CN1115325C - Method for synthesis of pyrethrin by catalytic esterification of 4-dimethylaminopyridine - Google Patents
Method for synthesis of pyrethrin by catalytic esterification of 4-dimethylaminopyridine Download PDFInfo
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- CN1115325C CN1115325C CN98113306A CN98113306A CN1115325C CN 1115325 C CN1115325 C CN 1115325C CN 98113306 A CN98113306 A CN 98113306A CN 98113306 A CN98113306 A CN 98113306A CN 1115325 C CN1115325 C CN 1115325C
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- acyl chlorides
- pyrethrin
- dimethylamino pyridine
- catalytic esterification
- alcohol
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Abstract
The present invention discloses a method for synthesizing pyrethrin pesticide by the catalytic esterification of 4-dimethylaminopyridine (DMAP). DMAP is used as an ultra-high catalyst esterified by acyl chloride and alcohol in the molar batch charging ratio of 0.95 to 1.20:1.00, organic amine or inorganic alkali or a mixture of the organic amine and the inorganic alkali is used as an acid-binding agent, wherein the molar dosage of the DMAP is 0.05 to 2% of that of the acyl chloride, the molar dosage of the acid-binding agent is 0.5 to 3 times of that of the acyl chloride, and the pyrethrin pesticide can be prepared by a reaction for 10 minutes to 24 hours at-15 DEG C to 100 DEG C. The product manufactured by the present invention has the advantages of high yield, good quality, low cost, little 'three waste 'and easy control for production.
Description
The present invention relates to a kind of manufacture method of agrochemicals, particularly relate to a kind of manufacture method of pyrethrin.
Pyrethroid is the big insecticides of one in the pesticide industry, especially in hygienic insecticide, because it occupies epochmaking position to pest efficient to people and animals' low toxicity in pesticide industry.The esterification synthetic method of this class agricultural chemicals mainly contains following several:
The 1st kind of method is classic methods, also be the method for present domestic and international industrial widespread usage, but this method exists weak point, mainly is must use anhydrous pyridine in the reaction as acid binding agent and catalyzer.Anhydrous pyridine not only costs an arm and a leg but also very easily suction, and is obvious to the influence of producing yield under the bigger environment of humidity; Next is that the pyridine smell is very unpleasant, influences surrounding environment; It is also very complicated to reclaim anhydrous pyridine in addition.As without pyridine, use cheap triethylamine instead, N, organic amines such as accelerine are as acid binding agent, and then esterification yield and quality product are lower 10～20 percentage points than pyridine method, all can not accept economically with on producing.
The 2nd kind of method is the industrialized preparing process of early stage Tetramethrin, permethrin and valerate, though do not use pyridine in this method as acid binding agent, but because corresponding alcohol moiety intermediate difficult quality guarantee, be reflected at long-time heating under the alkaline condition, to optical activity chrysanthemum ester also is disadvantageous, now progressively is eliminated.
The 3rd kind of method, i.e. ester exchange method.At some chrysanthemum ester then is important in permethrin synthetic for example, but the shortcoming of this method also is tangible.Because the catalyzer that present method adopts is a titanic acid ester, it is hydrolysis very easily, and hydrolysate can not be removed and can not be water-washed away with general filter method, is restricted when practical application.
The objective of the invention is to solve the deficiency of above-mentioned existing method and provide a kind of can make to produce be easy to control, the reaction conditions gentleness can make the product yield height again, the method for the measured esterification synthesis of pyrethrin of matter ester pesticides.
For reaching above-mentioned purpose, technical scheme of the present invention is: use the ultra-high efficiency catalyzer of 4-Dimethylamino pyridine as acyl chlorides and pure esterification, add acid binding agent, wherein the molar feed ratio of acyl chlorides and alcohol is an acyl chlorides: alcohol is 0.95～1.20: 1.00, the mole dosage of 4-Dimethylamino pyridine is 0.05～2% of an acyl chlorides, the mole dosage of acid binding agent is 0.5～3 times of acyl chlorides, and reaction promptly made pyrethrin in 10 minutes to 24 hours under-15 ℃～100 ℃ temperature, and its reaction equation is:
In the formula, X representative-CH
3,-Cl; R
1Representative
Acid binding agent of the present invention is organic amine, mineral alkali or both miscellanys.Organic amine comprises Trimethylamine 99, triethylamine, tri-isopropyl amine, N, accelerine, N, N-Diethyl Aniline.Mineral alkali comprises sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate and calcium hydroxide.
Acyl chlorides of the present invention comprises cis-trans chrysanthemum acyl chlorides, is 1～25/99～75 and corresponding optical isomer along anti-body ratio; Cis-trans two chloro-chrysanthemum acyl chlorides are 0～45/100～55 and the trans two chloro-chrysanthemum acyl chlorides of d-along anti-body ratio; The acyl chlorides that the present invention uses also can replace with corresponding acid anhydrides.
Alcohol of the present invention comprises the 3-phenoxy benzenemethanol, a-cyano group-3-phenoxy benzenemethanol, N-methylol-3,4,5,6-tetrahydrochysene phthalyl industry amine, 2,3,5,6-tetrafluorobenzyl alcohol, 2-methyl-3-(2-allyl group)-4-oxo-ring penta-2-enol and 2-methyl-3-(2-propargyl)-4-oxo-ring penta-2-enol.
Acyl chlorides of the present invention is preferably 1.00～1.05 with both molar feed ratios of alcohol: 1.00; The mole dosage of 4-Dimethylamino pyridine is preferably 0.1～0.5% of acyl chlorides; The mole dosage of acid binding agent is preferably 1～2.5 times of acyl chlorides; Temperature of reaction is preferably-5 ℃～60 ℃; Reaction times is preferably 1～8 hour.
The main raw material of usefulness required for the present invention, chrysanthemum acyl chlorides for example, purity will have certain requirement, should avoid bringing into activity and high-boiling-point impurity, as containing chrysanthemumic acid etc. in the chrysanthemum acyl chlorides.In the corresponding alcohol, its purity also has higher requirement, should not bring activity or high-boiling-point impurity into, for example should not bring 4-phenoxy benzenemethanol etc. in the 3-phenoxy benzenemethanol.
The present invention requires very not strict to reaction solvent, can be aromatic hydrocarbons, for example toluene, dimethylbenzene etc.; Also can be alkane, for example normal hexane, normal heptane, sherwood oil, hexanaphthene etc.; Even can be water or organic solvent/water two-phase system.
The present invention compares with the traditional method of producing pyrethrin in the past, have very big advantage: at first be fully need not expensive pyridine in producing as acid binding agent and catalyzer, reduce environmental pollution, also do not had the problem that reclaims pyridine, reduced production cost; Also without titanic acid ester as catalyzer, save the trouble of removing hydrolysate; Next is that catalyzer 4-Dimethylamino pyridine low price of the present invention, source are abundant, and the product yield height of producing, and quality is good; Be that the inventive method can be produced under the bigger environment of humidity once more, even can carry out, produce and to be easy to control, and traditional method is very strict to the requirement of moisture content at aqueous phase.
The present invention is described in further detail below in conjunction with embodiment.Example 1
Agitator is being housed, in the there-necked flask of thermometer, dropping funnel and calcium chloride tube, add amine alcohol 18.49 grams (0.10 mole), 50 milliliters of triethylamine 15.18 gram, 18 milligrams of 4-Dimethylamino pyridines and toluene, under agitation heating makes all dissolvings of amine alcohol slightly, is cooled to about about 10 ℃ of liquid temperature with ice-water bath again, begins to drip toluene solution 26.67 grams of chrysanthemum acyl chlorides, the control rate of addition makes reaction solution liquid temperature remain on 10～20 ℃, drips off the back and continues to react under room temperature to spend the night.With reacting liquid filtering, filtrate is used 5% hydrochloric acid successively, and 5% sodium bicarbonate and be washed to neutrality is sloughed toluene after drying and got light yellow Tetramethrin crude oil 34.55 grams, content 92.00%, yield 95.91%.Example 2
Agitator is being housed, in the there-necked flask of thermometer and dropping funnel, add phenylate alcohol 20.20 grams (0.10 mole), triethylamine 2.00 grams, liquid caustic soda 24.0 grams, 50 milliliters of 18 milligrams of 4-Dimethylamino pyridines and toluene, under agitation bathe the cooling reaction solution to below-5 ℃ with cryosel, slowly drip toluene solution 26.67 grams of dextrorotation chrysanthemum acyl chlorides, after dripping off at room temperature-stirring reaction 3 hours, reaction solution is used 5% hydrochloric acid after adding an amount of dilution of water successively, 5% sodium bicarbonate and be washed to neutrality, precipitation gets faint yellow d-phenothrin crude oil 35.00 grams after drying, product is through hydrolysis, with the optical agents menthol reaction, recording dextrorotation trans-chrysanthemate content is 82.37% after the chloride.Example 3
In the device with example 2, add phenylate aldehyde 20.00 grams (0.10 mole), triethylamine 2.00 grams, sodium cyanide 5.25 grams (0.105 mole), 50 milliliters of 18 milligrams of 4-Dimethylamino pyridines and sherwood oils, when under agitation being cooled to 5 ℃ of reaction solutions, begin to drip petroleum ether solution 27.47 grams of dextrorotation chrysanthemum acyl chlorides, drip off the back and continue reaction 6 hours in 5～10 ℃ with ice-water bath, reaction solution is through alkali cleaning, pickling, washing gets trans cyphenothrin crude oil 38.33 grams of dextrorotation behind the precipitation.Example 4
In the device with example 2, add phenylate alcohol 20.20 grams (0.10 mole), yellow soda ash 21.2 grams, 50 milliliters of 18 milligrams of 4-Dimethylamino pyridines and toluene, under agitation be cooled to reaction solution below 5 ℃ with ice-water bath, slowly drip toluene solution 32.50 grams of dichloro chrysanthemum acyl chlorides, drip off the back and under room temperature, continue reaction 4 hours, add 100 milliliters in water to reaction solution, wait solids all to dissolve the back and divide water-yielding stratum, oil reservoir washes with water to neutrality, get light yellow transparent permethrin crude oil 39.06 grams behind the decompression precipitation, content 94.92%, yield 94.75% does not change along anti-body ratio.
Claims (11)
1, a kind of method of 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides, raw material comprises acyl chlorides and alcohol, it is characterized in that: use the ultra-high efficiency catalyzer of 4-Dimethylamino pyridine as acyl chlorides and pure esterification, add acid binding agent, wherein the molar feed ratio of acyl chlorides and alcohol is an acyl chlorides: alcohol is 0.95～1.20: 1.00, the mole dosage of 4-Dimethylamino pyridine is 0.05～2% of an acyl chlorides, the mole dosage of acid binding agent is 0.5～3 times of acyl chlorides, and reaction promptly made pyrethrin in 10 minutes to 24 hours under-15 ℃～100 ℃ temperature.
2, the method for 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides as claimed in claim 1 is characterized in that: acyl chlorides is an acyl chlorides with both molar feed ratios of alcohol: alcohol is 1.00～1.05: 1.00; The mole dosage of 4-Dimethylamino pyridine is 0.1～0.5% of an acyl chlorides; The mole dosage of acid binding agent is 1～2.5 times of acyl chlorides; Temperature of reaction is-5 ℃～60 ℃; Reaction times is 1～8 hour.
3, the method for 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides as claimed in claim 2, it is characterized in that: described acid binding agent is an organic amine.
4, the method for 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides as claimed in claim 2, it is characterized in that: described acid binding agent is a mineral alkali.
5, the method for 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides as claimed in claim 2, it is characterized in that: described acid binding agent is the miscellany of organic amine and mineral alkali.
6, as claim 3 or 4 or 5 or the method for described 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides, it is characterized in that: described acyl chlorides is cis-trans chrysanthemum acyl chlorides and corresponding optical isomer, is 1～25/99～75 along anti-body ratio.
7, as the method for claim 3 or 4 or 5 described 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides, it is characterized in that: described acyl chlorides is cis-trans two chloro-chrysanthemum acyl chlorides and corresponding optical isomer, is 0～45/100～55 along anti-body ratio.
8, as the method for claim 3 or 4 or 5 described 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides, it is characterized in that: described acyl chlorides can replace with corresponding acid anhydrides.
9, as the method for claim 3 or 4 or 5 described 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides, it is characterized in that: described alcohol is the 3-phenoxy benzenemethanol, alpha-cyano-3-phenoxy benzenemethanol, N-methylol-3,4,5,6-tetrahydric phthalimide, 2,3,5,6-tetrafluorobenzyl alcohol, any in 2-methyl-3-(2-allyl group)-4-oxo-ring penta-2-enol and 2-methyl-3-(2-the propargyl)-4-oxo-ring penta-2-enol.
10, the method for 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides as claimed in claim 3, it is characterized in that: described organic amine is Trimethylamine 99, triethylamine, tri-isopropyl amine, N, accelerine, N, any in the N-Diethyl Aniline.
11, the method for 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides as claimed in claim 4, it is characterized in that: described mineral alkali is any in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate and the calcium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113306A CN1115325C (en) | 1998-08-05 | 1998-08-05 | Method for synthesis of pyrethrin by catalytic esterification of 4-dimethylaminopyridine |
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| CN98113306A CN1115325C (en) | 1998-08-05 | 1998-08-05 | Method for synthesis of pyrethrin by catalytic esterification of 4-dimethylaminopyridine |
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| CN1218030A CN1218030A (en) | 1999-06-02 |
| CN1115325C true CN1115325C (en) | 2003-07-23 |
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| CN98113306A Expired - Lifetime CN1115325C (en) | 1998-08-05 | 1998-08-05 | Method for synthesis of pyrethrin by catalytic esterification of 4-dimethylaminopyridine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6747167B2 (en) * | 2002-09-23 | 2004-06-08 | Crompton Corporation | Process for the preparation of acid esters |
| CN102351694A (en) * | 2011-10-17 | 2012-02-15 | 三明市海斯福化工有限责任公司 | Preparation method of trifluoroacetic acid ethyl ester |
| CN106810444B (en) * | 2015-12-01 | 2018-09-04 | 中国科学院大连化学物理研究所 | A kind of method of chlorobenzoyl chloride and halogenated alkane reaction generation ester |
| CN106810411B (en) * | 2015-12-01 | 2018-09-04 | 中国科学院大连化学物理研究所 | A kind of method of acyl chlorides and 1,2- dichloroethanes reaction generation ester |
| CN110256285B (en) * | 2019-07-09 | 2022-03-18 | 上海出入境检验检疫局动植物与食品检验检疫技术中心 | Synthetic method of stable isotope labeled pyrethroid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2055822A (en) * | 1979-07-27 | 1981-03-11 | Sumitomo Chemical Co | Carboxylic ester compounds for use as insecticides |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2055822A (en) * | 1979-07-27 | 1981-03-11 | Sumitomo Chemical Co | Carboxylic ester compounds for use as insecticides |
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Owner name: AESTAR (ZHONGSHAN) CO., LTD Free format text: FORMER NAME: ZHONGSHAN CITY AESTAR FINE CHEMICALS CO., LTD. |
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Address after: 528402 No. 116 Qingxi Road, Zhongshan, Guangdong Patentee after: Aestar (Zhongshan) Co., Ltd. Address before: 528402 No. 100 Qingxi Road, Zhongshan, Guangdong Patentee before: Kaida Fine Chemical Industry Co., Ltd., Zhongshan City |
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Granted publication date: 20030723 |