Rearrangement studies with 14C—VIII : External and internal returns in the solvolysis of 2-phenyl-1-14C-ethyl p-toluenesulfonate

doi:10.1016/S0040-4020(01)93187-4

Tetrahedron

Volume 7, Issues 3–4, 1959, Pages 206-212

https://doi.org/10.1016/S0040-4020(01)93187-4 Get rights and content

Abstract

Acetolysis and formolysis of 2-phenyl-1-¹⁴C-ethyl p-toluenesulfonate (I) were interrupted when the reactions were about 50 per cent complete. All samples of 2-phenylethyl p-toluenesulfonate recovered from the partially solvolyzed mixtures showed some rearrangements of the ¹⁴C-labeled atoms from the C-1 to the C-2 positions, indicating the occurrence of some return to covalent bonding through the intermediate ethylphenonium ion (V) or its equivalent. The fraction of V undergoing return as compared to the amount of V involved in product formation was greater for acetolysis than formolysis. The presence of lithium perchlorate gave rise to salt-promoted ionization resulting in an increase in the ¹⁴C rearrangement for the reaction products; however, lithium perchlorate also reduced the relative extent of return involving V. Solvolysis of I in the presence of sodium p-toluene-³⁵S-sulfonate made possible the simultaneous determinations of ¹⁴C rearrangement and ³⁵S exchange in the recovered 2-phenylethyl p-toluenesulfonate. Considerations of such data led to the conclusion that both external and internal returns take place during acetolysis and formolysis of I.

References (18)

C.C. Lee et al.
Canad. J. Chem.
(1957)
W.H. Saunders et al.
J. Amer. Chem. Soc.
(1958)
S. Winstein et al.
J. Amer. Chem. Soc.
(1956)
S. Winstein et al.
J. Amer. Chem. Soc.
(1958)
E. Grunwald
Analyt. Chem.
(1954)
S. Winstein et al.
J. Amer. Chem. Soc.
(1956)
A. Streitwieser
Chem. Rev.
(1956)
A.H. Fainberg et al.
J. Amer. Chem. Soc.
(1956)
S. Winstein et al.
J. Amer. Chem. Soc.
(1953)

There are more references available in the full text version of this article.

Cited by (8)

Electrooxydation d'iodures d'alkyle en solution dans l'acetonitrile-I. Etude des transpositions
1974, Tetrahedron
L'oxydation anodique d'iodures d'alkyle peut être une source de carbocations. Nous étudions les transpositions liées à la réaction: les réarrangements sont importants seulement dans le cas des iodures primaires, et difficilement explicables à partir d'un carbocation. Des comparaisons avec les résultats des trifluoroacétolyses de tosylate nous suggérent un mécanisme concerté pour la formation des produits mettant en concurrence l'assistance du solvant et celle d'un groupement voisin. Par électrolyse de l'iodure de β-phényléthyle-α,α-d₂, nous confirmons l'hypothèse de l'assistance d'un groupement voisin.
Homogeneous Sc(OTf)<inf>3</inf>-Catalyzed Direct Allylation Reactions of General Alcohols with Allylsilanes
2018, ACS Omega
Diagnostic fragmentations of adducts formed between carbanions and carbon disulfide in the gas phase. A joint experimental and theoretical study
2010, Organic and Biomolecular Chemistry
Effect of Solvent on β-Arylalkyl Solvolysis1
1978, Journal of the American Chemical Society
Ions and lon-pairs in nucleophilic aliphatic substitution
1975, Russian Chemical Reviews
π -Complexed β -Arylalkyl Derivatives. IV. The Preparation and Solvolysis of 2-[π -(Phenyl)chromium tricarbonyl]ethyl and 2-[π -(Phenyl)chromium tricarbonyl]-l-propyl Methanesulfonates and Their Noncomplexed Analogs<sup>1a</sup>
1973, Journal of Organic Chemistry

View all citing articles on Scopus

^☆: For paper VII, see A.J. Finlayson and C.C. Lee, Canad. J. Chem. 37, 940 (1959).

¹: Holder of Canadian Industries Limited Fellowship, 1956–1958.

View full text

Rearrangement studies with 14C—VIII : External and internal returns in the solvolysis of 2-phenyl-1-14C-ethyl p-toluenesulfonate☆

Abstract

Canad. J. Chem.

J. Amer. Chem. Soc.

J. Amer. Chem. Soc.

J. Amer. Chem. Soc.

Analyt. Chem.

J. Amer. Chem. Soc.

Chem. Rev.

J. Amer. Chem. Soc.

J. Amer. Chem. Soc.

Rearrangement studies with ¹⁴C—VIII : External and internal returns in the solvolysis of 2-phenyl-1-¹⁴C-ethyl p-toluenesulfonate☆