N.m.r. studies on aromatic compounds. I—13C n.m.r. spectra of some mono- and disulpho-substituted hydroxycarboxylic acids

Carbon-13 n.m.r. spectra of 3-hydroxy-4-sulpho-2-naphthoic, 3-hydroxy-5-sulpho-2-naphthoic, 3-hydroxy-7-sulpho-2-naphthoic, 5-sulphosalicylic, 3-hydroxy-5,7-disulpho-2-naphthoic, 1-hydroxy-4,7-disulpho-2-naphthoic, and 3,5-disulphosalicylic acids were recorded with and without proton noise-decoupling. Analyses of the spectra were carried out for all compounds except 3-hydroxy-5-sulpho-2-naphthoic acid which dimerized. The fine splitting caused by long-range coupling was used in identifying the lines of the ¹³C n.m.r. spectra.     

Complex formation equilibria between 1-hydroxy-7-sulpho-2-naphthoic or 1-hydroxy-4,7-disulpho-2-naphthoic acid and iron(III) in 0.1M NaClO4 medium

The equilibria for formation of iron(III) complexes with 1-hydroxy-7-sulpho-2-naphthoic and 1-hydroxy-4,7-disulpho-2-naphthoic acids in aqueous 0.1M sodium perchlorate medium at 25 degrees have been studied by spectrophotometric and potentiometric methods. The data are well described in terms of a series of stepwise complexes, FeL((3-rn)+)(r) in both systems (L(n-) denotes the unprotonated ligand anion).     

P2O5-Hexamethyldisiloxane (HMDS): An Efficient System to Induce the Three-Component Reaction of Enolic Systems,Aromatic Aldehydes,and Acetonitrile

Three-component reaction of an enolizable compound, such as acetophenone, methyl acetoacetate, 4-hydroxycoumarin, 2-naphthol, or 3-hydroxy-2-naphthoic acid; an aromatic aldehyde, and acetonitrile induced by phosphorus pentoxide and hexamethyldisiloxane leads to 2-acetylamino ketones, methyl 3-(acetylamino aryl methyl)-3-oxobutanoates, 3-(acetylamino aryl methyl)-4-hydroxycoumarins, 1-(acetylamino aryl methyl)-2-naphthols, or 4-(acetylamino aryl methyl)-3-hydroxy-2-naphthoic acids in excellent yields.     

Fluorescence of zirconium-naphthalene complexes: effect of ortho-naphthalene substitution

The effect of the position of substituents on the formation of metal-naphthalene complexes has been investigated. Two positional isomers, 1-hydroxy-2-naphthoic acid (1H2NA) and 3-hydroxy-2-naphthoic acid (3H2NA), have been chosen. A comparative study of the luminescence behaviour of the two isomers in the presence of Zr(IV) has been performed. Interesting results were obtained. While 1-hydroxy-2-naphthoic acid is quenched in the presence of Zr(IV), 3-hydroxy-2-naphthoic acid produced high-fluorescence enhancement. Several pH studies were performed between pH 2.5 and 5.0 and the stoichiometries of the complexes were also established at the different pH values tested, by use of the Benesi-Hildebrand method. In addition, the formation constants have been calculated. Finally, quenching and lifetime studies were performed in an attempt to establish the type of quenching (static or dynamic) that is produced when a complex is formed between 1-hydroxy-2-naphthoic acid and zirconium metal ion.     

Synthese von 1-Hydroxy-2-naphthoesäuren aus Isocumarinen

Zusammenfassung Durch Umsetzung von Isocumarinen mit Jodessigester und Zink erhält man die analog substituierten 1-Hydroxy-2-naphthoesäureester. Unter denselben Reaktionsbedingungen liefern Cumarine Chromenylidenessigester.

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Synthesis of 1-hydroxy-2-naphthoic acids from isocoumarins

On treating isocoumarins with ethyl iodoacetate and zinc, the corresponding 1-hydroxy-2-naphthoates are obtained. Under the same reaction conditions, coumarins yield chromenylidene acetates.

     

Method for the rapid synthesis of highly functionalized 2-hydroxy-1-naphthoates. Syntheses of the naphthoic acid components of neocarzinostatin chromophore and N1999A2

We describe a four-step sequence for the synthesis of complex 2-hydroxy-1-naphthoic acids involving Z-selective olefination of benzaldehyde derivatives with a novel dioxolenone-containing phenyl phosphonate reagent, followed by dioxolenone cleavage with alkaline trifluoroethanol and oxidative cyclization (Mn(OAc)(3)) of the resultant trifluoroethyl beta-keto esters. [reaction: see text]     

Formation constants of chromium(III), scandium(III) and yttrium(III) complexes of some hydroxy naphthoic acids

The complexes of chromium(III), scandium(III) and yttrium(III) formed by 1-hydroxy-2-naphthoic acid (1,2-HNA: H2L) and 3-hydroxy-2-naphthoic acid (3,2-HNA: H2L) were investigated by potentiometry and spectroscopy at 25+/-0.1 degrees C and at an ionic strength of 0.1 M KNO3 in 50% ethanol-water (v/v) medium. The stoichiometries of these three M(III) complexes formed with these hydroxy-naphthoic acids and with hydroxo ion were defined and their formation constants were determined and compared. Thus, the removing capacities of these ligands could be examined by calculating the equilibrium concentration of Cr(III) that exists in the discharge water of various industries since Cr(III) ions are the main pollutants present during waste water treatment in our city, Bursa.     

Synthesis and clathrates of oligomeric 2-O-naphthoide macrocycles

New macrocyclic O-naphthoides 4-6 were synthesized from dehydration reactions of 3-hydroxy- and 7-tert-butyl-3-hydroxy-2-naphthoic acids, respectively. Their X-ray structures were determined and their clathrate inclusion properties were investigated. Hexamer 6 formed an inclusion clathrate with four chloroform molecules. The trimer 5, by analogy with tri-o-thymotide, was studied for its potential optical resolution effects.     

Synthesis of 4-oxo-1,3-benz- and naphthoxazinium salts from o-hydroxyarylamides

The acid-catalyzed acylation of primary and secondary o-hydroxyarylamides, the probable reaction scheme, and the possibility of the formation of 4-oxo-1,3-arenooxazinium salts and analogs in the reaction of amides of salicylic, coumaric, and 1-hydroxy- and 3-hydroxynaphthoic acids and their N-alkyl(aryl)derivatives with excess amounts of aliphatic acid anhydrides and 70% perchloric acid, as well as by the acid cyclization of O- and N-mono- and diacyl derivatives of these amides, are examined. Twelve previously unknown 2-alkyl- and 2-styryl-4-oxo-1,3-naphth[3,2-e]-and -[1,2-e]oxazinium perchlorates were synthesized. N-Methyl- and N-benzylamides of 8-acetoxy-1-naphthoic acid are formed instead of the expected peri-cyclic analogs of oxazinium salts in the reaction of 8-hydroxy-1-naphthoic acid anilides with acetic anhydride and perchloric acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1611–1616, December, 1979.Original article submitted May 31, 1978; revision submitted April 2, 1979.     

Highly efficient synthesis and chemical separation of 5-amino- and 7-amino-4-hydroxy-2-naphthoic acids

5-Amino- and 7-amino-4-hydroxy-2-naphthoic acids were synthesized for the first time via a microwave-assisted pathway. The separation of the two isomers was then conveniently achieved by exploiting their different reactivities with CDI.     

Identification and quantification of polar naphthalene derivatives in contaminated groundwater of a former gas plant site by liquid chromatography-electrospray ionization tandem mass spectrometry

A liquid chromatography (LC) method followed by electrospray ionization (ESI) and tandem mass spectrometry (MS-MS) was developed for the quantification of acidic naphthalene derivatives in the concentration range 0.1 to 100 microg/l without excessive sample preparation. For optimal sensitivity the LC-MS-MS measurements were performed recording mass fragmentation by collision induced dissociation in the multiple reaction mode. The collision energy was optimized for every analyte. The matrix effects of the sample were investigated by spiking standards of 1-naphthoic acid with humic acid (HA) and with calcium chloride. While HA decreased the signal intensity an increase was observed in the presence of calcium chloride. For the investigated groundwater samples of a tar oil contaminated site a complete separation of the analytes from the sample matrix by reversed-phase separation could be obtained. The absence of matrix effects on quantification results was confirmed by comparison of results based on external calibration with those based on standard addition of the analytes to a groundwater sample. In four groundwater samples of the contaminated site naphthalene derivatives like 1-naphthoic acid, 2-naphthoic acid, 1-naphthylacetic acid, 2-naphthylacetic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, and naphthyl-2-methylenesuccinic acid have been detected.     

Development of thermotropic liquid crystalline polymers

Wholly aromatic, thermotropic liquid crystalline (LC) terpolyesters made from 6-hydroxy-2-naphthoic acid (HNA) and 4,4′-biphenol (BP) as key components have been prepared and evaluated for utility as high performance fiber precursors. The processability and fiber properties of a specific composition (1) made from both HNA and BP were compared with those of a more well-known LC terpolyester made from p-hydroxybenzoic acid, tere- and isophthalic acids and BP (Ekonol^® type). The advantages of polymer 1 and its high-modulus fiber are described.     

Synthesis of alkenyl 3-hydroxy-2-naphthoates

Esterification of 3-hydroxy-2-naphthoic acid with homologous primary and secondary alkenyl alcohols with different chain lengths in the presence of N,N'-carbonyldiimidazole (CDI) and 1,8-diazabicyclo[ 5.4.0]undec-7-ene (DBU) in N,N-dimethylformamide gave the corresponding esters.     

A thermodynamic study of the complexation reaction of beryllium(II), magnesium(II) and calcium(II) with 3-hydroxy-2-naphtoic acid

The thermodynamic stability constants and thermodynamic parameters for the complexation reaction of Be²⁺, Mg²⁺ and Ca²⁺ with 3-hydroxy-2-naphthoic acid have been determined pH metrically in a 70% v/v dioxane-water medium in the presence of potassium nitrate. The study showed the formation 1:1 and 1:2 complexes of Be²⁺, Mg²⁺ and 1:1 complex of Ca²⁺ with 3-hydroxy-2-naphthoic acid. The order of overall stability is Be²⁺>Mg²⁺>Ca²⁺.     

One-pot three-component reaction for the synthesis of novel series of fully substituted 1,3,4-oxadiazole derivatives bearing pyridine moiety

(N-isocyanimino)triphenylphosphorane, 2-pyridinecarbaldehyde, and aromatic carboxylic acids (benzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 3-methoxybenzoic acid, 1-naphthoic acid, and 2-naphthoic acid) undergo a 1:1:1 addition reaction under mild conditions in a one-pot reaction to afford novel series of fully substituted 1,3,4-oxadiazole derivatives in good yields.     

Die Reaktion von Phthalaldehyden mit 3-Nitropropionsäureestern. Ein einfacher Zugang zu 3-Nitro-2-naphthoesäuren

The Reaction of Phthalaldehydes with 3-Nitropropionates. A Simple Route to 3-Nitro-2-naphthoic Acids 3-Nitro-propionates condense with phthalaldehydes and related compounds in the presence of a base to give 3-nitro-2-naphthoic acids.     

Thermolysis of thorium precipitates : Salts of organic acids

The thermal decomposition of the thorium salts of tannic (digallic), 5-bromosalicyclic, 5-nitrosali cyclic, 1-hydroxy-2-naphthoic, phenylglycine-o-carbocylic, phenylpropionic, acetyl-o-salicylic, phenoxyacetic, 2,4,5-trichlorophenoxyacetic and 2,2'-diphenic acids was investigated on the thermobalance. Most of the precipitated compounds were of a basic composition, correspoding to the general formula, Th(OH)4-n(A)n, where A - is the organic acid ligand The first weight losses were found from 35 to 200° with minimum oxide level temperatures occuring in the 475 to 665° temperature range.     

Ternary complexes of copper(II), nickel(II) and zinc(II) with nitrilotriacetic acid as a primary ligand and some phenolic acids as secondary ligands

Summary The formation of ternary complexes of the MAL^3– type [where M = Cu^II, Ni^II and Zn^II ; A = nitrilotriacetic acid (NTA); L = 1-hydroxy-2-naphthoic acid (1,2 HNA) and 2-hydroxy-1-naphthoic acid (2,1 HNA)] have been studied potentiometrically in 50% v/v aqueous — ethanol (25° and µ = 0.1). Under identical conditions the binary complexes of the 1,2- and 2,1-HNA ligands have also been examined. The values of mixed ligand formation constants K_MAL have been found to be lower than K_ML (first step formation constant of binary complexes) and even less than (second step formation constant of binary complexes).     

Evidence for a trianion intermediate in the metalation of 4-hydroxy-6,7-dimethoxy-8-methyl-2-naphthoic acid. Methodology and application to racemic 5,5'-didesisopropyl-5,5'-dialkylapogossypol derivatives

The metalation of 4-hydroxy-6,7-dimethoxy-8-methyl-2-naphthoic acid (8) affording trianion 6 is presented and applied to the regioselective efficient construction of a series of 5,5'-didesisopropyl-5,5'-dialkylapogossypol derivatives 3 that are potent pan-active inhibitors of antiapoptotic Bcl-2 family proteins.     

Lewis acid-assisted oxidative cross-coupling of 2-naphthol derivatives with copper catalysts

The oxidative coupling reactions between 2-naphthol and 3-hydroxy-2-naphthoic acid derivatives using a copper catalyst under an O₂ atmosphere in the presence of a catalytic amount of the Lewis acid, such as Yb(OTf)₃, were carried out. A highly cross-coupling selective or specific reaction effectively proceeded to give a C₁ symmetrical BINOL derivative.