Chinese Journal of Organic Chemistry >
Improvement of the Synthesis of Isothiocyanates
Received date: 2015-03-18
Revised date: 2015-04-16
Online published: 2015-05-14
Supported by
Project supported by the National Natural Science Foundation of China (No. 21002009), the Major Program for the Natural Science Research of Jiangsu Colleges and Universities (Nos. 12KJA150002, 14KJA150002), the Scientific and Technological Project of Jiangsu Province (BY2014037-01), and the Qing Lan Project of Jiangsu Province.
Isothiocyanates were prepared from the reactions of phenyl chlorothionoformate and various primary amines vis one-step or two-step process without additional base. The one-step process is good at highly active amines, while two-step approach is suitable for all kinds of amines. This method has many merits such as environment-friendly, easily available raw materials, low toxicity and convenient operation, which has a good application prospect in industry.
Key words: isothiocyanate; phenyl chlorothionoformate; primary amine; synthesis
Li Zhengyi , Shi Song , Zhuang Yue , Zheng Chongqian , Zhang Jinlong , Sun Xiaoqiang . Improvement of the Synthesis of Isothiocyanates[J]. Chinese Journal of Organic Chemistry, 2015 , 35(9) : 1999 -2003 . DOI: 10.6023/cjoc201503026
[1] (a) Mukerjee, A. K.; Ashare, R. Chem. Rev. 1991, 91, 1.(b) Dobosz, M.; Wujec, M. Heterocycles 2002, 57, 1135.(c) Li, M.; Zhang, J. W.; Wen, L. R. Chin. J. Org. Chem. 2014, 34, 2478 (in Chinese).(李明, 张建薇, 文丽荣, 有机化学, 2014, 34, 2478.)(d) Liu, R. Y.; Yong, X.; Yang, X. D.; Yan, Y. C.; Lu, X. W.; Qu, J. Q. Chin. J. Org. Chem. 2014, 34, 561 (in Chinese). (刘瑞源, 勇雪, 杨小东, 严轶琛, 路新卫, 瞿金清, 有机化学, 2014, 34, 561.)
[2] (a) Fahey, J. W.; Talalay, P. Food Chem. Toxicol. 1999, 37, 973.(b) Fahey, J. W.; Zalcmann, A. T.; Talalay, P. Phytochemistry 2001, 56, 5. (c) Heckl, S.; Sturzu, A.; Regenbogen, M.; Beck, A.; Feil, G.; Gharabaghi, A.; Echner, H. Med. Chem. 2008, 4, 348. (d) Bommareddy, A.; Hahm, E-R.; Xiao, D.; Powolny, A. A.; Fisher, A. L.; Jiang, Y.; Singh, S. V. Cancer Res. 2009, 69, 3704.(e) Gupta, P.; Kim, B.; Kim, S.-H.; Srivastava S. K. Mol. Nutr. Food Res. 2014, 58, 1685.(f) Gupta P.; Wright, S. E.; Kim, S.-H.; Srivastava, S. K. Biochim. Biophys. Acta 2014, 1846, 405.
[3] He, M. H.; Zhong, H.; Zhang, B. Y. Fine Spec. Chem. 2010, 18, 9 (in Chinese). (何谋海, 钟宏, 张宝元, 精细与专用化学品, 2010, 18, 9.)
[4] (a) Gao, Z.-L.; Liu, X.-L.; Liu, D.; Zhang, L.-Y. Agrochemicals 2009, 48, 322 (in Chinese).(高中良, 刘秀莲, 刘东, 张丽英, 农药, 2009, 48, 322.)(b) Liang, X. P. Jiangxi Plant Protection 2011, 34, 129 (in Chinese).(梁学平, 江西植保, 2011, 34, 129.)
[5] Dyer, E.; Johnson, T. B. J. Am. Chem. Soc. 1932, 54, 777.
[6] (a) Larsen, C.; Stelliou, K.; Harpp, D. N. J. Org. Chem. 1978, 43, 337.(b) Larsen, C.; Harpp, D. N. J. Org. Chem. 1981, 46, 2465.(c) Kim, S.; Yi, K. Y. Tetrahedron Lett. 1985, 26, 1661.(d) Gottfried, R. Angew. Chem. 1966, 5, 963.
[7] (a) Yella, R.; Ghosh, H.; Murru, S.; Sahoo, S. K.; Patel, B. K. Synth. Commun. 2010, 40, 2083.(b) Jamir, L.; Ali, A. R.; Ghosh, H.; Chipem, F. A. S.; Patel, B. K. Org. Biomol. Chem. 2010, 8, 1674.(c) Nath, J.; Jamir, L.; Patel, B. K. Green Chem. Lett. Rev. 2011, 4, 1.(d) Jamir, L.; Alimenla, B.; Kumar, A.; Sinha, D.; Sinha, U. B. Synth. Commun. 2011, 41, 147.(e) Sun, N.; Li, B.; Shao, J.; Mo, W.; Hu, B.; Shen, Z.; Hu X. Beilstein J. Org. Chem. 2012, 8, 61.
[8] Zhang, X.; Lee, Y. K.; Kelley, J. A.; Burke, T. R., Jr. J. Org. Chem. 2000, 65, 6237.
[9] Chen, X.; Li, Z.; Sun, X.; Ma, H.; Chen, X.; Ren, J.; Hu, K. Synthesis 2011, 3991.
[10] Li, Z. Y,; Ma, H. Z.; Han, C,; Xi, H. T.; Meng, Q.; Chen, X.; Sun, X. Q. Synthesis 2013, 1667.
[11] Mays, J. R.; Roska, R. L. W.; Sarfaraz, S.; Mukhtar, H.; Rajski, S. R. ChemBioChem 2008, 9, 729.
[12] Butler, R. N.; Wallace, L. M. J. Chem. Soc., Perkin Trans. 1 2000, 4335.
[13] Hodgkins, J. E.; Reeves, W. P. J. Org. Chem. 1964, 29, 3098.
[14] Wang, R.; Dolman, S. J. J. Org. Chem. 2007, 72, 3969.
[15] Shan, W. G.; Bian, G. F.; Su, W. K.; Liang, X. R. Org. Prep. Proc. Int. 2004, 36, 283.
[16] Adam, W.; Bargon, R. M.; Bosio, S. G.; Schenk, W. A.; Stalke, D. J. Org. Chem. 2002, 67, 7037.
[17] Elderfield, R. C.; Short, F. W. J. Org. Chem. 1953, 18, 1092.
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