WO1992005128A1 - Procede de production des sels de l'acide 3,3-dideutero-2-fluoracrylique et de l'acide trideutero-2-fluoracrylique et leur utilisation - Google Patents

Procede de production des sels de l'acide 3,3-dideutero-2-fluoracrylique et de l'acide trideutero-2-fluoracrylique et leur utilisation Download PDF

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Publication number
WO1992005128A1
WO1992005128A1 PCT/EP1991/001739 EP9101739W WO9205128A1 WO 1992005128 A1 WO1992005128 A1 WO 1992005128A1 EP 9101739 W EP9101739 W EP 9101739W WO 9205128 A1 WO9205128 A1 WO 9205128A1
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WO
WIPO (PCT)
Prior art keywords
formula
group
compounds
branched
hydrogen
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.)
Ceased
Application number
PCT/EP1991/001739
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German (de)
English (en)
Inventor
Steffen Dapperheld
Rudolf HEUMÜLLER
Manfred Wildt
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.)
Hoechst AG
Original Assignee
Hoechst AG
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 Hoechst AG filed Critical Hoechst AG
Priority to JP91514725A priority Critical patent/JPH05506036A/ja
Priority to KR1019930700759A priority patent/KR930702253A/ko
Publication of WO1992005128A1 publication Critical patent/WO1992005128A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
    • C07B59/001—Acyclic or carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof

Definitions

  • esters of halogenated acrylic acids especially those
  • fluorine-containing esters of 2-fluoroacrylic acid are important intermediates in the production of plastics with special properties.
  • 2-Fluoroacrylic acid such as the phenyl, butyl, trifluoroisopropyl or hexafluoroisopropyl ester
  • Optical fiber cladding material can be used.
  • 2-fluoroacrylic acid preferably its ammonium salt, is used to produce the 2-fluoroacryloyl chloride, which in a subsequent step with hexafluoroisopropanol
  • Polymethyl methacrylate can be transferred, approx. 150 m.
  • Perdeuterated polymethyl methacrylate allows data to be transmitted over a distance of 1.5 km (Chem.-Ing.-Tech. 59 (1987) 643).
  • patent application 128517 deals with the use of esters of 3,3-dideutero-2-fluoroacrylic acid for the production of optical fibers.
  • Trideutero-2-fluoroacrylic acid can be made according to the
  • Patent application EP-A-0 280 120 described method by the exchange of chlorine atoms
  • Fluorinated esters of 3,3-dideutero-2-fluoroacrylic acid and trideutero-2-fluoroacrylic acid can be easily prepared from the corresponding ammonium or alkali salts.
  • Another advantage is the conversion of the sensitive acids into chemically stable and thus storable salts.
  • the present invention therefore relates to a process for the preparation of the salts of 3,3-dideutero-2-fluoroacrylic acid and trideutero-2-fluoroacrylic acid, and also their
  • octadecylammonium salts the tetramethyl, tetraethyl, tetra-n-propyl, tetra-n-butylammonium salts and the
  • Methyl-pyridinium or dimethylpyridinium, pyrrolidinium, piperidinium and morpholinium salts of 3,3-dideutero-2-fluoroacrylic acid Methyl-pyridinium or dimethylpyridinium, pyrrolidinium, piperidinium and morpholinium salts of 3,3-dideutero-2-fluoroacrylic acid.
  • a (+) in formula I represents an NH 4 (+) or an NH 3 D (+)
  • a metal M (+) preferably an alkali or alkaline earth metal, or a primary, secondary, tertiary or quaternary ammonium ion of the formula (II).
  • R 1 , R 2 , R 3 and R 4 can be the same or different from one another and independently of one another a hydrogen or deuterium atom, a straight-chain or branched one
  • Furylmethylammonium ions di- and trimethyl-, ethyl-, propyl-, -butyl-, -pentyl-, -hexyl-, -octyl-, -decyl-, -dodecyl-,
  • a (+) can furthermore represent a radical of the formula (III)
  • R 1 and R 2 have the meaning given above and R 5 one of the radicals
  • R 6 to R 10 can be the same or different and independently of one another a hydrogen atom, a branched or unbranched, optionally halogen-substituted C 1 -C 4 alkyl group, a halogen atom, a branched or unbranched C 1 -C 4 alkoxy group or a NO 2 , CO 2 R 11 or SO 3 R 11 group, wherein R 11 represents a C 1 -C 6 alkyl group or an alkali or alkaline earth metal ion.
  • Examples of formula III include pyrrolidinium, piperidinium and morpholinium.
  • two adjacent radicals R 6 to R 10 together form a -C 4 H 4 - or a -C 3 H 3 N group.
  • the salts of these partially or fully deuterated 2-fluoroacrylic acids are prepared by reacting the acid with a base in water or an organic solvent or a mixture of water with one or more organic solvents.
  • Preferred organic solvents are those solvents in which the acid and / or the base is soluble and the resulting salt is insoluble and is obtained in crystalline form or as an oil.
  • Suitable solvents include:
  • Preferred solvents are:
  • Ethers such as diethyl ether, di-isopropyl ether,
  • Decalin benzene, toluene, the isomeric xylenes, tetralin, halogenated hydrocarbons such as di-, tri- or
  • Amides such as dimethylformamide, dimethylacetamide,
  • N-methyl-2-pyrolidinone N-methyl-2-pyrolidinone, nitriles such as acetonitrile or
  • Propionitrile or alcohols such as methanol, ethanol, and the isomeric propanols or butanols and ketones such as acetone or methyl isobutyl ketone.
  • Reaction temperatures are between 0 ° C and 40 ° C.
  • the reaction solution can be worked up using the customary methods.
  • Crystalline products can be easily removed from the
  • Reaction mixture are suctioned off, while oily salts can best be obtained by phase separation or extraction with subsequent removal of the solvent by distillation.
  • Rotary evaporator distilled off at 50 ° C at a pressure of 200 mbar.
  • the following table contains a selection of salts of 3,3-dideutero-2-fluoroacrylic acid and
  • Trideutero-2-fluoroacrylic acid which are characterized by their melting point and or their F 19 -NMR spectrum.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Insulated Gate Type Field-Effect Transistor (AREA)
  • Formation Of Insulating Films (AREA)
  • Thin Film Transistor (AREA)

Abstract

Un procédé permet de produire des composés de la formule (I), dans laquelle n est égal à 1, 2 ou 3, par réaction de composés de la formule (V), dans laquelle R12 représente un atome d'hydrogène ou de deutérium, avec des quantités équimolaires d'une base dans de l'eau ou dans un solvant organique, ou dans un mélange d'eau avec un ou plusieurs solvants organiques, à une température située dans une plage comprise entre le point de solidification et le point d'ébullition de la solution de réaction. A(+) désigne un groupe NH4(+) ou NH3D(+), un métal M(+), de préférence un métal alcalin ou alcalino-terreux, ou un ion ammonium primaire, secondaire, tertiaire ou quaternaire de la formule (II), ou un résidu de la formule (III).
PCT/EP1991/001739 1990-09-13 1991-09-12 Procede de production des sels de l'acide 3,3-dideutero-2-fluoracrylique et de l'acide trideutero-2-fluoracrylique et leur utilisation Ceased WO1992005128A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP91514725A JPH05506036A (ja) 1990-09-13 1991-09-12 ３，３−ジデュテロ−２−フルオロアクリル酸塩とトリデュテロ−２−フルオロアクリル酸塩との製造方法及びそれらの用途
KR1019930700759A KR930702253A (ko) 1990-09-13 1991-09-12 3,3-디듀테로-2-플루오로아크릴산염과 트리듀테로-2-플루오로아크릴산염의 제조방법 및 이의 용도

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4029067.0 1990-09-13
DE4029067A DE4029067A1 (de) 1990-09-13 1990-09-13 Verfahren zur herstellung der salze der 3,3-dideutero-2-fluoracrylsaeure und der trideutero-2-fluoracrylsaeure und deren verwendung

Publications (1)

Publication Number Publication Date
WO1992005128A1 true WO1992005128A1 (fr) 1992-04-02

Family

ID=6414185

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/001739 Ceased WO1992005128A1 (fr) 1990-09-13 1991-09-12 Procede de production des sels de l'acide 3,3-dideutero-2-fluoracrylique et de l'acide trideutero-2-fluoracrylique et leur utilisation

Country Status (6)

Country Link
EP (1) EP0550475A1 (fr)
JP (1) JPH05506036A (fr)
KR (1) KR930702253A (fr)
CA (1) CA2092689A1 (fr)
DE (1) DE4029067A1 (fr)
WO (1) WO1992005128A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1760064A4 (fr) * 2004-06-25 2008-03-05 Wako Pure Chem Ind Ltd Procede de deuteration d'acide haloacrylique ou du sel de celui-ci

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0128517A2 (fr) * 1983-06-10 1984-12-19 Daikin Industries, Limited Matériau optique
EP0203462A2 (fr) * 1985-05-25 1986-12-03 Hoechst Aktiengesellschaft Esters alpha-fluoroacryliques et leurs polymères
EP0280120A1 (fr) * 1987-02-17 1988-08-31 Hoechst Aktiengesellschaft Procédé électrochimique d'échange d'atomes d'halogène dans un composé organique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0128517A2 (fr) * 1983-06-10 1984-12-19 Daikin Industries, Limited Matériau optique
EP0203462A2 (fr) * 1985-05-25 1986-12-03 Hoechst Aktiengesellschaft Esters alpha-fluoroacryliques et leurs polymères
EP0280120A1 (fr) * 1987-02-17 1988-08-31 Hoechst Aktiengesellschaft Procédé électrochimique d'échange d'atomes d'halogène dans un composé organique

Also Published As

Publication number Publication date
KR930702253A (ko) 1993-09-08
JPH05506036A (ja) 1993-09-02
DE4029067A1 (de) 1992-03-19
EP0550475A1 (fr) 1993-07-14
CA2092689A1 (fr) 1992-03-14

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