Rearrangement studies with 14C—VIII

Lee, C.C.; Tkachuk, R.; Slater, G. P.

doi:10.1016/s0040-4020(01)93187-4

Cited by 9 publications

(9 citation statements)

References 13 publications

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“…(17) m.p. 104-105" C), and the subsequent oxidation of V to p-anisic acid (VI) were carried out in a manner analogous to the conversioll of 2-phenylethyl iodide to hydrocinnamic acid and the oxidation of the latter to benzoic acid previously reported from this laboratory (18). Samples of V and VI were repeatedly crystallized and sublimed before they were assayed for radioactivity.…”

Section: Di-2-p-anisylethyl Sulphite ( I V )mentioning

confidence: 99%

REARRANGEMENT STUDIES WITH C¹⁴: XIV. THE REACTION OF 2-p-ANISYLETHANOL-1-C¹⁴ WITH THIONYL CHLORIDE

Lee¹,

Newman²,

Thornhill³

1963

Can. J. Chem.

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Reaction between 2-p-anisylethanol-1-C14 and thionyl chloride was carried out with pyridine, n-hexane, toluene, dioxane, or excess thionyl chloride as solvent. The 2-p-anisylethyl chloride obtained showed rearrangement of the C14 label from the C-1 to C-2 positions ranging from about 0.5y0 for the reaction in pyridine to about 4670 for the reaction in excess thionyl chloride. The results can be explained on the basis of varying degrees of involvement of the ethylene-p-methoxyphenonium chlorosulphite ion pair, thus supporting the suggestion that thermal decomposition of alkyl chlorosulphites to give chlorides may be considerably ionic in character. ISTRODUCTION

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Section: Di-2-p-anisylethyl Sulphite ( I V )mentioning

confidence: 99%

REARRANGEMENT STUDIES WITH C¹⁴: XIV. THE REACTION OF 2-p-ANISYLETHANOL-1-C¹⁴ WITH THIONYL CHLORIDE

Lee¹,

Newman²,

Thornhill³

1963

Can. J. Chem.

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“…Moreover, the S35 incorporated in I,, besides arising from external return, might have resulted also from a direct displacement reaction between I and the added p-toluenesulphonate-S35 anion, and (or) by exchange between the labeled p-toluenesulphonate anion and the p-toluenesulphonate anion of the intimate ion pair. However, a qualitative consideration of the S3j illcorporation in I, in conjunction with the C14 rearrangement in I, can be made (2). If the CL4 rearrangement in I, were to arise entirely from reaction between ethylphenonium ions (11) and the added 9-toluenesulpl~onate-S35 anions, in other words entirely froin external return, the percentage of incorporated in I, would be twice the percentage of CI4 rearrangenlent in I,.…”

Section: -% C' "mentioning

confidence: 99%

“…Solvolysis of I in the presence of sodium p-toluenesulphonate-S35 (111) made possible the simultaneous determinations of C14 rearrangeinent and S35 incorporation in the sulphonate I, recovered from the partially solvolyzed mixture. The data obtained for fornlolysis (2) indicated that some of the p-toluenesulphonate anions involved in the return to give the isotopically rearranged 2-phenylethyl-2-C1" p-toluenesulphonate were derived froin an intrainolecular process, thus pointing to the occurrence of some interllal return from an intinlate ion pair (3)(4)(5)(6) during the forinolysis of I.…”

Section: Introductionmentioning

confidence: 97%

“…In earlier publications (1,2), isotope position rearrangements observed in the solvolysis of 2-phenylethyl-1-C14 P-toluenesulphonate (I) under various conditions were reported.…”

Section: Introductionmentioning

confidence: 99%

“…A drawback in the earlier work (1,2) has been a lack of any concurrent kinetic data for consideration in conjunction with the observed C14 rearrangement and S35 exchange.…”

Section: Introductionmentioning

confidence: 99%

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REARRANGEMENT STUDIES WITH C¹⁴: XI. THE FORMOLYSIS OF 2-PHENYLETHYL-1-C¹⁴p-TOLUENESULPHONATE WITH OR WITHOUT ADDED SODIUM p-TOLUENESULPHONATE-S³⁵

Clayton¹,

Lee²

1961

Can. J. Chem.

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The formolysis of 0.350 M 2-phenylethyl-1-CL' p-toluenesulphonate (I) was carried out a t 7 4 f 0.2" C with or without the presence of at1 equirnolar amount of sodium p-toluenesulphonate-S3s ( [[I). The over-all hrst-order rate constant, k l , was found to be 2.6X10-j sec-1 and 3.0X10-s sec-I, respectively, for the reaction with and without added 111. The determination of the degrees of rearratigement of the C1"-labeled atoms from the C-1 to the C-2 positions in the 2-phetlylethyl p-toluenesulphonate (I,) recovered from the reaction mixture a t various reaction times permitted the evaluation of kL,', the rate of return from ionic intermediates to covalent bonding. Using the experimental data, it was possible to calculate k, and k~, the rates, respectively, for the anchimerically unassisted and assisted solvolysis. As expected, fortnolysis of 1 proceeded principally by the anchimerically assisted process. Calculations also showed that the fraction of the anchimerically assisted ionization r e t~~r n i n g t o covalent bonding was about 15% for the reaction in the presence of 111, while i l l the absence of 111, the return was about 9%. For the formolysis of I in the presence of 111, the extents of incorporati011 of S3j in the recovered sulphonate I, were also determined. The S3j incorporation in I,, when considered in conjunction with the CL" rearrangement in I,, led to the conclusion that the ret~lrn from ionic intermediates to covalent bonding during the fortnolysis of I included both internal and external returns, the extent of external return being the greater of the two. INTRODUCTIONIn earlier publications (1, 2), isotope position rearrangements observed in the solvolysis of 2-phenylethyl-1-C14 P-toluenesulphonate (I) under various conditions were reported.When acetolysis and forinolysis of I were interrupted a t about 50y0 completion, the rearrangement of C14-labeled atoins from the C-1 to C-2 positions in the recovered 2-phenylethyl-x-C14 p-toluenesulphonate (I,) indicated some return to covalent bonding through the intermediate ethylphenoniuill ion (11) or its equivalent. Solvolysis of I in the presence of sodium p-toluenesulphonate-S35 (111) made possible the simultaneous determinations of C14 rearrangeinent and S35 incorporation in the sulphonate I, recovered from the partially solvolyzed mixture. The data obtained for fornlolysis (2) indicated that some of the p-toluenesulphonate anions involved in the return to give the isotopically rearranged 2-phenylethyl-2-C1" p-toluenesulphonate were derived froin an intrainolecular process, thus pointing to the occurrence of some interllal return from an intinlate ion pair (3-6) during the forinolysis of I.'ilfa?zzcscript received itlarch 16, 1961.

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Electrooxydation d'iodures d'alkyle en solution dans l'acetonitrile—I

Laurent

Tardivel

1974

Tetrahedron

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Rearrangement studies with 14C—VIII

Cited by 9 publications

References 13 publications

REARRANGEMENT STUDIES WITH C¹⁴: XIV. THE REACTION OF 2-p-ANISYLETHANOL-1-C¹⁴ WITH THIONYL CHLORIDE

REARRANGEMENT STUDIES WITH C¹⁴: XIV. THE REACTION OF 2-p-ANISYLETHANOL-1-C¹⁴ WITH THIONYL CHLORIDE

REARRANGEMENT STUDIES WITH C¹⁴: XI. THE FORMOLYSIS OF 2-PHENYLETHYL-1-C¹⁴p-TOLUENESULPHONATE WITH OR WITHOUT ADDED SODIUM p-TOLUENESULPHONATE-S³⁵

Electrooxydation d'iodures d'alkyle en solution dans l'acetonitrile—I

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Rearrangement studies with 14C—VIII

Cited by 9 publications

References 13 publications

REARRANGEMENT STUDIES WITH C14: XIV. THE REACTION OF 2-p-ANISYLETHANOL-1-C14 WITH THIONYL CHLORIDE

REARRANGEMENT STUDIES WITH C14: XIV. THE REACTION OF 2-p-ANISYLETHANOL-1-C14 WITH THIONYL CHLORIDE

REARRANGEMENT STUDIES WITH C14: XI. THE FORMOLYSIS OF 2-PHENYLETHYL-1-C14p-TOLUENESULPHONATE WITH OR WITHOUT ADDED SODIUM p-TOLUENESULPHONATE-S35

Electrooxydation d'iodures d'alkyle en solution dans l'acetonitrile—I

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REARRANGEMENT STUDIES WITH C¹⁴: XIV. THE REACTION OF 2-p-ANISYLETHANOL-1-C¹⁴ WITH THIONYL CHLORIDE

REARRANGEMENT STUDIES WITH C¹⁴: XIV. THE REACTION OF 2-p-ANISYLETHANOL-1-C¹⁴ WITH THIONYL CHLORIDE

REARRANGEMENT STUDIES WITH C¹⁴: XI. THE FORMOLYSIS OF 2-PHENYLETHYL-1-C¹⁴p-TOLUENESULPHONATE WITH OR WITHOUT ADDED SODIUM p-TOLUENESULPHONATE-S³⁵