CN102964309A - Isoxazolyl substituted methoxy acrylate compound and preparation method thereof - Google Patents
Isoxazolyl substituted methoxy acrylate compound and preparation method thereof Download PDFInfo
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- CN102964309A CN102964309A CN2012105411307A CN201210541130A CN102964309A CN 102964309 A CN102964309 A CN 102964309A CN 2012105411307 A CN2012105411307 A CN 2012105411307A CN 201210541130 A CN201210541130 A CN 201210541130A CN 102964309 A CN102964309 A CN 102964309A
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Abstract
The invention provides an isoxazolyl substituted methoxy acrylate compound and a preparation method thereof. The isoxazolyl substituted methoxy acrylate compound is shown in a general formula I, wherein Q is selected from N or CH, R is selected from A or B, A represents hydrogen, C1-C5 alkyls or halogenated methyl, the halogenated methyl comprises trichloromethyl, trifluoromethyl and difluromethylation; R1 is selected from hydrogen, C1-C5 alkyls, vinyl, halogen, nitro, methoxy, cyano, carboxyl, formamyl, methoxycarbonyl, phenoxy or thiophenyl; in the definition of the compound shown in the general formula I, terms are collected to be defined generally as follows: halogen indicates fluorine, chlorine, bromine or iodine; the alkyl indicates a linear chain or branch chain alkyl such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl, tertiary butyl, amyl, isoamyl, sec-pentyl or tertiary pentyl; and the halogenated methyl indicates methyl fluoride, difluromethylation, trifluoromethyl or trichloromethyl.
Description
Technical field
The present invention relates to pesticide field, relate in particular to the methoxy acrylate compound that a kind of isoxazolyl replaces.
Background technology
Plant diseases brings about great losses to agricultural, and global farm crop reduce the about 500Mt of output thus every year on average.Once repeatedly occured because certain plant disease epidemics causes serious famine in history, even a large amount of populations calamity hungry to death.Using sterilant is a kind of cost-effective method of controlling plant diseases.Strobilurin fungicide is the very fast class disinfectant use in agriculture of growth in recent years, but strobilurin fungicide, and the isoxazole class compound also has good sterilizing function, therefore the isoxzzole structural unit is introduced in the methoxy acrylate to produce unique effect.
Summary of the invention
The purpose of this invention is to provide methoxy acrylate compound of a kind of isoxazolyl replacement and preparation method thereof, sterilization effect is good.
In order to solve the problems of the technologies described above, methoxy acrylate compound that a kind of isoxazolyl provided by the invention replaces and preparation method thereof is achieved in that
The methoxy acrylate compound that a kind of isoxazolyl replaces, shown in general formula I:
In the formula:
Q is selected from N or CH;
R is selected from A as follows or B:
The alkyl of A=hydrogen, C1～C5 or halogenated methyl, described halogenated methyl comprises trichloromethyl, trifluoromethyl, difluoromethyl;
R1 is selected from hydrogen, C1～C5 alkyl, vinyl, halogen, nitro, methoxyl group, cyano group, carboxyl, formamyl, methoxycarbonyl, phenoxy group or thiophenyl;
In the definition of the compound of Formula I that the above provides, compile used term general proxy as giving a definition:
Halogen: refer to fluorine, chlorine, bromine or iodine;
Alkyl: refer to the straight or branched alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl or tert-pentyl;
Halogenated methyl: refer to methyl fluoride, difluoromethyl, trifluoromethyl or trichloromethyl.
Optionally, described R is selected from H, CH3, CF3, CHF2, CHF, CCl3, C6H5,4-Cl-C6H4,4-Br-C6H4,4-I-C6H4,4-F-C6H4,3-Cl-C6H4,3-Br-C6H4,3-I-C6H4,3-F-C6H4,2-Cl-C6H4,2-Br-C6H4,2-I-C6H4,2-F-C6H4,2,4-2Cl-C6H3,2,6-2Cl-C6H3,3,5-2Cl-C6H3,2-CH3-C6H4,3-CH3-C6H4,4-CH3-C6H4,2,6-2CH3-C6H3,3,5-2CH3-C6H3,4-C2H5-C6H4,4-n-C3H7-C6H4,4-i-C3H7-C6H4,4-n-C4H9-C6H4,4-s-C4H9-C6H4,4-i-C4H9-C6H4,4-t-C4H9-C6H4,4-n-C5H11-C6H4,4-s-C5H11-C6H4,4-i-C5H11-C6H4,4-t-C5H11-C6H4,4-CN-C6H4,4-MeOOC-C6H4,4-H2NCO-C6H4,4-Me2NCO-C6H4,4-C6H5O-C6H4,4-C6H5S-C6H4,3-C6H5O-C6H4,3-C6H5S-C6H4,4-NO2-C6H4.
Optionally, compound shown in the general formula I is reacted under alkaline condition by the compound of general formula I I and general formula III representative and makes:
In the formula:
Q is selected from N or CH;
R is selected from A as follows or B:
The alkyl of A=hydrogen, C1～C5 or halogenated methyl, described halogenated methyl comprises trichloromethyl, trifluoromethyl, difluoromethyl;
Reaction is carried out in suitable solvent, and suitable solvent can be selected from benzene,toluene,xylene, tetrahydrofuran (THF), acetonitrile, acetone, butanone, DMF etc.;
Suitable alkali can be selected from potassium hydroxide, sodium hydroxide, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert.-butoxide, salt of wormwood, yellow soda ash etc.;
The temperature of reaction can be between 0 ℃ to 100 ℃, is generally between room temperature～50 ℃;
Reaction times is 1 to 8 hours, is generally 3 to 4 hours.
Optionally, described suitable solvent is: acetonitrile.
Optionally, described suitable alkali is: salt of wormwood.
A kind of application by compound of Formula I claimed in claim 1 control germ in agricultural and gardening field.
A kind of fungicidal composition contains compound of Formula I and the upper acceptable carrier of agricultural as active ingredient, and the weight percentage of active ingredient is 1-95% in the composition.
The methoxy acrylate compound that isoxazolyl provided by the invention replaces, sterilization effect is good, and wheat powdery mildew, rice sheath blight disease, sclerotinia rot of colza, cucumber downy mildew, pear scab, watermelon anthrax, tomato late blight, capsicum epidemic disease are had preferably germicidal action.Simultaneously, compound shown in the general formula I has hypotoxicity to the useful insect of environment, Mammals, bird and fish etc., and plant is not had toxicity.Because its positive characteristic, compound of Formula I can be used for protecting the staple crop in agricultural and the gardening to avoid the injury of harmful germ.The compound dosage of per hectare 20-500 gram can provide effectively preventing.In order to be effectively applied to agricultural opportunity, use the composition of one or more compound of Formula I normally useful.
Another kind of technical scheme of the present invention also comprises one group of Bactericide composition, contains compound of Formula I and the upper acceptable carrier of agricultural as active ingredient, and the weight percent of activeconstituents is 1%-99% in the composition.
The type of service of composition can be wettable powder, missible oil, microemulsion, suspension agent etc., and its type selecting depends on the needs of concrete application.
Composition prepares in known manner.The specific configuration method of several formulations is exemplified below:
The preparation of wettable powder: by the prescription requirement, the compositions such as active ingredient, various tensio-active agent and solid diluent (such as clay, silicate) are mixed, behind ultra-fine pulverizer disintegrating, namely obtain the wettable powder product of predetermined content (for example 10%-50%).
The preparation of suspension agent: the content of activeconstituents is 10%-30% in the common prescription.Take water or Chinese wax as medium, active ingredient, dispersion agent, suspending agent and antifreezing agent etc. are joined grind in the sand mill, make suspension agent.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
In the cited particular compound of table 1 can since the present invention is described, but do not limit the present invention.
Table 1
Preparation method embodiment
The preparation of embodiment 1. compounds 2 ((E)-3-methoxyl group-2-(2-(5-methyl isoxzzole-3-yloxymethyl) phenyl) methyl acrylate)
In the 50mL round-bottomed flask, add 1.10 gram (0.011mol) 5-methyl-3-hydroxyl isoxzzoles, Anhydrous potassium carbonate 1.51 grams (0.011mol), 2.40 the gram (0.01mol) (E)-2-(2-chloromethyl phenyl) methoxy-methyl acrylate, 30 milliliters of acetonitriles, reflux 4 hours.Cool to room temperature adds 20mL water, and ethyl acetate extraction (20mL * 3) merges organic phase, anhydrous sodium sulfate drying, and precipitation, column chromatography purification gets white solid 2.31 grams, fusing point 146-148 ℃.1H?NMR(CDCl3)δppm：2.13(s,3H)，3.48(s,3H)，3.66(s,3H)，5.24(s,2H)，5.64(s,1H)，7.05-7.25(m,4H)，7.46(s,1H)。
The preparation of embodiment 2. compounds 2 ((E)-2-methoxy imino-2-(2-(5-methyl isoxzzole-3-yloxymethyl) phenyl) methyl acetate)
In the 50mL round-bottomed flask, add 1.10 gram (0.011mol) 5-methyl-3-hydroxyl isoxzzoles, Anhydrous potassium carbonate 1.51 grams (0.011mol), 2.85 the gram (0.01mol) (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate, 30 milliliters of acetonitriles, reflux 4 hours.Cool to room temperature adds 20mL water, and ethyl acetate extraction (20mL * 3) merges organic phase, anhydrous sodium sulfate drying, and precipitation, column chromatography purification gets white solid 2.44 grams, fusing point 167-169 ℃.1H?NMR(CDCl3)δppm：2.16(s,3H)，3.65(s,3H)，3.95(s,3H)，5.21(s,2H)，5.63(s,1H)，7.25-7.44(m,4H)。
Embodiment 3.50% compound 1 wettable powder
After each component fully mixed, through ultra-fine pulverizer disintegrating, obtain 50% wettable powder
Embodiment 4.20% compound 49 suspension agents
Embodiment 5, the fungicidal activity that exsomatizes are measured
Under aseptic condition, picking test strain cake, the test organisms cake comprises: Gramineae dlumeria graminis (Blumeria graminis (DC.) Speer Erysiphe graminis DC.E.graminis DC.f.sp.tritici Marchal), thanatephorus cucumeris(frank) donk (Thanatephorus cucumeris (Frank) Donk.), sclerotinite (Sclerotinia sclerotiorum(Lib.) de Bary), (Phytophthora infestans (Mont.) De Bary, peppery (sweet) green pepper epidemic disease are mould for Pseudoperonospora fungi, phytophthora.The test strain cake is placed the PDA culture medium flat plate central authorities that contain different drug concentrations, set handling gradient.Every processing repeats 3 times, cultivates as contrast on the PDA substratum of adding medicine not, places 26 ℃ of constant incubators to cultivate, and checks after 24 hours.Growing state investigation pathogenic bacteria mycelial growth situation according to bacterium colony in the blank culture dish, after bacterium colony is fully grown in blank, measure the colony diameter that each is processed with the right-angled intersection method, the bacterium colony that increases diameter and chemicals treatment with the blank bacterium colony increases diameter and calculates each chemicals treatment to the inhibiting rate of the mycelial growth of various pathogenic bacterias, calculates the EC50 value according to the inhibiting rate under the different concns again.
Part of compounds isolated activity result is as shown in Table 2:
| Compound number in the table one | EC50 value (μ g/mL) | Contrast medicament EC50 value (μ g/mL) |
| 1 | 18.29 | 13.63(Azoxystrobin) |
| 2 | 19.28 | 13.63(Azoxystrobin) |
| 8 | 18.36 | 13.63(Azoxystrobin) |
| 20 | 20.56 | 13.63(Azoxystrobin) |
| 23 | 21.30 | 13.63(Azoxystrobin) |
| 29 | 17.58 | 13.63(Azoxystrobin) |
| 36 | 20.34 | 12.56(the methoxy acrylate class) |
| 39 | 19.37 | 12.56(the methoxy acrylate class) |
| 40 | 18.50 | 12.56(the methoxy acrylate class) |
| 47 | 21.78 | 12.56(the methoxy acrylate class) |
| 49 | 32.73 | 12.56(the methoxy acrylate class) |
| 50 | 30.56 | 11.78(isoxzzole) |
| 56 | 33.58 | 11.78(isoxzzole) |
| 68 | 35.86 | 11.78(isoxzzole) |
| 84 | 38.79 | 11.78(isoxzzole) |
| 95 | 37.15 | 11.78(isoxzzole) |
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. the methoxy acrylate compound that replaces of an isoxazolyl, shown in general formula I:
In the formula:
Q is selected from N or CH;
R is selected from A as follows or B:
The alkyl of A=hydrogen, C1～C5 or halogenated methyl, described halogenated methyl comprises trichloromethyl, trifluoromethyl, difluoromethyl;
R1 is selected from hydrogen, C1～C5 alkyl, vinyl, halogen, nitro, methoxyl group, cyano group, carboxyl, formamyl, methoxycarbonyl, phenoxy group or thiophenyl;
In the definition of the compound of Formula I that the above provides, compile used term general proxy as giving a definition:
Halogen: refer to fluorine, chlorine, bromine or iodine;
Alkyl: refer to the straight or branched alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl or tert-pentyl;
Halogenated methyl: refer to methyl fluoride, difluoromethyl, trifluoromethyl or trichloromethyl.
2. the methoxy acrylate compound that replaces of isoxazolyl according to claim 1, it is characterized in that, described R is selected from H, CH3, CF3, CHF2, CHF, CCl3, C6H5,4-Cl-C6H4,4-Br-C6H4,4-I-C6H4,4-F-C6H4,3-Cl-C6H4,3-Br-C6H4,3-I-C6H4,3-F-C6H4,2-Cl-C6H4,2-Br-C6H4,2-I-C6H4,2-F-C6H4,2,4-2Cl-C6H3,2,6-2Cl-C6H3,3,5-2Cl-C6H3,2-CH3-C6H4,3-CH3-C6H4,4-CH3-C6H4,2,6-2CH3-C6H3,3,5-2CH3-C6H3,4-C2H5-C6H4,4-n-C3H7-C6H4,4-i-C3H7-C6H4,4-n-C4H9-C6H4,4-s-C4H9-C6H4,4-i-C4H9-C6H4,4-t-C4H9-C6H4,4-n-C5H11-C6H4,4-s-C5H11-C6H4,4-i-C5H11-C6H4,4-t-C5H11-C6H4,4-CN-C6H4,4-MeOOC-C6H4,4-H2NCO-C6H4,4-Me2NCO-C6H4,4-C6H5O-C6H4,4-C6H5S-C6H4,3-C6H5O-C6H4,3-C6H5S-C6H4,4-NO2-C6H4.
3. the preparation method of general formula I described in the claim 1 is characterized in that, compound shown in the general formula I is reacted under alkaline condition by the compound of general formula I I and general formula III representative and makes:
In the formula:
Q is selected from N or CH;
R is selected from A as follows or B:
The alkyl of A=hydrogen, C1～C5 or halogenated methyl, described halogenated methyl comprises trichloromethyl, trifluoromethyl, difluoromethyl;
Reaction is carried out in suitable solvent, and suitable solvent can be selected from benzene,toluene,xylene, tetrahydrofuran (THF), acetonitrile, acetone, butanone, DMF etc.;
Suitable alkali can be selected from potassium hydroxide, sodium hydroxide, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert.-butoxide, salt of wormwood, yellow soda ash etc.;
The temperature of reaction can be between 0 ℃ to 100 ℃, is generally between room temperature～50 ℃;
Reaction times is 1 to 8 hours, is generally 3 to 4 hours.
4. the preparation method of general formula I according to claim 3 is characterized in that, described suitable solvent is: acetonitrile.
5. the preparation method of general formula I according to claim 3 is characterized in that, described suitable alkali is: salt of wormwood.
6. application by compound of Formula I claimed in claim 1 control germ in agricultural and gardening field.
7. fungicidal composition is characterized in that: contain compound of Formula I and the upper acceptable carrier of agricultural as active ingredient, the weight percentage of active ingredient is 1-99% in the composition.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109997855A (en) * | 2019-04-30 | 2019-07-12 | 江西鑫邦科技有限责任公司 | A kind of suspension seed-coating agent for preventing and treating smut of maize |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0398692A2 (en) * | 1989-05-17 | 1990-11-22 | SHIONOGI SEIYAKU KABUSHIKI KAISHA trading under the name of SHIONOGI & CO. LTD. | Alkoxyiminoacetamide derivatives and their use as fungicides |
| EP0363818B1 (en) * | 1988-10-14 | 1994-04-06 | BASF Aktiengesellschaft | Oximether derivatives, process for their preparation and fungicides containing them |
| CN1046275C (en) * | 1993-02-23 | 1999-11-10 | 巴斯福股份公司 | Ortho-substituted 2-methoxyiminophenylacetic acid methylamides |
| CN1306506A (en) * | 1998-07-16 | 2001-08-01 | 诺瓦提斯公司 | Phenyl-methoxyimino-acetic acid derivatives as pesticides |
-
2012
- 2012-12-13 CN CN2012105411307A patent/CN102964309A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0363818B1 (en) * | 1988-10-14 | 1994-04-06 | BASF Aktiengesellschaft | Oximether derivatives, process for their preparation and fungicides containing them |
| EP0398692A2 (en) * | 1989-05-17 | 1990-11-22 | SHIONOGI SEIYAKU KABUSHIKI KAISHA trading under the name of SHIONOGI & CO. LTD. | Alkoxyiminoacetamide derivatives and their use as fungicides |
| CN1046275C (en) * | 1993-02-23 | 1999-11-10 | 巴斯福股份公司 | Ortho-substituted 2-methoxyiminophenylacetic acid methylamides |
| CN1306506A (en) * | 1998-07-16 | 2001-08-01 | 诺瓦提斯公司 | Phenyl-methoxyimino-acetic acid derivatives as pesticides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109997855A (en) * | 2019-04-30 | 2019-07-12 | 江西鑫邦科技有限责任公司 | A kind of suspension seed-coating agent for preventing and treating smut of maize |
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Application publication date: 20130313 |