Nitro compounds selective

A number of selected aromatic nitro compounds are collected in Table IV,16A, It will be noted that a few nitro aromatic esters have been included in the Table. These are given here because the nitro group may be the first functional group to be identified aromatic nitro esters should be treated as other esters and hydrolysed for final identification. 

Various terminal allylic compounds are converted into l-alkenes at room temperature[362]. Regioselective hydrogenolysis with formate is used for the formation of an exo-methylene group from cyclic allylic compounds by the formal anti thermodynamic isomerization of internal double bonds to the exocyclic position[380]. Selective conversion of myrtenyl formate (579) into /9-pinene is an example. The allylic sulfone 580 and the allylic nitro compound... 

Formic acid is a good reducing agent in the presence of Pd on carbon as a catalyst. Aromatic nitro compounds are reduced to aniline with formic acid[100]. Selective reduction of one nitro group in 2,4-dinitrotoluene (112) with triethylammonium formate is possible[101]. o-Nitroacetophenone (113) is first reduced to o-aminoacetophenone, then to o-ethylaniline when an excess of formate is used[102]. Ammonium and potassium formate are also used for the reduction of aliphatic and aromatic nitro compounds. Pd on carbon is a good catalyst[103,104]. NaBH4 is also used for the Pd-catalyzed reduction of nitro compounds 105]. However, the ,/)-unsaturated nitroalkene 114 is partially reduced to the oxime 115 with ammonium formate[106]... 

Tertiary, benzyl, and aHyhc nitro compounds can also be used as Friedel-Crafts alkylating agents eg, reaction of (CH2)3CN02 (2-nitro-2-methyl propane [594-70-7]) with anisole in the presence of SnCl gives 4-/-butylanisole [5396-38-3] (7). SoHd acids, such as perfluorodecanesulfonic acid [335-77-3], and perfluorooctanesulfonic acid [1763-23-1] have been used as catalysts for regio-selective alkylations (8). 

Nitroso compounds are formed selectively via the oxidation of a primary aromatic amine with Caro s acid [7722-86-3] (H2SO ) or Oxone (Du Pont trademark) monopersulfate compound (2KHSO KHSO K SO aniline black [13007-86-8] is obtained if the oxidation is carried out with salts of persulfiiric acid (31). Oxidation of aromatic amines to nitro compounds can be carried out with peroxytrifluoroacetic acid (32). Hydrogen peroxide with acetonitrile converts aniline in a methanol solution to azoxybenzene [495-48-7] (33), perborate in glacial acetic acid yields azobenzene [103-33-3] (34). 

The nitration route shows insufficient alpha-selectivity in addition to producing considerable dinitro product. Although a large amount of work has been done to maximize the yield of 1-nitro compound, the best result is less than 80%. Several methods have been developed to remove 2-nitroanthraquinone and dinitroanthraquinones from cmde 1-nitroanthraquinone. Purification is carried out, for example, by recrystaUization from nitric acid, or from organic solvents (15). 

Catalytic reduction of fluormated aliphatic and aromatic nitro compounds to give oximes and amines was described previously, as was the use of dissolving metals to prepare amines [Si] Refmement of these techniques has resulted in optimized yields and, as indicated in equations 69 and 70, in selective reductions [S6, 87]... 

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. 

In molecules containing both an acetylenic and a nitro function, either or both may be reduced. Preferential reduction of the acetylenic function is best achieved with palladium (42,44). Ruthenium, on the other hand, favors selective reduction of an aromatic nitro function high yields of (3-aminophenyljacetylene were obtained from the corresponding nitro compound. Catalyst life is prolonged by protection of the acetylenic function (70). Cobalt polysulffde and ruthenium sulffde catalysts have been used similarly, but more vigorous conditions are required (100°C, 25-70 atm) (71). 

Arylisoxazol-5(4//)-oncs 21 react with benzene-1,2-diamines to yield 4-aryl-l,5-benzodiaze-pinones 22 by elimination of hydroxylamine from the intermediate oximes. Unsymmetrically substituted benzene-1,2-diamines are attacked at the more nucleophilic amino group. Thus, 4-methylbenzene-1,2-diamine gives 7-methylbenzodiazepinones 22f-h, whereas 4-nitrobenzene-1,2-diamine gives 8-nitro compounds 22k-n. The benzodiazepinones are accompanied by minor amounts of 2-methylbenzimidazoles 23. Selected examples are given.275... 

INDIUM/AMMONIUM CHLORIDE-MEDIATED SELECTIVE REDUCTION OF AROMATIC NITRO COMPOUNDS ETHYL 4-... 

For a review of selective reduction of aliphatic nitro compounds without disturbance of other functional groups, see Ioffe, S.L. Tartakovskii, V.A. Novikov, S.S. Russ. Chem. Rev., 1966, 35, 19. 

With this reaction available, a simple synthesis of unsymmctrical dibenzyl ketones (21) can be planned. The carbonyl group can be derived from a nitro group (22) by TlClg-catalysed hydrolysis (p T 183 ). Reversing the selective reduction gives (23) and a,6-dlsconnection separates this Into aldehyde (24) and nitro compound (25), available by reduction of (20). 

By analogy with aromatic nitro compounds, nitroolefins such as yS-nitrostyrene 1032 react with the O-silylketene acetal 1033 at -78 °C, in the presence of the selective Lewis acid MAD, in toluene, to give a 6.3 1 syn/anti mixture of the co-nitro ester 1034 and 94a [98] (Scheme 7.33). 

Hatziantoniou, V., Andersson, B., and Schbon, N.-H., Mass transfer and selectivity in liquid phase hydrogenation of nitro compounds in a monolithic catalyst reactor with segmented gas-liquid flow. Ind. Eng. Chem. Process Des. Dev. 25, 964-970 (1986). 

In some respects this is a trivial application. In order to select a protective glove for a new nitro compound, all we would do in practice would be to check to see what material provides good protection against known nitro compounds and assume that this material would be appropriate we do not need a computer to tell us how to do this. But the reason that the procedure in this case is simple is that we already have a means to group compounds by noting the presence or absence of particular functional groups. If the link between structure and protective material were subtler, a more sophisticated way to determine the appropriate material would be required. 

Allylic nitro compounds are obtained by the reaction of cyclic ketones with nitromethane in the presence of 1,2-diaminoethane (1 mol%) as catalyst. Because exo-cyclic nitroalkenes are rearranged to the endo-cyc c p,y-nitroalkenes, allylic nitro compounds are selectively produced (Eq. 3.21).31... 

Electrochemically generated nickel is very selective for the reduction of aromatic nitro compounds into anilines, in which alkenyl, alkynyl, halo, cyano, formyl, and benzyloxy groups are not affected.84 Sodium sulfide has been used for the selective reduction of aromatic nitro group in the presence of aliphatic nitro groups (Eq. 6.44).85... 

In recent years, the importance of aliphatic nitro compounds has greatly increased, due to the discovery of new selective transformations. These topics are discussed in the following chapters Stereoselective Henry reaction (chapter 3.3), Asymmetric Micheal additions (chapter 4.4), use of nitroalkenes as heterodienes in tandem [4+2]/[3+2] cycloadditions (chapter 8) and radical denitration (chapter 7.2). These reactions discovered in recent years constitute important tools in organic synthesis. They are discussed in more detail than the conventional reactions such as the Nef reaction, reduction to amines, synthesis of nitro sugars, alkylation and acylation (chapter 5). Concerning aromatic nitro chemistry, the preparation of substituted aromatic compounds via the SNAr reaction and nucleophilic aromatic substitution of hydrogen (VNS) are discussed (chapter 9). Preparation of heterocycles such as indoles, are covered (chapter 10). 

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