EP0000362B1 - Chlorures de carbamoyle portant en alpha, un groupement halogénoalcoyle et leur procédé de préparation. - Google Patents

Chlorures de carbamoyle portant en alpha, un groupement halogénoalcoyle et leur procédé de préparation. Download PDF

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Publication number
EP0000362B1
EP0000362B1 EP78100284A EP78100284A EP0000362B1 EP 0000362 B1 EP0000362 B1 EP 0000362B1 EP 78100284 A EP78100284 A EP 78100284A EP 78100284 A EP78100284 A EP 78100284A EP 0000362 B1 EP0000362 B1 EP 0000362B1
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European Patent Office
Prior art keywords
alkyl
chloride
dimethyl ether
hydrogen
ether
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EP78100284A
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German (de)
English (en)
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EP0000362A1 (fr
Inventor
Karl-Heinz Dr. Koenig
Christian Dr. Reitel
Dietrich Dr. Mangold
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BASF SE
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BASF SE
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Publication date
Priority claimed from DE19772732284 external-priority patent/DE2732284A1/de
Priority claimed from DE19772741980 external-priority patent/DE2741980A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP0000362A1 publication Critical patent/EP0000362A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/04—Carbamic acid halides

Definitions

  • the invention relates to a process for the preparation of ⁇ -haloalkylcarbamic acid halides by reacting vinyl isocyanate or N-tert.alkyl-N- (1-alkenyl) carbamic acid halides with hydrogen halide at -78 ° C. to + 80 ° C.
  • a-haloalkylcarbamic acid halides of the formula wherein R 4 represents a hydrogen atom or an alkyl radical having 1 to 20 carbon atoms and X denotes a halogen atom is advantageously obtained if vinyl isocyanate or N-tert.alkyl-N- (1-alkenyl) carbamic acid halides of the formula wherein R 4 represents a hydrogen atom or an alkyl radical having 1 to 20 carbon atoms and X denotes a halogen atom
  • the radicals R ', R 2 and R 3 may be the same or different and each represent alkyl radicals, with hydrogen halide at a temperature of -78 ° C. up to + 80 ° C.
  • N-tert.alkyl-N- (1-alkenyl) carbamic acid halides for example the chlorides
  • fragmentation occurs quantitatively in accordance with the reaction equation.
  • Alkyl chloride and a-chloroethyl carbamide chloride for example the chlorides
  • the process according to the invention provides ⁇ -haloalkylcarbamic acid halides in a better yield and purity in a simpler and more economical way. Working up is much easier since no component-rich reaction mixture is obtained.
  • thermostable halide in particular a-chloroalkylcarbamic acid chloride
  • thermostable halide in particular a-chloroalkylcarbamic acid chloride
  • product mixtures are obtained with regard to the position of the halogen atom entering and the degree of halogenation.
  • the tertiary alkyl halide which is obtained at the same time in the reaction is inert under the usual reaction conditions and therefore generally does not have to be removed in the further reactions of the a-chloroalkylcarbamic acid chloride.
  • Vinyl isocyanate can e.g. by reacting acrylic acid chloride with sodium azide (Bull., loc. cit.) or by thermal decomposition of N-tert-butyl-N-vinylcarbamic acid chloride.
  • the hydrogen halide advantageously hydrogen bromide and in particular hydrogen chloride, is used in a stoichiometric amount or in excess, preferably in an amount of from 2 to 2.2 mol of hydrogen halide per mol of vinyl isocyanate or N-tert.alkyl-N- (1-alkenyl) carbamic acid halide .
  • Suitable tertiary alkyl radicals, R 1 , R 2 and R 3 which may be the same or different, are those having 4 to 20, in particular 4 to 12, carbon atoms.
  • the tert-butyl and tert.A-myl radicals should be mentioned in particular.
  • the radicals R 'to R 3 in the formula given can be alkyl radicals having 1 to 6 carbon atoms, in particular methyl and ethyl.
  • R 4 advantageously denotes hydrogen or an alkyl radical having 1 to 20, in particular 1 to 12, preferably 1 to 6, carbon atoms; hydrogen, methyl and ethyl are preferred.
  • the reaction is carried out at a temperature of from -78 ° C. to + 80 ° C., advantageously from + 40 ° C. to -78 ° C., preferably in the case of vinyl isocyanate from + 30 ° C. to -78 ° C., in particular at 0 ° C. to -40 ° C, preferably in the case of N7tert.Alkyl-N- (1-alkenyl) carbamic acid halides from -10 ° C to 20 ° C, without pressure or under pressure, preferably at 0.7 to 2 bar, continuously or batchwise carried out.
  • suitable solvents are: aromatic hydrocarbons, for example toluene, ethylbenzene, o-, m-, p-xylene, isopropylbenzene, methylnaphthalene, aromatic ether; Halogenated hydrocarbons, in particular chlorinated hydrocarbon, for example tetrachlorethylene, 1,1,2,2- or 1,1,1; 2-tetrachiorethane, amyl chloride, cyclohexyl chloride, 1,2-dichloropropane, methylene chloride, dichlorobutane, isopropyl bromide, n-propyl bromide, butyl bromide, Chloroform, ethyl iodide, propyl iodide, chloronaphthalene, dichloronaphthalene, carbon tetrachloride, 1,1,1- or 1,1,2-trichloroethane, trichlorethylene, pentachloroethyne
  • the solvent is expediently used in an amount of 200 to 10,000 percent by weight, preferably 300 to 2,000 percent by weight, based on the starting material vinyl isocyanate.
  • concentration of the solutions of the N-tert.alkyl-N- (1-alkenyl) -carbamic acid chlorides is variable within wide limits. A concentration range between 1 and 50 percent by weight is preferably used.
  • the reaction can be carried out as follows: A mixture of the starting materials and advantageously solvents is kept at the reaction temperature for 0.1 to 4 hours. Vinyl isocyanate is advantageously placed in the solvent and gassed with the hydrogen halide at the reaction temperature. The reaction solution is expediently stirred for 0.25 hours to one hour. The N-tert.alkyl-N- (1-alkenyl) carbamic acid halide is advantageously placed in an inert solvent and gassed with hydrogen halide at a temperature of, for example, -10 ° C. to 0 ° C. After the reaction has ended, the reaction solution is stirred for some time, for example 15 minutes, and excess hydrogen halide is blown out using N 2 . Then the end product is separated from the mixture in a conventional manner, for example by crystallization and filtration.
  • a-haloalkylcarbamic acid halides produced by the process of the invention are valuable starting materials for the production of paint raw materials, textile coating compositions, dyes, pharmaceuticals and crop protection agents.
  • N-tert.butyl-N-vinylcarbamic acid chloride 161.5 parts are introduced at 0 ° C. and 75 parts of hydrogen chloride are gassed in for this purpose within 60 minutes. The reaction mixture is stirred for 15 minutes at this temperature and excess HCl is blown out with N 2 . Tert.butyl chloride is stripped off under reduced pressure and the ⁇ -chloroethylcarbamic acid chloride is recrystallized in CCI 4 . 136 parts (95% of theory); Mp 20/21 ° C.
  • reaction mixture is stirred for a further 30 minutes at room temperature and excess HCl is blown out with N 2 .
  • the tert. Amyl chloride is removed under reduced pressure.

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

Claims (4)

1. Haiogénures de carbamyle a-halo-alcoyl-substitués de la formule générale
Figure imgb0011
dans laquelle le symbole R4 représente un atome d'hydrogène ou un radical alcoyle en C1 à C20 et le symbole X un atome d'halogène.
2. Procédé de préparation d'un halogénure de carbamyle a-halo-alcoyl-substitué de la formule générale
Figure imgb0012
dans laquelle le symbole R4 représente un atome d'hydrogène ou un radical alcoyle en C1 à C20 et le symbole x un atome d'halogène, caractérisé en ce que l'on fait réagir l'isocyanate de vinyle ou un halogénure de N-tertio-alcoyl-N-(1-alcényl)-carbamyle de la formule générale
Figure imgb0013
dans laquelle les symboles R4 et X possèdent les significations définies et les symboles R', R2 et R3, qui peuvent être identiques ou différents, désignent chacun un radical alcoyle, entre -78°C et +80°C avec un hydracide halogéné.
3. Halogénure de a-halo-éthyl-carbamyle.
4. Chlorure de a-chlor-éthyl-carbamyle.
EP78100284A 1977-07-16 1978-06-30 Chlorures de carbamoyle portant en alpha, un groupement halogénoalcoyle et leur procédé de préparation. Expired EP0000362B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19772732284 DE2732284A1 (de) 1977-07-16 1977-07-16 Verfahren zur herstellung von alpha- halogenaethylcarbamidsaeurehalogeniden
DE2732284 1977-07-16
DE19772741980 DE2741980A1 (de) 1977-09-17 1977-09-17 Verfahren zur herstellung von alpha-chloralkylcarbamoylchloriden
DE2741980 1977-09-17

Publications (2)

Publication Number Publication Date
EP0000362A1 EP0000362A1 (fr) 1979-01-24
EP0000362B1 true EP0000362B1 (fr) 1980-09-03

Family

ID=25772337

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100284A Expired EP0000362B1 (fr) 1977-07-16 1978-06-30 Chlorures de carbamoyle portant en alpha, un groupement halogénoalcoyle et leur procédé de préparation.

Country Status (12)

Country Link
EP (1) EP0000362B1 (fr)
JP (1) JPS5419916A (fr)
AU (1) AU517065B2 (fr)
BR (1) BR7804551A (fr)
CA (1) CA1107759A (fr)
DD (1) DD137223A5 (fr)
DE (1) DE2860132D1 (fr)
HU (1) HU179671B (fr)
IL (1) IL55106A (fr)
IT (1) IT1096870B (fr)
PL (1) PL108071B1 (fr)
SU (1) SU906371A3 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2830969A1 (de) * 1978-07-14 1980-01-31 Basf Ag Neue alpha -halogenalkylcarbamidsaeurehalogenide und verfahren zur herstellung von alpha -halogenalkylcarbamidsaeurehalogeniden
AU2012299239A1 (en) 2011-08-23 2013-11-21 Rohm And Haas Company A multi-stage polymer composition and films and polarizer plates made therefrom

Also Published As

Publication number Publication date
IL55106A (en) 1981-12-31
JPS5419916A (en) 1979-02-15
DD137223A5 (de) 1979-08-22
PL108071B1 (pl) 1980-03-31
BR7804551A (pt) 1979-03-06
EP0000362A1 (fr) 1979-01-24
IT7825131A0 (it) 1978-06-29
AU3785578A (en) 1980-01-10
PL208386A1 (pl) 1979-06-04
IL55106A0 (en) 1978-09-29
AU517065B2 (en) 1981-07-09
SU906371A3 (ru) 1982-02-15
IT1096870B (it) 1985-08-26
HU179671B (en) 1982-11-29
CA1107759A (fr) 1981-08-25
DE2860132D1 (en) 1980-12-11

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