2-NITRO-4-METHOXY ANILINE

B. 2-Nitro-4-methoxy aniline. A mixture of 160 g. of 2-nitro-4-methoxyacetanilide and 250 ml. of cold Claisen s alkali (Note 4) in a 2-1. beaker is stirred and warmed on a steam bath for 15 minutes it first becomes liquid and then sets to a thick, red paste. After the addition of 250 ml. of hot water the mixture is stirred and digested on a steam bath for an additional 15 minutes and then cooled to 0-5°. The product is collected on a 19-cm. Buchner funnel, washed with three 160-ml. portions of ice-cold water, and pressed as dry as possible with a rubber dam. The yield of vacuum-dried product melting at 122.5-123° is 122-4 g. (95-97%). ... 

Methoxy-anilin 4-MethyI-anilin 4-Brom-anilin 3-Nitro-anilin I-Naphthylamin... 

The rearrangement reaction continues to be of synthetic utility, often involved in industrial processes. Patent references (e.g. Reference 48) refer to the formation of 4-amino phenols. Often the reactant nitro compound is reduced (to the hydroxylamine) in an acid environment so that the two-stage reaction can be accomplished as a one-pot synthesis. 4-Amino phenol itself 45 can be made in high yield directly from nitrobenzene49 and the 4-methoxy aniline derivative 46 similarly from 2-methylnitrobenzene by hydrogenation in MeOH/H2S0450. 

Nitro-4-meth- oxy 3-Nitro-4-methoxy- aniline Pyridine A-5 26% t... 

Nitro- meth- oxy 4-Nitro-2-methoxy- aniline Pyridine A-6 21% t... 

Methoxy-2 nitro-5 aniline 2-Methoxy-5-nitrobenzenamine. See 2-Methoxy-5-nitroaniline... 

Various mixed tridentate ligands with P,N,0/S/N donor sets have been explored in Ni11 chemistry. For example, condensation of 2-(diphenylphosphino)aniline with substituted (5-chloro-, 5-nitro, 5-bromo-, 5-methoxy-, and 3-methoxy-) salicylaldehydes yields (253).697 The deprotonated ligand coordinates through its P,N,0 donor set in a square planar geometry with some distortion, which is probably due to the bulk of the phosphine group and to the bite angle of the P,N chelate. 

To get a complex set of substituents by direct derivatization of benzotriazole is not feasible. In such situations, it is better to have all the substituents in place first and later construct the heterocyclic ring. High reactivity of anilines and their well-developed chemistry makes them good stating materials. In an example shown in Scheme 215, acetanilide 1288 is nitrated to afford nitro derivative 1289 in 73% yield. Catalytic reduction of the nitro group provides methyl 4-acetylamino-3-amino-5-chloro-2-methoxybenzoate 1290 in 96% yield. Nitrosation of compound 1290 in diluted sulfuric acid leads to intermediate 1291, which without separation is heated to be converted to 7-chloro-4-methoxy-l//-benzotriazole-5-carboxylic acid 1292, isolated in 64% yield <2002CPB941>. 

Beim Hofmann-Abbau von 3-Methoxy-2-nitro-benzamid erhalt man fiber 3-Methoxy-2-ni-tro-anilin 4-Methoxy-benzofurazan-l-oxid125 ... 

Die Umwandlung des etwas weniger reaktiven l-Methoxy-4-nitro-benzols in N-Methyl-4-nitro- (54%) oder N,N-Dimethyl-4-nitro-anilin (65%) kann durch Reaktion mit waflriger Methylamin- bzw. Dimethylamin-Losung unter UV-Bestrahlung erreicht werden5. 

Generally meta-substituted anilines give rise to a mixture of 4- and 6-substituted isatins9,13,19,33-37 although 4-trifluoromethyl,15,33,35,36 4-nitro,13 4-amino,13 4-hydroxy,13 4-carboxy,13 6-methoxy,35 and 6-bromo 4 isatins have been reported without the other isomer. 

The following compounds are reported to have been deaminated by decomposing their stabilized diazonijim salts aniline 8 o-, m-, and p-toluidine 6 o-, m-, and p-anisidine 6 o-, m-, and p-nitroaniline 8 2-methoxy-4-nitro-5-aminotoluene 101 m-phenylenediamine 8 wi-tolyl-enediamine 8 p-aminophenol 8 benzidine 8 a- and /3-naphthylamine. . ) ... 

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