4-Nitro-3- benzonitrile

Physical Properties. Nitrobenzene, C HjNOj pale yellow liquid, insoluble in and heavier than water, characteristic odour of bitter almonds, (similar to that of benzaldehyde and benzonitrile). /> Nitro toluene, C,H4(CH3)N02, usually pale yellow solid, insoluble in water, m-Dinitrobenzene, C8H4(N02)g, colourless solid when pure, but often pale yellow insoluble in water. 

Cohn 1 instanced a similar phenomenon in the similarity of the odours of, benzaldehyde, nitro-benzene, benzonitrile, azimidobenzene, and phenyldi-imide. He developed the osmophore theory and introduced the terms kakosmophore and enosmophore to indicate those groups which impart an upleasant and a pleasant odour respectively. The kakosmophore groups are —... 

Previously unknown deoxygenation was reported with o-, m-, and p-nitro-benzonitrile oxides on reactions with NO (112) this was interpreted as being due to the radical nature of the latter (Scheme 1.11). 

Nitrobenzenes react with potassium cyanide in the presence of cetyltrimethylammo-nium bromide to yield benzonitriles [71], The reaction also requires the presence of chloro substituents on the ring and at least two nitro groups (Table 2.9). Diazosulphides, ArN=NSPh, are converted into the benzonitriles, ArCN, by a photochemically induced SRN1 reaction with tetra-n-butylammonium cyanide [72, 73], Yields vary from <20% to >70%. Photocyanation of aromatic hydrocarbons has been achieved using tetra-n-butylammonium cyanide in acetonitrile or dichloromethane [74, 75]. 

Benzene, l-(l,l-dimethylethyl)-3-methyl-2, 4-dinitro Benzoyl chloride, 6-(l, l-dimethylethyl)-3-methyl-2, 4-dinitro-Benzene, 1, 3-dibromo-2- (l,l-dimethylethyl)-5-methoxy-4-nitro Benzonitrile, 2-(l,l-dimethylethyl)-4, 5-dimethyl-3-nitro-Benzene, l-(l,l-dimethylethyl)-3-methoxy-5-methyl-2, 4, 6-trinitro... 

Die N-alkylierten, substituierten o-Diamino-arene sind oft instabil und nicht rein zu isolieren. Sie sind nichtsdestoweniger begehrt, weil sie regiospezifisch zu den entsprechenden N-Alkyl-benzimidazolen cyclisieren. Die katalytische Reduktion von 2-Nitro-Gruppen zu 2,6-Diamino-3-methylamino-benzonitril kann in einer Eintopf-Synthese mit der Orthoester-Cyclisierung kombiniert werden205. 

In etherischer Losung erfolgt die Addition von Benzonitriloxid bzw. 3-Nitro-benzonitril-oxid an das dipolarophile Trinitro-acetonitril in guter Ausbeute143. 

Aryl-4,5-dihydro-l,2-oxazole aligemeine Arbeitsvorschrift2 0,02 mol (/ )-l-Nitro-l-alken in 20 m/ trockenem Ether werden tropfenweise unter starkem Riihren zu einer Losung von 0,01 mol Benzonitril-oxid in 80 ml trockenem Ether bei 0° gegeben. Nach 12 h Riihren bei 25° wird die Mischung 2 h zum RiickfluB erhitzt, i.Vak. eingeengt und dcr Riickstand i.Vak. destilliert oder umkristallisiert. 

Early examples of the cleavage of 5-unsubstituted isoxazoles were reported by Wieland (03LA154) and by Claisen (03CB3664). Claisen showed that 3-phenylisoxazole (58) was cleaved by ethanolic potassium hydroxide to give benzonitrile and potassium acetate Wieland observed an analogous reaction with 4-nitro-3-phenylisoxazole. The reactions can be interpreted as stepwise cleavage processes, as illustrated for the isoxazole 58. 

Three methods for making 4,5,6,7-tetrahydrotriazoIopyridines use two fragments to form the triazole ring. The lithium derivative of A/-nitro-sopiperidine reacts with benzonitrile to give the 3-phenyl derivative 19.28 Diazonium salts react with a-amino acids to give mesoionic triazole oxides if pipecolic acid is used, the product is a tetrahydrotriazolopyridine 3-oxide... 

A variety of substituted 3-aminobenzo[6]thiophenes have been obtained by ring closure reactions of nitriles (equation 57). Various o -cyanophenylthioacetyl derivatives, when treated with base, yield the 3-amino derivatives (Section 3.15.2.2.3). The benzonitriles may be obtained by displacement of the o-nitro group from o -nitrobenzonitriles (74JOC3440). 2-Arylthio-l-chloroenamines are cyclized to 3 -dialkylaminobenzo[6]thiophenes in the presence of Lewis acid catalysts (equation 58). The 1 -chloroenamines may be prepared from t-amides or ynamines <8lH(15)l 179>. 

Note Higher nitro derivs of benzonitrile were not found in Beil or in CA thru 1956... 

A rearrangement intermediate, protonated 4-hydroxy-3-(2-imino-propyl)benzonitrile (163) proved to be isolable (67TL2867). Analogously, from l-alkyl-4-nitrophenyloximinopiperidine (165) in ethanolic HC1, 2-methyl-6-nitro-l,2,3,4-tetrahydrobenzofuro[3,2-c]pyridine (167) was ob-... 

A remarkable fused tricyclic azetidine 360 is formed by reaction of benzonitrile oxide and 2-methyl-5-nitro-l-vinylimidazole and benzonitrile oxide but only in 3% yield <2005S2695>. 

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 ... 

The transformation of the herbicide bromoxynil (3,5-dibromo-4-hydroxy-benzonitrile) was studied upon direct photolysis in water and in the presence of added nitrite. The addition of nitrite reduces the transformation rate of the substrate, most likely due to competition for absorption of radiation, but induces the formation of nitro derivatives (3-bromo-4-hydroxy-5-nitrobenzonitrile, 4-hydroxy-3-nitrobenzonitrile) [140]. 

The cycloaddition of 1-halogeno-l-nitroethene with nitrile /V-oxides leads to the nitro derivatives of isoxazole [520-524], Thus, for example, the reaction of equimolar amounts of 1-chloro- or 1-bromonitroethene with benzonitrile /V-oxidc gave 5-nitro-3-phenylisoxazole [520], The same compound is formed in the reaction of nitrile /V-oxides with ra .s-2-chloro-1 -nitrocthcnc [485], The formation of nitroisoxazoles in these reactions can be explained by the fact that the initial products from the cycloaddition of halogenonitro-A2-isoxazolines more readily eliminate a molecule of hydrogen halide and not HNOr... 

In order to probe this phenomenon quantitatively in an uncharged system where solvation effects are known to be relatively unimportant, the rates of cycloadditions of two relatively electron-deficient 1,3-dipoles, p-methoxy and p-nitro benzonitrile oxides (MBNO and NMBO, respectively) to a series of simple alkenes — propene, 1-butene, 1-pentene, 1-hexene, 3-methyl-l-butene, 3,3-dimethyl-l-butene and isobutene — were measured70. In each of these reactions, only the 5-alkyl-3-aryliso-xazolines were formed. 

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