The reaction of triphenylmethyl halides with triphenylphosphine in cumene and tert-butylbenzene

P. Huszthy, M. Kajtár-Peredy, Károly Lempert, Judit Hegedus-Vajda

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Reactions of triphenylmethyl bromide and chloride with triphenylphosphine at elevated temperatures under argon furnish mixtures of the reductive dehalogenation product triphenylmethane and the tele substitution products 2a or 2b, the ratio of the products depending on the reaction conditions. The formation of triphenylmethane indicates that the reaction is, at least partly, initiated by halophilic attack [eqn. (2)] or by single-electron-transfer (SET) from the phosphine [eqn. (5)]. The resulting triphenylmethanide anions or triphenylmethyl radicals would then be converted into triphenylmethane by proton or hydrogen abstraction [eqns. (4) and (6), respectively] or recombine with their phosphorus containing co-products to yield the tele substitution products [eqns. (3a) and (7), respectively]. The latter could, at least partly, also be formed via eqn. (1a). Exclusive operation of the SET initiated mechanisms of formation of both products has been proved by combination of trapping studies with molecular oxygen and proof of the absence of triphenylmethanide anions from the reaction mixtures.

Original languageEnglish
Pages (from-to)347-353
Number of pages7
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number3
Publication statusPublished - 1992

Fingerprint

phosphine
Anions
Substitution reactions
Dehalogenation
Electrons
Molecular oxygen
Argon
Bromides
Phosphorus
Protons
Chlorides
Hydrogen
triphenylphosphine
triphenylmethane
tert-butylbenzene
cumene
Temperature

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

The reaction of triphenylmethyl halides with triphenylphosphine in cumene and tert-butylbenzene. / Huszthy, P.; Kajtár-Peredy, M.; Lempert, Károly; Hegedus-Vajda, Judit.

In: Journal of the Chemical Society, Perkin Transactions 2, No. 3, 1992, p. 347-353.

Research output: Contribution to journalArticle

@article{b2ac664cdf3c417dacb07bdd3b5c6f3e,
title = "The reaction of triphenylmethyl halides with triphenylphosphine in cumene and tert-butylbenzene",
abstract = "Reactions of triphenylmethyl bromide and chloride with triphenylphosphine at elevated temperatures under argon furnish mixtures of the reductive dehalogenation product triphenylmethane and the tele substitution products 2a or 2b, the ratio of the products depending on the reaction conditions. The formation of triphenylmethane indicates that the reaction is, at least partly, initiated by halophilic attack [eqn. (2)] or by single-electron-transfer (SET) from the phosphine [eqn. (5)]. The resulting triphenylmethanide anions or triphenylmethyl radicals would then be converted into triphenylmethane by proton or hydrogen abstraction [eqns. (4) and (6), respectively] or recombine with their phosphorus containing co-products to yield the tele substitution products [eqns. (3a) and (7), respectively]. The latter could, at least partly, also be formed via eqn. (1a). Exclusive operation of the SET initiated mechanisms of formation of both products has been proved by combination of trapping studies with molecular oxygen and proof of the absence of triphenylmethanide anions from the reaction mixtures.",
author = "P. Huszthy and M. Kajt{\'a}r-Peredy and K{\'a}roly Lempert and Judit Hegedus-Vajda",
year = "1992",
language = "English",
pages = "347--353",
journal = "Journal of the Chemical Society, Perkin Transactions 2",
issn = "1470-1820",
publisher = "Royal Society of Chemistry",
number = "3",

}

TY - JOUR

T1 - The reaction of triphenylmethyl halides with triphenylphosphine in cumene and tert-butylbenzene

AU - Huszthy, P.

AU - Kajtár-Peredy, M.

AU - Lempert, Károly

AU - Hegedus-Vajda, Judit

PY - 1992

Y1 - 1992

N2 - Reactions of triphenylmethyl bromide and chloride with triphenylphosphine at elevated temperatures under argon furnish mixtures of the reductive dehalogenation product triphenylmethane and the tele substitution products 2a or 2b, the ratio of the products depending on the reaction conditions. The formation of triphenylmethane indicates that the reaction is, at least partly, initiated by halophilic attack [eqn. (2)] or by single-electron-transfer (SET) from the phosphine [eqn. (5)]. The resulting triphenylmethanide anions or triphenylmethyl radicals would then be converted into triphenylmethane by proton or hydrogen abstraction [eqns. (4) and (6), respectively] or recombine with their phosphorus containing co-products to yield the tele substitution products [eqns. (3a) and (7), respectively]. The latter could, at least partly, also be formed via eqn. (1a). Exclusive operation of the SET initiated mechanisms of formation of both products has been proved by combination of trapping studies with molecular oxygen and proof of the absence of triphenylmethanide anions from the reaction mixtures.

AB - Reactions of triphenylmethyl bromide and chloride with triphenylphosphine at elevated temperatures under argon furnish mixtures of the reductive dehalogenation product triphenylmethane and the tele substitution products 2a or 2b, the ratio of the products depending on the reaction conditions. The formation of triphenylmethane indicates that the reaction is, at least partly, initiated by halophilic attack [eqn. (2)] or by single-electron-transfer (SET) from the phosphine [eqn. (5)]. The resulting triphenylmethanide anions or triphenylmethyl radicals would then be converted into triphenylmethane by proton or hydrogen abstraction [eqns. (4) and (6), respectively] or recombine with their phosphorus containing co-products to yield the tele substitution products [eqns. (3a) and (7), respectively]. The latter could, at least partly, also be formed via eqn. (1a). Exclusive operation of the SET initiated mechanisms of formation of both products has been proved by combination of trapping studies with molecular oxygen and proof of the absence of triphenylmethanide anions from the reaction mixtures.

UR - http://www.scopus.com/inward/record.url?scp=37049079383&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=37049079383&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:37049079383

SP - 347

EP - 353

JO - Journal of the Chemical Society, Perkin Transactions 2

JF - Journal of the Chemical Society, Perkin Transactions 2

SN - 1470-1820

IS - 3

ER -