CA1107759A - MANUFACTURE OF .alpha.-HALOALKYLCARBAMYL HALIDES - Google Patents
MANUFACTURE OF .alpha.-HALOALKYLCARBAMYL HALIDESInfo
- Publication number
- CA1107759A CA1107759A CA307,241A CA307241A CA1107759A CA 1107759 A CA1107759 A CA 1107759A CA 307241 A CA307241 A CA 307241A CA 1107759 A CA1107759 A CA 1107759A
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- CA
- Canada
- Prior art keywords
- chloride
- reaction
- tert
- halides
- halide
- 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.)
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the disclosure: .alpha.-haloalkyl carbamyl halides and a process for their manufacture by reacting vinyl iso-cyanate or N-tert.-alkyl-N-(l1alkenyl)-carbamyl halides with a hydrogen halide at from -78°C to +80°C.
Description
11~77~9 Manufacture of -haloalkylcarbam~1 halides The present invention relates to a process for the manufact~e of ~-haloalkylcarbamyl halides by reacting vinyl isocyanate or N-tert.-alkyl-N-(l-alkenyl)-carbamyl halides with a hydrogen halide at from -78C to +80C.
Angewandte Chemie, 74 (1962), 848-855 discloses the reaction of alkylcarbamyl chlorides with elementary chlorine to give the corresponding -cnloroalkylcarbamyl chlorides.
However, the products which result are mixtures, both in respect of the degree of halogenation and in respect of the position of the halogen atoms entering the molecule. The process is unsatisfactory in respect of yield and purity of the end product, and does not permit simple and economical operation.
We have found that -haloalkylcarbamyl halides are obtained in an advantageous manner if vinyl isocyanate or N-tert.-alkyl-N-(l-alkenyl)-carbamyl halides are reacted with a hydrogen halide at from -78C to +80C.
Further, we have found the novel a-haloal~ylcarbamyl halides of the formula R4-CH2-C-~-C~
where R is hydrogen or alkyl of 1 to 2~ car~Gn atoms and X i5 halogen, ,.~
lP'~7~9 o.Z. 0050/032692/794 Further, we have found the novel -haloethylcarbamyl halides, in particular the novel -chloroethylcarbamyl chloride-Where vinyl isocyanate and hydrogen chloride areused, the reaction may be represented by the following equation:
H H ~ 0 CH2=C-N-C0 + 2 HCl ~ CH~-C-N-C-Cl Cl Where a N-tert.-alkyl-N-(l-alkenyl)-carbamyl halide, eg. the chloride, is used, a quantitative fragmentation into tert.-alkyl chloride and a-chloroethylcarbamyl chloride takes place, in accordance with the equation below:
Rl ,,C001 R2 R~ H 0 --C-~ ~ 2HC~ Cl + X ~ C~
R2-" R~ ~ CX--CH R3 R42 Cl ~C1 Compared to the conventional process, the process of the invention gives a-haloalkylcarbamyl halides more simply and more economically, and in better yield and in greater purity. Working up is substantially simpler since the reaction mixture obtained does not contain a large number of different components.
The reaction of a tert.-alkyl-N-(l-alkeny~)-carbamyl halide, especialiy a chloride, with a hydrogen halide, especially hydrogen chloride, makes it possible to prepare the heat-stable halide, especially -chloroalkyl-carbamyl chloride~ in a particularly pure form and under mild reaction conditions, whilst the reaction of elementary ~'~'377~9 o. z. ooso/0~26s2/7s~
halogen with an alkylcarbamyl chloride (Angewandte Chemie, loc. cit.) gives product mixtures in respect of the position of the halogen atom entering the molecule, and in respect of the degree of halogenation. The tert.-alkyl halide also formed in the reaction is inert under the con-ventional reaction conditions and need therefore as a rule not be removed for carrying out the further reactions of the a-chloroalkylcarbamyl chloride.
All these advantageous results are surprising, since the formation of a variety of reaction products was to be expected from the great reactivity of the starting materials.
It was also to be expected that a,~-unsaturated nitrogen compounds would polymerize or hydrolyze very easily under the influence of acids. For example, N-vinylpyrrolidone is converted to a mixture of oligomers under the influence of even small amounts of an inorganic acid (Ullmanns Encyclopadie der technischen Chemie, volume 14, page 26~).
Bull Soc. Chim. Belg., 65 (1956), 291-296 discloses that vinyl isocyanate is hydrolyzed by aqueous 12-normal hydro-chloric acid in acetone to give acetaldehyde Vinyl isocyanate may be prepared, for example, by reacting acrylyl chloride with sodium azide (Bull.Soc.
Chim. Belg., loc. cit~ or by thermally decomposing N-tert.-butyl-N-vinylcarbamyl chloride The hydrogen halide, advantageously hydrogen bromide and especially hydrogen chloride, is used in the stoichiometric amount or in excess, preferably in an amount of from 2 to 2.2 moles per mole of vinyl isocyanate or of N-tert.-alkyl-N-(1-alkenyl)-carbamyl halide.
1~77~9 o. z. 0050~032692~794 Suitable tertiary alkyl radicals RlR2R3-C, where R , R
and R3 may be identical or different, are those of 4 to 20 carbon atoms, and especially of 4 to 12 carbon atoms Speclfic examples are tert.-butyl and tert.-amyl.
Accordingly, the radicals Rl to R3 in the formula given may be alkyl of 1 to 6 carbon atoms, especially methyl and ethyl. R is advantageously hydrogen or alkyl of 1 to 20, especially 1 to 12, preferably 1 to 6, carbon atoms; pre~erred meanings are hydrogen, methyl and ethyl.
The reaction is carried out at from -78C to l80C, ad~antageously at from +40C to -78C, in the case of vinyl isocyanate preferably at from +30C to -78C, especially at from 0C to -40C, and in the case of N-tert -alkyl-N-(l-alkenyl)-carbamyl halides pre~erably at from -10C to 20C, under atmospheric or superatmospheric pressure, preferably at from 0 7 to 2 bars, continuously or batchwise The reaction can be carried out in the absence of a solvent, but it is advantageous to use a solvent which is inert under the reaction condition~ Water is not used in the case of v~nyl isocyanate Because of the reactivity of the resulting a-haloalkylcar~amyl halides, the reaction carried out with the N-tert.-alkyl-N-(l-alkenyl)-carbamyl halides.is pre-ferably carried out under anhydrous conditions, but in prin-ciple it can also be carried out with aqueous hydrochloric acid.
77~9 o.Z. 0050~032592/794 Preferably, the reaction is carried out in a solvent which serves as the reaction medium for the further conversion of the end product, especially of a-chloroethylcarbamyl chloride Examples of suit-able solvents are aromatic hydrocarbons, eg toluene, ethyl-benzene, o-, m- and p-xylene, isopropylbenzene and methyl-naphthalene; aromatic ethers; halohydrocarbons, especially chlorohydrocar~ons, eg. tetrachloroethylene, 1,1,2,2- or 1,1,1,2-tetrachloroethane, amyl chloride, cyclohexyl chlor-ide, 1,2-dlchloropropane, methylene chloride, dichlorobutane, isopropyl bromide, n-propyl bromide, butyl bromide, chloro-form, ethyl iodide, propyl iodide, chloronaphthalene, di-chloronaphthalene, carbon tetrachloride, 1,1,1- or 1,1,2-trichloroethane, trichloroethylene, pentachloroethane, 1,2-dichloroethane, l,l-dichloroéthane, n-propyl chloride, 1,2-cis-dichloroethylene, n-butyl chloride, 2-, ~- and iso-butyl chloride, chlorobenzene, fluorobenzene, bromobenzene, iodober,zene, o-, p- and m-dichlorobenzene, o-, p- and m-dibromobenzene, o-, m- and p-chlorotoluene, 1,2,4-trichloro-benzene, 1,l-dibromodecane and 1,4-dibromobutane; ethers, eg. ethyl propyl ether, methyl tert -butyl ether, n-butyl ethyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, diisopropyl ether, anisole, phenetole, cyclohexyl methyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, thioanisole and ~ dichlorodi-ethyl ether; ketones, eg. methyl ethyl ketone, acetone, diisopropyl ketone, diethyl ketone, methyl isobutyl ketone, 7'7~9 O.Z. 0050/032692t794 mesityl oxide, acetophenone, cyclohexanone, ethyl isoamyl ketone, diisobutyl ketone, methylcyclohexanone and dimethyl-cyclGhexanone; esters, eg. methyl acetate, n-propyl acetate, methyl propionate, butyl acetate, ethyl formate, methyl phthalate, methyl benzoate, ethyl acetate, phenyl acetate and higher-boiling esters; aliphatic or cycloaliphatic hydrocarbons, eg. pentane, heptane, pinane, nonane, gaso-line fractions within a boiling range from 70 to 190C, cyclohexane, methylcyclohexane, decalin, petroleum ether, héxane, naphtha, 2,2,4-trimethylpentane, 2,2,3-trimethyl-pentane, 2,3,3-trimethylpentane and octane; and mixtures of these. The solvent is advantageously used in an amount of from 200 to 10,000 per cent by weight, preferably from 300 to 2,000 per cent by weigh~, based on the vinyl isocyan-ate starting material.
The concentration of the solutions of the N-tert.-alkyl-N-(l-allcf3nyl)-carbamyl chlorides may be varied within wide limits, a concentration range of from 1 to 50 per cent by weight being used preferentially.
~ he reaction may be carried out as follows: a mix-ture of the starting materials, advantageously with a sol-vent, is ~ept at the reaction tempera~ure for from 0.1 to 4 hours. Advantageously, the vinyl isocyanate is introduced into the solvent and hydrogen halide gas is introduced at the reaction temperature, The reaction solution is then advantageously stirred for from 0.2~ to one hour, In the case o~ the N-tert.-alkyl-N~
alkenyl)-carbamyl halide, the compound is advantageously introdu~ed into an inert solvent and hydrogen halide gas is 377~9 O.Z. 0050/032692/794 introduced at, for example, from -10C to 0C. After completion of the reaction, the reaction solution is stirred for some tlme longer, for example for i5 minutes, and excess hydrogen halide is blown out by means of N2.
The end product is then isolated from the mixture in the conventional manner, for example by crystallization and filtration.
The -haloalkylcarbamyl halides, especially a-chloroethylcarbamyl chloride, prepared by the process of the invention, are valuable starting materials for the manu-facture of surface-coating raw materials, textile coatings, dyes, drugs and crop protection agents.
In the Examples, parts are by weight.
69 parts of vinyl isocyanate are introduced into 250 parts of carbon tetrachloride. 73 parts of hydrogen chloride are passed into this solution in the course of one hour at -35C. The reaction solution is then stirred for a further 15 minutes at the same temperature. After filtering, 13f parts (95% of theory) of a-chloroethyl-carbamyl chloride of melting point 21C are obtained; the NMR spectrum in CC14 (with tetramethylsilane as the stan-dard) gives the following:
(CH3-) 1.8 ppm ~Cl-C-H3 5.8 ppm (NH) 7.5 ppm.
161.5 parts of N-tert.-butyl-~-vinylcarbamyl chloride at 0C are introduced into the reaction vessel and ~ 377~9 o. ~ . 0050~032692~7~4 75 parts of hydrogen chloride gas are passed in over 60 mi~-utes. The reaction mixture is 'hen stirred for a further 15 minutes at the same temperature, and excess HCl is blown out with N2. Tert.-butyl chloride is stripped off under reduced pressure and the a-chloroethylcarbamyl chloride is recrystallized from CC14. 136 parts (95%
of theory) are obtained; melting point 20/21C, 175,5 parts of N-tert,-amyl-N-vinylcarbamyl chloride are introduced into the reactor at 10C and 77 parts of HCl are passed in whilst stirring.
After completion of the reaction, the reaction mix-ture is stirred for a further 30 minutes at room temperature and excess HCl is blown out with N2.
The tert,amyl chloride is stripped off under reduced pressure, 130 parts (91,5% of theory) of a-chloroethyl-carbamyl chloride of melting point 20C remain.-50 parts of vinyl isocyanate are introduced into 150 parts of methylene chloride, 125 parts of hydrogen bromide are passed into this solution, at -20C, in the course of 70 minutes. The reaction solution is then stirred for a further 40 minutes at the same temperature.
After filtering, 150 parts (90% of theory) of a-bromoethyl-carbamyl bromide of meltingpoint 55C are obtained; the ~R
spectrum in CDC13 (using tetramethylsilane as the standard) gi~es:
(CH3-) 2.0 ppm (Br-C-H) 5.9 ppm (NH) 6.8 ppm. _ 8 -
Angewandte Chemie, 74 (1962), 848-855 discloses the reaction of alkylcarbamyl chlorides with elementary chlorine to give the corresponding -cnloroalkylcarbamyl chlorides.
However, the products which result are mixtures, both in respect of the degree of halogenation and in respect of the position of the halogen atoms entering the molecule. The process is unsatisfactory in respect of yield and purity of the end product, and does not permit simple and economical operation.
We have found that -haloalkylcarbamyl halides are obtained in an advantageous manner if vinyl isocyanate or N-tert.-alkyl-N-(l-alkenyl)-carbamyl halides are reacted with a hydrogen halide at from -78C to +80C.
Further, we have found the novel a-haloal~ylcarbamyl halides of the formula R4-CH2-C-~-C~
where R is hydrogen or alkyl of 1 to 2~ car~Gn atoms and X i5 halogen, ,.~
lP'~7~9 o.Z. 0050/032692/794 Further, we have found the novel -haloethylcarbamyl halides, in particular the novel -chloroethylcarbamyl chloride-Where vinyl isocyanate and hydrogen chloride areused, the reaction may be represented by the following equation:
H H ~ 0 CH2=C-N-C0 + 2 HCl ~ CH~-C-N-C-Cl Cl Where a N-tert.-alkyl-N-(l-alkenyl)-carbamyl halide, eg. the chloride, is used, a quantitative fragmentation into tert.-alkyl chloride and a-chloroethylcarbamyl chloride takes place, in accordance with the equation below:
Rl ,,C001 R2 R~ H 0 --C-~ ~ 2HC~ Cl + X ~ C~
R2-" R~ ~ CX--CH R3 R42 Cl ~C1 Compared to the conventional process, the process of the invention gives a-haloalkylcarbamyl halides more simply and more economically, and in better yield and in greater purity. Working up is substantially simpler since the reaction mixture obtained does not contain a large number of different components.
The reaction of a tert.-alkyl-N-(l-alkeny~)-carbamyl halide, especialiy a chloride, with a hydrogen halide, especially hydrogen chloride, makes it possible to prepare the heat-stable halide, especially -chloroalkyl-carbamyl chloride~ in a particularly pure form and under mild reaction conditions, whilst the reaction of elementary ~'~'377~9 o. z. ooso/0~26s2/7s~
halogen with an alkylcarbamyl chloride (Angewandte Chemie, loc. cit.) gives product mixtures in respect of the position of the halogen atom entering the molecule, and in respect of the degree of halogenation. The tert.-alkyl halide also formed in the reaction is inert under the con-ventional reaction conditions and need therefore as a rule not be removed for carrying out the further reactions of the a-chloroalkylcarbamyl chloride.
All these advantageous results are surprising, since the formation of a variety of reaction products was to be expected from the great reactivity of the starting materials.
It was also to be expected that a,~-unsaturated nitrogen compounds would polymerize or hydrolyze very easily under the influence of acids. For example, N-vinylpyrrolidone is converted to a mixture of oligomers under the influence of even small amounts of an inorganic acid (Ullmanns Encyclopadie der technischen Chemie, volume 14, page 26~).
Bull Soc. Chim. Belg., 65 (1956), 291-296 discloses that vinyl isocyanate is hydrolyzed by aqueous 12-normal hydro-chloric acid in acetone to give acetaldehyde Vinyl isocyanate may be prepared, for example, by reacting acrylyl chloride with sodium azide (Bull.Soc.
Chim. Belg., loc. cit~ or by thermally decomposing N-tert.-butyl-N-vinylcarbamyl chloride The hydrogen halide, advantageously hydrogen bromide and especially hydrogen chloride, is used in the stoichiometric amount or in excess, preferably in an amount of from 2 to 2.2 moles per mole of vinyl isocyanate or of N-tert.-alkyl-N-(1-alkenyl)-carbamyl halide.
1~77~9 o. z. 0050~032692~794 Suitable tertiary alkyl radicals RlR2R3-C, where R , R
and R3 may be identical or different, are those of 4 to 20 carbon atoms, and especially of 4 to 12 carbon atoms Speclfic examples are tert.-butyl and tert.-amyl.
Accordingly, the radicals Rl to R3 in the formula given may be alkyl of 1 to 6 carbon atoms, especially methyl and ethyl. R is advantageously hydrogen or alkyl of 1 to 20, especially 1 to 12, preferably 1 to 6, carbon atoms; pre~erred meanings are hydrogen, methyl and ethyl.
The reaction is carried out at from -78C to l80C, ad~antageously at from +40C to -78C, in the case of vinyl isocyanate preferably at from +30C to -78C, especially at from 0C to -40C, and in the case of N-tert -alkyl-N-(l-alkenyl)-carbamyl halides pre~erably at from -10C to 20C, under atmospheric or superatmospheric pressure, preferably at from 0 7 to 2 bars, continuously or batchwise The reaction can be carried out in the absence of a solvent, but it is advantageous to use a solvent which is inert under the reaction condition~ Water is not used in the case of v~nyl isocyanate Because of the reactivity of the resulting a-haloalkylcar~amyl halides, the reaction carried out with the N-tert.-alkyl-N-(l-alkenyl)-carbamyl halides.is pre-ferably carried out under anhydrous conditions, but in prin-ciple it can also be carried out with aqueous hydrochloric acid.
77~9 o.Z. 0050~032592/794 Preferably, the reaction is carried out in a solvent which serves as the reaction medium for the further conversion of the end product, especially of a-chloroethylcarbamyl chloride Examples of suit-able solvents are aromatic hydrocarbons, eg toluene, ethyl-benzene, o-, m- and p-xylene, isopropylbenzene and methyl-naphthalene; aromatic ethers; halohydrocarbons, especially chlorohydrocar~ons, eg. tetrachloroethylene, 1,1,2,2- or 1,1,1,2-tetrachloroethane, amyl chloride, cyclohexyl chlor-ide, 1,2-dlchloropropane, methylene chloride, dichlorobutane, isopropyl bromide, n-propyl bromide, butyl bromide, chloro-form, ethyl iodide, propyl iodide, chloronaphthalene, di-chloronaphthalene, carbon tetrachloride, 1,1,1- or 1,1,2-trichloroethane, trichloroethylene, pentachloroethane, 1,2-dichloroethane, l,l-dichloroéthane, n-propyl chloride, 1,2-cis-dichloroethylene, n-butyl chloride, 2-, ~- and iso-butyl chloride, chlorobenzene, fluorobenzene, bromobenzene, iodober,zene, o-, p- and m-dichlorobenzene, o-, p- and m-dibromobenzene, o-, m- and p-chlorotoluene, 1,2,4-trichloro-benzene, 1,l-dibromodecane and 1,4-dibromobutane; ethers, eg. ethyl propyl ether, methyl tert -butyl ether, n-butyl ethyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, diisopropyl ether, anisole, phenetole, cyclohexyl methyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, thioanisole and ~ dichlorodi-ethyl ether; ketones, eg. methyl ethyl ketone, acetone, diisopropyl ketone, diethyl ketone, methyl isobutyl ketone, 7'7~9 O.Z. 0050/032692t794 mesityl oxide, acetophenone, cyclohexanone, ethyl isoamyl ketone, diisobutyl ketone, methylcyclohexanone and dimethyl-cyclGhexanone; esters, eg. methyl acetate, n-propyl acetate, methyl propionate, butyl acetate, ethyl formate, methyl phthalate, methyl benzoate, ethyl acetate, phenyl acetate and higher-boiling esters; aliphatic or cycloaliphatic hydrocarbons, eg. pentane, heptane, pinane, nonane, gaso-line fractions within a boiling range from 70 to 190C, cyclohexane, methylcyclohexane, decalin, petroleum ether, héxane, naphtha, 2,2,4-trimethylpentane, 2,2,3-trimethyl-pentane, 2,3,3-trimethylpentane and octane; and mixtures of these. The solvent is advantageously used in an amount of from 200 to 10,000 per cent by weight, preferably from 300 to 2,000 per cent by weigh~, based on the vinyl isocyan-ate starting material.
The concentration of the solutions of the N-tert.-alkyl-N-(l-allcf3nyl)-carbamyl chlorides may be varied within wide limits, a concentration range of from 1 to 50 per cent by weight being used preferentially.
~ he reaction may be carried out as follows: a mix-ture of the starting materials, advantageously with a sol-vent, is ~ept at the reaction tempera~ure for from 0.1 to 4 hours. Advantageously, the vinyl isocyanate is introduced into the solvent and hydrogen halide gas is introduced at the reaction temperature, The reaction solution is then advantageously stirred for from 0.2~ to one hour, In the case o~ the N-tert.-alkyl-N~
alkenyl)-carbamyl halide, the compound is advantageously introdu~ed into an inert solvent and hydrogen halide gas is 377~9 O.Z. 0050/032692/794 introduced at, for example, from -10C to 0C. After completion of the reaction, the reaction solution is stirred for some tlme longer, for example for i5 minutes, and excess hydrogen halide is blown out by means of N2.
The end product is then isolated from the mixture in the conventional manner, for example by crystallization and filtration.
The -haloalkylcarbamyl halides, especially a-chloroethylcarbamyl chloride, prepared by the process of the invention, are valuable starting materials for the manu-facture of surface-coating raw materials, textile coatings, dyes, drugs and crop protection agents.
In the Examples, parts are by weight.
69 parts of vinyl isocyanate are introduced into 250 parts of carbon tetrachloride. 73 parts of hydrogen chloride are passed into this solution in the course of one hour at -35C. The reaction solution is then stirred for a further 15 minutes at the same temperature. After filtering, 13f parts (95% of theory) of a-chloroethyl-carbamyl chloride of melting point 21C are obtained; the NMR spectrum in CC14 (with tetramethylsilane as the stan-dard) gives the following:
(CH3-) 1.8 ppm ~Cl-C-H3 5.8 ppm (NH) 7.5 ppm.
161.5 parts of N-tert.-butyl-~-vinylcarbamyl chloride at 0C are introduced into the reaction vessel and ~ 377~9 o. ~ . 0050~032692~7~4 75 parts of hydrogen chloride gas are passed in over 60 mi~-utes. The reaction mixture is 'hen stirred for a further 15 minutes at the same temperature, and excess HCl is blown out with N2. Tert.-butyl chloride is stripped off under reduced pressure and the a-chloroethylcarbamyl chloride is recrystallized from CC14. 136 parts (95%
of theory) are obtained; melting point 20/21C, 175,5 parts of N-tert,-amyl-N-vinylcarbamyl chloride are introduced into the reactor at 10C and 77 parts of HCl are passed in whilst stirring.
After completion of the reaction, the reaction mix-ture is stirred for a further 30 minutes at room temperature and excess HCl is blown out with N2.
The tert,amyl chloride is stripped off under reduced pressure, 130 parts (91,5% of theory) of a-chloroethyl-carbamyl chloride of melting point 20C remain.-50 parts of vinyl isocyanate are introduced into 150 parts of methylene chloride, 125 parts of hydrogen bromide are passed into this solution, at -20C, in the course of 70 minutes. The reaction solution is then stirred for a further 40 minutes at the same temperature.
After filtering, 150 parts (90% of theory) of a-bromoethyl-carbamyl bromide of meltingpoint 55C are obtained; the ~R
spectrum in CDC13 (using tetramethylsilane as the standard) gi~es:
(CH3-) 2.0 ppm (Br-C-H) 5.9 ppm (NH) 6.8 ppm. _ 8 -
Claims (4)
1. A process for the manufacture of an .alpha.-haloalkyl-carbamyl halide which comprises reacting vinyl isocyanate or a N-tert.-alkyl-N-(1-alkenyl)-carbamyl halide with a hydrogen halide at from -78°C to +80°C.
2. An .alpha.-hal?alkylcarbamyl halide of the formula I
where R4 is hydrogen or alkyl of 1 to 20 carbon atoms and X
is halogen.
where R4 is hydrogen or alkyl of 1 to 20 carbon atoms and X
is halogen.
3. A compound according to claim 2 which is an .alpha.-haloethylcarbamyl halide.
4. A compound according to claim 3 which is .alpha.-chloroethylcarbamyl chloride,
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772732284 DE2732284A1 (en) | 1977-07-16 | 1977-07-16 | METHOD FOR THE PRODUCTION OF ALPHA-HALOGENETHYLCARBAMIDSAEUREHALOGENIDEN |
| DEP2732284.5 | 1977-07-16 | ||
| DE19772741980 DE2741980A1 (en) | 1977-09-17 | 1977-09-17 | PROCESS FOR THE PREPARATION OF ALPHA-CHLORALKYLCARBAMOYL CHLORIDES |
| DEP2741980.3 | 1977-09-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1107759A true CA1107759A (en) | 1981-08-25 |
Family
ID=25772337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA307,241A Expired CA1107759A (en) | 1977-07-16 | 1978-07-12 | MANUFACTURE OF .alpha.-HALOALKYLCARBAMYL HALIDES |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0000362B1 (en) |
| JP (1) | JPS5419916A (en) |
| AU (1) | AU517065B2 (en) |
| BR (1) | BR7804551A (en) |
| CA (1) | CA1107759A (en) |
| DD (1) | DD137223A5 (en) |
| DE (1) | DE2860132D1 (en) |
| HU (1) | HU179671B (en) |
| IL (1) | IL55106A (en) |
| IT (1) | IT1096870B (en) |
| PL (1) | PL108071B1 (en) |
| SU (1) | SU906371A3 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2830969A1 (en) * | 1978-07-14 | 1980-01-31 | Basf Ag | NEW ALPHA -HALOGENALKYLCARBAMIDSAEUREHALOGENIDE AND METHOD FOR PRODUCING ALPHA -HALOGENALKYLCARBAMIDSAEURHALOGENIDEN |
| AU2012299239A1 (en) | 2011-08-23 | 2013-11-21 | Rohm And Haas Company | A multi-stage polymer composition and films and polarizer plates made therefrom |
-
1978
- 1978-06-29 IT IT25131/78A patent/IT1096870B/en active
- 1978-06-30 EP EP78100284A patent/EP0000362B1/en not_active Expired
- 1978-06-30 DE DE7878100284T patent/DE2860132D1/en not_active Expired
- 1978-07-07 IL IL55106A patent/IL55106A/en unknown
- 1978-07-07 AU AU37855/78A patent/AU517065B2/en not_active Expired
- 1978-07-12 CA CA307,241A patent/CA1107759A/en not_active Expired
- 1978-07-13 PL PL1978208386A patent/PL108071B1/en unknown
- 1978-07-14 HU HU78BA3679A patent/HU179671B/en unknown
- 1978-07-14 SU SU782635898A patent/SU906371A3/en active
- 1978-07-14 JP JP8524578A patent/JPS5419916A/en active Pending
- 1978-07-14 BR BR7804551A patent/BR7804551A/en unknown
- 1978-07-14 DD DD78206730A patent/DD137223A5/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IL55106A (en) | 1981-12-31 |
| JPS5419916A (en) | 1979-02-15 |
| DD137223A5 (en) | 1979-08-22 |
| PL108071B1 (en) | 1980-03-31 |
| BR7804551A (en) | 1979-03-06 |
| EP0000362A1 (en) | 1979-01-24 |
| IT7825131A0 (en) | 1978-06-29 |
| AU3785578A (en) | 1980-01-10 |
| PL208386A1 (en) | 1979-06-04 |
| IL55106A0 (en) | 1978-09-29 |
| EP0000362B1 (en) | 1980-09-03 |
| AU517065B2 (en) | 1981-07-09 |
| SU906371A3 (en) | 1982-02-15 |
| IT1096870B (en) | 1985-08-26 |
| HU179671B (en) | 1982-11-29 |
| DE2860132D1 (en) | 1980-12-11 |
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