WO2012016881A1 - Procede de preparation de l'acide difluoroacetique, ses sels ou ses esters - Google Patents
Procede de preparation de l'acide difluoroacetique, ses sels ou ses esters Download PDFInfo
- Publication number
- WO2012016881A1 WO2012016881A1 PCT/EP2011/062779 EP2011062779W WO2012016881A1 WO 2012016881 A1 WO2012016881 A1 WO 2012016881A1 EP 2011062779 W EP2011062779 W EP 2011062779W WO 2012016881 A1 WO2012016881 A1 WO 2012016881A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fluoride
- process according
- carbon atoms
- group
- reaction
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
- C07C53/16—Halogenated acetic acids
- C07C53/18—Halogenated acetic acids containing fluorine
-
- 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
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/63—Halogen-containing esters of saturated acids
Definitions
- the present invention relates to a process for the preparation of difluoroacetic acid, its salts or its esters.
- the invention relates to a process for preparing said compounds according to a halogen exchange reaction.
- This method has the disadvantage of using a gaseous substrate that is explosive in air.
- the invention proposes a totally different method.
- a process for the preparation of difluoroacetic acid, its salts or its esters characterized in that it comprises the reaction in the presence of water, a salt providing a fluoride anion and mono- or dihalogenated acetic acid, in acid, salified or esterified form; at least one halogen atom being different from the fluorine atom.
- the acetic acid or one of its salts or esters, mono- or dihalogenated comprising at least one halogen atom different from the fluorine atom, is subjected to an exchange reaction. halogen / fluorine.
- halogen means chlorine or bromine.
- the starting substrate may be in acid form.
- the mono- or dihalogenated acetic acid is then meant with at least one halogen atom different from the fluorine atom.
- the starting substrate may be in salified form.
- the aforementioned acid is designated, the hydrogen atom of which is replaced by a metal cation.
- the starting substrate may be in esterified form.
- the abovementioned acid is designated, the hydrogen atom of which is replaced by a hydrocarbon group, preferably an alkyl or cycloalkyl group.
- halogenated substrate which can preferably be represented by the following formula:
- X 1 and X 2 which may be identical or different, represent a chlorine, bromine or fluorine atom with the proviso that at least one of the atoms X 1 ,
- X 2 is a chlorine or bromine atom
- a hydrocarbon group substituted or unsubstituted, which may be an alkyl or cycloalkyl group,
- alkyl a linear or branched hydrocarbon chain having 1 to 15 carbon atoms and preferably 1 or 2 to 10 carbon atoms.
- Examples of preferred alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl.
- cycloalkyl is meant a cyclic, monocyclic hydrocarbon group comprising from 3 to 8 carbon atoms, preferably a cyclopentyl or cyclohexyl group.
- one or more hydrogen atoms may be replaced by a substituent (eg, halogen), as long as it does not interfere with obtaining the desired product.
- a substituent eg, halogen
- the hydrocarbon chain may preferentially carry one or more fluorine atoms.
- R 1 can represent a fluorinated or perfluorinated alkyl group comprising from 1 to 10 carbon atoms and from 1 to 21 fluorine atoms, preferably from 3 to 21 fluorine atoms.
- R 1 represents a hydrogen atom and preferably an alkyl group having from 1 to 4 carbon atoms.
- R 1 preferably represents a methyl or ethyl group.
- R 1 also represents a metal cation, preferably a cation of a mono- or divalent metal.
- an alkali metal or alkaline earth metal cation may be mentioned.
- alkali metal cations preferably lithium, sodium, potassium or cesium
- alkaline earth metal cations preferably magnesium, calcium, barium
- the preferred metal cations are sodium or potassium cations.
- halogenated substrates used preferentially in the process of the invention are monochloroacetic acid, dichloroacetic acid, chlorofluoroacetic acid or their methyl or ethyl esters.
- the salt providing the fluoride anion it is possible to use a metal fluoride and more particularly metal fluoride groups (IA), (MA), (MB) of the periodic table of elements.
- IA metal fluoride groups
- MA metal fluoride groups
- MB metal fluoride groups
- group (IA) lithium, sodium, potassium and cesium
- group (MA) lithium, sodium, potassium and cesium
- MB magnesium and calcium group
- potassium fluoride is preferably chosen.
- Potassium bifluoride KHF 2 can also be used.
- the invention does not exclude the use of double salts such as double fluorides of aluminum and sodium or potassium; fluosilicates of sodium or potassium.
- - W represents N or P
- R 2, R 3, R 4 and R 5 which are identical or different, represent:
- an alkyl group linear or branched, having 1 to 16 carbon atoms and optionally substituted by one or more groups or atoms phenyl, hydroxyl, halogen, nitro, alkoxy or alkoxycarbonyl, alkoxy groups having 1 to 4 carbon atoms;
- an aryl group having 6 to 10 carbon atoms optionally substituted by one or more alkyl groups or atoms having 1 to 4 carbon atoms, alkoxy, alkoxycarbonyl, the alkoxy group having 1 to 4 carbon atoms, or halogen.
- Fluorides implemented preferably have a cation which has the formula (II) wherein W is a nitrogen or phosphorus atom and R 2, R 3, R 4 and R 5, identical or different, represent an alkyl group, linear or branched, having 1 to 4 carbon atoms and a benzyl group.
- tetrabutylammonium methyltri (n-butyl) ammonium, N-methyl-N, N, N-trioctylammonium, trimethylphenylphosphonium, tetrabutylphosphonium, methyltri (n-butyl) fluorides.
- tetrabutylammonium fluoride Preferentially tetrabutylammonium fluoride, tetrabutylphosphonium fluoride is chosen.
- the group R 6 represents an alkyl group having from 1 to 20 carbon atoms
- the group R 7 represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms
- the group R 8 represents an alkyl group having from 1 to 4 carbon atoms
- the group R 9 represents an alkyl group having from 1 to 6 carbon atoms.
- onium salts mention may be made of 1-alkyl-2,3-dimethylimidazolium fluorides such as 1-ethyl-2,3-dimethylimidazolium fluoride, 1-butyl-2,3-dimethylimidazolium 1-hexyl-2,3-dimethylimidazolium; 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-hexyl-2,3-dimethylimidazolium; 1-alkyl-3-methylimidazolium fluorides, such as 1-ethyl-3-methylimidazolium fluoride, 1-hexyl-3-methylimidazolium, 1-octyl-3-methylimidazolium fluoride, 1-decyl-3-methylimidazolium fluoride, 1-dodecyl-3-methylimidazolium, 1-tetradecyl-3-methylimidazolium, 1-hexade
- the invention does not exclude the use of halogenated precursors, chloride or bromide, the corresponding fluorides can be formed in situ, by reaction with a metal fluoride as defined above, preferably potassium fluoride.
- the amount of onium fluoride (or its precursor) may represent from 1 to 10 mol% expressed relative to the substrate of formula (I).
- the reaction is carried out between the halogenated substrate of formula (I) and the salt bringing the fluoride anion, in the presence of water.
- the ratio between the number of moles of salt expressed as fluoride anion and the number of moles of halogenated substrate of formula (I) may vary between 2 and 10, and is preferably between 5 and 6.
- reaction mixture is meant the halogenated substrate, the salt providing the fluoride anion, the water and optionally an organic solvent.
- reaction can be carried out in an aqueous medium or in a hydro-organic medium.
- the organic solvent is advantageously a protic polar solvent.
- protic polar solvents include alcohols.
- alcohols mention may be made of aliphatic primary alcohols having from 1 to 5 carbon atoms.
- Methanol and ethanol are the preferred solvents.
- the amount of alcohol used is such that the water / alcohol mixture has the following composition:
- the exchange reaction is generally carried out at a temperature between 80 ° C and 120 ° C when it is conducted under atmospheric pressure.
- the temperature is preferably chosen between 95 ° C. and 105 ° C.
- the reaction can be carried out at a higher temperature, for example between 100 ° C. and 150 ° C., under autogenous pressure of the reactants.
- the exchange reaction is generally carried out preferably under a controlled atmosphere of inert gases.
- inert gases we can establish an atmosphere rare gases, preferably argon but it is more economical to use nitrogen.
- the method of the invention is simple to implement.
- the reagents can be introduced in any order according to different variants but some are preferred.
- a preferred embodiment consists in mixing the water, optionally the organic solvent, preferably the alcohol and the halogenated substrate, and then introducing the salt providing the fluoride anion all at once or gradually, fractionally or continuously.
- the pH is advantageously adjusted during the reaction to a value of less than 10, preferably less than 9 and preferably chosen between 5 and 9 and very preferably between 7 and 9.
- the adjustment of the pH can be carried out in particular using hydrofluoric acid or a basic aqueous solution, preferably a solution of sodium hydroxide or potassium hydroxide, the concentration of which advantageously varies between 40 and 70% by weight.
- the reaction mixture is stirred at the temperature of the reaction selected in the range as previously defined.
- the heating of the reaction mixture is maintained for a variable period. It is specified by way of example that the duration of the reaction carried out at 100 ° C. generally varies between 10 hours and 40 hours.
- Ri has the meaning given above.
- the compound of formula (V) can be recovered from the reaction mixture, in particular by the separation technique described in WO 2010/03986.
- the process of the invention is advantageously carried out in equipment capable of withstanding the corrosion of the reaction medium.
- materials are chosen for the part in contact with the corrosion-resistant reaction medium such as alloys based on molybdenum, chromium, cobalt, iron, copper manganese, titanium, zirconium, aluminum, carbon and tungsten sold under the HASTELLOY ® brands or alloys of nickel, chromium, iron, manganese with added copper and / or molybdenum sold under the INCONEL ® name and more particularly alloys HASTELLOY C 276 or INCONEL 600, 625 or 718.
- Stainless steels such as austenitic steels can also be selected [Robert H. Perry et al, Perry's Chemical Engineers' Handbook, Sixth Edition (1984), page 23-44]. and more particularly 304, 304 L, 316 or 316 L stainless steels.
- the 304 and 304 L steels have a nickel content ranging between 8 and 12% and the 316 and 316 L steels have a nickel content ranging between 10 and 14%.
- 316L steels are more particularly chosen.
- the method of the invention can be implemented continuously or discontinuously.
- the conversion ratio (TT) corresponds to the ratio between the number of moles of dichloroacetic acid or its ester converted and the number of moles of dichloroacetic acid or its ester involved.
- the yield (RR) corresponds to the ratio between the number of moles of difluoroacetic acid or its ester formed and the number of moles of dichloroacetic acid or its ester involved. Examples 1 to 4:
- a solution of dichloroacetic acid or its ethyl ester in water or in admixture with ethanol is charged to a glass reactor.
- Solid potassium fluoride is added and the temperature of the medium is raised to 100 ° C for a period of 40 hours.
- Example 4 the water represents 1% of the weight of the EtOH / H 2 O mixture.
- chlorofluoroacetic acid is used as a halogenated substrate.
- the chlorofluoroacetic acid (5 g) dissolved in 50 g of water is brought into contact with potassium fluoride (15 g) and the whole is heated to a temperature of 100 ° C. for a period of 22 hours.
- the aqueous solution is then analyzed by 1 H NMR and 19 F NMR.
- the conversion rate of chlorofluoroacetic acid is 100%.
- the yield of difluoroacetic acid is 41%.
- a solution of dichloroacetic acid in water is charged to a glass reactor.
- a solid fluorinating agent is added and the temperature of the medium is brought to 120 ° C for 16 hours.
- dichloroacetic acid (2g) To a solution of KF in water heated to the temperature of 120 ° C is added dichloroacetic acid (2g). The medium is stirred at 120 ° C. for 1 hour.
- the degree of conversion of dichloroacetic acid is 100%.
- the yield of difluoroacetic acid is 94%.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2013109402/04A RU2013109402A (ru) | 2010-08-05 | 2011-07-26 | Способ получения дифторуксусной кислоты, ее солей или ее сложных эфиров |
CN2011800379243A CN103052621A (zh) | 2010-08-05 | 2011-07-26 | 制备二氟乙酸、其盐或其酯的方法 |
KR1020137002113A KR20130025436A (ko) | 2010-08-05 | 2011-07-26 | 디플루오로아세트산, 디플루오로아세트산 염 또는 디플루오로아세트산 에스테르의 제조 방법 |
CA2805018A CA2805018A1 (fr) | 2010-08-05 | 2011-07-26 | Procede de preparation de l'acide difluoroacetique, ses sels ou ses esters |
US13/814,471 US20130131375A1 (en) | 2010-08-05 | 2011-07-26 | Process for preparing difluoroacetic acid, salts thereof or esters thereof |
JP2013522198A JP2013532704A (ja) | 2010-08-05 | 2011-07-26 | ジフルオロ酢酸、その塩又はそのエステルの製造方法 |
EP11736360.6A EP2601169A1 (fr) | 2010-08-05 | 2011-07-26 | Procede de preparation de l'acide difluoroacetique, ses sels ou ses esters |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1003283A FR2963620B1 (fr) | 2010-08-05 | 2010-08-05 | Procede de preparation de l'acide difluoroacetique, ses sels ou ses esters |
FR1003283 | 2010-08-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012016881A1 true WO2012016881A1 (fr) | 2012-02-09 |
Family
ID=43728967
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2011/062779 WO2012016881A1 (fr) | 2010-08-05 | 2011-07-26 | Procede de preparation de l'acide difluoroacetique, ses sels ou ses esters |
Country Status (11)
Country | Link |
---|---|
US (1) | US20130131375A1 (fr) |
EP (1) | EP2601169A1 (fr) |
JP (1) | JP2013532704A (fr) |
KR (1) | KR20130025436A (fr) |
CN (1) | CN103052621A (fr) |
AR (1) | AR082557A1 (fr) |
CA (1) | CA2805018A1 (fr) |
FR (1) | FR2963620B1 (fr) |
RU (1) | RU2013109402A (fr) |
TW (1) | TW201213291A (fr) |
WO (1) | WO2012016881A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103420825A (zh) * | 2012-05-21 | 2013-12-04 | 上海品沃化工有限公司 | 二氟乙酸酯的合成方法 |
JP2015057379A (ja) * | 2013-08-09 | 2015-03-26 | ダイキン工業株式会社 | フッ化メタンの製造方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111548266A (zh) * | 2020-05-11 | 2020-08-18 | 无锡贝塔医药科技有限公司 | 一种稳定性同位素13c标记二氯乙酸的合成方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06228043A (ja) | 1993-02-05 | 1994-08-16 | Asahi Glass Co Ltd | ジフルオロ酢酸の製造方法 |
EP0694523A1 (fr) | 1994-07-28 | 1996-01-31 | Asahi Glass Company Ltd. | Préparation d'un fluorure d'acide difluoroacétique et des esters d'acide difluoroacétique |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6445321A (en) * | 1987-08-14 | 1989-02-17 | Asahi Glass Co Ltd | Fluorination of halogenated organic compound |
FR2928925B1 (fr) * | 2008-03-19 | 2011-01-07 | Centre Nat Rech Scient | Complexes de bore ou d'aluminium, et leurs utilisations. |
FR2933693B1 (fr) * | 2008-07-10 | 2010-09-03 | Rhodia Operations | Procede de separation d'un acide carboxylique sous forme salifiee porteur d'au moins un atome d'halogene |
-
2010
- 2010-08-05 FR FR1003283A patent/FR2963620B1/fr not_active Expired - Fee Related
-
2011
- 2011-07-26 KR KR1020137002113A patent/KR20130025436A/ko not_active Application Discontinuation
- 2011-07-26 WO PCT/EP2011/062779 patent/WO2012016881A1/fr active Application Filing
- 2011-07-26 EP EP11736360.6A patent/EP2601169A1/fr not_active Withdrawn
- 2011-07-26 RU RU2013109402/04A patent/RU2013109402A/ru unknown
- 2011-07-26 JP JP2013522198A patent/JP2013532704A/ja not_active Ceased
- 2011-07-26 CN CN2011800379243A patent/CN103052621A/zh active Pending
- 2011-07-26 CA CA2805018A patent/CA2805018A1/fr not_active Abandoned
- 2011-07-26 US US13/814,471 patent/US20130131375A1/en not_active Abandoned
- 2011-08-04 TW TW100127787A patent/TW201213291A/zh unknown
- 2011-08-04 AR ARP110102816A patent/AR082557A1/es unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06228043A (ja) | 1993-02-05 | 1994-08-16 | Asahi Glass Co Ltd | ジフルオロ酢酸の製造方法 |
EP0694523A1 (fr) | 1994-07-28 | 1996-01-31 | Asahi Glass Company Ltd. | Préparation d'un fluorure d'acide difluoroacétique et des esters d'acide difluoroacétique |
Non-Patent Citations (3)
Title |
---|
GRYSZKIEWICZ-TROCHIMOWSKI E ET AL: "RECHERCHES SUR LES COMPOSES ORGANIQUES FLUORES DANS LA SERIE ALIPHATIQUES. 1. METHODE GENERALE DE PREPARATION DES COMPOSES ORGANIQUES FLUORES", RECUEIL DES TRAVAUX CHIMIQUES DES PAYS-BAS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 66, 1 January 1947 (1947-01-01), pages 413 - 418, XP001194707, ISSN: 0165-0513 * |
LUZ M CECILIA ET AL: "A convenient synthesis of difluoroacetic acid", ORGANIC PREPARATIONS AND PROCEDURES INTERNATIONAL, ORGANIC PREPARATION AND PROCEDURES CO., NEWTON HIGHLANDS, MA, US, vol. 19, no. 6, 1 December 1987 (1987-12-01), pages 468 - 470, XP008134526, ISSN: 0030-4948, DOI: DOI:10.1080/00304948709356214 * |
ROBERT H. PERRY ET AL.: "Perry's Chemical Engineers", 1984, pages: 23 - 44 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103420825A (zh) * | 2012-05-21 | 2013-12-04 | 上海品沃化工有限公司 | 二氟乙酸酯的合成方法 |
JP2015057379A (ja) * | 2013-08-09 | 2015-03-26 | ダイキン工業株式会社 | フッ化メタンの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CA2805018A1 (fr) | 2012-02-09 |
RU2013109402A (ru) | 2014-09-10 |
FR2963620A1 (fr) | 2012-02-10 |
JP2013532704A (ja) | 2013-08-19 |
AR082557A1 (es) | 2012-12-19 |
TW201213291A (en) | 2012-04-01 |
US20130131375A1 (en) | 2013-05-23 |
KR20130025436A (ko) | 2013-03-11 |
EP2601169A1 (fr) | 2013-06-12 |
FR2963620B1 (fr) | 2012-07-27 |
CN103052621A (zh) | 2013-04-17 |
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