4-aminobenzonitrile

The preparation of quinazoline-2(and 4)-thiones follows those of the corresponding pyrimidines (67HC(24-1)270) but there is at least one special primary synthesis for quinazoline-4(3H)-thiones, illustrated by the reaction of o-aminobenzonitrile with thioacetic acid at 110 °C to give 2-methylquinazoline-4(3H)-thione in 90% yield (53JA675). 

Controlled hydrogenation over Ni or the electrochemical reduction of o -nitrobenzo itriles produced 3-amino-2,l-benzisoxazoles either as the major product or by-product, depending in part on the reaction media and ratio of reactants (72BSF2365, 65CB1562). Reduction of o-nitrobenzonitrile gave either 3-amino-2,l-benzisoxazole or 2-aminobenzonitrile. The benzisoxazole is presumed to arise via an intermediate hydroxylamine. The electrochemical reduction of o-nitrobenzonitrile at acid pH produced the hydroxylamine as the primary product. Reduction at neutral pH gave the amino-2,1-benzisoxazole and the hydroxylamine (72BSF2365). 

From the excited-state conversion rates (ka and kd), it is possible to calculate the ratio of the quantum yields between emission from the twisted and LE states. The ratio of the steady-state quantum yields from the locally excited state (f>LE and the TICT state r/>TI, T for DMABN and other aminobenzonitrile derivatives is described in (1) [12],... 

Parusel ABJ (2001) Excited state intramolecular charge transfer in N, N-heterocyclic-4-aminobenzonitriles a DFT study. Chem Phys Lett 340(5-6) 531-537... 

Zachariasse KA, von der Haar T, Hebecker A, Leinhos U, Kuhnle W (1993) Intramolecular charge transfer in aminobenzonitriles requirements for dual fluorescence. Pure Appl Chem 65(8) 1745-1750... 

Reagents and conditions i, p-bromoaniline or p-aminobenzonitrile, CHCI3 ii, hv, toluene/methanol (10 1) Scheme 10... 

The photocyclization of cis-diaminomaleonitrile (372) to 4-amino-5-cyanoimidazole (373) has been shown to proceed via the trans isomer 374.308 4-Amino-3-cyanopyrazole does not seem to be an intermediate in this transformation.309 Analogous cyclizations have been reported in the imidazole 373 which undergoes further photoreaction to yield the bicycle 375, and in o-aminobenzonitrile which is converted into indazole.310 This photocyclization has been extended to include enaminonitriles 376 spectroscopic evidence for the intermediacy of iminoketenimes 377 in this311 and other similar transformations312 have been reported. 

Figure 3.12 Metabolic profiling by capillary electrophoresis, (a) Comparative carbohydrate profiles of M. truncatula tissue obtained using 4-aminobenzonitrile derivatization, capillary electrophoresis with a 150 mM borate buffer, pH = 9, and on-column UV detection at 214 nm. (b) Anion profile from M. truncatula using capillary electrophoresis and indirect UV detection. The separation buffer was 5 mM K2C1O4, 1% Waters OFM-Anion BT, pH 8.0.

SCHWAIGER, H., OEFNER, P.J., HUBER, C GRILL, E., BONN, G.K., Capillary zone electrophoresis and micellar electrokinetic chromatography of 4-aminobenzonitrile carbohydrate, Electrophoresis, 1994,15, 941-952. 

Though rarely used, this methodology can be illustrated (Equation 28) by reaction at high temperature between 2-aminobenzonitrile (anthranilonitrile) and various cyanoacetic hydrazides of general structure 227 (Ar = Ph, 4-ClC6H4, 4-MeOC6H4). The 4,5-dihydro-[l,2,4]triazolo[4,3-tf]quinolines 228 were obtained in this way <2005SC2481>. 

In nitriles containing a nitro group the latter is reduced preferentially by iron and by stannous chloride. 2-Chloro-6-nitrobenzonitrile was reduced to 2-chloro-6-aminobenzonitrile with iron in methanol and hydrochloric acid in 89% yield [7769], and o-nitrobenzonitrile to o-aminobenzonitrile with stannous chloride and hydrochloric acid in 80% yield [779]. 

Aminobenzonitrile 35a produces the corresponding indolo benzazepine 36a when reacted with o-carboxymethyl bromoacetophenone in refluxing DME... 

Substituted 4-aminoquinazolines 847 can be prepared by combining 2-aminobenzonitriles 846 with nitriles under basic conditions <2000JME2227, 2005SC2481>, and a microwave-assisted procedure is now available that enables these compounds to be produced very efficiently <2000TL2215>. 

In the absence of an added nitrile, the 2-aminobenzonitrile undergoes a self-condensation to give 4-amino-2-(2-aminophenyOquinazoline 848 <2000TL2215>. 

A one-pot procedure for the synthesis of 4-aminoquinazolines 771 from 2-aminobenzonitrile 770, ammonium acetate, and trialkyl orthoesters under solvent-free microwave conditions has been developed <2006JHC913>. Product yields are comparable to those obtained under thermal conditions, although reaction times are significantly shorter. An attempt to extend the method to include aromatic orthoesters was unsuccessful. 

Derivatives of l,2-dihydro-l,3,2-diazaborines are prepared from 2-aminobenzonitrile or 2-aminobenzamides. Compounds (147) were obtained from 2-aminobenzonitrile (148) and boron trihalides (equation 12). However, it was stated that dichlorophenylborane or... 

Treatment of a number of isatin-3-oximes with sodium methoxide at 140°293 or simply thermally274,294 leads to o-aminobenzonitriles. Thermal treatment of isatin-2-oxime gave isatin and 79.294 Beckman rearrangement of isatin-3-oximes resulted in the formation of o-cyano-phenylisocyanates.26,295 With the Vilsmeier reagent, phosphorus... 

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