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Syntheses and Reactivities of Stable Halosilylenoids, (Tsi)X 2 SiLi (Tsi=C(SiMe 3 ) 3 , X=Br, Cl)
Author(s) -
Lee Myong Euy,
Cho Hyeon Mo,
Lim Young Mook,
Choi Jin Kyong,
Park Chang Hee,
Jeong Seong Eun,
Lee Uk
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305151
Subject(s) - nucleophile , chemistry , methanol , lithium (medication) , amphiphile , medicinal chemistry , catalysis , organic chemistry , copolymer , medicine , polymer , endocrinology
Halosilylenoids, stable at room temperature (Tsi)X 2 SiLi (Tsi=C(SiMe 3 ) 3 , X=Br, Cl), were synthesized from the reaction of TsiSiX 3 with lithium naphthalenide. Bromosilylenoid reacted with t BuOH and MeI both at −78 °C and at room temperature to give (Tsi)HSiBr 2 and (Tsi)MeSiBr 2 , respectively, in high yields; this clearly shows its nucleophilicity. In the reaction of bromosilylenoid with methanol, 2‐propanol, and 2,3‐dimethyl‐1,3‐butadiene, the corresponding products, (Tsi)HSi(OMe) 2 , (Tsi)HSi(O i Pr)Br, and bromo(Tsi)silacyclopent‐3‐ene, were obtained in high yields; this demonstrates its amphiphilic property, as if bromosilylene would be trapped. Chlorosilylenoid also exhibited both nucleophilic and amphiphilic properties. The 29 Si chemical shifts for (Tsi)Br 2 SiLi, (Tsi)Br 2 SiK, and (Tsi)Cl 2 SiLi were 106, 70, and 87 ppm, respectively.