Dimethyl phenylamine

SYNS BENZENAMINE, NJ4,-DIMETHYL-(9CI) (DIMETHYLAMINO)BENZENE N-DIMETHYD ANILINE (OSHA) NJ4-DIMETHYLBENZENEAMINE DIMETHYLPHENYLAMINE NJ<-DIMETHYL-PHENYLAMINE DWUMETYLOANILINA (POLISH) NCI-C56428 VERSNELLERNL 63/10... 

For the reaction of the previous problem, find the time required at 24.8°C for half of the methyl iodide to react if its initial concentration is 0.100 mol L and the initial concentration of the dimethyl phenylamine is equal to 0.0600 mol L . Assume that the reverse reaction can be neglected. 

The nitrogen of aHphatic and aromatic amines is alkylated rapidly by alkyl sulfates yielding the usual mixtures. Most tertiary amines and nitrogen heterocycles are converted to quaternary ammonium salts, unless the nitrogen is of very low basicity, eg, ia tn phenylamine. The position of dimethyl sulfate-produced methylation of several heterocycles with more than one heteroatom has been examined (22). Acyl cyanamides can be methylated (23). Metal cyanates are converted to methyl isocyanate or ethyl isocyanate ia high yields by heating the mixtures (24,25). 

SuIfona.tlon, Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of SO or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Tn phenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thaHium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

A drop of amine added to benzoyl peroxide is enough to cause a deflagration or a detonation of the peroxide, depending on to what extent the apparatus is confined. Phenylamine, N,N-dimethylaniline, N,N-dimethyl-p-toluidine react the same way. 

Anodic oxidation of phenylamines is irreversible and involves the loss of two electrons and a proton to give a delocalised carbonium ion, which reacts further. Oxidation of 2,4-dimethyl-aniline to give 51 illustrates the process [161]. Interae-... 

Hexanitro-3,3 -dimechyl-diphenylamine 4) Beil 12, 1013 (Hexanitro-4,4 -dimethyl-diphenylamine) 5) A. Lehne, Ber 13, 1545(1880) (Hexanicro-4,4 -dimethyl-di-phenylamine) 6) L. Brady et al, JCS 125, 2404(1924) (Hexanitro-3,3 dimethyldiphenyl-amine) 7) P. Tavernier M. Lamouroux,... 

Aromatic amines are subdivided into primary amines, ArNH, such as aniline, secondary amines, ArNHR, in which the amino group has been monoalkylated and typified by A-methylaniline (A-methyl-A-phenylamine, 3), and tertiary amines, ArNR, such as A,A-dimethyl-aniline (A,A-dimethyl-A-phenylamine, 4). 

Aromatic secondary and tertiary amines undergo thiocyanation, often more readily than primary amines. N,N-Dimethylaniline gives N,N-dimethyl-4-thiocyanoaniline (92% 3deld), and N,N-dimethyl-p-tolui-dine gives N,N-dimethyl-2-thiocyano-p-toluidine (21% yield). Di-phenylamine and triphenylamine are converted into dithiocyano derivatives, each with two of the phenyl rings substituted in the para positions. ... 

Condensation of l-bromo-2-methoxy-4-methyl benzene (64) with 5,6-dimethoxyaniline acetate (65) in pyridine in the presence of Cu and K2CO3 and subsequent hydrolysis with 20% KOH furnished the di-phenylamine derivative (66) which on treatment with palladium acetate in DMF afforded murrayastine (13). Condensation of l-bromo-3-methoxy-4-methylbenzene (67) with the dimethyl acetal of 6-formyl-5-methoxyaniline acetate (68) furnished the diphenylamine derivative (69) which on hydrolysis and on subsequent cyclisation furnished murray-aline (14). 

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