Nitro-acetanilide compounds

In the meantime a mixture of one volume of 50 per cent aqueous potassium hydroxide, 4 volumes of water, and one volume of alcohol is prepared, cooled to o°, and the nitration product thoroughly rubbed up (in portions) in a chilled mortar with about 600 cc. of the solution. The o-nitro-acetanilide dissolves, while the bora- compound remains insoluble in the cold mixture and is sucked off and washed with a little of the cold... 

Nitration of aniline as the acetyl derivative by mixed acid gives p-nitro-acetanilide as the main product, together with a little of the ortho-compound. The relative amounts are shifted very greatly in favor of the ortho-compound... 

Nitro compounds. Nitromethane Nitrobenzene ni-Dinitrobenzene. Amides and imides. Acetamide re-Caproamide Acetanilide Benz-anilide Phthalimide. 

Nitration. Direct nitration of aromatic amines with nitric acid is not a satisfactory method, because the amino group is susceptible to oxidation. The amino group can be protected by acetylation, and the acetylamino derivative is then used in the nitration step. Nitration of acetanilide in sulfuric acid yields the 4-nitro compound that is hydroly2ed to -rutroaruline [100-01-6]. 

The resulting acetyl compound is usually hydrolyzed with aqueous alkaU to give the free amine. Other A/-acyl derivatives may be used, particularly for the less soluble succinyl and phthaloyl products. The use of -nitrobenzenesulfonyl chloride, followed by reduction of the nitro to an amino function, is much more expensive and is rarely used. A/-Acetylsulfanilyl chloride [121 -60-8] is obtained by the chlorosulfonation of acetanilide [103-84-4] which is the basic material for most of the sulfonamides. 

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>. 

Tellurium Tetrahydrofuran Tetranitroaniline Tetranitromethane Thiocyanates Thionyl chloride Thiophene Thymol Halogens, metals Tetrahydridoaluminates, KOH, NaOH Reducing materials Aluminum, cotton, aromatic nitro compounds, hydrocarbons, cotton, toluene Chlorates, nitric acid, peroxides Ammonia, dimethylsulfoxide, linseed oil, quinoline, sodium Nitric acid Acetanilide, antipyrine, camphor, chlorohydrate, menthol, quinine sulfate, ure- thene... 

Fig. 47. Colours of addition products of various nitro compounds with hydrocarbons and amines I - Benzene II - Xylene El - Durene IV - Naphthalene V -Acetanilide VI - Phenanthrene VII - Tribromoaniline VIE - Safrole IX - Anthracene X - Aniline XI - Diphenylamine XII - Benzidine XIII -Dimethyl-aniline (Brackman [126]).

Furthermore, it has to be noted that the nitro groups in the NMCs are metabolized by microorganisms and animals such as fish and rats. It is known that aromatic amines (substituted anilines) are acetylated to acetanilides. Some of these compounds possess anti-androgenic properties [351 b, c, d]. It is supposed that some N-acetylated metabolites of NMCs, e.g. 2-methyl-3-nitro-4-methoxy-5-ferf-butyl-acetanilide (metabolite of musk ambrette) and 4-ferf-butyl-2,6-di-methyl-3,5-dinitro-acetanilide (metabolite of musk xylene) are bound to the androgen receptor (AR) and may act as weak anti-andxogens [351 e]. 

Nitro- and amrwo-aromatic compounds do not respond favorably. However, acylations of acetanilide with acetic anhydride using iodine... 

Nitration also takes place directly with the anilides (acetanilide or benzanilide), which may then be hydrolyzed yielding nitro aniline. In this case the para compound is obtained almost exclusively. 

These equilibria represent a more or less ideal case, since as a rule other substances are present, and also the nitro-amine which may be formed reacts farther. If sulfuric acid is present, a ternary intermediate compound would be formed. If acetanilide were used instead of aniline, the general reaction would be similar. If, however, a large excess of sulfuric acid were used in the reaction, then the aniline would be present practically entirely as aniline sulfate and there would not be the tautomeric form present. Under these circumstances, the intermediate compound would not be the same as before, and the nitration would proceed as if benzene itself were being nitrated. Mainly meta compound would be obtained under these conditions. The velocity of nitration of benzene derivatives containing different substituents was studied by H. Martinsen [Z. physik. Chem. 50, 385 (1905) 50, 605 (1907)1. He found the velocities to be dependent upon the substituents in the following way ... 

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