V-methyl aniline

Methyl violet [8004-87-3] Cl Basic Violet 1 (17), is made by the air oxidation of dimethyl aniline in the presence of salt, phenol, and a copper sulfate catalyst. Initially, some of the dimethyl aniline is oxidized to formaldehyde and /V-methyl aniline under those conditions. The formaldehyde then reacts with dimethyl aniline to produce N,N,]S7,1S7-tetramethyldiaminodiphenylmethane, which is oxidized to Michler s hydrol [119-58-4]. The hydrol condenses with... 

V-methyl aniline formed in the initial step to give the leuco base of methyl violet. Treatment with aqueous acid produces the dye. Because Michler s hydrol may also react with dimethyl aniline instead of the /V-methyl aniline to give crystal violet, commercial-grade methyl violet is usually a mixture. A cobalt complex has converted 4,T-dimethylaminodipheny1methane and dimethyl aniline in the presence of atmospheric oxygen to crystal violet in one step (50). 

The allylic HYCRAM derivative was subsequently modified by insertion of a standard amino acid between the aminomethyl resin and the hydroxy butenoic acid moiety. Using this allylic anchor, the resin-linked, glycosylated HIV peptide T-derivative 164 was synthesized by application of Fmoc amino protection and sidechain protection with lert-butyl groups. The lac-tosamine peptide T (165) could be released from the resin by application of the palladium(0)-catalyzed allyl-transfer reaction to V-methyl aniline as the allyl acceptor. 

A second assessment of the enthalpy of formation of 16 is made by extending equation 13 and its reaction enthalpy to include the /V-methylated anilines 16 and 15. 

As can be seen, di-ozt/zo-substitution seems to have the weakest effect both in the molecule and in the cation. This can be explained by a steric inhibition of the interaction between the lone-pair sp3-orbital and the aromatic n-system. The same trend can be seen if we compare the 15N NMR chemical shifts of aniline, 56.5 ppm, (V-methyl aniline, 52.8 ppm and Ak/V-dimelhylaniline. 44.6 ppm. In ortfco-substituted /V,/V-dimethylanilines the shielding effect is related to the number and size of the ort/zo-substituents (Table 2)24. 

One of the products resulting from the reaction between V-methyl-aniline and glycolaldehyde has been found to have structure XXXVIII... 

Allyl or benzyl groups on the nitrogen facilitate the process. The rearrangement appears to be intramolecular (13), proceeding by a cycHc mechanism as in the case of /V-2-buteny1-/V-metby1 aniline oxide giving /V-methyl-0-1-methylallyl-/V-phenyl-hydroxylamine. 

In the presence of sulfuric acid, aniline reacts with methanol to form /V-methyl- and /V,/V-dimethylaniline. This is a two-step process... 

Benzenamine, 3,5-dimethyl- [Aniline, 3,5-dimethyl ], p-biomination of, 55, 23 Benzenamine, 2,/V-dimethyl- [Aniline 2-methyl-A-methyl-]. p-biomination of, 55, 23... 

Initially, a reaction of A-acetoxy-A-butoxybenzamide 25c with A-methyl aniline 61 in butyl benzoate 63(R = Bu) and acetic acid. Close examination of these highly coloured reaction mixtures indicated the presence of crystals of A,A-dimethyl-A,A-diphenyltetrazene 65 (Scheme 11, R = Bu). The reaction is promoted by polar solvents as reactants are unchanged in pure acetonitrile. A crossover experiment using a mixture of /V- a ce t o x y - A-- b u t o x y - to 1 u a m i d e 26d and A-acetoxy-A-ethoxybenz-amide 25a afforded clean yields of butyl /Moluatc and ethyl benzoate thus pointing to an intramolecular rearrangement.41... 

Kinetic studies. HERON reactions of 7V-acyloxy-/V-alkoxyamides, which can be conveniently followed by NMR in <74-methanol by monitoring the disappearance of the mutagen or aniline and formation of ester and tetrazene, conform to classical bimolecular kinetics being first order in both mutagen and TV-methyl-aniline.41 43,46,105 Arrhenius parameters and bimolecular rate constants (308 K) for a range of /V- a cy 1 o x y - TV- a 1 k o x y a m i de s 25-30 are collated in Table 5. 

Steric effects on the nucleophile, aniline, were clearly evident. Rate constants for bimolecular attack of 2,6-dimethyl- 70a, 2,6-diethyl- 70b, and 3,5-dimethylaniline 70c at 308 K indicate that the ort/zo-substituted anilines react more than an order of magnitude slower at the same temperature (Table 7). Structure 70c must be able approach the reactive nitrogen more closely.42,43 A comparison of the rate constants for reaction of aniline 72c, /V-methyl- 71a and /V-phenylaniline 71b provides further evidence of steric effects although the very small rate constant for the diphenylamine could also be accounted for by reduced nucleophilicity on account of lone pair resonance into the additional phenyl ring. 

The /V-rncthyl-/V- l5N nitroanilinc, the V-methyl-lV-nitro-[4-14C]aniline and the /V-methyl-/V-nitro- 2-l4C anilinc required for this study were prepared using the reactions shown in Schemes 12-14. 

Considering the monoaminomercuration-demercuration of 1,4-hexadiene with /V-me-thylaniline leads to V-methyl-lV-(l-methylpent-3-enyl)aniline, the stereoselective synthesis of /V-alkoxycarbonyl or /V-tosyl s-2,5-dimethylpyrrolidine from the same diene has been explained172 on the basis of an initial amidomercuration reaction on the terminal bond followed by the second addition of mercury(II) salt to the internal double bond, on the less sterically hindered site (equation 171). 

Chloro-N-methyl-N-(trichloromethyl)aniline is fluorinated with antimony(III) fluoride in the absence of catalysts while catalysis with antimony(V) chloride is required to substitute chlorine atoms by fluorine in the trichloromethyl group of 4-chloro-A -(trichloromethyl)-/V-(trifluoromethyl)aniline (8).86,87... 

IV) Amines 0.20% calcd as methylamine when detd using the proced IV for secondary amines described under Centr 1 but calcg % methyl-aniline from the formula [l0.7(Vt-V2)N] /W Ax 1.78, where V ml of NaOH soln required to titrate blank Vz=ml of NaOH soln required to titrate sample N=normality of NaOH soln W=wt of sample and A=% acidity as AcOH Note This method is not specific for amines but will detect other groups such as OH... 

Aminodinitrotoluenes, x,x-Dinitro-x-amino-toluenes, x,x-Dmitro-x-methyl anilines or x,x-Dinitro- (o-, m-, p-) -toluidines). CH3.C6H2-NH2(N02)2, C7H7N304 mw 197.17 N 21.32% OB to C02 —109.55%, V sol in acet fairly sol in RT ethanol, eth and acetic acid si sol in coned hydrochloric acid... 

V-(4-chloro-2-methylphenyl)benzamide. A mixture of 4-chloro-2-methyl-aniline (14.2 g, 0.10 mol), benzoyl chloride (14.1 g, 0.10 mol) and triethylamine (10.1 g, 0.10 mol) in anhydrous toluene (150 ml) is stirred and refluxed for 3 hours and then allowed to stand for c. 16 hours at room temperature. The resulting solids (mixture of product and salts) are filtered off and stirred at room temperature for c. 1.5 hours with water (150.ml). The solid product is filtered off and recrystallised from dichloromethane-toluene (yield 87%, m.p. 170-171 °C). 

Methylene-1-oxo-1,2,3,4-tetrahydro-naphthalene l(2//)-Naph-thalenone, 3,4-dihydro-2-methylene- (8,9) (13203-73-1) N-Methylanilinium trifluoroacetate Aniline, A-methyl-, trifluo-roacetate (8) Benzenamine, /V-methyl-, trifluoroacetate (9) (29885-95-8)... 

Related to the Heck reaction is the Larock annulation of internal alkynes, which is a general route to heterocyclic and carbocyclic systems. Especially attractive is the construction of the pharmaceutically important indole ring system via palladium-catalyzed coupling of 2-iodo-aniline and the corresponding V-methyl, acetyl, and tosyl derivatives with a wide variety of internal alkynes. The catalytic process appears to involve arylpalladium formation, regioselective addition to the carbon-carbon triple bond, and subsequent intramolecular palladium displacement.- ... 

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