Benzylic Brominations with N-Bromosuccinimide in 1,2-Dichlorobenzene: Effective Preparation of (2-Bromomethyl-phenyl)-Methoxyiminoacetic Acid Methyl Ester

Sanghyuck Lee; Choon Sup Ra

Clean Technology, Vol.22, No.4, 269-273, December, 2016

DOI10.7464/ksct.2016.22.4.269 Export Citation

Benzylic Brominations with N-Bromosuccinimide in 1,2-Dichlorobenzene: Effective Preparation of (2-Bromomethyl-phenyl)-Methoxyiminoacetic Acid Methyl Ester

Sanghyuck Lee, and Choon Sup Ra^†

School of Chemistry and Biochemistry, Yeungnam University, 280 Daehak-Ro, Gyeongsan-si, Gyeongbuk 712-749, Korea

E-mail:

The benzylic bromination of methoxyimino-o-tolyl-acetic acid methyl ester (1) into (2-bromomethyl-phenyl)-methoxyiminoacetic acid methyl ester (2) using N-bromosuccinimide in the presence of 2,2'-azobisisobutyronitrile in various reaction solvents were investigated. The efficiency of the reaction was found to be sensitive to the kind of reaction solvents. We found the benzylic bromination of 1 to 2 can be performed in 1,2-dichlorobenzene as reaction solvent superior to the classic Wohl-Ziegler procedure in both reaction time and isolated yield (8 h vs 12 h, 92 vs 79%). This system provides clean, rapid, and high-yielding reactions with replacement of conventional solvents, such as tetrachloromethane, by less-toxic 1,2-dichlorobenzene.

Keywords:Benzylic radical bromination;Wohl-Ziegler procedure;1,2-dichlorobenzene;(2-bromomethyl-phenyl)-methoxyiminoacetic acid methyl ester

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[2] Coleman GH, Honeywell GE, Org. Synth., Coll. Vol., 2, 443 (1943)

[3] Snell JM, Weissberger A, Org. Synth., Coll. Vol., 3, 788 (1955)

[4] Stephenson FM, Org. Synth., Coll. Vol., 4, 984 (1963)

[5] Campaign E, Tuller BF, Org. Synth., Coll. Vol., 4, 921 (1963)

[6] Wohl A, Ber. Dtsch. Chem. Ges., 52, 51 (1919)

[7] Ziegler K, Schenck G, Krockow EW, Siebert A, Wenz A, Weber H, Justus Liebigs. Ann. Chem., 551, 80 (1942)

[8] WMO, Scientific Assessment of Ozone Depletion: 2006 Global Ozone Research and Monitoring Project; Report No. 50; World Meteorological Organization: Geneva, Switzerland (2007).

[9] United Nations Environment Programme, Ozone Secretariat. The Montreal Protocol on Substances that Deplete the Ozone Layer as either adjusted and/or amended in London (1990), Copenhagen (1992), Vienna (1995), Montreal (1997), and Beijing (1999); United Nations Environment Programme: Nairobi, Kenya (2000).

[10] Amijs CHM, van Klink GPM, van Koten G, Green Chem., 5, 470 (2003)

[11] Offermann W, Vogtle F, Synthesis, 272 (2007)

[12] Mestres R, Palenzuela J, Green Chem., 4, 314 (2002)

[13] Suarez D, Laval G, Tu SM, Jiang D, Robinson CL, Scott R, Golding BT, Synthesis, 1807 (2009)

[14] Salama TA, Novak Z, Tetrahedron Lett., 52, 4026 (2011)

[15] Podgorsek A, Stavber S, Zupan M, Iskra J, Tetrahedron Lett., 47, 1097 (2006)

[16] Kikuchi D, Sakaguchi S, Ishii Y, J. Org. Chem., 63, 6023 (1998)

[17] Togo H, Hirai T, Synlett, 702 (2003)

[18] Rahman ANMM, Bishop R, Tan R, Shan N, Green Chem., 7, 207 (2005)

[19] Jereb M, Zupan M, Stavber S, Helv. Chim. Acta, 92, 555 (2009)

[20] Jiang X, Shen M, Tang Y, Li C, Tetrahedron Lett., 46, 487 (2005)

[21] Ammermann E, Lorenz G, Schelberger K, Wenderoth B, Sauter H, Rentzea C, “BAS 490 F - a broad- spectrum fungicide with a new mode of action,” in Proceedings of Brighton Crop Protection Conference - Pests and Diseases, British Crop Protection Council: Brighton, England, pp. 403-410 (1992)

[22] Hwang IC, Kim JK, Kim HH, Kyung SH, Bull. Korean Chem. Soc., 30, 1475 (2009)

[23] Li Y, Zhang HQ, Liu J, Yang XP, Liu ZJ, J. Agric. Food Chem., 54, 3636 (2006)