Phenanthrene, 9 phenyl

Peroxytrifluoroacetic acid, in oxidation, of hexamethyl benzene, 48, 87 of polyalkylarenes, 48, 89, 90 Peroxyvanadic acid, 45, 27 Phenanthrene, 9-phenyl-, 46, 91... 

The opioids are derived from several chemical subgroups, including phenanthrenes, phenyl-heptylamines, phenylpiperidines, morphinans, and benzomorphans. A useful subdivision of the drugs is presented in Figure 31-1. 

Chapter IV. a-Chloromethylnaphthalene (IV,23) benzylamine (Gabriel synthesis) (IV,39) i r.N -dialkylanilines (from amines and trialkyl orthophosphates) (IV,42) a-naphthaldehyde (Sommelet reaction) (IV,120) a-phenyl-cinnamic acid (Perkin reaction using triethylamine) (IV,124) p-nitrostyrene (IV,129) p-bromonaphthalene and p naphthoic acid (from 2 naphthylamine-1 -sulphonic acid) (IV,62 and IV,164) diphenic acid (from phenanthrene) (IV,165). 

The classical syntheses of phenanthrene and fluorenone fit well into the electron transfer scheme discussed in Section 8.6 and in this chapter. The aryl radical is formed by electron transfer from a Cu1 ion, iodide ion, pyridine, hypophosphorous acid, or by electrochemical transfer. The aryl radical attacks the neighboring phenyl ring, and the oxidized electron transfer reagent (e. g., Cu11) reduces the hexadienyl radical to the arenium ion, which is finally deprotonated by the solvent (Scheme 10-76). 

Figure 6.10. Rate constants for quenching of sensitizers by cis- and trans-stilbenes (open and filled circles, respectively). Sensitizers are as follows (1) tri-phenylene, (2) thioxanthone, (3) phenanthrene, (4) 2-acetonaphthone, (3) 1-naphthyl phenyl ketone, (6) crysene, (7) fluorenone, (8) 1,2,5,6-dibenzanthracene, (9) benzil, (10) 1,2,3,4-dibenzanthracene, (11) pyrene, (12) 1,2-benzanthracene, (13) benzanthrone, (14) 3-acetyl pyrene, (15) acridine, (16) 9,10-dimethyl-l,2-benzanthracene, (17) anthracene, (18) 3,4-benzpyrene.<57> Reprinted by permission of the American Chemical Society.

These techniques proved to be successful for the majority of the hydrocarbons, but they failed for some compounds such as phenanthrene, terphenyl, or quater-phenyl. The failure has been interpreted by the effect of the electric field on the charge distribution [190]. Actually, these molecules have strongly anisotropic polarizabilities. In a more recent study, it was demonstrated that the isomeric ratio also depends on the counterion [191]. 

AI3-00040, see Cyclohexanol AI3-00041, see Cyclohexanone AI3-00045, see Diacetone alcohol AI3-00046, see Isophorone AI3-00050, see 1,4-Dichlorobenzene AI3-00052, see Trichloroethylene AI3-00053, see 1,2-Dichlorobenzene AI3-00054, see Acrylonitrile AI3-00072, see Hydroquinone AI3-00075, see p-Chloro-rrr-cresol AI3-00078, see 2,4-Dichlorophenol AI3-00085, see 1-Naphthylamine AI3-00100, see Nitroethane AI3-00105, see Anthracene AI3-00109, see 2-Nitropropane AI3-00111, see Nitromethane AI3-00118, see ferf-Butylbenzene AI3-00119, see Butylbenzene AI3-00121, see sec-Butylbenzene AI3-00124, see 4-Aminobiphenyl AI3-00128, see Acenaphthene AI3-00134, see Pentachlorophenol AI3-00137, see 2-Methylphenol AI3-00140, see Benzidine AI3-00142, see 2,4,6-Trichlorophenol AI3-00150, see 4-Methylphenol AI3-00154, see 4,6-Dinitro-o-cresol AI3-00262, see Dimethyl phthalate AI3-00278, see Naphthalene AI3-00283, see Di-rj-butyl phthalate AI3-00327, see Acetonitrile AI3-00329, see Diethyl phthalate AI3-00399, see Tributyl phosphate AI3-00404, see Ethyl acetate AI3-00405, see 1-Butanol AI3-00406, see Butyl acetate AI3-00407, see Ethyl formate AI3-00408, see Methyl formate AI3-00409, see Methanol AI3-00520, see Tri-ocresyl phosphate AI3-00576, see Isoamyl acetate AI3-00633, see Hexachloroethane AI3-00635, see 4-Nitrobiphenyl AI3-00698, see IV-Nitrosodiphenylamine AI3-00710, see p-Phenylenediamine AI3-00749, see Phenyl ether AI3-00790, see Phenanthrene AI3-00808, see Benzene AI3-00867, see Chrysene AI3-00987, see Thiram AI3-01021, see 4-Chlorophenyl phenyl ether AI3-01055, see 1.4-Dioxane AI3-01171, see Furfuryl alcohol AI3-01229, see 4-Methyl-2-pentanone AI3-01230, see 2-Heptanone AI3-01231, see Morpholine AI3-01236, see 2-Ethoxyethanol AI3-01238, see Acetone AI3-01239, see Nitrobenzene AI3-01240, see I idine AI3-01256, see Decahydronaphthalene AI3-01288, see ferf-Butyl alcohol AI3-01445, see Bis(2-chloroethoxy)methane AI3-01501, see 2,4-Toluene diisocyanate AI3-01506, see p,p -DDT AI3-01535, see 2,4-Dinitrophenol AI3-01537, see 2-Chloronaphthalene... 

Emulsions based on lipophilic iodized and/or bromated substances with emulsifiers and derivatives of cyclopenta-phenanthrene Polyiodinated phenyl fatty acid compoimds Emulsion of iodinated lipids 6-Iodoethylated starch... 

Reduction of phenyldiazonium chloride in acetonitrile containing a high concentration of an aromatic substrate, which can act as a free-radical trap, leads to phenylation of the substrate in 14 - 33% yields together with 50 - 50% of benzene formed by phenyl radical attack on the acetonitrile [132], Intramolecular capture of the phenyl radical, in an electrochemical equivalent of the Pschorr reaction, is much more successful and phenanthrene derivatives can be prepared in 90 - 96% yield [133],... 

Cohare and co-workers reported that aristolactam BU (22) was prepared, following Kupchen s method, by Perkin condensation of 6-bromo-3,4-di-methoxy phenyl acetic acid (119) and o-nitrobenzaldehyde (120) (Scheme 14). The 2-bromo-4,5-dimethoxy-2 -nitro-ds-stilbene-a-carboxylic acid (121) was obtained. The nitro group of 121 was reduced with ferrous sulfate and ammonium hydroxide, and the resulting 2-bromo-4,5-dimethoxy-2 -amino-cw-stilbene-a-carboxylic acid (122) without purification was submitted to the Pschorr phenanthrene synthesis to yield l-bromo-3,4-dimethoxyphen-anthrene-lO-carboxylic acid (123). The phenanthrylamine 124 was prepared from 123 via a Schmidt reaction, and, by treatment with n-butyllithium and CO2, 124, afforded 22 (42). 

Included in this section are oxidations of benzene and phenyl rings, and in general the oxidation of aromatic and polycyclic aromatic compounds. The main catalyst for this type of reaction is RuO. The earliest example was the use of stoich. RuOy CCI4 for phenanthrene oxidation [239], while the first catalytic reagent was RuO / aq. Na(I04)/acetone for oxidation of pyrene [240]. Another early example was the conversion of diketo compounds to the nor-diketo acids, with concomitant destruction of the two phenyl rings by RuO /aq. NallO l/acetone (Fig. 3.18, 3.2.2.1) [206]. 

Meanwhile P. de Koe could synthesize by a similar procedure cristalline air sensitive lO-Phenyl-9-pho ha-phenanthrene m.p. 124-131 °C,, ax 339 nm (11900) in ether (private communication by Dr. Vermeer). 

Dihydrophenanthrene has been prepared from 2,2 -bis(bromomethyl)biphenyl and sodium 8 from the reduction of 2,2 -diiodobibenzy 1 in the presence of 1% palladium on barium carbonate catalyst 8 by the hydrogenation of phenanthrene in the presence of nickel8 or copper-chromium oxide catalyst 10 and by the coupling of 2,2 -bis(bromomethyl)biphenyl with lithium phenyl.11... 

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