Methyl acetanilid benzene

Dinitw4 etbyl l metbyl benzener CH CcH CaHB(NOa)3 mw 210.20, N13.33% yel crysts, mp 48.5° Prepd from 5-ethyl 2 methyl-acetanilide by nitration at -1Q8-mp 177-8°, hydrolysis to the aniline-mp 186° followed by diazotization/removal of the amino group... 

Choice of solvent for recrystallisation. Obtain small samples (about 0 5 g.) of the following compounds from the storeroom (i) salicylic acid, (Li) acetanilide, (iii) m-dinitrobenzene, (iv) naphthalene, and (v) p-toluene-sulphonamide. Use the following solvents distilled water, methylated spirit, rectified spirit, acetone, benzene and glacial acetic acid. 

The conductometric results of Meerwein et al. (1957 b) mentioned above demonstrate that, in contrast to other products of the coupling of nucleophiles to arenediazonium ions, the diazosulfones are characterized by a relatively weak and polarized covalent bond between the p-nitrogen and the nucleophilic atom of the nucleophile. This also becomes evident in the ambidentate solvent effects found in the thermal decomposition of methyl benzenediazosulfone by Kice and Gabrielson (1970). In apolar solvents such as benzene or diphenylmethane, they were able to isolate decomposition products arising via a mechanism involving homolytic dissociation of the N — S bond. In a polar, aprotic solvent (acetonitrile), however, the primary product was acetanilide. The latter is thought to arise via an initial hetero-lytic dissociation and reaction of the diazonium ion with the solvent (Scheme 6-11). 

Compounds containing two primary amino groups attached to a benzene ring can be prepared by the reduction of dinitro compounds and of nitroanilines, usually with tin or stannous chloride and hydrochloric acid or with iron and very dilute hydrochloric acid. Pam-diamines may also be obtained by the reduction of aromatic amino-azo compounds (e.g., p-aminodimethylaniline from methyl orange, see Section IV,78). p-Phenylenediamine may also be prepared from p-nitroacetanilide reduction with iron and acid yields p-amino-acetanilide, which may be hydrolysed to the diamine. 

Another side reaction which occurs is reduction in the reaction the —N2C1 or —N(NO)COCH3 group is replaced by hydrogen. wi-Bromo-toluene was isolated in 6% yield from the reaction between the sodium diazotate from 2-bromo-4-methylaniline and benzene, and in 10% yield in a similar reaction from 2-methyl-4-bromoaniline.4 Some nitrobenzene is obtained in the preparation of 3-nitrobiphenyl from nitroso-w-nitro-acetanilide (p. 250). The source of the hydrogen effecting the reduction has not been determined. f... 

N-Methylacetanilide is obtained in 96% yield by the action of methyl iodide or dimethyl sulfate on the sodium salt of acetanilide. The last compound is prepared from acetanilide and sodium wire in hot benzene. The reaction has been extended to other aliphatic and aromatic N-sub-stituted amides. Sodium hydride serves to convert the amide to its salt, and a variety of simple halides have been successfully employed as alkylating agents, ... 

Beazyae. Reactions of acetanilide in dry benzene with PCBN in the presence of tctraphenylcyclopentadienonc, anthracene, 9,10-dimethoxyanthracene, and methyl methacrylate a.s trapping agents give the corresponding benzyne adducts, 1,2,3,4-... 

Figure 9.8 Log k vs. log Pow (a) and k vs. log (b) relationships predicted by eqs. 9.23 and 9.24 (solid lines), and experimental values (symbols) for a series of monosubstituted benzenes acetanilide, acetophenone, benzaldehyde, benzene, benzonitrile, benzyl alcohol, benzylamine, bromobenzene, butyrophenone, he phenone, methyl benzoate, methyl phenyl ether, nitrobenzene, propiophenone, toluene, and valerophenone. Molar concentrations of SDS in mobile phase (1,a) 0, (2, ) 0.016, (3,0) 0.05, (4,°) 0.1, and (5) 0.15. Reprinted from Ref 21 with permission of Elsevier.

Under phase transfer conditions (boiling benzene, 50% aquous sodium hydroxide solution and tetia-n-butylammonium hydrogenphosphate) benzamides are monoalkylated. In the solid-liquid PTC system potassium hydride, tetrahydrofuran and 18-crown-6, acidic trifluoroacetamides are rapidly deprotonated and alkylated with lower kyl, allyl and benzyl halogenides in high yield. Methylation of trifluoroacetamides is carried out under less basic conditions in KOH/acetone. A similar reaction in KOH/DMSO generally allows the efficient reaction of benzamide and acetanilide with primary alkyl halides with secondary halides only moderate yields are accomplished, whereas tertiary halogenides are not alkylated due to dehydrohalogenation. ... 

Reactions.—A-Alkylation of acetanilides has been achieved using a two-phase system of water and benzene with sodium hydroxide as base and triethylbenzylam-monium chloride yields are better than 80%. An efficient two-step process for the A-methylation of unsubstituted amides, lactams, and ureas has been described which involves initial formation of the corresponding methylol, by treatment with formaldehyde, followed by reduction with either triethylsilane and trifluoroacetic acid or with hydrogen over palladium in TFA. A method for the methylthiomethy-lation of both amides and lactanes has appeared. ... 

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