Acenaphthenols

Bei der WAGNER-MEERWEiN-Umlagerung eines Isomeren (vermutlich der cis-Form) von 2-Phenyl-l-acenaphthenol-[l-14C] mit P20B findet Phenylwanderung zu 7,5% statt [Bonner und Collins (26)]. 

B) Acenaphthenol.—The acetate obtained as above is dissolved in 275 cc. of methanol in a 2-1. round-bottomed flask, and a solution of 40 g. (1.2 equiv.) of sodium hydroxide in 400 cc. of water is added (Note 7). This mixture is refluxed for two hours (Note 7) and then cooled below 20°. The yellow crystalline acenaphthenol is collected on a filter and washed well with about... 

II., and the acenaphthenol is allowed to crystallize. After filtering with suction and washing with cold benzene (about 500 cc.) until the wash solvent is colorless, the acenaphthenol is obtained as practically colorless needles, m.p. 144.5-145.50 (corr.) (Note 9). It weighs 117-121 g. From the filtrate may be obtained an additional quantity of material which on one recrystallization gives only 3-5 g. of pure acenaphthenol. The total yield amounts to 120-126 g. (70-74 per cent of the theoretical amount based on the acenaphthene). 

The acenaphthenol acetate contains small amounts of acenaphthene and acenaphthenone but is pure enough for the next step. 

The dark violet color appearing on addition of the alkali is probably due to the presence of acenaphthenone. Crystalline acenaphthenol begins to separate almost immediately after the alkali has been added. Care must be taken in heating to refluxing because when heated too rapidly the acenaphthenol crystallizes suddenly from solution and the heat evolved may blow part of it out through the condenser. 

If the charcoal treatment is omitted, the acenaphthenol obtained is light yellow but practically pure. 

Acenaphthenol has been prepared in poor yield by the oxidation of acenaphthene with lead dioxide 2 and it is among... 

Irradiation of single crystals of 1 in the solid state yields cis-1,2-diphcnylacc-naphthen-l-ol 2 as main product, with up to 97% de and 86% ee. Only a small amount of rrans-acenaphthenol 3 is also generated in the solid state, presumably due to an increased thermal motion of the molecules in the crystal during the irradiation (40-55 °C). 

Acenaphthenequinone, 24,1 Acenaphthenol-7, 21,1 Acenaphthenol acetate, 21,1 Acenaphthenone, 21, 3 /9-3-Acenaphthenylcarbonylpropi-... 

From 1-acenaphthenol Olah et al. (1973b) generated the 1-acenaphthenium ion [331] and observed its H- and C-nmr spectra in the temperature range —90°C to -t-40°C. Above +40°C [331] decomposed rapidly. They found [331] to be the first static secondary carbocation having an adjacent methylene group since its spectrum was independent of temperature. The spectrum was similar to the spectra of several monosubstituted analogues [332 R = CH3, C2H5 or OH]. 

For example, oxidation of acenaphthene by red lead in acetic acid gives 7-acenaphthenol acetate, from which 7-acenaphthenol is obtained by saponification with methanolic sodium hydroxide. Phenols may be prepared indirectly from aromatic aldehydes by oxidation with peracetic acid followed by hydrolysis of the resulting aryl formate. "... 

The half-life of acenaphthene in the bluegill fish is less than 1 day. A Beijerinckia species and a mutant strain, Beijerinckia species strain B8/36, were shown to oxidize acenaphthene. Both organisms oxidize acenaphthene to the same spectrum of metabolites, which included 1-acenaphthenol, 1-acenaphthene-one, 1,2-acenaphthenediol, acenaphthenequinone, and a compound that was tentatively identified as 1,2-dihydroxyacenaphthylene. 

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