9,10-phenanthrenequinone

In a 3-1. three-necked flask equipped with a reflux condenser, a sealed mechanical stirrer, and a 1-1. dropping funnel, are placed 100 g. (0.56 mole) of phenanthrene (Note 1), 210 g. (2.1 moles) of chromic acid (Note 2), and 1-1. of water. The stirrer is started, and 450 ml. of concentrated sulfuric acid is added from the dropping funnel into the suspension at such a rate that gentle boiling is induced (Note 3). After addition of the sulfuric acid is complete, a mixture of 210 g. (2.1 moles) of chromic acid and 500 ml. of water is added carefully to the reaction mixture from the dropping funnel (Note 4). The resulting mixture is boiled under reflux for 20 minutes. 

After being cooled to room temperature the reaction mixture is poured into an equal volume of water and chilled to 10° in an ice bath. The crude precipitate is separated by suction filtration and thoroughly washed with cold water until the washings no longer show any chrome green color. The precipitate is triturated with three 300-ml. portions of boiling water and filtered to remove the diphenic acid formed in the reaction. The precipitate is then triturated with several (4-6) 300-ml. portions of hot 40% sodium 

Reilly Tar and Chemical Company practical grade phenan-threne is crystallized from boiling toluene using Norit. One crystallization is sufficient to produce material melting at about 99.5°. The checkers employed Eastman Kodak Company technical grade (90%) phenanthrene. 

Technical grade chromic acid (99.5% Cr03) in flake form was used. 

It is safe to add 100 ml. of acid all at once to start the oxidation, but as soon as the temperature rises to 70-75° the remainder must be added slowly in order to avoid violent boiling. 

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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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