Phenyl -amine, substituted

Pechmann and Nold utilized the reaction of diazomethane with phenyl isothiocyanate for one of the earliest syntheses of a 1,2,3-thiadiazole <84CHEC-I(6)447>. This method continues to be used <82MI 407-0l> for the synthesis of 5-amine substituted 1,2,3-thiadiazoles (34), and 4,5-disubstituted... 

The reaction works well when R and are alkyl or benzyl, or when NR R is a cyclic secondary amine. ° It also works with benzil and its para-substituted derivatives and with guanidine and its mono-substituted derivatives, giving high yields of products 35 having Ar = phenyl para-substituted with H, Cl, Me, and MeO, and R = R = R = H,... 

Reaction of 4-chloro-6-fluoropyrido[3,4- pyrimidine 59 with [3-methyl-4-(pyridin-3-yloxy)phenyl]amine 60, followed by coupling the formed amine 61 with (3-azabicyclo[3.1.0]hex-6-yl)carbamic acid fi r7-butyl ester, afforded the substituted derivative 62 <2002EPP1249451>. Compound 59 was also reacted with 3-bromoaniline to give the 4-anilino derivative 63 that upon treatment with either methyl- or dimethylamine gave the corresponding 4,6-diamino derivatives 64 (Scheme 2) <1997W09726259, 1995W09519774>. 

The reaction proceeds well with unhindered secondary amines as both nucleophiles and bases. The yield of allylic amine formed depends upon how easily palladium hydride elimination occurs from the intermediate. In cases such as the phenylation of 2,4-pentadienoic acid, elimination is very facile and no allylic amines are formed with secondary amine nucleophiles, while phenylation of isoprene in the presence of piperidine gives 29% phenylated diene and 69% phenylated allylic amine (equation 30).84 Arylation occurs at the least-substituted and least-hindered terminal diene carbon and the amine attacks the least-hindered terminal ir-allyl carbon. If one of the terminal ir-allyl carbons is substituted with two methyl groups, however, then amine substitution takes place at this carbon. The reasons for this unexpected result are not clear but perhaps the intermediate reacts in a a- rather than a ir-form and the tertiary center is more accessible to the nucleophile. Primary amines have been used in this reaction also, but yields are only low to moderate.85 A cyclic version occurs with o-iodoaniline and isoprene.85... 

Fleischmann et al s 34 report cyclic voltammetry data for the oxidation of a series of aromatic hydrocarbons in a molten salt electrolyte, AlCl3-NaCl-KCl at 150°. Electrooxidation in this medium occurs at unusually low oxidation potentials. Tris-(p-substituted phenyl)amines, with the exception of tri (p-nitrophenyl) amine, yield very stable radical cations by all electrochemical criteria 380>S42 Mono- and bis-p-substituted triphenylamines, however, dimerize with rate constants ranging from 101 to 10s M 1 sec 1 to benzidines 176 (Eq. (237)), which subsequently are oxidized to the radical cations 177, whose ESR-spectra are observed. Dimerization is fastest with the p-N02 andp-CN-derivative, in accordance with HMO calculations, which predict the highest spin sensity in the p-position of these compounds 542 ... 

When 7V-allyl-(2-chloro-phenyl)-amine 23 (Z = NH) is allowed to react with Me3Sn ions in liquid ammonia, a low yield of product 24 (Z = NH) is obtained (Sch. 24). When the amino group is protected as 23 (Z = TV-allyl, Wacetyl derivatives), good yields of ring closure—substitution products 24 (Z = Wallyl, TV-acetyl) are obtained [98]. 

All of the aromatic amines with the exception of tri-phenyl amine, whether primary, secondary or tertiary, are basic and form salts with acids. The basic character of the tertiary aromatic amines varies, however, in degree according to the additional radicals substituted for the amino hydrogen. On this account they react differently toward the alkyl halides. 

Leuco Base.—(i) The amine base is the simple amine substitution product of the hydrocarbon tri-phenyl methane. It may be obtained by reducing the other compounds and is thus the reduction product. It is colorless and is termed the leuco basCy the word leuco meaning colorless. 

As a substituent on an aromatic ring, the amine salt group has an unusually uniform effect on the chemical shifts of the ortho, meta and para hydrogens. The series of aniline salts presented indicate the minimal effect that the type of acid involved, the solvent employed and the degree of amine substitution have on the chemical shift of the phenyl protons. The aromatic resonance for all of these aniline salts appears as a relatively sharp peak in the narrow chemical shift range from 7.50-7.55 ppm. 

Note In the amine substituted phosphino-phosphenium cations, the four-coordinate phosphorus atom carrying the cationic charge resonates upfield from the tricoordinate phosphorus atom, while the reverse is the case in the phenyl substituted phosphino-phosphenium cations. The effect of the rr-bonding interaction of the amino groups is clearly visible. 

Finally we mention the study of Aguilar-Martinez et al. who synthesised and analyzed the substituent effects on the redox properties of 19 compounds of 3 -(meta) and A - para) substituted 2- (i -phenyl)amine -1,4-naphtalenediones in acetonitrile.153 Beside an UV-vis analysis and a voltammetric study the authors performed semi-empirical (PM3) and DFT calculations (B3LYP with double-C... 

Structural classes of Hi antihistamines can be represented by a general structure of two aromatic groups linked through a short chain to a tertiary aliphatic amine (Fig. 37.6). The aromatic groups (An, Ar2) usually are phenyl or substituted phenyl, thienyl, or pyridyl. These substituents are attached to the X group, which is a nitrogen atom in the ethylenediamines, a carbon attached to... 

Secondary diaryl amines phenyl naphthylamines, substituted diphenylamines, and para-phenylenediamines ... 

NH3, RNH2, and RR NH eliminations from primary, secondary, and tertiary amines, respectively, are negligible except from some multifunctional compounds (e.g., diamines and phenyl-phenoxy-substituted amines). 

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. ... 

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