Pyrene synthesis

Pitts, J. N., Jr., B. Zielinska, and W. P. Harger, Isomeric Mononi-trobenzo[ ]pyrenes Synthesis, Identification, and Mutagenic Activities, Mutat.. Res., 140, 81-85 (1984b). 

Keywords synthesis of functionalized cyclohexenes, pyrenes and pyridones... 

Photocyanation of Aromatic Hydrocarbons Investigated in Micro Reactors Oiganic synthesis 43 [OS 43] Photocyanation of pyrene... 

Ren RXF, Chaudhuri NC, Paris PL, Rumney S IV, Kool ET (1996) Naphthalene, phenan-threne, and pyrene as DNA base analogues synthesis, structure, and fluorescence in DNA. J Am Chem Soc 118 7671-7678... 

Mayer, E., Valis, L., Huber, R., Amann, N. and Wagenknecht, H. A. (2003). Preparation of pyrene-modified purine and pyrimidine nucleosides via Suzuki-Miyaura cross-couplings and characterization of their fluorescent properties. Synthesis 2335-2340. 

Methods for the synthesis of the biologically active dihydrodiol and diol epoxide metabolites of both carcinogenic and noncarcinogenic polycyclic aromatic hydrocarbons are reviewed. Four general synthetic routes to the trans-dihydrodiol precursors of the bay region anti and syn diol epoxide derivatives have been developed. Syntheses of the oxidized metabolites of the following hydrocarbons via these methods are described benzo(a)pyrene, benz(a)anthracene, benzo-(e)pyrene, dibenz(a,h)anthracene, triphenylene, phen-anthrene, anthracene, chrysene, benzo(c)phenanthrene, dibenzo(a,i)pyrene, dibenzo(a,h)pyrene, 7-methyl-benz(a)anthracene, 7,12-dimethylbenz(a)anthracene, 3-methylcholanthrene, 5-methylchrysene, fluoranthene, benzo(b)fluoranthene, benzo(j)fluoranthene, benzo(k)-fluoranthene, and dibenzo(a,e)fluoranthene. 

Figure 2. Synthesis of trans-7,8-dihydroxy-anti(and syn)-9,10-epoxy-7,8,9,10-tetrahydrobenzo(a)pyrene (anti- and syn-BPDE) via Method I ( ,2 ). Reagents (i) NaBH, (ii) H+ (iii) AgOBz, I- (iv) NBS (v) DBN (vi) NaOMe (vii) DDQ (viii) m-CPBA (ix) DMSO, H20 (x) t-BuOK.

This aldehyde synthesis is applicable to compounds of the aromatic series having a labile hydrogen atom (phenyl ethers,1 naphthols,2 dialkylanilines,3-4 naphthostyril,2 anthrones 2) and to certain hydrocarbons of requisite reactivity (anthracene,5-6 7 1,2-benzanthracene,6 3,4-benzpyrene,3 7 pyrene,8 styrene,9 and a, a-diarylethylenes 9). With polynuclear hydrocarbons the best results are secured by the use of a solvent such as o-dichloro-benzene. 9-Anthraldehyde has also been prepared by the action of hydrogen cyanide and aluminum chloride on anthracene in chlorobenzene.10... 

Sangaiah, R., and A. Gold, A Short and Convenient Synthesis of Cyclopenta[cd]pyrene and Its Oxygenated Derivatives, in Polynuclear Aromatic Hydrocarbons Mechanisms, Methods and Metabolism (M. Cooke and A. J. Dennis, Eds.), Eighth International Symposium on Polynuclear Aromatic Hydrocarbons, Bat-telle Press, Columbus, OH, 1985. 

Environmental chemicals and pollutants are also capable of inducing P450 enzymes. As previously noted, exposure to benzo[a]pyrene and other polycyclic aromatic hydrocarbons, which are present in tobacco smoke, charcoal-broiled meat, and other organic pyrolysis products, is known to induce CYP1A enzymes and to alter the rates of drug metabolism. Other environmental chemicals known to induce specific P450s include the polychlorinated biphenyls (PCBs), which were once used widely in industry as insulating materials and plasticizers, and 2,3,7,8-tetrachlorodibenzo-p-dioxin (dioxin, TCDD), a trace byproduct of the chemical synthesis of the defoliant 2,4,5-T (see Chapter 56). 

The Balz-Schiemann synthesis can be applied not only to substituted anilines but also to aminobiphcnyls1,131 or amino-substituted fused polyaromatic compounds, such as naphthalene,1114,119,129 anthracene,136 phenanthrene,1135 acenaphthene,133 fluorene,1,131,134 benzanthracene,130 136 pyrene,136 chrysene,136 fluoranthene,131 fluorenone,1,131 anthra-quinone,1,137,139,140 benzanthrone,1,117,118 phenanthraquinone,138 or xanthone.132 Fluorinated pyridines,1,141"146 methylpyridincs,126,147 149 pyridinecarboxylic acids,150 quinolines,1,151 isoquinolines,152 quinazolone,1 thiazoles,153,154 isothiazoles,156 benzothiazoles,157 thiadiazoles,155 and thiophenes154 can also be obtained from the corresponding aminated heterocycles. Modified Balz-Schiemann methods are recommended for amino nitrogen-containing heterocycles, the diazonium salts of which are rather water-soluble and unstable (a violent explosion was reported for pyridine-3-diazonium tetrafluoroborate).159 These new techniques have also been specially adapted for pyrazol-, imidazol-, or triazolamines which fail to react under classical conditions.158... 

With the aim of preparing photoinduced electron transfer devices or simply to be used as fluorescent reporter groups, the synthesis and utility of pyrene-L-alanine have been reported on several occasions. Regarding the development of charge-transfer devices, it was shown that intramolecular electron transfer occurred in 310- and a-helical peptidic systems, such as 182 and 185, between a pyrene and a dimethylaminophenyl chromophore (Scheme 51).[95 101] The rates depend on the relative orientation of the chromophoric side chains and on the framework conformation. Therefore, the preparation of tailor-made charge-transfer devices with tunable properties can be envisaged. 

On the other hand, pyrenyl-L-alanine 184 has also been used as a conformational probe in the characterization of an artificial 4-a-helix bundle protein.11,121 The 53-residue peptide 186 incorporating one residue of 184 in each of two different helical segments was synthesized by solid-phase synthesis using a segment condensation strategy and the oxime resin. Boc-pyrenyl-L-alanine 191 was coupled just like any other amino acid by the BOP/HOBt method in DMF. CD and fluorescence studies demonstrated that the two pyrene groups were in close proximity forming an excimer complex, which is possible only when the polypeptide chain folds into a 4-a-helix bundle structure. 

Other cycloadditions of interest include the photoaddition [Eq. (52)] of pyrimidine derivatives such as cytosine to the carcinogenic hydrocarbon benzo[a]pyrene,191 and the photoaddition of allene as a vital step [Eq. (53)] in the synthesis of an annotinine derivative.192... 

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