问题：求教：脂肪硝基合物能否以水合肼还原法还原成脂肪胺？？
类型：求助 (悬赏分:3分)
提问：pukenmin
等级：▲
版块：有机化学问题(jimuwei,fpcwin1211,netpanda,yjgzfl,Ftian,)
信誉：60%
回复：9
阅读：1985
时间：2006-03-11 21:55:35 编辑加入/取消收藏订制/取消短消息举报该贴

查了不少文献，只查到以水合肼还原法还原芳香硝基合物成芳香胺相关．脂肪硝基合物还原都是以氢化崔化、氢化铝锂等东东，要不就是以金属还原法。综合现在手上的可用资源，除水合肼还原法外别无他法啊～～～～～痛苦。
请教，脂肪硝基合物能否以此法还原．

哪位大虾有这类的文献分享啊，谢谢！

回复人：pukenmin,▲ (a) 时间：2006-03-12 11:52:45 编辑	1楼
谁来说说话啊！！！！！

回复人：pukenmin,▲ (a) 时间：2006-03-12 12:02:36 编辑	2楼
会否出现严重副产？脂肪硝基合物中的Ｃ－Ｎ键在强碱及水的体系中断裂，Ｃ与ＯＨ连上？

回复人：pukenmin,▲ (a) 时间：2006-03-12 14:56:15 编辑	3楼
..................

回复人：celan,▲▲▲▲ (化学品成分和结构剖析服务:www.chemnmr.com) 时间：2006-03-12 15:12:18 编辑

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Zinc/Hydrazinium Monoformate Reduction of Nitro Compounds to Amines
Syn Comm, Vol 33, No 2, pp 281-289 (2003)
Abstract:
The nitro group in aliphatic and aromatic nitro compounds also containing reducible substituents such as ethene, nitrile, acid, phenol, halogen, ester, etc., are selectively and rapidly reduced at room temperature to corresponding amines in good yields by employing hydrazinium monoformate, in the presence of commercial zinc dust. It was observed that, hydrazinium monoformate is more effective than hydrazine or formic acid and reduction of nitro group occurs without hydrogenolysis in the low cost zinc dust compared to expensive metals like palladium.

Rapid and selective reduction of nitro compounds is of importance for the preparation of amino derivatives in the organic synthesis both practically and industrially, particularly when a molecule has other reducible moieties.1? The synthesis and biological evaluation of aromatic amines are also active and most important areas of research and their chemistry by derivative formation is widely studied. (6,7) Numerous new reagents have been developed for the reduction of aromatic nitrocompounds. (8) Though some of these are widely used, still they have limitations based on safety and handling considerations. For example, catalytic transfer hydrogenation9?1 of nitro or azido compounds in the presence of metals such as palladium on carbon or platinum on carbon require stringent precautions, because of their flammable nature in the presence of air. In addition, some methods require compressed hydrogen gas, which is highly diffusible and flammable, and vacuum pump to create high pressure within reaction flask. To overcome these difficulties, several new methodologies have also been developed.12,13 However, little attention has been given to the reduction of aliphatic nitrocompounds, 14?6 which are traditionally reduced by high-pressure catalytic hydrogenation.17?9 In addition to above mentioned limitations, most of these methods are unfortunately subject to substantial limitations as concerns the reducible functionalities and lack therefore desired generality for the true synthetic utility. Moreover, poor selectivity was reported in the reduction of aromatic nitro compounds, which have halogen, nitrile, carboxyl, hydroxyl etc., as substituents. Reduction at reflux temperature for hours together can cause rearrangements and cyclization in poly functional nitrocompounds. Therefore, we examined several methods to improve reduction process, and especially to obtain selectivity over reducible or other labile substituents. In this context, use of 5% platinum on carbon was found to be efficient but not cost effective.20

Recently, metal mediated reactions have been found to have wide scope in organic synthesis, because of their simple work-up and selectivity. Several methods have been developed based on the use of a variety of metals such as magnesium,21 indium,8,22,23 tin,24 zinc.25 The utility of zinc for the synthesis of β-α-unsaturated ketones by a reaction of an acid chloride with allyl bromide26 and homoallylic alcohols27 has been demonstrated. Further, the zinc mediated preparation of triphenyl phosphonium ylides,28 Fridel朇rafts acylation20 and carbamates formation30 has been demonstrated.

In this communication, we wish to report, a rapid and simple reduction of aliphatic and aromatic nitrocompounds to the corresponding amino derivatives by using commercial zinc dust and hydrazinium monoformate, at room temperature (Scheme 1). This new system reduced with ease a wide variety of nitro compounds directly to the corresponding amines and many functional groups are tolerated. This system is not helpful to obtain directly an amino carbonyl compound, due to the formation of hydrazone derivative with donor. However, the nitro hydrazones are reduced to corresponding amino hydrazones by this system. But, the thing is, in order to get amino carbonyl derivative, hydrazone should be subjected to hydrolysis. In both nitro aldehydes as well as nitro ketones, the products were obtained in almost pure and comparable yields.

The reduction of nitrocompound in the presence of zinc dust and hydrazinium monoformate was complete within one to ten min. The course of reaction was monitored by thin layer chromatography and IR spectra. The work-up and isolation of the products were easy. Thus, all the compounds reduced (Table 1) by this system were obtained in good yields (90?5%). All the products were characterized by comparison of their TLC, IR spectra, and melting points with authentic samples. A control experiment was carried out using nitro compounds with hydrazinium monoformate but without zinc dust, does not yield the desired product. No other intermediates, such as nitroso or hydroxylamine could be detected in the reaction mixture. In order to test the selectivity, reduction was attempted with p-dichlorobenzene, p-chloro-m-cresol, β-naphthol, cinnamic acid, acetanilide, benzoic acid, anisole, benzonitrile, phenyl acetate, etc., at laboratory temperature. However, the reaction failed to give any reduced product.

Typical Procedure
The hydrazinium monoformate was prepared by neutralizing slowly, equal moles of hydrazine hydrate and 85% formic acid in an ice water bath, with constant stirring. Thus obtained hydrazinium monoformate solution is used as such for reduction. A suspension of an appropriate nitrocompound (5 mmol) and zinc dust (10 mmol) in methanol or in any suitable solvent (3 mL) was stirred under nitrogen atmosphere with hydrazinium monoformate (2 mL), at room temperature. The reaction was exothermic and effervescent. After the completion of reaction (monitored by TLC), the reaction mixture was filtered through celite. The organic layer is evaporated and the residue was dissolved in chloroform or dichloromethane or ether was washed with saturated sodium chloride solution to remove excess of hydrazinium monoformate. The organic layer after drying and evaporation gave the desired amino derivative.

In order to get good yield of volatile aliphatic amine, the reaction was carried out by controlled addition of hydrazinium monoformate, through the top of ice water circulated condenser and by immersing the reaction flask in a cold-water bath. After filtration, whole reaction mixture was neutralized with HCl. The solvent was evaporated under reduced pressure. The residue was lyophilized or subjected to column chromatography. Aliphatic amines are obtained as their hydrochloride salts up to 80% yield.

回复人：celan,▲▲▲▲ (化学品成分和结构剖析服务:www.chemnmr.com) 时间：2006-03-12 15:13:06 编辑

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References
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回复人：celan,▲▲▲▲ (化学品成分和结构剖析服务:www.chemnmr.com) 时间：2006-03-12 15:14:59 编辑	6楼
Preparative Organic Chemistry Zinc/Hydrazine: A Low Cost-Facile System for the Reduction of Nitro Compounds. ChemInform Volume 34, Issue 13

回复人：pukenmin,▲ (a) 时间：2006-03-12 16:12:53 编辑	7楼
celan兄够狠谢过.

回复人：jsxaw,▲ (超强的创造发明能力,可以不要工资为尊重人才的老板服务,开发新产品,降低成本的部分分一小部分就可以.) 时间：2010-09-09 20:36:23 编辑	8楼
钯碳作催化剂，加氢还原最好

回复人：huangphy,▲▲▲ (Go after science & technology in reason.) 时间：2010-09-09 13:22:46 编辑	9楼
你可以水合肼为氢源，加点雷尼镍或钯碳进去也可以还原硝基的说。。。

得分人：celan-2,

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