Naphthalenes 1-naphthols, 1,4-dihydro

Uses Intermediate for phthalic anhydride, naphthol, 1,4-naphthoquinone, 1,4-dihydro-naphthalene, 1,2,3,4-tetrahydronaphthalene (tetralin), decahydronaphthalene (decalin), 1-nitro-naphthalene, halogenated naphthalenes, naphthol derivatives, dyes, explosives mothballs manufacturing preparation of pesticides, fungicides, detergents and wetting agents, synthetic resins, celluloids, and lubricants synthetic tanning preservative emulsion breakers scintillation counters smokeless powders. 

Biological. In activated sludge, 9.0% of the applied amount mineralized to carbon dioxide after 5 d (Freitag et al, 1985). Under certain conditions. Pseudomonas oxidized naphthalene to cis-1,2-dihydro-1,2-dihydroxynaphthalene (Dagley, 1972). This metabolite may be oxidized by Pseudomonasputida to carbon dioxide and water (Jerina et ah, 1971). Under aerobic conditions, Cunninghamella elegans degraded naphthalene to 1-naphthol, 2-naphthol, trans-l, 2-A hyAxoxy-... 

Consecutive condensations of 2-naphthol, allylamine, and dibromomethane comprised another route to naphthalene-condensed 1,3-oxazines. A preheated mixture of allylamine and dibromomethane was reacted with 2-naphthol 152 to yield the aminophenol intermediate 520, which was cyclized with the salt formed in the reaction of dibromomethane and diethylamine to give 3-allyl-3,4-dihydro-2//-naphth[l,2-< ][l,3]oxazine 521 on further reaction (Scheme 98) <2004SC2253>. 

Condensation of 7-methoxy-3,4-dihydro-1(2H)-naphthal-enone with tetramethylene dibromide by means of NaH in benzene or tert amyl alcohol gives 3,4-dihydro-7-methoxy-2,2-tetramethylene-1(2H)-naphthalene (bp (0,05 mbar) 120-123 °C), which is treated with acetonitrile and butyllithium in THF yielding 1-hydroxy-7-methoxy-1,2,3,4-tetrahydro-2,2-tetramethylene-1-naphthalene-acetonitrile (mp 140-142 °C). This compound is reduced with LiAIH4 in THF to afford hydro-2,2-tetramethylene-1-naphthol (mp 178-180 °C), and isomerized to 4a-(2-aminoethyl)-1,2,3,4,4a,9-hexahydro-6-methoxy-phenantrene i (mp 187 °C). 

Further bromination of 3,4,6-tribromo-5-hydroxybenzo[6]thio-phene affords the 2,3,4,6-tetrabromo derivative in the absence of acetate ion, and 3,4,4,6-tetrabromo-4,5-dihydrobenzo[6]thiophen-5-one in the presence of acetate ion. 421 On treatment of 3,4-dibromo-, 4,6-dibromo-, 3,4,6-tribromo-, or 2,3,4,6-tetrabromo-5-hydroxybenzo-[6]thiophene with nitric acid in acetic acid, the corresponding unstable orange crystalline 4-bromo-4-nitro-4,5-dihydrobenzo[6]thio-phen-5-one is obtained.152,421 Hence, once both positions ortho to the hydroxyl group in 5-hydroxybenzo[6]thiophene are occupied by bromine, the properties of these compounds are analogous to the properties of l-bromo-2-naphthol which, on bromination in acetic acid in the presence of acetate ion, affords l,l-dibromo-l,2-dihydro-naphthalen-2-one whereas, in its absence, it affords l,6-dibromo-2-naphthol.616 The behavior of l-bromo-2-naphthol and its derivatives on nitration is similar to that of 4,0-dibromo-5-hydroxybenzo[6]thio-phene and its derivatives.162,616... 

Table 2 summarizes pK measurements for the simplest protonated aromatic hydrocarbons. The columns to the right and left of the benzenonium ion correspond to benzoannelation of ions subject to protonation at the 2- and 4-positions of the benzene ring, respectively. In the parent ion the two positions correspond to resonance forms (one of which has been rotated through 120° in the table). The naphthalenonium ion 17 is shown as being formed from the 1,4-water adduct (hydrate) of naphthalene. It may also be formed from the isomeric 2,1 hydrate (l,2-dihydro-2-naphthol) with pAR = -6.7 and pAn2o = 13.7. 

Touring studies at NIH, it was discovered that enzymatic hydroxyla-tion of (deuterated or tritiated) substrates leads to a novel and mechanistically important shift of the deuterium or tritium from the point of substitution by oxygen to an adjacent position in the aromatic ring (12). [It has been found recently that arene oxides are likely intermediates in the metabolism of aromatic compounds. They rearrange to phenols with concomitant NIH Shift, and they are enzymatically converted to dihydrodiols and premercapturic acids. In addition, naphthalene oxide has now been demonstrated as an intermediate in the conversion of naphthalene to a-naphthol, frari5-l,2-dihydro-I,2-dihydroxynaphthalene, and... 

Naphthalene, 21, 34, 44, 45 2-acetamido-, 60 dihydro-, 45 tetrahydro-, 45 Naphthoic acid, 51 a-Naphthol, 8, 44 /3-Naphthol, 8, 44 Naphthol, 6-acetamido-2-, 60 2-amino-1-, 60 Naphthoresorcinol, 5-8, 29 Naphthylamines, 60 Neomenthol, 73 Nicotinic acid, 63... 

Coho salmon naphthalene 1-naphthol 1-naphthyl-glucuronate 1-naphthyl-glucoside mercapturic acid 1-naphthyl sulphate 1,2-dihyroxy-1,2-dihydro-naphthalene... 

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