Reaction with polycyclic aromatics

Banik BK, Becker FF. Unprecedented stereoselectivity in the Staudinger reaction with polycyclic aromatic imines. Tetrahedron Lett. 2000 41 6551-6554. 

The reactions of the tetrahalogenobenzynes with polycyclic aromatic compounds follow the expected paths. Thus with naphthalenes 54,57) cyclo-addition at the 1,4-positions occurs even with 1,4,5,8-tetramethyl-naphthalene 64>. Thus the tetrahalogenobenzynes are only able to destroy the aromaticity of one ring to form example the compound (46). 

The NO + 03 chemiluminescent reaction [Reactions (1-3)] is utilized in two commercially available GC detectors, the TEA detector, manufactured by Thermal Electric Corporation (Saddle Brook, NJ), and two nitrogen-selective detectors, manufactured by Thermal Electric Corporation and Antek Instruments, respectively. The TEA detector provides a highly sensitive and selective means of analyzing samples for A-nitrosamines, many of which are known carcinogens. These compounds can be found in such diverse matrices as foods, cosmetics, tobacco products, and environmental samples of soil and water. The TEA detector can also be used to quantify nitroaromatics. This class of compounds includes many explosives and various reactive intermediates used in the chemical industry [121]. Several nitroaromatics are known carcinogens, and are found as environmental contaminants. They have been repeatedly identified in organic aerosol particles, formed from the reaction of polycyclic aromatic hydrocarbons with atmospheric nitric acid at the particle surface [122-124], The TEA detector is extremely selective, which aids analyses in complex matrices, but also severely limits the number of potential applications for the detector [125-127],... 

Pitts, J. N., Jr., J. A. Sweetman, B. Zielinska, A. M. Winer, R. Atkinson, and W. P. Harger, Formation of Nitroarenes from the Reaction of Polycyclic Aromatic Hydrocarbons with Dinitrogen Pentoxide, Environ. Sci. Technol., 19, III5-II2I (I985e). 

Two types of reaction are observed for thioketones that do not have parallels in ketone photochemistry. The first is photocyclization in thioketones with polycyclic aromatic groups (4.104), where the sulfur atom forms a new bond to the aromatic system. The second is photo-oxidation by singlet oxygen to give the corresponding carbonyl compound 4.10S), possibly via a 1,2,3-dioxathietane formed as a result of initial cycloaddition. 

TNT forms charge-transfer, or 7r, complexes with polycyclic aromatic hydrocarbons, aromatic amines, and aromatic nitro compds a number of these are listed below in Table 2. The complexes with three amines (diphenylamine, diethyl-aniline, p-anisidine) have characteristic colors this forms the basis for a rapid and convenient thin-layer chromatographic analytical procedure (Ref 34) for the identification of very small amounts of TNT. (For a discussion of the many color reactions of TNT, and of composite expls containing it, see Vol 3, C405-L ff)... 

Esteve W, Budzinski H, Villenave E (2006) Relative rate constants for the heterogeneous reactions of N02 and OH radicals with polycyclic aromatic hydrocarbons adsorbed on carbonaceous particles. Part 2 PAHs adsorbed on diesel particulate exhaust SRM 1650a. Atmos Environ 40 201-211... 

Kopinke, F.-D., Georgi, A., Mackenzie, K., and Kumke, M. U. (2000). Sorption and chemical reactions of polycyclic aromatic hydrocarbons with dissolved refractory organic subtances and related model compounds. In Refractory Organic Substances (ROS) in the Environment, Frimmel, F. H., Abbt-Braun, G., Heumann, K. G., Hock, B., Ludemann, H.-D., and Spiteller, M., eds., Wiley-VCH, Weinheim, pp. 475-515. 

Guo, D.S., Yuan, X.Y., Zhang, Z.Q., 2000. Binding reaction of polycyclic aromatic hydrocarbons AHs) in Taiyuan City with DNA. China Environ. Sci. 20, 5-7. 

Irradiation of styrene in the presence of oxygen leads to polymerisation (Kodaira et ai, 1978). Although radical cations may well be intermediates in such reactions it has proved impossible to detect them in the reactions of polycyclic aromatic hydrocarbons with oxygen in acetonitrile solution (Watkins, 1979a). 

According to ( erfontain 24] tetrafluorohydrazine can roiicl with polycyclic aromatic hydrocarbons in iso-octane as a solvent at 40 C. Thus aiitlujcone yielded 9,10-bisfluoroamino-9,10-dihydroanthracene. The product does not show good stability, it decomposed above I30 C with a gas evolution and at 220 C yielded mainly the parent hydrocarbon. Similarly the product of the reaction of stilbene with tetrafluorohydrazine (which was l.2-bisdinuo[oamim>-1,2-diphenylethane) decomposed above 80 ( ... 

Geacintov, N.E. (1988) Mechanisms of reaction of polycyclic aromatic epoxide derivatives with nucleic adds, in Polycyclic Aromatic Hydrocarbon Carcinogenesis Structure-Activity Relationships, vol. II (eds S.K. Yang and B.D. Silverman), CRC Press, Boca Raton, EL, pp. 181-206. 

There are several reports this year of photocycloaddition reactions between polycyclic aromatic hydrocarbons and 1,3-dienes. Anthracene (58 R = H) or 9-cyanoanthracene (58 R = CN) give [4 -I- 4] and [4 -I- 2]adducts on irradiation with buta-1,3-diene, but the different product ratios and temperature effects are used to support the previously proposed biradical mechanism for the reaction. Another report from the same group deals with anthracene-hexa-2,4-diene and 9-phenylanthracene-penta-1,3-diene or cyclohexa-1,3-diene systems in the case of 9-phenylanthracene (59) and cyclohexa-1,3-diene, two [2 -I- 2]cycloadducts involving a terminal aromatic ring are isolated, as well as the more usual [4 + 2] and [4 -f- 4]adducts involving the central ring. Irradiation of substituted anthracenes... 

Heterogeneous reactions on solid particles may also play a role in the removal of sulphur dioxide from the atmosphere. In atmospheric photochemical reactions, such particles may function as nucleation centres. Thus, they act as catalysts and grow in size by accumulating reaction products. The final result would be the production of an aerosol with a composition unlike that of the original particle. Little research has been done on the role that solid particles play in the oxidation of sulphur dioxide under conditions like those found in the atmosphere. Soot particles, which consist of elemental carbon contaminated with polycyclic aromatic hydrocarbons produced in the incomplete combustion of carbonacetous fuels, have been shown to catalyse the oxidation of sulphur dioxide to sulphates. 

The Abramov reaction proceeds normally with polycyclic aromatic aldehydes but of other, monocyclic, benzenoid aldehydes, the behaviour of 2-hydroxybenzaldehyde is anomalous here, the reaction product 172 is evidently formed by hydrolysis of the dihydrobenzo-1,2-oxaphosph(V)ole 171, in turn the result of the expulsion of 1 mol of the alcohol ROH from the initial 1 1 adduct 170. ... 

Pitts, J. N. Jr., Sweetman, J. A., Zielinska, B., Winer, A. M., Atkinson, R., and Harger, W. P. (1985b) Formation of nitroarenes from the reaction of polycyclic aromatic hydrocarbons with dinitrogen pentoxide. Environ. Sci. Technoi, 19, 1115-1121. 

There are many examples of this type of reaction with both aromatic and heteroaromatic substrates. For successful electrocyclization, the central alkene must have Z geometry, however, as the action of light on stilbenes promotes E-Z isomerization, it is possible to start with either geometrical isomer of the substrate, or indeed a mixture of isomers. In a synthesis of cervinomycin A, photochemical electrocyclization of the mixture of E- and Z-diaryl alkenes 347 gave the polycyclic aromatic compound 348 after oxidation with iodine (3.219). ... 

With polycyclic aromatic hydrocarbons, the site of ozone attack may be dependent upon substrate stmcture and reaction solvent (eq 21). ... 

The reaction of polycyclic aromatic hydrocarbons with [hydroxy(tosyloxy)iodo]benzene in the presence of trimethylsilyl isothiocyanate leads to the regioselective thiocyanation of an arene nucleus, as illustrated by the reaction of anthracene shown in Scheme 3.213 [274],... 

Aromatic rigid-rod polymers play an important role in a number of diverse technologies including high-performance engineering materials, conducting polymers, and nonhnear optical materials. The cross-coupling reaction of aryldiboronic acids and dihaloarenes for the synthesis of poly(p-phenylenes) was first reported by Rehahn et al. The method has been extensively applied to water-soluble poly(p-phenylene), planar poly(p-phenylenes) fixed with the ketoimine bonds, poly(phenylenes) fused with polycyclic aromatics,and nonlinear optical materials (Scheme 14). 

In all procedures of quantitative evaluation it is imperative to expose the substances both at the start point and on the developed chromatogram as briefly as possible to the influence of light and air oxidations and photochemical reactions (as has been described for example with polycyclic aromatic compounds [311]) are thereby minimised. Accurate application of the sample to the start point is also most... 

In this reaction, the rate of the intermolecular ET is slower than the rate of intramolecular ET/fragmentation However, with polycyclic aromatic halides, haloarenes sub-... 

Corsaro et al. [79] reported a solvent-free cycloaddition reaction of polycyclic aromatic hydrocarbon with nitrile oxide. The reaction was completed under microwave irradiation in 3-10 min. It was observed that conventional heating is not capable to perform this reaction because of the dehydration of 1,3-dipole (Scheme 11.26). Yet, the yield 18-21 % is low under microwave irradiation. 

Schuetz CA, Frenklach M. (2002) Nucleation of soot Molecular dynamics simulations of pyrene dimerization. Proc. Combust. Inst. 29 2307-2314. Ricca A, Bauschlicher CW. (2000) The reactions of polycyclic aromatic hydrocarbons with OH. Chem. Phys. Lett. 328 396-402. 

Cyanonaphthalene complexes of [Ni(dippe)] were also investigated. Reaction of 1-cyanonaphthalene with [Ni(dippe)H]2 produced two stable Ni(0) complexes at ambient temperature. One was the expected rj -(C//)-naphthalene-CN complex and the other was assigned as the r -(C,C)-naphthalene-CN complex with the metal bound to the arene C-C double bond. Earlier studies have shown that nickel forms stable r -complexes with polycyclic aromatics [37, 42]. Upon heating, these two complexes convert to the C-CN insertion product (21). DFT calculations were in... 

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