WO2018050213A1 - Procédé amélioré pour la préparation de pyréthroïdes - Google Patents
Procédé amélioré pour la préparation de pyréthroïdes Download PDFInfo
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- WO2018050213A1 WO2018050213A1 PCT/EP2016/071611 EP2016071611W WO2018050213A1 WO 2018050213 A1 WO2018050213 A1 WO 2018050213A1 EP 2016071611 W EP2016071611 W EP 2016071611W WO 2018050213 A1 WO2018050213 A1 WO 2018050213A1
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- 0 CC(C)([C@@]1C=C(*)I)C1C(Cl)=O Chemical compound CC(C)([C@@]1C=C(*)I)C1C(Cl)=O 0.000 description 2
- IFMLHVXMKNVXLC-UHFFFAOYSA-N CCN(C(C1=C2CCCC1)=O)C2=O Chemical compound CCN(C(C1=C2CCCC1)=O)C2=O IFMLHVXMKNVXLC-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
Definitions
- the present invention relates to an improved process for the preparation of cyclopropanecarboxylic acid ester and its derivatives in all stereochemical configuration as well as their mixtures.
- the cyclopropanecarboxylic acid ester are well known as pyrethroids and they are effectively active against a wide spectrum of insect species in household application, in professional pest control (PCO) and in agriculture. It's worth mentioning among the pyrethroids for household application different products containing the 2,2-dimethyl-3-(2-methylprop-1 -enyl)cyclopropane-1 -carboxylic acid moiety, the esters of which with the suitable alcohol are known as commercial products e.g Tetramethrin, D-allethrin, D-trans-allethrin, Imiprothrin, among the pyrethoids for PCO and agriculture applications different products containing a suitable halogenated cyclopropanecarboxylic acid , the ester of which with the suitable alcohol are known as commercial products e.g. ⁇ - Cyalothrin, Deltamethrin, Cypermethrin, Transfluthrin, Fenfluthrin, Meperfluthr
- the preparation process is based on the condensation of the chloride of the suitable cyclopropanecarboxylic acid in the suitable stereochemical configuration or in their configuration mixtures with the suitable alcohol in the suitable stereochemical configuration or in their configuration mixtures.
- D-allethrin is prepared by reacting the suitable stereochemical mixture of 2,2-dimethyl-3-(2-methylprop-1 -enyl)cyclopropane-1 -carboxylic acid chloride with the stereochemical mixture of 2-allyl-3-methylcyclopent-2-ene-1 - one -4 ol at temperatures between 40°C and 50°C in the presence of a solvent and in the presence of an acid binding agent.
- D-trans-allethrin is prepared by reacting the suitable stereochemical mixture of 2,2-dimethyl-3-(2-methylprop-1 -enyl)cyclopropane-1 -carboxylic acid chloride with (S)- 2-allyl-3-methylcyclopent-2-ene-1 -one -4-ol at temperatures between 50°C and 1 10°C in the presence of a solvent and in the presence of an acid binding agent.
- ⁇ -Cyalothrin, Deltamethrin and Cypermethrin are prepared by reacting the suitable stereochemical component of the suitable starting material represented by an ethenyl halogen substituted or propenyl halogen substituted -2,2-dimethyl-cyclopropane-1 -carboxylic acid chloride with the suitable alcohol in the suitable stereochemical composition at temperatures between 40°C and 1 10°C in the presence of a solvent and in the presence of an acid binding agent.
- Indian Patent 225306 a process for preparing transfluthrin is described.
- step 1 chlorination of (+)1 R-trans- permethric acid with thionyl chloride and step 2) condensation of (+)1 R-trans- permethric acid chloride with 2,3,5,6-tetrafluorobenzyl alcohol in the presence of toluene as organic solvent.
- Such a method comprises a first step of chlorinating (+)1 R-trans-permethric acid with at least one chlorinating agent to form (+)1 R-trans-permethric acid chloride, wherein such chlorinating agent can be thionyl chloride, phosphorous trichloride, phosphorous pentachloride or elemental chlorine.
- the first step can be carried out in the presence of a solvent.
- the second step is a condensing step of (+)1 R- trans-permethric acid chloride with 2,3,5,6-tetrafluorobenzyl alcohol, preferably in the of a solvent, more preferably-toluene.
- the patent provides for a stirring step in order to drive out the ensuing gasses.
- the method provides also for a further step of purifying the crude product to obtain transfluthrin.
- a purification step comprises the treatment of the crude product in a solvent, for instance through a steam distillation.
- Meperfluthrin is obtained by condensation of 4-methoxymethyl- 2,3,5,6-tetrafluorobenzyl alcohol with (1 R)-trans-permethric acid chloride in toluene in the presence of pyridine at 20 °C.
- Heptafluthrin is obtained by transesterification of a suitable alkyl 3-(3,3,3-trifluoro-1 -propenyl)-2,2-dimethylcyclopropanecarboxylate and 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl alcohol in an organic solvent in the presence of titanate catalyst at 80-150°C.
- the used titanate catalyst is represented by the formula Ti(OR) 4 .
- Tefluthrin is prepared by condensation of Z-(1 R,3R)-3-(2-chloro- 3,3,3-trifluoro-1 -propenyl)-2,2-dimethylcyclopropancarboxylic acid chloride with 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol in toluene and with pyridine as acid acceptor.
- the applicant has surprisingly found out a process which eliminates or decreases to very low amounts the presence of the corresponding anhydride.
- the invention hence concerns a process for preparing a pyrethroid of Formula (I)
- Xi and X2 are, independently of each other, selected from the group consisting of hydrogen, methyl, fluorine, chlorine, bromine and trifluoromethyl
- Z is a group of formula (IV), (V) or (VI) :
- Ri is allyl or propargyl
- R2 is hydrogen or methyl
- n is an integer from 1 to 5
- m is (5-n)
- Y is selected from the group consisting of hydrogen, (Ci-C 4 )alkyl and (Ci-C4)alkoxy(Ci-C4)alkyl
- A is -NH- or -0-
- b and d are independently to each other, an integer in the range of 1 -5
- c is an integer in the range of 2-5
- e is an integer from 0 to1
- p is an integer in the range of 0-5, is added in step a) or b) or after step a) and before step b).
- the process of the invention represents a substantial improvement in comparison with the processes of the prior art, allowing to get yields higher than 90% and very good purity of the pyrethroids finally obtained.
- the process of the invention doesn't give the formation of any anhydride allowing to improve the toxicity profile of the final pyrethroids.
- the amount of the related anhydride formed according to the process of the invention is less than 0.1 % (w/w), preferably less than 0.02% (w/w), being 0.02% (w/w) represented by the LOD ( limit of detection) of the related anhydride as measured with gas-chromatography.
- a further advantage of the invention is that no column or work up is needed to eliminate the anhydride (purification) from the main product.
- the present invention concerns a process for preparing a pyrethroid of Formula (I)
- Xi and X2 are, independently to each other, selected from the group consisting of hydrogen, methyl, fluorine, chlorine, bromine and trifluoromethyl with the proviso that Xi and X2 are not both hydrogen;
- Z is a group of formula (IV) or (V) or (VI):
- Ri is allyl or propargyl
- R2 IS hydrogen or methyl
- n is an integer from 1 to 5
- m is (5-n)
- Y is selected from the group consisting of hydrogen, (Ci-C 4 )alkyl and (Ci-C4)alkoxy(Ci-C4)alkyl
- A is -NH- or -0-
- b and d are independently to each other, an integer in the range of 1 -5
- c is an integer in the range of 2-5
- e is an integer from 0 to1
- p is an integer in the range of 0-5, is added in step a) or b) or after step a) and before step b).
- nitrogen acid acceptor is intended to indicate a compound having at least one nitrogen atom and capable to capture the hydrochloric acid formed during the condensation step
- the reaction of the acid chloride of formula (II) with the alcohol of formula (III) of step a) is carried out in the presence of a nitrogen acid acceptor.
- a nitrogen acid acceptor is preferably selected from the group consisting of pyridine and its derivatives, trimethylamine, triethylamine.
- Pyridine derivatives are preferably a - picoline, ⁇ -picoline r -picoline, 2,6-lutidine, 3,5-lutidine 5-ethyl-2-methylpyridine and 2,4,6-collidine (8).
- nitrogen acid acceptor pyridine is preferred.
- the ratio of the acid chloride of formula (II) to the nitrogen acid acceptor is preferably in the range from 0.5 to 1 equivalents, more preferably from 0.55 to
- the organic solvent of step a) is preferably selected from aliphatic solvents, cycloaliphatic solvents, chlorinated solvents, aromatic solvent and their mixtures.
- hexane heptane
- octane octane
- cycloaliphatic solvents cyclohexane, cycloheptane can be cited.
- chlorinated solvents methylene chloride, chloroform, carbon tetrachloride can be cited.
- aromatic solvents toluene, xylene and mesitylene can be cited.
- the solvent of step a) is more preferably toluene or cyclohexane.
- Xi is preferably methyl or chlorine.
- X2 is preferably methyl or chlorine.
- Z is preferably a group of Formula (IV) and of Formula (V).
- Ri is preferably allyl or propargyl.
- R2 is preferably hydrogen, n is preferably an integer 4-5, Y is preferably fluorine or methoxymethyl and m is preferably 1 .
- the ratio of the acid chloride of formula (II) to the alcohol of formula (III) in step a) is preferably in the range from 0.95 to 1 .20 equivalents, more preferably from 1 .00 to 1 .15 equivalents.
- the polyamine of formula (W) is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- A is -NH- or -0-
- b and d are independently to each other, an integer in the range of 1 -5
- c is an integer in the range of 2-5
- e is an integer from 0 to1
- p is an integer in the range of 0-5.
- polyamine (W) is selected from
- the polyamine (W) is still more preferably 1 ,2-diaminoethane, 1 ,3- diaminopropane, 3,3'-oxybis-1 -propanamine or 1 ,2-bis-(3- aminopropylamino)ethane.
- the most preferred polyamine is 1 ,2-diaminoethane or 1 ,3-diaminopropane.
- the amount of the polyamine is preferably in the range from 0.30 to 0.70 eq. with respect to the acid chloride of Formula (II), more preferably from 0.4 to 0.60 eq., still more preferably from 0.42 to 0.55 eq.
- the suitable amount of a polyamine (W) is added in step a) or b) or after step a) and before step b). Therefore the polyamine can be added in the reaction step a), preferably as soon as the chloride has been added or can added at the end of the condensation reaction together with water during the washing step b).
- the polyamine can be added after the condensation reaction of step a) and before the addition of water and/or basic aqueous solution of step b).
- a second washing step b) is preferably carried out.
- the reaction of step is carried out in a temperature range 0°C-40°C, more preferably in a temperature range of 5°C - 30°C.
- the washing step b) is carried out with water and/or with an aqueous basic solution. If needed, before the washing step, the product exiting from step a) is filtered.
- the reaction mixture is stirred for 1 -5 hrs.
- the addition of polyamine (W) is then carried out and then the mixture stirred for further Vz -2 hrs.
- the crude pyrethroid of formula (I) so obtained, is then optionally filtered and washed to eliminate the salt of the amine products.
- the reaction of step a) is carried out by reacting the acid chloride of formula (II) with the alcohol of formula (III) in the presence of pyridine as acid acceptor at, preferably temperatures in the range from 0- 10°C, thus stirring the mixture by heating in the range from 1 0°C to 30°C for 1 -3 hours.
- the addition of the polyamine (W) of step b) is preferably then carried out by stirring for further 1 /2-2 hours.
- the crude pyrethroid of formula (I) so obtained, is then washed as in step b) to eliminate the products deriving from the use of polyamine and evaporated u.v. to eliminate the solvent or the solvent mixtures.
- the amount of the related anhydride formed according to the process of the invention is less than 0.1 % (w/w), preferably less than 0.02% (w/w), being 0.02% (w/w) represented by the LOD (limit of detection) of the related anhydride as measured with gas-chromatography.
- the analyses as reported in the experimental part were carried out on GC Agilent mod.6890, detector FID. The analytical parameters for the analyses are reported here below:
- Capillary Column DB5-ms 30 m x 250 ⁇ , film thickness 0.25 ⁇ (or equivalent).
- Injection source autosampler
- the amount of chrysanthemic anhydride was less than 0.02% (%w/w) by GC analysis as previously reported.
- the amount of chrysanthemic anhydride was less than 0.02% (%w/w) by GC analysis as previously reported.
- the amount of chrysanthemic anhydride was less than 0.02% (%w/w) by GC analysis as previously reported
- the reaction was then added of an acid aqueous solution (0.40 moles of HCI 33% (% w/w) in 140 ml of water), stirred and the organic phase separated off.
- the organic phase was the washed with water and 4.0 g (0.04 moles) of N-(2- aminoethyl)-1 ,2-ethanediamine, separated and washed again with 60 ml of an aqueous solution containing 10% (% w/v) of sodium carbonate.
- the organic phase was separated and evaporated u.v at 40°C/ 0.2 kPa.
- the amount of chrysanthemic anhydride was less than 0.02% (%w/w) by GC analysis as previously reported
- the amount of permethric anhydride was less than 0.02% (% w/w) by GC analysis as previously reported.
- the amount of permethric anhydride was less than 0.02% (%w/w) by GC analysis as previously reported.
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Abstract
La présente invention concerne un procédé de préparation d'un pyréthroïde, ledit procédé comprenant les étapes consistant à :a) faire réagir un chlorure d'acide avec un alcool dans un solvant organique approprié et en présence d'un accepteur d'acide d'azote dans une plage de température de 0 °C à 40 °C ; et b) laver avec de l'eau et/ou une solution basique aqueuse, une quantité appropriée d'une polyamine (W) H 2 N- (CH 2 ) b -A e - [(CH 2 ) c -A-] p - (CH 2 ) d -NH 2 , où A est -NH- ou -O-, b et d sont indépendamment un nombre entier dans la plage de 1 à 5, c est un nombre entier dans la plage de 2 à 5, e est un nombre entier de 0 à 1, p est un nombre entier dans la plage de 0 à 5, est ajouté à l'étape a) ou b) ou après l'étape a) et avant l'étape b).
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PCT/EP2016/071611 WO2018050213A1 (fr) | 2016-09-14 | 2016-09-14 | Procédé amélioré pour la préparation de pyréthroïdes |
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PCT/EP2016/071611 WO2018050213A1 (fr) | 2016-09-14 | 2016-09-14 | Procédé amélioré pour la préparation de pyréthroïdes |
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3268398A (en) | 1963-04-11 | 1966-08-23 | Sumitomo Chemical Co | Cyclohexene-1, 2-dicarboximido methyl esters of cyclopropane carboxylic acid esters and insecticidal compositions thereof |
US3934023A (en) | 1972-09-29 | 1976-01-20 | Sumitomo Chemical Company, Limited | Insecticidal d-cis, trans-chrysanthemates |
US4176189A (en) | 1977-06-20 | 1979-11-27 | Sumitomo Chemical Company, Limited | Insecticidal and acaricidal hydantoin N-methylol esters |
US4275250A (en) | 1976-12-22 | 1981-06-23 | Bayer Aktiengesellschaft | Fluorobenzyl alcohols |
EP0107296A1 (fr) | 1982-10-18 | 1984-05-02 | Imperial Chemical Industries Plc | Produit insecticide et sa préparation |
IN2005MU00322A (fr) * | 2005-03-22 | 2007-06-29 | Bilag Industries Private Ltd | |
US7312366B2 (en) | 2003-10-10 | 2007-12-25 | Jiangsu Yangong Chemical Co., Ltd. | Preparation of one intermediate for pyrethroids |
CN101367730A (zh) | 2008-10-16 | 2009-02-18 | 贵阳柏丝特化工有限公司 | 一种拟除虫菊酯及合成 |
CN101580471A (zh) | 2008-05-16 | 2009-11-18 | 江苏扬农化工股份有限公司 | 一种拟除虫菊酯化合物及其制备方法和应用 |
-
2016
- 2016-09-14 WO PCT/EP2016/071611 patent/WO2018050213A1/fr active Application Filing
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3268398A (en) | 1963-04-11 | 1966-08-23 | Sumitomo Chemical Co | Cyclohexene-1, 2-dicarboximido methyl esters of cyclopropane carboxylic acid esters and insecticidal compositions thereof |
US3934023A (en) | 1972-09-29 | 1976-01-20 | Sumitomo Chemical Company, Limited | Insecticidal d-cis, trans-chrysanthemates |
US4275250A (en) | 1976-12-22 | 1981-06-23 | Bayer Aktiengesellschaft | Fluorobenzyl alcohols |
US4176189A (en) | 1977-06-20 | 1979-11-27 | Sumitomo Chemical Company, Limited | Insecticidal and acaricidal hydantoin N-methylol esters |
EP0107296A1 (fr) | 1982-10-18 | 1984-05-02 | Imperial Chemical Industries Plc | Produit insecticide et sa préparation |
US7312366B2 (en) | 2003-10-10 | 2007-12-25 | Jiangsu Yangong Chemical Co., Ltd. | Preparation of one intermediate for pyrethroids |
IN2005MU00322A (fr) * | 2005-03-22 | 2007-06-29 | Bilag Industries Private Ltd | |
CN101580471A (zh) | 2008-05-16 | 2009-11-18 | 江苏扬农化工股份有限公司 | 一种拟除虫菊酯化合物及其制备方法和应用 |
CN101367730A (zh) | 2008-10-16 | 2009-02-18 | 贵阳柏丝特化工有限公司 | 一种拟除虫菊酯及合成 |
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