CA2289658A1 - Method for the preparation of carbamates - Google Patents
Method for the preparation of carbamates Download PDFInfo
- Publication number
- CA2289658A1 CA2289658A1 CA002289658A CA2289658A CA2289658A1 CA 2289658 A1 CA2289658 A1 CA 2289658A1 CA 002289658 A CA002289658 A CA 002289658A CA 2289658 A CA2289658 A CA 2289658A CA 2289658 A1 CA2289658 A1 CA 2289658A1
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- reaction
- zinc
- carbamates
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 150000004657 carbamic acid derivatives Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 150000005677 organic carbonates Chemical class 0.000 claims abstract description 11
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical class C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 2
- 150000004998 toluenediamines Chemical class 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 14
- 150000001412 amines Chemical class 0.000 description 13
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 11
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical class CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 9
- -1 aromatic urethanes Chemical class 0.000 description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 9
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 150000003751 zinc Chemical class 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000000527 sonication Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- CNPWIVIIZHULCN-UHFFFAOYSA-N methyl n-[3-(methoxycarbonylamino)-4-methylphenyl]carbamate Chemical compound COC(=O)NC1=CC=C(C)C(NC(=O)OC)=C1 CNPWIVIIZHULCN-UHFFFAOYSA-N 0.000 description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- VXINBUDSGRUYNS-UHFFFAOYSA-N 4-(4-aminophenyl)aniline;methane Chemical compound C.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 VXINBUDSGRUYNS-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000005910 alkyl carbonate group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- JIXDOBAQOWOUPA-UHFFFAOYSA-N 1-fluoro-2-methoxybenzene Chemical compound COC1=CC=CC=C1F JIXDOBAQOWOUPA-UHFFFAOYSA-N 0.000 description 1
- ZWZGXLKXKAPXMZ-UHFFFAOYSA-N 2,2'-dihydroxy-3,3'-dimethoxy-5,5'-dipropyldiphenylmethane Chemical compound COC1=CC(CCC)=CC(CC=2C(=C(OC)C=C(CCC)C=2)O)=C1O ZWZGXLKXKAPXMZ-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- OHKOAJUTRVTYSW-UHFFFAOYSA-N 2-[(2-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC=C1CC1=CC=CC=C1N OHKOAJUTRVTYSW-UHFFFAOYSA-N 0.000 description 1
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical class OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 description 1
- FTZQXOJYPFINKJ-UHFFFAOYSA-N 2-fluoroaniline Chemical compound NC1=CC=CC=C1F FTZQXOJYPFINKJ-UHFFFAOYSA-N 0.000 description 1
- QKRLPMFIDBFKJJ-UHFFFAOYSA-N 2-methylidenebutanedioic acid;zinc Chemical compound [Zn].OC(=O)CC(=C)C(O)=O QKRLPMFIDBFKJJ-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- ZKOGUIGAVNCCKH-UHFFFAOYSA-N 4-phenyl-1,3-dioxolan-2-one Chemical compound O1C(=O)OCC1C1=CC=CC=C1 ZKOGUIGAVNCCKH-UHFFFAOYSA-N 0.000 description 1
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical class CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000004648 butanoic acid derivatives Chemical class 0.000 description 1
- FWBMVXOCTXTBAD-UHFFFAOYSA-N butyl methyl carbonate Chemical compound CCCCOC(=O)OC FWBMVXOCTXTBAD-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- OKQDSOXFNBWWJL-UHFFFAOYSA-N dihexyl carbonate Chemical compound CCCCCCOC(=O)OCCCCCC OKQDSOXFNBWWJL-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 125000005547 pivalate group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- HQBBDVUXOOMFQN-UHFFFAOYSA-L zinc;2,2-dimethylpropanoate Chemical compound [Zn+2].CC(C)(C)C([O-])=O.CC(C)(C)C([O-])=O HQBBDVUXOOMFQN-UHFFFAOYSA-L 0.000 description 1
- DQFGQDPDTGTFFJ-UHFFFAOYSA-L zinc;4-chlorobenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=C(Cl)C=C1.[O-]C(=O)C1=CC=C(Cl)C=C1 DQFGQDPDTGTFFJ-UHFFFAOYSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- YMTQMTSQMKJKPX-UHFFFAOYSA-L zinc;diphenoxide Chemical compound [Zn+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 YMTQMTSQMKJKPX-UHFFFAOYSA-L 0.000 description 1
- JXNCWJJAQLTWKR-UHFFFAOYSA-N zinc;methanolate Chemical compound [Zn+2].[O-]C.[O-]C JXNCWJJAQLTWKR-UHFFFAOYSA-N 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- 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
- C07C269/04—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 from amines with formation of carbamate groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
Abstract
Method for the preparation of carbamates by reaction of aromatic amines with organic carbonates in the presence of a metal based catalyst on an inert carrier support.
Description
METHOD FOR THE PREPARATION OF CARBAMATES
DESCRIPTION
The present invention relates to a method for the preparation of carbamates by reaction of aromatic amines with organic carbonates using a catalyst on an inert support.
It is known to react amines with organic carbonates in order to obtain carbamates.
US-A 5.347.034 discloses a process for producing poly(o-alkylurethanes) of the diphenylmethane series by reacting the corresponding amines with dialkyl ~ o carbonates in the presence of a catalyst, such that the formed poly(O-alkylurethanes) crystallize out in a highly pure form upon cooling.
EP-A 391.473 describes a process for producing carbamates using reduced amounts of catalyst by first reacting an amine with a (cyclo)alkyl carbonate in the presence of a carbamation catalyst to produce a mixture of a carbamate and an urea, further reacting the urea with carbonate to produce the corresponding carbamate, and finally recovering the carbamate from the reaction mixture.
in DE-A 3.202.690 a method for preparing aromatic urethanes is described by reacting aromatic amines and alkylcarbonates in the presence of an alcoholate of an alkali metal or an alkaline earth metal.
2o US-A 4.268.684 discloses a method for the preparation of carbamates by reacting an organic carbonate with an aromatic amine in the presence of certain zinc, tin or cobalt salts which are only active at temperatures of at least 200° C
whereas in US-A 4.268.683 zinc or tin salts are used which are soluble in the reaction mixture at the reaction conditions.
EP-A 48.371 describes the preparation of N,O-disubstituted urethanes by reacting primary amines with dialkylcarbonates in the presence of neutral or basic inorganic or organic lead, titanium, zinc or zirconium compounds.
In JP-A 07.328.435 a catalyst comprising an oxide composition containing Zr and Si is used for the production of carbamates from a diester carbonate and an 3o aliphatic amine in the liquid phase.
An improved method has now been found for the preparation of carbamates by reaction of aromatic amines with organic carbonates.
The invention thus concerns a method for the preparation of carbamates by reaction of aromatic amines with organic carbonates in the presence of a metal based catalyst on an inert carrier support.
The method allows easy recovery of the catalyst, thus improving the economics and environmental impact of the process.
In a further aspect, the invention relates to a catalyst comprising an organic metal salt on an inert carrier support.
Such catalysts show an improved processability in the conversion of aromatic amines to carbamates via reaction with an organic carbonate.
Aromatic amine compounds which can be used in the present method include mono-, di- or poiyamines.
Suitable amines according to the process of the invention include, for example, phenylamine, 4-chlorophenylamine, 2-fluorophenyl amine, 3,4-dichiorophenylamine, aniline, tolylamine, diisopropyl phenyfamine, ~0 2,4'-diaminodiphenyimethane, 4,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane and higher homologs (polyaminopolyphenylmethanes), 2,4-toluenediamine, 2,6-toluenediamine, m-phenylenediamine, 1,5-naphthylenediamine, and mixtures thereof.
Preferred are aromatic di- or polyamines like toluenediamines, i 5 diaminodiphenylmethanes or polyaminopoiyphenylrnethanes or any mixtures thereof.
Suitable organic carbonates include cyclic or alicyclic carbonates such as, for example, ethylene carbonate, propylene carbonate, styrene carbonate, Biphenyl 2o carbonate, methyl phenyl carbonate,dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dihexyl carbonate, methyl ethyl carbonate, methyl butyl carbonate and the like.
Organic or inorganic salts which may used include, for example, acetates, 25 chlorides, nitrates, sulfonates, propionates, isopropanoates, butanoates, 2-ethylhexanoates, n-octoates, isononanoates, benzoates, chlorobenzoates, naphthenates, stearates, itaconates, pivalates, phenolates, acetylacetonates, alkoxides, C,6/C,$ alkenylsuccinoates (ASA), C,2 alkenylsuccinoates (DSA) and the like.
3o Preferred are alkanoates having from 1 to 15 carbons atoms.
Suitable catalysts include, for example, zinc catalysts such as zinc chloride, zinc acetate, zinc propionate, zinc octoate, zinc benzoate, zinc p-chlorobenzoate, zinc naphthenate, zinc stearate, zinc itaconate, zinc pivalate, zinc phenolate, 35 zinc acetylacetonate, zinc methoxide, lead catalysts like lead acetate and lead octoate, and tin catalysts like stannous chloride, stannous octoate, and mixtures thereof.
Preferably, the metal in the catalyst is selected from the group consisting of Ti, Zr, Zn, Sn and Pb.
The heterogeneous metal based catalyst on the carrier may be made by impregnating the catalyst with or precipitating it on the carrier.
Suitable inert carrier supports include, for example, metal oxides such as alumina, silica, Ti02, Mg0 and the like, clays, zeolites, polymer supports, resins, graphite and carbon. A preferred carrier comprises Ti02, alumina or silica.
The supported catalyst is generally used in amounts between 10~ and 20 mole%
based on the amount of amines used.
The polyamines and the organic carbonates may be reacted in stoichiometric quantities. The use of an excess of organic carbonates however is preferred.
The reaction conditions largely depend on the type of reactants used.
~o The method may be carried out at atmospheric or superatmospheric pressures.The pressure is preferably not more than 20 bar.
The reaction time is dependent on the temperature and on the type and quantity of the carbamate compound, but will normally be between 0.5 and 6 hours.
Reaction times of less than 3 hours are common, and reaction times of less than ~s 2.5 hours have been achieved without any problem.
Generally, the reaction temperature will be between 50 and 300°C.
Preferably, the method of the invention is carried out at temperatures between 100 and 250°C.
The presence of a solvent is not required, but it may be added without adversely 2o affecting the reaction.
Any solvent or mixture of solvents which is inert to the reactants under the reaction conditions may be employed.
Suitable solvents which may be employed include, for example, aromatic hydrocarbons such as benzene, halogenated aromatic hydrocarbons such as 25 monochlorobenzene, ortho-dichlorobenzene, trichlorobenzene or 1-chloronaphthalene, alkylated aromatic hydrocarbons like toluene, xylene, ethylbenzene, cumene or tetrahydronaphthalene, other functionalised aromatic hydrocarbons such as anisole, diphenylether, ethoxybenzene, benzonitrile, 2-fluoroanisole, 2,3-dimethylanisoie or trifluorotoluene, alkanes such as so n-pentane, n-hexane, n-heptane or higher or branched alkanes, cyclic alkanes like cyclopentane, cyclohexane or derivatives thereof, halogenated alkanes like chloroform, dichloromethane, carbontetrachloride, and alkanes with other functional groups like diethylether, acetonitrile, dioxane or mixtures thereof, and the like. Inert aromatic solvents are preferred.
ss The method can be conducted in any apparatus which can be equipped, if required, with agitation means and heating andlor cooling means to keep the temperature within the desired range.
The method of the present invention may be conducted batchwise or as a semi-continuous or continuous process.
ao One type of continuous operation is in a fluidized bed reactor in which a catalyst is carried into the reactor as a slurry in one or more of the reactants. Still another way of operating continuously is in a moving bed reactor in which the catalyst bed and the reactants pass concurrently or countercurrently to each other. A
preferred type of continuous operation however is in a fixed bed reactor in which the reactants are passed over the catalyst bed.
During the reaction alcohols are formed as by-product. These can be removed from the reaction mixture either continuously during or after completion of the reaction by e.g. distillation.
~o The present invention is illustrated by, but not limited to, the following examples.
Examples Example 1 To a suspension of 2 g Ti02 in 100 ml acetone was added 0.3088 zinc octoate (in mineral terpentine oil, 6wt% Zn}, and the mixture was purged with Ar gas for 5 5 minutes. The flask was put in a sonication bath (frequency: 20 MHz), containing water at room temperature for 1 hour. After sonication, the solvent was removed under reduced pressure and the solid finally dried under reduced pressure at 70°C, for 1 hour. The solid thus obtained was used as such in the preparation of carbamates. Isolated yield: 2.28.
~o To a 100 ml steel autoclave was added 2.Og (10 mmol) 4,4' diamino diphenyl methane, 42.78 (0.47 mol) dimethyl carbonate and 0.188 TiOZ supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on Ti02). The mixture was purged with nitrogen. The reaction mixture was then heated at 180°C for 2 hours.
~5 After reaction completion, the autoclave was cooled to room temperature and the crude product was evaporated to dryness, redissolved in dichloromethane and finally filtered to separate out the catalyst. The filtrate thus obtained was evaporated to dryness under reduced pressure to yield a crystalline solid.
Conversion of amine was 100% based on starting material. Selectivity to 2o urethane was 96.3% based on quantitative HPLC.
Example 2 To a 100 rnl steel autoclave was added 2.Og (10 mmol) 4,4' diamino Biphenyl methane, 25.58 (0.28 mol) dimethyl carbonate, 16 ml toluene, and 0.188 TiOz supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on 25 Ti02). The mixture was purged with nitrogen. The reaction mixture was then heated at 180°C for 2 hours.
After reaction completion, the autoclave was cooled to room temperature and the crude product was evaporated to dryness, redissolved in dichloromethane and finally filtered to separate out the catalyst. The filtrate thus obtained was 3o evaporated to dryness under reduced pressure to yield a crystalline solid.
Conversion of amine was 100% based on starting material. Selectivity to urethane was 98% based on quantitative HPLC.
Example 3 To a 100 ml steel autoclave was added 2.Og (8 mmol) polymeric diamino 35 Biphenyl methane, 42.78 (0.47 mol) dimethyl carbonate and 0.188 (0.1 mmol active catalyst) Ti02 supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on Ti02). The mixture was purged with nitrogen. The reaction mixture was then heated at 180°C for 2 hours.
DESCRIPTION
The present invention relates to a method for the preparation of carbamates by reaction of aromatic amines with organic carbonates using a catalyst on an inert support.
It is known to react amines with organic carbonates in order to obtain carbamates.
US-A 5.347.034 discloses a process for producing poly(o-alkylurethanes) of the diphenylmethane series by reacting the corresponding amines with dialkyl ~ o carbonates in the presence of a catalyst, such that the formed poly(O-alkylurethanes) crystallize out in a highly pure form upon cooling.
EP-A 391.473 describes a process for producing carbamates using reduced amounts of catalyst by first reacting an amine with a (cyclo)alkyl carbonate in the presence of a carbamation catalyst to produce a mixture of a carbamate and an urea, further reacting the urea with carbonate to produce the corresponding carbamate, and finally recovering the carbamate from the reaction mixture.
in DE-A 3.202.690 a method for preparing aromatic urethanes is described by reacting aromatic amines and alkylcarbonates in the presence of an alcoholate of an alkali metal or an alkaline earth metal.
2o US-A 4.268.684 discloses a method for the preparation of carbamates by reacting an organic carbonate with an aromatic amine in the presence of certain zinc, tin or cobalt salts which are only active at temperatures of at least 200° C
whereas in US-A 4.268.683 zinc or tin salts are used which are soluble in the reaction mixture at the reaction conditions.
EP-A 48.371 describes the preparation of N,O-disubstituted urethanes by reacting primary amines with dialkylcarbonates in the presence of neutral or basic inorganic or organic lead, titanium, zinc or zirconium compounds.
In JP-A 07.328.435 a catalyst comprising an oxide composition containing Zr and Si is used for the production of carbamates from a diester carbonate and an 3o aliphatic amine in the liquid phase.
An improved method has now been found for the preparation of carbamates by reaction of aromatic amines with organic carbonates.
The invention thus concerns a method for the preparation of carbamates by reaction of aromatic amines with organic carbonates in the presence of a metal based catalyst on an inert carrier support.
The method allows easy recovery of the catalyst, thus improving the economics and environmental impact of the process.
In a further aspect, the invention relates to a catalyst comprising an organic metal salt on an inert carrier support.
Such catalysts show an improved processability in the conversion of aromatic amines to carbamates via reaction with an organic carbonate.
Aromatic amine compounds which can be used in the present method include mono-, di- or poiyamines.
Suitable amines according to the process of the invention include, for example, phenylamine, 4-chlorophenylamine, 2-fluorophenyl amine, 3,4-dichiorophenylamine, aniline, tolylamine, diisopropyl phenyfamine, ~0 2,4'-diaminodiphenyimethane, 4,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane and higher homologs (polyaminopolyphenylmethanes), 2,4-toluenediamine, 2,6-toluenediamine, m-phenylenediamine, 1,5-naphthylenediamine, and mixtures thereof.
Preferred are aromatic di- or polyamines like toluenediamines, i 5 diaminodiphenylmethanes or polyaminopoiyphenylrnethanes or any mixtures thereof.
Suitable organic carbonates include cyclic or alicyclic carbonates such as, for example, ethylene carbonate, propylene carbonate, styrene carbonate, Biphenyl 2o carbonate, methyl phenyl carbonate,dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dihexyl carbonate, methyl ethyl carbonate, methyl butyl carbonate and the like.
Organic or inorganic salts which may used include, for example, acetates, 25 chlorides, nitrates, sulfonates, propionates, isopropanoates, butanoates, 2-ethylhexanoates, n-octoates, isononanoates, benzoates, chlorobenzoates, naphthenates, stearates, itaconates, pivalates, phenolates, acetylacetonates, alkoxides, C,6/C,$ alkenylsuccinoates (ASA), C,2 alkenylsuccinoates (DSA) and the like.
3o Preferred are alkanoates having from 1 to 15 carbons atoms.
Suitable catalysts include, for example, zinc catalysts such as zinc chloride, zinc acetate, zinc propionate, zinc octoate, zinc benzoate, zinc p-chlorobenzoate, zinc naphthenate, zinc stearate, zinc itaconate, zinc pivalate, zinc phenolate, 35 zinc acetylacetonate, zinc methoxide, lead catalysts like lead acetate and lead octoate, and tin catalysts like stannous chloride, stannous octoate, and mixtures thereof.
Preferably, the metal in the catalyst is selected from the group consisting of Ti, Zr, Zn, Sn and Pb.
The heterogeneous metal based catalyst on the carrier may be made by impregnating the catalyst with or precipitating it on the carrier.
Suitable inert carrier supports include, for example, metal oxides such as alumina, silica, Ti02, Mg0 and the like, clays, zeolites, polymer supports, resins, graphite and carbon. A preferred carrier comprises Ti02, alumina or silica.
The supported catalyst is generally used in amounts between 10~ and 20 mole%
based on the amount of amines used.
The polyamines and the organic carbonates may be reacted in stoichiometric quantities. The use of an excess of organic carbonates however is preferred.
The reaction conditions largely depend on the type of reactants used.
~o The method may be carried out at atmospheric or superatmospheric pressures.The pressure is preferably not more than 20 bar.
The reaction time is dependent on the temperature and on the type and quantity of the carbamate compound, but will normally be between 0.5 and 6 hours.
Reaction times of less than 3 hours are common, and reaction times of less than ~s 2.5 hours have been achieved without any problem.
Generally, the reaction temperature will be between 50 and 300°C.
Preferably, the method of the invention is carried out at temperatures between 100 and 250°C.
The presence of a solvent is not required, but it may be added without adversely 2o affecting the reaction.
Any solvent or mixture of solvents which is inert to the reactants under the reaction conditions may be employed.
Suitable solvents which may be employed include, for example, aromatic hydrocarbons such as benzene, halogenated aromatic hydrocarbons such as 25 monochlorobenzene, ortho-dichlorobenzene, trichlorobenzene or 1-chloronaphthalene, alkylated aromatic hydrocarbons like toluene, xylene, ethylbenzene, cumene or tetrahydronaphthalene, other functionalised aromatic hydrocarbons such as anisole, diphenylether, ethoxybenzene, benzonitrile, 2-fluoroanisole, 2,3-dimethylanisoie or trifluorotoluene, alkanes such as so n-pentane, n-hexane, n-heptane or higher or branched alkanes, cyclic alkanes like cyclopentane, cyclohexane or derivatives thereof, halogenated alkanes like chloroform, dichloromethane, carbontetrachloride, and alkanes with other functional groups like diethylether, acetonitrile, dioxane or mixtures thereof, and the like. Inert aromatic solvents are preferred.
ss The method can be conducted in any apparatus which can be equipped, if required, with agitation means and heating andlor cooling means to keep the temperature within the desired range.
The method of the present invention may be conducted batchwise or as a semi-continuous or continuous process.
ao One type of continuous operation is in a fluidized bed reactor in which a catalyst is carried into the reactor as a slurry in one or more of the reactants. Still another way of operating continuously is in a moving bed reactor in which the catalyst bed and the reactants pass concurrently or countercurrently to each other. A
preferred type of continuous operation however is in a fixed bed reactor in which the reactants are passed over the catalyst bed.
During the reaction alcohols are formed as by-product. These can be removed from the reaction mixture either continuously during or after completion of the reaction by e.g. distillation.
~o The present invention is illustrated by, but not limited to, the following examples.
Examples Example 1 To a suspension of 2 g Ti02 in 100 ml acetone was added 0.3088 zinc octoate (in mineral terpentine oil, 6wt% Zn}, and the mixture was purged with Ar gas for 5 5 minutes. The flask was put in a sonication bath (frequency: 20 MHz), containing water at room temperature for 1 hour. After sonication, the solvent was removed under reduced pressure and the solid finally dried under reduced pressure at 70°C, for 1 hour. The solid thus obtained was used as such in the preparation of carbamates. Isolated yield: 2.28.
~o To a 100 ml steel autoclave was added 2.Og (10 mmol) 4,4' diamino diphenyl methane, 42.78 (0.47 mol) dimethyl carbonate and 0.188 TiOZ supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on Ti02). The mixture was purged with nitrogen. The reaction mixture was then heated at 180°C for 2 hours.
~5 After reaction completion, the autoclave was cooled to room temperature and the crude product was evaporated to dryness, redissolved in dichloromethane and finally filtered to separate out the catalyst. The filtrate thus obtained was evaporated to dryness under reduced pressure to yield a crystalline solid.
Conversion of amine was 100% based on starting material. Selectivity to 2o urethane was 96.3% based on quantitative HPLC.
Example 2 To a 100 rnl steel autoclave was added 2.Og (10 mmol) 4,4' diamino Biphenyl methane, 25.58 (0.28 mol) dimethyl carbonate, 16 ml toluene, and 0.188 TiOz supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on 25 Ti02). The mixture was purged with nitrogen. The reaction mixture was then heated at 180°C for 2 hours.
After reaction completion, the autoclave was cooled to room temperature and the crude product was evaporated to dryness, redissolved in dichloromethane and finally filtered to separate out the catalyst. The filtrate thus obtained was 3o evaporated to dryness under reduced pressure to yield a crystalline solid.
Conversion of amine was 100% based on starting material. Selectivity to urethane was 98% based on quantitative HPLC.
Example 3 To a 100 ml steel autoclave was added 2.Og (8 mmol) polymeric diamino 35 Biphenyl methane, 42.78 (0.47 mol) dimethyl carbonate and 0.188 (0.1 mmol active catalyst) Ti02 supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on Ti02). The mixture was purged with nitrogen. The reaction mixture was then heated at 180°C for 2 hours.
After reaction completion, the autoclave was cooled to room temperature and the catalyst was filtered off. The filtrate thus obtained was evaporated to dryness under reduced pressure to yield a solid. Conversion of amine was >98% based on starting material. Selectivity to urethane was estimated to be 89-92% based s on IR and '3C NMR.
Example 4 A mixture of 1.22g (10 mmol) 2,4-diaminotoluene , 42.7g (0.47 mol) dimethyl carbonate and 0.18g (0.1 mmol active catalyst) Ti02 supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on Ti02) was charged in a 100 ~o ml steel autoclave and purged with nitrogen. The reaction mixture was then heated at 180°C for 2h.
After completion of the reaction the autoclave was cooled to room temperature and an equal volume of dichloromethane was added to dissolve partly precipitated 2,4-bis(methoxycarbonylamino)toluene. The mixture was then 15 filtered off to separate out the catalyst. The filtrate thus obtained was evaporated to dryness under reduced pressure to obtain crystalline yellow 2,4-bis(methoxycarbonylamino)toluene solid. Conversion of amine and selectivity to urethane were found to be 100% and 92% respectively from quantitative HPLC technique.
2o Example 5 To a suspension of 2 g AI203 in 40 m1 acetone was added 1.2g zinc octoate (in mineral terpentine oil, 6wt% Zn), and the mixture was purged with Ar gas for 5 minutes. The flask was put in a sonication bath (frequency: 20 MHz), containing water at room temperature for 1 hour. After sonication, the solvent was removed 2~ under reduced pressure and the solid finally dried under reduced pressure at 70°C, for 1 hour. The solid thus obtained was used as such in the preparation of carbamates. Isolated yield: 2.8g.
To a 100 ml steel autoclave was added 2.Og (10 mmol) polymeric diamino Biphenyl methane, 42.7g (0.47 mol) dimethyl carbonate and 0.2128 (0.12 mmol so active catalyst) AI203 supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on AI203). The mixture was purged with nitrogen. The reaction mixture was then heated at 180°C for 2 hours.
After reaction completion, the autoclave was cooled to room temperature and the crude product was evaporated to dryness, redissolved in dichloromethane and 3s finally filtered to separate out the catalyst. The filtrate thus obtained was evaporated to dryness under reduced pressure to yield a crystalline solid.
Conversion of amine was 100% based on starting material. Selectivity to urethane was 91 % based on HPLC.
Example 4 A mixture of 1.22g (10 mmol) 2,4-diaminotoluene , 42.7g (0.47 mol) dimethyl carbonate and 0.18g (0.1 mmol active catalyst) Ti02 supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on Ti02) was charged in a 100 ~o ml steel autoclave and purged with nitrogen. The reaction mixture was then heated at 180°C for 2h.
After completion of the reaction the autoclave was cooled to room temperature and an equal volume of dichloromethane was added to dissolve partly precipitated 2,4-bis(methoxycarbonylamino)toluene. The mixture was then 15 filtered off to separate out the catalyst. The filtrate thus obtained was evaporated to dryness under reduced pressure to obtain crystalline yellow 2,4-bis(methoxycarbonylamino)toluene solid. Conversion of amine and selectivity to urethane were found to be 100% and 92% respectively from quantitative HPLC technique.
2o Example 5 To a suspension of 2 g AI203 in 40 m1 acetone was added 1.2g zinc octoate (in mineral terpentine oil, 6wt% Zn), and the mixture was purged with Ar gas for 5 minutes. The flask was put in a sonication bath (frequency: 20 MHz), containing water at room temperature for 1 hour. After sonication, the solvent was removed 2~ under reduced pressure and the solid finally dried under reduced pressure at 70°C, for 1 hour. The solid thus obtained was used as such in the preparation of carbamates. Isolated yield: 2.8g.
To a 100 ml steel autoclave was added 2.Og (10 mmol) polymeric diamino Biphenyl methane, 42.7g (0.47 mol) dimethyl carbonate and 0.2128 (0.12 mmol so active catalyst) AI203 supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on AI203). The mixture was purged with nitrogen. The reaction mixture was then heated at 180°C for 2 hours.
After reaction completion, the autoclave was cooled to room temperature and the crude product was evaporated to dryness, redissolved in dichloromethane and 3s finally filtered to separate out the catalyst. The filtrate thus obtained was evaporated to dryness under reduced pressure to yield a crystalline solid.
Conversion of amine was 100% based on starting material. Selectivity to urethane was 91 % based on HPLC.
Example 6 To a 100 ml steel autoclave was added 2.Og (8 mmol) polymeric diamino Biphenyl methane, 42.78 (0.47 mol) dimethyl carbonate and 0.212g (0.12 mmol active catalyst) AI203 supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on AI203). The mixture was purged with nitrogen. The reaction mixture was then heated at 180°C for 2 hours.
After reaction completion, the autoclave was cooled to room temperature and the crude product was filtered to separate out the catalyst. The filtrate thus obtained was evaporated to dryness under reduced pressure to yield a crystalline solid.
~o Conversion of amine was 98% based on starting material. Selectivity to urethane was 84-92% based on quantitative IR and'3C NMR.
Example 7 To a suspension of 2 g silica (silica gel for column chromatography, 200-300 mesh) in 40 ml acetone was added 1.2g zinc octoate (in mineral terpentine oil, ~56wt% Zn), and the mixture was purged with Ar gas for 5 minutes. The flask was put in a sonication bath (frequency: 20 MHz), containing water at room temperature for 1 hour. After sonication, the solvent was removed under reduced pressure and the solid finally dried under reduced pressure at 70°C, for 1 hour.
The solid thus obtained was used as such in the preparation of carbamates.
2o Isolated yield: 2.4g.
To a 100 ml steel autoclave was added 2.Og (10 mmol} 4,4' diamino Biphenyl methane, 42.8g (0.47 mol) dimethyl carbonate and 0.216g silica supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on sificagel).
The mixture was purged with nitrogen for 5-10 min. The reaction mixture was then 25 heated at 180°C for 2 hours.
After reaction completion, the autoclave was cooled to room temperature and the crude product was evaporated to dryness, redissolved in dichloromethane and finally filtered to separate out the catalyst. The filtrate thus obtained was evaporated to dryness under reduced pressure to yield a crystalline solid.
so Conversion of amine was 100% based on starting material. Selectivity to urethane was 81.8% based on quantitative HPLC.
Example 8 To a 100 ml steel autoclave was added 2.Og (8 mmol) polymeric diamino Biphenyl methane, 42.78 (0.47 mol) dimethyl carbonate and 0.216g (0.12 mmol s5 active catalyst) acidic silica supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on silicagel). The mixture was purged with nitrogen.
The reaction mixture was then heated at 180°C for 2 hours.
After reaction completion, the autoclave was cooled to room temperature and the crude product was filtered to separate out the catalyst. The filtrate thus obtained ao was evaporated to dryness under reduced pressure to yield a solid.
Conversion of amine was 97% based on starting material. Selectivity to urethane was 81-83% based on quantitative IR and '3C NMR.
After reaction completion, the autoclave was cooled to room temperature and the crude product was filtered to separate out the catalyst. The filtrate thus obtained was evaporated to dryness under reduced pressure to yield a crystalline solid.
~o Conversion of amine was 98% based on starting material. Selectivity to urethane was 84-92% based on quantitative IR and'3C NMR.
Example 7 To a suspension of 2 g silica (silica gel for column chromatography, 200-300 mesh) in 40 ml acetone was added 1.2g zinc octoate (in mineral terpentine oil, ~56wt% Zn), and the mixture was purged with Ar gas for 5 minutes. The flask was put in a sonication bath (frequency: 20 MHz), containing water at room temperature for 1 hour. After sonication, the solvent was removed under reduced pressure and the solid finally dried under reduced pressure at 70°C, for 1 hour.
The solid thus obtained was used as such in the preparation of carbamates.
2o Isolated yield: 2.4g.
To a 100 ml steel autoclave was added 2.Og (10 mmol} 4,4' diamino Biphenyl methane, 42.8g (0.47 mol) dimethyl carbonate and 0.216g silica supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on sificagel).
The mixture was purged with nitrogen for 5-10 min. The reaction mixture was then 25 heated at 180°C for 2 hours.
After reaction completion, the autoclave was cooled to room temperature and the crude product was evaporated to dryness, redissolved in dichloromethane and finally filtered to separate out the catalyst. The filtrate thus obtained was evaporated to dryness under reduced pressure to yield a crystalline solid.
so Conversion of amine was 100% based on starting material. Selectivity to urethane was 81.8% based on quantitative HPLC.
Example 8 To a 100 ml steel autoclave was added 2.Og (8 mmol) polymeric diamino Biphenyl methane, 42.78 (0.47 mol) dimethyl carbonate and 0.216g (0.12 mmol s5 active catalyst) acidic silica supported zinc octoate (20 wt% zinc salt of 2-ethyl hexanoic acid supported on silicagel). The mixture was purged with nitrogen.
The reaction mixture was then heated at 180°C for 2 hours.
After reaction completion, the autoclave was cooled to room temperature and the crude product was filtered to separate out the catalyst. The filtrate thus obtained ao was evaporated to dryness under reduced pressure to yield a solid.
Conversion of amine was 97% based on starting material. Selectivity to urethane was 81-83% based on quantitative IR and '3C NMR.
Claims (13)
1. Method for the preparation of carbamates by reaction of aromatic amines with organic carbonates in the presence of a metal based catalyst on an inert carrier support.
2. Method according to claim 1 wherein the catalyst comprises a metal selected from the group consisting of Ti, Zr, Zn, Sn and Pb.
3. Method according to claim 1 or 2 wherein the catalyst comprises an alkanoate having from 1 to 15 carbons atoms.
4. Method according to any one of the preceding claims wherein the carrier support comprises TiO2, alumina or silica.
5. Method according to any one of the preceding claims wherein the reaction is carried out at a temperature between 100 and 250°C.
6. Method according to any of the preceding claims wherein the aromatic amine is selected from the group consisting of toluenediamines, diaminodiphenylmethanes or polyaminopolyphenylmethanes or mixtures thereof.
7. Method according to any one of the preceding claims wherein the reaction is carried out at a pressure of not more than 20 bar.
8. Method according to any of the preceding claims which is carried out in the presence of an inert aromatic solvent.
9. Method according to any of the preceding claims having a reaction time of less than 2.5 hours.
10. A catalyst comprising an organic metal salt on an inert carrier support.
11. A catalyst according to claim 10 wherein the metal is selected from the group consisting of Ti, Zr, Zn, Sn and Pb.
12. A catalyst according to claim 10 or 11 wherein the organic salt is an alkanoate having from 1 to 15 carbons atoms.
13. A catalyst according to any one of claims 10-12 wherein the carrier support comprises TiO2, alumina or silica.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97109081 | 1997-06-05 | ||
EP97109081.6 | 1997-06-05 | ||
PCT/EP1998/002888 WO1998055450A1 (en) | 1997-06-05 | 1998-05-15 | Method for the preparation of carbamates |
Publications (1)
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CA2289658A1 true CA2289658A1 (en) | 1998-12-10 |
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ID=8226879
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CA002289658A Abandoned CA2289658A1 (en) | 1997-06-05 | 1998-05-15 | Method for the preparation of carbamates |
Country Status (9)
Country | Link |
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EP (1) | EP0988281A1 (en) |
JP (1) | JP2002512626A (en) |
KR (1) | KR20010013407A (en) |
CN (1) | CN1258274A (en) |
AU (1) | AU8018298A (en) |
CA (1) | CA2289658A1 (en) |
HU (1) | HUP0003114A3 (en) |
WO (1) | WO1998055450A1 (en) |
ZA (1) | ZA984538B (en) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1998037919A1 (en) | 1997-02-28 | 1998-09-03 | University Of Iowa Research Foundation | USE OF NUCLEIC ACIDS CONTAINING UNMETHYLATED CpG DINUCLEOTIDE IN THE TREATMENT OF LPS-ASSOCIATED DISORDERS |
US7022871B2 (en) * | 1999-12-27 | 2006-04-04 | Huntsman International Llc | Process for the synthesis of polycarbamates |
BRPI0616023A2 (en) * | 2005-07-20 | 2011-06-07 | Dow Global Technologies Inc | process for the preparation of aromatic carbamates and process for the formation of an isocyanate |
CN100358977C (en) * | 2005-09-08 | 2008-01-02 | 中国石油大学(华东) | Method for preparing catalyst |
JP4778844B2 (en) * | 2006-06-20 | 2011-09-21 | 三井化学株式会社 | Method for producing silicon-containing isocyanate compound |
EP2036884A1 (en) | 2007-09-14 | 2009-03-18 | Repsol Ypf S.A. | Process for producing fluorinated isocyanates and carbamates |
CN100566834C (en) * | 2008-05-19 | 2009-12-09 | 中国科学院山西煤炭化学研究所 | Be used for catalyst and the method for making and the application of synthesizing fragrant carbamic acid ester |
ES2331505B2 (en) * | 2008-07-04 | 2010-09-20 | Universidad Politecnica De Valencia | CARBAMATE PREPARATION WITH SOLID CATALYSTS. |
US8058469B2 (en) | 2008-11-03 | 2011-11-15 | Sabic Innovative Plastics Ip B.V. | Method for making carbamates, ureas and isocyanates |
PT2199278E (en) * | 2008-12-19 | 2011-11-10 | Dow Global Technologies Llc | Process for the production of aromatic urethanes |
EP2491011A1 (en) | 2009-10-21 | 2012-08-29 | Basf Se | Method for producing urethanes |
FR2960875B1 (en) | 2010-06-04 | 2012-12-28 | Sanofi Aventis | HEXAFLUOROISOPROPYL CARBAMATE DERIVATIVES, THEIR PREPARATION AND THEIR THERAPEUTIC APPLICATION |
TWI499605B (en) * | 2010-10-13 | 2015-09-11 | Nippon Synthetic Chem Ind | Method of producing urethane compound and urethane compound obtained by the method |
CN103012210B (en) * | 2012-12-13 | 2014-09-17 | 黄河三角洲京博化工研究院有限公司 | Preparation method of isophorone diamidoformate |
KR102016527B1 (en) * | 2013-06-20 | 2019-09-02 | 한국생산기술연구원 | Process for preparing aliphatic hydroxyalkyl carbamates from aromatic amines |
CN110650944B (en) * | 2017-05-15 | 2022-07-19 | 科思创德国股份有限公司 | Silica-based zinc catalysts, their preparation and use in the alkoxycarbonylation of amines |
EP3630717B1 (en) * | 2017-05-26 | 2022-02-09 | Council of Scientific and Industrial Research | A process for the synthesis of aromatic carbamates |
Family Cites Families (5)
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DE2525506C2 (en) * | 1975-06-07 | 1983-09-15 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of a catalyst containing nickel and / or cobalt and zinc oxide |
US4101446A (en) * | 1976-12-22 | 1978-07-18 | Stauffer Chemical Company | Lead acetate impregnated magnesium silicate for the production of perchloromethyl mercaptan |
US4268683A (en) * | 1980-02-21 | 1981-05-19 | The Dow Chemical Company | Preparation of carbamates from aromatic amines and organic carbonates |
US4268684A (en) * | 1980-02-25 | 1981-05-19 | The Dow Chemical Company | Preparation of carbamates from aromatic amines and organic carbonates |
JPH07328435A (en) * | 1994-06-15 | 1995-12-19 | Nippon Shokubai Co Ltd | Catalyst for production of carbamate and production of carbamate using that catalyst |
-
1998
- 1998-05-15 HU HU0003114A patent/HUP0003114A3/en unknown
- 1998-05-15 CN CN98805602A patent/CN1258274A/en active Pending
- 1998-05-15 JP JP50138299A patent/JP2002512626A/en active Pending
- 1998-05-15 KR KR19997011408A patent/KR20010013407A/en not_active Application Discontinuation
- 1998-05-15 EP EP98928279A patent/EP0988281A1/en not_active Withdrawn
- 1998-05-15 CA CA002289658A patent/CA2289658A1/en not_active Abandoned
- 1998-05-15 AU AU80182/98A patent/AU8018298A/en not_active Abandoned
- 1998-05-15 WO PCT/EP1998/002888 patent/WO1998055450A1/en not_active Application Discontinuation
- 1998-05-27 ZA ZA984538A patent/ZA984538B/en unknown
Also Published As
Publication number | Publication date |
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ZA984538B (en) | 1998-12-07 |
HUP0003114A2 (en) | 2001-02-28 |
HUP0003114A3 (en) | 2001-03-28 |
WO1998055450A1 (en) | 1998-12-10 |
AU8018298A (en) | 1998-12-21 |
EP0988281A1 (en) | 2000-03-29 |
JP2002512626A (en) | 2002-04-23 |
KR20010013407A (en) | 2001-02-26 |
CN1258274A (en) | 2000-06-28 |
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