Reactivities of mixed organozinc and mixed organocopper reagents. Part 7. Comparison of the transfer rate of the same group in allylation of mixed and homo diorganozinc reagents

KALKAN M., Erdik E.

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, cilt.26, sa.3, ss.256-260, 2013 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 26 Sayı: 3
  • Basım Tarihi: 2013
  • Doi Numarası: 10.1002/poc.3080
  • Dergi Adı: JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.256-260
  • Anahtar Kelimeler: mixed diorganozincs, group selectivity, kinetics of diorganozinc reagents, transferable group, allylation of diorganozinc reagents, ALLYLIC CARBOXYLATES, SECONDARY, DERIVATIVES, ALCOHOLS, 1,4-ADDITION, SUBSTITUTION, ALKYLATION, ARYLATION, ALDEHYDES, ADDITIONS
  • Ankara Üniversitesi Adresli: Evet

Özet

A detailed direct kinetic study has been carried out to compare the reaction rate of transferable group, Ph in mixed phenylzinc reagents, RPhZn (R=n-alkyl) and in homo diphenylzinc reagent, Ph2Zn in their reactions with allyl bromide in THF at 25(15) degrees C. Empirical rata law and activation parameters are consistent with a second-order substitution reaction. The allylation rate of transferable group Ph in RPhZn (R=n-alkyl) has been found higher than the rate of Ph group in Ph2Zn. A mechanism which accommodates the kinetic data and higher allylation rate of transferable group Ph in RPhZn than that in Ph2Zn is given. Copyright (c) 2013 John Wiley & Sons, Ltd.