# US 2019/0169115 A1 · Improved process for the preparation of carbamates > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0169115 A1 - Document ID: US20190169115A1 - Status: Published application - Kind: A1 - Application number: 16/321,543 - Filed: 2017-08-03 - Published: 2019-06-06 - Earliest claimed: 2016-08-04 - Assignees: Taminco BVBA - Applicants: Taminco BVBA - Inventors: Frederik Van Waes; Kristof Moonen; Dieter Ulrichts - Web page: https://patentgrep.com/patent/US20190169115A1 ## CPC - C07C 269/04: from amines with formation of carbamate groups - B01J 27/13: Platinum group metals - C07C 271/20: to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract A process for the preparation of N-(dialkylaminoalkyl)-carbamic acid esters, in particular (propyl N-[3-(dimethylamino)propyl] carbamate) comprising an oxidative carbonylation reaction of a compound of general structure (II) wherein each of R1 and R2, equal to or different from each other, are independently selected from an alkyl group having 1 to 10 carbon atoms, which is optionally substituted by at least one halogen atom, an aryl group or an aralkyl group; R3 is selected from an alkyl group having 1 to 36 carbon atoms, which is optionally substituted by at least one halogen atom, an aryl group or an aralkyl group; each of R′, R″ and R4, equal to or different from each other, are independently selected from H, an alkyl group having 1 to 10 carbon atoms, which is optionally substituted by at least one halogen atom, an aryl group or an aralkyl group; and n is an integer in the range from 1 to 8, with a hydroxyl compound of general formula (III), R3—OH (III) and in the presence of a catalyst system. ## Claims ### Claim 1 A process for the preparation of a compound of general structure (I) wherein each of R1 and R2, are equal to or different from each other, and are independently selected from an alkyl group having 1 to 10 carbon atoms, which is optionally substituted by at least one halogen atom, an aryl group or an aralkyl group; R3 is selected from an alkyl group having 1 to 36 carbon atoms, which is optionally substituted by at least one halogen atom, an aryl group or an aralkyl group; each of R′, R″ and R4, are equal to or different from each other, and are independently selected from H, an alkyl group having 1 to 10 carbon atoms, which is optionally substituted by at least one halogen atom, an aryl group or an aralkyl group; n is an integer in the range from 1 to 8, which process comprises an oxidative carbonylation reaction of a compound of general structure (II) wherein R1, R2, R4, R′, R″ and n have the same meaning as defined here above, with a hydroxyl compound of general formula (III), R3-OH (III), wherein R3 has the same meaning as defined here above, and in the presence of a catalyst system, wherein said catalyst system comprises at least one catalyst of the formula XkYl [compound (XkYl)] wherein X is Cu or a metal selected from metals from the Group VIIIB, Y is a halogen, a salt of an organic acid or a salt of an organic compound; and wherein k is an integer 1, 2, 3 or 4 and l is an integer 0, 1, 2, 3 or 4; at least one halogen containing promoter effective to promote said reaction. ### Claim 2 (depends on 1) The process according to claim 1, wherein X in the compound (XkYl) is Cu, Y is selected from the group consisting of chlorine, bromine, iodine, formate, acetate, oxalate, acetylacetonate; k is 1 and l is an integer 1 or 2 or X in the compound (XkYl) is cobalt, nickel, ruthenium, rhodium, palladium or platinum, Y is selected from the group consisting of chlorine, bromine, iodine, formate, acetate, oxalate, acetylacetonate; k is an integer 1, 2, 3 or 4 and l is an integer 0, 1, 2, 3 or 4. ### Claim 3 (depends on 1) The process according to claim 1, wherein the oxidative carbonylation reaction is carried out with a carbon monoxide compound and an oxidizing agent wherein said carbon monoxide compound is pure gaseous carbon monoxide or a gaseous mixture comprising carbon monoxide diluted with other gaseous substances selected from the group consisting of carbon dioxide, halogens or nitrogen gas, preferably pure gaseous carbon monoxide (carbon monoxide (CO), herein after) and wherein said oxidizing agent is selected from the group consisting of pure oxygen (02), ozone, hydrogen peroxide (H2O2) or a gas containing oxygen. ### Claim 4 (depends on 1) The process according to claim 1, wherein the oxidative carbonylation reaction is carried out in the presence of other ingredients (Ing) comprising a ligand, at least one additional inert solvent, an organic acid, an inorganic acid or a Lewis acid. ### Claim 5 (depends on 4) The process according to claim 4, wherein the ingredient (Ing) comprises a ligand wherein said ligand is selected from the group consisting of a phosphine compound, a phosphite compound, a diamine compound, a triamine compound, a carbene compound or a water soluble compound or mixtures thereof, preferably a phosphine compound. ### Claim 6 (depends on 1) The process according to claim 1, wherein the oxidative carbonylation reaction is performed at a pressure of at least 1 bar and at a pressure of at most 150 bar and at a temperature of at least 90° C. and at a temperature of at most 200° C. ### Claim 7 (depends on 1) The process according to claim 1, wherein a mixture (M) is first prepared by admixing the hydroxyl compound of general formula R3-OH (III), wherein R3 has the same meaning as defined above, with the catalyst system as defined above. ### Claim 8 (depends on 7) The process according to claim 7, wherein the mixture (M) comprises the hydroxyl compound of general formula wherein R3 has the same meaning as defined above, the catalyst system, as defined above, and at least one additional inert solvent wherein said additional inert solvent comprises aromatic hydrocarbons, nitriles, ethers, esters, ketones, amides, pyrrolidones and ionic liquids. ### Claim 9 (depends on 8) The process according to claim 8, wherein the compound of general structure (II) is added to the mixture (M) in an amount corresponding to a molar ratio of the compound of general structure (II) to the hydroxyl compound of general formula (III) of at least 0.05:1, and the molar ratio of the compound of general structure (II) to the hydroxyl compound of general formula (III) in the mixture (M) is at most 1.2:1. ### Claim 10 (depends on 7) The process according to claim 7, wherein the process is carried out in the absence of an additional inert solvent and wherein the hydroxyl compound of general formula (III) functions as a solvent. ### Claim 11 (depends on 10) The process according to claim 10, wherein the compound of general structure (II) is added to the mixture (M) in an amount corresponding to a molar ratio of the compound of general structure (II) to the hydroxyl compound of general formula (III) in the mixture (M) of at least 0.01:1 and the molar ratio of the compound of general structure (II) to the hydroxyl compound of general formula (III) in the mixture (M) is at most 0.5:1. ### Claim 12 (depends on 7) The process according to claim 7, wherein the compound of general structure (II) is added intermittently to the mixture (M) or the compound of general structure (II) is added continuously to the mixture (M). ### Claim 13 (depends on 12) The process according to claim 12, wherein the compound of general structure (II) is added continuously to the mixture (M) at an addition rate of at least 30 mmole/h, and the compound of general structure (II) is added continuously to the mixture (M) at an addition rate of at most 250 mmole/h, relative to every mole of hydroxyl compound of general formula (III) present in the mixture (M). ### Claim 14 (depends on 7) The process according to any claim 7, wherein the molar ratio of the catalyst of the formula XkYl [compound (XkYl)] to the compound of general structure (II) in the mixture (M) is at least 0.00001:1 and the molar ratio of the catalyst of the formula XkYl [compound (XkYl)] to the compound of general structure (II) in the mixture (M) is at most 0.5:1. ### Claim 15 (depends on 7) The process according to claim 7, wherein CO and/or the oxidizing agent are added intermittently to the mixture (M) or CO and/or the oxidizing agent are added continuously to the mixture (M) during the reaction. ### Claim 16 (depends on 15) The process according to claim 15, wherein CO is added continuously to the mixture (M) during the reaction and at an addition rate, relative to every mole of compound of general structure (II) present in the mixture (M), of at least 0.8 mole/h and at an addition rate, relative to every mole of compound of general structure (II) present in the mixture (M), of at most 50 mole/h, and the oxidizing agent is added continuously to the mixture (M) during the reaction and at an addition rate, relative to every mole of compound of general structure (II) present in the mixture (M), of at least 100 mmole/h, and at an addition rate, relative to every mole of compound of general structure (II) present in the mixture (M), of at most mmole 2000 mmole/h.