2 -Hydroxy-1- naphthalene-4-acid

Supplement (combined with Volume XII) XI, 2nd 1933 1605-1739 2. Sulphonic acids Benzenesulphonic acid, 26. p-Toluenesulphonic acid, 97. Naphthalene - sulphonic acid, 155. Hydroxy-Sulphonic acids Phenol-sulphonic acid, 234. Naphthol-sulphonic... 

Some green algae are able to use aromatic sulfonic acids (Figure 2.4a) (Soeder et al. 1987) and aliphatic sulfonic acids (Figure 2.4b) (Biedlingmeier and Schmidt 1983) as sources of sulfur. Cultures of Scenedesmus obliquus under conditions of sulfate limitation metabolized naphthalene-l-sulfonate to l-hydroxy-naphthalene-2-sulfonate and the gluco-side of naphth-l-ol (Kneifel et al. 1997). These results are consistent with formation of a 1,2-epoxide followed by an NIH shift. 

Partial reduction of polyarenes has been reported. Use of boron trifluoride hydrate (BF3 OH2) as the acid in conjunction with triethylsilane causes the reduction of certain activated aromatic systems 217,262 Thus, treatment of anthracene with a 4-6 molar excess of BE3 OH2 and a 30% molar excess of triethylsilane gives 9,10-dihydroanthracene in 89% yield after 1 hour at room temperature (Eq. 120). Naphthacene gives the analogously reduced product in 88% yield under the same conditions. These conditions also result in the formation of tetralin from 1-hydroxynaphthalene (52%, 4 hours), 2-hydroxy naphthalene (37%, 7 hours), 1-methoxynaphthalene (37%, 10 hours), 2-methoxynaphthalene (26%, 10 hours), and 1-naphthalenethiol (13%, 6 hours). Naphthalene, phenanthrene, 1-methylnaphthalene, 2-naphthalenethiol, phenol, anisole, toluene, and benzene all resist reduction under these conditions.217 Use of deuterated triethylsilane to reduce 1-methoxynaphthalene gives tetralin-l,l,3-yielding information on the mechanism of these reductions.262 2-Mercaptonaphthalenes are reduced to 2,3,4,5-tetrahydronaphthalenes in poor to modest yields.217 263... 

Fig. 34. Orthorhombic system. (See also Fig. 25.) a. Unit cell type.. (H.COO),Sr.2HsO. Cla8s222. Left-and right-handed crystals, c. 1-Brom, 2-hydroxy-naphthalene. Class 222. d. Picric acid, Class mm. e. Oxalic acid. Class mmm. /. C,Br. Class mmm.

Lower-sulfonated subsidiary colors of sunset yellow, among them 5-(phenylazo)-6-hydroxy-naphthalene-2-sulfonic acid (ANSC) and 4-[(2-hydroxynaphthalene-l-yl)azo]benzenesulfonic acid (BNSC), were determined by reverse-phase HPLC using Novapak Cl 8 and gradient elution with a water-tetrahydrofuran solvent system buffered with ammonium acetate (192). 

A method frequently used to determine aromatic amines in water-soluble dyes involves their extraction with chloroform, followed by diazotization of amines and coupling of diazonium salts with a reagent R-salt (disodium-3-hydroxy-naphthalene-2,7-disulfonate) or pyrazolone T (4,5-dihydro-5-oxo-l-(4-sulfophenyl-)l/7-pyrazole-3-carboxylic acid). The separated products are detected by UV-VIS spectrophotometry or fluorescence (210-212). 

Jew and Park achieved a highly enantioselective synthesis of (2S)-a-(hydroxy-methyljglutamic acid, a potent metabotropic receptor ligand, through the Michael addition of 2-naphthalen-l-yl-2-oxazoline-4-carboxylic acid tert-butyl ester 72 to ethyl acrylate under phase-transfer conditions [38]. As shown in Scheme 5.36, the use of BEMP as a base at —60 °C with the catalysis of N-spiro chiral quaternary ammonium bromide le appeared to be essential for attaining an excellent selectivity. 

Concrete may use plasticizers (e.g., sulphonated melamine and naphthalene formaldehyde condensates), air-entraining agents (aIkyI/aryl sulfonate surfactants), retarders (hydroxy carboxylic acids such as polyethylene glycol mono-p-nonylphenyl ether) and surface washes (benzalkonium chloride) (RAIA 1997). Little has been published on air emissions from concrete additives, their leaching into surface waters appearing to be of greater environmental concern (Ruckstuhl, 2001). 

A particularly important class of coupling components are the aminohydroxy-naphthalenesulfonic acids. Appropriate variation of the disazo component permits the development of shades ranging from orange to black. Orange and scarlet are achieved with I-acid (6-amino-l-hydroxy-naphthalene-3-sulfonic acid) and y-acid (7-amino-1-hydroxynaphthaIcne-3-sulfonic acid), whereas H-acid (8-amino-l-hydroxynaphthalene-3,6-disulfonic acid) and K-acid (8-amino-l-hydroxy-naphthalene-3,5-disulfonic acid) derivatives are useful for red to bluish-red hues. Extremely lightfast red shades are also accessible with disazo dyes ( brown dyes ). For chemical structures see Section 3.1.5). 

Alkaline glucose converts the diazonium salts of l-amino-2-hydroxy-naphthalene-4-sulfonic acid and its halogen, nitro, carboxyl, or sulfonic acid derivatives into the corresponding 2-hydroxynaphthalene-4-sul-fonic acids.126 According to this patent, the yields are nearly quantitative. 

From Phenyl Vinyl Acetic Acid.—A second synthesis very closely analogous to the preceding is from phenyl vinyl acetic acid (p. 700), which has the constitution CeHs—CH = CH—CH2—COOH. When this is heated it loses water and yields a hydroxy naphthalene or naph-thol in which the hydroxyl is linked to the carbon next to the ortho carbon of the ring. 

The nitro substitution products of naphthalene are easily prepared by the action of nitric acid on the hydrocarbon. By such direct nitration the product obtained is alpha-nitro naphthalene. This is proven by the following series of reactions. Nitro-naphfhalene by reduction yields amino naphthalene, naphthylamine, which by the diazo reaction yields hydroxy naphthalene, naphthol. Now the naphthol so obtained is identical with the one resulting from the phenyl vinyl acetic acid synthesis (p. 768) and this must be the alpha compound. 

Naproxen was introduced to the market by Syntex in 1976 as a nonsteroidal antiinflammatory drug in an optically pure form. The original manufacturing process (Scheme 1) before product launch started from P-naphthol (1) which was brominated in methylene chloride to produce 1,6-dibromonaphthol (2). The labile bromine at the 1-position was removed with bisulfite to give 2-bromo-6-hydroxy-naphthalene that was then methylated with methyl chloride in water-isopropanol to obtain 2-bromo-6-methoxynaphthalene (3) in 85-90% yield from p-naphthol. The bromo compound was treated with magnesium followed by zinc chloride. The resultant naphthylzinc was coupled with ethyl bromopropionate to give naproxen ethyl ester that was hydrolyzed to afford the racemic acid 4. The final optically active naproxen (5) was obtained by a classic resolution process. The racemic acid 4 was treated with cinchonidine to fonn diastereomeric salts. The S -naproxen-cinchonidine salt was crystallized and then released with acid to give S -naproxen (5) in 95% of the theoretical yield (48% chemical yield) [8,9]. 

Direct evidence for these assignments was obtained from critical composition values obtained for two series of polyesterimides synthesised by Krichel-dorf and co-workers [76] (Table 9). In both series, a preformed unit comprising the trimellitimide of raefa-aminophenol is copolymerised with either 2-hydroxy naphthalene 6-carboxylic acid or 4-hydroxybenzoic acid. In both series, the critical value at which a mesogenic phase is first observed is 10.0, at a 1 1 composition. An isotropic phase was observed at 9.6 and below. Hence the critical value must lie between the limits of 9.6 and 10. 

Table 9 lists two series of PEIs based on copolymers of precondensed units of trimellitic anhydride and m-aminophenol, reacted with varying molar fractions (20-100%) of 2-hydroxy naphthalene 6-carboxylic acid or 4-hydroxybenzoic acid. In both series an MI score of 10 corresponded to the onset of liquid crystallinity, and an isotropic copolymer was obtained for MI < 9.6. A series of PEIs is given in Table 25, in which varying ratios of N-carboxyphenyl trimellitimide and isophthalic acid are co-reacted with phenylhydroquinone [82]. The MI values vary by only 0.1 units between compositions and more accurately pinpoint the transition between the mesogenic and isotropic state to the range 9.5-9.6. 

Suh et al.65 have reported a formal total synthesis of Mansonone F and this is described in Scheme 12. 5-Methoxy-a-tetralone (127) was converted to 1-methyl-5-hydroxy-naphthalene (128) by the standard organic reactions. Treatment of (128) with phenyl boronic acid, paraformaldehyde and propionic acid followed by catalytic hydrogenation yielded compound (129). This on alkylation gave the compound (130) which on alkaline hydrolysis was converted to acid. The acid halide underwent intramolecular Friedal-Crafts acylation affording an intermediate (131) whose transformation to Mansonone F has been accomplished by Best and Wege.59... 

Nevertheless, using the 1,8-ANS (5) method, with ANS as a guest, fluorescence increases with 10 and 11 and therefrom complex formation constants have been obtained, which are remarkably higher than that of the cyclodextrins and of open chained reference host compounds. The complex constants of 10 towards the hydroxy-naphthalene carboxylates 13 and 14 as guests have also been determined The authors suppose the intermediate formation of inclusion complexes also because of the capability of 10 and especially 12 to accelerate the hydrolysis of chloroacetic acid phenolates in water solution. The increase of the hydrolysis rate is explained by the activation of the complexed esters. 

Avoidance of Wastewater and Residues in the Production of H Acid (l-Amino-8-hydroxy-naphthalene-3 6-disulfonic acid)... 

Acetylamino-2-sulfophenylazo)-6-amino-4-hydroxy naphthalene-2-sulfonic acid, disodium salt. See Acid red 37... 

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