- Radical formation in the oxidation of 2,2′-azo-2-methyl-6-heptene by thianthrene cation radical
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Reaction of 2,2′-azo-2-methyl-6-heptene (1) with thianthrene cation radical perchlorate (Th?+ClO4-) in CH2Cl2 solution containing 2,6-di-tert-butyl-4-methylpyridine (DTBMP) gave a mixture of nine C8 hydrocarbons, namely, 1,1,2-trimethylcyclopentane (4, 2.2%), 6-methyl-1-heptene (5, 2.2%), 2-methyl-1,6-heptadiene (6, 9.8%), 2,2-dimethyl-1-methylenecyclopentane (7, 2.9%), 6-methyl-1,5-heptadiene (8, 39%), 3,3-dimethyl- (9, 7.6%), 4,4-dimethyl- (10, 11%), 1,2-dimethyl- (11, 5.4%), and 1,6-dimethylcyclohexene (12, 1.5%). The amounts of acyclic dienes (6, 8) fell and of cyclohexenes (9, 10) rose when DTBMP was omitted from or diminished in the solution. The results provide firm evidence (products 4, 5, and 7) for the formation of the 2-methyl-6-hepten-2-yl radical (2), although the major fate of 2 is its oxidation to the corresponding cation 13, the origin of the bulk of the other products.
- Chen, Tonghua,Shine, Henry J.
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p. 4716 - 4719
(2007/10/03)
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- REACTIONS OF 1-HALO-5-HEXENES WITH ALKYLLITHIUMS. EVIDENCE FOR A PRONOUNCED HALOGEN EFFECT ON THE MECHANISM OF THE METAL-HALOGEN INTERCHANGE REACTION OF PRIMARY ALKYL HALIDES
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Reaction of t-BuLi with 1-halo-5-hexenes and 1-halo-6-methyl-5-heptenes at -78 gradC has revealed that, whereas 1 deg alkyl iodides are cleanly converted to alkyllithiums in a non-radical process, the corresponding 1 deg alkyl bromides undergo interchange at least partially via a radical-mediated, SET pathway.
- Bailey, William F.,Patricia, Jeffrey J.,Nurmi, Timo T.
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p. 1865 - 1868
(2007/10/02)
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- SELECTIVE REDUCTION OF TERTIARY ALKYL, BENZYL, AND ALLYL HALIDES TO HYDROCARBONS USING LITHIUM 9,9-DI-N-BUTYL-9-BORABICYCLONONANATE
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The title 9-borabicyclononane(9-BBN) ate complex (1) brings about selective removal of tertiary alkyl, benzyl, and allyl halides to give the corresponding hydrocarbons in excellent yields without concomitant attack on secondary, primary and aryl derivatives.The reduction of cis- and trans-4-t-butyl-1-methylcyclohexyl chlorides (2) with 1 gives 4-t-butyl-1-methylcyclohexanes (3) with partial inversion of configuration in cyclohexane, while that in benzene gives thermodynamically trans-3 predominantly.The reactions of 1,1-dimethyl-5-hexenyl chloride (4) and 1,7,7-trimethylbicyclohept-2-yl chloride (8) with 1 proceed with the rearrangements characteristic to a carbonium ion intermediate.The reduction of 1-ethyl-1-methylpentyl chloride with 1 follows a second-order rate equation.
- Toi, Hiroo,Yamamoto, Yoshinori,Sonoda, Akio,Murahashi, Shun-Ichi
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p. 2261 - 2268
(2007/10/02)
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