CN101513183A - Method for preparing stable epoxiconazole raw drug - Google Patents
Method for preparing stable epoxiconazole raw drug Download PDFInfo
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- CN101513183A CN101513183A CNA2008100577738A CN200810057773A CN101513183A CN 101513183 A CN101513183 A CN 101513183A CN A2008100577738 A CNA2008100577738 A CN A2008100577738A CN 200810057773 A CN200810057773 A CN 200810057773A CN 101513183 A CN101513183 A CN 101513183A
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Abstract
The invention relates to the field of pesticides, in particular to a method for preparing a stable epoxiconazole raw drug. The epoxiconazole is an efficient, low-toxicity and low-residual broad-spectrum bactericide, and has good control effects on various fungus diseases for crops including oil-bearing crops of peanut and rape, cereal crops of wheat and rice, vegetables of cucumber, strawberry and tomato, fruit trees of apple and banana, sugar beet, cotton, and the like.
Description
Technical field
The present invention relates to pesticide field, relate to a kind of stable epoxiconazole raw medicament preparation specifically.Fluorine ring azoles is the broad-spectrum germicide of a kind of efficient, low toxicity, low-residual, to wheat and the paddy rice of the peanuts of oil crop and rape, cereal crop, the multiple fungal disease of crops such as the apple in cucumber in the vegetables and strawberry and tomato, the fruit tree and fragrant Jiao, sugar beet, cotton has good control efficiency.
Technical background
Along with China joined WTO, external " Green Trade Barrier " becomes the primary limiting factor of agricultural products in China foreign exchange earning.At home, the person poultry poisoning, the agricultural product that bring of abuse high-toxic pesticide are residual exceeds standard and problem such as environmental pollution has also caused central authorities leader's great attention.On December 6th, 2000, Premier Wen Jiabao makes comments and instructions on specially notifying breath No. 368: " will improve the pesticide species structure, reduce high-toxic pesticide proportion ".Simultaneously, people's living standard and environmental consciousness are also improving constantly, safety, agricultural chemicals will become peasant's first-selected medicine variety efficiently, green management also will become the new concept of enterprise operation.Therefore, reduction and even superseded high-toxic pesticide kind have been trend of the times.In current pesticide industry, bactericide has the maximum potential of long-term growth, and this mainly is because the technical development of weed control and control of insect causes.The exploitation of the anti-pest crop of herbicide-resistant crop and Bt toxin has begun to influence the market share of weed killer herbicide and insecticide.In the North America, China, Asia other parts country and some Latin American countries, the crops such as transgenic corns, cotton, paddy rice with resistance to insects extensively plants, use has caused great impact to the insecticide on these crops.As in China, last century the nineties, the control medication of cotton bollworm is firmly in occupation of the highest share in agricultural chemicals market.In recent years, along with the popularization of Bt transgenic cotton, the generating capacity of cotton bollworm had obtained better controlled, no longer was primary pest on the cotton a lot of cotton regions cotton bollworm, and dosage also descends thereupon; The imidazolidinone weedicide of American Cyanamid Company meets with Meng Shan genetically engineered soybean all in the U.S. and Brazil for another example, suffers heavy losses.In order to avoid the transgenosis glyphosate tolerance type seed of Meng Shandou, U.S.A encloses many agricultural chemicals company and has adjusted development strategy, weakens even abandon the exploitation of new chemical herbicide.But up to the present, also do not have bactericide market to be produced as the same influence of Insecticides (tech) ﹠ Herbicides (tech) near commercial similar genetically modified crops or enhancing technology.Yet the prospect of the dimness that weed killer herbicide and insecticide market are faced in 10 years of future is not unique factor that bactericide market is in long-term growth, along with the raising of agricultural production intensification degree, can constantly rise to the demand of bactericide yet.In the low-intensity agricultural production, be to fight for the weeds of sunlight, nutrition and moisture with it to the biggest threat of crop yield.Yet along with the continuation that intensive agriculture is produced is carried out, disease will become the biggest factor that crop yield is had a negative impact.In the world, Japan that supporting most intensifies produces and the France in the European countries, Germany and Dutch, their bactericide product proportion is the highest.In China, the adjustment of the national structure of agricultural production just towards continuous minimizing field crop cultivated area, guides and advances the peasant to develop the direction effort of high value economic crops energetically, in the hope of progressively forming the industrial zone and the industry district of specialization, scale, intensification.This growth can find out on the nations of China and India agricultural chemicals market, because are unique products that supply falls short of demand at these two national bactericide.No matter be in the world or China, bactericide all had than insecticide and the more distinct prospect of weed killer herbicide at following 10 years.At present, the bactericide major part that China's agricultural production is used is the old kind based on the triazolone in organic sulfur class, organic phosphates and the triazole type, Triadimenol, and resistance problem becomes increasingly conspicuous, and dosage constantly increases, and causes the pollution of environment is on the rise.Fluorine ring azoles is triazole type high activity of new generation, broad-spectrum germicide, and the target disease is had special efficacy.
Compare with the conventional sterilization agent, fluorine ring azoles has the following advantages:
1, efficient, the wide spectrum of fluorine ring azoles, it is narrow to have remedied many conventional sterilization agent bactericidal ranges such as carbendazim, thiophanate methyl, triazolone and mancozeb, to the relatively poor deficiency that waits of its crop target diseases control, adapts to the actual needs of China's agricultural production.
2, because the using for a long time and abusing of conventional chemical bactericide (abuse), caused most diseases that it is produced resistance, even resistance is serious, cause preventive effect to descend significantly to the target disease, just effective when having only heavy dose of the use, this method of preventing and treating disease has not only strengthened the control cost, but also can cause the phenomenon that Higher output is not accompanied by a higher income.Many agricultural product residue of pesticide exceed standard, and the conventional chemical bactericide market share is sharply dwindled.And fluorine ring azoles consumption low (extension rate is very high), the mu use cost is low, and the pressure of environmental pollution also greatly alleviates.
3, fluorine ring azoles is low toxicity, safe bactericide, meets World Health Organization's medicament residual toxicity standard.According to China's agricultural chemicals acute toxicity grading criteria, no matter be oral or the percutaneous toxicity index, all belong to low-toxin farm chemicals.Active ingredient and chemical property
Compound title: epoxy bacterium azoles, fluorine ring azoles (epoxiconazole)
Trade name: Opus Europe despot is the triazole bactericidal agent by BASF AG's exploitation
Chemical name: (2RS, 3RS)-1-[3-(2-chlorphenyl)-2,3-epoxy-2-(4-fluorophenyl) propyl group]-1 hydrogen-1,2, the 4-triazole
English chemical name: (2RS, 3RS)-1-[3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophenyl) propyl]-1H-1,2,4-triazole
Structural formula:
Molecular formula: C17H13ClFN30
Molecular weight: 329.8
Physicochemical property: its pure product are the colourless crystallization body, 136.2 ℃ of fusing points, relative density 1.384 (25 ℃), vapour pressure＜1.0*10-5Pa (25 ℃), distribution coefficient (PH=7) 1gP=3.1, solvability (20 ℃, mg/L) water 6.63, acetone 14.4, carrene 29.1, stability not hydrolysis of 12d under PH7 and PH9 condition.
Summary of the invention
The objective of the invention is to propose a kind of stable epoxiconazole raw medicament preparation.
The present invention is achieved by the following technical solutions:
The synthetic route of fluorine ring azoles all is to be intermediate with the fluorobenzene, through acidylate, alkylene, obtains acryloyl derivative, obtains the bromo epoxides through bromination, oxidation then, and last and triazole sodium reaction obtains fluorine ring azoles.Reaction equation is as follows:
The invention provides a kind of stable epoxiconazole raw medicament preparation, comprise the steps:
1, synthesizing fluoro acetophenone.The catalyzer that adds fluorobenzene 0.2mol, solvent 200ml, amount of calculation in having the glass reaction bottle of agitator, condenser stirs the chloroacetic chloride that is added dropwise to 0.15mol down, the control reaction temperature.Use hydrochloric acid hydrolysis, steam distillation to go out excessive fluorobenzene after reaction finishes, the solvent extraction precipitation promptly obtains fluoro acetophenone.The present invention mainly screens proportioning, solvent, reaction time.
(1) proportioning of fluorobenzene and chloroacetic chloride (seeing table 1 for details).As can be seen from Table 1 the proportioning of fluorobenzene and chloroacetic chloride be 1.15 when above for best, consider and can reclaim by fluorobenzene, so adopt the fluorobenzene of volume slightly.
The proportioning of table 1 fluorobenzene and chloroacetic chloride
| The experiment lot number | Material proportion | Must measure | Content | Yield |
| 1 | 1.05 | 17.0g | 95.6％ | 78.51％ |
| 2 | 1.1 | 17.3g | 95.4％ | 79.73％ |
| 3 | 1.15 | 18.3g | 97.5％ | 86.20％ |
| 4 | 1.2 | 18.4g | 96.0％ | 85.33％ |
(2) screening of solvent.We have selected chloroform, carbon tetrachloride, dichloroethane is solvent, and The selection result shows that each solvent is close, considers toxicity and cost, uses dichloroethane to make solvent effect best (seeing table 2 for details).
The The selection result of table 2 solvent
| The experiment lot number | Solvent | Must measure | Content % | Yield % |
| 5 | Chloroform | 18.3g | 95.3 | 84.25％ |
| 6 | Carbon tetrachloride | 18.4g | 96.0 | 85.33％ |
| 7 | Dichloroethane | 18.3g | 95.7 | 84.60％ |
(3) screening in reaction time (seeing Table 3).As can be seen from Table 3, the reaction time was the best with 5 hours.
The The selection result in table 3 reaction time
| The experiment lot number | Reaction time | Must measure | Content % | Yield % |
| 8 | 2h | 17.6g | 94.9 | 80.69 |
| 9 | 3h | 17.8g | 96.4 | 82.89 |
| 10 | 4h | 18.4g | 96.1 | 85.42 |
| 11 | 5h | 18.3g | 96.9 | 85.67 |
| 12 | 6h | 18.3g | 95.0 | 83.98 |
(4) reaction equation
2, acryloyl derivative is synthetic
Add o-chlorobenzyl phosphoesterase 30 .12mol, solvent 150ml, catalyzer in the reaction bulb that has agitator, condenser, the control uniform temperature drips fluoro acetophenone 0.1mol under stirring, and insulation reaction 12 hours promptly obtains acryloyl derivative after the processing.The present invention optimizes proportioning, reaction time, the solvent of reaction mass.
(1) the o-chlorobenzyl phosphate with to the proportioning (seeing Table 4) of fluoro acetophenone.
Table 4 o-chlorobenzyl phosphate with to the proportioning of fluoro acetophenone
| The experiment lot number | Material proportion | Must measure | Content | Yield |
| 13 | 1.0 | 18.3g | 90.1 | 67.99 |
| 14 | 1.1 | 19.5g | 93.3 | 75.02 |
| 15 | 1.2 | 20.5g | 95.5 | 80.73 |
| 16 | 1.3 | 20.2g | 94.4 | 78.63 |
As can be seen from Table 4, proportioning be 1.2 o'clock for best.
(2) screening in reaction time (seeing Table 5).React 12 hours the bests as can be seen from Table 5, the time that increases does not again have effect yet.
The The selection result in table 5 reaction time
(3) screening of solvent (seeing Table 6).As shown in Table 6, solvent is best with the n-butanol.
The The selection result of table 6 solvent
(4) reaction equation
3, the bromo acryloyl derivative is synthetic
In the reaction bulb that has agitator, condenser, add acryloyl derivative 0.1mol, solvent 200ml, catalyzer 0.5g, the cooling of dissolving back drips bromine 0.105mol for 0 ℃, after reacting completely, air blows out the hydrogen bromide (recyclable) in the system, and decompression distillation gets product bromo acryloyl derivative.The present invention optimizes proportioning, reaction time, the selection of catalysts of reaction mass.
(1) proportioning of bromine and acryloyl derivative (seeing Table 7).The bromine consumption is crossed low then the conversion not exclusively as can be seen from Table 7, and it is all undesirable that too high then side reaction increases yield, have only proportioning be 1.05 o'clock for best.
The proportioning of table 7 bromine and acryloyl derivative
| The experiment lot number | Material proportion | Must measure | Content | Yield % |
| 25 | 1.0 | 28.7g | 90.1 | 80.43 |
| 26 | 1.05 | 28.4g | 96.3 | 85.07 |
| 27 | 1.1 | 28.2g | 93.5 | 82.01 |
| 28 | 1.2 | 30.4g | 87.4 | 82.64 |
(2) screening in reaction time (seeing Table 8).React 14 hours the bests as can be seen from Table 8, the time that increases does not again have effect yet.
The The selection result in table 8 reaction time
| The experiment lot number | Reaction time | Must measure | Content | Yield % |
| 29 | 10 | 28.2g | 91.8％ | 80.52 |
| 30 | 12 | 29.0g | 92.6％ | 83.53 |
| 31 | 14 | 28.4g | 96.2％ | 84.98 |
| 32 | 16 | 28.4g | 96.0％ | 84.80 |
(3) selection of catalysts (seeing Table 9).By table 9 and production actual conditions as can be known, catalyst n HF-1 is best.
Table 9 catalyzer selection result
| The experiment lot number | Solvent load | Must measure | Content % | Yield % |
| 21 | Without CAT | 25.0g | 36.2 | 28.15 |
| 22 | CAT1 | 28.3g | 95.9 | 84.42 |
| 23 | NHF-1 | 28.5g | 96.1 | 85.19 |
| 24 | CAT3 | 28.4g | 96.2 | 84.98 |
(4) reaction equation
4, the triazole acryloyl derivative is synthetic
In the reaction bulb that has agitator, condenser, add bromopropene derivative 0.1mol, solvent 150ml, 1 (H)-1,2,4 TTA-Na 0.12mol stir and are warming up to uniform temperature, and after reaction finished, the precipitation post processing promptly obtained the triazole acryloyl derivative.The present invention optimizes proportioning, reaction time, the choice of Solvent of reaction mass.
(1) proportioning of triazole sodium and bromopropene (seeing Table 10).As can be seen from Table 10 triazole sodium and bromopropene proportioning be 1.2 o'clock for best.
The proportioning of table 10 triazole sodium and bromopropene
| The experiment lot number | Material proportion | Must measure | Content | Yield |
| 25 | 1.0 | 28.7g | 92.1 | 85.40 |
| 26 | 1.2 | 29.0g | 96.3 | 90.23 |
| 27 | 1.5 | 28.9g | 96.5 | 90.11 |
| 28 | 2.0 | 29.3g | 95.8 | 90.69 |
(2) screening in reaction time (seeing Table 11).React three hours the bests as can be seen from Table 11, the time that increases does not again have effect yet.
The The selection result in table 11 reaction time
| The experiment lot number | Reaction time | Must measure | Content | Yield |
| 29 | 1 | 28.7g | 91.8％ | 85.13％ |
| 30 | 2 | 29.5g | 94.6％ | 90.17％ |
| 31 | 3 | 29.2g | 95.9％ | 90.48％ |
| 32 | 4 | 29.0g | 96.3％ | 90.23％ |
(3) choice of Solvent (seeing Table 12).As shown in Table 12, solvent is best with DMF.
The The selection result that table 12 solvent is selected
| The experiment lot number | Solvent load | Must measure | Content % | Yield % |
| 33 | Toluene | 33.2g | 0 | 0 |
| 34 | Acetone | 32.8g | 0 | 0 |
| 35 | DMF | 29.2g | 96.1 | 90.67 |
| 36 | DMSO | 28.7g | 76.2 | 70.66 |
(4) reaction equation
5, fluorine ring azoles is synthetic
In the reaction bulb of being furnished with agitator, condenser, add azoles propylene 0.1mol, catalyzer 0.5g, solvent 200ml keeps uniform temperature, drips 27% hydrogen peroxide, and the control reaction temperature adds back insulation 5 hours, and separating treatment promptly obtains fluorine ring azoles.The present invention optimizes proportioning, reaction time, the selection of catalysts of reaction mass.
(1) proportioning of hydrogen peroxide and azoles propylene (seeing Table 13).As can be seen from Table 13 the proportioning of hydrogen peroxide and azoles propylene be 1.5 o'clock for best.
The proportioning of table 13 hydrogen peroxide and azoles propylene
| The experiment lot number | Material proportion | Must measure | Content % | Yield % |
| 37 | 1.0 | 25.8g | 90.1 | 70.55 |
| 38 | 1.2 | 26.2g | 94.3 | 74.98 |
| 39 | 1.5 | 27.4g | 96.5 | 80.25 |
| 40 | 2.0 | 27.7g | 93.4 | 78.52 |
(2) screening in reaction time (seeing Table 14).React 5 hours the bests as can be seen from Table 14.
The The selection result in table 14 reaction time
| The experiment lot number | Reaction time | Must measure | Content | Yield |
| 41 | 3 | 25.1g | 91.8％ | 69.93％ |
| 42 | 4 | 28.0g | 92.6％ | 78.69％ |
| 43 | 5 | 27.8g | 95.9％ | 80.91％ |
| 44 | 7 | 27.4g | 96.3％ | 80.08％ |
(3) screening of CAT (seeing Table 15).We have carried out a large amount of screenings to CAT, have finally determined the kind of CAT.The use of catalyzer not only makes yield and content all improve greatly, also makes the reaction time shorten to 5 hours by original 15 hours.
The The selection result of table 15CAT
| The experiment lot number | Catalyzer | Must measure | Content % | Yield % |
| 45 | Without CAT | 28.2 | 0 | 0 |
| 46 | CAT4 | 29.4 | 82.5 | 73.61 |
| 47 | CAT5 | 27.0 | 92.3 | 75.63 |
| 48 | CAT6 | 27.6 | 95.9 | 80.33 |
(4) reaction equation
Claims (2)
1, a kind of epoxiconazole raw drug bactericide is characterized in that this bactericide contains 96.0% fluorine ring azoles by weight percentage.
2, the proportioning of epoxiconazole raw drug according to claim 1 is by weight percentage:
Epoxiconazole raw drug active constituent content 〉=96.0%
Acetone insoluble matter≤0.5%
Moisture≤0.5%
Acidity (in H2SO4)≤0.5%
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304014A (en) * | 2011-07-07 | 2012-01-04 | 江苏七洲绿色化工股份有限公司 | Method for preparing epoxiconazole intermediate |
| CN102643162A (en) * | 2011-02-18 | 2012-08-22 | 中国中化股份有限公司 | A method for preparing 1-(2-chlorophenyl)-2-(4-fluorophenyl) propylene |
| EP2746275A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | New substituted triazoles and imidazoles and their use as fungicides |
| CN103936723A (en) * | 2013-01-23 | 2014-07-23 | 中国中化股份有限公司 | Method of preparing epoxiconazole by catalyzing epoxidation of triazole olefin |
| CN108752326A (en) * | 2018-09-06 | 2018-11-06 | 南通雅本化学有限公司 | A kind of compounding method of epoxiconazole |
| CN109336733A (en) * | 2018-10-26 | 2019-02-15 | 江苏七洲绿色化工股份有限公司 | A kind of preparation method of epoxiconazole intermediate and epoxiconazole |
-
2008
- 2008-02-18 CN CNA2008100577738A patent/CN101513183A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643162A (en) * | 2011-02-18 | 2012-08-22 | 中国中化股份有限公司 | A method for preparing 1-(2-chlorophenyl)-2-(4-fluorophenyl) propylene |
| CN102643162B (en) * | 2011-02-18 | 2014-08-06 | 中国中化股份有限公司 | A method for preparing 1-(2-chlorophenyl)-2-(4-fluorophenyl) propylene |
| CN102304014A (en) * | 2011-07-07 | 2012-01-04 | 江苏七洲绿色化工股份有限公司 | Method for preparing epoxiconazole intermediate |
| EP2746275A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | New substituted triazoles and imidazoles and their use as fungicides |
| CN103936723A (en) * | 2013-01-23 | 2014-07-23 | 中国中化股份有限公司 | Method of preparing epoxiconazole by catalyzing epoxidation of triazole olefin |
| CN103936723B (en) * | 2013-01-23 | 2016-06-29 | 沈阳中化农药化工研发有限公司 | A kind of method that catalysis triazole alkene epoxidation prepares epoxiconazole |
| CN108752326A (en) * | 2018-09-06 | 2018-11-06 | 南通雅本化学有限公司 | A kind of compounding method of epoxiconazole |
| CN109336733A (en) * | 2018-10-26 | 2019-02-15 | 江苏七洲绿色化工股份有限公司 | A kind of preparation method of epoxiconazole intermediate and epoxiconazole |
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