Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Mechanistic Aspects in the Grignard Coupling Reaction of Bis(chloromethyl)dimethylsilane with Trimethylchlorosilane

  • Published : 1999.04.20
Download PDF
⟨ Previous Next ⟩

Abstract

The Grignard reactions of bis(chloromethyl)dimethylsilane (1) with trimethylchlorosilane (2) in THF give both the intermolecular C-Si coupling and intramolecular C-C coupling products. At beginning stage, 1 reacts with Mg to give the mono-Grignard reagent ClCH2Me2SiCH2MgCl (1) which undergoes the C-Si coupling reaction to give MC2Si(CH2SiMe3)2 3, or C-C coupling to a mixture of formula Me3SiCH2(SiMe2CH2CH2)nR1 (n = 1, 2, 3, ..; 4a, R1I = H: 4b, R1 = SiMe3). In the reaction, two reaction pathways are involved: a) Ⅰ reacts with 2 to give Me3SiCH2SiMe2CH2Cl 6 which further reacts with Mg to afford a Me2SiCH2Mel-SiCH2MgCl (Ⅱ) or b) I cyclizes intramolecularly to a silacyclopropane intermediate A, which undergoes a ring-opening polymerization by the nucleophilic attack of the intermediates I or Ⅱ, followed by the termination reaction with H2O and 2, to give 4a and 4b, respectively. As the mole ratio of 2/1 increased from 2 to 16 folds, the formation of product 3 increased from 16% to 47% while the formation of polymeric products 4 was reduced from 60% to 40%. The intermolecular C-Si coupling reaction of the pathway a becomes more favorable than the intramolecular C-C coupling reaction of the pathways b at the higher mole ratio of 2/1.

Keywords

References

  1. Jpn. Kokai Tokkyo Koho, Jap. Pat. 63 05092, 1982; Chem. Agstr. v.109 Yamada, Y.;Takano, J.;Yamashita, N.
  2. J. Am. Chem. Soc. v.94 Lambert, R.L.;Reyferth, D.
  3. J. Organomet. Chem. v.201 Seyferth, D.;Annarelli, D.C.;Vick, S.C.;Duncan, D.P.
  4. J. Organomet. Chem. v.97 Seyferth, D.;Annarelli, D.C.
  5. J. Am. Chem. Soc. v.119 Ando, W.;Shiba, T.;Hidaka, T.;Morhashi, K.;Kikuchi, O.
  6. J. Am. Chem. Soc. v.98 Delker, G.L.;Wang, Y.;Stucky, G.D.;Lanbert, R.L.;Haas, C.K.;Seyferth, D.
  7. Organometallics v.10 Whitmarsh, C.K.;Interrante, L.V.
  8. J. Org. Chem. v.29 Kriner, W.A.
  9. Carbosilances: Syntheses and Reactions Fritz, G.;Matern, E.
  10. Organometallics v.17 Cho, Y.S.;Han, J.S.;Yoo, B.R.;Kang, S.O.;Jung, I.N.
  11. J. Am. Chem. Soc. v.67 Krieble, R.H.;Elliott, J.R.
  12. Chem. Ber. v.87 Runge, F;Zimmermann, W.
  13. Chem. Abstr. v.49
  14. American Chemical Society Symposium Series No.355 Synthesis and Chemistry of Agrochemicals Moberg, W.K.;Basarab, G.S.;Cuomo, J.;Liang, P.H.;Baker, D.R.;Fenyes, J.G.(ed.);Moberg W.K.(ed.);Cross, B.(ed.)
  15. J. Am. Chem. Soc. v.77 Seyferth, D.;Rochow, E.G.
  16. J. Organomet. Chem. v.21 Seyferth, D.;Attridge, C.J.
  17. Organometalics v.17 Ahn, S.;Cho, Y.S.;Yoo, B.R.;Jung, I.N.
  18. J. Am. Chem. Soc. v.77 Seyferth, D.;Rochow, E.G.
  19. Anorg. Allg. Chem. v.615 Fritz, G.;Grobe, J.Z.
  20. Chem. Abstr. v.57
  21. J. Organomet. Chem. v.240 Halevi, E.A.;West, R.
  22. J. Am. Chem. Soc. v.97 Seyferth, D.;Annarelli, D.C.
  23. J. Organomet. Chem. v.271 Seyferth, D.;Goldman, E.W.;Excudie, J.
  24. J. Organomet. Chem. v.272 Seyferth, D.;Annarelli, D.C.;Vick, S.C.
  25. Angew, Chem., Int. Ed. Engl. v.27 Boudjouk, P.;Samaraweera, U.;Sooriyakumaran, R.;Chrusciel, J.;Anderson, K.R.