3.3- Diphenyl-4-nitro- -nitril

In the first synthesis of T, the diphenyl ether was formed from -methoxyphenol and 3,4,5-triiodonitrobenzene. The nitro group was replaced by a nitril which was then built up into the alanyl side chain by a series of steps (10). 

Die Fluorid-Ionen-katalysierte Michael-Addition von l,l-Diphenyl-2-nitro-ethcn mit Acetonitril liefert 3,3-Diphenyl-4-nilro-butansdure-nitril (45%)l,s 2 ... 

Nickel, dichloro [ethylenebis(dimethyl-phosphine)], 58, 133 Nickel, dichloro[ethj lenebis(diphenyl-phosphine)], 58,133 [Ni (-)-diop Cl2 ], (-)-diop=2,3-0-iso-propylidene-2,3-dihydroxy-l,4-bis(di-phenylphosphino)butane, 58, 133 Nickel, dichloro [ trimethylenebis(diphenyl-phosphine)], 58,133 NITRILES, alkylation of, 55, 91 NITRILES FROM KETONES, 58, 101 NITRILES, a vinyl, 55, 99, 101 p-Nitrobenzenesulfonyl cyanide, 57, 89 p-Nitrobenzyl alcohol, 57, 72 p-NITROBENZYL FLUORIDE, 57, 72 Nitro compounds, 56, 36 Nitronates, 56, 36... 

Activated nitro and halo substituents have been efficiently replaced by a variety of alkyl groups via SsAx reaction with carbanions. Examples include the displacement of the nitro group in compounds (10 X = 4-PhCO, 4-MeOCO, 4-CN, 4-N02, 4-PhS02, 3,5-(CF3>2) by the anion of 2-nitropropane in HMPA at room temperature (equation 2),83 and the reaction of p-dinitrobenzene with several ketones, esters and nitriles (RH equation 3) in Bu OK/liquid NH3 at -70 C.84 Interestingly, under the latter reaction conditions, p-chloronitrobenzene gave the product of alkylation rather than of SNAr displacement of chloride, as in equation (4).85 Further examples include the dehalogenation of p-halonitrobenzenes by 9-fluorenyl anions in DMSO at room temperature,34 and dehalogenation and denitration reactions by the carbanions of phenyl- and diphenyl-acetonitrile in DMSO or under PTC conditions.86... 

Neben Aldehyden und Ketonen konnen auch heteroanaloge Carbonyl-Funktionen mit sek. Phosphanoxiden zur Reaktion gebracht werden (vgl. Bd. XII/1, S. 155) z.B. Addition an Schiffsche Basen57a, Tosylhydrazone57b oder aktivierte Nitrile 18-61, die im Falle von 4-Nitro-benzonitril und Diphenylphosphanoxid Diphenyl- (a-imino-4-nitro-benzyl)-phosphanoxid (Schmp. 169°) zu 52%61 liefert ... 

Type H (C—N—C + C—S) Syntheses.—In the course of their detailed studies of nitrile-ylides, Huisgen and his co-workers have examined cycloadditions of benzonitrile 4-nitrobenzylide (27) [arising from N-(4-nitro-benzyl)benzimidoyl chloride, (26 Ar = P-C6H4NO2)] to a variety of carbon-heteroatom multiple bonds. Thus, the interaction of (26) with em excess of methyl dithiobenzoate in triethylamine gave 85% yields of 2,5-diphenyl-4-(4-nitrophenyl)thiazole (29), with loss of methanethiol, two stereoisomeric A -thiazolines (28) being formed intermediately. The same thiazole arose by the use of monothiobenzoate from the primarily formed 5-methoxythiazoline (30) by spontaneous loss of methanol. ... 

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