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Publicly Available Published by De Gruyter January 6, 2012

Phosgene-free synthesis of 1,3-diphenylurea via catalyzed reductive carbonylation of nitrobenzene

  • Andrea Vavasori and Lucio Ronchin

1,3-Diphenylurea (DPU) has been proposed as a synthetic intermediate for phosgene-free synthesis of methyl N-phenylcarbamate and phenyl isocyanate, which are easily obtained from the urea by reaction with methanol. Such an alternative route to synthesis of carbamates and isocyanates necessitates an improved phosgene-free synthesis of the corresponding urea. In this work, it is reported that Pd(II)-diphosphine catalyzed reductive carbonylation of nitrobenzene in acetic acid (AcOH)-methanol proceeds in high yield and selectivity as a one-step synthesis of DPU. We have found that the catalytic activity and selectivity of this process depends on solvent composition and on the bite angle of the diphosphine ligands. Under optimum reaction conditions, yields in excess of 90 molar % and near-quantitative selectivity can be achieved.


1 10.1070/RC1985v054n03ABEH003022, T. P. Vishnyakova, I. A. Golubeva, E. V. Glebova. Russ. Chem. Rev. (Engl. Transl.)54, 249 (1985).Search in Google Scholar

2 10.1002/jps.2600680342, W. A. Skinner, H. T. Crawford, L. C. Rutledge, M. A. Moussa. J. Pharm. Sci.68, 391 (1979).Search in Google Scholar PubMed

3 10.1248/cpb.51.1025, R. M. Nieto, A. Coelho, A. Martinez, A. Stefanachi, E. Sotelo, E. Ravina. Chem. Pharm. Bull.51, 1025 (2003).Search in Google Scholar PubMed

4 10.1021/jm030908a, E. Mounetou, J. Legault, J. Lacroix, R. C. Gaudreault. J. Med. Chem.46, 5055 (2003).Search in Google Scholar PubMed

5 P. V. G. Reddy, C. S. Reddy, C. N. Raju. Chem. Pharm. Bull.51, 860 (2003).Search in Google Scholar

6 10.1046/j.1432-1033.2003.03483.x, M. Kumar, M. V. Hosur. Eur. J. Biochem.270, 1231 (2003).Search in Google Scholar PubMed

7 A. Ricci, A. Carra, E. Rolli C. Bertoletti, G. Morini, M. Incerti, P. Vicini. J. Plant. Growth Regul.23, 207 (2004).Search in Google Scholar

8 10.1007/BF02708412, M. Srinivasan, V. Nachiappan, R. Rajasekharan. J. Biosci.31, 599 (2006).Search in Google Scholar PubMed

9 10.1021/jo00202a006, A. G. M. Barrett, M. J. Betts, A. Fenwick. J. Org. Chem.50, 169 (1985).Search in Google Scholar

10 E. T. Shawl, H. S. Kesling. U.S. Patent 4,871,871 (1989).Search in Google Scholar

11 10.1039/p19950000249, R. T. Wheelhouse, D. E. V. Wilman, W. Thomson, M. F. G. Svevens. J. Chem. Soc., Perkin Trans. 1 249 (1995).Search in Google Scholar

12 10.1039/a800572i, Y. Wang, R. T. Wheelhouse, L. Zhao, D. A. F. Langnel, M. F. G. Stevens. J. Chem. Soc., Perkin Trans. 1 1669 (1998).Search in Google Scholar

13 10.1006/jcat.1999.2458, H. S. Kim, Y. J. Kim, H. Lee, S. D. Lee, C. S. Chin. J. Catal.184, 526 (1999).Search in Google Scholar

14 10.1039/b107947f, S. P. Gupte, A. B. Shivarkar, R. V. Chaudhari. Chem. Commun. 2620 (2001).Search in Google Scholar

15 10.1002/1521-3773(20020902)41:17<3247::AID-ANIE3247>3.0.CO;2-P, H. Yoshida, E. Shirakawa, Y. Honda, T. Hiyama. Angew. Chem., Int. Ed.41, 3247 (2002).Search in Google Scholar

16 10.1021/ja0202964, J. M. Humphrey, Y. S. Liao, A. Ali, T. Rein, Y. L. Wong, H. J. Chen, A. K. Courtney, S. F. Martin. J. Am. Chem. Soc.124, 8584 (2002).Search in Google Scholar

17 10.1021/ja012610k, J. J. Yin, S. L. Buchwald. J. Am. Chem. Soc.124, 6043 (2002).Search in Google Scholar

18 10.1021/ja012124x, K. C. Nicolaou, P. S. Baran, Y. L. Zhong, K. Sugita. J. Am. Chem. Soc.124, 2212 (2002).Search in Google Scholar

19 10.1021/ol035647d, J. R. Dunetz, R. L. Danheiser. Org. Lett.5, 4011 (2003).Search in Google Scholar

20 10.1016/S0040-4039(03)01051-7, A. G. Sergeev, G. A. Artamkina, I. P. Beletskaya. Tetrahedron Lett.44, 4719 (2003).Search in Google Scholar

21 10.1021/ol035282x, G. G. Muccioli, J. Wouters, J. H. Poupaert, B. Norberg, W. Poppitz, G. K. E. Scriba, D. M. Lambert. Org. Lett.5, 3599 (2003).Search in Google Scholar

22 10.1021/ol020244j, S. H. Lee, B. Clapham, G. Koch, J. Zimmermann, K. D. Janda. Org. Lett.5, 511 (2003).Search in Google Scholar

23 10.1039/cs9740300209, H. J. Twitchett. Chem. Soc. Rev.3, 209 (1974).Search in Google Scholar

24 10.1021/ie00055a009, J. S. Oh, S. M. Lee, J. K. Yeo, C. W. Lee, J. S. Lee. Ind. Eng. Chem. Res.30, 1456 (1991).Search in Google Scholar

25 10.1016/0022-328X(85)80207-2, J. E. Alessio, G. Mestroni. J. Organomet. Chem.291, 117 (1985).Search in Google Scholar

26 S. Cenini, F. Ragaini. Catalytic Reductive Carbonylation of Organic Nitro Compounds, Kluwer, Dordrecht (1996).10.1007/978-94-017-0986-6Search in Google Scholar

27 10.1021/cr950083f, A. M. Tafesh, J. Weiguny. Chem. Rev.96, 2035 (1996).Search in Google Scholar

28 10.1016/1381-1169(96)00004-0, F. Ragaini, S. Cenini. J. Mol. Catal., A: Chem.109, 1 (1996).Search in Google Scholar

29 10.1016/S0022-328X(97)00029-6, P. Wehman, H. M. A. van Donge, A. Hagos, P. C. J. Kamer, P. W. N. M. van Leeuwen. J. Organomet. Chem.535, 183 (1997).Search in Google Scholar

30 10.1039/b902425p, F. Ragaini. Dalton Trans. 6251 (2009).Search in Google Scholar

31 10.1016/0022-328X(87)87174-7, P. Giannoccaro. J. Organomet. Chem.336, 271 (1987).Search in Google Scholar

32 10.1016/S0020-1693(00)80662-3, P. Giannoccaro. Inorg. Chim. Acta142, 81 (1988).Search in Google Scholar

33 10.1039/b002127j, F. Bigi, R. Maggi, G. Sartori. Green Chem.2, 140 (2000).Search in Google Scholar

34 10.1016/j.tetlet.2003.09.140, I. Maya, O. Lopez, S. Maza, J. G. Fernandez-Bolanos, J. Fuentes. Tetrahedron Lett.44, 8539 (2003).Search in Google Scholar

35 10.1021/jo0346297, L. Lemoucheux, J. Rouden, M. Ibazizene, F. Sobrio, M. C. Lasne. J. Org. Chem.68, 7289 (2003).Search in Google Scholar

36 10.1039/b301951a, R. Ballini, D. Fiorini, R. Maggi, P. Righi, G. Sartori, R. Sartorio. Green Chem.5, 396 (2003).Search in Google Scholar

37 10.1039/b304481p, G. Yang, Z. X. Chen, H. Q. Zhang. Green Chem.5, 441 (2003).Search in Google Scholar

38 10.1002/jhet.5570400320, P. V. G. Reddy, Y. H. Babu, C. S. Reddy. J. Heterocycl. Chem.40, 535 (2003).Search in Google Scholar

39 10.1021/jo0300690, R. V. Hoffman, S. Madan. J. Org. Chem.68, 4876 (2003).Search in Google Scholar

40 10.1021/ol034287r, A. S. Ripka, D. D. Diaz, K. B. Sharpless, M. G. Finn. Org. Lett.5, 1531 (2003).Search in Google Scholar

41 10.1016/S0010-8545(99)00230-1, F. Paul. Coord. Chem. Rev.203, 269 (2000).Search in Google Scholar

42 10.1021/om990578l, F. Ragaini, A. Ghitti, S. Cenini. Organometallics18, 4925 (1999).Search in Google Scholar

43 10.1016/S1381-1169(00)00311-3, F. Ragaini, S. Cenini. J. Mol. Catal., A: Chem.161, 31 (2000).Search in Google Scholar

44 10.1016/1381-1169(96)00198-7, E. Bolzacchini, R. Lucini, S. Meinardi, M. Orlandi, B. Rindone. J. Mol. Catal. A: Chem.110, 227 (1996).Search in Google Scholar

45 10.1016/1381-1169(96)00006-4, V. Macho, M. Kralik, F. Halmo. J. Mol. Catal., A: Chem.109, 119 (1996).Search in Google Scholar

46 10.1016/1381-1169(96)00221-X, P. Wehman, L. Borst, P. C. J. Kamer, P. W. N. M. van Leeuwen. J. Mol. Catal., A: Chem.112, 23 (1996).Search in Google Scholar

47 10.1039/cc9960000217, P. Wehman, P. C. J. Kamer, P. W. N. M. van Leeuwen. Chem. Commun. 217 (1996).Search in Google Scholar

48 10.1016/S1381-1169(03)00188-2, G. Ling, J. Z. Chen, S. W. Lu. J. Mol. Catal., A: Chem.202, 23 (2003).Search in Google Scholar

49 Y. Ya, S. Lu. Tetrahedron Lett.40, 4845 (1999).Search in Google Scholar

50 10.1021/om00024a031, P. Wehman, G. C. Dol, E. R. Moorman, P. C. J. Kamer, P. W. N. M. van Leeuwen, J. Fraanje, K. Goubitz. Organometallics13, 4856 (1994).Search in Google Scholar

51 10.1021/om00008a024, P. Wehman, V. E. Kaasjager, W. G. J. de Lange, F. Hartl, P. C. J. Kamer, P. W. N. M. van Leeuwen, J. Fraanje, K. Goubitz. Organometallics14, 3751 (1995).Search in Google Scholar

52 J. S. Lee, C. W. Lee, S. M. Lee, K. H. Park. J. Mol. Catal.61, L15 (1990).10.1016/0304-5102(90)85150-GSearch in Google Scholar

53 C. W. Lee, J. S. Lee, S. M. Lee, K. D. Kim, N. S. Cho, J. S. Oh. J. Mol. Catal.81, 17 (1993).Search in Google Scholar

54 10.1016/S1381-1169(01)00235-7, A. Vavasori, G. Cavinato, L. Toniolo. J. Mol. Catal., A: Chem.176, 11 (2001).Search in Google Scholar

55 10.1016/S1381-1169(02)00174-7, A. Vavasori, G. Cavinato, L. Toniolo. J. Mol. Catal., A: Chem.191, 209 (2003).Search in Google Scholar

56 10.1016/S1381-1169(03)00311-X, A. Vavasori, L. Toniolo, G. Cavinato, F. Visentin. J. Mol. Catal., A: Chem.204-205, 295 (2003).Search in Google Scholar

57 10.1016/j.molcata.2006.10.035, C. Bianchini, A. Meli, W. Oberhauser, A. M. Segarra, C. Claver, E. J. Garcia Suarez. J. Mol. Catal., A: Chem.265, 292 (2007).Search in Google Scholar

58 10.1039/a807799a, P. Dierkes, P. W. N. M. van Leeuwen. J. Chem. Soc., Dalton Trans. 1519 (1999).Search in Google Scholar

59 C. W. Lee, S. M. Lee, J. S. Oh. Ind. Eng. Chem. Res.30, 1456 (1991).Search in Google Scholar

60 S. M. Lee, N. S. Cho, K. D. Kim, J. S. Oh, C. W. Lee, J. S. Lee. J. Mol. Catal.73, 43 (1992).Search in Google Scholar

61 S. Cenini, C. Crotti. Metal Promoted Selectivity in Organic Synthesis, Kluwer, Dordrecht (1991).Search in Google Scholar

62 10.1002/chem.200801882, F. Ragaini, M. Gasperini, S. Cenini, L. Arnera, A. Caselli, P. Macchi, N. Casati. Chem.—Eur. J.15, 8064 (2009).Search in Google Scholar

63 10.1016/0022-328X(91)80175-J, R. Ugo, R. Psaro, M. Pizzotti, P. Nardi, C. Dossi, A. Andreetta, G. Capparella. J. Organomet. Chem.417, 211 (1991).Search in Google Scholar

64 10.1016/S0022-328X(97)00191-5, A. Sessanta, B. Milani, G. Mestroni, E. Zangrando, L. Randaccio. J. Organomet. Chem.545-546, 89 (1997).Search in Google Scholar

65 10.1002/chem.200900367, W. J. van Zeist, R. Visser, F. M. Bickelhaupt. Chem.—Eur. J.15, 6112 (2009).Search in Google Scholar PubMed

66 10.1021/ic50164a025, W. L. Steffen, G. J. Palenik. Inorg. Chem.15, 2432 (1976).Search in Google Scholar

67 10.1007/BF00771757, C. W. Lee, S. M. Lee, J. S. Oh, J. S. Lee. Catal. Lett.19, 217 (1993).Search in Google Scholar

Online erschienen: 2012-1-6
Erschienen im Druck: 2012-1-6

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