77587-05-4

Upstream product

• 623-26-7 terephthalonitrile 
• 563-79-1 2,3-Dimethyl-2-butene 
• 67-56-1 methanol 
• 75-89-8 2,2,2-trifluoroethanol 
• 75-31-0 isopropylamine 

Relevant academic research and scientific papers

Photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reaction, Part 15. Investigations involving fluoride anion as the nucleophile and the effect of fluorine substitution on the relative stability of the reaction intermediates

The scope of the photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reaction has been extended to include fluoride anion as the nucleophile. The 4-cyanophenyl substituted fluoroalkanes were obtained in moderate yields with 2

Redox-photosensitized amination of alkenes and alkadienes with ammonia and alkylamines

Using 1,2,4-triphenylbenzene as a photosensitizer, the photoamination of alkenes and alkadienes (1), which had no absorption at >300 nm proceeded efficiently in the presence of p-dicyanobenzene to give addition products by incorporating both amino and p-c

On the mechanism of the photochemical reaction between 1,4-dicyanobenzene and 2,3-dimethylbutene in the presence of nucleophiles

The irradiation of 1,4-dicyanobenzene (DCB) in the presence of 2,3-dimethyl-2-butene (DMB) leads to allylation of the aromatic. In the presence of nucleophiles (MeOH, H2O, CF3CH2OH) this reaction is substituted by the nucleophile olefin combination - aromatic substitution (NOCAS) process. The quantum yield increases from 0.006 in the absence to a limiting value of ca 0.02 in the presence of the nucleophiles. The reaction involves competing deprotonation and nucleophile addition to the olefin radical cation, followed by coupling of the thus formed radical with DCB-. Minor processes are hydrogen abstraction from the solvent by the allyl radical, revealed by isolation of the phenylpentanonitrile 3 and coupling of the radical ions before separation, revealed by a small amount of the cyclohexadiene 6.

Radical ions in photochemistry, 15. The photosubstitution reaction between dicyanobenzenes and alkyl olefins

The photosubstitution (electron transfer) reaction between 1,4-dicyanobenzene (1) and 2,3-dimethyl-2-butene (2), which gives 1-(4-cyanophenyl)-2,3-dimethyl-2-butene (3) and 3-(4-cyanophenyl)-2,3-dimethyl-1-butene (4), has been extended to other dicyanobenzene-olefin mixtures.Substitution of cyano group occurs when both 1 or 1,2-dicyanobenzene (5) are irradiated in acetonitrile solution, in the presence of 2 or cyclohexane (16).Under comparable conditions 1,3-dicyanobenzene (6) failed to react.Little or no substitution was observed in any case when the olefin was methylpropene (19).The results for 1 and 5 are in agreement with empirical free energy calculations (Weller equation) for the electron transfer process which, howover, fail to explain the general lack of reactivity of 1,3-dicyanobenzene.Phenanthrene (11) has been shown to photosensitize the photosubstitution reaction between dicyanobenzenes and 2.Under these conditions the olefin reacts with 6 predominantly at the 4-position, resulting in overall substitution of a hydrogen atom.This reaction occurs regiospecifically, resulting in the formation of only one of the two possible isomeric side chains.The mechanistic details of these reactions have been substantiated by means of deuterium labelling studies.The aromatic nitriles also undergo photosubstitution by 2, in acetonitrile-methanol solution, resulting in methanol-incorporated products.Whereas reaction with 1 or 5 results in substitution of a cyano group, 6 was observed to give isomeric dicyanocyclohexenes, resulting from initial reaction at the 4-position, followed by reduction.A detailed mechanism for this secondary photoreduction has been substantiated by deuterium labelling studies.The anomalous behaviour of 1,3-dicyanobenzene has been attributed to a difference in the reactivity of the radical anion.