EP0000362B1 - Alpha-halogeno-alkyl carbamyl halides and preparation thereof. - Google Patents
Alpha-halogeno-alkyl carbamyl halides and preparation thereof. Download PDFInfo
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- 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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- 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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Description
Die Erfindung betrifft ein Verfahren zur Herstellung von α-Halogenalkylcarbamidsäurehalogeniden durch Umsetzung von Vinylisocyanat oder N-tert.Alkyl-N-(1-alkenyl)carbamidsäure- halogeniden mit Halogenwasserstoff bei -78°C bis +80°C.The invention relates to a process for the preparation of α-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.
Es ist aus der Angewandten Chemie, Band 74 (1962), Seiten 848 bis 855 bekannt, daß man Alkylcarbamidsäurechloride mit elementarem Chlor in die entsprechenden a-Chloralkylcarbamidsäurechloride umsetzt. Die dabei anfallenden Produkte sind jedoch Gemische sowohl mit Bezug auf den halogenierungsgrad wie auf die Stellung der eintretenden Halogenatome. Das Verfahren ist im Hinblick auf Ausbeute und Reinheit des Endstoffs sowie einfachen und wirtschaftlichen Betrieb nicht befriedigend.It is known from Angewandte Chemie, Volume 74 (1962), pages 848 to 855, that alkylcarbamic acid chlorides are reacted with elemental chlorine in the corresponding α-chloroalkylcarbamic acid chlorides. The resulting products, however, are mixtures with regard to both the degree of halogenation and the position of the halogen atoms entering. The process is unsatisfactory in terms of yield and purity of the end product and simple and economical operation.
Es werden nun die neuen a-Halogenalkylcarbamidsäurehalogenide der Formel
Es wurde weiterhin gefunden, daß man a-Halogenalkylcarbamidsäurehalogenide der Formel
Weiterhin wurden die neuen a-Halogenäthylcarbamidsäurehalogenide, insbesondere das neue a-Chloräthylcarbamidsäurechlorid, gefunden.Furthermore, the new a-haloethylcarbamoyl halides, especially the new a-chloroethylcarbamoyl chloride, were found.
Die Umsetzung kann im Falle der Verwendung von Vinylisocyanat und Chlorwasserstoff durch die folgenden Formeln wiedergegeben werden:
Im Falle der N-tert.Alkyl-N-(1-alkenyl)-carbamidsäurehalogenide, z.B. der Chloride, tritt entsprechend der Reaktionsgleichung quantitativ ein Fragmentierung in tert. Alkylchlorid und a-Chloräthylcarbamidchlorid ein.
Im Hindblick auf das bekannte Verfahren liefert das Verfahren nach der Erfindung auf einfacherem und wirtschaftlicherem Wege α-Halogenalkylcarbamidsäurehalogenide in besserer Ausbeute und Reinheit. Die Aufarbeitung ist wesentlich einfacher, da kein komponentenreiches Reaktionsgemisch erhalten wird.In view of the known process, the process according to the invention provides α-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.
Die Umsetzung von tert.Alkyl-N-(1-alkenyl)-carbamidsäurehalogeniden, insbesondere den Chloriden, mit Halogen-wasserstoff, insbesondere Chlorwasserstoff, gestattet es, in besonders reiner Form und unter schonenden Reaktionsbedingungen das thermostabile Halogenid, insbesondre a-Chloralkylcarbamidsäurechlorid, herzustellen, wohingegegen bei der Einwirkung von elementarem Halogen auf Alkylcarbamidsäurechloride (Ang., loc. cit.) Produktgemische hinsichtlich der Stellung des eintretenden Halogenatoms sowie des Halogenierungsgrades erhalten werden. Das bei der Reaktion gleichzeitig anfallende tert.Alkylhalogenid ist unter den üblichen Reaktionsbedindungen inert und muß daher in der Regel bei den weiteren Umsetzungen des a-Chloralkylcarbamidsäurechlorids nicht entfernt werden.The reaction of tert-alkyl-N- (1-alkenyl) carbamic acid halides, in particular the chlorides, with hydrogen halide, in particular hydrogen chloride, allows the thermostable halide, in particular a-chloroalkylcarbamic acid chloride, to be prepared in a particularly pure form and under gentle reaction conditions , whereas with the action of elemental halogen on alkyl carbamic acid chlorides (Ang., loc. cit.) 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.
Alle diese vorteilhaften Ergebnisse sind überraschend, denn angesichts der sehr reaktionsfreudigen Ausgangsstoffe war mit der Bildung verschiedenartiger Reaktionsprodukte zu rechnen. Auch war zu vermuten, daß a,ß-ungesättigte Stickstoffverbindungen sehr leicht unter der Einwirkung von Säuren polymerisieren oder hydrolysieren. So geht z.B. N-Vinylpyrrolidon durch Einwirkung schon geringer Mengen an anorganischen Säuren in ein Gemisch von Oligomeren über (Ullmanns Encyclopädie der technischen Chemie, Band 14, Seite 261). Bull. Soc. Chim. Belg., Band 65, Seiten 291 bis 296 (1956) zeigt, daß Vinylisocyanat mit wäßriger 12-N-Salzsäure in Aceton zu Acetaldehyd hydrolysiert.All of these advantageous results are surprising, because in view of the very reactive starting materials, the formation of various reaction products was to be expected. It was also assumed that α, β-unsaturated nitrogen compounds polymerize or hydrolyze very easily under the action of acids. For example, N-vinylpyrrolidone by the action of even small amounts of inorganic acids in a mixture of oligomers via (Ullmanns Encyclopedia of Industrial Chemistry, Volume 14, page 261). Bull. Soc. Chim. Belg., Vol. 65, pages 291 to 296 (1956) shows that vinyl isocyanate hydrolyzes with aqueous 12 N hydrochloric acid in acetone to acetaldehyde.
Vinylisocyanat kann z.B. durch Umsetzung von Acrylsäurechlorid mit Natriumazid (Bull., loc. cit.) oder durch thermische Zerlegung von N-tert.-Butyl-N-vinylcarbamidsäurechlorid hergestellt werden. Man verwendet den Halogenwasserstoff, vorteilhaft Bromwasserstoff und insbesondere Chlorwasserstoff, in stöchiometrischer Menge oder im Überschuß, vorzugsweise in einer Menge von 2 bis 2,2' Mol Halogenwasserstoff je Mol Vinylisocyanat oder N-tert.Alkyl-N-( 1-alkenyl)-carbamidsäurehalogenid.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 .
Als tertiäre Alkylreste, R1, R2 und R3, die gleich oder verschieden sein können, solche mit 4 bis 20 insbesondere 4 bis 12 Kohlenstoffatomen, in Betracht. Insbesondere sind der tert.Butyl- und tert.A-mylrest zu nennen. Demgemäß können die Reste R'.bis R3 in der angegebenen Formel Alkylreste mit 1 bis 6 Kohlenstoffatomen, insbesondre Methyl und Äthyl bedeuten. R4 bezeichnet vorteilhaft Wasserstoff oder einen Alkylrest mit 1 bis 20, insbesondere 1 bis 12, vorzugsweise 1 bis 6 Kohlenstoffatomen; bevorzugt sind Wasserstoff, Methyl und Äthyl.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. Accordingly, 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.
Die Umsetzung wird bei einer Temperatur von -78°C bis +80°C, vorteilhaft von +40°C bis -78°C, vorzugsweise im Falle von Vinylisocyanat von +30°C bis -78°C, insbesondere bei 0°C bis -40°C, vorzugsweise im Falle von N7tert.Alkyl-N-(1-Alkenyl)-carbamidsäurehalogeniden von -10°C bis 20°C, drucklos oder unter Druck, vorzugsweise bei 0,7 bis 2 bar, kontinuierlich oder diskontinuierlich durchgeführt. Man kann ohne Lösungsmittel unsetzen, zweckmäßig verwendet man aber unter den Reaktionsbedingungen inerte Lösungsmittel, Wasser wird in Falle von Vinylisocyanat nicht verwendet. Wegen der Reaktivität der entstehenden a-Halogenalkylcarbamidsäurehalogenide arbeitet man bevorzugt wasserfrei; prinzipiell kann man aber auch mit wäßriger Salzasäure arbeiten. Bevorzugt arbeitet man in Lösungsmitteln, die bei der weiteren Umsetzung des Endsstoffs, insbesondere des a-Chlor- äthylencarbamidsäurechlorids, als Reaktionsmedium Verwendung finden. Als Lösungsmittel kommen z.B. in Frage: aromatische Kohlenwasserstoffe, z.B. Toluol, Äthylbenzol, o-, m-, p-Xylol, Isopropylbenzol, Methylnaphthalin, aromatische Äther; Halogenkohlenwasserstoffe, insbesondere Chlorkohlenwasserstoff, z.B. Tetrachloräthylen, 1,1,2,2- oder 1,1,1;2-Tetrachioräthan, Amylchlorid, Cyclohexylchlorid, 1,2,-Dichlorpropan, Methylenchlorid, Dichlorbutan, Isopropylbromid, n-Propylbromid, Butylbromid, Chloroform, Äthyljodid, Propyljodid, Chlornaphthalin, Dichlornaphthalin, Tetrachlorkohlenstoff,1,1,1- oder 1,1,2-Trichloräthan, Trichloräthylen, Pentachloräthyn, 1,2-Dichloräthan, 1,1-Dichloräthan, n-Propylchlorid, 1,2-cis-Dichloräthylen, n-Butylchlorid, 2-, 3- und iso-Butylchlorid, Chlorbenzol, Fluorbenzol, Brombenzol, Jodbenzol, o-, p- und m-Dichlorbenzol, o-, p-, m-Dibrombenzol, o-, m-, p-Chlortoluol, 1,2,4-Trichlorbenzol, 1,10-Dibromdekan, 1,4-Dibrombutän; Äther," z.B. Äthylenpropyläther, Methyl-tert.-butyläther, n-Butyläther, Di-n-butyläther, Diisobutyl- äther, Diisoamyläther, Diisopropyläther, Anisol, Phenetol, Cyclohexylmethyläther, Diäthyläther, Äthylenglykoldimethyläther, Tetrahydrofuran, Dioxan, Thianisol, ß,ß'-Dichlordiäthyläther; Ketone wie Methyläthylketon, Aceton, Diisopropylketon, Diäthylketon, Methylisobutylketon, Mesityloxid, Acetophenon, Cyclohexanon, Äthylisoamylketon, Diisobutylketon, Methylcyclohexanon, Dimethylcyclohexanon; Ester wie Methylacetat, n-Propylacetat, Methylpropionat, Butylacetat, Äthylformiat, Phthalsäuremethylester, Benzoesäuremethylester, Essigester, Phenylacetat und höher siedende Ester; aliphatische oder cycloaliphatische Kohlenwasserstoff, z.B. Pentan, Heptan, Pinan, Nonan, Benzinfraktionen innerhalb eines Siedepunktintervalls von 70 bis 190°C, Cyclohexan, Methylcyclohexan, Dekalin, Petroläther, Hexan, Ligroin, 2,2,4-Trimethylpentan, 2,2,3-Trimethylpentan, 2,3,3,-Trimethylpentan, Octan; und entsprechende Gemische. Zweckmäßig verwendet man das Lösungsmittel in einer Menge von 200 bis 10 000 Gewichtsprozent, vorzugsweise von 300 bis 2 000 Gewichtsprozent, bezogen auf den Ausgangsstoff Vinylisocyanat.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. You can sit without solvent, but it is expedient to use solvents which are inert under the reaction conditions, and water is not used in the case of vinyl isocyanate. Because of the reactivity of the resulting a-haloalkyl carbamic acid halides, it is preferred to work anhydrous; in principle, you can also work with aqueous hydrochloric acid. It is preferred to work in solvents which are used as the reaction medium in the further reaction of the end product, in particular the a-chloroethylene carbamic acid chloride. Examples of 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, 1,2-dichloroethane, 1,1-dichloroethane, n-propyl chloride, 1,2 -cis-dichloroethylene, n-butyl chloride, 2-, 3- and iso-butyl chloride, chlorobenzene, fluorobenzene, bromobenzene, iodobenzene, o-, p- and m-dichlorobenzene, o-, p-, m-dibromobenzene, o-, m-, p-chlorotoluene, 1,2,4-trichlorobenzene, 1,10-dibromodecane, 1,4-dibromobutane; Ether, "for example ethylene propyl ether, methyl tert-butyl ether, n-butyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, diisopropyl ether, anisole, phenetol, cyclohexylmethyl ether, diethyl ether, ethylene glycol, dimethyl ether, t-ethyl dimethyl ether, t-dimethyl ether, t-ethyl dimethyl ether, t-dimethyl ether, t-dimethyl ether, t-dimethyl ether, t-dimethyl ether, t-dimethyl ether, t-dimethyl ether, t-ethyl dimethyl ether, t-dimethyl ether, t-dimethyl ether, t-ethyl dimethyl ether, t-ethyl dimethyl ether, t-ethyl dimethyl ether, t-dimethyl ether, t-dimethyl ether, t-dimethyl ether, t-dimethyl ether, t-ethyl ether, t-dimethyl ether, t-dimethyl ether, t-dimethyl ether, t-dimethyl ether, t-ether, t-ethyl ether '-Dichlordiäthyläther; ketones such as methyl ethyl ketone, acetone, diisopropyl ketone, diethyl ketone, methyl isobutyl ketone, mesityl oxide, acetophenone, cyclohexanone, Äthylisoamylketon, diisobutyl ketone, methylcyclohexanone, dimethylcyclohexanone; esters such as methyl, n-propyl acetate, methyl propionate, butyl acetate, ethyl formate, phthalic methyl acid ester, methyl benzoate, ethyl acetate, phenyl acetate and higher-boiling esters; aliphatic or cycloaliphatic hydrocarbon, e.g. pentane, heptane, pinane, nonane, gasoline fractions within a boiling point interval of 70 to 190 ° C, cyclohexane, methylcyclohexane, decalin, petroleum ether, hexane, ligroin, 2,2,4-trimethylpentane, 2,2,3 -Trimethylpentane, 2,3,3, -trimethylpentane, octane; and corresponding mixtures. 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.
Die Konzentration der Lösungen der N-tert.Alkyl-N-(1-alkenyl)-carbamidsäurechloride ist in weiten Grenzen variabel. Bevorzugt wird ein Konzentrationsbereich zwischen 1 und 50 Gewichtsprozent angewandt.The 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.
Die Reaktion kann wie folgt durchgeführt werden: Ein Gemisch der Ausgangsstoffe und zweckmäßig Lösungsmittel wird während 0,1 bis 4 Stunden bei der Reaktionstemperatur gehalten. Vinylisocyanat wird vorteilhaft im Lösungsmittel vorgelegt und bei der Reaktionstemperatur mit dem Halogen- wasserstoff begast. Zweckmäßig rührt man die Reaktionslösung 0,25 Stunden bis ein Stunde nach. Das N-tert.Alkyl-N-(1-alkenyl)-carbamidsäurehalogenid wird zweckmäßig in einem inerten Lösungsmittel vorgelegt und bei einer Temperatur von z.B. -10°C bis 0°C mit Halogenwasserstoff begast. Nach Beendigung der Umsetzung rührt man die Reaktionslösung einige Zeit, z.B. 15 Minuten, nach und bläst überschüssigen Halogenwasserstoff mittels N2 aus. Dann wird der Endstoff aus dem Gemisch in üblicher Weise, z.B. durch Kristallisation und Filtration, abgetrennt.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.
Die nach dem Verfahren der Erfindung hergestellten a-Halogenalkylcarbamidsäurehalogenide, insbesondere das a-Chloräthylcarbamidsäurechlorid, sind wertvolle Ausgangsstoffe für die Herstellung von Lackrohstoffen, Textilbeschichtungsmitteln, Farbstoffen, Pharmaceutica und Pflanzenschutzmitteln.The a-haloalkylcarbamic acid halides produced by the process of the invention, in particular the a-chloroethylcarbamic acid chloride, are valuable starting materials for the production of paint raw materials, textile coating compositions, dyes, pharmaceuticals and crop protection agents.
Die in den Beispielen genannten Teile sind Gewichtsteile.The parts mentioned in the examples are parts by weight.
69 Teile Vinylisocyanat werden in 250 Teilen Tetrachlorkohlenstoff vorgelegt. In diese Lösung werden bei -35°C innerhalb einer Stund 73 Teile Chlorwasserstoff eingeleitet. Die Reaktionslösung wird weitere 15 Minuten bei dieser Temperatur gerührt. Man erhält nach Filtration 137 Teile (95% der Theorie) a-Chloräthylcarbamidsäurechlorid vom Fp. 21 °C und NMR-Spektrum in CCI4 (Standard Tetramethylsilan).69 parts of vinyl isocyanate are placed in 250 parts of carbon tetrachloride. 73 parts of hydrogen chloride are introduced into this solution at -35 ° C. within one hour. The reaction solution is stirred for a further 15 minutes at this temperature. After filtration, 137 parts (95% of theory) of a-chloroethylcarbamoyl chloride, melting at 21 ° C., and an NMR spectrum in CCI 4 (standard tetramethylsilane) are obtained.
161,5 Teile N-tert.butyl-N-vinylcarbamidsäurechlorid werden bei 0°C vorgelegt und hierzu innerhalb 60 Minuten 75 Teile Chlorwasserstoff eingegast. Die Reaktionsmischung wird 15 Minuten bei dieser Temperatur nachgerührt und überschüssiger HCI mit N2 ausgeblasen. Tert.Butylchlorid wird bei vermindertem Druck abgezogen und das α-Chloräthylcarbamidsaürechlorid in CCI4 umkristallisiert. 136 Teile (95% der Theorie); Fp. 20/21 °C.161.5 parts of N-tert.butyl-N-vinylcarbamic acid chloride 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 α-chloroethylcarbamic acid chloride is recrystallized in CCI 4 . 136 parts (95% of theory); Mp 20/21 ° C.
175,5 Teile N-tert.Amyl-N-vinylcarbamidsäurechlorid werden bei 10°C vorgelegt und unter Rühren 75 Teile HCI eingeleitet.175.5 parts of N-tert.amyl-N-vinylcarbamic acid chloride are introduced at 10 ° C. and 75 parts of HCl are introduced with stirring.
Nach Beendigung der Umsetzung wird die Reaktionsmischung noch 30 Minuten bei Raumtemperatur nachgerührt und überschüssiger HCI mit N2 ausgeblasen.After the reaction has ended, the reaction mixture is stirred for a further 30 minutes at room temperature and excess HCl is blown out with N 2 .
Das tert. Amylchlorid wird bei vermindertem Druck abgezogen.The tert. Amyl chloride is removed under reduced pressure.
Es hinterbleiben 130 Teile (91,5% der Theorie) a-Chloräthylcarbamidsäurechlorid vom Fp. 20°C.There remain 130 parts (91.5% of theory) of a-chloroethylcarbamoyl chloride, mp. 20 ° C.
50 Teile Vinylisocanat werden in 150 Teilen Dichlormethan vorgelegt. Innerhalb von 70 Minuten werden in diese Lösung 125 Teile Bromwasserstoff bei -20°C eingeleitet. Die Reaktionslösung wird weitere 40 Minuten bei dieser Temperatur gerührt. Nach Filtration erhält man 150 Teile (90% der Theorie) a-Bromäthylcarbamidsäurebromid vom Fp. 55°C und NMR-Spektrum in CDCI3 (Standard Tetramethylsilan).50 parts of vinyl isocanate are placed in 150 parts of dichloromethane. 125 parts of hydrogen bromide at -20 ° C. are introduced into this solution within 70 minutes. The reaction solution is stirred for a further 40 minutes at this temperature. After filtration, 150 parts (90% of theory) of a-bromoethylcarbamic acid bromide, melting at 55 ° C., and an NMR spectrum in CDCI 3 (standard tetramethylsilane) are obtained.
Claims (4)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2732284 | 1977-07-16 | ||
DE19772732284 DE2732284A1 (en) | 1977-07-16 | 1977-07-16 | METHOD FOR THE PRODUCTION OF ALPHA-HALOGENETHYLCARBAMIDSAEUREHALOGENIDEN |
DE2741980 | 1977-09-17 | ||
DE19772741980 DE2741980A1 (en) | 1977-09-17 | 1977-09-17 | PROCESS FOR THE PREPARATION OF ALPHA-CHLORALKYLCARBAMOYL CHLORIDES |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000362A1 EP0000362A1 (en) | 1979-01-24 |
EP0000362B1 true EP0000362B1 (en) | 1980-09-03 |
Family
ID=25772337
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100284A Expired EP0000362B1 (en) | 1977-07-16 | 1978-06-30 | Alpha-halogeno-alkyl carbamyl halides and preparation thereof. |
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 |
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/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 DD DD78206730A patent/DD137223A5/en unknown
- 1978-07-14 JP JP8524578A patent/JPS5419916A/en active Pending
- 1978-07-14 SU SU782635898A patent/SU906371A3/en active
- 1978-07-14 BR BR7804551A patent/BR7804551A/en unknown
- 1978-07-14 HU HU78BA3679A patent/HU179671B/en unknown
Also Published As
Publication number | Publication date |
---|---|
DE2860132D1 (en) | 1980-12-11 |
IL55106A0 (en) | 1978-09-29 |
IT7825131A0 (en) | 1978-06-29 |
PL208386A1 (en) | 1979-06-04 |
JPS5419916A (en) | 1979-02-15 |
AU3785578A (en) | 1980-01-10 |
EP0000362A1 (en) | 1979-01-24 |
IL55106A (en) | 1981-12-31 |
PL108071B1 (en) | 1980-03-31 |
HU179671B (en) | 1982-11-29 |
SU906371A3 (en) | 1982-02-15 |
DD137223A5 (en) | 1979-08-22 |
AU517065B2 (en) | 1981-07-09 |
IT1096870B (en) | 1985-08-26 |
CA1107759A (en) | 1981-08-25 |
BR7804551A (en) | 1979-03-06 |
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