Cyano-anthracene

From ref. 27. Data for the dimerization of 9-cyano-anthracene anion radical in N,N-dimethylformamide—Bu4NBF4 (0.1 M) in the presence of acetic acid (8.8 mM) at 281.7 K. 

Stevens, B., T. Dickinson, and R. R. Sharpe Photodimerisation in crystalline 9-cyano-anthracene. Nature 204, 876 (1964). 

In MeCN the products of photo -oxidation of Ph2C=CH2, cis- and trans-PhCH=CHPh, and Ph2C=CPh2 using 9,10-dicyanoanthracene and 9-cyano-anthracene as sensitizers include benzophenone, benzaldehyde, epoxides, and products of cu-trfln5-isomerization. " A correlation is established between the rate constants for electron-transfer processes and those determined from the acceptor concentration-dependence of product formation. These observations appear to implicate a sensitizer radical anion that subsequently reduces O2 to Oj-... 

It is well established that mono-meso-substituted anthracenes yield head-to-tail dimers as a result of steric and/or electrostatic repulsions between the substituents.180 The first head-to-head mixed dimers have now, however, been reported, and control of the selectivity of this addition is considered to result from charge-transfer and dipole-dipole interactions.181 Thus irradiation of a mixture of 9-methoxy- and 9-cyano-anthracenes in ether yields solely the head-to-head dimer (142), with no trace of the head-to-tail isomer. At room temperature (142) is thermally converted into the starting materials. Irradiation of the mixture of anthracenes in a polar solvent, such as acetonitrile, which is able to stabilize the... 

Electron microscopy has been used successfully in the elucidation of the mechanism of reactions in organic crystals which occur at defects, such as the dimerization of 9-cyano-anthracene. 

Reaction of 2-129 with NaCN followed by treatment with NaH and TIPSC1 led to the anthracene 2-130 in 68% yield (Scheme 2.30). The desired lactam 2-131 was then obtained by reduction of the cyano group and ring closure using CoCl2/ NaBH4. Quite recently, this procedure has also been used for a formal total synthesis of tetracenomycin [63]. 

It is well known that cyano derivatives of anthracene form charge transfer (CT) complexes with certain aromatic compounds. It was reported [67] that the radical cations formed upon irradiation of these complexes played an important role in initiation of cationic polymerization of cyclic ethers. Pyridinium salts were also found [68] to form CT complexes with hexamethyl benzene and trimethoxy benzene which result in the formation of a new absorption band at longer wavelengths where both donor and acceptor molecules have no absorption. This way the light sensitivity of the pyridinium salts may be extended towards the visible range. According to the results obtained from the... 

Many examples of anthracenes photodimerisatlon have been reported, but there are relatively few examples of naphthalene photodimerisatlon. Alblnl and co-workers have re-examined the photochemistry of 2-cyanonaphthaiene and have Isolated two products identified as the cage dimers (224) and (225) the position of the cyano group on the benzene ring in (225) was not assignable from the data obtained. A similar cage dimer was formed between 2-cyano naphthalene... 

The direct nature of attack of CN on radical cations of aromatic compounds has been demonstrated by CV [221]. The reversible one-electron oxidation of anthracene becomes irreversible in the presence of CN, and 2 F electrolysis gives a mixture of cyano and isocyano addition across the 9,10-position. Interestingly, it appears that cyanation of 9,10-diphenylanthracene gives the 9,10-diphenyl-9,10-dicyano-9,10-dihydroanthra-cene only [233]. 

Radicals and Aromatics. I. Reaction of Anthracene and of Pyrene with 2-Cyano-2-propyl Radicals. 

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