JPH0460463B2 - - Google Patents
Info
- Publication number
- JPH0460463B2 JPH0460463B2 JP60195306A JP19530685A JPH0460463B2 JP H0460463 B2 JPH0460463 B2 JP H0460463B2 JP 60195306 A JP60195306 A JP 60195306A JP 19530685 A JP19530685 A JP 19530685A JP H0460463 B2 JPH0460463 B2 JP H0460463B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- reaction
- urea
- primary amine
- 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.)
- Expired - Lifetime
Links
- 238000006243 chemical reaction Methods 0.000 claims description 48
- -1 aromatic primary amine Chemical class 0.000 claims description 44
- 125000003118 aryl group Chemical group 0.000 claims description 33
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 13
- 239000010948 rhodium Substances 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 24
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000007858 starting material Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 235000013877 carbamide Nutrition 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 150000002366 halogen compounds Chemical class 0.000 description 5
- IAGUPODHENSJEZ-UHFFFAOYSA-N methyl n-phenylcarbamate Chemical compound COC(=O)NC1=CC=CC=C1 IAGUPODHENSJEZ-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000003672 ureas Chemical class 0.000 description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical class C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 1
- BSFHJMGROOFSRA-UHFFFAOYSA-N 1,4-dimethyl-2-nitrobenzene Chemical group CC1=CC=C(C)C([N+]([O-])=O)=C1 BSFHJMGROOFSRA-UHFFFAOYSA-N 0.000 description 1
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 1
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-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
- RJKGJBPXVHTNJL-UHFFFAOYSA-N 1-nitronaphthalene Chemical class C1=CC=C2C([N+](=O)[O-])=CC=CC2=C1 RJKGJBPXVHTNJL-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- IZNWACYOILBFEG-UHFFFAOYSA-N 2-methyl-1-nitronaphthalene Chemical compound C1=CC=CC2=C([N+]([O-])=O)C(C)=CC=C21 IZNWACYOILBFEG-UHFFFAOYSA-N 0.000 description 1
- JMBLSGAXSMOKPN-UHFFFAOYSA-N 2-methylnaphthalen-1-amine Chemical compound C1=CC=CC2=C(N)C(C)=CC=C21 JMBLSGAXSMOKPN-UHFFFAOYSA-N 0.000 description 1
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 1
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-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
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- RHKGZYVYKXVQSD-MECAPONASA-N [Rh].[O+]#[C-].C\C(O)=C\C(C)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound [Rh].[O+]#[C-].C\C(O)=C\C(C)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RHKGZYVYKXVQSD-MECAPONASA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- YUENFNPLGJCNRB-UHFFFAOYSA-N anthracen-1-amine Chemical class C1=CC=C2C=C3C(N)=CC=CC3=CC2=C1 YUENFNPLGJCNRB-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 1
- IETKMTGYQIVLRF-UHFFFAOYSA-N carbon monoxide;rhodium;triphenylphosphane Chemical compound [Rh].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 IETKMTGYQIVLRF-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- LBKPGNUOUPTQKA-UHFFFAOYSA-N ethyl n-phenylcarbamate Chemical compound CCOC(=O)NC1=CC=CC=C1 LBKPGNUOUPTQKA-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- YPLPZEKZDGQOOQ-UHFFFAOYSA-M iron oxychloride Chemical compound [O][Fe]Cl YPLPZEKZDGQOOQ-UHFFFAOYSA-M 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000008096 xylene Substances 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、芳香族ウレタンの製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to a method for producing aromatic urethane.
従来芳香族ウレタンの製法が種々提案されてい
るが、これらは芳香族ニトロ化合物を出発原料と
する方法と、芳香族第１アミンを出発原料とする
方法とに大別される。
Various methods for producing aromatic urethanes have been proposed in the past, and these can be broadly classified into methods using aromatic nitro compounds as starting materials and methods using aromatic primary amines as starting materials.
芳香族ニトロ化合物を出発原料とする方法は、
芳香族ニトロ化合物（例えばニトロベンゼン）
と、水酸基を含有する有機化合物（例えばアルコ
ール類）と一酸化炭素とを、パラジウム、ロジウ
ム等の白金族金属化合物を主体とする触媒の存在
下で反応させて還元的に芳香族ウレタンを製造す
る方法である、この方法は、例えば特開昭51−
98240、特開昭54−22339、特公昭43−23939等に
提案されている。 The method using an aromatic nitro compound as a starting material is
Aromatic nitro compounds (e.g. nitrobenzene)
Aromatic urethane is produced reductively by reacting an organic compound containing a hydroxyl group (e.g. alcohol) with carbon monoxide in the presence of a catalyst mainly consisting of a platinum group metal compound such as palladium or rhodium. This method is described, for example, in Japanese Patent Application Laid-Open No. 1986-
98240, Japanese Patent Publication No. 54-22339, Japanese Patent Publication No. 43-23939, etc.
また芳香族第１アミンを出発原料とする方法
は、酸素又は有機ニトロ化合物などの酸化剤の存
在下に、芳香族第１アミン（例えばアニリン）と
水酸基を含有する有機化合物（例えばアルコール
類）と一酸化炭素とを、パラジウム、ロジウム等
の白金族金属化合物を主体とする触媒の存在下に
反応させて、酸化的に芳香族ウレタンを製造する
方法である。この方法は、例えば特開昭55−
124750、特開昭55−120551、特開昭59−172451等
に提案されている。 In addition, a method using an aromatic primary amine as a starting material involves combining an aromatic primary amine (e.g., aniline) and an organic compound containing a hydroxyl group (e.g., alcohols) in the presence of an oxidizing agent such as oxygen or an organic nitro compound. This is a method for producing aromatic urethane oxidatively by reacting carbon monoxide with a catalyst mainly composed of a platinum group metal compound such as palladium or rhodium. This method is used, for example, in JP-A-55-
124750, JP-A-55-120551, JP-A-59-172451, etc.
この場合、いずれの方法も触媒主成分である白
金族金属化合物単独ではウレタン合成活性が低い
ため助触媒として塩化鉄、オキシ塩化鉄、オキシ
塩化バナジウム、ヨウ化カリウム等のハロゲン化
合物を用い、これを反応系に溶解している。しか
しハロゲン化合物は反応容器や配管バルブなどの
金属材料に対する腐食性が大きく、このため耐食
性の優れた高価な金属材料を使用しなければなら
ない。 In this case, in both methods, urethane synthesis activity is low when the platinum group metal compound alone, which is the main component of the catalyst, is used as a promoter, so halogen compounds such as iron chloride, iron oxychloride, vanadium oxychloride, potassium iodide, etc. Dissolved in the reaction system. However, halogen compounds are highly corrosive to metal materials such as reaction vessels and piping valves, and therefore expensive metal materials with excellent corrosion resistance must be used.
更に主触媒である白金族金属化合物を反応溶液
中に溶解させて使用する場合はもちろん金属状態
の固体として使用する場合でも、白金族金属の一
部はハロゲン化合物のために反応溶液中に溶出す
る。しかし反応終了後反応溶液中から白金族金属
化合物を回収するには、煩雑な操作と多大な費用
を要する。 Furthermore, when the platinum group metal compound, which is the main catalyst, is used dissolved in the reaction solution, and even when used as a solid in a metallic state, some of the platinum group metal is eluted into the reaction solution due to the halogen compound. . However, recovering the platinum group metal compound from the reaction solution after the completion of the reaction requires complicated operations and a large amount of cost.
また反応溶媒として、反応原料である水酸基含
有有機化合物を使用するが、芳香族ウレタンは、
この水酸基含有有機化合物に対する溶解度が非常
に大きい。このため反応後の溶液から芳香族ウレ
タンを晶析により分離回収する場合、溶液を零下
数十度の極低温まで冷却するか、あるいは溶液を
濃縮した後冷却して結晶を析出させる操作が必要
となる。しかもこの操作を行つても芳香族ウレタ
ンと溶液中に溶解している触媒成分とを分別して
回収することは困難である。また芳香族ウレタン
の別の回収方法として蒸留による方法も考えられ
る。しかしこの場合、溶解している触媒を蒸留残
留物として回収するために、芳香族ウレタンを留
出させなければならない。ところが芳香族ウレタ
ンは、高沸点化合物であり、１mmＨｇ程度の高真
空下、100〜150℃の中温度域で蒸留を行なわなけ
ればならない。 In addition, as a reaction solvent, a hydroxyl group-containing organic compound, which is a reaction raw material, is used, but aromatic urethane is
It has a very high solubility in this hydroxyl group-containing organic compound. Therefore, when aromatic urethane is separated and recovered from the solution after the reaction by crystallization, it is necessary to cool the solution to an extremely low temperature of several tens of degrees below zero, or to concentrate the solution and then cool it to precipitate crystals. Become. Moreover, even if this operation is performed, it is difficult to separate and recover the aromatic urethane and the catalyst component dissolved in the solution. Distillation may also be considered as another method for recovering aromatic urethane. However, in this case the aromatic urethane must be distilled off in order to recover the dissolved catalyst as a distillation residue. However, aromatic urethane is a high boiling point compound and must be distilled under a high vacuum of about 1 mmHg and at a medium temperature range of 100 to 150°C.
更に芳香族ニトロ化合物を出発原料とした場
合、反応終了後の溶液中に未反応の芳香族ニトロ
化合物が少量残留する。この状態で蒸留を行なう
と、芳香族ウレタンが芳香族ニトロ化合物により
褐色に着色してしまう。 Furthermore, when an aromatic nitro compound is used as a starting material, a small amount of unreacted aromatic nitro compound remains in the solution after the reaction is completed. If distillation is carried out in this state, the aromatic urethane will be colored brown by the aromatic nitro compound.
以上の如く、芳香族ウレタンを溶液から分離回
収し、更に触媒を回収して再使用することは、晶
析にせよ蒸留にせよ困難である。 As described above, it is difficult to separate and recover aromatic urethane from a solution, and further recover and reuse the catalyst, whether by crystallization or distillation.
更にまた芳香族ニトロ化合物を出発原料とする
場合は芳香族アミンが、芳香族第１アミンを出発
原料とする場合はＮ，N′−ジ置換ウレアが副生
し、芳香族ウレタンの収率が低下する欠点があ
る。 Furthermore, when an aromatic nitro compound is used as a starting material, aromatic amine is produced, and when an aromatic primary amine is used as a starting material, N,N'-disubstituted urea is produced as a by-product, and the yield of aromatic urethane is reduced. There is a drawback that it decreases.
この発明は、上記事情に鑑みてなされたもの
で、その目的とするところは、ハロゲン化合物を
助触媒として使用せずこの使用による各種問題を
解消できるとともに、２段の反応で芳香族ウレタ
ンを製造することにより、その収率を向上し、し
かも触媒及び生成した芳香族ウレタンの回収を容
易におこなえる芳香族ウレタンの製造方法を得ん
とするものである。
This invention was made in view of the above circumstances, and its purpose is to eliminate various problems caused by the use of halogen compounds as promoters without using them, and to produce aromatic urethane through a two-stage reaction. By doing so, it is an object of the present invention to provide a method for producing aromatic urethane in which the yield can be improved and the catalyst and the produced aromatic urethane can be easily recovered.
この発明は、芳香族モノニトロ化合物と芳香族
第１アミンと一酸化炭素とをロジウム錯体化合物
を主体とする触媒を用いて反応させて、Ｎ，
N′−ジ置換ウレアを生成し、次いで生成したＮ，
N′−ジ置換ウレアを反応液から分離回収するウ
レア生成工程と、前記ウレア生成工程で得られた
Ｎ，N′−ジ置換ウレアと水酸基を含有する有機
化合物とを反応させて芳香族第１アミンと芳香族
ウレタンとを生成し、次いで芳香族第１アミンを
分離して芳香族ウレタンを得る工程と、分離した
芳香族第１アミンを前記ウレア生成工程へ循環す
る工程と、を具備してなる芳香族ウレタンの製造
方法である。
In this invention, an aromatic mononitro compound, an aromatic primary amine, and carbon monoxide are reacted using a catalyst mainly composed of a rhodium complex compound.
N'-disubstituted urea is produced, and then the produced N,
A urea production step in which N'-disubstituted urea is separated and recovered from the reaction solution, and an aromatic first The method comprises a step of producing an amine and an aromatic urethane, and then separating the aromatic primary amine to obtain an aromatic urethane, and a step of recycling the separated aromatic primary amine to the urea production step. This is a method for producing aromatic urethane.
まず下式に示すように芳香族モノニトロ化合物
と芳香族第１アミンと一酸化炭素とをロジウム錯
体化合物を主体とする触媒を使用して反応させ
る。
First, as shown in the following formula, an aromatic mononitro compound, an aromatic primary amine, and carbon monoxide are reacted using a catalyst mainly composed of a rhodium complex compound.
この第１段目の反応には、通常ヘプタン、シク
ロヘキサン、ベンゼン、トルエン、キシレン、各
種石油留分のような脂肪族、脂環族および芳香族
炭化水素類が溶剤として用いられる。ただし溶剤
を使用しなくてもよい。 In this first stage reaction, aliphatic, alicyclic and aromatic hydrocarbons such as heptane, cyclohexane, benzene, toluene, xylene and various petroleum fractions are usually used as solvents. However, it is not necessary to use a solvent.
芳香族モノニトロ化合物としては、ニトロベン
ゼン類、ニトロナフタレン類、ニトロアンスラセ
ン類、ニトロビフエニル類などがあり、具体的な
化合物として、ニトロベンゼン、ｏ−，ｍ−，及
びｐ−ニトロトルエン、ｏ−ニトロ−ｐ−キシレ
ン、２−メチル−１−ニトロナフタレン、ｏ−，
ｍ−，及びｐ−クロロニトロベンゼン、１−ブロ
モ−４−ニトロベンゼン、並びにこれらの芳香族
モノニトロ化合物の異性体更にはこれらの混合物
などが挙げられる。 Aromatic mononitro compounds include nitrobenzenes, nitronaphthalenes, nitroanthracenes, nitrobiphenyls, etc. Specific compounds include nitrobenzene, o-, m-, and p-nitrotoluene, o-nitro-p- xylene, 2-methyl-1-nitronaphthalene, o-,
Examples include m- and p-chloronitrobenzene, 1-bromo-4-nitrobenzene, isomers of these aromatic mononitro compounds, and mixtures thereof.
芳香族第１アミンとしては、アニリン類、アミ
ノナフタレン類、アミノアンスラセン類、アミノ
ビフエニル類などがあり、具体的な化合物として
アニリン、ｏ−，ｍ−，及びｐ−トルイジン、ｏ
−，ｍ−，及びｐ−クロロアニリン、α及びβナ
フチルアミン、２−メチル−１−アミノナフタレ
ン、並びにこれら芳香族第１アミンの異性体更に
はこれらの混合物などが挙げられる。 Examples of aromatic primary amines include anilines, aminonaphthalenes, aminoanthracenes, aminobiphenyls, etc. Specific compounds include aniline, o-, m-, and p-toluidine,
-, m-, and p-chloroaniline, α- and β-naphthylamine, 2-methyl-1-aminonaphthalene, isomers of these aromatic primary amines, and mixtures thereof.
一般化炭素は、純粋なものであつてもよく、又
窒素、アルゴン、ヘリウム、炭素ガス、炭化水
素、ハロゲン化炭化水素などを含むものであつて
もよい。 Generalized carbon may be pure or may contain nitrogen, argon, helium, carbon gas, hydrocarbons, halogenated hydrocarbons, and the like.
触媒として使用するロジウム錯体化合物として
は、Rh6（CO）16，RhH（CO）（PPh3）3，Rh
（acac）（CO）（PPh3），Rh（acac）（CO）2，Rh
（acac）3などが挙げられる。ただしacacはアセチ
ルアセトテートを示す。またルテニウム錯体化合
物単独に限らず、コバルト、鉄、ロジウム、パラ
ジウム等を複合して使用することもできる。 Rhodium complex compounds used as catalysts include Rh 6 (CO) 16 , RhH (CO) (PPh 3 ) 3 , Rh
(acac) (CO) (PPh 3 ), Rh (acac) (CO) 2 , Rh
(acac) 3 etc. However, acac indicates acetylacetate. Moreover, the ruthenium complex compound is not limited to a single compound, but a combination of cobalt, iron, rhodium, palladium, etc. can also be used.
反応温度は通常80〜300℃、好ましくは120〜
200℃で行なうのがよい。反応圧力は１〜500Kg／
cm2、好ましくは20〜300Kg／cm2の範囲で行なうの
がよい。反応時間は反応系、触媒およびその他の
反応条件によつて異なるが、通常数分乃至数時間
である。 The reaction temperature is usually 80~300℃, preferably 120~
It is best to do this at 200℃. Reaction pressure is 1~500Kg/
cm 2 , preferably in the range of 20 to 300 kg/cm 2 . The reaction time varies depending on the reaction system, catalyst and other reaction conditions, but is usually from several minutes to several hours.
しかしてこの反応で得られたＮ，N′−置換ウ
レアは前述の溶剤に対する溶解度が低い。このた
め反応終了後の溶液を室温程度に冷却するだけ
で、生成したＮ，N′−ジ置換ウレアが結晶とし
て析出してくる。従つてこの溶液を過すること
によりＮ，N′−ジ置換ウレアを固形物として得
られる。一方触媒は溶剤とともに溶液として得ら
れる。この触媒を含有した溶剤は、この反応に再
使用可能である。 However, the N,N'-substituted urea obtained by this reaction has low solubility in the above-mentioned solvents. Therefore, simply by cooling the solution after the reaction to about room temperature, the produced N,N'-disubstituted urea will precipitate as crystals. Therefore, by filtering this solution, N,N'-disubstituted urea can be obtained as a solid. On the other hand, the catalyst is obtained as a solution together with a solvent. This catalyst-containing solvent can be reused in this reaction.
次に得られたＮ，N′−置換ウレアと水酸基を
含有する有機化合物とを下式の如く反応させて芳
香族第１アミンと芳香族ウレタンとを生成する。 Next, the obtained N,N'-substituted urea and an organic compound containing a hydroxyl group are reacted as shown in the following formula to produce an aromatic primary amine and an aromatic urethane.
水酸基を含有する有機化合物としては、一価ア
ルコール類、一価フエノール類などがあり、具体
的には、メチル、エチル、ｎ−プロピル、イソ−
プロピル、ｎ−ブチル、イソ−ブチル及びｔ−ブ
チルの如き一価アルコール並びにフエノール、ク
ロロフエノール、メチル、エチル、ｎ−プロピ
ル、イソ−プロピルの如きアルキルフエノールな
どが挙げられる。 Organic compounds containing hydroxyl groups include monohydric alcohols, monohydric phenols, etc. Specifically, methyl, ethyl, n-propyl, iso-
Mention may be made of monohydric alcohols such as propyl, n-butyl, iso-butyl and t-butyl, and alkylphenols such as phenol, chlorophenol, methyl, ethyl, n-propyl, iso-propyl.
反応温度は、通常80〜300℃、好ましくは120〜
200℃の温度範囲で行なうのがよい。圧力は、通
常使用する水酸基含有有機化合物あるいは溶剤の
反応温度における自生圧下で行なう。 The reaction temperature is usually 80-300℃, preferably 120-300℃.
It is best to perform this at a temperature range of 200℃. The pressure is the autogenous pressure at the reaction temperature of the hydroxyl group-containing organic compound or solvent normally used.
そしてこの反応は触媒を使用することなく行う
ことができる。 And this reaction can be carried out without using a catalyst.
この反応終了後、蒸留操作を行ない、芳香族ウ
レタンを蒸留残留物として回収し、一方蒸留によ
り芳香族第１アミンを回収する。この芳香族第１
アミンは第１段目のＮ，N′−ジ置換ウレアの生
成反応に再使用する。 After completion of this reaction, a distillation operation is performed to recover the aromatic urethane as a distillation residue, while the aromatic primary amine is recovered by distillation. This aromatic first
The amine is reused in the first stage reaction for producing N,N'-disubstituted urea.
この発明によれば、第１段目の反応において生
成するＮ，N′−ジ置換ウレアが溶剤に対して溶
解度が低いので、これを容易に晶析でき、過に
より効率よくＮ，N′−ジ置換ウレアを回収する
ことができる。しかも触媒は溶剤とともに液中
に含まれるもので、これを第１段の反応に再使用
することができる。
According to this invention, since the N,N'-disubstituted urea produced in the first stage reaction has low solubility in a solvent, it can be easily crystallized and more efficiently N,N'-disubstituted urea can be crystallized. Di-substituted ureas can be recovered. Moreover, since the catalyst is contained in the liquid together with the solvent, it can be reused in the first stage reaction.
また触媒は、ロジウム錯体化合物を主体とする
もので、ハロゲン化合物を使用する必要がない。
このため材料の腐食が極めて少なく、高価な材料
を使用する必要がなくなる。 Further, the catalyst is mainly composed of a rhodium complex compound, and there is no need to use a halogen compound.
Therefore, corrosion of the material is extremely low, and there is no need to use expensive materials.
更に第１段目の反応は、副反応が少なく、高い
収率でＮ，N′−ジ置換ウレアを得ることができ
る。 Furthermore, in the first stage reaction, there are few side reactions and N,N'-disubstituted urea can be obtained in high yield.
また第２段目の反応では、触媒を使用する必要
がないので、芳香族ウレタンを留出せず、蒸留残
留物として回収できる。しかも蒸留する物質であ
る芳香族第１アミンと残留水酸基含有有機化合物
とは、比較的低沸点の物質であるため、温和な条
件で蒸留操作を行うことができ、操作が容易とな
る。しかも回収した芳香族第１アミンは、第１段
目のＮ，N′−ジ置換ウレア生成反応に再使用で
きる。更にまた第２段目の反応は、第１段目の反
応と同様副反応が少ない。このため二段階反応で
はあるが高い収率で芳香族ウレタンを製造するこ
とができる。 Furthermore, since there is no need to use a catalyst in the second stage reaction, the aromatic urethane cannot be distilled off and can be recovered as a distillation residue. Moreover, since the aromatic primary amine and the residual hydroxyl group-containing organic compound, which are the substances to be distilled, have relatively low boiling points, the distillation operation can be carried out under mild conditions, making the operation easy. Moreover, the recovered aromatic primary amine can be reused in the first stage N,N'-disubstituted urea production reaction. Furthermore, the second stage reaction has fewer side reactions, similar to the first stage reaction. Therefore, although it is a two-step reaction, aromatic urethane can be produced in high yield.
次に本発明の実施例につき説明する。なお各実
施例では、一般的な慣用名である「ウレタン」の
用語に代えて「カルバミン酸アルキル」の用語を
用い、個々の物質名を明確に表示している。
Next, examples of the present invention will be described. In each example, the term "alkyl carbamate" is used in place of the commonly used term "urethane", and the names of the individual substances are clearly indicated.
実施例 １
内容積200mlの電磁撹拌式オートクレーブにニ
トロベンゼン3.77ｇ、アニリン2.78ｇ、トルエン
34.03ｇ、Rh6（CO）160.38ｇ、トリフエニルホスフ
イン1.24ｇを入れ、系内を一酸化炭素で置換した
後、一酸化炭素を50Kg／cm2となるように圧入し
た。撹拌しながら160cmで９時間反応した。反応
終了後、室温まで冷却し、排気後反応溶液を過
し、結晶6.05ｇを得た。この結晶を液体クロマト
グラフイーにより分析した結果ニトロベンゼン基
準のＮ，N′−ジフエニル尿素の収率は93％であ
つた。Example 1 3.77 g of nitrobenzene, 2.78 g of aniline, and toluene were placed in a magnetic stirring autoclave with an internal volume of 200 ml.
34.03 g, Rh 6 (CO) 16 0.38 g, and 1.24 g of triphenylphosphine were added, and after replacing the inside of the system with carbon monoxide, carbon monoxide was pressurized at 50 kg/cm 2 . The reaction was carried out at 160 cm for 9 hours while stirring. After the reaction was completed, the reaction solution was cooled to room temperature, evacuated, and filtered to obtain 6.05 g of crystals. Analysis of the crystals by liquid chromatography revealed that the yield of N,N'-diphenylurea was 93% based on nitrobenzene.
次にこの結果3.00ｇ、メチルアルコール50.00
ｇを別の内容積200mlの電磁撹拌式オートクレー
ブに仕込み、撹拌しながら160℃で３時間反応さ
せた。反応終了後、反応溶液を分析した結果Ｎ−
フエニルカルバミン酸メチルの収率は93％、アニ
リンの収率は94％であつた。 Next, the result is 3.00g, methyl alcohol 50.00
g was placed in another electromagnetic stirring autoclave with an internal volume of 200 ml, and reacted at 160° C. for 3 hours with stirring. After the reaction was completed, the reaction solution was analyzed and the result was N-
The yield of methyl phenylcarbamate was 93%, and the yield of aniline was 94%.
比較例 １
内容積200mlの電磁撹拌式オートクレーブにニ
トロベンゼン6.12ｇ，メタノール37.00ｇ、Ru3
（CO）120.11ｇを入れ、系内を一酸化炭素で置換し
た後、一酸化炭素を50Kg／cm2となるように圧入し
た。次いで撹拌しながら160℃で５時間反応させ、
反応終了後この溶液を液体クロマトグラフイーに
より分析した結果、ニトロベンゼンの転化率は32
％、Ｎ−フエニルカルバミン酸メチルの選択率は
13％と低く、副生アニリンの選択率は40％であつ
た。即ち収率で示すとＮ−フエニルカルバミン酸
メチルの収率は４％、副生アニリンの収率は13％
であつた。Comparative Example 1 Nitrobenzene 6.12g, methanol 37.00g, Ru 3 in a magnetic stirring autoclave with an internal volume of 200ml.
After 0.11 g of (CO) 12 was added and the inside of the system was replaced with carbon monoxide, carbon monoxide was injected at a concentration of 50 kg/cm 2 . Next, the mixture was reacted at 160°C for 5 hours while stirring.
After the reaction was completed, this solution was analyzed by liquid chromatography, and the conversion rate of nitrobenzene was 32.
%, the selectivity of methyl N-phenylcarbamate is
The selectivity for by-product aniline was as low as 13%, and 40%. In other words, in terms of yield, the yield of methyl N-phenylcarbamate is 4%, and the yield of by-product aniline is 13%.
It was hot.
実施例 ２
触媒としてRh4（COc）12を0.39ｇ使用し、反応
時間を10時間とした以外は実施例１と同様の操作
によりニトロベンゼンとアニリンと一酸化炭素と
を反応させて、Ｎ，N′−ジフエニル尿素の結晶
5.76ｇを得た。ニトロベンゼン基準のＮ，N′−ジ
フエニル尿素の収率は95％であつた。次に実施例
１と同様の操作によりこの結晶3.00ｇとエチルア
ルコール50.00ｇとを反応させた。反応終了後、
反応溶液を分析した結果、Ｎ−フエニルカルバミ
ン酸エチルの収率は93％、アニリンの収率は95％
であつた。Example 2 Nitrobenzene, aniline, and carbon monoxide were reacted in the same manner as in Example 1 except that 0.39 g of Rh 4 (COc) 12 was used as a catalyst and the reaction time was 10 hours. ′-Diphenyl urea crystals
5.76g was obtained. The yield of N,N'-diphenylurea based on nitrobenzene was 95%. Next, in the same manner as in Example 1, 3.00 g of this crystal was reacted with 50.00 g of ethyl alcohol. After the reaction is complete,
Analysis of the reaction solution revealed that the yield of ethyl N-phenylcarbamate was 93% and the yield of aniline was 95%.
It was hot.
実施例 ３
触媒としてRh6（CO）16を0.38ｇ使用し、トリフ
エニルホスフインを添加しなかつたこと以外は実
施例１と同様の操作によりニトロベンゼンとアニ
リンと一酸化炭素とを反応させて、Ｎ，N′−ジ
フエニル尿素の結晶1.16ｇを得た。この結晶と反
応溶液を分析した結果ニトロベンゼンの反応率は
20％、ニトロベンゼン基準のＮ，N′−ジフエニ
ル尿素の選択率は93％であつた。Example 3 Nitrobenzene, aniline, and carbon monoxide were reacted in the same manner as in Example 1 except that 0.38 g of Rh 6 (CO) 16 was used as a catalyst and triphenylphosphine was not added. 1.16 g of N,N'-diphenylurea crystals were obtained. As a result of analyzing this crystal and the reaction solution, the reaction rate of nitrobenzene was
The selectivity of N,N'-diphenylurea was 93% based on 20% and nitrobenzene.
次に実施例１と同様の操作によりこの結晶1.00
ｇとメチルアルコール20.00ｇとを反応させた。
反応終了後、反応溶液を分析した結果、Ｎ−フエ
ニルカルバミン酸メチルの収率は92％、アニリン
の収率は93％であつた。 Next, by the same operation as in Example 1, 1.00% of this crystal was obtained.
g and 20.00 g of methyl alcohol were reacted.
After the reaction was completed, the reaction solution was analyzed and the yield of methyl N-phenylcarbamate was 92% and the yield of aniline was 93%.
比較例 ２
内容積200mlの電磁撹拌式オートクレーブに、
アニリン4.63ｇ、ニトロベンゼン6.12ｇ、メタノ
ール37.00ｇ、Ru3（CO）120.11ｇを入れ系内を一酸
化炭素で置換した後、一酸化炭素を50Kg／cm2とな
るように圧入した。次いで撹拌しながら160℃で
５時間反応させ、反応終了後この溶液を液体クロ
マトグラフイーで分析した。その結果ニトロベン
ゼン基準のＮ−フエニルカルバミン酸メチルの収
率は61％であり、Ｎ，N′−ジフエニル尿素の収
率は４％であつた。Comparative Example 2 In a magnetic stirring autoclave with an internal volume of 200ml,
After adding 4.63 g of aniline, 6.12 g of nitrobenzene, 37.00 g of methanol, and 0.11 g of Ru 3 (CO) 12 to replace the inside of the system with carbon monoxide, carbon monoxide was injected under pressure to a concentration of 50 kg/cm 2 . Next, the reaction was carried out at 160° C. for 5 hours with stirring, and after the reaction was completed, this solution was analyzed by liquid chromatography. As a result, the yield of methyl N-phenylcarbamate was 61% and the yield of N,N'-diphenylurea was 4% based on nitrobenzene.
次いでこの溶液を−５℃の冷凍庫に一昼夜放置
したが、何ら結晶は析出しなかつた。 Next, this solution was left in a -5°C freezer for a day and night, but no crystals were deposited.
Claims (1)
と一酸化炭素とをロジウム錯体化合物を主体とす
る触媒を用いて反応させてＮ，N′−ジ置換ウレ
アを生成し、次いで生成したＮ，N′−ジ置換ウ
レアを反応液から分離回収するウレア生成工程
と、 前記ウレア生成工程で得られたＮ，N′−ジ置
換ウレアと水酸基を含有する有機化合物とを反応
させて芳香族第１アミンと芳香族ウレタンとを生
成し、次いで芳香族第１アミンを分離して芳香族
ウレタンを得る工程と、 分離した芳香族第１アミンを前記ウレア生成工
程へ循環する工程と、 を具備してなる芳香族ウレタンの製造方法。 ２ Ｎ，N′−ジ置換ウレアと水酸基を含有する
有機化合物との反応を触媒を使用することなくお
こなう特許請求の範囲第１項記載の芳香族ウレタ
ンの製造方法。[Claims] 1. An aromatic mononitro compound, an aromatic primary amine, and carbon monoxide are reacted using a catalyst mainly containing a rhodium complex compound to produce an N,N'-disubstituted urea, and then a urea generation step in which the generated N,N'-disubstituted urea is separated and recovered from the reaction solution; and a urea generation step in which the N,N'-disubstituted urea obtained in the urea generation step is reacted with an organic compound containing a hydroxyl group. a step of producing an aromatic primary amine and an aromatic urethane, and then separating the aromatic primary amine to obtain an aromatic urethane; a step of recycling the separated aromatic primary amine to the urea production step; A method for producing an aromatic urethane, comprising: 2. The method for producing an aromatic urethane according to claim 1, wherein the reaction between the N,N'-disubstituted urea and the organic compound containing a hydroxyl group is carried out without using a catalyst.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60195306A JPS6259251A (en) | 1985-09-04 | 1985-09-04 | Production of aromatic urethane |
| KR1019860007290A KR890005036B1 (en) | 1985-09-04 | 1986-09-01 | Process for the preparation of aromatic urethane and intermediate thereof |
| US06/902,527 US4678856A (en) | 1985-09-04 | 1986-09-02 | Method of manufacturing aromatic urethane and intermediate product thereof |
| DE8686112169T DE3683232D1 (en) | 1985-09-04 | 1986-09-03 | METHOD FOR PRODUCING AROMATIC URETHANES AND AN INTERMEDIATE PRODUCT. |
| CA000517404A CA1251221A (en) | 1985-09-04 | 1986-09-03 | Method of manufacturing aromatic urethane and intermediate product thereof |
| EP86112169A EP0217166B1 (en) | 1985-09-04 | 1986-09-03 | Method of manufacturing aromatic urethane and intermediate product thereof |
| US07/420,364 USRE34137E (en) | 1985-09-04 | 1989-10-12 | Method of manufacturing aromatic urethane and intermediate product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60195306A JPS6259251A (en) | 1985-09-04 | 1985-09-04 | Production of aromatic urethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6259251A JPS6259251A (en) | 1987-03-14 |
| JPH0460463B2 true JPH0460463B2 (en) | 1992-09-28 |
Family
ID=16338959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60195306A Granted JPS6259251A (en) | 1985-09-04 | 1985-09-04 | Production of aromatic urethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6259251A (en) |
-
1985
- 1985-09-04 JP JP60195306A patent/JPS6259251A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6259251A (en) | 1987-03-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |