WO2018050213A1 - Procédé amélioré pour la préparation de pyréthroïdes - Google Patents

Procédé amélioré pour la préparation de pyréthroïdes Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
formula
process according
integer
anyone
range
Prior art date
Application number
PCT/EP2016/071611
Other languages
English (en)
Inventor
Giuliano ZAMBONIN
Simona LOLLI
Alberto Guerrini
Valerio Borzatta
Original Assignee
Endura S.P.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Endura S.P.A. filed Critical Endura S.P.A.
Priority to PCT/EP2016/071611 priority Critical patent/WO2018050213A1/fr
Publication of WO2018050213A1 publication Critical patent/WO2018050213A1/fr

Links

Classifications

    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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).
PCT/EP2016/071611 2016-09-14 2016-09-14 Procédé amélioré pour la préparation de pyréthroïdes WO2018050213A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2016/071611 WO2018050213A1 (fr) 2016-09-14 2016-09-14 Procédé amélioré pour la préparation de pyréthroïdes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2016/071611 WO2018050213A1 (fr) 2016-09-14 2016-09-14 Procédé amélioré pour la préparation de pyréthroïdes

Publications (1)

Publication Number Publication Date
WO2018050213A1 true WO2018050213A1 (fr) 2018-03-22

Family

ID=57121186

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/071611 WO2018050213A1 (fr) 2016-09-14 2016-09-14 Procédé amélioré pour la préparation de pyréthroïdes

Country Status (1)

Country Link
WO (1) WO2018050213A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
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

Patent Citations (9)

* Cited by examiner, † Cited by third party
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

Similar Documents

Publication Publication Date Title
TWI484912B (zh) 新穎之經鹵素取代的化合物
CN102341378B (zh) 1-烷基-5-苯甲酰基-1h-四唑衍生物的制备方法
JPH04154741A (ja) アミン誘導体、その製造方法及び殺虫剤
AU5682200A (en) Substituted arylmalonic acid dinitriles as intermediates for the preparation of herbicides
Yamago et al. Thermal hetero [3+ 2] cycloaddition of dipolar trimethylenemethane to O-alkyloximes. Straightforward synthetic routes to substituted pyrrolidines and prolines
CN1072213C (zh) 胍衍生物的制备方法及其中间体
JP2806998B2 (ja) 置換された‐２‐クロロ‐ピリジン類の製造方法
Palacios et al. Efficient synthesis of fluorinated α-and β-amino nitriles from fluoroalkylated α, β-unsaturated imines
JPH04210964A (ja) 置換２−クロロピリジンの製法
WO2018050213A1 (fr) Procédé amélioré pour la préparation de pyréthroïdes
JP3280373B2 (ja) フルオロビニルオキシフェニル残基を有する殺菌化合物およびその製造方法
JPS6041061B2 (ja) シクロプロパンカルボン酸の前駆物質
JPS6335569A (ja) フルフリルアルコ−ル類の製造方法
EP0759429B1 (fr) Trifluorméthylpyridines substituées utiles comme intermédiaires pour 1-(pyridyl)-pyrazoles herbicides
Buttke et al. A convenient and improved procedure for the cyanation of enamines and 1, 3-dicarbonyl compounds
CN105801415A (zh) 一种含氟手性烯丙基类化合物及其制备方法
JPS6319501B2 (fr)
CN110156668A (zh) 一种合成4-多氟烷基-2,6-二芳基取代吡啶化合物的方法
WO2006137389A1 (fr) Nouvel agent insecticide/miticide
JPH09255668A (ja) ビスオキサゾリン類の製造方法
JP4781678B2 (ja) 含フッ素ケテンシリルアセタールを用いたβ−ケトエステルの製造方法
JP3918348B2 (ja) γ−ハロゲノ−β−ケトエステル類の製法
JP2021098666A (ja) ｇｅｍ−ジフルオロシクロプロペンテトラフルオロスルファニルアレーン化合物
CN105461683A (zh) 邻氨基苯甲酰胺化合物的制备方法
JP4485638B2 (ja) 塩化ｎ−［１−クロロ−１−（ペルフルオロアルキル）メチル］アリールイミドイル化合物からの２−アリール−５−（ペルフルオロアルキル）ピロール化合物の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16778689

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16778689

Country of ref document: EP

Kind code of ref document: A1