Pyridines anilino

Rayama, A., Rinoshita-Nagaoka, J., Rawano, H., Rameda, S. and Mukuriya, M. (1998) Cycloauration of 2-substituted pyridine derivatives. Synthesis, structure and reactivity of srx-membered cycloaurated complexes of 2-anilino-, 2-phenoxy- and 2-(phenylsulfanyl)-pyridine. Journal of the Chemical Society Dalton Transactions, (24), 4095. 

The present method is a modification of that first reported by Dim-roth.6 The method of irreversible isomerization in boiling pyridine was first reported by Dimroth 7 for the conversion of l-phenyl-5-amino-1,2,3-triazole to 5-anilino-l,2,3-triazole. 

B. 4-Phenyl-5-anilino-l,2,3-triazole. Six grams (0.025 mole) of 1,4-diphenyl-5-amino-l,2,3-triazole is dissolved in 20 g. of dry pyridine (distilled from solid sodium hydroxide) and heated under reflux for 24 hours (Note 6). The reaction mixture (Note 7) is poured into 11. of ice water. The product separates as a slightly yellowish milky oil which is converted to white needle-like crystals by stirring the mixture and scratching the beaker with a glass rod. The product is collected by suction filtration, washed with water, suction-dried, and recrystallized from aqueous ethanol (Note 8). The yield is 5.5-5.6 g. (92-93%) of fine white needle-like crystals, m.p. 167-169° (Note 9), soluble in hot water and ether, but difficultly soluble in benzene. 

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>. 

Dagegen gelingt die oxidative Dehydrierung mit Dibenzoylperoxid (Benzol 80°) oder mit Brom (Chloroform/Pyridin 10°) bereits unter milden Bedingungen414 Fur beide Methoden ist allcr-dings nur ein Beispiel, namlich die Herstellung von l-Anilino-2-phenyl-imidazol aus dem entsprechenden 4,5-Dihydro-imidazol (40% mit Dibenzoylperoxid bzw. 95% mit Brom) beschrie-ben. 

Auch Phenole lassen sich an Aldimine addieren (Bd.XI/1, S. 337). Ein neueres Beispiel ist die Herstellung von 2-[Anilino-( 2-pyridyl)-methvl]-phenol aus 2-(Phenylimino-methyl)-pyridin und Phenol in siedendem Benzol2. 

Die Reaktion von Pyridin-l-oxid mit Phenyl-isocyanat in Dimethylformamid ergibt unter Abspaltung von Kohlendioxid 2-Anilino-pyridin (77%) In ahnlicher Weise erhalt man l-Anilino-isochinolin (75%) ... 

The liquid viscosities of DMF/11 anilino and pyri dincr 3,1 have been measured up to 120"C, Golubev prevents liquid viscosity data on uni line from 0SC to I2CPC and pyridine from (TC to 90 C The viscosity of DMA ut room temperature is available., Tl- W Data for DMA were estimated by the method of Thunius1 The equation of Von Vclzcn, Cur-Ou/o, and i.angenxampJ was used Jo extend the data for the niher compounds. 

Condensation of (441) [306, 307] with 1,2-di-O-stearoyl-DL-glycerol 3-phosphate in the presence of 2,4,6-triisopropylbenzene sulfonyl chloride in pyridine gave a mixture of the required products (442) (52%) and the isomer (443) (26%) which were separated by chromatography. The anilino groups were removed from (442) by the... 

Decarbonylation has been reported in the reaction of a-anilino-a,a-diphenylacetic acid with p-toluenesulfonylchloride and pyridine furnishing CO and the imine of benzophenone and aniline Sheenan, J. C., Frankenfeld, J. W. J. Org. Chem. 1962, 27, 628. 

Ethoxycarbonyl-2-(triphenylphosphoranylidenamino)vinyl]pyridine (43) with phenyl isocyanate gave a separable mixture of ethyl 8-anilino-l,7-naphthyr-idine-6-carboxylate (44) and an isomeric 2,6-naphthyridine derivative (formed by an alternative cyclocondensation) (reactants, PhMe, 20°C, 2 h then 180°C, sealed, 72 h 23% and 22%, respectively, after separation) analogs likewise.442... 

Ethoxycarbonyl-2-(triphenylphosphoranylideneamino)vinyl]pyridine (21) and phenyl isocyanate gave ethyl l-anilino-2,7-naphthyridine-3-carboxylate (22) (PhMe, 150°C 59%) analogs likewise).442... 

Reactions of 1,2,4-thiadiazoles with radicals and electron deficient species are virtually unknown. Catalytic and dissolving metal reductions usually result in S—N bond cleavage. For example, the 5-anilino-3-hydroxy derivative (51) gives a good yield of l-phenyl-2-thiobiuret (52) on Zn-HCl reduction (Scheme 27). Reduction of the diamino derivative (53) gives amidinothiourea (54) from which it may be prepared by oxidation (Scheme 28). Under similar conditions, cleavage of the 3,5-diphenyl derivative (55) results in loss of sulfur and formation of benzylbenzamidine (56 Scheme 29). Reduction of 5-alkylamino-or 5-arylamino-3-alkylthio derivatives (57) with H2S in pyridine-triethylamine or sodium in liquid ammonia yields 1-substituted dithiobiurets (58 Scheme 30). 

Amino-1-brom-1 -phenyl- ( —HC1) E16d, 1196 (En + -NBr2) 2-Anilino-l-brom- V/4, 376 Pyridin 2-Brom-4-propyl- V/4, 450... 

Propen l-Methoxy-2-(N-methyl-anilino)- E15/1, 627 (RO-CH2-C = CH + Amin) Pyridin 2-(3,3-Dimethyl-2-oxo-butyl)- El9a, 1033 (Ar-Br + Enolat/-f Cyclokond.)... 

N-Methyl-anilino)- -methylester E16d, 783 (Hydroaminierung) Pyridin... 

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