Ace naphthenes

Davies and Warren have investigated the nitration of naphthalene, ace-naphthene and eight dimethylnaphthalenes in acetic anhydride at o °C. Rates relative to naphthalene were determined by the competition method, and the nitro-isomers formed were separated by chromatographic and identified by spectrophotometric means. The results, which are summarised in the table, were discussed in terms of various steric effects, and the applicability of the additivity rule was examined. For the latter purpose use was made of the data of Alcorn and Wells (table 10.2) relating to the nitration of monomethyl-naphthalenes at 25 °C. The additivity rule was found to have only limited utility, and it was suggested that the discrepancies might be due in part to the... 

Whereas tetrafluorobenzyne only forms one adduct (49) with ace-naphthene, two adducts (50) and (51) were formed with acenaphthylene 9°). The formation of the compound (51) clearly reflects the high nucleo-philicity of the 1,2-double bond even though the cyclo-adduct cannot be formed by an orbital symmetry allowed concerted process. 

A major group of photochemical reduction reactions are oxidation-reduction processes. As typical examples, phenazine (CXXI) and alloxan (CXXIII) are reduced by ethanol to give dihydrophenazine (CXXIl)/ 2 and alloxantin (CXXIV).42 Isatin (CXXV) in the presence of ace-naphthene (CXXVI) is reduced to isatide (CXXVII).204 The photoreaction proceeds at the expense of the alcohol, or (CXXVI) acetaldehyde and acenaphthylene (CXXVIII), are formed as by-products respectively. The formation of CXXVII may be due to the interaction of CXXV with the intermediate oxindole (CXXIX). 

To date the mercurated arene radical cation is known for biphenylene [87], ace-naphthene, pyracene, hexahydropyrene, triptycene, p-terphenyl, tetramethylnaph-thopyran, anthracene, dibenzodioxin [89], and 4-tert-butylanisole [88]. In certain cases multiple mercuration is observed, for example in case of diphenylene [87] and dibenzodioxin [89]. Mercuration causes a decrease in -value and always occurs at the site where the local coefficient of the Huckel HOMO of the hydrocarbon is greatest, and there is a constant ratio of about 20.6 between the hyperfine couplings by the Hg [l, abundance 16.84 %) which has been introduced, and by the proton which has been displaced [89]. EPR spectroscopic evidence is reported for 8, 9, 10, 11, 12, 13, 14, 15 and 16 as new examples of recently recognized alternative mechanism of arene mercuration in which collapse of ArH +Hg(TFA)2 radical ion pair leads to arylmercury trifluoroacetate ArHg(TFA) + [90]. 

The stereochemistry of acetoxylation at benzyl positions of substituted indanes and ace-naphthenes was investigated in detail [294-296]. the cis—trans ratio of diactoxylated products is significantly larger in the anodic than in chemical processes. 

Other reactions. Blum et a/.15 report that the organometallic complex causes decarbonylation of carbonyl compounds and desulfonation of aromatic sulfonyl chlorides. They noted also that 20-g. samples of ethylbenzene, fluorene, and ace-naphthene on being heated with 100 mg. of rhodium complex for 5 hrs. at 130° are oxidized to the extent of 10-60% to acetophenone, fluorenone, and acenaphthenone. 

Acenaphthene. The catalytic vapor phase oxidation of ace-naphthene results in the formation of a variety of products such as acenaphthylene, aceuaplithoquinone, naphthaldehydic add, naphthalic anhydride, maldc acid, etc.48 Catalysts similar to those used in the oxidation of anthracene... 

Depth Acenaphthylene Ace-naphthene Fluorene Phenanthrene Anthracene Fluoranthrene Pyrene... 

It is of interest that, through steric inhibition of r onance of the free amine, i T,A-dimethyl-l-naphthylamine is a slightly stronger base than A, iV-dimethyl-2-naphthylamine, but the obstruction in ace-naphthene is insufficient to make A, A-dimethyl-4-aminoacenaphthene a stronger base than A,A-dimethyl-5-aminoacenaphthene. 

---