CA1193278A - Process for the production of n- and o-substituted monourethanes - Google Patents
Process for the production of n- and o-substituted monourethanesInfo
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- CA1193278A CA1193278A CA000420366A CA420366A CA1193278A CA 1193278 A CA1193278 A CA 1193278A CA 000420366 A CA000420366 A CA 000420366A CA 420366 A CA420366 A CA 420366A CA 1193278 A CA1193278 A CA 1193278A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
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Abstract
A PROCESS FOR THE PRODUCTION OF
N- AND O-SUBSTITUTED MONOURETHANES
ABSTRACT OF THE DISCLOSURE
N- and O-substituted monourethanes are produced by reacting at elevated temperature an N-aryl-O-alkyl urethane with a primary monoamine in the presence of a high boiling alcohol and removing the arylamine formed during this reaction from the reaction mixture. The primary monoamine starting material should be such that it will not distill off during the reaction but must have a boiling point (at 1013 mbar) at least 5°C higher than the arylamine which forms during the reaction. The high boiling alcohol has a boiling point of at least 190°C
at atmospheric pressure. The reaction is carried out at a temperature of from 180 to 300°C.
N- AND O-SUBSTITUTED MONOURETHANES
ABSTRACT OF THE DISCLOSURE
N- and O-substituted monourethanes are produced by reacting at elevated temperature an N-aryl-O-alkyl urethane with a primary monoamine in the presence of a high boiling alcohol and removing the arylamine formed during this reaction from the reaction mixture. The primary monoamine starting material should be such that it will not distill off during the reaction but must have a boiling point (at 1013 mbar) at least 5°C higher than the arylamine which forms during the reaction. The high boiling alcohol has a boiling point of at least 190°C
at atmospheric pressure. The reaction is carried out at a temperature of from 180 to 300°C.
Description
2~
Mo-2444 LeA 21,562 A PROCESS FOR THE PRODUCTION OF
N- AND O-SUBSTITUTED MONOUP~ETHANES
BACKGRO~N~ OF THE INVENTION
This invention relates to a process for the pro-5 duction of N- and O-substituted, aliphatic or aromatic monourethanes.
Production of urethanes in the absence o~ phos-gene and subsequent thermal decomposition of those ure-thanes to form the corresponding isocyanates (even 10 monoisocyanates) is an interesting alternative to the known phosgenation of the amines on which the isocyanates are based~ The processes disclosed in European Patent Applications 27,952; 27,940; 28,331; 27,953; 18,581 and 18,583 and in German Offenlegungsschriften 2,~17,490 and 15 2,917,568 may theoretically also be used ~or the pro-duction of N-O-substituted monourethanes. In accordance with the principles disclosed in these publications, it is possible to produce monourethanes substituted aromati-cally on the nitrogen and aliphatically on the o~ygen (such as N-phenyl-O-ethyl urethane) in high yields. How-ever, the known processes are much less suitable for the production of N-al]cyl, N-cycloalkyl or N-aryl urethanes containing electron-attracti.ng substituents cn the aryl radical as is evidenced by the low yields obtainedO This 25 problem is also encountered in the known processes described in European Patent Applications 18,581; 18 r 583;
27,952 and German Offenlegungsschriften 2,917,490 and 2,917,568.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a process for the production of N- and 0 substituted monourethanes in high yields.
It is also an object of the present invention to provide a process ~or the production of monourethanes 35 which are substituted on the nitrogen with an aliphatic Mo-2444 ~eA 21,562-US
~k :, 271~3 or aromatic group and on the oxygen with an aliphatic group in high yield.
It is another object of the present invention to provide a process for the production of substituted monourethanes in which an aromatic group containing electron-attracting radicals (such as halogen atoms) is the nitrogen substituent.
It is a fur~her object of the present invention to provide a process for the production of N- and O-substituted monourethanes in high yield in a comparativelyshort reaction time during which no gaseous ammonia is given off.
These and other objects which will be apparent to those skilled in the art are accomplished by reacting lS (i) an ~-aryl-O-alkyl urethane with ~ii) a primary mono-amine in the presence of (iii) a high boiling alcohol and removing the arylamine formed during this reaction from the reaction mixture. The primary monoamine (ii) should have a boiling point at 1013 mbar which is higher than the reaction temperature or at least 5C higher than the boiling point of the arylamine formed during the reaction.
DET~I1ED DESC~IPTION OF THE IN~ENTIO~
The present invention relates to a process for the production of N and O-substituted monoure-thanes from a primary monoamine and an N-aryl-O-alkyl urethane in the presence of a high boiling alcohol. The primary monoamines employed should be such that it will n~t distill at 1013 mbars or have a boiling point (at 1013 mbars) which is at least 5C (preferably at least 20C) above the boiling point of the aryl amine which is formed during the reaction. The reaction is carried out at elevated temperature and the aryl amine spontaneously formed during the reaction (corresponds to the N-aryl-Mo-2444 ~3~
O-alkyl urethane) is continuously removed from the reac-tion mixture (e.g., by distillation).
Suitable primary amines are any high-boiling organic compounds which, apart from the amino group, are iner-t under the reaction conditions of -the process of the present invention. Examples o~ suitable primary amines are -those corresponding to the formula ~ -~H2 which amines either cannot be distilled at 1013 mbar or have a boiling point at 1013 mbar which is at least 5C
(preferably at least 20C) above the boiling point of the monoamine corresponding to the monourethane used as starting material. In the above formula, Rl represents an aliphatic C4-C18 hydrocarbon radical optionally con-taining inert substituents; a cycloaliphatic C6-C28 hydro-carbon radical optionally containing inert substituents and/or optionally oxygen, sulfur or alkylene groups as bxidge members; an aromatic C6-C28 hydrocarbon radical optionally containing inert substituents and/or oxygen, sulfur or alkylene groups as bridge members; or an araliphatic C7-C28 hydrocarbon radical optionally con-taining inert substituents.
It is preferred to use monoamines corresponding to the above-given formula in which Rl represents a saturated, unsubstituted or halogen (particularly chlorine)-substituted aliphatic Cg-Cl8 hydrocarbon radical; a saturated cycloaliphatic C6-C25 hydrocarbon radical optionally substituted by halogen (particularly chlorine~ or by alkyl or chloroalkyl groups and/or con-taining methylene bridges; or an aromatic C6-C25 hydro-carbon radical optionally substituted by halogen (par-ticularly chlorine) or by alkyl or ch].oroalkyl groups and/or containing methylene bridges.
Mo-2444 ~3~
Specific examples of suitable primary amines are nonyl amlne; decyl amine; undecyl amine; dodecyl amine;
tridecyl amlne; tetradecyl amine; pentadecyl amine; hexa~
decyl amine; heptadecyl amine; stearyl amine; cyclooctyl amine; 4-(trichloromethyl)-cyclohexyl amine; 2-chloro-cycloheptyl amine; bicyclohexyl-4-amine and its isomers;
p-amino-N,N-dlmethyl aniline; 4-aminodiphenyl and its isomers; ~-~-naphthyl amine; o-, m-,p-benzyl aniline;
hexahydrobenzyl aniline; perhydrobenzyl aniline; isomers of benzyl toluidine; isomers of hexahydro~ and perhydro-benzyl toluidine; 1-, 2~, 3 , 4-methyl cyclohexyl amine;
Mo-2444 LeA 21,562 A PROCESS FOR THE PRODUCTION OF
N- AND O-SUBSTITUTED MONOUP~ETHANES
BACKGRO~N~ OF THE INVENTION
This invention relates to a process for the pro-5 duction of N- and O-substituted, aliphatic or aromatic monourethanes.
Production of urethanes in the absence o~ phos-gene and subsequent thermal decomposition of those ure-thanes to form the corresponding isocyanates (even 10 monoisocyanates) is an interesting alternative to the known phosgenation of the amines on which the isocyanates are based~ The processes disclosed in European Patent Applications 27,952; 27,940; 28,331; 27,953; 18,581 and 18,583 and in German Offenlegungsschriften 2,~17,490 and 15 2,917,568 may theoretically also be used ~or the pro-duction of N-O-substituted monourethanes. In accordance with the principles disclosed in these publications, it is possible to produce monourethanes substituted aromati-cally on the nitrogen and aliphatically on the o~ygen (such as N-phenyl-O-ethyl urethane) in high yields. How-ever, the known processes are much less suitable for the production of N-al]cyl, N-cycloalkyl or N-aryl urethanes containing electron-attracti.ng substituents cn the aryl radical as is evidenced by the low yields obtainedO This 25 problem is also encountered in the known processes described in European Patent Applications 18,581; 18 r 583;
27,952 and German Offenlegungsschriften 2,917,490 and 2,917,568.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a process for the production of N- and 0 substituted monourethanes in high yields.
It is also an object of the present invention to provide a process ~or the production of monourethanes 35 which are substituted on the nitrogen with an aliphatic Mo-2444 ~eA 21,562-US
~k :, 271~3 or aromatic group and on the oxygen with an aliphatic group in high yield.
It is another object of the present invention to provide a process for the production of substituted monourethanes in which an aromatic group containing electron-attracting radicals (such as halogen atoms) is the nitrogen substituent.
It is a fur~her object of the present invention to provide a process for the production of N- and O-substituted monourethanes in high yield in a comparativelyshort reaction time during which no gaseous ammonia is given off.
These and other objects which will be apparent to those skilled in the art are accomplished by reacting lS (i) an ~-aryl-O-alkyl urethane with ~ii) a primary mono-amine in the presence of (iii) a high boiling alcohol and removing the arylamine formed during this reaction from the reaction mixture. The primary monoamine (ii) should have a boiling point at 1013 mbar which is higher than the reaction temperature or at least 5C higher than the boiling point of the arylamine formed during the reaction.
DET~I1ED DESC~IPTION OF THE IN~ENTIO~
The present invention relates to a process for the production of N and O-substituted monoure-thanes from a primary monoamine and an N-aryl-O-alkyl urethane in the presence of a high boiling alcohol. The primary monoamines employed should be such that it will n~t distill at 1013 mbars or have a boiling point (at 1013 mbars) which is at least 5C (preferably at least 20C) above the boiling point of the aryl amine which is formed during the reaction. The reaction is carried out at elevated temperature and the aryl amine spontaneously formed during the reaction (corresponds to the N-aryl-Mo-2444 ~3~
O-alkyl urethane) is continuously removed from the reac-tion mixture (e.g., by distillation).
Suitable primary amines are any high-boiling organic compounds which, apart from the amino group, are iner-t under the reaction conditions of -the process of the present invention. Examples o~ suitable primary amines are -those corresponding to the formula ~ -~H2 which amines either cannot be distilled at 1013 mbar or have a boiling point at 1013 mbar which is at least 5C
(preferably at least 20C) above the boiling point of the monoamine corresponding to the monourethane used as starting material. In the above formula, Rl represents an aliphatic C4-C18 hydrocarbon radical optionally con-taining inert substituents; a cycloaliphatic C6-C28 hydro-carbon radical optionally containing inert substituents and/or optionally oxygen, sulfur or alkylene groups as bxidge members; an aromatic C6-C28 hydrocarbon radical optionally containing inert substituents and/or oxygen, sulfur or alkylene groups as bridge members; or an araliphatic C7-C28 hydrocarbon radical optionally con-taining inert substituents.
It is preferred to use monoamines corresponding to the above-given formula in which Rl represents a saturated, unsubstituted or halogen (particularly chlorine)-substituted aliphatic Cg-Cl8 hydrocarbon radical; a saturated cycloaliphatic C6-C25 hydrocarbon radical optionally substituted by halogen (particularly chlorine~ or by alkyl or chloroalkyl groups and/or con-taining methylene bridges; or an aromatic C6-C25 hydro-carbon radical optionally substituted by halogen (par-ticularly chlorine) or by alkyl or ch].oroalkyl groups and/or containing methylene bridges.
Mo-2444 ~3~
Specific examples of suitable primary amines are nonyl amlne; decyl amine; undecyl amine; dodecyl amine;
tridecyl amlne; tetradecyl amine; pentadecyl amine; hexa~
decyl amine; heptadecyl amine; stearyl amine; cyclooctyl amine; 4-(trichloromethyl)-cyclohexyl amine; 2-chloro-cycloheptyl amine; bicyclohexyl-4-amine and its isomers;
p-amino-N,N-dlmethyl aniline; 4-aminodiphenyl and its isomers; ~-~-naphthyl amine; o-, m-,p-benzyl aniline;
hexahydrobenzyl aniline; perhydrobenzyl aniline; isomers of benzyl toluidine; isomers of hexahydro~ and perhydro-benzyl toluidine; 1-, 2~, 3 , 4-methyl cyclohexyl amine;
3,4-dichloroaniline; 3,5-dichloroaniline; 4-chloroaniline;
o-, m-, p-toluidine; and 3~chloro-4-methyl aniline.
Relatively high boiling alcohols suitable for use in the process of the present invention include any oryanic compound which contains an aliphatically, cyclo-aliphatically or araliphatically bound, primary or second-ary hydroxyl group, (preferably primary), which has a boiling point at atmospheric pressure of at least 190C
and which, apart from the hydroxyl group, are inert under the reaction conditions~ Suitable relatively high boiling alcohols are, for example, those corresponding to the formula in which R2 represents an aliphatic C6-C18 hydrocarbon radical optionally containing inert substituents and/or ether groups; a cycloaliphatic C8-C15 hydrocarbon radical optionally containing inert substituents; or an arali-phatic C7-C18 hydrocarbon radical optionally containing inert substituents. It is preferred to use alcohols corresponding to the above formula in which R2 represents Mo-2444 7~
a saturated primary aliphatic C8-C18 hydrocarbon radical optionally containing ether bridges.
Specific examples of suitahle alcohols are l-octanol, l-nonanol, l-decanol, l-undecanol, l-dodecanol, l-tetradecanol, l-hexadecanol, l-octadecano:L, 2-nonanol, diethylene glycol monoethyl ether, benzyl alcohol, 2,4,5-~rimethyl cyclohexanol, 3-methyl benzyl alcohol, cyclooctanol, 1,2,4-trimethyl-5-cyclohexanol and 4-methyl benzyl alcohol. Mixtures of these alcohols may of course also be used.
N~aryl-O-alkyl urethanes suitable as starting materia].s in the process oE the present invention include those corresponding to the formula R3 N~coo-R
in which R3 represents an aromatic C6-C10 hydrocarbon radical optionally containing methyl substituents and R4 represents an allphatic Cl-C18 hydrocarbon radical optionally containing inert substituents and/or ether bridges, a cycloaliphatic C4-C15 hydrocarbon radical optionally containing inert substituents or an arali-phatic C7-C18 hydrocarbon radical optionally containing inert substituents. It is preferred to use urethanes corresponding to the above given formula in which R3 represents a phenyl or tolyl radical, particularly a phenyl radical and R4 represents a radical within the definition o R2 and most preferably which is the same as R2.
Specific examples of such urethane starting materials are N-phenyl~ (or N-tolyl-)-O-l-octyl-, -l-decyl-, -l-undecyl-, -l-dodecyl-, -l-tetradecyl-, -l-hexadecyl-, -l-octadecyl-, -2-nonyl-, -etho~y-ethoxy-ethyl-, -2,4,5-trimethyl cyclohexyl-, -3-methyl-~enzyl- and -4-methyl-benzyl-urethane. The alcohol on Mo-2444 which the urethane is based contains primary or secondary, preferably primary hydroxyl groups.
It is possible to use a urethane startiny material corresponding to the above-yiven formula in which the radical R4 is derived ~rom an alcohol boiling below 1~0C at atmospheric pressure in the process of the present invention. It is also possible to use a urethane starting material corresponding to the above formula in which R4 represents a primary or secondary (preferably a primary) saturated aliphatic hydrocarbon radical con-taining from l to 4 carbon atoms in the process of the present invention. Where the urethane starting material contains such R4 groups, the low-boiling alcohol R4-oH
is displaced by the high-boiling alcohol R2-OH before, during and/or after the reaction in which the aryl amine R3-NH2 is formed. This low-boiling alcohol may be distilled off from the reaction mixture before and/or together with and/or after the aryl amine is removed from the reaction mixture. In general, this trans-urethanation process will take place more quickly than the reaction of the present invention. Consequently, use of R4 groups having corresponding low boiling alco-hols is tantamount to in situ production of the urethane starting material of the present invention.
The urethane starting material of the present invention may be produced by any known process such as reactlon of aryl amine R3-NH2 with urea and alcohol R -OH. The urethane starting materials based on alcohols R4-oH havi.ng a boiling point at atmospheric pressure of 30 at least 190C which are preferably used in the process of the present invention may also be produced by trans-urethanation of corresponding (with regard to the N-substituent) urethanes based on low-boiling alcohols prior to carrying out the process of the present inven-35 tionO Such trans-urethanation may be conducted by heating the urethane based on a low-boiling alcohol to approximately 130 to 300C in the presence of a 0.1 to Mo-2444 3~78 5-molar excess o~ an alcohol R2-OH, and continuously removing the low-boiling alcohol formed by distillation.
The N-aryl-O-alkyl urethanes based on low-bolling alcohols required for this purpose may be produced by known methods.
In the practical application of the process of the presen-t invention, the reactants are generally used in quantities such that the molar ratio of high boiling alcohol to monoamine is from 1:1 to 50:1, pre~erably from 2:1 to lS:l. The reactants may also be used in quanti-ties such that the molar ratio of urethane to monoamine is from 1:1 to 5:1 pre~erably from 1:1 to 2.5:1. The molar ratio of high boilin~ alcohol to urethane is general-ly between 1:1 and 10:1.
It is also possible, although not generally necessary, to use a catalyst in carrying out the process of the present invention. Suitable catalysts include any catalyst which has a catalytic effect upon the esterification of carboxylic acids. Examples of such catalysts are: (i) inorganic or organic bases which are inert under the reaction conditions, (ii) Lewis acids and (iii) salts or complex compounds, particularly chelates of transition metals.
Specific examples of bases inert under reaction conditions which are suitable catalysts include tertiary amines such as triisopentyl amine, diethyl benzyl amine, N,N-dimethyl benzyl amine, hexahydro-dimethyl aniline, N-ethyl piperazine, diethyl-(2-methoxy-propyl)-amine, 2-(diethylaminoethyl)-phenyl ether, ethoxyl morpholine, N-(2-diethylaminoethyl)-benzamide, N-(2-diethylamino-ethyl)-propionamide, 1,4-diaza-(2,2,2)-bicyclooctane, N,N-dimethyl~4-aminopyridine, 1 azabicyclo-heptanes, l-azabicyclooctanes; saturated heterocyclic polyamines, such as 3-methyl conidine; 1-azabicyclo-(3,2,1~-octane and quinuclidines; alcoholates such as sodium methylate;
Mo-2444 32~
sodium ethylate, potassium-t-butylate, titanium tetra-butylate; phenolates such as sodium phenolate and titanium tetraphenolate; inorganic bases such as beryllium hydroxide and sodium, potassium, lithium, ma~nesium, 5 barium and calcium hydroxide; basic alkali salts such as sodium carbonate, sodium sulfide, potassium carbonate and trisodium phosphate and also alkali salts of fatty acids and sulfonic acids. Lewis acids suitable as catalysts are iron-II-chloride, iron-III-chloride, zinc chloride, 10 tin-II-chloride, tin-IV-chloride, aluminum chloride, zinc cyanide, thallium trichloride, boron trifluoride and boron trifluoride etherate.
Suitable catalysts which are salts of transition metals (which do not already belong to the group of Lewis 15 acids) and also complex compounds (particularly chelates) of these metals include: cobalt, manganese and lead naphthanates; iron oleates and carbonyls, acetal aceto-nates of iron, nickel, cobalt, zinc, lead, aluminum, manganese, magnesium, molybdenum, titanium, thorium, zirconium and vanadium; bis-(dibenzoyl methane)-copper;
bis-(ethyl acetoacetate)-copper, -iron; coordination compounds of titanium, zirconium, hafnium, thorium and manganese with ~-diketones, ~-keto esters and ~-hydroxy aldehydes; dibutyl tin ~dilaurate; dibutyl tin diacetate;
25 di-(2-ethylhexyl)-tin oxide; dioctyl tin oxide; tin salts of Cl-C20-carboxylic acids, such as tin-II-naphthenate, hexoate, palmitate, stearate and dimethyl valerate, acetates, chlorides, sulfates and octoates of divalent or trivalent cobalt, monovalent or divalent copper, zinc or divalent lead.
Particularly suitable catalysts are ZillC
chloride, zinc acetate, zinc octoate, zinc oxide, zinc cyanide, dibutyl tin oxide, dibutyl tin diethylate, dimethyl tin dichloride, tin-II~chloride, tin-IV-chloride, 35 dibutyl tin dilaurate, coba].t triacetate, cobalt tri-Mo~2444 32~
chloride, cobalt trioctoate, copper~ acetate, copper-I-chloride, copper-II-sulfate, lead acetate and lead chloride.
The quantity in which the particular catalyst may be used is generally between 1 ppm and 20 wt. ~, prefer-ably between 100 ppm and 5 wt. % (based on the sum of the alcohol, urethane and amine starting materials). In practice, it is generally advantageous to keep the con-centration of catalyst as low as possible. The optimum catalyst concentration which depends upon the starting materials and the activity of the particular catalyst may be readily determined by a simple preliminary test.
Where a monourethane which is based on a mono-isocyanate that does not distill is produced in accord-ance with the present invention, it is preferred that acatalyst not be used in order to avoid formation of mono-isocyanates contaminated by catalyst.
The reaction of the invention is generally carried out at a temperature in the range from 180 to 300C, preferably from 200 to 250C under a pressure of from 0.1 to 1500 mbars, preferably from 10 to 1000 mbars and most preferably from 200 to 800 mbars (i.e. prefer-ably under reduced pressure). The pressure is advan-tageously adjusted in such a way that aryl amine R3-NH2 ~5 or a mixture of aryl amine R3-NH2 and alcohol R2-OH and, optionally alcohol R4-oH and, optionally, small quanti-ties of amine Rl~NH2 (but preferably pure aryl amine R3-NH2) distill throu~h an effective column into a receiver.
I'he reaction in accordance with the present invention is generally complete after from 1 to 20 hours, preferably from 2 to 10 hours and, most preferably from 3 to 6 hours.
Mo-2~44 3~
The process of the present invention is prefer~
ably carried out by initially introducing the high boil-ing alcohol and urethane starting materlals in the above-mentioned quantitative ratios into the reaction vessel. Subsequently, the monoamine starting material (optionally in solution in the alcohol R2-OH) is intro-duced with thorough mixing into the reaction vessel.
The volatile constituents of the reaction mixture and the volatile by-products formed during the reaction of the present invention, (particularly the aryl amine R3-NH2 formed) should be continuously removed from the reaction mixture (e.g., by distillation) so that the reaction equilibrium is forced towards formation of the required end product. This continuous removal of such products ensures a substantiall~ ~uantitative conversion of the monoamine to urethane. On completion of the reaction, the high boiling alcohol present in excess may be removed from the end product by vacuum distillation, preferably in a thin-layer evaporator.
The end products formed by the process of the present invention are N,O-substituted monourethanes corresponding to the formula Rl-NHCOO-R
in which Rl and R2 are as defined above.
Where the urethane starting material is based on a high boiling alcohol which is not identical with the alcohol R2-OH is used, monourethanes corresponding to the formula Rl-NHCooR4 as well as those corresponding to the formula Rl-NHCOOR2 are formed.
Where the urethane star-ting material has an alcohol component which corresponds to the high boiling alcohol, the process of the present invention takes place in accordance with the following e~uation:
RlNH2 + R3-NHCoo-R2 ~ OH> Rl-NHCOOR2 -~ R3-NH2.
Mo-2444 ~3~
Where the urethane starting material is based on readily volatile alcohols R4-oH, the reaction of the present invention takes place in accordance with the following equation:
R NH2 + R3-NHCoo-R ~ R -OH
R NHCOOR -~ R -NH2 + R4-oH.
It must be regarded as surprising that hardly any N,N'-disubstituted urea is formed in the process of the present invention e-~en though the reaction is carried 10 out at a temperature at which urethanes are normally split into the isocyanates and alcohols on which they are based. I~ had been expected that the isocyanate RlNCO present in addition to the amine starting material would combine with the primary amine to form unwanted 15 N,N'-disubstituted urea. However, this undesirable secondary reaction does not occur to any significant degreeO
The end products obtained by the process of the present invention may be trans-urethanized with low-20 boiling alcohols havin~ a boiling point at atmosphericpressure of below 140C. C1-C4-alkanols corresponding to the formula R -OH
in which 25 R5 represents an aliphatic Cl-C4 hydrocarbon radical are examples of such low-boiling alcohols. Such trans-urethanation yields monourethanes corresponding to the formula Rl-NHCOOR
30 Transurethanation is generally conducted under pressure at a temperature in the range from 120 to 300~C. The alcohol ~5-oH is generally used in a quantity of from 5 to 60 moles (preferabl~ from 10 to 20 moles) Mo-2444 of alcohol for each urethane group. After a reaction time of from 0.5 to 10 hours (preferably from 1 to 4 hours) the low-hoiling alcohol i5 evaporated off. The high-boiling alcohol released is subsequently distill,ed off from the reaction mixture at 0.1 to 5 mbar.
The mo~ourethanes thus obtained which correspond to the formula may then be thermally split off in known manner ,into 0 organic monoisocyanates corresponding to the formula and alcohols corresponding to the formula R -OH.
Having thus described our invention, the 15 following Examples are given by way of illustration.
The percentages quoted in the following Examples represent percentages by weight unless otherwise indicated.
EXAMPI,ES
305 g (1 mole) of N-phenyl O-dodecyl urethane and 558 g of dodecanol were introduced into a 2-liter four-necked flask equipped with a stirrer, a heatable dropping funnel and a packed column and heated with ~tirring to 240C. 185 g (1 mole) of molten dodecyl amine were added dropwise over a period of 50 minutes under a pressure of 800 mbars. The aniline which formed was distilled off through the column. The reaction mixture was then stirred for another 3 hours 30 during which aniline was removed by distillation (the vacuum was increased to 460 mbars~. 377 g (95% of the Mo~2444 !~
theoretical) of N-dodecyl-O-dodecyl urethane (determined by gel chromatoyraphy) were formed.
305 g (1 mole) of N-phenyL-O-dodecyl urethane and 558 g of dodecanol were heated with stirriny to 240C
in the apparatus descrihed in Example 1. 269 y (1 mole) of stearyl amine were added dropwise over a period of 1 hour at 800 mbar. The aniline formed was distilled off.
The reaction mixture was then stirred for 4.5 hours at the same temperature. The vacuum was steadily increased to 420 mbars and 89.8 g (97~ of the theoretical) of aniline were distilled off. The crude product contained 461 g (96~ of the theoretical) of N-stearyl-O-dodecyl urethane (determined by gel chromatography).
-162 g (1 mole) of 3,4-dichloroaniline, 381.2 g (1.25 moles) of N-phenyl-O-dodecyl urethane and 372 g of dodecanol were heated with stirring to 240C in a 2-liter three-necked flask equipped with a stirrer, 20 internal thermometer and packed column. The aniline formed during the reaction was distilled off undex a ~acuum of 800 mbars. After a reaction time of 6.75 hours, during which the vacuum was contlnuously increased to 300 mbar, 34.8 g of aniline (91% of the 25 theoretical) and 2.8 gof 3,4-dichloroaniline were found in the distillate. Analysis by high-pressure liquid chromatography indicated that the crude product contained 337.3 g (92~ of the theoretical) of N-(3,4-dichloro-phenyl)-O dodecyl urethane.
381.2 g ~1.25 moles) of N-phenyl-O-dodecyl urethane and 372 g of dodecanol were heated to 240C
in the apparatus described in Example 1. 127~5 g (1 mole) of molten p-chloroaniline were then ~dded dropwise Mo-2444 ~3~78 with stirring over a period of 1 hour. 84.6 g (91% of the theoretical) of aniline and 18.0 g o~ p-chloro-aniline were distilled o~f over a period of ~.S hours under a vacuum of 800 to 335 mbars. As determined by high-pressure liquid chromatography, the crude product contained 264.5 g (91~ of the theoretical).
129.5 g (1.25 mole) of N-phenyl-O-dodecyl urethane and 372 g of dodecanol were heated with stirriny to 240C in the apparatus described in E~ample 1. 125.9 g (0.915 mole) of 3-chloro-4-methyl aniline were then added dropwise over a period of 1 hour. The aniline which formed was distilled off at 600 to 370 mbars.
After a reaction time of 6 hours, the distillate con-tained 75 g (88~ of the theoretical) of aniline and 5.4 gof 3-chloro-4-methyl aniline. 268.5 g (88~ o the theoretical) of N-(3-chloro-4-methyl phenyl)-O-dodecyl urethane were in the reaction flask (determined by high-pressure liquid chromatography).
381 g ~1.25 moles) of N~phenyl-O-dodecyl urethane and 183 g (1 mole) of 4-benzyl aniline were reacted in 372 g of dodecanol in the apparatus described in ~xample 1. After a reaction time of 5.25 hours, 76.4 g (82~o of the theoretical) of aniline and 3.1 g of
o-, m-, p-toluidine; and 3~chloro-4-methyl aniline.
Relatively high boiling alcohols suitable for use in the process of the present invention include any oryanic compound which contains an aliphatically, cyclo-aliphatically or araliphatically bound, primary or second-ary hydroxyl group, (preferably primary), which has a boiling point at atmospheric pressure of at least 190C
and which, apart from the hydroxyl group, are inert under the reaction conditions~ Suitable relatively high boiling alcohols are, for example, those corresponding to the formula in which R2 represents an aliphatic C6-C18 hydrocarbon radical optionally containing inert substituents and/or ether groups; a cycloaliphatic C8-C15 hydrocarbon radical optionally containing inert substituents; or an arali-phatic C7-C18 hydrocarbon radical optionally containing inert substituents. It is preferred to use alcohols corresponding to the above formula in which R2 represents Mo-2444 7~
a saturated primary aliphatic C8-C18 hydrocarbon radical optionally containing ether bridges.
Specific examples of suitahle alcohols are l-octanol, l-nonanol, l-decanol, l-undecanol, l-dodecanol, l-tetradecanol, l-hexadecanol, l-octadecano:L, 2-nonanol, diethylene glycol monoethyl ether, benzyl alcohol, 2,4,5-~rimethyl cyclohexanol, 3-methyl benzyl alcohol, cyclooctanol, 1,2,4-trimethyl-5-cyclohexanol and 4-methyl benzyl alcohol. Mixtures of these alcohols may of course also be used.
N~aryl-O-alkyl urethanes suitable as starting materia].s in the process oE the present invention include those corresponding to the formula R3 N~coo-R
in which R3 represents an aromatic C6-C10 hydrocarbon radical optionally containing methyl substituents and R4 represents an allphatic Cl-C18 hydrocarbon radical optionally containing inert substituents and/or ether bridges, a cycloaliphatic C4-C15 hydrocarbon radical optionally containing inert substituents or an arali-phatic C7-C18 hydrocarbon radical optionally containing inert substituents. It is preferred to use urethanes corresponding to the above given formula in which R3 represents a phenyl or tolyl radical, particularly a phenyl radical and R4 represents a radical within the definition o R2 and most preferably which is the same as R2.
Specific examples of such urethane starting materials are N-phenyl~ (or N-tolyl-)-O-l-octyl-, -l-decyl-, -l-undecyl-, -l-dodecyl-, -l-tetradecyl-, -l-hexadecyl-, -l-octadecyl-, -2-nonyl-, -etho~y-ethoxy-ethyl-, -2,4,5-trimethyl cyclohexyl-, -3-methyl-~enzyl- and -4-methyl-benzyl-urethane. The alcohol on Mo-2444 which the urethane is based contains primary or secondary, preferably primary hydroxyl groups.
It is possible to use a urethane startiny material corresponding to the above-yiven formula in which the radical R4 is derived ~rom an alcohol boiling below 1~0C at atmospheric pressure in the process of the present invention. It is also possible to use a urethane starting material corresponding to the above formula in which R4 represents a primary or secondary (preferably a primary) saturated aliphatic hydrocarbon radical con-taining from l to 4 carbon atoms in the process of the present invention. Where the urethane starting material contains such R4 groups, the low-boiling alcohol R4-oH
is displaced by the high-boiling alcohol R2-OH before, during and/or after the reaction in which the aryl amine R3-NH2 is formed. This low-boiling alcohol may be distilled off from the reaction mixture before and/or together with and/or after the aryl amine is removed from the reaction mixture. In general, this trans-urethanation process will take place more quickly than the reaction of the present invention. Consequently, use of R4 groups having corresponding low boiling alco-hols is tantamount to in situ production of the urethane starting material of the present invention.
The urethane starting material of the present invention may be produced by any known process such as reactlon of aryl amine R3-NH2 with urea and alcohol R -OH. The urethane starting materials based on alcohols R4-oH havi.ng a boiling point at atmospheric pressure of 30 at least 190C which are preferably used in the process of the present invention may also be produced by trans-urethanation of corresponding (with regard to the N-substituent) urethanes based on low-boiling alcohols prior to carrying out the process of the present inven-35 tionO Such trans-urethanation may be conducted by heating the urethane based on a low-boiling alcohol to approximately 130 to 300C in the presence of a 0.1 to Mo-2444 3~78 5-molar excess o~ an alcohol R2-OH, and continuously removing the low-boiling alcohol formed by distillation.
The N-aryl-O-alkyl urethanes based on low-bolling alcohols required for this purpose may be produced by known methods.
In the practical application of the process of the presen-t invention, the reactants are generally used in quantities such that the molar ratio of high boiling alcohol to monoamine is from 1:1 to 50:1, pre~erably from 2:1 to lS:l. The reactants may also be used in quanti-ties such that the molar ratio of urethane to monoamine is from 1:1 to 5:1 pre~erably from 1:1 to 2.5:1. The molar ratio of high boilin~ alcohol to urethane is general-ly between 1:1 and 10:1.
It is also possible, although not generally necessary, to use a catalyst in carrying out the process of the present invention. Suitable catalysts include any catalyst which has a catalytic effect upon the esterification of carboxylic acids. Examples of such catalysts are: (i) inorganic or organic bases which are inert under the reaction conditions, (ii) Lewis acids and (iii) salts or complex compounds, particularly chelates of transition metals.
Specific examples of bases inert under reaction conditions which are suitable catalysts include tertiary amines such as triisopentyl amine, diethyl benzyl amine, N,N-dimethyl benzyl amine, hexahydro-dimethyl aniline, N-ethyl piperazine, diethyl-(2-methoxy-propyl)-amine, 2-(diethylaminoethyl)-phenyl ether, ethoxyl morpholine, N-(2-diethylaminoethyl)-benzamide, N-(2-diethylamino-ethyl)-propionamide, 1,4-diaza-(2,2,2)-bicyclooctane, N,N-dimethyl~4-aminopyridine, 1 azabicyclo-heptanes, l-azabicyclooctanes; saturated heterocyclic polyamines, such as 3-methyl conidine; 1-azabicyclo-(3,2,1~-octane and quinuclidines; alcoholates such as sodium methylate;
Mo-2444 32~
sodium ethylate, potassium-t-butylate, titanium tetra-butylate; phenolates such as sodium phenolate and titanium tetraphenolate; inorganic bases such as beryllium hydroxide and sodium, potassium, lithium, ma~nesium, 5 barium and calcium hydroxide; basic alkali salts such as sodium carbonate, sodium sulfide, potassium carbonate and trisodium phosphate and also alkali salts of fatty acids and sulfonic acids. Lewis acids suitable as catalysts are iron-II-chloride, iron-III-chloride, zinc chloride, 10 tin-II-chloride, tin-IV-chloride, aluminum chloride, zinc cyanide, thallium trichloride, boron trifluoride and boron trifluoride etherate.
Suitable catalysts which are salts of transition metals (which do not already belong to the group of Lewis 15 acids) and also complex compounds (particularly chelates) of these metals include: cobalt, manganese and lead naphthanates; iron oleates and carbonyls, acetal aceto-nates of iron, nickel, cobalt, zinc, lead, aluminum, manganese, magnesium, molybdenum, titanium, thorium, zirconium and vanadium; bis-(dibenzoyl methane)-copper;
bis-(ethyl acetoacetate)-copper, -iron; coordination compounds of titanium, zirconium, hafnium, thorium and manganese with ~-diketones, ~-keto esters and ~-hydroxy aldehydes; dibutyl tin ~dilaurate; dibutyl tin diacetate;
25 di-(2-ethylhexyl)-tin oxide; dioctyl tin oxide; tin salts of Cl-C20-carboxylic acids, such as tin-II-naphthenate, hexoate, palmitate, stearate and dimethyl valerate, acetates, chlorides, sulfates and octoates of divalent or trivalent cobalt, monovalent or divalent copper, zinc or divalent lead.
Particularly suitable catalysts are ZillC
chloride, zinc acetate, zinc octoate, zinc oxide, zinc cyanide, dibutyl tin oxide, dibutyl tin diethylate, dimethyl tin dichloride, tin-II~chloride, tin-IV-chloride, 35 dibutyl tin dilaurate, coba].t triacetate, cobalt tri-Mo~2444 32~
chloride, cobalt trioctoate, copper~ acetate, copper-I-chloride, copper-II-sulfate, lead acetate and lead chloride.
The quantity in which the particular catalyst may be used is generally between 1 ppm and 20 wt. ~, prefer-ably between 100 ppm and 5 wt. % (based on the sum of the alcohol, urethane and amine starting materials). In practice, it is generally advantageous to keep the con-centration of catalyst as low as possible. The optimum catalyst concentration which depends upon the starting materials and the activity of the particular catalyst may be readily determined by a simple preliminary test.
Where a monourethane which is based on a mono-isocyanate that does not distill is produced in accord-ance with the present invention, it is preferred that acatalyst not be used in order to avoid formation of mono-isocyanates contaminated by catalyst.
The reaction of the invention is generally carried out at a temperature in the range from 180 to 300C, preferably from 200 to 250C under a pressure of from 0.1 to 1500 mbars, preferably from 10 to 1000 mbars and most preferably from 200 to 800 mbars (i.e. prefer-ably under reduced pressure). The pressure is advan-tageously adjusted in such a way that aryl amine R3-NH2 ~5 or a mixture of aryl amine R3-NH2 and alcohol R2-OH and, optionally alcohol R4-oH and, optionally, small quanti-ties of amine Rl~NH2 (but preferably pure aryl amine R3-NH2) distill throu~h an effective column into a receiver.
I'he reaction in accordance with the present invention is generally complete after from 1 to 20 hours, preferably from 2 to 10 hours and, most preferably from 3 to 6 hours.
Mo-2~44 3~
The process of the present invention is prefer~
ably carried out by initially introducing the high boil-ing alcohol and urethane starting materlals in the above-mentioned quantitative ratios into the reaction vessel. Subsequently, the monoamine starting material (optionally in solution in the alcohol R2-OH) is intro-duced with thorough mixing into the reaction vessel.
The volatile constituents of the reaction mixture and the volatile by-products formed during the reaction of the present invention, (particularly the aryl amine R3-NH2 formed) should be continuously removed from the reaction mixture (e.g., by distillation) so that the reaction equilibrium is forced towards formation of the required end product. This continuous removal of such products ensures a substantiall~ ~uantitative conversion of the monoamine to urethane. On completion of the reaction, the high boiling alcohol present in excess may be removed from the end product by vacuum distillation, preferably in a thin-layer evaporator.
The end products formed by the process of the present invention are N,O-substituted monourethanes corresponding to the formula Rl-NHCOO-R
in which Rl and R2 are as defined above.
Where the urethane starting material is based on a high boiling alcohol which is not identical with the alcohol R2-OH is used, monourethanes corresponding to the formula Rl-NHCooR4 as well as those corresponding to the formula Rl-NHCOOR2 are formed.
Where the urethane star-ting material has an alcohol component which corresponds to the high boiling alcohol, the process of the present invention takes place in accordance with the following e~uation:
RlNH2 + R3-NHCoo-R2 ~ OH> Rl-NHCOOR2 -~ R3-NH2.
Mo-2444 ~3~
Where the urethane starting material is based on readily volatile alcohols R4-oH, the reaction of the present invention takes place in accordance with the following equation:
R NH2 + R3-NHCoo-R ~ R -OH
R NHCOOR -~ R -NH2 + R4-oH.
It must be regarded as surprising that hardly any N,N'-disubstituted urea is formed in the process of the present invention e-~en though the reaction is carried 10 out at a temperature at which urethanes are normally split into the isocyanates and alcohols on which they are based. I~ had been expected that the isocyanate RlNCO present in addition to the amine starting material would combine with the primary amine to form unwanted 15 N,N'-disubstituted urea. However, this undesirable secondary reaction does not occur to any significant degreeO
The end products obtained by the process of the present invention may be trans-urethanized with low-20 boiling alcohols havin~ a boiling point at atmosphericpressure of below 140C. C1-C4-alkanols corresponding to the formula R -OH
in which 25 R5 represents an aliphatic Cl-C4 hydrocarbon radical are examples of such low-boiling alcohols. Such trans-urethanation yields monourethanes corresponding to the formula Rl-NHCOOR
30 Transurethanation is generally conducted under pressure at a temperature in the range from 120 to 300~C. The alcohol ~5-oH is generally used in a quantity of from 5 to 60 moles (preferabl~ from 10 to 20 moles) Mo-2444 of alcohol for each urethane group. After a reaction time of from 0.5 to 10 hours (preferably from 1 to 4 hours) the low-hoiling alcohol i5 evaporated off. The high-boiling alcohol released is subsequently distill,ed off from the reaction mixture at 0.1 to 5 mbar.
The mo~ourethanes thus obtained which correspond to the formula may then be thermally split off in known manner ,into 0 organic monoisocyanates corresponding to the formula and alcohols corresponding to the formula R -OH.
Having thus described our invention, the 15 following Examples are given by way of illustration.
The percentages quoted in the following Examples represent percentages by weight unless otherwise indicated.
EXAMPI,ES
305 g (1 mole) of N-phenyl O-dodecyl urethane and 558 g of dodecanol were introduced into a 2-liter four-necked flask equipped with a stirrer, a heatable dropping funnel and a packed column and heated with ~tirring to 240C. 185 g (1 mole) of molten dodecyl amine were added dropwise over a period of 50 minutes under a pressure of 800 mbars. The aniline which formed was distilled off through the column. The reaction mixture was then stirred for another 3 hours 30 during which aniline was removed by distillation (the vacuum was increased to 460 mbars~. 377 g (95% of the Mo~2444 !~
theoretical) of N-dodecyl-O-dodecyl urethane (determined by gel chromatoyraphy) were formed.
305 g (1 mole) of N-phenyL-O-dodecyl urethane and 558 g of dodecanol were heated with stirriny to 240C
in the apparatus descrihed in Example 1. 269 y (1 mole) of stearyl amine were added dropwise over a period of 1 hour at 800 mbar. The aniline formed was distilled off.
The reaction mixture was then stirred for 4.5 hours at the same temperature. The vacuum was steadily increased to 420 mbars and 89.8 g (97~ of the theoretical) of aniline were distilled off. The crude product contained 461 g (96~ of the theoretical) of N-stearyl-O-dodecyl urethane (determined by gel chromatography).
-162 g (1 mole) of 3,4-dichloroaniline, 381.2 g (1.25 moles) of N-phenyl-O-dodecyl urethane and 372 g of dodecanol were heated with stirring to 240C in a 2-liter three-necked flask equipped with a stirrer, 20 internal thermometer and packed column. The aniline formed during the reaction was distilled off undex a ~acuum of 800 mbars. After a reaction time of 6.75 hours, during which the vacuum was contlnuously increased to 300 mbar, 34.8 g of aniline (91% of the 25 theoretical) and 2.8 gof 3,4-dichloroaniline were found in the distillate. Analysis by high-pressure liquid chromatography indicated that the crude product contained 337.3 g (92~ of the theoretical) of N-(3,4-dichloro-phenyl)-O dodecyl urethane.
381.2 g ~1.25 moles) of N-phenyl-O-dodecyl urethane and 372 g of dodecanol were heated to 240C
in the apparatus described in Example 1. 127~5 g (1 mole) of molten p-chloroaniline were then ~dded dropwise Mo-2444 ~3~78 with stirring over a period of 1 hour. 84.6 g (91% of the theoretical) of aniline and 18.0 g o~ p-chloro-aniline were distilled o~f over a period of ~.S hours under a vacuum of 800 to 335 mbars. As determined by high-pressure liquid chromatography, the crude product contained 264.5 g (91~ of the theoretical).
129.5 g (1.25 mole) of N-phenyl-O-dodecyl urethane and 372 g of dodecanol were heated with stirriny to 240C in the apparatus described in E~ample 1. 125.9 g (0.915 mole) of 3-chloro-4-methyl aniline were then added dropwise over a period of 1 hour. The aniline which formed was distilled off at 600 to 370 mbars.
After a reaction time of 6 hours, the distillate con-tained 75 g (88~ of the theoretical) of aniline and 5.4 gof 3-chloro-4-methyl aniline. 268.5 g (88~ o the theoretical) of N-(3-chloro-4-methyl phenyl)-O-dodecyl urethane were in the reaction flask (determined by high-pressure liquid chromatography).
381 g ~1.25 moles) of N~phenyl-O-dodecyl urethane and 183 g (1 mole) of 4-benzyl aniline were reacted in 372 g of dodecanol in the apparatus described in ~xample 1. After a reaction time of 5.25 hours, 76.4 g (82~o of the theoretical) of aniline and 3.1 g of
4-benzyl aniline were distilled off under a pressure of from 800 to 280 mbarsO As determined by hi~h-pre~sure liquid chromatography, the reaction flask contained 299.7 g (77~ of the theoretical) of N-(4-benzyl-phenyl)-O-dodecyl urethane.
EXAMP~E 7 381.3 g ~1~25 moles) of N-phenyl-O-dodecyl urethane were heated with stirring to 240C in 372 g of dodecanol in a 2-liter mul~1-necked flask equipped wlth Mo-2444 3~
a stirrer, dropping funnel and packed column. 107 g (1 mole) of m-toluidine were then added dropwise over a period of 30 minutes under a vacuum of 600 mbars. The vacuum increased to 350 mbars over a period of 6.5 hours, during which 67.4 g of aniline and 30.1 g of toluidine were distilled off. As determined by high-pressure liquid chromatography, the reaction flask contained 210.7 g (92~ of the theoretical) of N-(m-tolyl)-O-dodecyl urethane.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo-2444
EXAMP~E 7 381.3 g ~1~25 moles) of N-phenyl-O-dodecyl urethane were heated with stirring to 240C in 372 g of dodecanol in a 2-liter mul~1-necked flask equipped wlth Mo-2444 3~
a stirrer, dropping funnel and packed column. 107 g (1 mole) of m-toluidine were then added dropwise over a period of 30 minutes under a vacuum of 600 mbars. The vacuum increased to 350 mbars over a period of 6.5 hours, during which 67.4 g of aniline and 30.1 g of toluidine were distilled off. As determined by high-pressure liquid chromatography, the reaction flask contained 210.7 g (92~ of the theoretical) of N-(m-tolyl)-O-dodecyl urethane.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo-2444
Claims (14)
1. A process for the production of N,O-substituted monourethanes comprising:
a) reacting (i) an N-aryl-O-alkyl urethane with (ii) a primary monoamine which does not distill off at 1013 mbar or which has a boiling point at 1013 mbar that is at least 5°C above the boiling point of aryl amine corresponding to the N-aryl-O-alkyl urethane (i) in the presence of (iii) a high boiling alcohol at elevated temperature to form an aryl amine corresponding to the N-aryl-O-alkyl urethane (i); and b) removing the aryl amine formed in a) from the reaction mixture.
a) reacting (i) an N-aryl-O-alkyl urethane with (ii) a primary monoamine which does not distill off at 1013 mbar or which has a boiling point at 1013 mbar that is at least 5°C above the boiling point of aryl amine corresponding to the N-aryl-O-alkyl urethane (i) in the presence of (iii) a high boiling alcohol at elevated temperature to form an aryl amine corresponding to the N-aryl-O-alkyl urethane (i); and b) removing the aryl amine formed in a) from the reaction mixture.
2. The process of Claim 1 wherein step b) is carried out by distillation.
3. The process of Claim 1 wherein the primary monoamine (ii) corresponds to the formula R1NH2 in which R1 represents an aliphatic C4-C18 hydrocarbon radical optionally containing inert substituents, a cycloali-phatic C6-C28 hydrocarbon radical optionally containing inert substituents and/or oxygen, sulfur or alkylene groups as bridge members, an aromatic C6-C28 hydro-carbon radical optionally containing inert substituents and/or oxygen, sulfur, or alkylene groups as bridge members or an araliphatic C7-C28 hydrocaxbon radical optionally containing inert substituents.
4. The process of Claim 1 wherein the high-boiling alcohol (iii) is a primary or secondary ali-phatlc, cycloallphatic and/or araliphatic alcohol which has a boiling point at atmospheric pressure of at least 190°C and which corresponds to the formula in which R2 represents an aliphatic C6-C18 hydrocarbon radical optionally containing inert substituents and/or ether groups, a cycloaliphatic C8-C15 hydrocarbon radical optionally containing inert substituents or an arali-phatic C7-C18 hydrocarbon radical optionally containing inert substituents.
5. The process of Claim 1 wherein the N-aryl-O-alkyl urethane (i) corresponds to the formula in which R3 represents an aromatic C6-C10 hydrocarbon radical optionally containing methyl substituents and R4 represents an aliphatic Cl-C18 hydrocarbon radical optionally containing inert substituents and/or ether bridges, a cycloaliphatic C4-C15 hydrocarbon radical optionally containing inert substituents or an arali-phatic C7-C18 hydrocarbon radical optionally containing inert substituents.
6. The process of Claim 1 wherein the high boiling alcohol (iii) corresponds to the alcohol compo-nent of the N-aryl-O-alkyl urethane (i).
7. The process of Claim 6 wherein the N-aryl-O-alkyl urethane (i) is prepared in situ by reacting an N-aryl-O-alkyl urethane having an alcohol component which has a lower boiling point than the reactant high boiling alcohol (iii) with an excess of the high boil-ing alcohol (iii) at an elevated temperature before or during the reaction with primary monoamine (ii) in step a).
Mo-2444
Mo-2444
8. The process of Claim 7 wherein the lower boiling alcohol which forms during the in situ prepara-tion is removed from the reaction mixture by distillation,
9. The process of Claim 1 wherein the reaction of a) is carried out at a temperature of from 180 to 300°C.
10. The process of Claim 1 wherein the reaction of a) is carried out at reduced pressure.
11. The process of Claim 1 wherein step a) is carried out by initially introducing a mixture of N-aryl-O-alkyl urethane (i) with high boiling alcohol (iii) in a molar ratio of (iii) to (i) of from 1:1 to 10:1 into a reaction vessel and heating the mixture to reac-tion temperature before the primary monoamine (ii) is introduced.
12. The process of Claim 11 wherein the primary monoamine (ii) is introduced into the mixture of N-aryl-O-alkyl urethane (i) and high boiling alcohol (iii) with intensive mixing.
13. The process of Claim 12 wherein the primary monoamine (ii) is employed in a quantity such that for every primary amino group present in monoamine (ii) there are from 1 to 5 urethane groups present in the urethane (i).
14. The process of Claim 1 wherein the reaction step a) is conducted in the presence of a catalyst selected from the group consisting of organic bases, inorganic bases, Lewis acids, salts of transition metals, complex compounds of transition metals and mixtures thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823205891 DE3205891A1 (en) | 1982-02-18 | 1982-02-18 | METHOD FOR PRODUCING N- AND O-SUBSTITUTED MONOURETHANES |
| DEP3205891.8 | 1982-02-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1193278A true CA1193278A (en) | 1985-09-10 |
Family
ID=6156112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000420366A Expired CA1193278A (en) | 1982-02-18 | 1983-01-27 | Process for the production of n- and o-substituted monourethanes |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0087047B1 (en) |
| JP (1) | JPS58154545A (en) |
| BR (1) | BR8300777A (en) |
| CA (1) | CA1193278A (en) |
| DE (2) | DE3205891A1 (en) |
| ES (1) | ES519872A0 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2917490A1 (en) * | 1979-04-30 | 1980-11-13 | Basf Ag | METHOD FOR PRODUCING ALIPHATIC AND CYCLOALIPHATIC DI- AND POLYURETHANES |
| DE2917568A1 (en) * | 1979-04-30 | 1980-11-13 | Basf Ag | METHOD FOR PRODUCING AROMATIC DI- AND POLYURETHANES |
| US4375000A (en) * | 1979-04-30 | 1983-02-22 | Basf Aktiengesellschaft | Process for the preparation of an aryl mono-, di-, and/or polyurethane |
| DE3110573A1 (en) * | 1981-03-18 | 1982-10-21 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING N- AND O-SUBSTITUTED DI- AND / OR POLYURETHANES |
-
1982
- 1982-02-18 DE DE19823205891 patent/DE3205891A1/en not_active Withdrawn
-
1983
- 1983-01-27 CA CA000420366A patent/CA1193278A/en not_active Expired
- 1983-02-07 EP EP83101121A patent/EP0087047B1/en not_active Expired
- 1983-02-07 DE DE8383101121T patent/DE3360488D1/en not_active Expired
- 1983-02-17 ES ES519872A patent/ES519872A0/en active Granted
- 1983-02-17 BR BR8300777A patent/BR8300777A/en unknown
- 1983-02-17 JP JP58023887A patent/JPS58154545A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| ES8401018A1 (en) | 1983-12-01 |
| JPS58154545A (en) | 1983-09-14 |
| DE3360488D1 (en) | 1985-09-12 |
| BR8300777A (en) | 1983-11-16 |
| DE3205891A1 (en) | 1983-08-25 |
| EP0087047A3 (en) | 1983-11-23 |
| ES519872A0 (en) | 1983-12-01 |
| JPH034065B2 (en) | 1991-01-22 |
| EP0087047B1 (en) | 1985-08-07 |
| EP0087047A2 (en) | 1983-08-31 |
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