N methylaniline

Perfluorobenzene undergoes Sf Ar reactions readily with dimethylarmne, aniline, N methylaniline [AS], piperidine, A/-tnmethylsilyliminotnmcthylphos-phorane [69], and bthinm aniUde [70], but the reactions are often accompanied by sigmficant amounts of di- or polysubstitubon However, with the lithium salt of A -tnmethylsilylanilme, only one fluorine atom in pcrfluorobenzeneis replaced [71] (equation 36)... 

Another case in point is the N-methylaniline enamine of 2-methylcyclo-hexanone (22), which has been reported 15) to consist exclusively of the tetrasubstituted isomer. Here the electron pair on the nitrogen atom could... 

In the NMR spectrum of the N-methylaniline enamine of cyclohexanone (135), the vinylic proton appears at a much lower field, i.e., at 324 Hz (75). Here the electron pair on nitrogen tends to conjugate with the phenyl group thus exhibiting a very small degree of overlap with the enamine double bond. 

Li et al. [87,88] found that aniline will process the photopolymerization of AN either in N,N-dimethylformamide (DMF) solution or in bulk with a fair rate of polymerization only next to DMT. From UV spectra it is proved that aniline will form a CTC with AN. Using 313-nm radiation that CTC is excited to an exciplex and polymerization proceeds. N-methylaniline will polymerize AN similarly. The following mechanism was proposed ... 

The well-known photopolymerization of acrylic monomers usually involves a charge transfer system with carbonyl compound as an acceptor and aliphatic tertiary amine, triethylamine (TEA), as a donor. Instead of tertiary amine such as TEA or DMT, Li et al. [89] investigated the photopolymerization of AN in the presence of benzophenone (BP) and aniline (A) or N-methylaniline (NMA) and found that the BP-A or BP-NMA system will give a higher rate of polymerization than that of the well-known system BP-TEA. Still, we know that secondary aromatic amine would be deprotonated of the H-atom mostly on the N-atom so we proposed the mechanism as follows ... 

Pure samples are best prepd by the methylation of acetanilide or benzanilide to the N-methyl compds followed by acid hyd. It has been prepd commercially by the action of methyl ale on aniline in an autoclave under press and by the action of methyl amine on halobenzenes. For a summary of prepns see Refs 6 9. It may be separated from aniline and dime thy laniline by treatment of the mixt with benzenesulfonyl chloride. Dimethylamline fails to react and is extd out with dil acid. Aniline forms benzenesulfonanilide which is acidic and is removed by washing with dil base, leaving the N-methylbenzenesulfonanilide. Purified N-methylaniline is obtd by acid hyd (Ref 8). N-Methylaniline is used as an additive to raise the octane no of motor fuels (Ref 6), as a dyestuff intermediate (Ref 3), in the prepn of Tetryl (see below), and in the prepn of Methylcentralite (Encycl, Vol 2, C137-R)... 

Salts and Complexes of N-Methylaniline with Inorganic Compounds ... 

Dinitrobenzoate light yellow crysts, mp 121.8° prepd by the interaction of the components in hot abs ethyl ale. It is also used to isolate and identify N-methylaniline... 

Azido and Azo Derivatives of N-Methylaniline p-A zido-N-Methy aniline, p-MeNHC6 H4N 3, C7H8N4 mw 148.17, N 37.82% crysts, mp 52° prepd by the action of hydroxylamine hydrochloride on N-methyJ p-nitrosoaniline in aq Na carbonate. Upon exposure to light in thin layers, it turns red, then violet Refs 1) Beil 12, 429 2) A. Angeli ... 

Nitro Derivatives of N-Methylaniline Nitro-N-Methylanillnes, C7H8N202, mw 152.15, N 18.41%, OB to C02 —168%. The following isomers are described in the literature N-Nitro-N-methylaniline, needles or leaflets from eth, mp 38.5—9.5°, volatile in steam without decompn (Ref 1) CA Registry No 7119-93-9... 

Nitro-N-methylaniline, red needles with blue/ violet reflections from petr eth, mp 37° (Ref 2), decomps above the mp (Ref 13) CA Registry No 612-28-2... 

Nitro-N-methylaniline, reddish yellow needles or prisms from ethyl ale, mp 68° (Ref 3) ... 

N,4-DinitrO N-methylaniline, bright yellow needles from benz, mp 142.5° (Ref 2) CA Registry No 16698-03-6. It is prepu by the alkylation of N,p-dinitroaniline with methyl iodide in alk soln (Refs 8 9). It is one compd isolated from aged NC propints stabilized with N-methyl-p-nitroaniline. Hollingsworth at ERDE examined the reaction of nitrogen dioxide with this stabilizer in order to elucidate the mechanism of the formation of the compds isolated. He found that after 7 days at 35°,. a good yield of N,4-dinitro-N-methylaniline was obtd and postulated that it arose from the oxidn of N-nitroso-4-nitroaniline (Ref 16)... 

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