EP1725513A1 - Preparation de composes comprenant un groupe chf2 ou chf - Google Patents

Preparation de composes comprenant un groupe chf2 ou chf

Info

Publication number
EP1725513A1
EP1725513A1 EP05707195A EP05707195A EP1725513A1 EP 1725513 A1 EP1725513 A1 EP 1725513A1 EP 05707195 A EP05707195 A EP 05707195A EP 05707195 A EP05707195 A EP 05707195A EP 1725513 A1 EP1725513 A1 EP 1725513A1
Authority
EP
European Patent Office
Prior art keywords
compounds
alkyl
alcohol
group
substituted
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP05707195A
Other languages
German (de)
English (en)
Inventor
Max Braun
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay GmbH
Original Assignee
Solvay Organics GmbH
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 Organics GmbH filed Critical Solvay Organics GmbH
Priority to EP05707195A priority Critical patent/EP1725513A1/fr
Publication of EP1725513A1 publication Critical patent/EP1725513A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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

Definitions

  • the invention relates to a process for the preparation of compounds having a CHF2 C (O) or CHFC (O) group by hydrodehalogenation, preferably
  • Hydrodechlorination from corresponding bromine, iodine or chlorine compounds preferably from compounds with a CCIF2 C (O) or CCIFC (O) group.
  • the object of the present invention is to provide an improved process for the preparation of compounds having a CHF2C (O) or CHFC (O) group, in particular corresponding ester or diester compounds. This object is achieved by the method according to the invention.
  • the process according to the invention provides for the preparation of compounds having a CF n HC (O) group from a CF n XC (O) group and zinc in the presence of an alcohol as a proton source, where n is 1 or 2 and X is bromine, iodine or preferably chlorine, where X is replaced by hydrogen, excluding compounds which are substituted by X both in the ⁇ -position and in the ⁇ -position.
  • This also includes compounds with an (O) CCHFC (O) group which are produced from a compound with an (O) CCCIFC (O) group.
  • X is exchanged for hydrogen; therefore, those compounds with two (or more) X substituents which result in the exchange of X for hydrogen as well as for an alkoxy radical (derived from alcohol present) are not encompassed by the invention.
  • compounds with two or more CF n HC (O) groups can also be made from compounds with two or more CF n XC (O) groups.
  • the alcohol serves as a proton source for the reaction; it can also be used in excess and then also serves as a solvent.
  • the respective product compound can also be added as a solvent.
  • Dimethylformamide or other carboxylic acid amides are preferably not contained in the reaction mixture.
  • a preferred embodiment of the process according to the invention is characterized in that compounds with one or two CF n HC (0) groups are prepared from a compound with one or two CF n XC (O) groups, where n and X have the abovementioned meaning , Compounds having one or two CF n HC (O) groups are preferably prepared from a compound having one or two CF n CIC (0) groups.
  • R 1 stands for F; for C1-C5 alkyl; or for C1-C5-alkyl which is substituted by at least 1 fluorine atom; and R 2 represents C1-C5 alkyl; or for C1-C5-alkyl which is substituted by at least 1 fluorine atom. It is also preferred to make a diester of
  • R 3 OC (O) CFHC (O) OR 3 , wherein R 3 is C1-C5-alkyl; or for C1-C5-alkyl which is substituted by at least 1 fluorine atom.
  • Preferred starting compounds are the respective chlorine-substituted compounds.
  • R 1 very particularly preferably represents F or C1-C3, which is partially fluorinated or perfluorinated.
  • R 2 and R 3 are preferably methyl, ethyl, n-propyl or i-propyl.
  • R 1 preferably represents F or CF 3 .
  • the alcohol used as the proton source suitably corresponds to the radical R 2 or R 3 .
  • the ester is prepared in situ from the corresponding acid chloride and alcohol.
  • the alcohol is not only a source of protons, but also serves to esterify the acid chloride. Accordingly, more alcohol has to be used. However, since the alcohol is expediently used in excess as a solvent, this is not a problem.
  • the non-protic solvent used is preferably at least predominantly the product to be produced, e.g. the ester or diester with one or more CHF2C (O) or CHFC (O) groups.
  • Nitriles are preferably not included as a solvent.
  • carboxylic acid amides such as DMF are also preferably not used as solvents.
  • 0.9 to 2.1 equivalents of zinc are preferably used per chlorine atom to be exchanged. It is preferred to use about 1.1 to 2 zinc atoms per chlorine atom; a stoichiometric excess of zinc has proven to be advantageous.
  • the temperature at which the reaction between bromine-, iodine- or chlorine-containing starting compound, zinc and alcohol is carried out is advantageously between 50 ° C. and the boiling point of the corresponding alcohol.
  • the isolation can be done according to conventional methods.
  • Another object of the invention is the azeotrope of methyl difluoroacetate and methanol, which in the reaction of methyl chlorodifluoroacetate, Zinc and methanol can be distilled.
  • This azeotrope can be used, for example, as a solvent or cleaning agent.
  • the advantage is that it can be purified by redistillation without changing its composition.
  • it can also be added to the reaction mixture of zinc and methyl chlorodifluoroacetate and, if appropriate, methanol.
  • the amount of methanol serving as the proton source can be reduced; if necessary, the methanol required as a proton source can be omitted entirely.
  • the azeotrope then serves as a solvent and - because of the methanol contained - as a proton source.
  • the process according to the invention has the advantage that high yields and high selectivities are achieved. Solvents like DMF are also more difficult to dispose of.
  • Example 1 Preparation of difluoroacetic acid methyl ester from chlorodifluoroacetic acid methyl ester and zinc
  • CDFAMe methyl chlorodifluoroacetate
  • CDFAEt chlorodifluoroethyl ester
  • CDFACI chlorodifluoroacetyl chloride

Landscapes

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

Abstract

L'invention concerne des composés présentant un groupe CHF2C(O) ou CHFC(O), lesquels composés peuvent être produits à partir des composés correspondants présentant un groupe CCIF2C(O) ou CCIFC(O) ou du composé bromé ou iodé correspondant et de zinc en présence d'un alcool comme source de protons. De préférence, des monoesters présentant un groupe CHF2C(O) ou des diesters présentant deux groupes CHFC(O) ou un groupe (O)CCHFC(O) sont produits de cette manière.
EP05707195A 2004-03-08 2005-02-04 Preparation de composes comprenant un groupe chf2 ou chf Withdrawn EP1725513A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05707195A EP1725513A1 (fr) 2004-03-08 2005-02-04 Preparation de composes comprenant un groupe chf2 ou chf

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP04005507A EP1574496A1 (fr) 2004-03-08 2004-03-08 Préparation de composés comprenant un groupe CHF2 ou CHF
EP05707195A EP1725513A1 (fr) 2004-03-08 2005-02-04 Preparation de composes comprenant un groupe chf2 ou chf
PCT/EP2005/001123 WO2005085173A1 (fr) 2004-03-08 2005-02-04 Production de composes a groupe chf2 ou chf

Publications (1)

Publication Number Publication Date
EP1725513A1 true EP1725513A1 (fr) 2006-11-29

Family

ID=34814269

Family Applications (2)

Application Number Title Priority Date Filing Date
EP04005507A Withdrawn EP1574496A1 (fr) 2004-03-08 2004-03-08 Préparation de composés comprenant un groupe CHF2 ou CHF
EP05707195A Withdrawn EP1725513A1 (fr) 2004-03-08 2005-02-04 Preparation de composes comprenant un groupe chf2 ou chf

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP04005507A Withdrawn EP1574496A1 (fr) 2004-03-08 2004-03-08 Préparation de composés comprenant un groupe CHF2 ou CHF

Country Status (6)

Country Link
US (1) US20070191632A1 (fr)
EP (2) EP1574496A1 (fr)
JP (1) JP2007527874A (fr)
CN (1) CN1930113A (fr)
TW (1) TW200538431A (fr)
WO (1) WO2005085173A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009021987A1 (fr) * 2007-08-16 2009-02-19 Solvay (Société Anonyme) Procédé de préparation d'esters d'acides 3-oxo-alcanoïques substitués par fluoro en position 4
US20110297883A1 (en) * 2009-02-19 2011-12-08 Solvay Fluor Gmbh Compositions of esters of fluorosubstituted alcanoic acids
FR2948659B1 (fr) * 2009-08-03 2012-07-06 Rhodia Operations Procede de preparation des esters de l'acide difluoroacetique
EP2595962B1 (fr) 2010-07-23 2018-07-11 Solvay Sa Procédé de préparation d'esters d'acides 3-fluoroalkyl-pyrazole-4-carboxyliques substitués en position 1
IT1401696B1 (it) * 2010-09-10 2013-08-02 Miteni Spa Procedimento per la preparazione di esteri dell acido 4,4-difluoroacetilacetico
CN105859553B (zh) * 2016-04-26 2019-05-21 南通宝凯化工有限公司 一种二氟乙酸乙酯的制备工艺
CN117843519A (zh) * 2024-01-02 2024-04-09 南京工业大学 一种二氟烯酮的制备及其转化为二氟乙酸酯及酰胺的方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2787107B1 (fr) * 1998-12-11 2003-11-14 Rhodia Chimie Sa Procede d'hydrogenodeshalogenation selective

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005085173A1 *

Also Published As

Publication number Publication date
CN1930113A (zh) 2007-03-14
WO2005085173A1 (fr) 2005-09-15
JP2007527874A (ja) 2007-10-04
EP1574496A1 (fr) 2005-09-14
TW200538431A (en) 2005-12-01
US20070191632A1 (en) 2007-08-16

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