9,10-Phenanthrenequinones

Deriv Diacetylpolyporic acid, yellow needles (benzene), mp 212 °C, by acetylation of polyporic acid with AcjO-pyridine StL Pseudocyphellaria coronata (Mull.Arg.) Malme 

Deriv Diacetylbiruloquinone, yellowish crystals, mp 132-134 °C, from biruloquinone with AC2O-H2SO4 

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Molecular electrostatic potentials have been used to explain the regioselectivity exhibited in the Diels-Alder cycloaddition reactions between 1-trimethylsilyloxy-butadiene and the quinones 5-formyl-8-methyl-1,4-naphthoquinone, 5-methoxy-7-methyl-1,4-phenanthrenequinone, and 5,6,7-trimethyl-1,4-phenanthrenequinone.128 The intramolecular Diels-Alder reaction of masked o-benzoquinones (123) with a variety of dienes provides adducts (124) which rearrange to functionalized ris-decal ins (125) with complete stereocontrol of up to five stereocentres. This methodology ... 

Phenanthrenequinone [84-11-7] dioxane or 95% EtOH and dried under vacuum. 

Cyclohexanedione, trimethyl orthoformate, CSA, MeOH, 61 yield. 9,10-Phenanthrenequinone and 2,3-butanedione were similarly converted to diacetals by this method." ... 

Brennan, J.F., and Beutel, J. (1969) Quinone photochemistry. II. The mechanism of photoreduction of 9,10-phenanthrenequinone and 2-tert-butyl-9,10-anthraquinone in ethanol. J. Phys. Chem. 73, 3245-3249. 

Peroxyacyl nitrates, see Acetaldehyde, Butane, 2-Bntanone, 2,3-Dimethylbntane Peroxybenzoic acid, see Toluene Peroxynitric acid, see Formaldehyde Peroxypropionyl nitrate, see 2-Methylpentane, Pentane Phenanthrene, see Anthracene, Bis(2-ethylhexyl) phthalate, Naphthalene Phenanthrene-9,10-dione, see Phenanthrene 9,10-Phenanthrenequinone, see Phenanthrene 4-Phenanthroic acid, see Pyrene... 

A broad choice of 1,4,5-trisubstituted imidazoles can be prepared with the aid of the novel synthon BETMIP (68) and primary amines, as shown in Scheme 55. The resulting intermediate 139 reacts without isolation directly with a-diarylketones (140) to afford 1-substituted 4,5-diarylim-idazoles (141). Cycloheptylamine, benzylamine, dodecylamine, and 4-dimethylaminoaniline can be employed as amines. Reactive 1,2-diketones include benzil, 4-chlorobenzil, and 9,10-phenanthrenequinones (90H2187). 

Djerassi and Engle showed that stoich. RuOyCCl oxidised phenanthrene to 9,10-phenanthrenequinone (Table 3.5) [239], The first catalytic reaction involving RuO was that of pyrene with RuO /aq. Na(IO )/acetone, giving a mixture of pyrene-4,5-quinone, pyrene-1,6-quinone, the lactol of 4-form-ylphenanthrene-5-carboxylic acid (OsOyH O /acetone was more specific, giving pyrene-4,5-quinone) [240],... 

Cycloadditions have also been used to form benzoxazines, especially in the syntheses of photochromic materials. The reactants are typically an alkene such as 296 and a phenanthrenequinone monoxime or a l-nitroso-2-naphthol 295. Scheme 32 shows the synthesis of two photochromic materials 297 and 116 <1981TL3945>. The latter is a spirooxazine, for which a two-step mechanism, also shown in Scheme 32, was later suggested <2004BMC1037>. 

Isocyanates 345 react with phenanthrenequinone 346 and triphenylarsine oxide to give photochromic oxazines 347 (Equation 48) <1993PS(81)37>. The isocyanate can be replaced by a phosphinimine and the phenanthrene structure can also be replaced by the corresponding phenanthroline (Equation 49) <2003WO42195>. The /ra r-fused tetrahydrooxazine 349 was prepared from epoxide 348 and 2-aminoethyl sulfate (ethanolamine 0-sulfonic acid) (Equation 50) <1987AP625>. 

The solid state photochemical reaction of indole with 1,4-naphthoquinone yielded 5H-dinaphtho(2,3-a 2, 3 -c)carbazole-6,ll,12,17-tetrone in addition to 2-(3-indolyl)-1,4-naphthoquinone which was also the only product in the solution photoreaction. Solventless thermochemical reactions of indole with phenanthrenequinone in the presence or absence of zinc chloride gave 10-(lH-indol-3-yl)-9-phenanthrenol and 9,10-dihydro-9-(lH-indol-3-yl)-10-(3H-indol-3-ylidene)-9-phenanthrenol or 10,10-di-lH-indol-3-yl-9(10H)-phenanthrenone, respectively. All of these products were only obtained in trace amounts in corresponding solution reactions, and are different from the adduct 10-hydroxy-10-(lH-indol-3-yl)-9(10H)-phenanthrenone obtained in the solution photoreaction (Wang et al., 1998). 

Phenanthrenequinone has been prepared by treatment of phe-nanthrene with chromic acid in acetic acid 5 potassium dichromate in sulfuric acid 3-6 hydrogen peroxide in acetic acid 6 7 and selenium dioxide above 250°.8 It can also be prepared from benzil with aluminum chloride at 120° 9 and from biphenyl-2,2 -dialdehyde with potassium cyanide.10... 

Figure 5.16. Attachment of a -conjugated molecule to the Si(100)-2x 1 surface using a hetero-Diels-Alder cycloaddition. Hamers and workers reacted 9,10-phenanthrenequinone, a di-carbonyl, with the surface, leading to aromatic rings oriented perpendicular to the surface [261].

Phenanthrenequinone free of anthraquinone is available from Aldrich Chemical Company, Inc., or from J. T. Baker Chemical Company. It should be recrystallized from benzene before use. 

Phenanthrenequinone (8) 9,10-Phenanthrenedione (9) (84-11-7) Lithium aluminum hydride Aluminate (1-), tetrahydro, lithium (8), Aluminate (1-), tetrahydro-, lithium, (T-4)- (9) (16853-85-3) N,/V-Dimethylformamide dimethyl acetal Trimethylamine, 1,1-dimethoxy- (8) Methanamine, 1,1-dimethoxy-(V,N-dimethyl- (9) (4637-24-5)... 

In order to investigate the structural requirements for the strong redox dependence, AEia values were also measured for anthraquinone, 12, and benzyl, 13, in the presence of 5 equivalents of diphenylurea in DMF. Under these conditions, phenan-threnequinone gives a shift of 61 mV, whereas anthraquinone gives a shift of only 8 mV and benzil 5 mV. Unlike phenanthrenequinone, the urea can only H-bond to one carbonyl oxygen at a time with anthraquinone. Two bifurcated H-bonds are possible, but these together would be much weaker than the two close to linear H-bonds possible with oquinones. A similar situation arises with benzil, since rotation about the central —C bond will be hindered in the radical anion and the favored conformation will have the oxygens trans due to electrostatic repulsion and steric effects. 

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