WO2008009674A1 - Procédé de synthèse d'esters d'acides carboxyliques à insaturation oléfinique - Google Patents

Procédé de synthèse d'esters d'acides carboxyliques à insaturation oléfinique Download PDF

Info

Publication number
WO2008009674A1
WO2008009674A1 PCT/EP2007/057366 EP2007057366W WO2008009674A1 WO 2008009674 A1 WO2008009674 A1 WO 2008009674A1 EP 2007057366 W EP2007057366 W EP 2007057366W WO 2008009674 A1 WO2008009674 A1 WO 2008009674A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
alkyl
process according
formula
substituted
Prior art date
Application number
PCT/EP2007/057366
Other languages
English (en)
Inventor
Wolfgang Wiesenhöfer
Olivier Buyle
Véronique Mathieu
Original Assignee
Solvay (Société Anonyme)
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 Solvay (Société Anonyme) filed Critical Solvay (Société Anonyme)
Publication of WO2008009674A1 publication Critical patent/WO2008009674A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/27—Preparation of carboxylic acid esters from ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C07C67/327—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by elimination of functional groups containing oxygen only in singly bound form

Definitions

  • the invention relates to a process for the synthesis of olefinically unsaturated carboxylic acid esters.
  • the invention relates in particular to a process for the synthesis of olefinically unsaturated carboxylic acid esters by reacting carbonyl compounds with orthoesters of carboxylic acids.
  • Olefinically unsaturated carboxylic acid esters are important intermediate products for the synthesis of for example insecticides and acaricides, and also for the synthesis of pharmaceutically active compounds.
  • An important group among these compounds consists of fluorine containing olefinically unsaturated carboxylic acid esters.
  • ethyl 4,4,4-trifluoro-3-trifluoromethyl crotonate (ETFMC) is an important intermediate for the synthesis of new pharmaceuticals. Only few synthesis routes are however described in the literature.
  • DE 41 01 737 Al discloses a process for the production of olefinically unsaturated carboxylic acid esters by reacting carbonyl compounds and diazo compounds in the presence of a tertiary phosphine and a catalytic amount of an organo rhenium oxide in an organic solvent.
  • hexafluoroacetone (HFA) is reacted with diazo acetic acid ethyl ester in toluene in the presence of CHsReO 3 and triphenyl phosphine to yield ETFMC.
  • GB 2062620 A relates to haloalkyl cyclopropane carboxylic acid derivatives and their use as insecticides and acaricides.
  • R 1 is an alkyl, aryl or heteroaryl group that may be substituted with one or more halogen atoms and/or Ci-C 3 -alkyl groups
  • R 2 is an alkyl, aryl or heteroaryl group that may be substituted with one or more halogen atoms and/or Ci-C 3 -alkyl groups, or a hydrogen, or R 1 and R 2 form together with the carbon atom connecting them a C 4 -C 7 _carbocyclus that may be substituted with one or more halogen atoms and/or Ci_C 3 -alkyl groups
  • R 3 is hydrogen or a C 1 -C 5 alkyl group
  • halogen atoms used according to the present invention are in particular chlorine, fluorine or bromine atoms, most preferably fluorine atoms.
  • R 1 and R 2 are independently from each other an alkyl, aryl or heteroaryl group that may be substituted with one or more halogen atoms and/or Ci-C 3 -alkyl groups.
  • R 1 and/or R 2 is a fluorine containing Ci-Cs-alkyl group which contains in particular at least two fluorine atoms.
  • the two fluorine containing Ci-Cs-alkyl group comprises preferably a CF 3 group, and most preferably, R 1 and/or R 2 is a CF 3 group.
  • R 3 is hydrogen.
  • R 4 is preferably a Ci-Cs-alkyl group, most preferably an ethyl group.
  • the heteroaryl group present in the compounds used in the process according to the present invention contains in general one or more nitrogen, sulfur and/or oxygen atom.
  • the aryl group present in the compounds used in the process according to the present invention comprises in particular a phenyl or naphthyl group.
  • Ci-C 5 -alkyl groups according to the invention are in particular the methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, n-pentyl or iso-pentyl group.
  • the orthoesters of formula CH 2 R 3 C(OR 4 ) 3 are commercially obtainable or are synthetically readily available.
  • trimethyl or triethyl orthoacetate and ethyl orthopropionate are available from DEGUSSA, Germany.
  • the orthoesters of formula CH 2 R 3 C(OR 4 ) 3 are synthetically obtainable from the corresponding carboxylic esters by reacting the corresponding nitriles with the alcohol HOR 4 in the presence of HCl.
  • further reaction in the second step of the intermediate compound R 1 R 2 COH-CHR 3 (COOR 4 ) can be carried out in the presence or absence of an organic solvent.
  • an inert organic solvent is used.
  • Suitable organic solvents are benzene, toluene, diethyl ether, dioxane, tetrahydrofurane, methylene chloride or chloroform.
  • methylene chloride is used as the solvent.
  • the most preferred alcohol is ethanol. It was found surprisingly that higher yields of the intermediate compound R 1 R 2 COH-CHR 3 (COOR 4 ) are obtained when ethanol is present in the reaction medium of the first step.
  • R 1 R 2 COH-CHR ⁇ COOR 4 The product obtained after the first step, R 1 R 2 COH-CHR ⁇ COOR 4 ), may be isolated before the dehydration is carried out in a second step. Alternatively, the dehydration may be carried out in the same reaction medium. In a preferred - A -
  • the product obtained after the first step is first isolated, and the second step is carried out separately.
  • R 1 R 2 COH-CHR 3 (COOR 4 )
  • the dehydration can be effected without the addition of a solvent or in the presence of a solvent.
  • Suitable solvents are aprotic solvents, in particular acetonitrile, propionitrile and DMF.
  • the OH-group in R 1 R 2 COH-CHR ⁇ COOR 4 is replaced by a better leaving group in order to facilitate the dehydration step.
  • a suitable leaving group is the OC(O)CF 3 -group.
  • the introduction of the leaving group for a preferred embodiment of the present invention can be expressed by the following reaction sequence (TFAC is CFsC(O)Cl) : °Vvv )
  • the dehydration is carried out by firstly replacing the OH-group in R 1 R 2 COH-CHR ⁇ COOR 4 ) with a better leaving group which is then eliminated under formation of a double bond.
  • a base is preferably used.
  • Suitable bases are for example pyridine, pyrimidine, and
  • R 1 R 2 COH-CHR ⁇ COOR 4 If the OH-group in R 1 R 2 COH-CHR ⁇ COOR 4 ) is replaced by a better leaving group, the introduction of the leaving group, for example by reacting R 1 R 2 COH-CHR 3 (COOR 4 ) with CF 3 C(O)Cl (TFAC), is preferably effected at a temperature of from O to 4O 0 C.
  • TFAC CF 3 C(O)Cl
  • ETFMC is produced by reacting in a first step hexafluoroacetone (HFA) with triethyl orthoacetate to an intermediate product which is then dehydrated in a second step to yield the desired ETFMC.
  • HFA hexafluoroacetone
  • the process of the present invention has several advantages.
  • the process does neither require an expensive catalyst (like for example MeReO 3 ) nor a phosphine which would generate a large (stoechiometric) amount of phosphine oxide.
  • the starting compounds are readily available.
  • the process of the present invention allows to obtain the desired product in high yield.
  • ETFMC was produced by reacting in a first step hexafluoroacetone (HFA) with triethyl orthoacetate to give ethyl 4,4,4-trifluoro-3-trifluoromethyl-3-hydroxy butanoate using an excess of HFA in either the absence of ethanol (Example Ia) or in the presence of ethanol (Example Ib).
  • HFA hexafluoroacetone
  • Example Ib ethanol
  • Example Ib 82 g (0.49 mol) of ethyl orthoacetate were introduced in a conic reactor in Hastelloy B2 of a volume of 500 cc. The reactor was cooled down to -6O 0 C and 223.1 g (1.34 mol) of hexafluoroacetone were condensed into the reactor via a dipping tube. After the complete introduction of the hexafluoroacetone, the reactor temperature was set to 135 0 C during 5.5 h. The temperature was then further increased to 153 0 C during an additional period of 5 h.
  • ETFMC ethyl 4,4,4-trifluoro-3-trifluoroacetyl-butanoate

Landscapes

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

Abstract

L'invention concerne un procédé de synthèse d'esters d'acides carboxyliques à insaturation oléfinique de la formule R1R2C=CR3(COOR4), dans laquelle R1 est un groupe alkyle, aryle ou hétéroaryle qui peut être substitué par un ou plusieurs atomes d'halogène et/ou des groupes alkyle en C1-C3, R2 est un groupe alkyle, aryle ou hétéroaryle qui peut être substitué par un ou plusieurs atomes d'halogène et/ou des groupes alkyle en C1-C3, ou hydrogène, ou bien R1 et R2 forment conjointement avec l'atome de carbone les reliant un carocycle en C4-C7 qui peut être substitué par un ou plusieurs atomes d'halogène et/ou des groupe alkyle en C1-C3, R3 représente l'hydrogène ou un groupe alkyle en C1-C5, et R4 est un groupe alkyle ou aryle ayant jusqu'à 20 atomes de carbone, par réaction dans une première étape d'un composé carbonyle de formule R1R2C=O avec un orthoester de formule CH2R3C(OR4)3, et par déshydratation dans une seconde étape du composé intermédiaire obtenu R1R2COH-CHR3(COOR4).
PCT/EP2007/057366 2006-07-20 2007-07-17 Procédé de synthèse d'esters d'acides carboxyliques à insaturation oléfinique WO2008009674A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06117581.6 2006-07-20
EP06117581 2006-07-20

Publications (1)

Publication Number Publication Date
WO2008009674A1 true WO2008009674A1 (fr) 2008-01-24

Family

ID=37607228

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/057366 WO2008009674A1 (fr) 2006-07-20 2007-07-17 Procédé de synthèse d'esters d'acides carboxyliques à insaturation oléfinique

Country Status (1)

Country Link
WO (1) WO2008009674A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102211999A (zh) * 2011-05-25 2011-10-12 原平市同利化工有限责任公司 2-氟代丙烯酸烷基酯的制备方法
CN109790113A (zh) * 2016-09-26 2019-05-21 3M创新有限公司 含氮和/或氧的氢氟烯烃及其制备和使用方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2062620A (en) * 1979-10-23 1981-05-28 Ici Ltd Haloalkyl cyclopropane carboxylic acid derivatives
DE4101737A1 (de) * 1990-01-29 1991-08-01 Hoechst Ag Verfahren zur herstellung von olefinischen verbindungen aus carbonyl-verbindungen und diazoalkanen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2062620A (en) * 1979-10-23 1981-05-28 Ici Ltd Haloalkyl cyclopropane carboxylic acid derivatives
DE4101737A1 (de) * 1990-01-29 1991-08-01 Hoechst Ag Verfahren zur herstellung von olefinischen verbindungen aus carbonyl-verbindungen und diazoalkanen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
H. M. SAMPATH KUMAR, M. SHESHA RAO, SIPAK JOYASAWAL AND J. S. YADAV: "Condensation of orthoacetates with aldehydes: a new strategy for the preparation of alpha-beta-unsaturated esters", TETRAHEDRON LETTERS., vol. 44, no. 22, 26 May 2003 (2003-05-26), ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM., NL, pages 4287 - 4289, XP002415872 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102211999A (zh) * 2011-05-25 2011-10-12 原平市同利化工有限责任公司 2-氟代丙烯酸烷基酯的制备方法
CN109790113A (zh) * 2016-09-26 2019-05-21 3M创新有限公司 含氮和/或氧的氢氟烯烃及其制备和使用方法

Similar Documents

Publication Publication Date Title
US6700011B1 (en) Process for the preparation of naproxene nitroxyalkylesters
EP1104750B1 (fr) Procedes de preparation de derives d'acide 5-hydroxy-3- oxopentanoique
US5955627A (en) Process for the preparation of cyclopropylacetylene derivatives
ES2371063T5 (es) Método para producir 2-(alquil)cicloalquenona
CN109535120B (zh) 7-取代-3,4,4,7-四氢环丁烷并香豆素-5-酮的制备方法
CN105175346A (zh) 一种合成瑞舒伐他汀钙中间体的方法
WO2008009674A1 (fr) Procédé de synthèse d'esters d'acides carboxyliques à insaturation oléfinique
JP2002348260A (ja) ２，７−ジメチル−２，４，６−オクタトリエナールモノアセタールの製造方法
JP5574476B2 (ja) 炭酸エステルの製造方法
WO2005095317A1 (fr) Procede pour produire un compose de carbonyle insature hallogené
JPH05286902A (ja) α−クロロ−β−ケトエステル誘導体の製造方法
JP5158926B2 (ja) 不斉マンニッヒ型反応用キラルジルコニウム触媒の製造方法
JP5170987B2 (ja) 新規な含フッ素不飽和シリルエーテル化合物及び該化合物を中間体とする含フッ素不飽和アルコール誘導体の製造方法
JPH11255759A (ja) 光学活住β−ラクトン類の製造方法
EP0652213B1 (fr) Procédé de préparation de alkyle 3-phtalidenylideneacetate
GB2088354A (en) Preparation of a-pivaloyl acetic esters
EP1731495B1 (fr) Processus pour la production de derives et produits intermediaires monoacetal cyclopropane
JP4313166B2 (ja) 光学活性β−トリフルオロメチル−β−ヒドロキシカルボニル化合物の製造方法
JP4002114B2 (ja) アリルアルコール類の製造方法
JP2743198B2 (ja) シクロペンタン類
JP2002128734A (ja) ベンジルｔｅｒｔ−ブチルマロネートの製造方法
HU182691B (en) Process for preparing 3-/2,2-dichloro-vinyl/-2,2-dimethyl-cyclopropane-carboxylic acid and esters thereof
JPH05140113A (ja) アミノピラゾール誘導体の製法
JP3805510B2 (ja) シクロプロピルアセチレン誘導体の製造方法
EP4107143A1 (fr) Voie efficace et sélective pour la synthèse de 2-benzoylbenzoate d'alkyle

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: 07787632

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 07787632

Country of ref document: EP

Kind code of ref document: A1