The Alleged Role of Nitroxyl in Certain Reactions of Aldehydes and Alkyl Halides1
The Alleged Role of Nitroxyl in Certain Reactions of Aldehydes and Alkyl Halides1
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DOI：
10.1021/ja01506a043
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发表时间：
1960-11
影响因子：
15
通讯作者：
P. Smith;G. Hein
中科院分区：
文献类型：
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作者：
P. Smith;G. Hein
Angeli报道伯卤代烷与Piloty酸（C* HBS_（08）NHOH）或Angeli盐（Na_（8 N）O_（08））反应生成醛肟，已表明分别通过苯磺酰异羟肟酸或硝基异羟肟酸离子的烷基化进行，而不是通过这些化合物产生的硝酰基HNO的烷基化进行。亚硝酰钠不会将卤代烷转化为肟，也不会将醛转化为异羟肟酸（Angeli-Rimini醛试验）。已发现Angeli盐分解为亚硝酸盐和硝酰基的速率遵循一级动力学，并且不受溶剂从水到乙醇的变化的影响，但它被氢氧化钠显著地延迟。环己基羟胺的碱性硝化通过不稳定的N-环己基硝基异羟肟酸根阴离子得到环己酮肟。Piloty酸的O-乙酰基和O-四氢吡喃基衍生物可有效地在氮上烷基化，得到可分离的产物，其可通过水解裂解保护基团和用碱处理而转化为醛肟。用上述各种方法将苄基氯、2，4，6-三甲基苄基氯、乙基碘和氢化肉桂基碘转化为相应的肟。
The reaction of primary alkyl halides withPiloty’s acid (C* HBS08NHOH) or Angeli's salt (Na8N80 «), reported by Angelí to give aldoximes, has been shownto proceed by alkylation of the beuzenesulfonhydroxamate or nitrohydroxamate ion, respec-tively, rather than by alkylation of nitroxyl, HNO, which these compounds generate. Sodium nitrosyl does not convert alkyl halides to oximes, nor does it convert aldehydes to hydroxamic acids (Angeli-Rimini aldehyde test). The rate of breakdown of Angeli’s salt to nitrite and nitroxyl has been found to follow first-order kinetics, and to be unaffected by a change in solvent from water to ethanol, but it is markedly retarded by sodium hydroxide. Alkaline nitration of cyclohexylhydroxylamine gives cyclohexanone oxime through the unstable N-cyclohexyInitrohydroxamate anion. The O-acetyl and O-tetrahydropyranyl derivatives of Piloty’s acid can be alkylated efficiently on the nitrogen to give isolable products, which can be converted to aldoximes by hydrolytic cleavage of the blocking group andtreatment with base. By the various methods mentioned benzyl and 2, 4, 6-trimethylbenzyl chlorides and ethyl and hydrocinnamyl iodides havebeen converted to the corresponding oximes.