4- Methylnitrobenzene

Rondevstedt, C. S., Chem. Eng. News, 1977, 55(27), 38 Synthesis, 1977, 851-852 In an attempt to reduce 2-chloro-5-methylnitrobenzene to the aniline by treatment with excess hydrazine and Pd/C catalyst, the hydroxylamine was unexpectedly produced as major product. During isolation of the product, after removal of solvent it was heated to 120°C under vacuum and exploded fairly violently. Many aryl-hydroxylamines decompose violently when heated above 90-100°C, especially in presence of acids. GLC is not suitable as an analytical diagnostic for arylhydroxyl-amines because of this thermal decomposition. 

Recently, synthesis of the 4-arylindole portion of the antitumor agent diazonamide has been achieved starling from 3-bromo-2-methylnitrobenzene via Suzuki coupling and the Batcho reaction.67b... 

Methyl methacrylate 4-Methylnitrobenzene 2- Methylpyridine Methylsodium Molybdenum trioxide Naphthalene 2-Naphthol Air, benzoyl peroxide Sulfuric acid, tetranitromethane Hydrogen peroxide, iron(II) sulfate, sulfuric acid 4-Chloronitrobenzene Chlorine trifluoride, interhalogens, metals Chromium trioxide, dinitrogen pentaoxide Antipyrine, camphor, phenol, iron(III) salts, menthol, oxidizing materials, permanganates, urethane... 

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. 

Synonyms AI3-16311 BRN 1907580 CCRIS 1224 EINECS 201-853-3 l-Methyl-2-nitro-benzene 2-Methylnitrobenzene o-Methylnitrobenzene o-Nitrotoluene 2-Nitrotoluol NSC 9577 ... 

Synonyms BRN 1906910 CCRIS 2312 EINECS 202-728-6 l-Methyl-3-nitrobenzene 3-Methylnitrobenzene m-Methylnitrobenzene MNT / 3-Nitrotoluene 3-Nitrotoluol NSC 9578 UN 1664. 

Synonyms AI3-15394 BRN 1906911 CCRIS 2313 EINECS 202-808-0 l-Methyl-4-nitro-benzene 4-methylnitrobenzene p-Methylnitrobenzene NCI-C60537 p-Nitrotoluene 4-Nitro-toluol NCI-C60537 NSC 9579 PNT UN 1664. 

Table 4.3 presents the relative rate constants of the chlorine-to-methoxy substitution in the nitrobenzene series (Epiotis 1973). The methoxide ion replaces chlorine in 4-chloro-3-methyl-nitrobenzene more rapidly than in 6-chloro-3-methylnitrobenzene (Table 4.3, entries 1 and 2). This... 

Table 4-3 presents the relative rate constants of chlorine-to-methoxy substitution in the nitrobenzene series (Epiotis 1973). The methoxide ion replaces chlorine in 4-chloro-3-methylnitrobenzene more rapidly than in 6-chloro-3-methylnitrobenzene (Table 4-3, nos. 1 and 2). This agrees with the fact that the anion radical of 3-methylnitrobenzene has a greater spin density in position 4 than in position 6. The aforementioned HFC constants of the 3-nitrochlorobenzene anion radical and the relative rate constants (kre ) for the substitution of methoxyl for chlorine at the / th carbons (Table 4-3, nos. 3 and 4) correlate in the same way. 

INDOLES FROM 2-METHYLNITROBENZENES BY CONDENSATION WITH N.N-OIMETHYLFORMAMIDE ACETALS AND REDUCTION... 

Synonyms and trade names nitrotolul, methylnitrobenzene, 2-nitrotoluene, 2-NT... 

DOT CLASSIFICATION 6.1 Label Poison SAFETY PROFILE Poison by ingestion. Moderately toxic by inhalation. Combustible when exposed to heat, flame, or oxidizers. To fight fire, use water, CO2, dry chemical. Probably an explosive. When heated to decomposition it emits toxic fumes of NO. See also other methylnitrobenzene entries and NITRO COMPOUNDS OF AROMATIC HYDROCARBONS. 

SYNS 4-METHYLNITROBENZENE p-METHYL NITROBENZENE NCI-C60537 4-NITROTOLUENE 4-NITROTOLUOL PNT... 

METHYLNITROBENZENE see NMO550 m-METHYLNITROBENZENE see NM0500 o-METHYI2s iTRODENZENE see NM0525... 

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