CN1164557C - Prepn of dibromochrysanthemic acid - Google Patents
Prepn of dibromochrysanthemic acid Download PDFInfo
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- CN1164557C CN1164557C CNB01136890XA CN01136890A CN1164557C CN 1164557 C CN1164557 C CN 1164557C CN B01136890X A CNB01136890X A CN B01136890XA CN 01136890 A CN01136890 A CN 01136890A CN 1164557 C CN1164557 C CN 1164557C
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Abstract
The present invention relates to a method using permethrinic acid as raw material to synthesize chrysanthemic acid. The chrysanthemic acid and tribromo by-products are obtained on the basis of a synthetic method using AlBr3 and the permethrinic acid to directly carry out halogen exchange reaction; one-step HBr elimination reaction is increased to convert the tribromo by-products into the chrysanthemic acid; the deltamethric acid with the purity of 97 % is directly obtained, and the total yield is 91%. The configuration of the product and the raw material are kept consistent in the process of the reaction.
Description
Technical field
The present invention relates to a kind of is the method for the synthetic dibromo chrysanthemic acid of raw material with the dichlor chrysanthemic acid.
Background technology
Dibromo chrysanthemic acid is the intermediate compound of synthesizing efficient sterilant-Deltamethrin.Dibromo chrysanthemic acid, promptly 2,2-dimethyl-3-(2, the 2-dibromo vinyl) cyclopropanic acid is shown in (I)
The configuration that dibromo chrysanthemic acid partly needs in Deltamethrin is the cis dextrorotatory form.
The method of at present synthetic dibromo chrysanthemic acid is a lot, but often raw material is difficult to obtain at home, or higher to equipment requirements, needs high-power ozonizer, so the domestic scale operation that does not still realize dibromo chrysanthemic acid at present.
At document (1) dichlor chrysanthemic acid and ester are converted into dibromo analogue (Kiyoshi Kondo et al.US.4,188,492), (2) a kind of synthetic method (Kiyohide Matsui et al.Bull.Chem.Soc.Jpn. that the dichlor chrysanthemic acid ethyl ester is converted into the dibromo chrysanthemic acid ethyl ester, 59,221-227 (1986)) and (3) utilize halogen exchange reaction that the dichlor chrysanthemic acid ethyl ester is converted into dibromo chrysanthemic acid ethyl ester (KiyohideMatsui et al.Bull.Chem.Soc.Jpn., 59,1021-1026 (1986)) all reported in and utilized AlBr
3Or the reactant of aluminium and HBr and dichlor chrysanthemic acid or the reaction of dichlor chrysanthemic acid ester obtain corresponding dibromo chrysanthemic acid and dibromo chrysanthemic acid ester.Reach 94% for dichlor chrysanthemic acid ethyl ester yield, purity reaches 90%; For dichlor chrysanthemic acid, can obtain 93% purity after the process distillation is purified, but not mention yield.The shortcoming of its synthetic dibromo chrysanthemic acid method is:
1, adopt the method that constantly feeds HBr in the reaction, HBr is excessive greatly, pollutes and wastes, and requires also higher to the equipment pipeline;
2, when dichlor chrysanthemic acid and bromine reactant salt, must under the certain vacuum degree, (20mmHg) constantly feed argon gas, lose a large amount of argon gas and solvent and complex process, unstable product quality;
3, byproduct of reaction is many, and the dibromo chrysanthemic acid that obtains after the reaction is brown, must reaction yield be descended through the purification process of recrystallization and distillation, and operating process is loaded down with trivial details.
Summary of the invention
The object of the present invention is to provide a kind of is the method for feedstock production dibromo chrysanthemic acid with the dichlor chrysanthemic acid, provides a kind of convenient economic method for producing dibromo chrysanthemic acid.The present invention is a main purpose with synthesizing cis dextrorotatory form dibromo chrysanthemic acid, but also is applicable to the dibromo chrysanthemic acid of other three kinds of configurations.
For achieving the above object, provided by the invention a kind of be the method for the synthetic dibromo chrysanthemic acid of raw material with the dichlor chrysanthemic acid, based on utilizing AlBr
3Directly carry out the synthetic method of halogen exchange reaction with dichlor chrysanthemic acid, obtain dibromo chrysanthemic acid and tribromo by product, increase one-step removal HBr reaction the tribromo by product is converted into dibromo chrysanthemic acid, directly obtain the dibromo chrysanthemic acid of purity 97%, total recovery 91%.Product is consistent with the retention of configuration of raw material in reaction process.
Its reaction process is represented with following two formulas:
Shown in reaction formula, halogen exchange reaction takes place with dichlor chrysanthemic acid in the present invention under the alchlor system, removes hydrogen bromide then, and halogen exchange reaction carries out in organic solvent, removes hydrogen bromide and carries out in basic solution.Concrete grammar is as follows:
(1) dichlor chrysanthemic acid is dissolved in the organic solvent, is added drop-wise in the alchlor solution under-35-5 ℃ again and reacts, the reaction times is 1-24 hour, and the mol ratio of alchlor and dichlor chrysanthemic acid is 1.5: 1-3: 1;
(2) reaction solution is poured into hydrolysis in the mixed solution of dilute hydrochloric acid and ice cube;
(3) standing demix, organic extractant phase;
(4) organic phase is obtained crude product with 10-20% basic solution extraction back aqueous phase as acidified, perhaps directly the organic phase evaporate to dryness is obtained crude product;
(5) crude product is dissolved in the basic solution, the mol ratio of crude product and alkali is 1: 1-1: 5, and be heated to 40-80 ℃ and remove hydrogen bromide;
Above-mentioned organic solvent is methylene bromide, ethylene dibromide, bromofom or dithiocarbonic anhydride, preferred methylene bromide.
Above-mentioned basic solution is sodium hydroxide, potassium hydroxide, yellow soda ash, ammoniacal liquor or ethylenediamine solution.
The suitable inverse ratio of product and the assay of byproduct are used gas Chromatographic Determination after by the methyl alcohol derivatize, and the ratio of revolving about product is used the chiral column gas Chromatographic Determination after with the menthol derivatize.In the chromatographic determination, each component concentration all calculates with area normalization method.The total acid value determination of acid-basetitration.
The present invention possesses following advantage:
(1) technological process before having changed needn't feed bromize hydrogen gas, has reduced pollution and waste water, also will vacuumize when needn't feed argon gas in halogen exchange reaction, has simplified reaction conditions, has saved the argon gas consumption, has reduced solvent loss.Processing condition are simple, stable, are fit to industrial production.
(2) improved degree of purity of production and yield, reached respectively more than 97% and 90%.
(3) use soda acid instead and transform and to have realized purifying and byproduct is converted into two big purposes of product, needn't utilize the distillation grade to be difficult to realize and purification step that efficient is not high just obtains white solid, improved product color.
Embodiment
Embodiment 1: add 160ml ethylene dibromide and a small amount of aluminium powder in three mouthfuls of reaction flasks of 500ml, (62g 0.388mol) pours in the reaction flask with 20ml exsiccant bromine under 20 ℃.Afterreaction started in 15 minutes, and temperature remains on 30-50 ℃, and (9.3g 0.345mol), generates brown thing up to all aluminium powder reactions to add aluminium powder gradually.System temperature is dropped to 5 ℃ then, feed 5 minutes nitrogen to system, system is airtight.(26.6g 0.127mol) is added drop-wise in the alchlor solution, and controlled temperature is between-5 to 5 ℃ will to be dissolved in content 97% cis dextrorotation dichlor chrysanthemic acid in the 70ml ethylene dibromide.Dropping is controlled to be finished half an hour, keeps temperature to continue reaction 1 hour.Solution is poured into violent stirring in the mixed solution of 200ml dilute hydrochloric acid and ice cube, static layering, water with the extraction of 20ml ethylene dibromide once merges oil phase with the 100ml washing once.Oil phase with 15% aqueous sodium hydroxide solution 100ml extraction 3 times, is merged water, be acidified to pH＜2, be settled out the thick product of white with concentrated hydrochloric acid.Filter dibromo chrysanthemic acid content 45% in this moment product, byproduct tribromo product content 53%.With this thick product and NaOH (8g, 0.2mol) and 400ml water mix, be heated to 60 ℃, kept 2 hours, reaction solution is acidified to pH＜2 with concentrated hydrochloric acid, the product filtering drying that is precipitated out is obtained 34.5g white powder solid, yield 91.0%.Chromatographic determination cis-dibromo chrysanthemic acid content 98.1%, about revolve constant rate, acid number 99.8%, fusing point 124-126 ℃, specific rotation [α] 20=+26.65 (C=2%DMF).
Embodiment 2: (10.3g 0.381mol), is heated to 45 ℃ with suspension, and (62g 0.388mol) is dissolved in the 100ml methylene bromide, slowly is added drop-wise in the aluminium powder with 20ml exsiccant bromine to add 60ml methylene bromide and aluminium powder in three mouthfuls of reaction flasks of 500ml.Temperature remains on 30-50 ℃, generates brown thing up to all aluminium powder reactions.System temperature is dropped to 0 ℃ then, feed 5 minutes nitrogen to system, system is airtight.(suitable/anti-=45/55,26.6g 0.127mol) is added drop-wise in the alchlor solution, and controlled temperature is between-5 to 5 ℃ will to be dissolved in dichlor chrysanthemic acid in the 70ml methylene bromide.Dropping is controlled to be finished half an hour, keeps temperature to continue reaction 2 hours.Solution is poured into violent stirring in the mixed solution of 200ml dilute hydrochloric acid and ice cube, static layering, water with the extraction of 20ml methylene bromide once merges oil phase with the 100ml washing once.Oil phase with 15% aqueous sodium hydroxide solution 100ml extraction 3 times, is merged water, be acidified to pH＜2, be settled out the thick product of white with concentrated hydrochloric acid.Suitable anti-dibromo chrysanthemic acid content sum is 30% in the product at this moment, and byproduct tribromo product content sum is 68%.With this thick product and yellow soda ash (10.6g, 0.1mol) and 400ml water mix, be heated to 70 ℃, kept 2 hours, reaction solution is acidified to pH＜2 with concentrated hydrochloric acid, the product filtering drying that is precipitated out is obtained 35.4g white powder solid, yield 93.3%.Dibromo chrysanthemic acid is 45/55 constant along inverse ratio, chromatographic determination cis-dibromo chrysanthemic acid content 98%, acid number 99.9%.
Embodiment 3: add 160ml dithiocarbonic anhydride and a small amount of aluminium powder in three mouthfuls of reaction flasks of 500ml, (62g 0.388mol) pours in the reaction flask with 20ml exsiccant bromine under 20 ℃.Afterreaction started in 15 minutes, and temperature remains on 30-40 ℃, and (9.3g 0.345mol), generates the black thing up to all aluminium powder reactions to add aluminium powder gradually.Then system temperature is dropped to-30 ℃, feed 5 minutes nitrogen to system, system is airtight.(26.6g 0.127mol) is added drop-wise in the alchlor solution, and controlled temperature is between-35 to-25 ℃ will to be dissolved in content 97% cis dichlor chrysanthemic acid in the 70ml dithiocarbonic anhydride.Dropping is controlled to be finished half an hour, keeps temperature to continue reaction 24 hours.Solution is poured into violent stirring in the mixed solution of 200ml dilute hydrochloric acid and ice cube, static layering with the organic phase evaporate to dryness, obtains the thick product 41g of brown.With this thick product and KOH (5.6g, 0.1mol) and 400ml water mix, be heated to 40 ℃, kept 2 hours, after the filtration, reaction solution is acidified to pH＜2 with concentrated hydrochloric acid, the product filtering drying that is precipitated out is obtained 30.0g white powder solid, yield 79.3%.
Embodiment 4: the halogen exchange reaction condition changes solvent into bromofom with embodiment 1, and temperature of reaction was reacted 0.5 hour at 10 ℃.With thick product and ammoniacal liquor (15ml, ammonia content 25-28%, 0.22mol) and 400ml water mix, be heated to 70 ℃, kept 2 hours, reaction solution is acidified to pH＜2 with concentrated hydrochloric acid, the product filtering drying that is precipitated out is obtained 35.0g white powder solid, yield 92.3%.
Embodiment 5: the halogen exchange reaction condition is with embodiment 1, with thick product and quadrol (36g, 0.6mol) and the mixing of 200ml water, be heated to 80 ℃, kept 4 hours, reaction solution is acidified to pH＜2 with concentrated hydrochloric acid, the product filtering drying that is precipitated out is obtained 34.1g white powder solid, yield 90.1%.
Comparative example: press embodiment 1 described method and reaction conditions, adopt different ratios in halogen exchange reaction, react after two hours, the transformation efficiency of dichlor chrysanthemic acid is as follows:
Comparative example aluminium powder: dichlor chrysanthemic acid dichlor chrysanthemic acid transformation efficiency %
1 1∶1 45
2 1.5∶1 96.4
3 2∶1 98.5
Press embodiment 1 described method and reaction conditions, do not remove the reaction of hydrogen bromide behind halogen exchange reaction, the content of dibromo chrysanthemic acid can not surpass 60%.If feed the vacuum tightness that argon gas keeps 20mmHg simultaneously in reaction, the content of dibromo chrysanthemic acid can reach 93%, and solvent loss is more than 40%.
Can simplify technological process, reduce production costs by above-mentioned visible the present invention, improve the quality of products.
Claims (3)
- Halogen exchange reaction takes place with dichlor chrysanthemic acid in 1, a kind of preparation method of dibromo chrysanthemic acid under the alchlor system, remove hydrogen bromide then, it is characterized in that, halogen exchange reaction carries out in organic solvent, removes hydrogen bromide and carries out in basic solution, and concrete grammar is as follows:(1) dichlor chrysanthemic acid is dissolved in the organic solvent, is added drop-wise in the alchlor solution under-35-5 ℃ again and reacts, the reaction times is 1-24 hour, and the mol ratio of alchlor and dichlor chrysanthemic acid is 1.5: 1-3: 1;(2) reaction solution is poured into hydrolysis in the mixed solution of dilute hydrochloric acid and ice cube;(3) standing demix, organic extractant phase;(4) organic phase is obtained crude product with 10-20% basic solution extraction back aqueous phase as acidified;(5) crude product is dissolved in the basic solution, the mol ratio of crude product and alkali is 1: 1-1: 5, and be heated to 40-80 ℃ and remove hydrogen bromide;Described organic solvent is methylene bromide, ethylene dibromide, bromofom or dithiocarbonic anhydride;Described basic solution is sodium hydroxide, potassium hydroxide, yellow soda ash, ammoniacal liquor or ethylenediamine solution.
- 2, the preparation method of dichlor chrysanthemic acid as claimed in claim 1 is characterized in that, the direct evaporate to dryness of organic phase of step (3) obtains crude product, and then carries out step (5).
- 3, the preparation method of dichlor chrysanthemic acid as claimed in claim 1 is characterized in that, the preferred methylene bromide of described organic solvent.
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