2- Methyl 4 nitroaniline activity

In one of their patents (13WO018928), Sumitomo chemists described the preparation of S-SFs-benzimidazole 70 and its use as an active pest-control agent. In their method, SFs-nitroaniHne 60, obtained in two steps from 4-SFs-anihne (11) by N-acetylation and subsequent nitration, was first converted into JV-methyl nitroaniline 71, the nitro group of which was then reduced to amino and coupled with 3-chloropyridine-2-carboxyUc acid to give amide 72. One-pot nucleophihc substitution of chlorine in 72 with sodium ethanethiolate and further condensation furnished 2-substituted 5-SFs-benzimidazole 73, the sulfide function of which was later oxidized to sulfone using 3-chloroperoxyhenzoic acid (MCPBA), thus providing the desired insecticide 70 (Scheme 18). 

Preparation of SHG-Active Composites. We have developed a new technique, including the construction of a device, which has made it possible to grow crystals of 3-nitroaniline (mNA), in a matrix of poly(methyl methacrylate) (PMMA) or poly(vinylcarbazole) (PVK) in an aligned fashion, to produce transparent, SHG-active composites (33). This approach is based upon the Temperature... 

A 13C—NMR study of several dimethylamino derivatives of pyridine, pyrimidine, and 2-oxopyrimidine with and without o-methyl substitution indicates a progressive twist of the dimethylamino group in hindered derivatives (78JCS(P2)1119). Unfortunately, the barriers have not yet been determined. The free energy of activation for 4-(Af-methylamino)pyridine (80JCS(P2)1704) is AG = 42.6 kJ mol-1 and is close to that of N-methyl-4-nitroaniline. 

N-oxides of this type are accessible from o-nitroaniline-based syntheses (see earlier section). l,2-Dihydro-2-oxoquinoxaline 4-oxide (64) and its N-methyl derivative (65) condense with compoimds containing an active methylene group in the presence of piperidine, yielding 3-alkylated quinoxalinones (66). The oxide 64, when warmed with aqueous potassium cyanide, affords 3-cyano-l,2-dihydro-2-oxoquinoxaline, whereas oxide 65 gives l,2-dihydro-3-hydroxy-2-oxo-l-methylquinoxaline. ... 

The catalytic transfer reductions of ethyl methyl ketone, isopropyl methyl ketone, and 4-methylacetophenone were studied over the wide series of basic, acidic and semiconducting oxides supported on Si02. Most of them exhibited remarkable activity in the studied transformations. The existence of the strong oxide oxide interaction between deposited phases and Si02 was noted. The nature of catalytic active sites was identified using catalytic titration with Hammett indicators and tetracyanoethylene. An unforeseen modifying effect of n-propylamine, o-nitroaniline, and TCNE onto AI2O3 was observed which led to the enhancement of catalyst activity. 

In order to circumvent the problem of the use of selenium, analogous systems based on the use of sulphur compounds have been developed [85-88]. Aromatic nitro compounds can be reduced by CO in water/methanol media at 120-150 °C and 1-1.5 bar pressure [85, 86]. From nitrobenzene, aniline was obtained with selectivity over 97 % at 100 % PhN02 conversion. The reaction proceeds in the presence of a multicomponent catalyst consisting of a base (preferably a strong base such as sodium hydroxide or methoxide) and sulphur compounds. The ratio of catalytic effectiveness of sulphur compounds is as follows S CS2 H2S COS = 1 1.3 10 10. Vanadium(V) compounds can be added to improve selectivity in aniline formation. Aromatic dinitro derivatives undergo this reaction and selectivity to one of the two main products (phenylenediamine and nitroaniline) can be switched by the choice of reaction conditions. The main byproduct of the reaction of nitrobenzene is PhNHCOOMe [85, 86]. It has been shown that, under the catalytic conditions, methyl phenylcarbamate can be hydrolysed to afford aniline. More forcing conditions (up to 300 bar CO) have also been employed in order to increase the activity [87]. The same catalytic system has been used to reduce nitrophenols to the corresponding aminophenols [88]. 

---