Catalytic chlorination of methylphenyldichlorosilane with gaseous chlorine to chlorinated methylphenyldichlorosilanes over Lewis acids

Yujun Fu; Yiqian Jiang; Hengbo Yin; Lingqin Shen; Yonghai Feng; Aili Wang

Journal of Industrial and Engineering Chemistry, Vol.20, No.3, 1022-1029, May, 2014

DOI10.1016/j.jiec.2013.06.038 Export Citation

Catalytic chlorination of methylphenyldichlorosilane with gaseous chlorine to chlorinated methylphenyldichlorosilanes over Lewis acids

Yujun Fu, Yiqian Jiang, Hengbo Yin^†, Lingqin Shen, Yonghai Feng, and Aili Wang

Faculty of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China

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Methylchlorophenyldichlorosilane (MeClPhSiCl2) and methyldichlorophenyldichlorosilane (MeCl2Ph-SiCl2) were synthesized by the catalytic chlorination of methylphenyldichlorosilane (MePhSiCl2) with Cl2 over Lewis acid catalysts. The catalytic activities of Lewis acid catalysts were in an order of FeCl3 > SbCl5 > AlCl3 > SnCl4. However, FeCl3 also highly catalyzed the cleavage of chlorophenyl.silicon bond to form chlorobenzene. At a low mole ratio of SbCl5 to MePhSiCl2 of 1.4 × 10^(-5):0.45, the yield of MeClPhSiCl2 was around 60% after reacting at 25-100 ℃ for 15-20 h. At a high mole ratio of 1.4 × 10^(-4):0.45, the yield of MeCl2PhSiCl2 reached 44% after reacting at 80-100 ℃ for 20 h.

Keywords:Methylphenyldichlorosilane;Chlorination;Lewis acid;Methylchlorophenyldichlorosilane;Methyldichlorophenyldichlorosilane

[References]

Clarson SJ, ACS Symposium Series, 838, 1 (2003)
Gu GT, Wu ZS, Zhang ZJ, Qing FL, Tribol. Int., 42, 397 (2009)
Wang A, Jiang Y, Chen W, Yin H, Liu Y, Shen Y, Jiang T, Wu Z, J. Ind. Eng. Chem., 18(1), 237 (2012)
Nazir H, Lv PP, Wang LY, Lian GP, Zhu SP, Ma GH, J. Colloid Interface Sci., 364(1), 56 (2011)
Jiang YQ, Chen WG, Liu YJ, Yin HB, Shen YT, Wang AL, Yu LB, Jiang TS, Ind. Eng. Chem. Res., 50(4), 1893 (2011)
Brown ED, U.S. Patent 3,505,378 (1970). (1970)
Fletcher HJ, Hunter MJ, U.S. Patent 2,599,984 (1952). (1952)
Hommel MC, U.S. Patent 2,599,917 (1950). (1950)
Burkhard CA, J. Am. Ceram. Soc., 74, 6275 (1952)
Guan ZD, Huang XY, Yao HQ, Z. Chem. Ind., 37, 4 (2006)
Di Giorgio PA, Sommer LH, Whitmore FC, J. Am. Chem. Soc., 70, 3512 (1948)
Speier JL, J. Am. Chem. Soc., 73, 824 (1951)
Rochow EG, U.S. Patent 2,258,219 (1939). (1939)
Holdstock NG, U.S. Patent 2,887,503 (1957). (1957)
Holdstock NG U.S. Patent 2,803,638 (1954). (1954)
Graham JC, Feng CH, Orticochea M, Ahmed G, J. Org. Chem., 55, 4102 (1990)
Singh AP, Kumar SB, Appl. Catal. A: Gen., 126(1), 27 (1995)
Delaude L, Laszlo P, J. Org. Chem., 55, 5260 (1990)
Kale SM, Singh AP, Appl. Catal. A: Gen., 228(1-2), 1 (2002)
Zhou XZ, Zhang ZY, Liang G, Guo CY, Chem. J. Chin. University, 2, 195 (1981)

[1] Clarson SJ, ACS Symposium Series, 838, 1 (2003)

[2] Gu GT, Wu ZS, Zhang ZJ, Qing FL, Tribol. Int., 42, 397 (2009)

[3] Wang A, Jiang Y, Chen W, Yin H, Liu Y, Shen Y, Jiang T, Wu Z, J. Ind. Eng. Chem., 18(1), 237 (2012)

[4] Nazir H, Lv PP, Wang LY, Lian GP, Zhu SP, Ma GH, J. Colloid Interface Sci., 364(1), 56 (2011)

[5] Jiang YQ, Chen WG, Liu YJ, Yin HB, Shen YT, Wang AL, Yu LB, Jiang TS, Ind. Eng. Chem. Res., 50(4), 1893 (2011)

[6] Brown ED, U.S. Patent 3,505,378 (1970). (1970)

[7] Fletcher HJ, Hunter MJ, U.S. Patent 2,599,984 (1952). (1952)

[8] Hommel MC, U.S. Patent 2,599,917 (1950). (1950)

[9] Burkhard CA, J. Am. Ceram. Soc., 74, 6275 (1952)

[10] Guan ZD, Huang XY, Yao HQ, Z. Chem. Ind., 37, 4 (2006)

[11] Di Giorgio PA, Sommer LH, Whitmore FC, J. Am. Chem. Soc., 70, 3512 (1948)

[12] Speier JL, J. Am. Chem. Soc., 73, 824 (1951)

[13] Rochow EG, U.S. Patent 2,258,219 (1939). (1939)

[14] Holdstock NG, U.S. Patent 2,887,503 (1957). (1957)

[15] Holdstock NG U.S. Patent 2,803,638 (1954). (1954)

[16] Graham JC, Feng CH, Orticochea M, Ahmed G, J. Org. Chem., 55, 4102 (1990)

[17] Singh AP, Kumar SB, Appl. Catal. A: Gen., 126(1), 27 (1995)

[18] Delaude L, Laszlo P, J. Org. Chem., 55, 5260 (1990)

[19] Kale SM, Singh AP, Appl. Catal. A: Gen., 228(1-2), 1 (2002)

[20] Zhou XZ, Zhang ZY, Liang G, Guo CY, Chem. J. Chin. University, 2, 195 (1981)