New synthesis of Fischer-type hydrazino(alkyl) complexes. First X-ray characterisation of a chelate hydrazino derivative
摘要:
通过适当的乙酰肼和 Na2Cr(CO)5,合成了第一个费舍尔型肼基(甲基)碳络合物;与氨基碳络合物相比,这种新络合物具有一些特殊的特征:(i) E 转子可以通过形成阴离子完全转变为 Z 转子,(ii) 由于热反应的结果,Z 异构体产生了一种新的不寻常的螯合物肼基(甲基)碳络合物,可以单烷基化或二烷基化。
DOI:
10.1039/a708018b
作为产物:
描述:
alkaline earth salt of/the/ methylsulfuric acid 在
air 作用下,
以
乙酸乙酯 为溶剂,
反应 168.0h,
以89.7%的产率得到1-benzyl-1-acetyl-2,2-dimethylhydrazine
参考文献:
名称:
Fischer-type alkyl(hydrazino)carbene complexes: new synthetic potential in comparison with aminocarbene complexes
摘要:
A general picture is given of the reactivity of the two Fischer-type alkyl(hydrazino)carbene complexes (CO)(5)Cr=C(CH3)N(Bn)N(CH3)(2) (1) and (CO)(4)Cr=C(CH3)N(Bn)N(CH3)(2) (3). Unlike their organic isolobal hydrazide analogues, they easily yield the corresponding alpha -anions at -78 degreesC, which react with various electrophiles. Furthermore, the tetracarbonyl chelate 3 (easily generated from 1) has greater synthetic potential than aminocarbenes: for example, it can be alkylated stepwise twice in the alpha -position, thus making it possible to introduce a new stereogenic centre in the molecule. (C) 2001 Elsevier Science B.V. All rights reserved.
A new, high-yielding methodology for reducing hydrazones to hydrazines is described, which allows the synthesis of different mono-, di- and trisubstituted hydrazines. Moreover, the reduction step can be followed by an in situ reaction with a carboxylic acid making possible a ‘one-pot’ synthesis of trisubstituted hydrazides. The method is relatively general and, in principle, suitable for industrial