O- benzonitrile

The photochemical cyclization of anthranilonitriles (190 Section 4.04.2.1.2) yields indazoles (72CC126). Reduction of o-benzonitrile with lithium aluminum hydride yields indazole (75ACS(B)1089). 2-Aminoindazole (576) has been prepared in 94% yield from (574) via the o-phthaloyl derivative (575 = o-phthaloyl) (72JOC2351). Similarly, treatment... 

Figure 4. Reciprocal reduced volume as a function of the volume percentage of polymer for nonaqueous suspensions A, DMF O, benzonitrile , cyclohexanone A, acetophenone O, 1,4-dioxane V, methyl benzoate , ethyl acetate O, benzyl alcohol, D =...

Nitration using this reagent was first investigated, by Francis. He showed that benzene and some of its homologues bromobenzene, benzonitrile, benzoyl chloride, benzaldehyde and some related compounds, and phenol were mono-nitrated in solutions of benzoyl nitrate in carbon tetrachloride anilines would not react cleanly and a series of naphthols yielded dinitro compounds. Further work on the orientation of substitution associated this reagent with higher proportions of o-substitution than that brought about by nitric acid this point is discussed below ( 5.3.4). 

Attempts have been made to catalyze the arrangement of 3-oxaquadricyclane to oxepins with transition-metal complexes.1 32 1 35 When dimethyl 2,4-dimethyl-3-oxaquadricyclane-l,5-dicarboxylate is treated with bis(benzonitrile)dichloroplatinum(II) or dicarbonylrhodium chloride dimer, an oxepin with a substitution pattern different from that following thermolysis is obtained as the main product. Instead of dimethyl 2,7-dimethyloxepin-4,5-dicarboxylate, the product of the thermal isomerization, dimethyl 2,5-dimethyloxepin-3,4-dicarboxylate (12), is formed due to the cleavage of a C O bond. This transition metal catalyzed cleavage accounts also for the formation of a 6-hydroxyfulvene [(cyclopentadienylidene)methanol] derivative (10-15%) and a substituted phenol (2-6%) as minor products.135 The proportion of reaction products is dependent on solvent, catalyst, and temperature. 

Die Reduktion von Nitrilen zu prim. Aminen mit Natrium- oder Kaliumboranat wird durch Obergangsmetall-Salze katalysiert2-4. Zur Reduktion wird allerdings sehr viel Hydrid verbraucht. Aus Benzonitril erhalt man z.B. in Gegenwart von Kobalt(II)-chlo-rid-Hexakis-hydrat 72°/o d. Th. Benzylamin5. 

Auf ahnliche Weise erhalt man aus Chlor(Brom)-benzonitrilen (Platin-Elektroden DMF -2,1 V) unter Helium in ungeteilter Zelle Benzonitril (85-92°/o d.Th.)4. 

Benzyl- 112, 240, 346, 355 f., 358, 436, 611 ff., 680 aus Benzaldehyd-O-methyl-oxim und Diboran377 aus Benzonitril und Natriumboranat 115 aus O-Benzoyl-benzhydroxamsaure und Lithium-alanat 264... 

A closely related reaction that is currently receiving much attention is the palladium-catalysed Suzuki coupling of arylboronic acids with aryl halides (Fu and Littke, 1998). For example, this technology has recently been applied by Clariant workers for the production of o-tolyl-benzonitrile (Eqn. (13)), an intermediate to a series of so-called angiotensin-II antagonists, a new class of antihypertensive drugs (Bernhagen, 1998). 

Unfortunately, appearance energy measnrements become more complicated with larger substrates, where the cations are more prone to rearrangement during ionization. Eor example, numerous attempts have been made to measnre the energy for formation of o-benzyne cation, CgH4+ by using benzonitrile as a precursor (Eq. 5.6). 

In particular, the reactions of electrophilically activated benzonitrile A-oxides with 3-methylenephthalimidines with formation of 2-isoxazolines and oximes and the cycloaddition between alkynyl metal(O) Fischer carbenes and nitrones leading to 4-isoxazolines have been investigated by density functional theory methods <06JOC9319 06JOC6178>. 

Thermal dehydrochlorination of hydroximoyl chlorides affords nitrile oxides (50-52). O-Ethoxycarbonylbenzohydroximoyl chloride, generating benzonitrile oxide, was used as a stable nitrile oxide precursor, which was efficiently used in... 

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). 

Formation of mixtures of the above type, which is common with internal olefins, do not occur with many functionalized alkenes. Thus, tertiary cinnamates and cinnamides undergo cycloadditions with benzonitrile oxides to give the 5-Ph and 4-Ph regioisomers in a 25-30 75-70 ratio. This result is in contrast to that obtained when methyl cinnamate was used as the dipolarophile (177). 1,3-Dipolar cycloaddition of nitrile oxides to ethyl o -hydroxycinnamate proceeds regiose-lectively to afford the corresponding ethyl fra s-3-aryl-4,5-dihydro-5-(2-hydro-xyphenyl)-4-isoxazolecarboxylates 36 (178). Reaction of 4-[( )-(2-ethoxycarbo-nylvinyl)] coumarin with acetonitrile oxide gives 37 (R = Me) and 38 in 73% and 3% yields, respectively, while reaction of the same dipolarophile with 4-methoxy-benzonitrile oxide affords only 37 (R = 4-MeOCr>H4) (85%) (179). 

Capon et al., 1978. No reference bimolecular reaction is available, but o-cyanobenzoic acid is hydrolysed over 10 times faster than phthalamic acid (A.3.9), although benzonitrile is less reactive than benzamide towards acid hydrolysis. [Rate constants for hydrolysis are (1-2) x 10 s for benzonitrile in 1 M acid (Hyland and O Connor, 1973) and 3.5 x 10-4 dm3 mol-1 s 1 for benzamide (Bender et al., 1958), both measured at 100°]... 

Fig. 3 Electrochemical and homogeneous standard free energies of activation for self-exchange in the reduction of aromatic hydrocarbons in iV.A -dimethylformamide as a function of their equivalent hard sphere radius, a. 1, Benzonitrile 2, 4-cyanopyridine 3, o-toluonitrile 4, w-toluonitrile 5, p-toluonitrile 6, phthalonitrile 7, terephthalonitrile 8, nitrobenzene 9, w-dinitrobenzene 10, p-dinitrobenzene 11, w-nitrobenzonitrile 12, dibenzofuran 13, dibenzothiophene 14, p-naphthoquinone 15, anthracene 16, perylene 17, naphthalene 18, tra 5-stilbene. Solid lines denote theoretical predictions. (Adapted from Kojima and Bard, 1975.)...

C7H3C12F3 2,4-DICHLOROBENZOTRIFLUORIDE 3,4-DICHLOROPHENYL ISOCYANATE p-CHLOROBENZOTRIFLUORIDE m-CHLOROBENZOYL CHLORIDE 3-NITROBENZOTRI FLUORIDE BENZOYL CHLORIDE o-CHLOROBENZOIC ACID BENZOTRI CHLORIDE BENZOTRI FLUORIDE BENZONITRILE PHENYL ISOCYANATE 2,4,6-TRINITROTOLUENE... 

Photolytic. When dichlobenil was irradiated in methanol with a 450-W mercury lamp and a Corex filter for 8 h, o-chlorobenzonitrile and benzonitrile formed as the major and minor products, respectively (Plimmer, 1970). 

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