Naphthols from naphthalene

Cerniglia, C. E., Gibson, D. T. Van Baalen, C. (1979)- Algal oxidation of aromatic hydrocarbons formation of 1-naphthol from naphthalene by Agmenellum quadruplicatum strain PR-6. Biochemistry and Biophysics Research Communications, 88, 50-8. 

Dinitro-1-Naphthol (2,4-Dinitro-l-oxy-naphthalene). Yellow crysts, mp 139.5°. Sol in ale chlf. Prepn from naphthalene as a byproduct during nitration with dil nitric acid Hg(II) nitrate. The Lead Salt of the above can be shown as Pb[O.C loHs(N02)2]2, mw 729.57, N 7.68%, OB to C02 -76.75%. The explosive sensitivity of this salt compared to PA is 49%... 

The transformation of arenes in the troposphere has been discussed in detail (Arey 1998). Their destruction can be mediated by reaction with hydroxyl radicals, and from naphthalene a wide range of compounds is produced, including 1- and 2-naphthols, 2-formylcinnamaldehyde, phthalic anhydride, and with less certainty 1,4-naphthoquinone and 2,3-epoxynaphthoquinone. Both 1- and 2-nitronaphthalene were formed through the intervention of NO2 (Bunce et al. 1997). Attention has also been directed to the composition of secondary organic aerosols from the photooxidation of monocyclic aromatic hydrocarbons in the presence of NO (Eorstner et al. 1997) the main products from a range of alkylated aromatics were 2,5-furandione and the 3-methyl and 3-ethyl congeners. 

This displacement is accomplished by heating the sulphonated derivative at a high temperature with sodium or potassium hydroxide [64]. Typical is the preparation of 2-naphthol (4.15) from naphthalene-2-sulphonic acid (Scheme 4.21). Displacement of the sulphonic acid group occurs more readily when it is located at the a- rather then at the P-position, the former requiring a fusion temperature of about 200 °C and the latter one of about 250 °C. This difference in reactivity can be exploited to prepare naphtholsulphonic acids by fusion of suitable naphthalenedisulphonic acids. 

Supplement to b) 2-Hydroxynaphthalene ((3-naphthol) is obtained from naphthalene. The reaction sequence includes sulfonation of the starting material at 150-160°C and subsequent alkaline baking of the intermediate sodium naphthalene-2-sulfonate with sodium hydroxide at 300 to 320°C for 6 to 8 hours. After the reac-... 

Naphthylamine and also its sulphonic acids are likewise employed technically for the manufacture of azo-dyes. In the same way a-naph-thol is made from naphthalene-a-sulphonic acid by fusion with sodium hydroxide although on a smaller scale than /3-naphthol. a-Naphthyla-mine, on the other hand, is obtained by the reduction of a-nitronaph-thalene (analogy to aniline). The fusion of alkali salts of arylsulphonic acids with alkali also serves technically for the production of pure phenol and of many phenol derivatives. 

Probtem 18.63 Synthesize from naphthalene and any other reagents (a) naphthionic acid (4-amino-l-naphthalenesulfonic acid), (b) 4-amino-l-naphthol, (c) 1,3-dinitronaphthalene, (d) 1,4-diaminonaphthalene, (e) 1,2-dinitronaphthalene. Do not repeat the synthesis of any compound. ... 

Fast Red B, Bordeaux B.—One more example of an azo dye derived from naphthalene may be given in which naphthylamine is diazotized and coupled as an azo compound with a naphthol sulphonic acid. The compound 2-naphthol 3-6-di-sulphonic acid is a dyestuff intermediate known as R-salt (red salt) because it is used in making red dyes. When alpha-naphthylamine is diazotized and coupled with R-salt the resulting azo dye is known as fast red B or Bordeaux B. Its constitution is... 

Example ft-Naphthol from Sodium-0-Naphthalene Sulphonate and Sodium Hydroxide1... 

Both a-naphthol and /1-naphthols are important organic intermediates particularly for pesticides and dyes manufacturing. Traditionally, both are made from naphthalene, a two-ringed... 

The transformation of arenes in the troposphere has been discussed in detail (Arey 1998). Destruction can be mediated by reaction with hydroxyl radicals, and from naphthalene, a wide range of compounds is produced, including 1- and 2-naphthols, 2-formylcinnamaldehyde, phthalic anhydride, and, with less certainty, 1,4-naphthoquinone and 2,3-epoxynaphthoquinone. Both... 

Bieberich scarlet, one of the naphthol azo dyes, a very important group, is, like indigo, prepared from, naphthalene as starting material. 

In the naphthol series direct sulfonation is usually restricted to / -naphthols, since a-naphtholsulfonic acids are generally obtained in other ways, such as from naphthalene-di- and -tri-sulfonic acids in an alkali meii or from 1-amino-naphthalenesulfonic acids by the Bucherer reaction. 

When cresylic acid (or cresol, C 6 H 4 (CH 3 )OH.) is acted upon by nitric acid it produces a series of nitro compounds very similar to those formed by nitric acids on phenol, such as soditrm di-nitro-cresylate, known in the arts as victoria yellow. Naphthol, a phenol-like body obtained from naphthalene, under the same conditions, produces sodium di-nitro- naphthalic acid, C 10 H 6 (NO 2 ) 2 0. The explosive known as "roburite" contains chloro-nitro-naphthalene, and romit, a Swedish explosive, nitro-naphthalene. 

A Intermediates derived from naphthalene. Naphthalene is the source of jS-naphthol (2.6.1.2), a-nitronaphthalene (1-nitronaphthalene) and 1,3,6-naphthalenetrisulphonic acid (Figure 2.7). A selection of the chief intermediates from jS-naphthol and the above two primary products is given in Figures 2.18, 2.19 and 2.20 and the corresponding Tables 2.13,2.14 and 2.15. 

Figure 11.18 Two processes for the production of paraphenylenediamine (PPDA) jS-Naphthol is produced from naphthalene as follows in Figure 11.19.

Perhydroxylation and Epoxidation. By metabolic perhydroiqrl-ation is meant formation of dihydrodiols from compounds containing double bonds. lodobenzene, chlorobenzene, naphthalene, anthrar cene, phenanthrene, benzpyrene, and 1-chloro- and 1-bromonaphtha-lene are known to undergo this transformation (Table XIII). 1,2-Dihydroxy-l,2-dihydronaphthalene, but not oc-naphthol, is formed from naphthalene in the presence of liver slices (95) conversion of diol to phenol under these conditions cannot be detected. The major product formed from naphthalene by rabbit liver microsomes is a dihydrodiol-like material which yields a-naphthol upon add hydrolysis (558). 

The role played by dihydrodiols in the metabolic formation of phenols and their conjugated derivatives from aromatic substances is at present undecided. In theory, upon dehydrating a dihydrodiol, the phenolic hydroxyl should remain at that carbon most activated toward electrophilic substitution (14,625). This criterion of mechanism is satisfied in some instances (i.e., the halogenobenzenes (379, 682) and benzonittile (681). Furthermore, compounds that arise from the metabolism of aromatic hydrocarbons also arise from metabolism of dihydrodiols which are formed from them (94,163). However, hver slices and Uver microsomes capable of forming dihydrodiol from naphthalene form neg%ible amounts of naphthol (95,558). 

Bucherer Reaction. The reversible conversion of a naphthylamine to a naphthol in the presence of an aqueous sulfite or bisulfite is valuable in the synthesis of naphthalene dye intermediates. It is used in the preparation of naphthols from naphthylamine or is employed for the reverse transformation—naphthyl-amines from naphthols ... 

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