Solvent network at the transition state in the solvolysis of hindered sulfonyl compounds

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• 作者：Mykyta Iazykov ; Ludmila Rublova ; Mois&eacute ; s Canle L. and J. Arturo Santaballa
• 刊名：Journal of Physical Organic Chemistry
• 出版年：2017
• 出版时间：January 2017
• 年：2017
• 卷：30
• 期：1
• 全文大小：603K
• ISSN：1099-1395

文摘

Alcoholysis rates of unhindered benzenesulfonyl chlorides (X-ArSO₂Cl, X = H-; 4-Br-; 4-Me-) are similar in methanol; the same behavior is also observed in ethanol, whereas the reactivity order in iso-propanol is 4 Me- < H- < 4-Br-. On the other hand, alcoholysis of sterically hindered arenesulfonyl chlorides (X-ArSO₂Cl) (X = 2,4,6-Me₃-3-NO₂-; 2,6-Me₂-4-tBu-; 2,4,6-Me₃-; 2,3,5,6-Me₄-; 2,4,6-iPr₃-; 2,4-Me₂-; 2,4,6-(OMe)₃-) in all studied alcohols show a significant increase in reactivity, the so-called positive steric effect.