The o-Claisen rearrangement. VIII. Solvent effects
The o-Claisen rearrangement. VIII. Solvent effects
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o-克莱森重排。
DOI：
10.1021/jo00832a019
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发表时间：
1970
影响因子：
3.6
通讯作者：
E. F. Wolfarth
中科院分区：
文献类型：
--
作者：
W. N. White;E. F. Wolfarth
结果测定了烯丙基对甲苯基醚在气相和17种不同极性溶剂中的重排速率。根据溶剂的性质，以三种不同方式之一测量比速率常数。如果溶剂在紫外-可见光范围内的吸收可忽略不计，则将反应混合物的等分试样溶解在水性或醇性碱中，并通过吸收2-烯丙基-4-甲基苯酚根离子来形成产物。通过观察烯丙基对甲苯基醚红外光谱中12.91 µ处的谱带变化，监测在紫外-可见光区具有显著吸收的溶剂中的反应。在气相色谱中，（a）WN白色，D. Gwynn，K.施利特角吉拉德和WK法夫，美国化学学会杂志80，3271（1958）;（B）WN白色和B。E.诺克罗斯，同上，83，1968（1961）;（c）WN白色和BE诺克罗斯，同上，83，3265（1961）;（d）WN白色和WK法夫，同上，83，3846（1961）;（e）WN白色和C. D，斯莱特，有机化学杂志，26，3631（1961）;（f）WN白色和C. D.斯莱特，同上，27，2908（1962）;（g）WN白色和E. F. Wolfarth，同上，26，3509（1961）;（h）WN白色，C. D.斯莱特和WK法夫，同上，26，627（1961）中所述。(2)这项研究得到了美国国家科学基金会的赠款G-7345和GP-1970的支持。
ResultsThe rates of rearrangement of allyl p-tolyl ether in the gas phase and in 17 solvents of differing polarities were determined. The specific rate constant was measured in one of three different ways, depending on the nature of the solvent. If the solvent had negligible absorption in the ultraviolet-visible range, aliquots of the reaction mixture were dissolved in aqueous or alcoholic base and the formation of product was fol-lowed through the absorption of the 2-allyl-4-methyl-phenoxide ion. The reaction in solvents that have significant absorption in the ultraviolet-visible region was monitored by observing the change in a band at 12.91 µ that appears in the infrared spectrum of allyl p-tolyl ether. In the gas phaseruns, samples of the (1) Previous papers in this series:(a) WN White, D. Gwynn, K. Schlitt, C. Girard, and WK Fife, J. Amer. Chem. Soc. t 80, 3271 (1958);(b) WN White and B. E. Norcross, ibid., 83, 1968 (1961);(c) WN White and BE Norcross, ibid., 83, 3265 (1961);(d) WN White and WK Fife, ibid., 83, 3846 (1961);(e) WN White and C. D, Slater, J. Org. Chem., 26, 3631 (1961);(f) WN White and C. D. Slater, ibid., 27, 2908 (1962);(g) WN White and E. F. Wolfarth, ibid., 26, 3509 (1961);(h) WN White, C. D. Slater, and WK Fife, ibid., 26, 627 (1961).(2) This investigation was supported by Grants G-7345 and GP-1970 from the National Science Foundation.