1-Naphthol reaction with

In Chapter 6 the use of isoprene (Table 6.1) and of geranyl halides in reactions with naphthol and phenol respectively has been briefly referred to. In early work, isoprene with phenol in toluene containing 71% phosphoric acid, when reacted over 16 hours at ambient temperature (ref. 2) gave 4-(3-methylbut-2-enyl)phenol, the corresponding 2- isomer and 4-(3-methyl-3-hydroxybutyl)phenol in the phenolic products and in the neutral fraction, smaller proportions of 2,2-dimethylchroman and 6-(3-hydroxyisopentyl)-2,2-dimethylchroman. Hydrogenation of the unsaturated phenols afforded the respective 4- and 2-isopentylphenols. 

The first attack of the reagent is a direct oxidation by the Cu+ complex abstracting an electron and giving rise to free radicals which dimerize (Fig. 15). Figure 15 shows the reaction with naphthol and the influence of substituents on the subsequent reactions of the free radical. Phenol or naphthol free radicals do not easily react with oxygen. They rather undergo homolysis. Naphthoquinones are formed in a further... 

Sulfation by sulfamic acid has been used ia the preparation of detergents from dodecyl, oleyl, and other higher alcohols. It is also used ia sulfating phenols and phenol—ethylene oxide condensation products. Secondary alcohols react ia the presence of an amide catalyst, eg, acetamide or urea (24). Pyridine has also been used. Tertiary alcohols do not react. Reactions with phenols yield phenyl ammonium sulfates. These reactions iaclude those of naphthols, cresol, anisole, anethole, pyrocatechol, and hydroquinone. Ammonium aryl sulfates are formed as iatermediates and sulfonates are formed by subsequent rearrangement (25,26). 

Ca.rhoxyla.tlon, This is the process of iatroduciag a carboxyUc acid group iato a phenol or naphthol by reaction with carbon dioxide under appropriate conditions of heat and pressure. Important examples are the carboxylation of phenol and 2-naphthol to give sahcyhc acid and 2-hydroxy-3-naphthoic acid, respectively. 

The AMAPs (2-[ arylmethyl amino]-l,3-propanediols) are a class of planar polycyclic aromatic derivatives, which contain polar side-chains. They are known to be DNA intercalators and possess broad spectrum antitumour activity. An approach to C-radiolabelled AMAP derivative 40 used the Bucherer reaction as an initial starting reaction. 2-Naphthol was reacted with 4-bromophenylhydrazine 38 in the presence of sodium metabisulfite and HCl to afford 39. Subsequent derivatisation of 39 afforded 40. 

Methyl-[ 5,7-dinitro-8-hydroxy-naphthyl-(l)] -ether, 2,4-Dinitro-8-methoxy-naphthol-(l) ). (02N)2CioH4(OH).O.CH3, mw 264.21, N 10.61%, OB to C02 -121.12%, gold plates from ale, mp 179—80° (decompn). Sol in dil alkali ale. Prepn from 2,4-dinitro-1,8-dime thoxy-naphthalene by reaction with 2N NaOH Ref Beil 6, 5284 ... 

Nitro-3,4,6-Tribromo-2-Naphthol (1-Nitio-3,4,6-tribromo-2-oxy-naphthalene). 02N.CloH3Br3.OH, mw 425.87, N 3.29%, OB toC02 -71.38%, turns black at 135°, mp 136° (decompn). Prepn from l,3,4,6 tetrabromo-l-nitro-2-naphthol by reaction with nitric acid, then alkali Ref Beil 6,655... 

Di n itr o-8- Hyd roxy 1 -Acetoxy-Naphtha bob (2,4-Dinitro-8-acetoxy-naphthol-(l), acetic acid-r >.7-dinit.ro-8-hvdrnxv-nanhthv14r1 V tf rl f5 7. dinitro-8-hydroxy-naphthyl-(l)-acetate]. H0.(O2N)2C10H4.OCOCH3, mw 292.22, N 9.59%, OB to C02 —149.81%, gold prisms from AcOH, mp 200° (decompn). Sol in ale boiling AcOH. Prepn from 1,8-diacetoxy-naphthalene by reaction with dil nitric acid (d 1.4g/cc) at 25-30°... 

Fig. 12-8. Schematic representation of an azo coupling reaction with 1-naphthol. O diazo component, + coupling component, O monoazo compound(s), disazo compound (from Zollinger, 1973 b).

The electrostatic impasse mentioned can be circumvented (Moss and Rav-Acha, 1980) if a cationic surfactant is functionalized with an arenediazonium ion moiety. The azo coupling with the micellar diazonium ion surfactant 12.160 was found to be faster than the azo coupling with the model diazonium ion 12.161 by factors of 122 and 244, in reactions with 2-naphthol and with 2-naphthol-6-sulfonate respectively. 

While (Z)-l,2-bis(phenylsulfonyl)ethylene (140) does not add to dienes such as furan, cyclopentadiene, cyclo-octatetraene, indene and /f-naphthol, ( )-l,2-bis(phenylsulfonyl)ethylene (141) is more reactive and the reaction with furan proceeds at room temperature for 2 h to give the adduct in 95% yield. The reactivity of dienophiles having sulfonyl group in the [4 + 2]cycloaddition is shown in equation 10393,101. 

Benzo[c]furans (isobenzofurans) are very reactive but generally unstable dienes which are prepared in situ and trapped. The in ihu-generated isobenzo-furan 33 was trapped by cycloaddition reaction with bis(methyl (S)-lactyl) ester 34 to afford [32] optically active naphthols (Equation 2.12). The cycloaddition was carried out in the presence of a catalytic amount of glacial acetic acid and represents a facile one-pot procedure to synthesize substituted naphthols. 

The reaction of naphthols with ammonia and sodium bisulfite is called the Bucherer reaction. Primary amines can be used instead of ammonia, in which case N-substituted naphthylamines are obtained. In addition, primary naphthylamines can be converted to secondary, by a transamination reaction ... 

Acetylene compounds Dicobaltoctacarbonyl Formation of colored complexes. After the reagent excess has been washed out, reaction with bromine vapor yields cobalt bromide, which reacts with a-nitroso-P-naphthol to yield red chromatogram zones on an almost colorless background. [11]... 

Peroxides 1-Naphthol + N -ethyl-N (2-methanesulfon-amidoethyl)-2-niethyl-1,4-phenylenediamine (peroxide reagent) A quinonimine dyestuff is produced on reaction with peroxides. [3]... 

Solid-state reaction of p-cresol (18) and 2-naphthol (20) with 7 gave 19 (88%) and 21 (98%), respectively, in the yields indicated (Scheme 2), although these products cannot be obtained by solution reaction with Br2 (Table 5) [5]. 

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. 

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