature is 100 ℃, and other are operated with embodiment 1, get light green crystal 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxyl-3-chloromethyl propylene nitrile 3.70g, and yield is 59%.
Embodiment 8
With 4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 3.05g (30mmol) triethylamine joins in the 20mL tetrahydrofuran (THF), drip 3.76g (24mmol) phenyllacetyl chloride, 40min drips complete, and 66 ℃ are reacted 12h down then, reaction is finished, filter, filter cake chloroform recrystallization gets faint yellow solid 2-[4-(2, the 6-difluorophenyl)-the 2-thiazolyl]-3-hydroxyl-3-phenmethyl vinyl cyanide 5.88g, yield is 83%.
Embodiment 9
With 4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 3.05g (30mmol) triethylamine joins in the 20mL tetrahydrofuran (THF), drip 4.54g (24mmol) paranitrobenzoyl chloride, 40min drips complete, and 66 ℃ are reacted 12h down then, reaction is finished, filter, filter cake chloroform recrystallization gets yellow solid 2-[4-(2, the 6-difluorophenyl)-the 2-thiazolyl]-3-hydroxyl-3-p-nitrophenyl vinyl cyanide 6.24g, yield is 81%.
Embodiment 10
4.72g (20mmol) 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 3.05g (30mmol) triethylamine are joined in the 20mL tetrahydrofuran (THF) Dropwise 5 .58g (24mmol) dichloro chrysanthemum acyl chlorides, 40min drips complete, 66 ℃ are reacted 12h down then, and reaction is finished, and filters, filter cake chloroform recrystallization, get white solid 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxyl-3-[3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropyl] vinyl cyanide 5.80g, yield is 68%.
Embodiment 11
Temperature is 0 ℃, and the reaction times is 20h, and other reactants, consumption and processing parameter get light green crystal 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxyl-3-chloromethyl propylene nitrile 2.27g all with embodiment 1, and yield is 36%.
Embodiment 12
Solvent is a toluene, and temperature is 100 ℃, and the reaction times is 1h, and other are operated with embodiment 1, gets light green crystal 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxyl-3-chloromethyl propylene nitrile 3.15g, and yield is 50%.
Embodiment 13
With 4.72g (20mmol) 20mmol 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole and 1.96g (48mmol) sodium hydroxide joins 50mL1, the 4-dioxane, drip 2.40g (30mmol) Acetyl Chloride 98Min., other operations are with embodiment 2, get white plates crystal 2-[4-(2, the 6-difluorophenyl)-2-thiazolyl]-3-hydroxy-3-methyl vinyl cyanide 2.57g, yield is 46%.
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 Chloroacetyl chloride 24mmol Triethylamine 30mmol Tetrahydrofuran (THF) 20mL 66 12 70 ％ C 13H 7SN 2ClOF 2
2 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Acetyl Chloride 98Min. 26mmol Sodium hydroxide 28mmol 1,4 dioxane 25mL 100 6 78 ％ C 13H 8SN 2OF 2
3 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Propionyl chloride 24mmol Yellow soda ash 30mmol Methylene dichloride 20mL 40 12 72 ％ C 14H 10SN 2OF 2
4 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Benzoyl chloride 20mmol Pyridine 20mmol Methylene dichloride 20mL 40 12 61 ％ C 18H 10SN 2OF 2
5 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Butyltriphenylphosphonium chloride 22mmol Potassium hydroxide 26mmol Ethyl acetate 20mL 77 8 59 ％ C 19H 12SN 2OF 2
6 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Chloroacetyl chloride 24mmol Triethylamine 30mmol Toluene 20mL 66 12 67 ％ C 13H 7SN 2ClOF 2
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
7 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Chloroacetyl chloride 24mmol Triethylamine 30mmol 1, the 4-dioxane 200mL 100 12 59 ％ C 13H 7SN 2ClOF 2
8 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Phenyllacetyl chloride 24mmol Triethylamine 30mmol Tetrahydrofuran (THF) 20mL 66 12 83 ％ C 14H 15Cl 2N 5O 2
9 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Paranitrobenzoyl chloride 24mmol Triethylamine 30mmol Tetrahydrofuran (THF) 20mL 66 12 81 ％ C 18H 9SN 3O 3F 2
10 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Dichloro chrysanthemum acyl chlorides 24mmol Triethylamine 30mmol Tetrahydrofuran (THF) 20mL 66 12 68 ％ C 19H 14SCl 2N 2OF 2
11 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Chloroacetyl chloride 24mmol Triethylamine 30mmol Tetrahydrofuran (THF) 20mL 0 20 36 ％ C 13H 7SN 2ClOF 2
12 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Chloroacetyl chloride 24mmol Triethylamine 30mmol Toluene 20mL 100 1 50 ％ C 13H 7SN 2ClOF 2
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
13 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole 20mmol Acetyl Chloride 98Min. 30mmol Sodium hydroxide 48mmol 1, the 4-dioxane 50mL 100 6 46 ％ C 13H 8SN 2OF 2
The test of embodiment 14 weeding activity
1 specimen
Embodiment 2,4 makes the 2-thiazolyl acrylonitrile compounds.
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 the restraining effect of 2-thiazolyl acrylonitrile compounds to grass
Figure G2007103072463D00101
Carry out the weeding activity classification according to preventive effect: A level preventive effect＞90%B level preventive effect 75～90%C level
Preventive effect 50～75%D level preventive effect 25～50%E level preventive effect＜25%
The general sieve of embodiment 15 insecticidal activities
1 for the examination target
Black bean aphid (Aphis fabae) is indoor sensitive strain of throughout the year raising with the broad bean seedling; Two-spotted spider mite (Tetranychus urticae) is indoor sensitive strain of throughout the year raising with the broad bean seedling.Indoor conditions: 25 ± 5 ℃ of temperature, relative humidity 65 ± 5% and periodicity of illumination 12/12h (L/D).
2 reagent agents
Embodiment 1,2,3,4,8 makes the 2-thiazolyl acrylonitrile compounds.
3 test methods
The black bean aphid test method adopts pickling process (seeing the SCBZ/CH-HN-2000-004 bar), and concentration is 250mg/L.
The two-spotted spider mite test method adopts pickling process (seeing the SCBZ/CH-HN-2000-004 bar), and concentration is 250mg/L.
Check result after 48 hours, as shown in table 3.
4 evaluated biological activity
Mortality ratio is being the A level more than 90%, is the B level between 70～90%, is the C level between 50～70%, is the D level between 0～50%.Activity enters primary dcreening operation for the compound of A level.
Table 3 contains the test of 2-thiazolyl acrylonitrile compounds insecticidal activity
Figure G2007103072463D00111
The screening of embodiment 16 fungicidal activities
1 for the examination bacterial classification
Cotton-wilt fusarium (Fusarium oxysporium), fusarium graminearum (Gibberellazeae), ring rot of apple bacterium (Dothiorella gregaria), cotton anthracnose bacterium (Colltotrichum 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 1～4 and 8 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 the test of 2-thiazolyl acrylonitrile compounds fungicidal activity
Figure G2007103072463D00121

Claims (10)

1. a structure is suc as formula the 2-thiazolyl acrylonitrile compounds shown in (I),
Figure F2007103072463C00011
Wherein R is C 1～C 10Alkyl, C 1～C 5Haloalkyl, C 3～C 6Cycloalkyl or benzyl.
2. 2-thiazolyl acrylonitrile compounds as claimed in claim 1 is characterized in that R is chloro methyl, methyl, ethyl, benzyl or C in the formula (I) 3～C 6Cycloalkyl.
3. the synthetic method of 2-thiazolyl acrylonitrile compounds as claimed in claim 1, it is characterized in that described method is: suc as formula the 2-cyanogen methyl-4-(2 shown in (II), the 6-difluorophenyl) acyl chlorides shown in thiazole and the formula (III) in protic or non-proton 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 the 2-thiazolyl acrylonitrile compounds;
Figure F2007103072463C00012
Wherein, R is C 1～C 10Alkyl, C 1～C 5Haloalkyl, C 3～C 6Cycloalkyl or benzyl.
4. the synthetic method of 2-thiazolyl acrylonitrile compounds as claimed in claim 3 is characterized in that described organic solvent is tetrahydrofuran (THF), ethyl acetate, methylene dichloride, toluene or 1, the 4-dioxane.
5. the synthetic method of 2-thiazolyl acrylonitrile compounds as claimed in claim 3 is characterized in that described acid binding agent is sodium hydroxide, potassium hydroxide, alkaline carbonate, alkali metal hydrocarbonate, triethylamine or pyridine.
6. the synthetic method of 2-thiazolyl acrylonitrile compounds as claimed in claim 3, it is characterized in that the acyl chlorides shown in described 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole, the formula (III) and the amount of substance ratio that feeds intake of acid binding agent are 1: 1～1.5: 1～2.4.
7. the synthetic method of 2-thiazolyl acrylonitrile compounds as claimed in claim 3 is characterized in that described volume of organic solvent consumption is 4～45 times (ml/g) of 2-cyanogen methyl-4-(2, the 6-difluorophenyl) thiazole quality.
8. 2-thiazolyl acrylonitrile compounds as claimed in claim 1 is as herbicide applications.
9. 2-thiazolyl acrylonitrile compounds as claimed in claim 1 is as the application of sterilant.
10. 2-thiazolyl acrylonitrile compounds as claimed in claim 1 is as the application of bactericide.
CN2007103072463A 2007-12-29 2007-12-29 2-thiazolylacrylonitrile compounds and its synthetic method and application Expired - Fee Related CN101215269B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2007103072463A CN101215269B (en) 2007-12-29 2007-12-29 2-thiazolylacrylonitrile compounds and its synthetic method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2007103072463A CN101215269B (en) 2007-12-29 2007-12-29 2-thiazolylacrylonitrile compounds and its synthetic method and application

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN200910212276A Division CN101723914A (en) 2007-12-29 2007-12-29 2-thiazolyl acrylonitrile compounds and synthesis and application thereof

Publications (2)

Publication Number Publication Date
CN101215269A CN101215269A (en) 2008-07-09
CN101215269B true CN101215269B (en) 2010-06-09

Family

ID=39621787

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007103072463A Expired - Fee Related CN101215269B (en) 2007-12-29 2007-12-29 2-thiazolylacrylonitrile compounds and its synthetic method and application

Country Status (1)

Country Link
CN (1) CN101215269B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101906079B (en) * 2010-07-23 2012-07-18 浙江工业大学 Thiazolyl acrylonitrile ester compound, preparation method and application thereof
CN108863977B (en) * 2018-06-19 2020-09-22 浙江工业大学 Stilbene compound containing bromothiazole ring and synthesis method and application thereof
CN110476994B (en) * 2019-08-26 2021-09-14 浙江工业大学 Application of toluylene compound containing thiazole ring as bactericide

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1318061A (en) * 1998-09-17 2001-10-17 日本曹达株式会社 Thiazolylcinnamonitriles and pest controlling agents
CN1413201A (en) * 1999-12-27 2003-04-23 日本曹达株式会社 Thiazolylcinnamonitrile compounds and insecticides and miticides
CN1473147A (en) * 2000-11-02 2004-02-04 �ձ�������ʽ���� Organic compound having cyano group and insecticides/miticides
WO2004035554A1 (en) * 2002-10-17 2004-04-29 Nippon Soda Co.,Ltd. Thiazolylcinnamonitrile compound and pest control agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1318061A (en) * 1998-09-17 2001-10-17 日本曹达株式会社 Thiazolylcinnamonitriles and pest controlling agents
CN1413201A (en) * 1999-12-27 2003-04-23 日本曹达株式会社 Thiazolylcinnamonitrile compounds and insecticides and miticides
CN1473147A (en) * 2000-11-02 2004-02-04 �ձ�������ʽ���� Organic compound having cyano group and insecticides/miticides
WO2004035554A1 (en) * 2002-10-17 2004-04-29 Nippon Soda Co.,Ltd. Thiazolylcinnamonitrile compound and pest control agent

Also Published As

Publication number Publication date
CN101215269A (en) 2008-07-09

Similar Documents

Publication Publication Date Title
CN106916084B (en) A kind of malononitrile oximido ether compound and application thereof
JP5089581B2 (en) 1,2-Benzisothiazole derivatives and plant disease control agents for agriculture and horticulture
CN104649973B (en) Pyrazole amide compound and application thereof
JPS6052146B2 (en) N-pyridylaniline compounds, their production methods, and pest control agents containing them
UA104293C2 (en) Thiadiazolyloxy-phenylamidines anduse thereof as fungicides
JP2897789B2 (en) Alkoxyiminoacetic acid amide compounds and their use as agricultural fungicides
CN102276596A (en) Thiadiazole compound as well as preparation and application thereof
CN105753808A (en) Thiazole amide compounds, preparing method thereof and applications of the compounds
CN101215269B (en) 2-thiazolylacrylonitrile compounds and its synthetic method and application
CN106008496A (en) S-(5-substituted-1, 3, 4-thiadiazole)-(5-substituted phenyl)-2-furancarbothioic acid ester compound, preparation method and application thereof
CN102633697A (en) Naphthenic sulfonamide series compounds and preparation method thereof as well as application of compounds serving as bactericides and herbicides
EP0288275B1 (en) Phenoxypropionic acid derivatives for use as herbicides
CN108912056B (en) Benzoyl pyrimidine urea compound and preparation and application thereof
CN109824742A (en) A kind of trehalase inhibitor and preparation method thereof
US10674723B2 (en) 1,8-bis(Schiff base)-p-menthane derivatives as well as preparation method and applications thereof
CN101723914A (en) 2-thiazolyl acrylonitrile compounds and synthesis and application thereof
CA1148958A (en) Heterocyclic substituted 4-oxyphenoxyalkane-carboxylic acid derivatives
CN101195617A (en) 2-thiazolyl-3-pyridinyl vinyl cyanide compounds and production and application thereof
CN104910093B (en) The contraposition of 4 phenyl contains alcohol oxime ether structure oxazoline compounds and its preparation and the application in terms of worm mite Juncao is prevented and treated
CN101337945B (en) 4-acetamino-3-(4-arylthiazole-2-amino)benzoate, method for preparing same and applications
CN1321983C (en) Pyrazole-containing semicarbazide compound and its preparation method and use
CN101407503A (en) 2-(4-aryl thiazole-2-yl)-3-alkyloxy acrylonitrile compounds and uses thereof
CN104557619A (en) Methoxyimino phenylacetate compounds containing nitrohydrazinecarboximidamide structures as well as preparation method and application of methoxyimino phenylacetate compounds
CN107089975A (en) Thiazole salt compounds containing 1,3,4 oxadiazolyls and preparation method and application
CN104072455A (en) 6-aryloxy acetoxy aurone compound and application thereof on pesticide

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20100609

Termination date: 20131229