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REARRANGEMENT STUDIES WITH C14: V. THE SOLVOLYSIS OF 2-PHENYLETHYL-1-C14p-TOLUENESULPHONATE

 

作者: C. C. Lee,   G. P. Slater,   J. W. T. Spinks,  

 

期刊: Canadian Journal of Chemistry  (NRC Available online 1957)
卷期: Volume 35, issue 12  

页码: 1417-1422

 

ISSN:0008-4042

 

年代: 1957

 

DOI:10.1139/v57-187

 

出版商: NRC Research Press

 

数据来源: NRC

 

摘要:

The solvolysis of 2-phenylethyl-1-C14p-toluenesulphonate in absolute ethanol, glacial acetic acid, 90% formic acid, and anhydrous formic acid gave rise to products which showed rearrangements of the C14-labeled atoms from the C-1 to the C-2 positions to the extent of 0.3%, 5.5%, 40%, and 45%, respectively. The results constitute an unequivocal proof that phenyl participation occurs in the reactions studied. The different degrees of rearrangement found for the different solvent systems are in agreement with the concept that the solvolysis process may have a range of mechanisms between the two extremes of the nucleophilic or SN2 type and the limiting or SN1 type. In the solvolysis in absolute ethanol, a small amount of "unreacted" 2-phenylethylp-toluenesulphonate recovered from the reaction mixture was found to show isotope position rearrangement of almost the same degree as the ethanolysis product. This finding is tentatively attributed to the phenomenon of internal return involving an ethyl-phenoniump-toluenesulphonate ion-pair.

 

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