CN1055609C - Process for preparing agricultural fungicide myclobutanil - Google Patents
Process for preparing agricultural fungicide myclobutanil Download PDFInfo
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- CN1055609C CN1055609C CN94111446A CN94111446A CN1055609C CN 1055609 C CN1055609 C CN 1055609C CN 94111446 A CN94111446 A CN 94111446A CN 94111446 A CN94111446 A CN 94111446A CN 1055609 C CN1055609 C CN 1055609C
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- chlorphenyl
- nitrile
- myclobutanil
- agricultural fungicide
- chloromethyl
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Abstract
The present invention relates to a process for preparing agricultural fungicide myclobutanil. The chemical name of the myclobutanil is 2-(4-chlorphenyl)-2-(1H-1, 2, 4-triazolyl methyl) hexanenitrile which is systematic agricultural fungicide with high efficiency and low toxicity. The present invention uses p-chloropheny-lacetonitrile as a raw material which is reacted with halogenating normal butane to obtain 2-(4-chlorphenyl) hexanenitrile, 1 to 5 times of solvent dimethyl sulfoxide and sodium hydroxide of an acid-binding agent are then added for stirring, chloromethyl triazole hydrochloride is added, a reacting substance is stirred by adding water, and the myclobutanil is obtained by chloroform extraction and exsolution. Dibromomethane is not used by the process, and thus, production cost is reduced, and the myclobutanil can be widely used as the agricultural fungicide.
Description
The present invention relates to a kind of preparation method of agricultural fungicide myclobutanil, this bactericide is mainly used in fruit diseases and stinking smut, smut, wheat glume blight bacterium, sickle-like bacteria and the microbial seed-borne diseases of wheat class nuclear cavity such as preventing and treating apple scab, powdery mildew, black rot of vine grape, also can prevent and treat the Penicillium notatum of results back citrus.
The chemical name of nitrile bacterium azoles is the own nitrile of 2-(4-chlorphenyl)-2-(1H-1,2,4-triazolyl methyl), and chemical structural formula is
Be-the interior absorption disinfectant use in agriculture of kind of high-efficiency low-toxicity, be used to prevent and treat apple scab, powdery mildew, grape scab, stinking smut, smut and wheat glume blight bacterium, sickle-like bacteria, the microbial seed-borne disease of nuclear cavity, also can prevent and treat the Penicillium notatum of results back citrus.Europe patent EP145,294 have proposed the preparation method of nitrile bacterium azoles: carry out alkylated reaction with p-chlorobenzyl cyanide and halo normal butane in the presence of sodium hydroxide and phase transfer catalyst (PTC), make the own nitrile of 2-(4-chlorphenyl) (calling compound 1 in the following text), itself and methylene bromide reaction are made 1-bromo-2-cyano group-2-(4-chlorphenyl) hexane (compound 2), last with 1,2, the condensation of 4-triazole sylvite gets nitrile bacterium azoles (compound 3).
Reaction equation is as follows:
Because China methylene bromide source is few, needs import, cost an arm and a leg, thereby too high with method for preparing myclobutanil fungicide production cost, be difficult to apply.
The purpose of this invention is to provide a kind of method for preparing myclobutanil fungicide, it avoids using methylene bromide, to reduce the production cost of nitrile bacterium azoles, is beneficial to large-scale production and extensive use.
The preparation method of nitrile bacterium azoles of the present invention is raw material with the p-chlorobenzyl cyanide, in the presence of the phase transfer catalyst tetraethylammonium bromide, add chloro-normal butane, and dropping sodium react the own nitrile of 2-(4-chlorphenyl) (compound 1), in compound 1, add 1～5 times of (weight) solvent dimethyl sulfoxide (DMSO) and excessive acid binding agent sodium hydroxide, stir the chloromethyl triazolium salt hydrochlorate that slowly adds down with compound 1 equimolar amounts, react to compound 1 disappearance, add suitable quantity of water stirring chloroform extraction, the distillation precipitation gets nitrile bacterium azoles.
Chemical reaction is as follows:
Among the present invention, compound 1 is good with the reaction temperature of chloromethyl triazolium salt hydrochlorate with 10～30 ℃, and temperature is too low, and reaction velocity is too slow, and temperature is too high, can cause the decomposition of chloromethyl triazolium salt hydrochlorate.Acid binding agent in the above-mentioned reaction also can adopt potassium hydroxide.Chloromethyl triazolium salt hydrochlorate can be according to Europe patent EP60, disclosed method preparation in 223 and EP63,099, promptly first by 1H-1,2,4-triazole and paraformaldehyde react in the presence of triethylamine, question response liquid clarification back adds acetone recrystallization and gets 1-methylol-1H-1,2, the 4-triazole is reacted with thionyl chloride then, remove residual excess chlorination sulfoxide with the chloroform washing, promptly get 1-chloromethyl-1H-1,2,4-triazolium salt hydrochlorate.
Adopt the present invention to make the method for nitrile bacterium azoles, make the preparation process of nitrile bacterium azoles avoid using expensive methylene bromide, thereby the production cost reduction, help the large-scale production of this bactericide and application widely.
Further specify preparation technology of the present invention below by embodiment.
Embodiment: the preparation process of nitrile bacterium azoles
1. 1-chloromethyl-1H-1,2, the preparation of 4-triazolium salt hydrochlorate
A.100 the milliliter there-necked flask installs additional and adds 28 gram 1H-1 in agitator, thermometer and the reflux condensation mode phial, 2,4-triazole and 12 gram paraformaldehydes, several triethylamines are in 70 ℃ of following stirring reactions, clarify until reactant liquor, add acetone recrystallization, get 1-methylol-1H-1,2, the 4-triazole, 65～67 ℃ of fusing points.
B.250 Hao Sheng four-hole bottle installs agitator, thermometer, reflux condensing tube, dropping funel additional, adds 100 gram thionyl chlorides in the bottle, is warming up to 55 ℃, stir and slowly add 33 gram 1-methylol-1H-1,2,4-triazole down, be warming up to backflow after adding, no acidic gas is emitted in tail gas, is reaction end, excessive thionyl chloride distillation is removed, and uses the residual thionyl chloride of chloroform flush away again, promptly gets 1-chloromethyl-1H-1,2,4-triazolium salt hydrochlorate, 120～125 ℃ of fusing points, molecular formula is
2. the preparation of the own nitrile of 2-(4-chlorphenyl) (being above-claimed cpd 1)
1000 milliliters of there-necked flasks install agitator, thermometer, dropping funel additional, add 152 gram p-chlorobenzyl cyanides, 18C gram chloro-normal butane, 4.2 gram tetraethylammonium bromides in the bottle, keep 20～25 ℃ of reaction temperatures, stir the sodium hydroxide that splashes into 320 grams 50% down, the gas spectrum tracks to the raw material p-chlorobenzyl cyanide and disappears, add suitable quantity of water and stir standing demix, water layer chloroform extraction three times, organic layer washes secondary with water, merge organic layer, 146～150 ℃/7～8mmHg fraction is collected in distillation, promptly gets the own nitrile of colourless viscous fluid 2-(4-chlorphenyl).
3. the preparation of the own nitrile of 2-(4-chlorphenyl)-2-(1H-1,2,4-triazolyl methyl) (being nitrile bacterium azoles)
250 milliliters of there-necked flasks install agitator additional, thermometer, add the 17.5 gram own nitriles of 2-(4-chlorphenyl) (content 99%) earlier, 26.5 restrain the sodium hydrate aqueous solution of 50% concentration, 60 milliliters of dimethyl sulfoxide (DMSO)s, stir and slowly add 15 gram 1-chloromethyl-1H-1,2,4-triazolium salt hydrochlorate down, keep reaction temperature about 25 ℃, the gas spectrum tracks to the own nitrile of 2-(4-chlorphenyl) and disappears, and promptly arrives reaction end, adds water and stirs, with chloroform extraction three times, each 60 gram chloroforms merge organic layer, and distillation is removed chloroform and got product 2-(4-chlorphenyl)-2-(1H-1,2, the 4-triazolyl methyl) own nitrile crude product 24 grams (content 74.88%).
Claims (1)
1. the preparation method of agricultural fungicide myclobutanil, with the p-chlorobenzyl cyanide is raw material, in the presence of the phase transfer catalyst tetraethylammonium bromide, add halo normal butane and dropping sodium, react the own nitrile of 2-(4-chlorphenyl), it is characterized in that in the own nitrile of 2-(4-chlorphenyl), adding 1～5 times of (weight meter) solvent dimethyl sulfoxide (DMSO) and excessive sodium hydrate or potassium hydroxide, stir the chloromethyl triazolium salt hydrochlorate that slowly adds down with the own nitrile equimolar amounts of 2-(4-chlorphenyl), reaction temperature is 10～30 ℃, react own nitrile disappearance to 2-(4-chlorphenyl), add excessive water and stir, get nitrile bacterium azoles with distillation desolventizing behind the chloroform extraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94111446A CN1055609C (en) | 1994-09-22 | 1994-09-22 | Process for preparing agricultural fungicide myclobutanil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94111446A CN1055609C (en) | 1994-09-22 | 1994-09-22 | Process for preparing agricultural fungicide myclobutanil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1119062A CN1119062A (en) | 1996-03-27 |
| CN1055609C true CN1055609C (en) | 2000-08-23 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94111446A Expired - Fee Related CN1055609C (en) | 1994-09-22 | 1994-09-22 | Process for preparing agricultural fungicide myclobutanil |
Country Status (1)
| Country | Link |
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| CN (1) | CN1055609C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348104C (en) * | 2003-09-10 | 2007-11-14 | 西安克胜新依达农药有限公司 | Water dispersive myclobutanil particle and formula |
| CN101538250B (en) * | 2009-04-09 | 2012-03-07 | 湖北仙隆化工股份有限公司 | Preparation method of bulk myclobutanil |
| CN102060791B (en) * | 2010-12-17 | 2012-12-26 | 张家港瀚康化工有限公司 | Preparation method of myclobutanil as a triazole bactericide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4225732A (en) * | 1977-12-22 | 1980-09-30 | General Electric Company | Selective ortho-alkylation of phenolic compounds with an alkane in the presence of a supported nickel oxide catalyst |
| EP0060223A2 (en) * | 1981-03-10 | 1982-09-15 | Ciba-Geigy Ag | Microbicide agent |
| EP0063099A2 (en) * | 1981-03-10 | 1982-10-20 | Ciba-Geigy Ag | Process for the preparation of phenylethyl triazoles |
-
1994
- 1994-09-22 CN CN94111446A patent/CN1055609C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4225732A (en) * | 1977-12-22 | 1980-09-30 | General Electric Company | Selective ortho-alkylation of phenolic compounds with an alkane in the presence of a supported nickel oxide catalyst |
| EP0060223A2 (en) * | 1981-03-10 | 1982-09-15 | Ciba-Geigy Ag | Microbicide agent |
| EP0063099A2 (en) * | 1981-03-10 | 1982-10-20 | Ciba-Geigy Ag | Process for the preparation of phenylethyl triazoles |
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| Publication number | Publication date |
|---|---|
| CN1119062A (en) | 1996-03-27 |
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