1,3-SI-TO-SI MIGRATION OF A METHYL-GROUP - RATIO OF REARRANGED AND UNREARRANGED PRODUCTS IN THE REACTIONS OF THE IODIDE (ME3SI)(3)CSI(CD3)(2)I WITH ICL

Authors
ALMANSOUR AI ABUBISHAIT HA EABORN C
Citation
Ai. Almansour et al., 1,3-SI-TO-SI MIGRATION OF A METHYL-GROUP - RATIO OF REARRANGED AND UNREARRANGED PRODUCTS IN THE REACTIONS OF THE IODIDE (ME3SI)(3)CSI(CD3)(2)I WITH ICL, Journal of organometallic chemistry, 531(1-2), 1997, pp. 171-174
Citations number
11
Categorie Soggetti
Chemistry Inorganic & Nuclear","Chemistry Inorganic & Nuclear
Journal title
Journal of organometallic chemistry → ACNP
ISSN journal
0022328X
Volume
531
Issue
1-2
Year of publication
1997
Pages
171 - 174
Database
ISI
SICI code
0022-328X(1997)531:1-2<171:1MOAM->2.0.ZU;2-F
Abstract
In the reactions of (Me3Si)(3)CSi(CD3)(2)I with ICl in inert solvents the unrearranged product (Me3Si)(3)CSi(CD3)(2)Cl predominates over the rearranged isomer (Me3Si)(2)C[Si(CD3)(2)Me](SiMe2Cl). The proportion of rearranged isomer falls from ca. 42% in CH2Cl2 to ca. 25% in benzen e, 20% in CCl4, and 15% in CHCl3. In MeOH the reaction gives 84% of th e methoxides (Me3Si)(3)CSi(CD3)(2)OMe and (Me3Si)(2)C[Si(CD3)(2)Me](Si Me2OMe) in 62/22 ratio, along with 16% of the unrearranged chloride (M e3Si)(3)CSi(CD3)(2)Cl. The results indicate that the intermediate cati ons generated by abstraction of I- by ICI are mainly not fully free be fore undergoing nucleophilic attack.