N-Methyl-p-nitroaniline

N,4-DinitrO N-methylaniline, bright yellow needles from benz, mp 142.5° (Ref 2) CA Registry No 16698-03-6. It is prepu by the alkylation of N,p-dinitroaniline with methyl iodide in alk soln (Refs 8 9). It is one compd isolated from aged NC propints stabilized with N-methyl-p-nitroaniline. Hollingsworth at ERDE examined the reaction of nitrogen dioxide with this stabilizer in order to elucidate the mechanism of the formation of the compds isolated. He found that after 7 days at 35°,. a good yield of N,4-dinitro-N-methylaniline was obtd and postulated that it arose from the oxidn of N-nitroso-4-nitroaniline (Ref 16)... 

N-Methyl-p-nitroaniline Nickel Raney Palladium on carbon Calcium sulfate... 

To 500 ml of acetic anhydride was added portionwise, 100.0 g (0.658) of N-methyl-p-nitroaniline. Following the addition, the solution was heated on a steam bath for 2 h, then stirred overnight at room temperature. The white precipitate of the N-methyl-4-nitroacetanilide was collected by filtration, washed with ether and air-dried to give 53.0 g, melting point 153°-156°C. 

Magnetic field effects on the luminescence of a liquid polyphenoxy polymer excited in the VUV region show that highly excited singlet states of aromatic chromophores can relax to form two triplets. A spectroscopic and ODMR study has been reported on the triplet state of N-methyl-p-nitroaniline ° . 

There are other stabilisers of a similar nature, which are 4-nitrodiphenylamine, 2-nitrodiphenylamine, N-methyl-p-nitroaniline and diphenylamine. 

N-nitrosation and simultaneous C-nitration of secondary aromatic amines by aqueous solution of N204 has been studied by Stoermer [61] and Ruff and Stein [62], Thus N-methylaniline yielded N-methyl-n-nitroso-p-nitroaniline. 

Fig. 39. Absorption spectra of N,N-dimethyl-p-nitroaniline (I) and its methyl derivatives 3-methyl- (II), 3,5-dimethyl-p-nitrodimethylaniliie (III) (Remington [S]).

In this experiment, three nitroaniline derivatives, i.e. p-nitro -aniline (p-NA), 2-hydroxy-i -nitroaniline(HNA) and N-methyl-i -nitroaniline (NMNA), were chosen as guest molecules because of their large optical nonlinearity. As a host molecule, dimethyl /-cyclodextrin (dimethyl f -CD) was used. It is well known that dimethyl /-CD forms an inclusion complex with many kinds of aromatic derivatives. 

The same authors also introduced a r scale of solvent dipolarity/polarizability [84a]. This n scale is so named because it is derived from solvent effects on the n n electronic transitions of a selection of seven positively solvatochromic nitroaromatics of the type D-C6H4-A, where D and A stand for electron-donor e.g. NMe2) and electron-acceptor e.g. NO2) groups, respectively 4-nitroanisole, A,A-diethyl-3-nitroaniline, 4-methoxy-/ -nitrostyrene, 1-ethyl-4-nitrobenzene, A-methyl-2-nitro-p-toluidine, N,N-diethyl-4-nitroaniline, and 4-(dimethylamino)benzophenone. Given a solvatochromic indicator compound, the n value for a solvent S was defined according to Eq. (7-32) ... 

In a second method, the amine is treated with aqueous formaldehyde in acetonitrile and the resulting imine reduced with sodium cyanoborohydridc (this volume). Yields for the most part ate high, 80-90%. Even the very weak ba.se p-nitroaniline (pK, 1.00) is converted into a mixture of mono- and dimethylatcd products. Hindered amines can be used (e.g., N-Lsopropylcyclohexylamine is methylated in 87% yield). 

Lithio-fluoro (or -chloro) methyl phenyl sulfoxide reacts with N-(benzylidene)aniline derivatives (105) to afford the corresponding aziridines (106) in good yields. Two diastereomeric isomers are produced, but the trans isomer is the major product except in the case of A(-benzylidene-p-nitroaniline (Scheme 30).94... 

Cl 37100. See 2-Methyl-4-nitroaniline Cl 37105. See 2-Methyl-5-nitroaniline Cl 37107. See p-Toluidine Cl 37110. See 3-Nitro-p-toluidine Cl 37115. See o-Anisidine hydrochloride Cl 37130. See 2-Methoxy-5-nitroaniline Cl 37225. See Benzidine Cl 37230. See o-Tolidine Cl 37235. See Dianisidine Cl 37240. See N-Phenyl-p-phenylenediamine Cl 37500. See P-Naphthol Cl 40000. See Direct yellow 11 Cl 40002 Cl 40003. See 4,4 -Diaminostilbene-2,2 -disulfonic acid Cl 40645. See Sodium-2-(4-styrvl-3-sulfophenyl)-2H-naphtho-(1,2-d)-triazole Cl 40800... 

N-4-Methyl-2-nitro-1,4-benzenediamine. See N-Methyl-3-nitro-p-phenylenediamine 2-Methyl-4-nitrophenylamine. See 2-Methyl-4-nitroaniline... 

N,N-Diethyl-m-toluidine Dimethyl adipate Dimethylaminopropylamine Dimethyl malonate 1,3-Dinitrobenzene 1,8-Dinitronaphthalene N,N -Diphenyl-p-phenylenediamine Emodin 3-Ethylamino-4-methylphenol 3-Ethylaminophenol Ethyl benzoylacetate Ethylbenzylaniline Ethyl chloride N-Ethyl-N-hydroxyethyl-m-toluidine Ethyl morpholine Hexachlorocyclopentadiene Hexamethyleneimine 1-Hexene Hydrazobenzene Hydroquinone Imidazole Isopropylamine Isopropyl bromide 2-Mercaptoethanol 2-Methoxy-5-nitroaniline Methylamine Methyl anthranilate Methyl benzoate 2-Methyl benzoxazole 4,4 -Methylenedianiline... 

Aniline derivatives such as toluidines, chloroanilines and nitroanilines were methylated in toluene by the treatment with dimethyl sulfate, since the N-methylation of aniline derivatives proceeded in higher selectivity in toluene than in benzene (Table II). Except for o- and p-nitroaniline, N-methylation was facilitated well by the use of KY. 

Besides the 0-glycosides mentioned so far, also attention has been paid to the synthesis of N- and S-analogues. The p-nitrophenyl N-glycoside of a-N-acetylneuraminic acid has been prepared by silver carbonate-promoted reaction of 4,7,8,9-tetra-0-acetyl-2-chloro-2-deoxy-p-N-acetylneuraminic acid methyl ester with p-nitroaniline and subsequent deprotection (Privalova and Khorlin 1969). Treatment of the same precursor with sodium azide, followed by de-esterification, led to the formation of 2-azido-2-deoxy-a-N-acetylneuraminic acid (Supp et al. 1980). The same authors reported also the preparation of the p-form. The azides can readily be converted into the 2-amino derivatives of N-acetylneuraminic acid. Subsequently, the amino function has been benzoylated. Data on the syntheses of the methyl and p-nitrophenyl S-glycosides of a-N-acetylneuraminic acid have been presented by Privalova and Khorlin (1969), whereas Ponpipom et al. (1980) have described a method for the synthesis of 5-acetamido-2-S-[6-(5-cholesten-3p-yloxy)hexyl]-3,5-dideoxy-2-thio-p-D-g/vccro-D-ga/acto-2-nonulopyranosonic acid. 

A number of 5- and N-ketosyl derivatives of NANA were prepared by Privalova and Khorlin (1969). The use of p-nitroaniline in a Koenigs-Knorr type reaction with the acetylglycosyl chloride methyl ester of NANA gave (after subsequent deacylation) the 2-deoxy-2-p-nitropheny-lamino A-glycoside of NANA, assigned structure XXXI (Figure 10). 

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