Mechanism and Reactivity of Hydrolysis of Aliphatic Sulfonate Esters

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概要

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• It was shown with a five-membered sultone that the hydrolysis of aliphatic sultones in water proceeds substantially by B<SUB>AL</SUB>1-E1 mechanism, and that it is a nucleophilic substitution reaction caused by hydroxyl ion and water. We carried out a kinetic experiment on the hydrolysis of 1,4-butanesultone and ethyl ethanesulfonate, both in water and in water-acetone mixed solvent. It was found that these aliphatic sulfonate esters were hydrolyzed substantially by B<SUB>AL</SUB>1-E1 mechanism as in the case of a five-membered sultone, and in particular, ethyl ethanesulfonate was hydrolyzed by complete B<SUB>AL</SUB>1-E1 mechanism. The results seem to be justified by a tracer experiment with H<SUB>2</SUB><SUP>18</SUP>O. Namely, the ratios of the C–O fission to the S–O fission in 1,3-propanesultone and ethyl ethanesulfonate were 85.6:14.4 and 100:0, respectively. In strong alkaline solutions and approtic solvent-water systems, the S<SUB>N</SUB>2 reaction involving attack of the nucleophile on sulfur atom took place partly in sultones, but practically not in linear sulfonate esters. On the other hand, the ratio of relative reaction rates of a five-membered sultone, a six-membered sultone, and a linear sulfonate ester in water is 37:1:7. Since <I>E<SUB>a</SUB></I> is nearly the same for these three compounds, the contribution of strain in the molecular structure to the reactivity is small, and in consequence the above ratio seems to be attributed to <I>ΔS</I><SUP>\neweq</SUP>.

• 公益社団法人 日本化学会の論文

著者

• Mori Akira

  Research Department Of Mechanical Control Research Center Research Division Komatsu Ltd.

• Nagayama Masuzo

  Research Department, Lion Fat & Oil Co., Ltd.

• Mandai Hiroshi

  Research Department, Lion Fat & Oil Co., Ltd.

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