PROTONATED CYCLOPROPANES .7. EVIDENCE FOR EDGE PROTONATION
PROTONATED CYCLOPROPANES .7. EVIDENCE FOR EDGE PROTONATION
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DOI：
10.1021/ja00780a062
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发表时间：
1972-01-01
影响因子：
15
通讯作者：
KO, ECF
中科院分区：
文献类型：
--
作者：
LEE, CC;VASSIE, S;KO, ECF
(1)C. J.柯林斯，化学评论，69，543（1969）。（2）（a）CC Lee及KM Wan，J. Amer. Chem. Soc.，91，6416（1969）;（B）C. C. Lee和W. KY Chwang，Can.化学杂志，48，1025（1970）;（c）CC Lee和J. Law，同上，49，2746（1971）中所述。(3)CC Lee和D. J. Woodcock，J. Amer. Chem. Soc.，92，5992（1970）。在这种情况下，1-和2-氯丙烷之间的可逆异构化使这些结果不适用于柯林斯的结论。我们现在报道，1-丙基-7-14 C-过氧化汞（1-HgC_（104 -7- 14 C））的三氟乙酰化反应确实产生了一种1-丙基产物，其C-3比C-2更乱序。将1-HgC 104-J-14 C2c（约0.5M）在F3 CCOOH中的溶液加热回流8小时。通过vpc分析，产物分别由7和93%的1-和2-丙基三氟乙酸酯（1-OAcF 3 - 14 C和2-OAcF 3 - 14 Q）组成（通过同位素稀释测量，总产率为92-95%）。衍生自1-OAcF 3 - 14 C的vpc纯化的1-OH-14 C的降解20给出总结在表I中的结果。
(1) C. J. Collins, Chem. Rev., 69, 543 (1969).(2)(a) CC Lee and KM Wan, J. Amer. Chem. Soc., 91, 6416 (1969);(b) C. C. Lee and W. KY Chwang, Can. J. Chem., 48, 1025 (1970);(c) CC Lee and J. Law, ibid., 49, 2746 (1971).(3) CC Lee and D. J. Woodcock, J. Amer. Chem. Soc., 92, 5992 (1970). this case, reversible isomerization between 1-and 2-chloropropanes renderedthese results inapplicable to the conclusions of Collins. We now report that the trifiuoroacetolysis of 1-propyl-7-14C-mercuric perchlo-rate (l-HgC104-7-14C) indeed gave a 1-propyl product with more scrambling to C-3 than C-2. A solution of l-HgC104-J-14C2c (about 0.5 M) in FsCCOOH was heated under reflux for 8 hr. The products, analyzed by vpc, consisted of 7 and 93%, respectively, of the 1-and 2-propyl trifluoroacetates (1-OAcF3-14C and 2-OAcFs-14Q (total yield was 92-95% as measured by isotope dilution). Degradation20 of the vpc purified l-OH-14C derived from the 1-OAcF3-14C gave the results summarized in Table I.