The Yukawa-Tsuno Relationship for the β-Silicon Effect in the Solvolysis Rates of 2-(Aryldimethylsilyl)ethyl Chlorides

• Mizue Fujio

• Mai Uchida

• Ayumi Okada

Bibliographic Information

Other Title

• Yukawa Tsuno Relationship for the ベータ Silicon Effect in the Solvolysis Rates of 2 Aryldimethylsilyl ethyl Chlorides

Abstract

Solvolysis rates of 2-(aryldimethylsilyl)ethyl chlorides were determined conductimetrically in 60% (v/v) aqueous ethanol. The effects of aryl substituents at the silyl atom on the solvolysis rates at 50 °C were correlated with essentially nonresonant parameters of r = 0.10 in terms of Yukawa–Tsuno (Y–T) Eq. 1, giving a ρ value of −1.75. Such a high ρ value may be regarded as the effect of aryl ring on the bridged Si in the rate-determining step. The Si-bridging is consistent with the fact that the solvolysis of the unsubstituted substrate with d2-labeled ethylene moiety gave substitution products with label scrambling. The arylsilyl substituent effects were likewise analyzed for several relevant sets of β-silyl systems in order to ascertain significant variations of ρ values from system to system; Y–T Eq. 1 correlated quite excellently with essentially nonresonant sigmas of negligible resonance demand (r 0.10), to exhibit significant variations of ρ from −1.75 to −0.95.

Journal

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 78 (10), 1834-1842, 2005

  Tokyo : Chemical Society of Japan

Keywords

• General Chemistry

Details

• CRID: 1523106604885053952
• NII Article ID: 130004151829
• NII Book ID: AA00580132
• ISSN: 00092673
• ISSN: 13480634
• DOI: 10.1246/bcsj.78.1834
• NDL BIB ID: 7469084
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I7469084
• Web Site: https://academic.oup.com/bcsj/article-pdf/78/10/1834/56266528/bcsj.78.1834.pdf
• Text Lang: en
• NDL Source Classification:
  • ZP1(科学技術--化学・化学工業)
• Data Source:
  • NDL
  • Crossref
  • CiNii Articles