Solvent-Free Preparation of N,N′-Dialkylbenzenediamines

Abstract

A diiridium complex, stabilized by a bis(N-heterocyclic carbene) ligand, was found to be an effective precatalyst for the N,N′-dialkylation of o-, m-, and p-benzenediamine in excellent yields. Benzyl and primary aliphatic alcohols were used as alkylating reagents. Furthermore, the reactions were carried out without using any organic solvent, offering an environmentally benign process.

Key words

alkylation - amination - iridium - catalysis - carbene complex

• References

• 1 Lawrence SA. Amines: Synthesis, Properties and Applications . Cambridge University Press; Cambridge: 2004
• 2a Covitch MJ, Pudelski JK, Friend C, Gleselman MD, Eveland RA, Ragnz MG, Schober BJ. US Patent 7790661B2, 2010
• 2b Schneller ER, Moehle WE, Zhao G. PCT Int. Appl WO 2009029373 A1 20090305, 2009
• 3a Kariuki S, Babady-Bila P, Duquette B. Environ. Chem. 2008; 5: 226
• 3b Gendler S, Zelikoff AL, Kopilov J, Goldberg I, Kol M. J. Am. Chem. Soc. 2008; 130: 2144
• 4a Grigg R, Mitchell TR. B, Sutthivaiyakit S, Tongpenyai N. J. Chem. Soc., Chem. Commun. 1981; 611
• 4b Tsuji Y, Huh K.-T, Ohsugi Y, Watanabe Y. J. Org. Chem. 1985; 50: 1365

For recent reviews, see:
• 5a Guillena G, Ramón DJ, Yus M. Chem. Rev. 2010; 110: 1611
• 5b Nixon TD, Whittlesey MK, Williams JM. J. Dalton Trans. 2009; 753
• 5c Suzuki T. Chem. Rev. 2011; 111: 1825
• 5d Dobereiner GE, Crabtree RH. Chem. Rev. 2010; 110: 681
• 5e Bähn S, Imm S, Neubert L, Zhang M, Neumann H, Beller M. ChemCatChem 2011; 3: 1853
• 5f Alonso F, Riente P, Yus M. Acc. Chem. Res. 2011; 44: 379
• 6a Michlik S, Hille T, Kempe R. Adv. Synth. Catal. 2012; 354: 847
• 6b Michlik S, Kempe R. Chem. Eur. J. 2010; 16: 13193
• 7a Hanasaka F, Fujita K.-i, Yamaguchi R. Organometallics 2004; 23: 1490
• 7b Nair V, Menon RS, Biju AT, Sinu CR, Paul RR, Jose A, Sreekumar V. Chem. Soc. Rev. 2011; 40: 5336
• 7c Patil NT. Angew. Chem. Int. Ed. 2011; 50: 1759; and references cited therein
• 8 Kuo H.-Y, Liu Y.-H, Peng S.-M, Liu S.-T. Organometallics 2012; 31: 7248
• 9 Lee C.-C, Liu S.-T. Chem. Commun. 2011; 47: 6981
• 10 Sharma M, Joshi P, Kumar N, Joshi S, Rohilla RK, Roy N, Rawat DS. Eur. J. Med. Chem. 2011; 46: 480
• 11 Hofmann E, Holtschmidt U. Ger. Offen DE 2055208 A19720518, 1972
• 12 Majumdar KC, De N, Chakravorty S. Synth. Commun. 2011; 41: 121