Nitro-4-methoxyaniline

Nitro-4-methoxyaniline has been prepared by heating nitro-hydroquinone dimethyl ether with aqueous ammonia 2 by heating the tetramethylammonium salt of 3-nitro-4-aminophenol 3 by the hydrolysis of 2-nitro-4-methoxyacetanilide la with alcoholic potassium hydroxide 11 lc or hydrochloric acid ld and by the hydrolysis of the />-toluenesul fonamide,4 the 3-nitrobenzenesul-fonamide,5 the 3-nitro-/>-toIuenesulfonamide,3 and the acetyl derivative of the />-toluenesulfonamide6 of 2-nitro-4-methoxyani-line with concentrated sulfuric acid. 

General Conditions for each step and selectivity of m-substituted anilines As previously mentioned, Hauser and Reynolds reported on factors governing the first step of the Conrad-Limpach reaction but they tvere by no means exhaustive. Other than the conditions reported above for the first step, HClAleOH, CHCI3 or CHCI2 (neat or with acid catalyst), PhMe or PhH with removal of water with or without acid catalyst, or EtOH/AcOH/CaS04 were reported to provide the desired enamino-ester from an aryl amine and 3-keto-ester. Hauser and Reynolds also noted that o-nitroaniline and o-nitro-p-methoxyaniline failed to form the desired enamino-ester under conditions which they reported. 

Ligands in complexes I. = tetrathiafulvalenium, L2 = H2NCOC6H4NH3-2, L3 = 2-H2NC5H4NH, L4 = 2,6-diacetylpyridine-bis(2-furoylhydrazone)dimethyltin, L5 =N,N -dimethyl-5-nitro-2,2/-bi-imidazol-3/-ium, L6 = cytosinium, L7 = 8-methylaminoquinolinium, L8 = iV-(4-hydroxybenzylidene)-4-methoxyaniline, L9 = 8-meth-oxyquinolinium, 1.19 = (3-MePz)3SnBuCl2, T = thiamine, Pz = Pyrazole. cCentrosymmetric anion. 

SYNS 2-AMINO-1-METHOXY-4-NITROBENZENE 3-AiMINO-4-METHOXYNITROBENZENE 2-AMINO-4-NITROANISOLE o-ANISIDINE NITRATE AZOAMINE SCARLET AZOGENE ECARLATE R AZOIC DIAZO COMPONENT 13 BASE C.I. AZOIC DIAZO COMPONENT 13 C.I. 37130 FAST SCARLET R 2-METHOXY-5-NITROANILINE 2-METHOXY-5-NITROBENZENAMINE NCI-C01934 3-NTTRO-6-METHOXYANTLINE 5-NITRO-2-METHOXYANILINE... 

Reference 81 also reports the solid phase enthalpies of formation of the isomeric 4- and 5-nitro-2-methoxyanilines, —197 and —232 kJmol-1. These values are disconcertingly disparate. The two isomers should have very nearly identical enthalpies of formation because in both cases there are electron-donating groups para to the nitro group and so there should be comparable stabilization. From equation 18, an estimated value of solid anisole, and the average enthalpy of formation of m- and p-nitroaniline, a calculated enthalpy of formation of the nitro-o-anisidines is ca — 210 kJ mol-1. 

Nltro-6-methoxyaniline 5-Nitro-2-methoxyaniline. See 2-Methoxy-5-nitroaniline... 

Carboxylic acids, including formic, acetic, lactic, propionic, malic, tartaric, and citric acids, can be tran.sformed with benzyl, naphthacyl, phenacyl, or bromophenacyl bromides [263], [264] / -nitro-benzyl bromide [265] / -nitrophenacyl bromide methoxyaniline or... 

Kinetic studies have been reported for the reactions of some 5-nitro-2-(4-nitrophenoxy)-3-X-thiophenes (10) with aniline and 4-methoxyaniline in methanol, which yield the corresponding 2-anilino derivatives. Base catalysis was interpreted by the SB-GA (specific base-general acid) mechanism. The reactions of 5-bromothiophene-2-carboxaldehyde (11) with secondary amines in water have been shown to produce the corresponding 5-aminated derivatives by the SnAt mechanism. ... 

Although known, the literature synthesis of 2-fluoro-4-methoxyaniline (7) outlined in Scheme 3 presented scale-up problems. The syndiesis involves a non-selective nitration of 3-fluorophenoL Separation of the desired regioisomer, methylation, and nitro reduction provides the target aniline (10). Findmg a more practical synthesis of this aniline was the first issue addressed on this project. 

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