Catalyst free, one pot synthesis of phosphoramidates under environment friendly conditions

Bashir Ahmad Dar

Journal of Industrial and Engineering Chemistry, Vol.36, 194-197, April, 2016

DOI10.1016/j.jiec.2016.01.041 Export Citation

Catalyst free, one pot synthesis of phosphoramidates under environment friendly conditions

Bashir Ahmad Dar^†

Department of CSE (Chemistry), University of Kashmir, North Campus, Delina Baramulla, Kashmir 193103, India

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An efficient and mild one pot synthesis of phosphoramidates has been reported from simple azide precursors like benzyl, allyl and propargyl halides. The method is simple, metal free giving products in good to excellent yields with wide substrate scope. Benzyl halide derivatives (Ysingle bondC6H4single bondCH2single bondX: X = Cl, Br; Y = p-F, Br, NO2 & o-Cl, NO2) reacted with NaN3 and P(OR’)3 at room temperature gave the corresponding phosphoramidates in 86?96% yields, while the reaction with allyl halides (R1,R2C = CHsingle bondCH2single bondX: X = Cl, Br, R1 & R2 = H, Me) in 60?73% yields. In polar solvents like DMF, DMSO, THF, acetonitrile, methanol moderate yields were obtained (60%?67%) with incomplete substrate conversion. Yields were better in binary polar solvents and water?ethanol was found to be the optimum green solvent in which upto 96% yield was obtained within 4.5 h. It was also observed that triethylphosphite showed better reactivity than trimethylphosphite. Secondary and tertiary halides did not react at all under the optimized conditions. This is the first catalyst free method for the one pot synthesis of phosphoramidates which offers significant green advantages like avoids hazardous organic azides, use of environment friendly ethanol and water as a green reaction medium.

Keywords:Phosphoramidates;Benzyl halides;Triethylphosphite;Multicomponent reaction;Green protocol

[References]

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[2] Denmark SE, Chung WJ, Angew. Chem.-Int. Edit., 47, 1890 (2008)

[3] Rueping M, Ieawsuwan W, Chem. Commun., 47, 11450 (2011)

[4] Denmark SE, Chung WJ, Angew. Chem.-Int. Edit., 47, 1890 (2008)

[5] Denmark SE, Fu J, Coe DM, Su X, Pratt NE, Griedel BD, J. Org. Chem., 71, 1513 (2006)

[6] Chang SI, Griesgraber GW, Southern PJ, Wagner CR, J. Med. Chem., 44, 223 (2001)

[7] Egron D, Imbach JL, Gosselin G, Aubertin AM, Perigaud C, J. Med. Chem., 46, 4564 (2003)

[8] Meyers CLF, Borch RF, J. Med. Chem., 43, 4319 (2000)

[9] Yadav LDS, Srivastava VP, Patel R, Tetrahedron Lett., 49, 5652 (2008)

[10] Yadav LDS, Awasthi C, Rai VK, Rai A, Tetrahedron Lett., 48, 8037 (2007)

[11] Yadav LDS, Awasthi C, Rai A, Tetrahedron Lett., 49, 6360 (2008)

[12] Ciufolini MA, Spencer GO, J. Org. Chem., 54, 4739 (1989)

[13] Minami T, Ogata M, Hirao I, Tanaka M, Agawa T, Synthesis, 1982, 231 (1982)

[14] Wilkening I, del Signore G, Hackenberger CP, Chem. Commun., 47, 349 (2011)

[15] Adelfinskaya O, Herdewijn P, Angew. Chem.-Int. Edit., 46, 4356 (2007)

[16] Perrone P, Daverio F, Valente R, Rajyaguru S, Martin JA, Leveque V, Pogam SL, Najera, Klumpp K, Smith DB, J. Med. Chem., 50, 5463 (2007)

[17] Roberts W, Tate M, Nature, 265, 379 (1977)

[18] Phillips DR, Uramoto M, Isono K, McCloskey JA, J. Org. Chem., 58, 854 (1993)

[19] Guijarro JI, Gonzalez-Pastor JE, Baleux F, Millan JLS, Castilla MA, Rico M, Moreno F, Delepierre M, J. Biol. Chem., 270, 23520 (1995)

[20] Gao X, Tang Z, Lu M, Liu H, Jiang Y, Zhao Y, Cai Z, Chem. Commun., 48, 10198 (2012)

[21] Nguyen TM, Chang SC, Condon B, Slopek R, Graves E, Yoshioka-Tarver M, Ind. Eng. Chem. Res., 52(13), 4715 (2013)

[22] Cai YM, Gao X, Huang XT, Wang TJ, Zhao YF, Chin. J. Org. Chem., 26, 1677 (2006)

[23] Atherton FR, Openshaw HT, Todd AR, J. Chem. Soc., 660 (1945)

[24] John N, Marvin HC, J. Am. Chem. Soc., 110, 6275 (1988)

[25] Jamie F, Laura JW, Rebecca KB, Christopher JH, Chem. Commun., 49, 8919 (2013)

[26] Serwa R, Wilkening I, del Signore G, Muhlberg M, Claußnitzer I, Weise C, Gerrits M, Hackenberger CPR, Angew. Chem.-Int. Edit., 121, 8382 (2009)

[27] Bohrsch V, Serwa R, Majkut P, Krause E, Hackenberger CPR, Chem. Commun., 46, 3176 (2010)

[28] Bertran-Vicente J, Serwa RA, Schumann M, Schmieder P, Krause E, Hackenberger CPR, J. Am. Chem. Soc., 136(39), 13622 (2014)

[29] Brase S, Gil C, Knepper K, Zimmermann V, Angew. Chem.-Int. Edit., 44, 5188 (2005)

[30] Wilkening I, del Signore G, Ahlbrecht W, Hackenberger CPR, Synthesis, 17, 2709 (2011)

[31] Wilkening I, del Signore G, Hackenberger CPR, Chem. Commun., 2932 (2008)

[32] Dar BA, Singh S, Pandey N, Singh AP, Sharma P, Lazar A, Sharma M, Vishwakarma RA, Singh B, Appl. Catal. A: Gen., 470, 232 (2014)

[33] Dar BA, Syed NA, Wagay MA, Hussain A, Ahmad N, Bhat KA, Khuroo MA, Sharma M, Singh B, Tetrahedron Lett., 54, 4880 (2013)

[34] Dar BA, Singh A, Sahu A, Patidar P, Chakraborty A, Sharma M, Singh B, Tetrahedron Lett., 53, 5497 (2012)

[35] Gefflaut T, Lemaire M, Valentin ML, Bolte J, J. Org. Chem., 62, 5920 (1997)