Method of manufacturing aromatic urethane and intermediate product thereof

Abstract

The present invention relates to a method of manufacturing aromatic urethane, an aromatic mononitro-compound, an aromatic primary amine, and carbon monoxide being reacted using a catalyst containing a platinum group metal-containing compound as a major constituent to prepare N,N'-di-substituted urea. The resultant N,N'-di-substituted urea is reacted with a hydroxyl group-containing organic compound to prepare an aromatic primary amine and aromatic urethane, and the aromatic primary amine is separated to obtain aromatic urethane.

What is claimed is: 
     
       1. A method of manufacturing aromatic urethane, comprising: the urea producing step of reacting an aromatic mononitro-compound, an aromatic primary amine, and carbon monoxide by using a catalyst having a platinum group metal-containing compound as a major constituent to prepare N,N'-di-substituted urea and of separating and recovering the resultant N,N'-di-substituted urea from a reaction solution.Iadd., said aromatic primary amine being in an excessive amount to function as a solvent and said reaction is in the absence of halogen or a halogen compound.Iaddend.;   the step of reacting the N,N'-di-substituted urea as an intermediate product prepared in the urea producing step with an organic compound containing a hydroxyl group to prepare an aromatic primary amine and aromatic urethane, and of separating the aromatic primary amine from the aromatic urethane, thereby obtaining the aromatic urethane; and   the step of recirculating the separated aromatic primary amine .[.in the.]. .Iadd.to said .Iaddend.urea producing step.   
     
     
       2. A method according to claim 1, wherein the platinum group metal-containing compound is a rhodium complex compound. 
     
     
       3. A method according to claim 1, wherein the platinum group metal-containing compound is a ruthenium complex compound. 
     
     
       4. A method according to claim 1, wherein the N,N'-di-substituted urea reacts with the hydroxyl group-containing organic compound without using a catalyst. .[.5. A method according to claim 1, wherein the aromatic primary amine is added in an excessive amount so as to use the aromatic primary amine as a solvent..]. .[.6. A method of manufacturing ureas by reacting an aromatic primary amine, an aromatic nitro-compound, and carbon monoxide by using a catalyst essentially consisting of a platinum group metal-containing compound..]. .[.7. A method according to claim 6, wherein the platinum group metal-containing compound is a rhodium complex compound..]. .[.8. A method according to claim 6, wherein the platinum group metal-containing compound is a ruthenium complex compound..]. .[.9. A method according to claim 6, wherein the aromatic primary amine is used in an excessive amount to use the aromatic primary amine as a solvent..]. 
     
     
        .Iadd.10.  A method according to claim 1 wherein said catalyst is selected from the group consisting of Ru 3  (CO) 12 , H 4  Ru 4  (CO) 12 , Ru(CO) 3  (PPh 3 ) 2 , Ru(CO) 3  (dppe), (Ru(CO) 2  (HCO) 2  P(C-C 6  H 11 ) 3 ) 2 , Ru(acac) 3 , Rh 6  (CO) 16 , RhH(CO)(PPh 3 ) 3 , (Rh(acac)(CO)(PPh 3 ), Rh(acac)(CO) 2 , and Rh(acac) 3 , wherein dppe represents diphenylphosphinoethane and acac represents acetylacetonato..Iaddend. .Iadd.11. A method according to claim 1 wherein said catalyst is selected from the group consisting of Ru 3  (CO) 12 , H 4  Ru 4  (CO) 12 , Ru(CO) 3  (PPh 3 ) 2 , Ru(CO) 3  (dppe), (Ru(CO) 2  (HCO) 2  P(C-C 6  H 11 ) 3 ) 2 , and Ru(acac) 3 , wherein dppe represents diphenylphosphinoethane and acac represents acetylacetonato..Iaddend. .Iadd.12. A method according to claim 1, wherein said aromatic mononitro-compound corresponds to said aromatic primary amine..Iaddend. .Iadd.13. A method according to claim 1, wherein said aromatic primary amine is aniline..Iaddend. .Iadd.14. A method according to claim 1, wherein said aromatic primary amine is aniline; and said aromatic mononitro-compound is nitrobenzene..Iaddend. .Iadd.15. A method according to claim 10, wherein said aromatic mononitro-compound corresponds to said aromatic primary amine..Iaddend. .Iadd.16. A method according to claim 2, wherein said aromatic primary amine is aniline; and said aromatic mononitro-compound is nitrobenzene..Iaddend. .Iadd.17. A method according to claim 3, wherein said aromatic primary amine is aniline; and said aromatic mononitro-compound is nitrobenzene..Iaddend. .Iadd.18. A method according to claim 10, wherein said aromatic primary amine is aniline; and said aromatic mononitro-compound is nitrobenzene..Iaddend. .Iadd.19. A method according to claim 11, wherein said aromatic primary amine is aniline; and said aromatic mononitro-compound is nitrobenzene..Iaddend. .Iadd.20. A method according to claim 1 wherein said urea producing step is carried out in a first reactor and said step of producing the aromatic urethane is carried out in a second reactor.