Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

Photochemical Generation of Phenylsilylene and Its Chemistry

광분해 반응에 의한 Phenylsilylene의 생성과 그 반응성에 관한 연구

  • 이도남 (연세대학교 이과대학 화학과) ;
  • 신한섭 (연세대학교 이과대학 화학과) ;
  • 김장환 (연세대학교 이과대학 화학과) ;
  • 이명의 (연세대학교 이과대학 화학과)
  • Published : 1993.08.20
Download PDF
⟨ Previous Next ⟩

Abstract

The photochemical precursors, 1,1,1,3,3,3-hexamethyl-2-phenyltrisilane(2) and 2,3-dicarbomethoxy-1,4,5,6,7-pentaphenyl-7-silanorbornadiene(5) were synthesized in the yield of 10% and 73%, respectively. Irradiation of 2 at 254 nm in the presence of triethylsilane gave 1,1,1-triethyl-2-phenyldisilane (6) in 44% yield which was the product of phenylsilylene insertion into the Si-H bond. Irradiation of 2 in the presence of diphenylacetylene gave 1-phenyl-1-silacyclopenta-2,4-diene(4) in 68% yield together with 1,2-diphenyl-1,2-disilacyclohexa-2,5-diene(26%) which were formed from [2＋2] addition of the silacyclopropene to diphenylacethylene and formed from dimerization of silacyclopropene, respectively. From the neat photolysis of precursor 2,1,5-dihydrosilanthrene(11), intermolecular C-H insertion product of phenylsilylene and 1,2-diphenyltrisilane(12), Si-H insertion product of phenylsilylene to the precursor were obtained in the yield of 5% and 7%, respectively. In the same experimental condition, both photolyses of 5 in the presence of triethylsilane and methanol showed that the intramolecular 1,5-sigmatropic rearrangement of precursor 5 to give the formation of silylenolether was more favorable process than the generation of phenylsilylene.

Phenylsilylene(PhHSi:)의 광분해 전구체인, 1,1,1,3,3,3-hexamethyl-2-phenyltrisilane(2)과 2,3-dicarbomethoxy-1,4,5,6,7-pentaphenyl-7-silanorbornadiene(5)을 10%와 73%의 수율로 각각 합성하였다. 전구체 2를 254 nm의 빛을 조사시켜 광분해 실험시킨 결과 triethylsilane 존재하에서는 phenylsilylene이 Si-H 결합에 삽입된 생성물인 1,1,1-triethyl-2-phenyldisilane (6)이 44%의 수율로 얻어졌고, diphenylacetylene 존재하에서는 phenylsilylene이 삼중결합에 첨가된 후 diphenylacetylene과 [2＋2] 첨가반응이 일어나 얻어진 생성물, 1-phenyl-1-silacyclopenta-2,4-diene(4)과 phenyl-silylene이 삼중결합에 첨가된 다음 곧 이합체화되어진 화합물인 1,2-diphenyl-1,2-disilacyclohexa-2,5-diene(10)이 각각 68% 와 26%의 수율로 얻어졌다. Neat 광반응에서는 생성된 phenylsilylene이 분자간 C-H 삽입반응을 하여 생성된 화합물, 1,5-dihydrosilanthren(11)과 전구체 2가 Si-H 결합에 삽입된 화합물, 1,2-diphenyltrisilane(12)이 5%와 7%의 수율로 각각 얻어졌다. 같은 조건에서 화합물 5를 triethylsilane과 methanol 존재하에서 광분해시킨 결과 phenylsilylene은 생성되지 않고 분자내 1,5-sigmatropic 자리옮김에 의한 silylenolether가 생성됨을 확인하였다.

Keywords

References

  1. J. Am. Chem. Soc. v.109 R. J. MacMahon;J. A. Christopher;O. L. Chapma;J. W. Johnson;C. L. Kjreil;J.-P. LeRoux;A. M. Mooring;P. R. West
  2. J. Am. Chem. Soc. v.91 R. C. Joines;A. B. Turner;W. M. Jones
  3. Chem. Phys. Letters. v.125 J. E. Baggott;H. A. Frey;P. D. Lightfoot;R. Walsh
  4. Tetrahedron Lett. v.21 W. P. Newmann;B. Mayer
  5. J. Organomet. Chem. v.225 T. J. Barton;W. D. Wulff
  6. J. Organomet. Chem. v.42 M. Ishikawa;M. Kumada
  7. Bull. Korean Chem. Soc. v.11 no.1 W. C. Joo;J. H. Hong;H. L. Sohn;E. K. Kang;C. H. Kim
  8. J. Am. Chem. Soc. v.85 R. West;R. E. Bailey
  9. J. Organomet. Chem. v.3 F. Johnson;R. S. Gohlke;W. H. Nasutavicus
  10. Proceedings of the Third Korea-Japan Joint Symposium on Organometallic and Coordination Chemistry Generation of Phenylsilylene and Its Chemistry M. E. Lee;D. N. Lee;C. H. Kim
  11. J. Am. Chem. Soc. v.86 H. Gilman;W. H. Atwell
  12. J. Chem. Soc., Chem. Commun. W. Ando;J Hamada
  13. J. Am. Chem. Soc. v.110 S. Bain;T. J. Barton
  14. J. Organomet. Chem. v.291 H. Appler;L. W. Gross;B. Mayer;W. Newmann