# US 5,349,081 A · Process for preparing isocyanates > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,349,081 A - Document ID: US5349081A - Status: Granted - Kind: A - Application number: 08/006,409 - Filed: 1993-01-21 - Granted: 1994-09-20 - Earliest claimed: 1993-01-21 - Assignees: Monsanto Company - Inventors: William D. McGhee - Web page: https://patentgrep.com/patent/US5349081A ## CPC - C07C 263/04: from or via carbamates or carbamoyl halides - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract A process for preparing isocyanates comprising (a) contacting carbon dioxide and a primary amine in the presence of an aprotic organic solvent and a base selected from the group consisting of a phosphazene compound, an organic, nitrogenous base and mixtures thereof, wherein the organic, nitrogenous base selected from the group consisting of guanidine compounds, amidine compounds, tertiary amines, pyridine and mixtures thereof to produce the corresponding ammonium carbamate salt, and (b) reacting the ammonium carbamate salt with an electrophilic or oxophilic dehydrating agent to produce the corresponding isocyanate. A second embodiment comprises recovering the ammonium carbamate salt of step (a) prior to reacting the ammonium carbamate salt with an electrophilic or oxophilic dehydrating agent in the presence of an aprotic organic solvent and a base selected from the group consisting of a phosphazene compound, an organic, nitrogenous base and mixtures thereof, wherein the organic, nitrogenous base selected from the group consisting of guanidine compounds, amidine compounds, tertiary amines, pyridine and mixtures thereof. ## Claims ### Claim 1 A process for preparing an isocyanate comprising: (a) contacting CO.sub.2 and a primary amine in the presence of an aprotic organic solvent and a base selected from the group consisting of a phosphazene compound, an organic, nitrogenous base and mixtures thereof, wherein said organic, nitrogenous base is selected from the group consisting of guanidine compounds, amidine compounds, tertiary amines, pyridine and mixtures thereof, under reaction conditions of time and temperature sufficient to produce the corresponding ammonium carbamate salt, and (b) reacting said ammonium carbamate salt with an electrophilic or oxophilic dehydrating agent selected from the group consisting of anhydrides having the formulas: ##STR13## thioanhydrides having the formula: ##STR14## and mixtures thereof wherein X and Y are independently selected from the group consisting of ##STR15## R.sub.5 and R.sub.6 are independently selected from the group consisting of alkyl, fluoroalkyl, aryl, alkaryl and aralkyl radicals having 1 to about 22 carbon atoms, or R.sub.5 and R.sub.6 together form a cyclic anhydride or cyclic thioanhydride containing a fused aromatic or cycloaliphatic ring at a temperature of -78.degree. C. to 100.degree. C. and a time sufficient to produce the corresponding isocyanate. ### Claim 2 (depends on 1) The process according to claim 1 wherein said aprotic organic solvent is selected from the group consisting of dichloromethane, tetrahydrofuran, acetonitrile, o-dichlorobenzene, toluene, N,N-dimethylacetamide and pyridine. ### Claim 3 (depends on 2) The process according to claim 2 wherein said aprotic organic solvent is present in at least an amount sufficient to solubilize said ammonium carbamate salt. ### Claim 4 (depends on 1) The process according to claim 1 wherein the ratio of the number of moles of said base to the number of equivalents of amine in said primary amine starting material is 1:1 to about 20:1. ### Claim 5 (depends on 4) The process according to claim 4 wherein the ratio of the number of moles of said base to the number of equivalents of amine in said primary amine starting material is about 2:1 to about 10:1. ### Claim 6 (depends on 1) The process according to claim 1 wherein the ratio of the number of moles of said electrophilic or oxophilic dehydrating agent to the number of equivalents of amine in said primary amine starting material is about 0.4:1 to about 10:1. ### Claim 7 (depends on 1) The process according to claim 1 wherein said primary amine is selected from the group consisting of compounds represented by the formula R--NH.sub.2, polyoxyalkylene diamines represented by the formula: ##STR16## and polyoxyalkylene triamines represented by the formula: ##STR17## wherein R is selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl radicals having 1 to about 22 carbon atoms, a radical represented by the formula: ##STR18## and a radical represented by the formula --R.sub.4 --NH.sub.2, or R as defined above containing nonnucleophilic functional groups; wherein R.sub.1 and R.sub.4 are independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl radicals having 1 to about 22 carbon atoms, m represents an integer from 0 to about 100n represents an integer from 0 to about 8, R.sub.3 is hydrogen or methyl, x+w represents an integer from about 2 to about 70, z represents an integer from 0 to about 90, x+w+z represents an integer from about 2 to about 100, a, b and c independently represent an integer from about 2 to about 30, and A represents a trihydric alcohol initiator. ### Claim 8 (depends on 7) The process according to claim 7 wherein said nonnucleophilic functional groups are selected from the group consisting of esters, amides, urethanes, carbonates and salts thereof. ### Claim 9 (depends on 1) A process according to claim 1 wherein said isocyanate is represented by the formula: R.sub.2 --N.dbd.C.dbd.O wherein R.sub.2 is selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl radicals having 1 to about 22 carbon atoms, a radical represented by the formula: ##STR19## a radical represented by the formula: --R.sub.4 --N.dbd.C.dbd.O, a radical represented by the formula: ##STR20## or R.sub.2 as defined above containing nonnucleophilic functional groups; or said isocyanate is represented by the formula: ##STR21## wherein R.sub.1 and R.sub.4 are independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl radicals having 1 to about 22 carbon atoms, m represents an integer from 0 to about 100, n represents an integer from 0 to about 8, R.sub.3 is hydrogen or methyl, x+w represents an integer from about 2 to about 10, z represents an integer from 0 to about 90, x+w+z represents an integer from about 2 to about 100, a, b and c independently represent an integer from about 2 to about 30, and A represents a trihydric alcohol initiator. ### Claim 10 (depends on 9) The process according to claim 9 wherein said nonnucleophilic functional groups are selected from the group consisting of esters, amides, urethanes, carbonates and salts thereof. ### Claim 11 (depends on 1) The process according to claim 1 wherein said electrophilic or oxophilic dehydrating agent is 2sulfobenzoic anhydride. ### Claim 12 (depends on 1) The process according to claim 1 wherein said temperature of (b) is about -20.degree. C. to about 30.degree. C. ### Claim 13 A process for preparing an isocyanate comprising: (a) contacting CO.sub.2 and a primary amine in the presence of an aprotic organic solvent and a base selected from the group consisting of a phosphazene compound, an organic, nitrogenous base and mixtures thereof wherein said organic, nitrogenous base is selected from the group consisting of guanidine compounds, amidine compounds, tertiary amines, pyridine and mixtures thereof, under reaction conditions of time and temperature sufficient to produce the corresponding ammonium carbamate salt, (b) recovering said ammonium carbamate salt, and (c) reacting said ammonium carbamate salt with an electrophilic or oxophilic dehydrating agent selected from the group consisting of anhydrides having the formulas: ##STR22## thioanhydrides having the formula: ##STR23## and mixtures thereof wherein X and Y are independently selected from the group consisting of ##STR24## R.sub.5 and R.sub.6 are independently selected from the group consisting of alkyl, fluoroalkyl, aryl, alkaryl and aralkyl radicals having 1 to about 22 carbon atoms, or R.sub.5 and R.sub.6 together form a cyclic thioanhydride containing a fused aromatic or cycloaliphatic ring in the presence of an aprotic organic solvent and a base selected from the group consisting of a phosphazene compound, an organic, nitrogenous base and mixtures thereof, wherein said organic, nitrogenous base is selected from the group consisting of guanidine compounds, amidine compounds, tertiary amines, pyridine and mixtures thereof, at a temperature of -78.degree. C. to 100.degree. C. and a time sufficient to produce the corresponding isocyanate. ### Claim 14 (depends on 13) The process according to claim 13 wherein said aprotic organic solvent is selected from the group consisting of dichloromethane, tetrahydrofuran, acetonitrile, o-dichlorobenzene, toluene, N,N-dimethylacetamide and pyridine. ### Claim 15 (depends on 14) The process according to claim 14 wherein said aprotic organic solvent is present in at least an amount sufficient to solubilize said ammonium carbamate salt. ### Claim 16 (depends on 13) The process according to claim 13 wherein the ratio of the number of moles of said base to the number of equivalents of amine in said primary amine starting material in step (a) is 0.5:1 to about 10:1, and the ratio of the number of moles of said base to the number of equivalents of carbamate in said ammonium carbamate salt starting material in step (c) is 0.5:1 to about 10:1. ### Claim 17 (depends on 16) The process according to claim 16 wherein the ratio of the number of moles of said base to the number of equivalents of amine in said primary amine starting material in step (a) is 1:1 to about 5:1, and the ratio of the number of moles of said base to the number of equivalents of carbamate in said ammonium carbamate salt starting material in step (c) is 1:1 to about 5:1. ### Claim 18 (depends on 13) The process according to claim 13 wherein the ratio of the number of moles of said electrophilic or oxophilic dehydrating agent to the number of equivalents of carbamate in said ammonium carbamate salt starting material in step (c) is about 0.4:1 to about 10:1. ### Claim 19 (depends on 13) The process according to claim 13 wherein said primary amine is selected from the group consisting of compounds represented by the formula R--NH.sub.2, polyoxyalkylene diamines represented by the formula: ##STR25## and polyoxyalkylene triamines represented by the formula: ##STR26## wherein R is selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl radials having 1 to about 22 carbon atoms, a radial represented by the formula: ##STR27## and a radical represented by the formula --R.sub.4 --NH.sub.2, or R as defined above containing nonnucleophilic functional groups; wherein R.sub.1 and R.sub.4 are independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl radicals having 1 to about 22 carbon atoms, m represents an integer from 0 to about 100, n represents an integer from 0 to about 8, R.sub.3 is hydrogen or methyl, x+w represents an integer from about 2 to about 70, z represents an integer from 0 to about 90, x+w+z represents an integer from about 2 to about 100, a, b and c independently represent an integer from about 2 to about 30, and A represents a trihydric alcohol initiator. ### Claim 20 (depends on 19) The process according to claim 19 wherein said nonnucleophilic functional groups are selected from the group consisting of esters, amides, urethanes, carbonates and salts thereof. ### Claim 21 (depends on 13) A process according to claim 13 wherein said isocyanate is represented by the formula: R.sub.2 --N.dbd.C.dbd.O wherein R.sub.2 is selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl radicals having 1 to about 22 carbon atoms, a radical represented by the formula: ##STR28## a radical represented by the formula: --R.sub.4--N.dbd.C.dbd.O, a radical represented by the formula: ##STR29## or R.sub.2 as defined above containing nonnucleophilic functional groups; or said isocyanate is represented by the formula: ##STR30## wherein R.sub.1 and R.sub.4 are independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl radicals having 1 to about 22 carbon atoms, m represents an integer from 0 to about 100, n represents an integer from 0 to about 8, R.sub.3 is hydrogen or methyl, x+w represents an integer from about 2 to about 70, z represents an integer from 0 to about 90, x+w+z represents an integer from about 2 to about 100, a, b and c independently represent an integer from about 2 to about 30, and A represents a trihydric alcohol initiator. ### Claim 22 (depends on 21) The process according to claim 21 wherein said nonnucleophilic functional groups are selected from the group consisting of esters, amides, urethanes, carbonates and salts thereof. ### Claim 23 (depends on 13) The process according to claim 13 wherein said electrophilic or oxophilic dehydrating agent is 2-sulfobenzoic anhydride. ### Claim 24 (depends on 13) The process according to claim 13 wherein said temperature of (c) is about -20.degree. C. to about 30.degree. C.