- Fragmentation of cyclobutoxychlorocarbene: The cyclopropylcarbinyl/cyclobutyl cations revisited
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Fragmentations of cyclobutoxychlorocarbene (13, kfrag= 7.1 × 105 s-1) and cyclopropylmethoxychlorocarbene (14, kfrag = 7.6 × 105 s-1) in MeCN proceed to tight and distinct [R+ OC Cl-] ion pairs, which collapse to different distributions of cyclopropylcarbinyl, cyclobutyl and allylcarbinyl chlorides. B3LYP/6-31G* calculations support these conclusions, affording computed fragmentation activation energies of 6.4 (13) and 3.0 (14) kcal mol-1.
- Moss, Robert A.,Zheng, Fengmei,Johnson, Lauren A.,Sauers, Ronald R.
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p. 400 - 406
(2007/10/03)
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- FRAGMENTATION OF CYCLOPROPYLMETHOXYCHLOROCARBENE: FORMATION OF CYCLOPROPYLCARBINYL/CHLORIDE ION PAIRS
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The decomposition of cyclopropylmethyloxychlorodiazirine in MeCN proceeds via N2 and CO loss, mainly to tight cyclopropylcarbinyl cation-chloride anion pairs that collapse to C4 chlorides with substantial skeletal and label retention; the ion pairs can be intercepted by ethanol with less skeletal retention.
- Moss, Robert A.,Ho, Guo Jie,Wilk, Bogdan K.
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p. 2473 - 2476
(2007/10/02)
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