Kinetics of coupling of diazotized sulfanilamid with 1-naphthylamine

In this study, the coupling kinetics of sulfanilamid diazonium salt with 1-naphthylamine has been studied by spectrophotometric method. In the experiments conducted at constant temperature, 25°C, pH has been varied between 2.2?3.4, reactant concentration between 1.25 × 10^?5 ? 5 × 10^?5 M, and ionic strength between 0.1?1 M. The reaction has been confirmed to be of second-order and rate constants and the dissociation constant of 1-naphthylamine have been calculated. © 1993 John Wiley & Sons, Inc.     

The structure of the diazonium coupling products of phenacyl thiocyanate and phenacyl selenocyanate with diazotized 3-phenyl-5-aminopyrazole

The reaction of diazotized 3-phenyl-5-aminopyrazole with phenacyl thiocyanate 1a and phenacyl selenocyanate 1b afforded directly 2-imino-3-(3-phenyl-5-pyrazolyl)-5-benzoyl-2,3-dihydro-1,3,4-thiadiazole monohydrate 9a and 2-imino-3-(3-phenyl-5-pyrazolyl)-5-benzoyl-2,3-dihydro-1,3,4-selenadiazole monohydrate 9b , respectively. The products 9a and 9b were also obtained from the reaction of C-benzoyl-N-(3-phenyl-5-pyrazolyl)formohydrazidoyl bromide 10 with potassium thiocyanate and potassium selenocyanate, respectively. Acetylation, benzoylation, and nitrosation of 9 afforded the corresponding diacetyl, dibenzoyl, and nitroso derivatives 11-13 , respectively. Cyclization of C-benzoyl-N-(3-phenyl-5-pyrazolyl)-nitrilimine 6 was shown to give the pyrazolo [5,1-d]triazole 8 and not the pyrazolo[5,1-c]-as-triazine derivative 7 , as previously reported.     

Oxidative coupling of 1,5-dihydroxynaphthalene with aromatic amines

The oxidative coupling of 1,5-dihydroxynaphthalene with aromatic amines leads to the formation of N-aryl-5-hydroxy-1,4-naphthoquinone-4-imines. The yield of these products depends on the nature of the oxidizing agent.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2851–2854, December, 1990.     

Flow-injection spectrophotometric determination of phenolic drugs and carbamate pesticides by coupling with diazotized 2,4,6-trimethylaniline.

A flow-injection (FI) spectrophotometric system is proposed for the determination of phenols and carbamates. In the FI manifolds, the solutions of phenols or carbamates (the latter after hydrolysis with NaOH) were injected into a diazonium ion carrier stream at pH 9.5 (buffered with tetrahydroborate), which was formed by mixing 2,4,6-trimethylaniline (TMA) with nitrate in a sodium dodecyl sulfate aqueous micellar medium. Absorbance was measured at 550 nm. The system combines the advantages derived from the use of TMA for the coupling of phenols in basic micellar media, because of the inhibition of the self-coupling reaction of the reagent, with the precision and speed of the FI procedures. Other diazotized reagents produced excessive blank signals. The procedures were successfully applied to the determination of phenolic drugs (epinephrine, acetaminophen, and gualacol) in pharmaceuticals and carbamates (bendiocarb, benfuracarb, carbaryl, carbofuran, methiocarb, promecarb, and propoxur) in pesticide products and water samples.     

Investigation of the products of reaction of epichlorohydrin with aromatic amines

It is shown that the reaction of thionyl chloride with 1, 2, 3, 4-tetrahydro-3-hydroxy-6-methyl[h]benzoquinoline leads not only to aromatization of the tetrahydroquinoline ring, but also to chlorination of the methyl group.For Part II see [3].     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

4-Hydroxy- and 4-oxo-1,2,3,4-tetrahydrobenzo[h]quinolines were synthesized. Benzo[h]-quinoline, 1,2,3,4-tetrahydrobenzo[h]quinoline, and a dimeric compound are formed when the 4-hydroxy derivative is heated with hydrochloric acid or without it. The reaction of 4-hydroxy-1,2,3,4-tetrahydrobenzoth]quinoline with thionyl chloride was carried out.See [1] for communication X.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 548–551, April, 1972.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

The synthesis of 2-(hydroxymethyl)benz [g]indoline derivatives by heating N-acyl derivatives of 2-(chloromethyl)benz[g]indoline in dimethyl sulfoxide is described. 3,6-Dichloro-1,2,3,4-tetrahydrobenzo[h]quinoline, 5-chloroazirido[1,2-a]benz[g]indoline, and derivatives of 2-substituted 5-chlorobenz [g]indoline were synthesized.See [1] for communication XITranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1111–1116, August, 1972.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

N-(-Chloro--hydroxy)propyl derivatives of 5-chloro-1-naphthylamine, 8-chloro-1-naphthylamine, and 5-cyano-1-naphthylamine were obtained. They were cyclized to 1,2,3,4-tetrahydro-3-hydroxy-7-chlorobenzo[f]quinoline (II), 1,2,3,4-tetrahydro-3-hydroxy-10-chlorobenzo-[fJquinoline (VII), and 1,2,3,4-tetrahydro-3-hydroxy-7-cyanobenzo[f]quinoline (X). Chlorination at the 6 position to form 1,2,3,4-tetrahydro-3-hydroxy-6,7-dichlorobenzo[f]quinoline occurs under the action of thionyl chloride on II at room temperature. The action of thionyl chloride on II, VII, and X at elevated temperatures leads not only to chlorination at the 6 position but also to aromatization of the tetrahydropyridine ring to form, respectively, 6,7-dichlorobenzo[f]quinoline (V), 6,10-dichlorobenzo[f]quinoline (VIII), and 6-chloro-7-cyanobenzo[f]quinoline (XIII).See [5] for Communication V.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1522–1525, November, 1970.     

Investigations of the products of the reaction of epichlorohydrin with aromatic amines

Heating 3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline with phosphorus oxychloride gave a mixture of isomeric 3-chloro-1,2,3,4-tetrahydrobenzo[h]quinoline and 2-(chloromethyl)-benz[g]indoline, which are converted to a mixture of 3-benzoyloxy-1,2,3,4-tetrahydrobenzo-[h]quinoline and 2-(benzoyloxymethyl)benz[g]indoline on reaction with potassium benzoate. Saponification of 2-(benzoyloxymethyl)benz[g]indoline gave 2-(hydroxymethyl)benz[g]indoline. The reaction of the isomeric chloro derivatives with potassium cyanide gave 2-(benz[g]-indolinyl)acetonitrile.See [1] for communication IX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 362–366, March, 1972.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

The ethyl group of 3-hydroxy-6-ethyl-1,2,3,4-tetrahydrobenzo[h]quinoline is chlorinated and the tetrahydropyridine ring is aromatized under the influence of thionyl chloride. The corresponding 6-alkylbenzo[h]quinolines and 6-alkyl-1,2,3,4-tetrahydrobenzo[h]quinolines are formed when 3-hydroxy-6-alkyl-1,2,3,4-tetrahydrobenzo[h]quinolines are heated with polyphosphoric acid at 200–205°C, but only 6-alkylbenzo[h]quinolines are formed at up to 270°.See [1] for communication VIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1403–1406, October, 1971.     

Investigation of the products of the oxidation of gossypol structure of gossindan

A new compound, which we have called gossindan, has been isolated from the products of the oxidation of gossypol by oxygen in an alkaline medium. The structure of gossindan has been established on the basis of a study of IR, mass, PMR, and¹³C NMR spectra and x-ray structural analysis as 6,6-di-(2,7-dihydroxy-3-isopropyl-5-methylindan-1-one).A. S. Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan, Tashkent, Fax 627071. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 50–58, January–February, 1994.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

5,6-Dichlorobenzo[f]quinoline is formed by the action of thionyl chloride on 3-hydroxy-5-chloro-1,2,3,4-tetrahydrobenzo[f]quinoline hydrochloride. 7-Chlorobenzo[f]quinoline and 7-chloro-1,2,3,4-tetrahydrobenzo[f]quinoline are obtained in good yields by heating 3-hydroxy-7-chloro-1,2,3,4-tetrahydrobenzo[f]quinoline with orthophosphoric acid, while benzo[f]quinoline is also obtained by heating it with polyphosphoric acid.See [1] for communication VII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 108–111, January, 1971.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

The action of hydrogen halides on 7a,8-dihydro-7H-azirino[1,2-]benz[g]indole gives 2-halomethyl-2,3-dihydro-1H-benz[g]indoles and 3-halo-1,2,3,4-tetrahydrobenzo[h]quinolines, which were converted to the corresponding N-nitroso derivatives and then to the isonitroso derivatives. 2-(Benzoxymethyl)-2,3-dihydro-1H-benz[g]indole hydrohalides were obtained by heating 1-benzoyl-2-halomethyl-2,3-dihydro-1H-benz[g]indoles. The reaction of 3-halo-1,2,3,4-tetrahydrobenzo[h]quinolines with thionyl chloride at room temperature gives 3-halo-6-chloro-1,2,3,4-tetrahydrobenzo[h]quinolines, while refluxing with thionyl chloride gives 6-chlorobenzo[h]quinoline.See [1] for communication XVI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 342–346, March, 1973.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

A relatively simple method is proposed for the preparation of 4-hydroxyquinoline derivatives from the corresponding 4-oxo-1,2,3,4-tetrahydroquinoline derivatives. 4-Hydroxy-6-chloro-1,2,3,4-tetrahydrobenzo[h]quinoline is readily converted to a mixture of 6-chlorobenzo[h]-quinoline and 6-chloro-1,2,3,4-tetrahydrobenzo[h]quinoline.See [1] for communication XIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1224–1227, September, 1972.     

Coupling of two diazotized 3‐aminothieno[3,4‐c]coumarins with aromatic amines

The coupling reactions of two diazotized 3‐aminothieno[3,4‐c]coumarins were investigated. Compounds 1a , 1b both react with sodium nitrite in concentrated sulphuric acid at 0–5°C to give the diazotized intermediates 2 and 3 , the latter resulting from the acid ‐catalyzed hydrolysis of the lactonic ring of 2 . The in situ formed diazonium salts react with aromatic amines ( 4 ) to afford a series of arylazothiophenes dyes in the form of their ammonium sulfate salts. With diazotized aniline, besides the normally expected phenylazothiophene 10 from the reaction with compound 1a , the corresponding product of acid hydrolysis 11 was also isolated. In at least one of the cases, the thienyl diazonium salt 2 undergoes a Gomberg–Bachmann arylation reaction with p‐nitroaniline to give the 2‐arylthiophene 9 . The direct hydrolysis of compounds 1a , 1b by concentrated sulphuric acid and subsequent oxidative dimerization of the primary product of acid hydrolysis led to compound 12 . J. Heterocyclic Chem., (2011).     

Reactions of 3-cyanochromones with primary amines: structures of the products

Reactions of 3-cyanochromones with primary aromatic amines in boiling benzene gave mixtures of Z- and E-3-arylamino-2-(2-hydroxyaroyl)acrylonitriles and 2-amino-3-(aryl-iminomethyl)chromones. The latter can easily be obtained in the individual state when the reaction is carried out in the presence of triethylamine. In the case of primary aliphatic amines, the open-chain reaction product immediately undergoes cyclization into 3-alkyliminomethyl-2-aminochromones. The structures of the products were examined by 1D and 2D ¹H, ¹³C, and ¹⁵N NMR spectroscopy in DMSO-d₆ and CDCl₃.     

A study of the products of the reaction of epichlorohydrin with aromatic amines

The halogenation of 1,2,3,4-tetrahydrobenzo[h]quinoline and of 3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline and its O-benzoyl and N,O-dibenzoyl derivatives has been studied. The action of thionyl chloride or bromide on 1,2,3,4-tetrahydrobenzo[h]quinoline at room temperature gives 6-chloro-1,2,3,4-tetrahydrobenzo[h]quinoline and 6-bromo-1,2,3,4-tetrahydrobenzo[h]quinoline. When 6-chloro-3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline is heated with thionyl chloride, aromatization of the tetrahydropyridine ring takes place, and when 6-bromo-3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline is heated with thionyl chloride, in addition to the aromatization of the tetrahydropyridine ring the bromine atom is replaced by a chlorine atom with the formation of 6-chlorobenzo[h]quinoline. 6-Bromobenzo[h]quinolme has been obtained by heating 3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline with thionyl bromide.For Communication IV, see [6].Translated from Khimiya Geterotsiklicheskikh Soedinenii.Vol. 6,No.7, pp. 969–973, July, 1970.