EP0000362A1 - 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 PDFInfo
- Publication number
- EP0000362A1 EP0000362A1 EP78100284A EP78100284A EP0000362A1 EP 0000362 A1 EP0000362 A1 EP 0000362A1 EP 78100284 A EP78100284 A EP 78100284A EP 78100284 A EP78100284 A EP 78100284A EP 0000362 A1 EP0000362 A1 EP 0000362A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chloride
- alkyl
- ether
- reaction
- tert
- 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.)
- Granted
Links
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.
- N-tert.alkyl-N- (l-alkenyl) carbamic acid halides for example the chlorides
- fragmentation occurs quantitatively in accordance with the reaction equation.
- Alkyl chloride and chloroethyl carbamide chloride for example the chlorides
- the method 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.
- Vinyl isocyanate can e.g. by reaction of 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 2 to 2.2 moles of hydrogen halide per mole 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-amyl radicals should be mentioned in particular.
- the radicals R 1 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 N-tert-alkyl-N- (l-alkenyl) carbamic acid halides from -10 ° C to 20 ° C, pressureless or under pressure, preferably at 0.7 to 2 bar, continuously or carried out discontinuously.
- the reaction can be carried out without a solvent, but solvents which are inert under the reaction conditions are expediently used.
- suitable solvents are: aromatic hydrocarbons, for example toluene, ethylbenzene, o-, m-, p-xylene, isopropylbenzene, methylnaphthalene, aromatic ether; Halogenated hydrocarbons, especially chlorinated hydrocarbon, for example tetrachlorethylene, 1,1,2,2- or 1,1,1,2-tetrachloroethane, 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, 1,
- 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 g e 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.
- ⁇ -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 removed under reduced pressure and the ⁇ -chloroethylcaramic acid chloride is recrystallized in CCl 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2732284 | 1977-07-16 | ||
DE19772732284 DE2732284A1 (de) | 1977-07-16 | 1977-07-16 | Verfahren zur herstellung von alpha- halogenaethylcarbamidsaeurehalogeniden |
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 true EP0000362A1 (fr) | 1979-01-24 |
EP0000362B1 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) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0007498A1 (fr) * | 1978-07-14 | 1980-02-06 | BASF Aktiengesellschaft | Halogénures de carbamyle portant en alpha, un groupement halogénoalkyle et leur procédé de préparation |
US9156976B2 (en) | 2011-08-23 | 2015-10-13 | Rohm And Haas Company | Multi-stage polymer composition and films and polarizer plates made therefrom |
-
1978
- 1978-06-29 IT IT25131/78A patent/IT1096870B/it active
- 1978-06-30 DE DE7878100284T patent/DE2860132D1/de not_active Expired
- 1978-06-30 EP EP78100284A patent/EP0000362B1/fr not_active Expired
- 1978-07-07 AU AU37855/78A patent/AU517065B2/en not_active Expired
- 1978-07-07 IL IL55106A patent/IL55106A/xx unknown
- 1978-07-12 CA CA307,241A patent/CA1107759A/fr not_active Expired
- 1978-07-13 PL PL1978208386A patent/PL108071B1/pl unknown
- 1978-07-14 DD DD78206730A patent/DD137223A5/xx unknown
- 1978-07-14 JP JP8524578A patent/JPS5419916A/ja active Pending
- 1978-07-14 SU SU782635898A patent/SU906371A3/ru active
- 1978-07-14 BR BR7804551A patent/BR7804551A/pt unknown
- 1978-07-14 HU HU78BA3679A patent/HU179671B/hu unknown
Non-Patent Citations (1)
Title |
---|
THE JOURNAL OF ORGANIC CHEMISTRY Band, 28(7) Seiten 1825-1830 (1963). * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0007498A1 (fr) * | 1978-07-14 | 1980-02-06 | BASF Aktiengesellschaft | Halogénures de carbamyle portant en alpha, un groupement halogénoalkyle et leur procédé de préparation |
US9156976B2 (en) | 2011-08-23 | 2015-10-13 | Rohm And Haas Company | Multi-stage polymer composition and films and polarizer plates made therefrom |
Also Published As
Publication number | Publication date |
---|---|
IT1096870B (it) | 1985-08-26 |
JPS5419916A (en) | 1979-02-15 |
IT7825131A0 (it) | 1978-06-29 |
HU179671B (en) | 1982-11-29 |
AU3785578A (en) | 1980-01-10 |
EP0000362B1 (fr) | 1980-09-03 |
PL108071B1 (pl) | 1980-03-31 |
AU517065B2 (en) | 1981-07-09 |
DD137223A5 (de) | 1979-08-22 |
IL55106A0 (en) | 1978-09-29 |
PL208386A1 (pl) | 1979-06-04 |
IL55106A (en) | 1981-12-31 |
DE2860132D1 (en) | 1980-12-11 |
BR7804551A (pt) | 1979-03-06 |
CA1107759A (fr) | 1981-08-25 |
SU906371A3 (ru) | 1982-02-15 |
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