JPH0278651A - Production of carbamic acid esters - Google Patents
Production of carbamic acid estersInfo
- Publication number
- JPH0278651A JPH0278651A JP63228948A JP22894888A JPH0278651A JP H0278651 A JPH0278651 A JP H0278651A JP 63228948 A JP63228948 A JP 63228948A JP 22894888 A JP22894888 A JP 22894888A JP H0278651 A JPH0278651 A JP H0278651A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- hydrogen
- reaction
- group
- catalyst
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title description 2
- 229940112021 centrally acting muscle relaxants carbamic acid ester Drugs 0.000 title 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000004820 halides Chemical class 0.000 claims abstract description 7
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 150000003623 transition metal compounds Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000007789 gas Substances 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012948 isocyanate Substances 0.000 abstract description 4
- 150000002513 isocyanates Chemical class 0.000 abstract description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 3
- 239000003905 agrochemical Substances 0.000 abstract 1
- 229910000765 intermetallic Inorganic materials 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 35
- -1 carbamate ester Chemical class 0.000 description 30
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- LBKPGNUOUPTQKA-UHFFFAOYSA-N ethyl n-phenylcarbamate Chemical compound CCOC(=O)NC1=CC=CC=C1 LBKPGNUOUPTQKA-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002828 nitro derivatives Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 230000009897 systematic effect Effects 0.000 description 3
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- MWAGUKZCDDRDCS-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenoxy)benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C([N+]([O-])=O)C=C1 MWAGUKZCDDRDCS-UHFFFAOYSA-N 0.000 description 2
- BVHNGWRPAFKGFP-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenyl)sulfonylbenzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 BVHNGWRPAFKGFP-UHFFFAOYSA-N 0.000 description 2
- RJKGJBPXVHTNJL-UHFFFAOYSA-N 1-nitronaphthalene Chemical class C1=CC=C2C([N+](=O)[O-])=CC=CC2=C1 RJKGJBPXVHTNJL-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- OWJVEZJJRYZWNI-UHFFFAOYSA-N 1,1-dinitrocyclohexane Chemical compound [O-][N+](=O)C1([N+]([O-])=O)CCCCC1 OWJVEZJJRYZWNI-UHFFFAOYSA-N 0.000 description 1
- LKKHEZBRRGJBGH-UHFFFAOYSA-N 1,1-dinitroethane Chemical compound [O-][N+](=O)C(C)[N+]([O-])=O LKKHEZBRRGJBGH-UHFFFAOYSA-N 0.000 description 1
- HLUAPIYZVLAARK-UHFFFAOYSA-N 1,1-dinitrohexane Chemical compound CCCCCC([N+]([O-])=O)[N+]([O-])=O HLUAPIYZVLAARK-UHFFFAOYSA-N 0.000 description 1
- BSNKHEKTRWNNAC-UHFFFAOYSA-N 1,2-Bis(4-nitrophenyl)ethane Chemical group C1=CC([N+](=O)[O-])=CC=C1CCC1=CC=C([N+]([O-])=O)C=C1 BSNKHEKTRWNNAC-UHFFFAOYSA-N 0.000 description 1
- XNKFCDGEFCOQOM-UHFFFAOYSA-N 1,2-dinitronaphthalene Chemical compound C1=CC=CC2=C([N+]([O-])=O)C([N+](=O)[O-])=CC=C21 XNKFCDGEFCOQOM-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 1
- WGAXJEXVOSVLFY-UHFFFAOYSA-N 1-(2,4-dinitrophenoxy)-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O WGAXJEXVOSVLFY-UHFFFAOYSA-N 0.000 description 1
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 description 1
- UJCOXURVZQOGFN-UHFFFAOYSA-N 1-methoxy-4-(nitromethyl)benzene Chemical compound COC1=CC=C(C[N+]([O-])=O)C=C1 UJCOXURVZQOGFN-UHFFFAOYSA-N 0.000 description 1
- ALTGNKHNQHUIKE-UHFFFAOYSA-N 1-nitro-10h-phenothiazine Chemical class S1C2=CC=CC=C2NC2=C1C=CC=C2[N+](=O)[O-] ALTGNKHNQHUIKE-UHFFFAOYSA-N 0.000 description 1
- BDLNCFCZHNKBGI-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenyl)benzene Chemical group C1=CC([N+](=O)[O-])=CC=C1C1=CC=C([N+]([O-])=O)C=C1 BDLNCFCZHNKBGI-UHFFFAOYSA-N 0.000 description 1
- ZZTJMQPRKBNGNX-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenyl)sulfanylbenzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1SC1=CC=C([N+]([O-])=O)C=C1 ZZTJMQPRKBNGNX-UHFFFAOYSA-N 0.000 description 1
- JBDYKGMNMDIHFL-UHFFFAOYSA-N 1-nitroanthracene Chemical class C1=CC=C2C=C3C([N+](=O)[O-])=CC=CC3=CC2=C1 JBDYKGMNMDIHFL-UHFFFAOYSA-N 0.000 description 1
- NALZTFARIYUCBY-UHFFFAOYSA-N 1-nitrobutane Chemical compound CCCC[N+]([O-])=O NALZTFARIYUCBY-UHFFFAOYSA-N 0.000 description 1
- KLGHUFNKRIWCDQ-UHFFFAOYSA-N 1-nitrooctane Chemical compound CCCCCCCC[N+]([O-])=O KLGHUFNKRIWCDQ-UHFFFAOYSA-N 0.000 description 1
- WKFQMDFSDQFAIC-UHFFFAOYSA-N 2,4-dimethylthiolane 1,1-dioxide Chemical compound CC1CC(C)S(=O)(=O)C1 WKFQMDFSDQFAIC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- FEJLPMVSVDSKHJ-UHFFFAOYSA-N 3-methyl-1-nitrobutane Chemical compound CC(C)CC[N+]([O-])=O FEJLPMVSVDSKHJ-UHFFFAOYSA-N 0.000 description 1
- ZETIVVHRRQLWFW-UHFFFAOYSA-N 3-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1 ZETIVVHRRQLWFW-UHFFFAOYSA-N 0.000 description 1
- MWWNNNAOGWPTQY-UHFFFAOYSA-N 3-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=CC(S(Cl)(=O)=O)=C1 MWWNNNAOGWPTQY-UHFFFAOYSA-N 0.000 description 1
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- NOYDQGFVFOQSAJ-UHFFFAOYSA-N 5-nitropyrimidine Chemical compound [O-][N+](=O)C1=CN=CN=C1 NOYDQGFVFOQSAJ-UHFFFAOYSA-N 0.000 description 1
- 101100037762 Caenorhabditis elegans rnh-2 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- FUMLKAFCVQJVEZ-UHFFFAOYSA-N [bromo(nitro)methyl]benzene Chemical compound [O-][N+](=O)C(Br)C1=CC=CC=C1 FUMLKAFCVQJVEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HEZQRPHEDDAJTF-UHFFFAOYSA-N chloro(phenyl)methanol Chemical compound OC(Cl)C1=CC=CC=C1 HEZQRPHEDDAJTF-UHFFFAOYSA-N 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000005182 dinitrobenzenes Chemical class 0.000 description 1
- VMMLSJNPNVTYMN-UHFFFAOYSA-N dinitromethylbenzene Chemical class [O-][N+](=O)C([N+]([O-])=O)C1=CC=CC=C1 VMMLSJNPNVTYMN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- PHWSCBWNPZDYRI-UHFFFAOYSA-N ethyl 4-nitrobenzoate Chemical compound CCOC(=O)C1=CC=C([N+]([O-])=O)C=C1 PHWSCBWNPZDYRI-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical compound ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- PWXJULSLLONQHY-UHFFFAOYSA-N phenylcarbamic acid Chemical compound OC(=O)NC1=CC=CC=C1 PWXJULSLLONQHY-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、カルバミン酸エステル類の製造方法に関し、
特にニトロ基を有する化合物、一酸化炭素（ＣＯ） 、
水素（Ｈ２）、および有機含水酸基化合物からカルバミ
ン酸エステル類を製造する方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing carbamate esters,
Especially compounds with nitro groups, carbon monoxide (CO),
The present invention relates to a method for producing carbamate esters from hydrogen (H2) and an organic hydrous acid group compound.
カルバミン酸エステルは、農薬またはイソシアナートの
前駆体として重要である。イソシアナートは軟硬質フオ
ーム、塗料、防水剤、接着剤、弾性繊維等のウレタン製
品の原料として広く用いられている。特にジフェニルメ
タンジイソシアナート（ＭＤＩ）は断熱材、自動車用耐
衝撃軽量化材料としての新用途開発も盛んで、その需要
は大幅な伸びを見せている。Carbamate esters are important as precursors for pesticides or isocyanates. Isocyanates are widely used as raw materials for urethane products such as soft and hard foams, paints, waterproofing agents, adhesives, and elastic fibers. In particular, demand for diphenylmethane diisocyanate (MDI) is rapidly increasing, with active development of new applications as insulation materials and impact-resistant and lightweight materials for automobiles.
カルバミン酸エステルは従来アミンとホスゲンとの反応
で合成されるイソシアナート（反応式１）とアルコール
から合成されている（反応式２）。Carbamate esters have conventionally been synthesized from alcohols and isocyanates (reaction formula 1), which are synthesized by the reaction of amines and phosgene (reaction formula 2).
ＲＮＨ２＋ＣＯＣｌ２２−ＲＮＣＯ＋２ＨＣｊ！ （
１）ＲＮＣＯ＋Ｒ’ ０Ｈ−ＲＮＨＣＯＯＲ’
（２１ホスゲンは猛毒であり、電力を多く必要とする塩
素を用いるので、プロセスの簡略化と省エネルギー化を
図るため、ホスゲンを用いないカルバミン酸エステルの
製造法が検討されてきた。RNH2+COCl22-RNCO+2HCj! (
1) RNCO+R'0H-RNHCOOR'
(21 Phosgene is highly toxic and uses chlorine, which requires a lot of electricity. Therefore, in order to simplify the process and save energy, methods for producing carbamate esters that do not use phosgene have been studied.
このうち、例えばニトロベンゼンとｃｏとアルコールか
ら１段でカルバミン酸エステルを合成する方法（反応式
３）では、エステル１モル当り３モルのＣＯが消費され
る。このＣＯの１／３はカルバミン酸基形成に利用され
るが、残りの２／３は無用の不活性ＣＯ２として消費さ
れさらにｃ。Among these, for example, in the method of synthesizing carbamate ester in one step from nitrobenzene, co, and alcohol (reaction formula 3), 3 moles of CO are consumed per mole of ester. 1/3 of this CO is utilized for carbamate group formation, but the remaining 2/3 is consumed as useless inert CO2 and further c.
２の発熱生成において大量の熱が放出されるため、高価
な反応熱除熱装置が必要となり、また反応圧力も８０〜
２００ ｋｇ ／ ｃｎｔと高く、さらに助触媒の使用
は液をスラリー化し、ハンドリングを困難にしたり、製
品純度の低下を招くので、実用化に至っていない（特公
昭５２−４３８２２号、特開昭５１−９８２４０号、特
開昭５４−１４５６０１号）。Since a large amount of heat is released during the exothermic generation in step 2, an expensive reaction heat removal device is required, and the reaction pressure is also 80~80℃.
It is as high as 200 kg/cnt, and furthermore, the use of a co-catalyst turns the liquid into a slurry, making handling difficult and reducing product purity, so it has not been put into practical use (Japanese Patent Publication No. 43822-1982, Japanese Patent Application Laid-Open No. 1983-1989). No. 98240, JP-A-54-145601).
一方、最近、アミンとＣＯとアルコールと０２からＰｄ
黒とＩ−を触媒としてカルバミン酸エステルを直接合成
する方法が試みられている（反応式４、Ｓ、Ｆｕｋｕｏ
ｋａ ｅｔ ａｌ、、Ｃｈｅｍ、Ｃｏｍｍｕ、１９
８４．３９９）。On the other hand, recently, amine, CO, alcohol, and Pd from 02
A method of directly synthesizing carbamate ester using black and I- as a catalyst has been attempted (reaction formula 4, S, Fukuo
ka et al,, Chem, Commu, 19
84.399).
Ｃ声０２ ＋３ＣＯ＋’ＲＯＨ
→（９Ｎ ＨＣＯＯＲ＋ ２ ＣＯ２（３１σＮＨ２＋
ＣＯ＋ＲＯＨ＋１／２０２
−＠−ＮＨｃｏｏＲ＋Ｈ２ｏ ｔ４）この方法は、
生成するエステル１モルに対し、わずか１モルのＣＯＬ
か必要とせず、さらに反応式（３）のニトロ化合物を原
料とする場合のように２モルの水しか副生ぜず、反応に
よる発熱も少なくなる。しかしながら、Ｃｏ圧は８０ｋ
ｇ／ｃ＋ｄと高（，１７０℃、２時間でアニリン転化率
は９５％と低い。C voice 02 +3CO+'ROH →(9N HCOOR+ 2 CO2(31σNH2+
CO+ROH+1/202 -@-NHcooR+H2o t4) This method is
Only 1 mole of COL per mole of ester produced
In addition, only 2 moles of water are produced as a by-product when the nitro compound of reaction formula (3) is used as a raw material, and the heat generated by the reaction is also reduced. However, the Co pressure is 80k
The aniline conversion rate was as low as 95% at 170°C for 2 hours.
また同上の原料から、ｐａｃ１２とＦｅ０（１！、のよ
うな助触媒を用いた場合でも、反応温度１５０℃、反応
時間２ｈ、Ｃｏ圧１００ｂａｒと高く、アニリン転化率
７７％、エステル選択率９０％である（特開昭５５−１
２０５５１号）。さらに、有機ニトロ化合物を酸化剤と
して、第１級アミン、ＣＯ１アルコールから、カルバミ
ン酸エステルを合成する方法が提案されている（特開昭
５５−１２０５５１号）。例えば、アニリン、ニトロベ
ンゼン、ＣＯ、アルコールから反応式（５）にしたがっ
てＮ−フェニルカルバミン酸エチルを合成する場合、最
高の収率を得るためには、ニトロ基１モルに対し、２モ
ルのアミノ基を供給することが好ましい。Furthermore, even when using the same raw materials as pac12 and co-catalysts such as Fe0(1!), the reaction temperature is 150°C, the reaction time is 2h, and the Co pressure is 100bar, which is high, the aniline conversion rate is 77%, and the ester selectivity is 90%. (Unexamined Japanese Patent Publication No. 55-1
No. 20551). Furthermore, a method has been proposed in which a carbamate ester is synthesized from a primary amine and a CO1 alcohol using an organic nitro compound as an oxidizing agent (Japanese Unexamined Patent Publication No. 120551/1982). For example, when synthesizing ethyl N-phenylcarbamate from aniline, nitrobenzene, CO, and alcohol according to reaction formula (5), in order to obtain the highest yield, 2 moles of amino groups should be added per mole of nitro group. It is preferable to supply
２ ｏ−ＮＨ２＋ ｏ−、ＮＯ２＋ ３ Ｃｏ ＋ ３
ＲＯＨ＝３分ＮＨＣＯＯＲ＋ ２ Ｈ２０（５１ニト
ロ化合物中のニトロ基が当量より少ない場合は、アミン
の転化率が低くなるため、ニトロ化合物を過剰にするこ
とが好ましい。しかしながら、反応式（５）の場合には
ＣＯの一部は反応式（６）に示すようにＣＯ２として消
費されて不利である。2 o-NH2+ o-, NO2+ 3 Co + 3
ROH = 3 min NHCOOR + 2 H20 (51 If the number of nitro groups in the nitro compound is less than the equivalent amount, the conversion rate of the amine will be low, so it is preferable to use an excess of the nitro compound. However, in the case of reaction formula (5) Part of the CO is disadvantageously consumed as CO2 as shown in reaction formula (6).
σＮＯ２＋３’ＣＯ＋ＲＯＨ
−＠−ＮＨＣＯＯＲ＋ ２ ＣＯ２＋ｃまた、ニトロベ
ンゼン、アニリンとＣＯからまずジフェニールウレアを
アルコール分解しフェニールカルバミン酸エステルを合
成する方法（反応式７．８）である。この方法では助触
媒を用いずＲｕ （Ｃｏ）１２クラスタ触媒（特開昭６
２−５９２５２号）を用いるもので反応液のスラリー化
の問題がない。しかし、反応に長時間を要すること、少
量の水素のガスにより活性が著しく低下し水素含有ＣＯ
ガスを使用できない等の問題がある。σNO2+3'CO+ROH -@-NHCOOR+ 2 CO2+c Also, there is a method (reaction formula 7.8) in which diphenylurea is first alcohololyzed from nitrobenzene, aniline, and CO to synthesize phenylcarbamate ester. This method does not use a cocatalyst and uses a Ru(Co)12 cluster catalyst (Japanese Patent Laid-open No. 6
No. 2-59252), there is no problem of slurrying the reaction solution. However, the reaction requires a long time, and the activity is significantly reduced due to a small amount of hydrogen gas.
There are problems such as not being able to use gas.
（３ＮＨ２＋ ｏ−ＮＯ２＋ ３ Ｃ０→［相］Ｎ Ｈ
Ｃ，ＯＨＮ［相］＋２ ＣＯ２（７）σＮＨＣＯＩＮ＠
＋、ＲＯＨ
−＠−ＮＨＣＯＯＲ＋（ｇＮＨｚ （８１〔発明が
解決しようとする課題〕
近年、ホスゲンを使用しない製造法として、芳香族ニト
ロ化合物を原料とし、触媒の存在下、有機含水酸基化合
物および一酸化炭素と高温高圧下で反応させる方法が種
々提案されているが、課題も多くその工業化は困難であ
る。特に本発明で扱ｉ） っているパラジウムなどの貴
金属系触媒反応では、ルイス酸および第３級アミンの使
用に伴い液に難溶な化合物を多量に形成し、反応液が濃
厚なスラリー状となってしまう。これによって、液の取
扱い、貴金属系触媒の回収、さらに生成ウレタンの分離
、精製が困難となる。(3NH2+ o-NO2+ 3 C0 → [phase] NH
C, OHN [phase] + 2 CO2 (7) σNHCOIN@
+, ROH -@-NHCOOR+ (gNHz (81 [Problem to be solved by the invention]) In recent years, as a production method that does not use phosgene, aromatic nitro compounds are used as raw materials, and in the presence of a catalyst, organic hydrous acid group compounds and monoxide Various methods have been proposed for reacting with carbon under high temperature and high pressure, but there are many problems that make it difficult to industrialize.In particular, in the catalytic reaction based on noble metals such as palladium, which is covered in this invention, Lewis acids and With the use of tertiary amines, a large amount of poorly soluble compounds are formed in the liquid, and the reaction liquid becomes a thick slurry. Purification becomes difficult.
一方、本発明者らは特開昭５７−１２００５５号明細書
記載の方法にしたがって、アニリン、ニトロベンゼン、
エタノールおよび水素を１０％含有したＣＯを用いて触
媒として５％Ｐｄ／Ｃを用いて反応を試みたところ、カ
ルバミン酸エステルはほとんど生成しなかった。さらに
、触媒として２価のＰｄを用いるほかは、上記と同様の
実験を行ったところカルバミン酸エステルがかなり生成
した。そこで、ＣＯ供給源として水素含有ｃＯガスを用
いた場合でも十分な量のカルバミン酸エステルが生成す
るように鋭意検討したところ、二１−口ベンゼンのみを
用いて上記目的を達成するに至った。On the other hand, the present inventors used aniline, nitrobenzene,
When a reaction was attempted using ethanol and CO containing 10% hydrogen and 5% Pd/C as a catalyst, almost no carbamate ester was produced. Furthermore, when an experiment similar to the above was conducted except that divalent Pd was used as a catalyst, a considerable amount of carbamate ester was produced. Therefore, as a result of intensive study to produce a sufficient amount of carbamate ester even when hydrogen-containing CO gas is used as a CO supply source, the above objective was achieved using only 21-benzene.
上記目的は、ニトロ基を有する化合物、一酸化炭素、水
素および有機含水酸基化合物を触媒として周期律第■族
の白金族に属する遷移金属化合物、非金属ハロゲン化物
および水の存在下で反応させることによって達成される
。The above purpose is to react a compound having a nitro group, carbon monoxide, hydrogen, and an organic hydrous acid group compound in the presence of a transition metal compound belonging to the platinum group of Group I of the Periodic Table, a nonmetal halide, and water. achieved by.
本発明においては、水素を含有したＣＯガスを用いても
触媒の性能低下もなく、同様に目的を達成することがで
きる。また原料はニトロベンゼン、アルコール、水素、
ＣＯで高収率でカルバミン酸エステルの合成が可能であ
る。In the present invention, even if CO gas containing hydrogen is used, there is no deterioration in the performance of the catalyst, and the objective can be achieved in the same way. The raw materials are nitrobenzene, alcohol, hydrogen,
Carbamate esters can be synthesized in high yields using CO.
触媒として、周期律第■族の白金族の遷移金属単体また
は／およびその化合物を担体に担持し、さらにハロゲン
化水溶液を用いていることにより、有機含水酸基化合物
を過剰に添加しても金属触媒の酸化還元反応に伴う活性
低下はほとんどなく、さらにジフェニルウレアの副生を
かなり抑制することができ、カルバミン酸エステル収率
を向上させ、さらに反応液のスラリー化をなくし、触媒
の分離、回収が容易になる。As a catalyst, a single transition metal of the platinum group of Group I of the Periodic Table or/and its compound is supported on a carrier, and an aqueous halogenated solution is used, so that even if an excessive amount of an organic hydrous acid group compound is added, the metal catalyst remains There is almost no decrease in activity associated with the redox reaction of , and the by-product of diphenylurea can be significantly suppressed, improving the carbamate ester yield, eliminating slurrying of the reaction solution, and facilitating separation and recovery of the catalyst. becomes easier.
水素を含んだガスをまず反応式（９）によりニトロベン
ゼンとによりアニリンを生成し、その後生成したアニリ
ン、ニトロベンゼン、ＣＯおよびエタノールとで反応式
（１０）によりＮ−フェニルカルバミン酸エチルを製造
することによって水素を含むガスを有効に利用できる。First, hydrogen-containing gas is reacted with nitrobenzene according to reaction formula (9) to produce aniline, and then the produced aniline, nitrobenzene, CO and ethanol are used to produce ethyl N-phenylcarbamate according to reaction formula (10). Gas containing hydrogen can be used effectively.
Ｃ南０２＋３Ｈ２→ｅＮＩ−１２＋ ２ Ｈ２０（９＋
＠Ｎ Ｈ２＋ （（Σ）−ＮＯ２＋ ３ Ｃｏ
−） ２ ＲＯＨ−２（２）−ＮＨｃｏｏＲ＋Ｈ２
ｏ＋ｃ○２ （１０）本発明で触媒として用いられる
白金族の遷移全屈は、Ｐｄ、Ｐｈ、Ｒｕの単体または化
合物であり、それらは１種またはそれ以上混合してもよ
い。C South 02+3H2 → eNI-12+ 2 H20 (9+
@N H2+ ((Σ)-NO2+ 3 Co
-) 2 ROH-2(2)-NHcooR+H2
o+c○2 (10) The platinum group transition metal used as a catalyst in the present invention is Pd, Ph, and Ru alone or as a compound, and one or more of them may be mixed.
その化合物としてはハロゲン化物、チオシアン化物、シ
アン化物、イソシアン化物、硫酸塩、硝酸塩、酢酸塩、
酸化物などがあげられる。担体として、炭酸カルシウム
、ケイ酸アルミニウム、ケイ酸マグネシウム、硫酸バリ
ウム、シリカ、アルミナアスベスト、ベントナイト、け
いそう土、フラー土、有機イオン交換体、無機イオン交
換体、モレキュラーシーブなどに担持させて用いてもよ
い。The compounds include halides, thiocyanides, cyanides, isocyanides, sulfates, nitrates, acetates,
Examples include oxides. As a carrier, it can be supported on calcium carbonate, aluminum silicate, magnesium silicate, barium sulfate, silica, alumina asbestos, bentonite, diatomaceous earth, Fuller's earth, organic ion exchanger, inorganic ion exchanger, molecular sieve, etc. Good too.
さらにこれらはＰｄ、Ｒｈ、Ｒｕとは別に反応器に仕込
んでもよい。Furthermore, these may be charged into the reactor separately from Pd, Rh, and Ru.
白金族化合物の量はその種類、反応条件によって変化す
るがニトロ基化合物に対して金属単体として重量比でｌ
〜ｌＸｌ０−”、好ましくは５×ＩＱ−１〜ｌＸｌ０−
”の範囲で用いられる。また担体の使用量は金属単体に
対してｔｉｔ比で５〜１０００倍程度、好ましくは１０
〜５００倍程度である。The amount of the platinum group compound varies depending on its type and reaction conditions, but the weight ratio of the platinum group compound as a single metal to the nitro group compound is 1.
˜lXl0−”, preferably 5×IQ−1˜lXl0−
The amount of carrier used is about 5 to 1000 times, preferably 10
~500 times.
助触媒として用いる非金属ハロゲン化物としては塩化水
素、臭化水素、ヨウ化水素等のハロゲン化水素、塩化ア
ンモニウム、臭化アンモニウム、ヨウ化アンモニウム等
のハロゲン化アンモニウム、塩化チオニル等のイオウの
酸ハロゲン化物、三塩化ホスホリル等のオキシハロゲン
化リン、塩化ベンジル、ヨウ化ベンジル等のハロゲン化
ベンジル化合物、ヨウ化メチル等のハロゲン化アルキル
が用いられるが塩化水素が特に好ましい。助触媒として
用いる非金属ハロゲン化物の量は、白金族金属単体１グ
ラム原子に対してハロゲン原子が２〜１５００グラム原
子、好ましくは１０〜５００グラム原子程度である。Examples of nonmetal halides used as promoters include hydrogen halides such as hydrogen chloride, hydrogen bromide, and hydrogen iodide; ammonium halides such as ammonium chloride, ammonium bromide, and ammonium iodide; and sulfur acid halides such as thionyl chloride. Phosphorus oxyhalides such as phosphoryl trichloride, benzyl halides such as benzyl chloride and benzyl iodide, and alkyl halides such as methyl iodide are used, but hydrogen chloride is particularly preferred. The amount of the nonmetal halide used as a cocatalyst is about 2 to 1,500 g atoms, preferably about 10 to 500 g atoms of halogen per 1 g atom of the platinum group metal alone.
本発明において主原料の有機ニトロ化合物は、芳香族モ
ノニトロ化合物、ポリニトロ化合物、脂肪族モノニトロ
化合物またはポリニトロ化合物のいずれでもよい。例え
ば、芳香族ニトロ化合物の中には、ニトロベンゼン類、
ジニトロベンゼン類、ジニトロトルエン類、ニトロナフ
タレン類、ニトロアンスラセン類、ニトロビフェニル類
、ビスにトロフェニル）アルカン類、ビスにトロフェニ
ル）エーテル類、ビスにトロフェニル）チオエーテル類
、ビスにトロフェニル）スルホン類、ニトロジフェノキ
シアルカン類、ニトロフェノチアジン類あるいは５−ニ
トロピリミジンのようなヘテロ芳香族化合物などがあげ
られる。具体的な化合物としては、ニトロブンゼン、０
−ｌｍ−またはｐ−二Ｉ・ロトルエン、０−ニトロ−ｐ
−キシレン、１−ニトロナフタレン、ｍ−またはｐ−
ジニトロベンゼン、２，４−または２．６−シニトロト
ルエン、ジニトロナフタレン、４，４′−ジニトロビフ
ェニル、４．４’−ジニトロジベンジル、ビス（４−ニ
トロフェニル）エーテル、ビス（２，４−ジニトロフェ
ニル）エーテル、ビス（４−ニトロフェニル）チオエー
テル、ビス（４−ニトロフェニル）スルホン、ビス（４
−二トロフエノキシ）エタン、α、α９−ジニトロ−ｐ
−キシレン、α、α１−ジニトロ−ｍ−キシレン、２゜
４．６−ドリニＩ・ロトルエン、〇−１ｍ−またはｐ
−クロロニＩ・ロヘンゼン、ｌ−クロｔｌｌｌ−２，４
−ジニトロベンゼン、１−７’ロモー４−二ｌ−ロヘン
ゼン、１−フルオロ−２，４−ジニトロベンゼン、０−
ｌｍ−またはｐ−ニトロフェニルカルバミン酸エステル
、ｏ−ｌｍ−またはｐ−ニトロアニソール、２．４−ジ
ニトロフェネト−ル、ｍ−ニトロベンズアルデヒド、ｐ
−二トロベンゾクロライド、エチル−ｐ−ニトロベンゾ
エート、ｍ −ニトロヘンゼンスルホニルクロリド、ｐ
−二１・ロ無水フタール酸、３．３°−ジメチルまたは
４゜４′−ジニトロビフェニル、１．５−ジニトロナフ
タレンなどがあげられる。また、脂肪族二１・口化合物
としては、ニトロメタン、ニトロブタン、２．２１−ジ
メチルニトロブタン、ニトロシクロベンクン、３−メチ
ルニトロブタン、ニトロオクタン、３−ニトロプロペン
−１、フェニルニトロメタン、ｐ−ブロモフェニルニト
ロメタン、ｐ−メトキシフェニルニトロメタン、ジニト
ロエタン、ジニトロヘキサン、ジニトロシクロヘキサン
、ジーにトロヘキシル）メタンが挙げられる。さらに、
これらの化合物の異性体、混合物、同族体も使用できる
。In the present invention, the organic nitro compound as the main raw material may be any of an aromatic mononitro compound, a polynitro compound, an aliphatic mononitro compound, or a polynitro compound. For example, aromatic nitro compounds include nitrobenzenes,
Dinitrobenzenes, dinitrotoluenes, nitronaphthalenes, nitroanthracenes, nitrobiphenyls, bis-trophenyl) alkanes, bis-trophenyl) ethers, bis-trophenyl) thioethers, bis-trophenyl) Examples thereof include sulfones, nitrodiphenoxyalkanes, nitrophenothiazines, and heteroaromatic compounds such as 5-nitropyrimidine. Specific compounds include nitrobenzene, 0
-lm- or p-2I-rotoluene, 0-nitro-p
-xylene, 1-nitronaphthalene, m- or p-
Dinitrobenzene, 2,4- or 2,6-sinitrotoluene, dinitronaphthalene, 4,4'-dinitrobiphenyl, 4,4'-dinitrodibenzyl, bis(4-nitrophenyl) ether, bis(2,4- dinitrophenyl) ether, bis(4-nitrophenyl) thioether, bis(4-nitrophenyl) sulfone, bis(4-nitrophenyl) ether, bis(4-nitrophenyl) sulfone,
-nitrophenoxy)ethane, α,α9-dinitro-p
-xylene, α, α1-dinitro-m-xylene, 2゜4.6-dolini-I-rotoluene, 〇-1m- or p
- Chloroni I Lohenzen, l-crotllll-2,4
-Dinitrobenzene, 1-7' lomo-4-2-lohenzene, 1-fluoro-2,4-dinitrobenzene, 0-
lm- or p-nitrophenylcarbamate ester, o-lm- or p-nitroanisole, 2,4-dinitrophenethol, m-nitrobenzaldehyde, p
-nitrobenzochloride, ethyl-p-nitrobenzoate, m -nitrobenzenesulfonyl chloride, p
Examples include -21-rophthalic anhydride, 3.3°-dimethyl or 4°4'-dinitrobiphenyl, and 1.5-dinitronaphthalene. In addition, examples of aliphatic 21-methane compounds include nitromethane, nitrobutane, 2,21-dimethylnitrobutane, nitrocyclobencune, 3-methylnitrobutane, nitrooctane, 3-nitropropene-1, phenylnitromethane, p- Examples include bromophenylnitromethane, p-methoxyphenylnitromethane, dinitroethane, dinitrohexane, dinitrocyclohexane, and di(trohexyl)methane. moreover,
Isomers, mixtures and homologs of these compounds can also be used.
有機含水酸基化合物としては、第一、第二または第三級
水酸基を含む一価アルコールまたは多価アルコールがあ
げられる。具体的にはメチルアルコール、エチルアルコ
ール、ｎ−およヒｉ ｓ ｏ −ブチルアルコール、ｎ
−１ｉｓｏ−およびｔ−ブチルアルコール、ｎ−または
１ｓｏ−アミルアルコール、ヘキシルアルコール、ラウ
リルアルコール、七チルアルコール等の脂肪族−価アル
コール、シクロペンタノール、シクロヘキシルアルコー
ル等（７） 脂１’Ｊ Ｋ −（ｉ［５アルコール、ベ
ンジルアルコール、クロルベンジルアルコールおよびメ
トキシベンジルアルコール等の芳香族−価アルコール、
エチレングリコール、ジエチレングリコール、プロピレ
ングリコール、ジプロピレングリコール等の二価アルコ
ール、グリセロール、ヘキサントリオール等の三価アル
コールがあげられる。Examples of organic hydrous acid group compounds include monohydric alcohols or polyhydric alcohols containing primary, secondary or tertiary hydroxyl groups. Specifically, methyl alcohol, ethyl alcohol, n- and iso-butyl alcohol, n
Aliphatic alcohols such as -1iso- and t-butyl alcohol, n- or 1so-amyl alcohol, hexyl alcohol, lauryl alcohol, heptyl alcohol, cyclopentanol, cyclohexyl alcohol, etc. (7) Fat 1'J K - (i[5 alcohol, aromatic-hydric alcohols such as benzyl alcohol, chlorobenzyl alcohol and methoxybenzyl alcohol,
Examples include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, and trihydric alcohols such as glycerol and hexanetriol.
本発明の方法は、溶媒を存在させずに行うこともできる
が、溶媒を用いてもよい。溶媒としては、ベンゼン、ト
ルエン、キシレンのような芳香族炭化水素、アセトニト
リル、プロピオニトリル、ベンゾニトリルのようなニト
リル類、ｈ ｍ ｐ ａのような有機リン化合物、スル
ホラン、ジメチルスルホランのようなスルホラン系溶媒
、モノクロルベンゼン、ジクロルベンゼンのようなハロ
ゲン化芳香族炭化水素、ヘプタン、メチルシクロヘキサ
ン、ケトン類、エステル類、ＴＨＦ、１．４−ジオキサ
ン、プロピレンカーボネート、Ｎ−メチルピロリドン、
ｌ、２−ジメトキシエタンなどから選ばれた少なくとも
１種の溶媒、またはこれらの混合物を用いることができ
る。The method of the invention can be carried out without the presence of a solvent, but a solvent may also be used. Examples of solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, nitriles such as acetonitrile, propionitrile, and benzonitrile, organic phosphorus compounds such as hmpa, and sulfolane such as sulfolane and dimethylsulfolane. System solvents, halogenated aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene, heptane, methylcyclohexane, ketones, esters, THF, 1,4-dioxane, propylene carbonate, N-methylpyrrolidone,
At least one solvent selected from 1, 2-dimethoxyethane, etc., or a mixture thereof can be used.
ＣＯおよび水素は単体ガスとしてまたは混合ガスの形と
して使用される。これらのガスとしてはナフサ等の熱分
解ガス、石炭ガス化からのガス各種製鉄所の副生ガスが
利用できる。CO and hydrogen are used as single gases or in the form of a gas mixture. As these gases, pyrolysis gas such as naphtha, gas from coal gasification, and various by-product gases from steel plants can be used.
ハロゲン化水素水溶液中の水は、あまり過剰に存在する
と反応速度を小さくして好ましくなく、その濃度は５０
０ｐｐｍ以上５０００ｐｐｍ以下であることが好ましい
。If water in the hydrogen halide aqueous solution is present in too much excess, it will reduce the reaction rate, which is undesirable;
It is preferably 0 ppm or more and 5000 ppm or less.
反応圧力は、ＣＯの分圧として１〜５０ ｋＨ／ ｃｒ
Ａ。The reaction pressure is 1 to 50 kH/cr as partial pressure of CO.
A.
好ましくは５〜３０ｋｇ／ｃｒｌである。Preferably it is 5 to 30 kg/crl.
反応温度は６０〜２３０℃、特に１５０〜２１Ｏ℃が好
ましい。The reaction temperature is preferably 60 to 230°C, particularly 150 to 210°C.
反応時間は、用いる該ニトロ基化合物の種類、他の反応
条件によって異なるが、一般に５分〜６時間の範囲で行
われる。反応終了後、反応混合物を冷却し、排気後、濾
過等により反応母液と触媒を分離して、母液から蒸留ま
たは他の適当な分離法により、カルバミン酸エステルを
分離する。The reaction time varies depending on the type of the nitro group compound used and other reaction conditions, but is generally carried out within a range of 5 minutes to 6 hours. After the reaction is completed, the reaction mixture is cooled, evacuated, and the reaction mother liquor and catalyst are separated by filtration or the like, and the carbamate ester is separated from the mother liquor by distillation or other suitable separation method.
以下、本発明に用いる装置系統を図面により説明する。Hereinafter, the apparatus system used in the present invention will be explained with reference to the drawings.
第１図は、本発明におけるカルバミン酸エステル製造の
系統図である。水素およびＣＯを含有するガスＡは合成
塔１に加圧後供給される。また、原料の二トロヘンゼン
Ｂ、エタノールＣも合成塔１へ供給される。合成塔１で
は塔内に白金族触媒／担体が充填されており、反応温度
、反応圧力、反応時間を所定値に葆って操作される。反
応液は触媒との接触を十分に行うためポンプにより合成
塔１内を循環することもできる。未反応のＣＯおよび水
素ガスは副生成ガスのＣＯ２Ｅを除去後再び合成塔１に
循環される。反応後の液は低沸蒸留塔２に導かれる。こ
こで、水、エタノール、溶媒等が塔頂より、ニトロベン
ゼン、Ｎ−フェニルカルバミン酸エチルは塔底より抜き
出される。塔底からの抜き出し液は蒸留塔４に導かれ、
塔底よりＮ−フェニルカルバミン酸エチルＩを回収する
。FIG. 1 is a systematic diagram of carbamate ester production in the present invention. Gas A containing hydrogen and CO is supplied to the synthesis column 1 after being pressurized. In addition, the raw materials Nitrohenzene B and Ethanol C are also supplied to the synthesis column 1. The synthesis column 1 is filled with a platinum group catalyst/carrier, and is operated by adjusting the reaction temperature, reaction pressure, and reaction time to predetermined values. The reaction solution can also be circulated within the synthesis column 1 using a pump to ensure sufficient contact with the catalyst. Unreacted CO and hydrogen gas are recycled to the synthesis column 1 again after removing CO2E as a by-product gas. The liquid after the reaction is led to a low-boiling distillation column 2. Here, water, ethanol, solvent, etc. are extracted from the top of the column, and nitrobenzene and ethyl N-phenylcarbamate are extracted from the bottom of the column. The liquid extracted from the bottom of the column is led to a distillation column 4,
Ethyl N-phenylcarbamate I is recovered from the bottom of the column.
低沸蒸留塔２の塔頂からの液は副生成物の水Ｇを除去後
再び合成塔１に循環される。蒸留塔４の塔頂からの回収
液も再び合成塔１に循環される。The liquid from the top of the low-boiling distillation column 2 is recycled to the synthesis column 1 again after removing the by-product water G. The recovered liquid from the top of the distillation column 4 is also circulated to the synthesis column 1 again.
第２図は、本発明におけるカルバミン酸エステル製造の
他の系統図である。水素およびＣＯを含有するガスＡは
アニリン合成塔８に加圧後供給され、また原料のニトロ
ベンゼンＢもアニリン合成塔８へ供給される。アニリン
合成塔８では塔内に白金族触媒／担体が充填されており
、反応温度、反応圧力、反応時間を所定値で操作される
。アニリン生成後の液は原料エタノールＣと合成塔ｌ・
＼供給される。合成塔１では塔内に白金族触媒／担体が
充瞑されており、反応温度、反応圧力、反応４時間を所
定値で操作される。合成塔で生成したＮ−フェニルカル
バミン酸エチルｌは前述と同様の操作により蒸留塔４の
塔底より回収される。FIG. 2 is another systematic diagram of carbamate ester production in the present invention. Gas A containing hydrogen and CO is supplied to the aniline synthesis tower 8 after being pressurized, and the raw material nitrobenzene B is also supplied to the aniline synthesis tower 8. The aniline synthesis tower 8 is filled with a platinum group catalyst/support, and the reaction temperature, reaction pressure, and reaction time are controlled at predetermined values. The liquid after aniline production is mixed with raw material ethanol C and synthesis tower L.
\Supplied. In the synthesis column 1, a platinum group catalyst/carrier is filled in the column, and the reaction temperature, reaction pressure, and reaction time are operated at predetermined values. Ethyl N-phenylcarbamate 1 produced in the synthesis column is recovered from the bottom of distillation column 4 in the same manner as described above.
第３図は、フェニルカルバミン酸エチルの収率に及ぼす
水素分圧の影響を示す図である。FIG. 3 is a diagram showing the influence of hydrogen partial pressure on the yield of ethyl phenylcarbamate.
本発明は、下記の実施例によって、さらに詳細に説明さ
れるが、下記の例に制限されるものではない。The invention will be explained in more detail by the following examples, but is not limited thereto.
比較例１
アルミナ１ｇにＰｄ（ＮＯ３）２水溶液を含浸し、１１
０℃、２ｈ乾燥後、５００℃、２ｈ乾燥し、担体付き触
媒を調製した。触媒はＰｄＯであり、Ｐｄ単位で３．４
４重量％であった。Comparative Example 1 1 g of alumina was impregnated with Pd(NO3)2 aqueous solution,
After drying at 0°C for 2 hours, it was dried at 500°C for 2 hours to prepare a supported catalyst. The catalyst is PdO, with Pd units of 3.4
It was 4% by weight.
内容積１００ｍｊ！のテフロン加工したステンレス製オ
ートクレーブに上記触媒６１．９■（０，０２０モル）
、アニリン０．９３１ｇ（０，０１０モル）、ニトロベ
ンゼン１．２３ ｇ （０，０１０モル）、エタノール
４．６１ｇ（０，１０モル）、トルエン１０．６ｇ（０
，１１モル）および３５％塩酸水溶液０．０７１ ｇ
（Ｈ（１！＝０．６８ミリモル、Ｈ２０＝０．０ロア
ミリモルを仕込み、系内の空気をパージせずに室温で１
００％ＣＯガスを２８ｋｇ／ｃ＋＋ｔまで導入し反応温
度１９０℃で３時間反応させた。反応後、室温まで冷却
し系内を大気圧に戻し反応生成物をガスクロマトグラフ
ィーおよび液体クロマトグラフィーで分析したところ、
Ｎ−フェニルカルバミン酸エステル（以下、ＮＰＵと省
略する）が２．９７ｇ生成した（Ｎ Ｐ Ｕ収率９０％
）。Inner volume 100mj! 61.9 μ (0,020 mol) of the above catalyst was placed in a Teflon-treated stainless steel autoclave.
, 0.931 g (0,010 mol) of aniline, 1.23 g (0,010 mol) of nitrobenzene, 4.61 g (0,10 mol) of ethanol, 10.6 g (0,000 mol) of toluene.
, 11 mol) and 35% aqueous hydrochloric acid solution 0.071 g
(H (1! = 0.68 mmol, H20 = 0.0 mmol was charged, 1! = 0.68 mmol, H20 = 0.0 mmol,
00% CO gas was introduced to 28 kg/c++t, and the reaction was carried out at a reaction temperature of 190° C. for 3 hours. After the reaction, the system was cooled to room temperature and returned to atmospheric pressure, and the reaction products were analyzed by gas chromatography and liquid chromatography.
2.97g of N-phenylcarbamate ester (hereinafter abbreviated as NPU) was produced (NPU yield 90%).
).
比較例２．３
水素分圧を種々変え、比較例１と同様の実験を行ったと
ころ第３図に示す結果を得た。Comparative Example 2.3 When the same experiment as in Comparative Example 1 was conducted with various hydrogen partial pressures, the results shown in FIG. 3 were obtained.
比較例４
水素分圧２１ａｔｍ、Ｃｏ分圧７ａｔｍのガスを用いて
、比較例１と同様の実験を行ったところＮＰＵの収率は
１０％以下となった。Comparative Example 4 When an experiment similar to Comparative Example 1 was conducted using gas with a hydrogen partial pressure of 21 atm and a Co partial pressure of 7 atm, the yield of NPU was 10% or less.
実施例１
アニリン量を０としてニトロベンゼン２．４６ ｇ（０
，０２モル）とし、ほかは比較例４と同様の実験を行っ
たところ、ＮＰＵの生成量は２．９５ｇ（ＮＰＵ収率８
９％）となった。Example 1 Nitrobenzene 2.46 g (0
, 02 mol), and otherwise conducted the same experiment as in Comparative Example 4, the amount of NPU produced was 2.95 g (NPU yield 8
9%).
実施例２
アニリン量を０としてニトロベンゼン１．２３ ｇ（０
，０２モル）と水素分圧２１ａＬｍ、Ｃｏ分圧７ａｔｍ
を触媒存在下で接触させた後、ニトロベンゼン１．２３
ｇ （０，０１０モル）、エタノール４゜６１ｇ（０
，１０モル）、トルエンｌｏ、６ｇ（０，１１モル）お
よび３５％塩酸水溶液０．０７１ ｇ （ＨＣβ＝０．
６８ミリモル、Ｈ２０＝０．０ロアミリモルを仕込、ガ
スはＣＯ分圧２８ａｔｍで、反応温度１９０℃で３時間
反応させた。反応後、室温まで冷却し系内を大気圧に戻
し、反応生成物をガスクロマトグラフィーおよび液体ク
ロマトグラフィーで分析したところ、Ｎ−フェニルカル
バミン酸エステルが２．９９７ ｇ生成した（Ｎ Ｐ
Ｕ収率９２％）。Example 2 Nitrobenzene 1.23 g (0
, 02 mol), hydrogen partial pressure 21aLm, Co partial pressure 7atm
After contacting in the presence of a catalyst, nitrobenzene 1.23
g (0,010 mol), ethanol 4°61 g (0
, 10 mol), toluene lo, 6 g (0.11 mol) and 35% aqueous hydrochloric acid solution 0.071 g (HCβ=0.
68 mmol, H20 = 0.0 mmol were charged, and the gas was reacted at a CO partial pressure of 28 atm and a reaction temperature of 190° C. for 3 hours. After the reaction, the system was cooled to room temperature and returned to atmospheric pressure, and the reaction product was analyzed by gas chromatography and liquid chromatography. As a result, 2.997 g of N-phenylcarbamate was produced (NP
U yield 92%).
本発明によれば、白金族金属化合物および担体存在下、
有機ニトロ化合物、一酸化炭素、水素および有機含水酸
基化合物からカルバミン酸エステルを製造する際、該触
媒の使用量が著しく低く、原料ガスは水素を含有したＣ
Ｏガスを用いることができ、しかもＣＯ圧が１〜５０ｋ
ｇ／ｃｆｌｌという低圧で、カルバミン酸エステルを高
収率で合成でき、工業的に有利である。According to the present invention, in the presence of a platinum group metal compound and a carrier,
When producing carbamate esters from organic nitro compounds, carbon monoxide, hydrogen, and organic hydrous acid group compounds, the amount of the catalyst used is extremely low, and the raw material gas is carbon containing hydrogen.
O gas can be used, and the CO pressure is 1 to 50 k
Carbamate esters can be synthesized in high yields at low pressures of g/cfll, which is industrially advantageous.
第１図および第２図は、本発明におけるカルバミン酸エ
ステルの系統図、第３図はＮ−フェニルカルバミン酸エ
チル（ＮＰＵ）収率に及ぼす水素分圧の影響の実験結果
である。
特許出願人 バブコック日立株式会社
代理人 弁理士 川 北 武 長
】：合成塔
２：低沸蒸留塔
３：脱水塔
１：蒸留塔
Ａ：Ｃ○、Ｈ２含有ガヌ
Ｂ：ニトロベンゼン
Ｃ：エタノール
Ｅ：ＣＯ２
Ｆ：回収エタノール
Ｇ：水
Ｈ：回収液
Ｉ：ＮＰｔＪ
】】：触媒層
第２図
５：脱水塔
８ニアニリン合成塔
１２：触媒槽FIGS. 1 and 2 are systematic diagrams of carbamate esters in the present invention, and FIG. 3 is an experimental result of the influence of hydrogen partial pressure on the yield of ethyl N-phenylcarbamate (NPU). Patent applicant Babcock-Hitachi Co., Ltd. Representative Patent attorney Takeshi Kawakita]: Synthesis tower 2: Low-boiling distillation tower 3: Dehydration tower 1: Distillation tower A: C○, H2-containing Ganu B: Nitrobenzene C: Ethanol E: CO2 F: Recovered ethanol G: Water H: Recovered liquid I: NPtJ ]]: Catalyst layer Figure 2 5: Dehydration tower 8 Nianiline synthesis tower 12: Catalyst tank
Claims (1)
び有機含水酸基化合物を触媒として周期律第VIII族の白
金族に属する遷移金属化合物、非金属ハロゲン化物およ
び水の存在下で反応させることを特徴とするカルバミン
酸エステル類の製造方法。(1) Reaction using a compound having a nitro group, carbon monoxide, hydrogen, and an organic hydrous acid group compound as a catalyst in the presence of a transition metal compound belonging to the platinum group of Group VIII of the Periodic Table, a nonmetal halide, and water. Characteristic method for producing carbamate esters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63228948A JPH0278651A (en) | 1988-09-13 | 1988-09-13 | Production of carbamic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63228948A JPH0278651A (en) | 1988-09-13 | 1988-09-13 | Production of carbamic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0278651A true JPH0278651A (en) | 1990-03-19 |
Family
ID=16884365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63228948A Pending JPH0278651A (en) | 1988-09-13 | 1988-09-13 | Production of carbamic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0278651A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5447706A (en) * | 1991-03-05 | 1995-09-05 | Solvay Interox | Direct synthesis of hydrogen peroxide by heterogeneous catalysis, catalyst for the said synthesis and method of preparation of the said catalyst |
-
1988
- 1988-09-13 JP JP63228948A patent/JPH0278651A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5447706A (en) * | 1991-03-05 | 1995-09-05 | Solvay Interox | Direct synthesis of hydrogen peroxide by heterogeneous catalysis, catalyst for the said synthesis and method of preparation of the said catalyst |
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