Perylene alkylation

Perylene Pigments. The perylenes ate a class of red and maroon pigments. In the general formula, Rmay represent a simple alkyl, methyl, or a substituted phenyl, eg, PR 123, R = p-ethoxyphenyl. 

Chemiluminescence also occurs during electrolysis of mixtures of DPACI2 99 and rubrene or perylene In the case of rubrene the chemiluminescence matches the fluorescence of the latter at the reduction potential of rubrene radical anion formation ( — 1.4 V) at —1.9 V, the reduction potential of DPA radical anion, a mixed emission is observed consisting of rubrene and DPA fluorescence. Similar results were obtained with the dibromide 100 and DPA and/or rubrene. An energy-transfer mechanism from excited DPA to rubrene could not be detected under the reaction conditions (see also 154>). There seems to be no explanation yet as to why, in mixtures of halides like DPACI2 and aromatic hydrocarbons, electrogenerated chemiluminescence always stems from that hydrocarbon which is most easily reduced. A great number of aryl and alkyl halides is reported to exhibit this type of rather efficient chemiluminescence 155>. 

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... 

There are several natural non-combustion sources of PAHs. A study in 1980 by Wakeham [43] concluded that phenanthrene could be created by the dehydrogenation of steroids, retene could be produced by the diagenesis of abietic acid, and alkyl chrysenes could form from the degradation of the pentacyclic triterpenes alpha- and beta-amyrin, which are components of higher plant waxes. In this section we will look at the natural non-combustion sources of retene and perylene and how these sources might impact the Great Lakes. 

R. J. Chesterfield, J. C. McKeen, C. R. Newman, P. C. Ewbank, D. Filho, J.-L. Bredas, L. L. Miller, K. Mann, and C. D. Frisbie, Organic thin film transistors based on N-alkyl perylene diimides Charge transport kinetics as a function of gate voltage and temperature , Journal of Physical Chemistry B 108, 19281 (2004). 

Fig. 5. Back electron transfer rates in photogenerated radical ion pairs in acetonitrile (a) 9,10-Dicyanoanthracene in its excited state served as the acceptor. Aryl, alkyl, methoxy and amino benzene derivatives as well as aliphatic amines served as donors [62] (V = 23 cm-1, 2, = 0.97 eV, Aj = 0.64 eV). (b) Perylene, pyrene, benzperylene, and aromatic amines served as donors. Tetracyanoethylene (TCNE), pyromellitic dianhydride (PMDA), phthalic anhydride (PA), maleic anhydride, pyrene and perylene served as electron acceptors [63], Various combinations of donors or acceptors were excited (V = 20 cm , As = 1.45 eV, A, = 0.07 eV). The parabolas drawn are different from those offered in the original analysis. The parameters that were used were selected to emphasize the similarity to Fig. 4 (in all cases v = 1500 cm-1)...

Also, the PET between polynuclear aromatic hydrocarbons (naphthalene, anthracene, phenanthrene, perylene) or heteroaromatics (phenazine, acridine) as acceptors and amines as donors can be used for polymerization initiation of AN and alkyl methacrylates [111-113]. In general, a reaction course as outlined in Scheme 3 also acts with these combinations. 

The low solubility of perylene carboxylic bisimides is a general obstacle for their application in homogeneous solution. This can be solved by the introduction of long-chain secondary alkyl groups ( swallow-tail-substituents ) [15, 16,17] to the nitrogen atoms such as R= 1-hexylheptyl. 

The addition of alkyl halides to aromatic anion radicals, generated by alkali metal reduction in etheral solvents, was already known in the 1950s [176] and was reviewed by Garst in 1971 [177]. The first electrochemical analogue was observed by Lund et al. [178]. These authors cathodically reduced hydrocarbons such as naphthalene, anthracene, stilbene [128,129], and perylene [130] in the presence of alkyl halides and isolated hydrogenated and alkylated products. Similar reactions are observed when the halides are replaced by ammonium or sulfonium [179]. 

Petroleum. The presence of PCAH in petroleum is well known. Naphthalene, phenanthrene, fiuorene, pyrene, chrysene, triphenylene, perylene, several benzanthracenes, and various alkyl substituted derivatives of these compounds have been foimd in crude petroleum (7). In addition, the PCAH content of those petroleum products which have been produced by thermal cracking is much greater than in the crude oil. 

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... 

While studying the reactions of perylene, Ziegler (21) observed that treatment of perylene with methyllithium in boiling benzene gives only a 0.1-2.0% yield of the alkylation product, 1-methylperylene 90 to 95% of the starting hydrocarbon is invariably recovered. 

Aromatic hydrocarbons are cyclic, planar compounds that are stabilized by a delocalized tt electron system. Aromatics include the mono aromatic hydrocarbons such as BTEX (benzene, toluene, ethylbenzene, and o-, m-, and p-xylenes) and other alkyl-substituted benzene compounds (C -benzenes), and polycyclic aromatic hydrocarbons (including oil-characteristic alkylated PAH homologues and the other U.S. EPA priority PAHs). Benzene is the simplest one ring aromatic compound. The commonly analyzed PAH compounds range from two ring PAHs (such as naphthalene) up through six ring PAHs (benzo g, h, i) perylene). BTEX and PAHs are of concern because of their toxic properties in the environment. 

Reductive Alkylation of Aromatic Compounds Perylene, Decacyclene, and Dibenzothiophene... 

The reduction of three polynuclear aromatic compounds, namely, perylene, decacyclene, and dibenzothiophene, with potassium metal in tetrahydrofuran at 25 °C, followed by quenching with alkyl iodides, was investigated. With perylene, a dianion was obtained, which on reaction with methyl iodide added two methyl groups the main re-gioisomer had one methyl group on C-l and one methyl group on the adjacent nonprotonated carbon, C-14. The reductive alkylation of decacyclene also led to alkyl groups on quaternary carbon atoms. The reduction of dibenzothiophene led to a loss of sulfur and proton uptake from solvent to yield biphenyl as the product after 24 h of reduction. 

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