Halonitro aromatics

In general, platinum, with or without modifiers, makes the best catalyst for minimizing dehalogenalion, combined with a fast rate of reduction of the nilro function. Excellent results have been obtained by use of supported noble-metal sulfides (4/). These catalysts [manufactured by Engelhard Industries, Newark, New Jersey (5/)] have a high intrinsic selectivity for this type of reduction and have given excellent results under a wide range of conditions. Elevated temperatures and pressures are necessary to achieve reasonable rates (33,34). 

A variety of inorganic (31,87) and organic bases have been added to the catalyst to improve selectivity. The effectiveness of organic bases is very sensitive to structure. Morpholine is an effective inhibitor, more so than /Si-melhylmorphollne N-elhylmorpholine 3,5-dimethylmorpholine (55). Piperazine is effective, but ethanolamine and ethylenediamine are poisons. 

Many other systems have been disclosed (85a). Pressure has a marked effect on the course of this reduction, especially when excess morpholine is used. At low pressure ( 50 psi) complete displacement of halogen by morpholine occurs to give p-(N-morpholino)nitrobenzene above 200 psi, the product is p-chloroaniline (55). 

Aliphatic, nonconjugated niiroolehns can be reduced to the saturated nitro compound without difficulty (30y36a,40,76). Both platinum and palladium have been used. The reverse selectivity seems not to have been reported. 

Excellent yields of the oximes of phenylacetaldehydes are obtained by reduction of 6-nitrostyrenes over Pd-on-C in a pyridine solvent (74,75). The technique gives yields of only about 60% when applied to aliphatic unsaturated nitrocompounds better yields are obtained in acidic media(6 5). Over 5% Rh-on-Al203 in ethanol-acetic acid-ethyl acetate, 2- 6-dinitro-styrenes are converted to 2-nitrophenylacetaldehyde oximes (13). 

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This reaction is illustrative of a general procedure for the alkylation of active methylene functions in the presence of concentrated aqueous alkali catalyzed by tetraalkylammonium salts. This catalytic method has been used to alkylate arylacetonitriles with monohaloalkanes,2 dihaloalkanes,3 a-chloroethers,4 chloronitriles,.5 haloacetic acid esters,6 and halonitro aromatic compounds.7 It has also been used to alkylate ketones,8 lf/ indene,9 9i/-fluorene,ll) and the Reissert compound.11 The reaction is inhibited by alcohols and by iodide ion.2... 

Hydrogenation of halonitro aromatics to the corresponding haloanilines is achieved on an industrial scale with limited dehalogenation. Sulfides of all noble metals have been used, under vigorous conditions"-. ... 

In contrast to aromatic halonitro compounds, selective removal of halogen in aliphatic halonitro compounds presents little problem. The reaction can be done by hydrogenation over palladium-on-carbon in the presence of a hydrohalide acceptor 46,73). 

Superelectrophilic halonitro-2,l,3-benzoxadiazole 243 undergoes remarkably facile carbon-carbon couplings with some electron-rich aromatics and heteroaromatics, affording quantitatively products exhibiting an intense visible absorption due to strong intramolecular charge transfer (Scheme 62) <2003CC2150>. 

Schematic representation of typical curves for hydrogen uptake and catalyst potential for the hydrogenation of aromatic halonitro compounds.

Amidine derivatives are effective dehalogenation inhibitors for the chemoselective hydrogenation of aromatic halonitro compounds with Raney nickel catalysts. The best modifiers are unsubstituted or N-alkyl substituted formamidine acetates and dicyandiamide which are able to prevent dehalogenation even of very sensitive substrates. Our results indicate that the dehalogenation occurs after the nitro group has been completely reduced i.e. as a consecutive reaction from the halogenated aniline. A possible explanation for these observations is the competitive adsorption between haloaniline, nitro compound, reaction intermediates and/or modifier. The measurement of the catalyst potential can be used to determine the endpoint of the desired nitro reduction very accurately. 

Reduction of nitro compounds to amines is a synthetically important reaction (98) and is practiced since the birth of modern chemical industry—many aromatic amines are key intermediates in production of dyes and pesticides. However, the stoichiometric reductions using iron or alkali metal hydrogen sulfides or catalytic hydrogenations with heterogeneous catalysts leave room for improvements in selectivity, especially with reference to halonitro-derivatives. There are many homogeneous catalysts such as the rhodium carbonyls in the presence of amines or chelating diamines, or [Rus(CO)i2] in basic amine solutions that are... 

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