A -methylaniline

Possible impurities of the tertiary amine include primary and secondary amines. The presence of aniline slows the reaction, while the presence of A-methylaniline actually accelerates the polymerization [51]. As the secondary amine may be formed during polymerization (especially in the presence of water) reaction kinetics may be complicated. 

As small molecule fragments resulting from the initiator may plasticize the polymer and lower performance, approaches have been developed to avoid this. A dihydroxyamine can be used to form a polyester [52]. This accelerator gave a modest increase in the strength of unsaturated polyester resins. A polymerizable tertiary amine has been prepared by the reaction of A-methylaniline with glycidyl methacrylate [53] (Scheme 8). 

Note As in related series, the addition of pyridine or (better) A,A-dimethylani-line (free of A-methylaniline, a common contaminant in some grades of this reagent) to phosphoryl chloride, appears to improve the yield of chloroqui-noxaline, especially if electron-withdrawing passenger groups are present. 

Table 5 Arrhenius activation energies, entropies of activation and rate constants at 308 K for reaction of A-acetoxy-A-alkoxybenzamides 25, iV-acetoxy-iV-butoxybenzamides 26, iV-benzoyloxy-iV-benzyloxybenzamides 2842,43 and other iV-acyloxy-iV-alkoxyamides with A-methylaniline in d4-methanol...

In accordance with the increased charge separation in the transition state and products, the gas-phase EA of 22.6 kcal mol-1 for the reaction reduces to just 4.4 kcal mol-1 with inclusion of semiempirical solvation energies in water while the overall reaction, which is very endothermic in the gas phase becomes exothermic by 5.1 kcal mol-1 with solvation.179 The calculated EA is lower than the experimental values for substitution by A-methylaniline in methanol which fall in the range of 6-15 kcalmol-1 (Table 5).42,43 However, in aqueous solution these barriers would be lower than in methanol. 

Activation energies and entropies of activation are in the same region as those for Sn2 reactions of neutral A-methylaniline. Large negative AS values are again in accord with increased charge separation with attendant solvation in the transition state. The rate constants at 298 K correlate with Hammett a values with p — 1.13 (r — 0.985) in keeping with a development of benzoate character in the transition state. 

Lack of reactivity towards SN2 reactions at nitrogen would in itself account for low mutagenic activity. However, the tert-butyl groups on 31c f and 32a,b are well removed from the reactive nitrogen and, as well, SN2 reactions of mutagens 31c e with A-methylaniline in methanol at 303 °C occur with relatively similar rate constants to that of unsubstituted 28a, and of mono tert-butylated systems 28i and 31 a,b (Table 18). 

In the reaction of A-methylaniline, ethyl orthoformate, and Meldrum s acid (421) in the presence of p-toluenesulfonic acid monohydrate at 100°C for 2 hr, then for 3 days at ambient temperature, (jV-methyl-TV-phenylamino)methylenemalonate (443) was obtained in 41% yield (69BRP1147759). 

Amino groups may act not only as proton acceptor, but also as proton donor. Acidic N—H protons interact with basic solvents. In these cases an ortho-nitro group in an aniline system competes with the solvent by an internal hydrogen bond66, as depicted in 12. The stretching frequencies (by IR spectra in carbon tetrachloride) of vnh of complexes between A-methylaniline or diphenylamine (and some nitro-anilines66) and solvents depend on the proton accepting ability of the solvent (which is a moderate base)67. The frequency shifts are linearly related to the solvent s donor number (DN)3. 

Acylhydrazines R1 CONF1NF1R2 (R1 = Ph or PhCH2 R2 = Bu, PhCH2 or Ph) are produced by the action of hydroxamic acids R ONHOH on the primary amines R2NH2 in the presence of tosyl chloride or 2-chloro-l-methylpyridinium chloride94. O-(Diphenylphosphinoyl)-A-arylhydroxylamines 77 (R = NO2, Ac, Tos or CN) react with A-methylaniline to afford the hydrazine derivatives 7895. 

Synonyms AI3-19498 AIDS-18972 Anilinomethane BRN 0741982 CCRIS 2870 EINECS 202-870-9 MA (Methylamino)benzene 7V-Methylaminobenzene A-Methylaniline IV-Methyl-benzenamine Methylphenylamine 7V-Methylphenylamine Monomethylaniline A-Monomethyl-aniline NSC 3502 7V-Phenylmethylamine UN 2294. 

Amine substrates whose rings are strongly deactivated with nitro groups are Al-nitrated with relative ease 2,4-dinitro-A-methylaniline undergoes Al-nitration on treatment with 70 % nitric acid at room temperature. It is known that the Al-nitration of anilines is favoured by... 

A number of important explosives contain nitramino functionality in conjunction with nitrate ester or C-nitro functionality. A-Nitrodiethanolamine dinitrate (DINA) (7) is a powerful explosive which can be melt-cast into charges. A,2,4,6-Tetranitro-A-methylaniline (tetryl) (8) exhibits high brisance (VOD 7920 m/s, d = 1.73 g/cm ) and has found application in both detonators and boosters, in addition to being a component of some composite high explosives. 

More recently, Polish chemists have reported a synthesis of both aryl and aliphatic secondary nitramines by treating amine substrates with ethyl magnesium bromide followed by reaction with n-butyl nitrate (Equation 5.8). This method, which uses nonpolar solvents like hexane or benzene, has been used to synthesize aliphatic secondary nitramines, and At-nitro-A-methylanilines which otherwise undergo facile Bamberger rearrangement in the presence of acid. The direct nitration of At-unsubstituted arylamines usually requires the presence of an electron-withdrawing group. Reactions are retarded and yields are low for sterically hindered amines. 

Numerous aromatic nitramines have been synthesized but only A,2,4,6-tetranitro-A-methylaniline (tetryl) and l-(2-nitroxyethylnitramino)-2,4,6-trinitrobenzene (pentryl) have found practical use as explosives. Both tetryl and pentryl are more powerful than TNT. Tetryl is widely used in boosters and as a component of explosive formulations like tetrytol (tetryl/TNT), PTX-1 (tetryl/RDX/TNT) and Composition C-3 (tetryl/RDX/TNT/DNT/MNT/NC). 

---