Nitromethylation

Kamlet, M.J. and Adolph, H.G., Some Comments Regarding the Sensitivities, Thermal Stabilities, and Explosive Performance Characteristics of Fluorodi-nitromethyl Compounds, in Seventh Symposium (International) on Detonation, NSWC MP 82-334 (edited by Short, J.M.), Naval Surface Weapons Center, White Oak, Silver Spring, MD, 1982, pp. 84-92. 

Although the nitro group plays a crucial role in most of these SrnI reactions, reactions of this type have synthetic application beyond the area of nitro compounds. The nitromethyl groups can be converted to other functional groups, including aldehydes and carboxylic acids.Nitro groups at tertiary positions can be reductively removed by reaction with the methanethiol anion.This reaction also appears to be of the electron-transfer type, with the methanethiolate anion acting as the electron donor ... 

Ring opening with subsequent recyclization to compound 15 occurred when 3,4-bis(hydroximinomethyl)furoxan 14 was heated in water prolonged heating afforded the nitromethyl derivative 16 (Scheme 5). Ring opening on attack by ammonia on the furoxan 14 led to the intermediate 17, which may be recyclized to hydroxamic acid 18 (75LA1029). 

Another example of this rearrangement has been used to prepare 1,2,3-triazole 146 from furazanic phenylhydrazone 147 (Scheme 84) [93JCS(P1)2491]. Interestingly, furoxanic Z-phenylhydrazones 150 underwent thermal recyclization to 1,2,3-triazole A-oxides 152, evidently through intermediate 151. Treatment of the hydrazone 150 with rerr-BuOK leads to the nitromethyl derivative 149 [OOOMIl] (Scheme 84). Lead tetraacetate oxidation of 147 with subsequent Lewis acid treatment of the initially formed intermediate afforded indazole 148 (Scheme 84) (85JHC29). 

The base-catalyzed reacdon of nitromethane with ct-amidoalkyl sulfones gives the nitto compounds as in Eq 4 117 the nitromethyl group is converted into a carboxylic group to give ct-amino acids by the Nef reacdon using KMnO. ... 

During oxidn of mesitylene with nitric acid in an autoclave at 115° to give 3,5-dimethylbenzoic acid, a violent expln occurred. The reaction was attributed to local overheating, formation of a trinitro compd, 1,3,5-tri (nitromethyl) benzene, and to violent decompn of the latter. Smaller scale prepns with better temp control were uneventful (Ref 3)... 

Dinitro Methyl Anisole (4-Nitro-2-nitromethyl anisole, 3-Nitro-6-methoxynitromethyI toluol. or Methyl-[5-nitro-2-nitromethylphenyl] -ether). CH3.0.(N02)C6H3.CH2N02, mw 212.18, N 13.21%, OB to C02 —113.11%, cryst, mp 93—94°. Prepd from 4-nitro-2(lodomethyl) anisole in ether-ben2ene soln by treatment for 3 days at RT with Ag nitrate. The sodium salt explodes violently on heating Refs 1) Beil, not found 2) G. Bendy,... 

Dimethyl-2,2,4,4-tetranitropentane 2,3-Dimethyl-3,4-dinitro-2,3-bis (nttromethyl) butane 2,5-Dimethyl-2,33,4,4,5-hexanitro-hexane 3,4-Dimethyl-2,2,3,4,5,5-hexanitro-hexane and 2,2,4,4-Tetrakis (nitromethyl) pentane. Ref 2 details a listing of a variety of methods attempted in these unsuccessful syntheses... 

CniHifiN205 138681-67-1) see Zafirlukast a -(nitromethyl)-3-(phenylmethoxy)-2,6-pyridine-dimethanol... 

Change in the way a reaction occurs because of inappropriate temperatures. At 20 C nitric acid converts mesitylene into 3,5-dimethylbenzoic acid without danger, but at 115°C the explosive 1,3,5-tris(nitromethyl)benzene is formed. Excessive heating of thiophosphoryl trichloride with pentaerythritol at 160°C leads to the formation of phosphine, which combusts spontaneously. 

Nickel(II) complexes of type (599) unsaturated 14-membered tetrazamacrocycles react with the anion of nitromethane under basic conditions to give the 5-nitromethyl derivatives (600), and the square planar diperchlorates (601) upon treatment with HC104 (Equation (19)) 151... 

See also Sodium l,3-dihydroxy-l,3-bis(ac7-nitromethyl)-2,2,4,4-tetramethylcyclo-butandiide... 

Nitromethylation of aldehydes has been carried out in a one pot procedure consisting of the Henry reaction, acetylation, and reduction with sodium borohydride, which provides a good method for the preparation of l-nitroalkanes.16b 79 It has been improved by several modifications. The initial condensation reaction is accelerated by use of KF and 18-crown-6 in isopropanol. Acetylation is effected with acetic anhydride at 25 °C and 4-dimethylaminopyridine (DMAP) as a catalyst. These mild conditions are compatible with various functional groups which are often... 

The anion of nitromethane is particularly reactive in S l reactions. Various kinds of tertiary nitro groups are replaced by a nitromethyl group on treatment with the anion of nitromethane (Section 7.1).49 2-Iodoadamantane reacts with the anion of nitromethane in the presence of acetone enolate (entrainment reaction) under irradiation of a 400-W UV lamp to give 2-ni-tromethyladamantane in 68% yield, (see Eq. 5.32).50a 1-Iodoadamantane also reacts with the anion of nitromethane in a similar way.50b... 

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