RADICAL-INDUCED DEIODINATION OF ARYL IODIDES IN ALKALINE METHANOL
RADICAL-INDUCED DEIODINATION OF ARYL IODIDES IN ALKALINE METHANOL
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DOI：
10.1021/ja01001a055
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发表时间：
1967-01-01
影响因子：
15
通讯作者：
WAMSER, CC
中科院分区：
文献类型：
--
作者：
BUNNETT, JF;WAMSER, CC
当间氯碘苯暴露于活性自由基源和高浓度甲醇钠的甲醇溶液中时，间氯碘苯裂解为氯苯和碘离子。有效的自由基来源包括1-苯基-2-苯磺酰肼（3）（与大气中的氧），过二硫酸根离子，苯重氮离子，苯基偶氮三苯基甲烷，偶氮二异丁腈。在CH_3 OD溶液中形成的氯苯基本上不含氘，在富苯溶剂中形成锌-氯联苯;表明了间氯苯基的中间性。硝基苯，即使在很小的量，在很大程度上抑制脱碘。提出了方程6-11的循环机理。它的独特之处是在酸碱反应中从-CH 2 OH形成-CH 2 O-，电子从-CH 2 O-转移到芳基碘，伴随或随后排出碘离子并形成芳基自由基。
m-Chloroiodobenzene is cleaved to chlorobenzene and iodide ion whenexposed to the combination of a source of reactive radicals and a high concentration of sodium methoxide in methanol. Effective radical sources include 1-phenyl-2-benzenesulfonhydrazide (3)(with atmospheric oxygen), peroxydisulfate ion, benzene-diazonium ion, phenylazotriphenylmethane, and azobisisobutyronitrile. The chlorobenzene formed in CH3OD solution is substantially free of deuterium and zn-chlorobiphenyl is formed in a benzene-rich solvent; the inter-mediacy of w-chlorophenyl radicals is indicated. Nitrobenzene, even in small amount, largely inhibits deiodination. The cyclic mechanism of eq 6-11 is proposed. Its unique features are formation of-CH20-from-CH2OH in an acid-base reaction and electron transferfrom-CH20-to the aryl iodide, with concomitant or subsequent ejection of iodide ion and formation of aryl radical.