Perylene condensation

Perylenes (70) are diimides of perylene-3,4,9,10-tetracarboxylic acid, and may be prepared by reaction of the bis-anhydride of this acid, 89 (1 mol) with the appropriate amine (2 mol) in a high-boiling solvent as illustrated in Scheme 4.11. The synthesis of perinones 71 and 72 involves condensation of naphthalene-1,4,5,8-tetracarboxylic acid with benzene-1,2-diamine in refluxing acetic acid. This affords a mixture of the two isomers, which may be separated by a variety of methods, generally involving their differential solubility in acids and alkalis. 

The p.K -values of Table 22 are plotted against the localization energies in Fig. 26. The straight line which can to a good approximation be drawn through these points confirms this relationship. Greater deviations occur particularly in the case of the peri-condensed aromatic substances pyrene and perylene. The pX values are lower than one would have expected on the basis of localization energies. 

The Jackson laboratory of the du Pont Company soon became interested in the catalytic power of hydrogen fluoride. The results of its work are recorded in three excellent papers. Using acrolein as the alkylating agent and hydrogen fluoride as the catalyst, peri syntheses have been performed (Calcott et al, 32), both those that are catalyzed by sulfuric acid and others that are not. By appropriate condensation, dehydration, and reduction, perylene was obtained from phenanthrene... 

Perinones are structurally similar to perylenes being made by condensing naphthalene tetracarboxylic dianhydride with amines, but in this case 1,2-diamines, e.g. Cl Pigment Orange 43 (2.71), or its cis isomer. The isomers can be separated by fractionation of their salts. They offer orange to bordeaux shades with similar properties to perylenes, but are less commercially important. 

The series of peri-condensed naphthalene analogues perylene (5), terrylene (73), and quaterrylene (74) represent types of condensed ring... 

These pigments may be defined as those that will meet the exacting demands of today s environment with respect particularly to the outdoor exposure requirements demanded by climates such as those that occur in Florida and Arizona for as little as two and as long as five years. The high-performance reds considered fall into four basic classes quinacridone reds and violets, vat dyestuff reds such as perylenes, benzimidazolone reds, and disazo condensation reds. 

Pyrolysis of a perylene-tetracarboxylic dianhydride monomer above 520 C resulted in vapor-phase condensation of poly-peri-naphthalene (PPN), a representative one-dimensional graphite polymer. PPN was obtained as fine whiskers with rectangular cross sections and exhibited electrical conduction behaviors characteristic of low-dimensional disordered systems. At HTT s above 2800 C,... 

Imahori, S. and Hirako, S. (1976). jS-crystalline phase perylene pigment— prepn by condensing with xylidine derived in organic solvent. Mitsubishi Chemical Industries Co. Ltd. Patent JP 51-7025 Chem. Abstr, 84, 16625D. [261t]... 

A paper by Suppan draws attention to electrostatic interaction effects on condensed phase photoinduced electron transfer and the need to take account of the fact that solvent is not in reality a uniform dielectric material. Pressure effects on exciplex formation has been exemplified in the pyrene-p-cyanobenzene system. Ternary electron donor acceptor complexes are formed and in the case of anthracene-tetracyanoethylene gives rise to (DO ) dimer radical cations. Laser flash photolysis shows that perylene in acetonitrile undergoes three distinct electron transfer processes, (i) gives pt + MeCNT, (ii) gives... 

Mixtures. Chronic dermal exposure of NMRI mice to a tar condensate that contained several PAHs (pyrene, fluoranthene, chrysene, benz[a]anthracene, benzo[a]pyrene, indeno[1,2,3- c,d]pyrene, benzo[g,h,i,]perylene) in addition to other compounds produced a carcinogenic effect as evidenced by an increase in the incidence of skin papillomas and carcinomas (Habs et al. 1984). Because of the presence of other compounds in the tar condensate, the carcinogenic effect cannot be definitely attributed to the PAHs present in the mixture. 

For the last time a great number of new dyes, such as azo dyes, derivatives of antrapyridon and antrapyrimidon [44], derivatives of perylene [91], water-soluble ethers of antrachinon [92] condensation products of symmetric and asymmetric indigoide colours with aryl-cyclohalogenides [93], derivatives of phthalocyanine [94] and others have been synthesized. 

Distributions of pyrolytic PAFls are characterized by the dominance of the non-alkylated species shown in Fig. 7.3. Particularly abundant are the highly peri-condensed compounds—such as pyrene, the benzopyrenes, benzo[gfe]perylene and coronene—that result from extensive angular fusion of benzenoid systems.The presence of such PAF1 distributions in the aromatic... 

Pyrolytic PAH distributions in ancient sediments sometimes differ from those typical of Recent sediments in exhibiting enhanced levels of the more highly peri-condensed structures, especially benzofe]pyrene, benzo[gfe]perylene and coronene (Fig. 7.4 Killops Massoud 1992). The reasons are as yet unknown but may reflect the effects of either different formation conditions or varying geochemical processes over geological time periods. 

There is normal diene reactivity in highly condensed aromatic systems such as perylene and benzanthrene here the conjugated double bonds belong to different rings, the positions at which the philodiene is added being indicated by arrows in the following formulae ... 

It is possible to remove hydrogen catalytically, with formation of new carbon-carbon bonds, especially by means of aluminum chloride. The main importance of this process lies in the preparation of condensed ring systems in the aromatic series. It is convenient to differentiate an intermolecular reaction such as the formation of perylene from naphthalene from an intramolecular reaction such as formation of the same product from 1,1 -binaphthalene 269... 

Stilbene-type photocyclizations provide a good route to condensed polycyclic aromatic hydrocarbons, and a study of distyrylbenzenes and styryl- and distyryl-naphthalenes provides syntheses of a range of such hydrocarbons, including benzo[g/ ]perylene (131) and fulminene (132). Two studies relating to... 

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