Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Synthesis of Isopropyldichlorosilane by Direct Process

  • Lim, Weon-Cheol (Organosilicon Chemistry Laboratory, Korea Institute of Science and Technology) ;
  • Cho, Joo-Hyun (Organosilicon Chemistry Laboratory, Korea Institute of Science and Technology) ;
  • Han, Joon-Soo (Organosilicon Chemistry Laboratory, Korea Institute of Science and Technology) ;
  • Yoo, Bok-Ryul (Organosilicon Chemistry Laboratory, Korea Institute of Science and Technology)
  • Published : 2007.10.20
Download PDF
⟨ Previous Next ⟩

Abstract

Direct reaction of elemental silicon with a gaseous mixture of isopropyl chloride (1) and hydrogen chloride in the presence of copper catalyst using a stirred bed reactor equipped with a spiral band agitator gave isopropyldichlorosilane having a Si-H bond (2a) as a major product and isopropyltrichlorosilane (2b) along with chlorosilanes, trichlorosilane and tetrachlorosilane. A process for production of 2a was maximized using the 1:0.5 mole ratio of 1 to HCl and smaller size of elemental silicon at a reaction temperature of 220 °C. When a reaction was carried out by feeding a gaseous mixture of 1 [12.9 g/h (0.164 mol/h)] and HCl [2.98 g/h (0.082 mol/h)] to a contact mixture of elemental silicon (360 g) and copper (40 g) under the optimum condition for 45 h, 2a among volatile products kept up about 82 mol % until 35 h and then slowly decreased down 68 mol % in 45 h reaction. Finally 2a was obtained in 38% isolated yield (based on 1 used) with an 85% consumption of elemental silicon in a 45 h reaction. In addition to 2a, 2b was obtained as minor product along with chlorosilanes, trichlorosilane, and tetrachlorosilane. The decomposition of 1 was suppressed and the production of 2a improved by adding HCl to 1.

Keywords

References

  1. Petrov, A. D.; Mironov, V. F.; Ponomarenko, V. A.; Chernyshev, E. A. Synthesis of Organosilicon Monomers; Consultants Bureau: New York, 1964
  2. Voorhoeve, R. J. H. Organohalosilanes, Precursors to Silicones; Elsevier: New York, 1967
  3. Lewis, K. M.; Rethwisch, D. G. Catalyzed Direct Reactions of Silicon; Elsevier: Amsterdam, 1993
  4. Rochow, E. G. J. Am. Chem. Soc. 1945, 67, 963 https://doi.org/10.1021/ja01222a026
  5. Rochow, E. G. U.S. Patent 2,380,995
  6. Chem. Abstr. 1945, 39, 29968
  7. Rochow, E. G. U.S. Patent 2,380,996
  8. Chem. Abstr. 1945, 39, 29969
  9. Klebansky, A. L.; Fikhtengolts, V. S. J. Gen. Chem. U.S.S.R. 1957, 27, 2648
  10. Noll, W. Chemistry and Technology of Silicone; Academic Press: New York and London, 1968
  11. Kim, J. H.; Han, J. S.; Lim, W. C.; Yoo, B. R. J. Ind. Eng. Chem. 2007, 13, 480
  12. Xu, J. PCT Int. Appl. WO 200736135 A1
  13. Chem. Abstr. 2007, 146, 380492
  14. Nakajo, T.; Yanagihara, H.; Fushimi, M. JP 04185613 A, 1992
  15. Chem. Abstr. 1993, 118, 22801
  16. Petrov, A. D.; Smetankina, N. P.; Nikishin, G. I. J. Gen. Chem. U.S.S.R. 1955, 25, 2305
  17. Okamoto, M.; Onodera, S.; Yamamoto, Y.; Suzuki, E.; Ono, Y. Chem. Commun. 1998, 12, 1272
  18. Okamoto, M.; Onodera, S.; Yamamoto, Y.; Suzuki, E.; Ono, Y. J. Chem. Soc., Dalton Trans. 2001, 71
  19. Marciniec, B. Comprehensive Handbook on Hydrosilylation; Pergamon Press: Oxford, 1992
  20. Jung, I. N.; Yeon, S. H.; Han, J. S. Organometallics 1993, 12, 2360 https://doi.org/10.1021/om00030a052
  21. Jung, I. N.; Lee, G.-H.; Yeon, S. H.; Suk, M.-Y. Bull. Korean Chem. Soc. 1991, 12, 445
  22. Yeon, S. H.; Lee, B. W.; Kim, S.-I.; Jung, I. N. Organometallics 1993, 12, 4887 https://doi.org/10.1021/om00036a031
  23. Yeon, S. H.; Han, J. S.; Yoo, B. R.; Jung, I. N. J. Organomet. Chem. 1996, 516, 91 https://doi.org/10.1016/0022-328X(96)06129-3
  24. Han, J. S.; Yeon, S. H.; Yoo, B. R.; Jung, I. N. Organometallics 1997, 16, 93 https://doi.org/10.1021/om9605342
  25. Voorhoeve, R. J.; Vulugter, J. C. Recl. Trav. Chim. Pays-Bas 1963, 82, 605
  26. Koklik, J.; Bazant, V. Collect. Czech. Chem. Commun. 1961, 26, 417 https://doi.org/10.1135/cccc19610417
  27. Reed, C. E.; Coe, J. T. U.S. Patent 2,389,931
  28. Chem. Abstr. 1946, 40, 8476
  29. Grohm, H.; Paudert, R. Chem. Tech. (Leipzig) 1951, 10, 307
  30. Sellers, J. E.; Davis, J. L. U.S. Patent 2,449,821
  31. Chem. Abstr. 1949, 43, 4562

Cited by

  1. ChemInform Abstract: Synthesis of Isopropyldichlorosilane by Direct Process. vol.39, pp.10, 2008, https://doi.org/10.1002/chin.200810188
  2. Slurry Phase Reaction of Elemental Silicon with Methanol in the Presence of Copper: Direct Synthesis of Trimethoxysilane vol.30, pp.3, 2009, https://doi.org/10.5012/bkcs.2009.30.3.683