2-Naphthol, nitrosation

Naphthol, nitrosation of, 950 Natta, Giulio, 246, 567-570, 573 Natural gas, 57, 69 Nembutal, 845 Neomenthol, 164 Neomenthyl chloride, 206... 

Sodium Bisulfite. Sodium bisulfite [7631-90-5] NaHSO, is occasionally used to perform simultaneous reduction of a nitro group to an amine and the addition of a sulfonic acid group. For example, 4-amino-3-hydroxyl-l-naphthalenesulfonic acid [116-63-2] C qH NO S, is manufactured from 2-naphthol in a process which uses sodium bisulfite (59). The process involves nitrosation of 2-naphthol in aqueous medium, followed by addition of sodium bisulfite and acidification with sulfuric acid. 

Dyes. Sodium nitrite is a convenient source of nitrous acid in the nitrosation and diatozation of aromatic amines. When primary aromatic amines react with nitrous acid, the intermediate diamine salts are produced which, on coupling to amines, phenols, naphthols, and other compounds, form the important azo dyes (qv). The color center of the dye or pigment is the -N=N- group and attached groups modify the color. Many dyes and pigments (qv) have been manufactured with shades of the entire color spectmm. 

Bindschedler s Green (6.204) can be made by condensing p-nitroso-N,N-dimethylaniline with N,N- dimethyl aniline. A similar condensation with 2-naphthol gives Meldola s Blue (6.209 Cl Basic Blue 6), the first oxazine dye, discovered in 1879. The symmetrical Cl Basic Blue 3 (6.210) is of more commercial significance. It is synthesised by nitrosation of N,N-diethybrn-anisidine followed by condensation with N,N-diethybm-aminophenol, and is used for dyeing acrylic fibres. This dye is now classified by ETAD as toxic [73]. 

The crucial requirement of excited-state proton transfer (ESPT) is suggested by the failure of 1-naphthyl methyl ether to undergo self-nitrosation under similar photolysis conditions. The ESPT is further established by quenching of the photonitrosation as well as 1-naphthol fluorescence by general bases, such as water and triethylamine, with comparable quenching rate constants and quantum yield. ESPT shows the significance in relation to the requirement of acid in photolysis of nitrosamines and acid association is a photolabile species. 

The nitrosation of phenols proceeds in a manner similar to that of tertiary amines. For example, l-nitroso-2-naphthol has been prepared from the sodium salt of /9-naphthol by treatment with sodium nitrite and sulfuric acid near 0°C [29], This general procedure, suitably modified, has been used to prepare other nitrosophenols such as p-nitrosophenol (m.p. 135°-136°C) [30]. 

Electrophilic substitution reactions of 5-hydroxybenzo[6]thiophene have been investigated in some detail. The 4-position is the most reactive toward nitration,152 nitrosation,497 bromination,422 and formylation (Duff procedure).338 Dibromination in the presence of acetate ion affords 4,6-dibromo-5-hydroxybenzo[6]thiophene,421,422, 497 and not the 3,4-dibromo derivative, as previously believed.542 Dichlorination similarly affords the 4,6-dichloro derivative,421 and not 4,4-dich loro-4,5-dihydrobenzo[6]thiophen-5-one, as reported earlier by Fries d al.542 An interesting comparison can be made between the behavior of 5-hydroxy benzo[6]thiophene and 2-naphthol in electrophilic substitution reactions. It is clear that both positions ortho to the hydroxyl group in 5-hydroxybenzo[6]thiophene are attacked, in contrast to 2-naphthol, where only the 1-position is attacked even in the presence of an excess of the reagent. Disubstitu-... 

If the phenol is allowed to react with nitrous acid (generated in an acidified solution of sodium nitrite), the nitrosophenol may be obtained in good yield. An example is provided by the nitrosation of 2-naphthol which yields l-nitroso-2-naphthol (Expt 6.103). 

The other main source of evidence on the mechanisms of nitrosation comes from the C-nitrosation of aromatic compounds but, for this reaction, the final proton loss from the rate-determining (Challis and Higgins, 1972). Under these conditions, the overall rate and kinetic form of the reaction provide no evidence on the rate and mechanism of the nitrosation stage. Fortunately the work of Challis and his co-workers (Challis and Higgins, 1973 Challis and Higgins, 1975 Challis and Lawson, 1973) has shown that the C-nitrosation stage is rate-determining for the nitrosation of some reactive aromatic substrates (2-naphthol, azulene, 1,2-dimethylindole) in feebly acidic media and these are the reactions referred to below. 

Aromatic tertiary amines and phenolic compounds undergo nuclear nitro sation, as illustrated by the synthesis of p>nitrosodimethyl aniline (89%)i nitrosophenol (80%), and l-nitroso-2-naphthol (99%) In the reaction of a-naphthol, an isomeric mixture of the nitrosonaphthols is obtained. The nitrosation of phenols with nitrous acid usually produces p nitroso compounds however, o-nitiosophenols can be prepared by nitrosating phenols in the presence of cupric sulfate. ... 

By far the most stable nitroso compounds are those of the aromatic series. The smoothest C-nitrosation is achieved with phenols and tertiary amines having a free para-position. In benzene derivatives the nitroso group enters almost exclusively284 the para-position to the hydroxyl or amino group. In the naphthalene series the reaction is not always unidirectional 1-nitroso-2-naphthol is obtained almost quantitatively from 2-naphthol,285 but 1-naph-thol gives a mixture of about equal parts of 2- and 4-nitroso-l-naphthol.286... 

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