Isolation and properties of the products of the covalent hydration of 4H-imidazoles

The neutralization of 5-hydroxy-4,4-dimethyl-2-imidazolinium chlorides yields in the free state the products of the covalent hydration of the corresponding 4H-imidazoles — 5-hydroxy-4, 4-dimethyl-2-imidazolines. On being heated, the compounds obtained undergo various transformations, depending on the presence and position of oxygen-containing functions: 5-hydroxy-2-imidazoline gives 2-acetylamino-2-methyl-1-phenylpropan-1-ol; 3,5-dihydroxy-2-imidazoline dehydrates to 4H-imidazole 3-oxide; and 1,5-dihydroxy-2-imidazolines are converted into 2,3-dihydro-4H-1,2,5-oxadiazines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1087–1092, August, 1973.     

Synthesis of methyl -substituted 4-amino methyl-4-butanolides and 5 -hydroxy-2-piperidones

Esters of 5-amino-4-hydroxy-3-methylvaleric acids, which exist as pairs of diastereomers and are readily converted to the corresponding methyl-substituted 4-aminomethyl-4-butanolides or 5-hydroxy-2-piperidones, are obtained by reaction of esters of 3-methyl-4, 5-epoxy-2-pentenoic acid with amines and subsequent hydrogenation of the resulting esters of 5-amino-4-hydroxy-3-methyl-2-pentenoic acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 594–598, May, 1975.     

Phytoestrogens

Conclusions 1. Eight new representatives of methyl- and methoxycoumestans were obtained.2. For the synthesis of the coumestans, the following previously undescribed coumarins have been synthesize 4,7-dihydroxy-5-methyl-, 4,7-dihydroxy-5-methoxy-, and 4-hydroxy-7-methoxy-5-methylcoumarins.Khimiya Prirodnykh Soedinenii, Vol. 6, No. 3, pp. 355–358, 1970.For part IV, see [4].     

Synthesis and Transformations of 4-(4-Ethoxycarbonylphenylamino)- and 4-(2-Carboxyphenylamino)quinolines

Synthesis was performed of 4-(4-ethoxycarbonylphenylamino)- and 4-(2-carboxyphenylamino)-2-methylquinolines by reaction of 2-methyl-4-chloroquinoline with anesthesin and anthranilic acid. In concentrated sulfuric acid 4-(2-carboxyphenylamino)-2-methylquinoline underwent cyclization into 6-hydroxy-7-methylquinolino[3,2-c]quinoline, and the alkaline hydrolysis of 4-(4-ethoxycarbonylphenyl-amino)quinoline afforded 2-methyl-4-(4-carboxyphenylamino)quinoline.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 786–787.Original Russian Text Copyright © 2005 by Avetisyan, Aleksanyan, Ambartsumyan.     

13C NMR spectroscopy of isomerism in series of arylazo derivatives of sulfonaphthols and aminosulfonaphthols

¹³C NMR has been used in a study of the isomers formed in azo coupling of 1,8-dihydroxy-3,6-naphthalenedisulfonic acid (chromotropic acid), 1-hydroxy-8-amino-3,6-naphthalenedisulfonic acid (H acid), 1-hydroxy-6-amino-3-naphthalenesulfonic acid (J acid), and 1-hydroxy-7-amino-3-naphthalenesulfonic acid (gamma acid); and indicators have been established through which individual isomers in mixtures can be recognized spectroscopically.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2721–2728, December, 1989.     

Homolytic replacement of a hydrogen atom in 2-methylquinoline by A 1,3-dioxolanyl residue

The reaction of 1,3-dioxolane with sulfuric-acid-protonated 2-methylquinoline initiated by the ROOH + Fe²⁺ system [where R = H, (CH₃)₃C, or C₆H₅C(CH₃)₂] at 5–10 °C in water forms 4-(1,3-dioxacyclopent-2-yl)-2-methylquinoline and 4-(1,3-dioxacy-clopent-4-yl)-2-methylquinoline. The selectivity of the formation of the first reaction product increases on passing from hydrogen peroxide to cumyl and tert-butyl hydroperoxide and with an increase in the pH of the medium.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 25–28, January, 1984.     

Acyclic analogs of nucleosides. Synthesis of hydroxyalkyl derivatives of 2-trifluoromethyl- and 2-trifluoromethylthiobenzimidazole

1-(2,3-Dihydroxypropyl)-, 1-(4-hydroxy-2-oxabutyl)-, 1-(3-hydroxymethyl-4-hydroxy-2-oxabutyl)-, 1-(1,5-dihydroxy-3-oxa-2-pentyl)-, 1-(5-hydroxy-3-oxa-2-pentyl)-, and 1-(4,5-dihydroxy-2-oxapentyl)-2-trifluoromethyl- and -2-trifluoromethylthiobenzimidazoles were obtained by condensation of trimethylsilyl derivatives of 2-substituted benzimidazoles with alkylating agents in the presence of SnCl₄, or by direct alkylation of the sodium salts of the heterocycles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 632–636, May, 1988.     

2-R-7-Hydroxy-8-methyl-3-(2-quinolyl)chromones

By condensation of 2-methyl resorcinol with 2-quinolyl acetonitrile, we have synthesized α-(2-quinolyl)-2,4-dihydroxy-3-methylacetophenone, which when reacted with carboxylic acid anhydrides followed by hydrolysis yields 2-R-7-hydroxy-8-methyl-3-(2-quinolyl)chromones.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 407–415, March, 2005.     

Acetylenic α-aziridinylcarbinols in reactions with hydrazine and methyl-substituted hydrazines

It is shown that hydrazones of phenylpropiolaldehyde are formed in the reaction of an acetylenic -aziridinylcarbinol — 1-hydroxy-1-aziridinyl-3-phenyl-2-propyne — with hydrazine and methyl — and 1, 1-dimethylhydrazine. The reaction of this carbinol with sym-dimethylhydrazine leads to the formation of phenylacetylene and 1-formyl-1, 2-dimethylhydrazine,1-aziridinyl-1-hydrazino-3-phenyl-2-propyne, or 3, 6-diphenylethynyl-1,2,4,5-tetramethyltetrazine, depending on the reaction conditions. It was established that the reaction of 1-hydroxy-1-aziridinyl-3-phenyl-2-propyne and 1-hydroxy-1-(2-methylaziridinyl)-2-propyne with hydrazine and methyl-substituted hydrazines is realized through an intermediate step involving the decomposition of the acetylenic aziridinylcarbinols to an -alkynyl aldehyde and ziridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 753–757, June, 1978.     

Synthetic analogues of Peganum alkaloids. III. Pentamethylenequinazolones

Monosubstituted 5-, 6-, and 8-methoxy-3,4-dihydro-2,3-pentamethylenequinazolones (1–3) have been syntehsized by the condensation of monosubstituted methoxyanthranilic acids with caprolactam. Demethylation with hydrobromic acid gave the corresponding hydroxy compounds [4–6]. When the 6- and 8-methoxy- and 6- and 8-hydroxy-3,4-dihydro-2,3-pentamethylenequinazolones (2, 3, 5, and 6) were reduced with zinc in hydrochloric acid, the corresponding quinazoline derivatives (7–10) were obtained. The melting points of the basis and their hydrochlorides are given. Some features of their UV, mass, and PMR spectra are reported.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 465–469, July–August, 1986.     

Influence of structure on the circular dichroism of methyl-substituted 1,3,4-tetrahydrobenz[b]azepin-2-ones

The chirooptical properties of methyl-substituted 1,3,4,5-tetrahydrobenz[b]azepin-2-ones have been studied. A considerable increase in the intensity of the Cotton effect (CE) in the 240–250 nm region with an enlargement of the lactam ring has been observed. The sign of this CE for seven-membered benzolactams correlates with the type of conformation of the lactam ring. A change in the nature of the conjugation (passage from lactams of the benzamide type -C₆H₄-CO-NH- to lactams of the anilide type -C₆H₄-NH-CO-) leads to an inversion of the signs of the CEs in the 230–250-nm region.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 97–100, January, 1984.     

Derivatives of azaindoles. 65. Synthesis of 1-benzyl-4-methyl-5-cyano-6-hydroxy-7-azaindoline

Treatment of the ammonium (I) or benzylammonium salt of 2,6-dihydroxy-3-(-hydroxyethyl)-4-methyl-5-cyanopyridine (II) with a mixture of benzylamine and phosphorus pentoxide yielded 2-benzylamino-3-(-hydroxyethyl)-4-methyl-5-cyano-6-hydroxypyri-dine (III), which, when heated with phosphorus oxychloride, is converted to 1-benzyl-4-methyl-5-cyano-6-hydroxy-7-azaindoline (IV). The products of thermal fragmentation of II with benzylamine were studied by the method of chromato-mass spectrometry. In addition to compound III, N,N-dibenzylurea (V) and the dibenzylamide of malonic acid (VI) were preparatively isolated from the reaction products. The cyclization of I and II to 4-methyl-6-hydroxy-2,3-dihydro-7-azabenzofuran (VII) and 4-methyl-5-cyano-6-hydroxy-2,3-dihydro-7-azabenzofuran (VIII) was carried out. Heating VIII with benzylamine at 200–210°C led to compound III.For communication 64, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1105–1109, August, 1984.     

Secondary metabolites of Pyricularia oryzae I. o-Nitrophenol derivatives

o-Nitrophenol derivatives have been isolated from the culture liquid of the deuteromycetePyricularia oryzae Cav.: 4-hydroxy-3-nitrophenylacetic acid, 4-hydroxy-3-nitrobenzyl alcohol, 1- and 2-(4-hydroxy-3-nitrophenyl(ethanols, N-(4-hydroxy-3-nitrophenylethyl)acetamide, and pyriculamide. This is the first time that any of these compounds has been isolated from natural sources. The o-nitrophenols obtained possess moderate growth-inhibiting activity in relation to rice shoots.All-Union Scientific-Research Institute of Phytopathology, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 811–818, November–December, 1990.     

Investigation of heterocyclic quinones

Amino derivatives of 4-hydroxyquinazoline quinones were obtained by the oxidative amination of 6-hydroxy-4-quinazolone and 2-phenyl-6-hydroxy-4-quinazolone. The IR spectra established that 2,8-dipiperidino(dimorpholino)-4-hydroxyquinazoline 5,6-quinone exists in the hydroxy form, while 2-phenyl-4-hydroxy-8-piperidinoquinazoline 5,6-quinone can exist in both the oxo and hydroxy forms.See [1] for communication XVII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 836–840, June, 1972.     

New metallochromic indicators for compleximetric titration of calcium

Seven o,o'-dihydroxyazo dyes were synthesized and tested as metallochromic indicators for calcium: 1-(2-hydroxy-3-sulfo-5-chloro-1-phenylazo)-2-hydroxy-3-naphthoic acid (I), 1-(2-hydroxy-3-sulfo-5-chloro-1-phenylazo)-2-naphthol-3,6-disulfonic acid (II), 1-(2-hydroxy-6-sulfo-1-naphthylazo)-2-naphthol-3,6-disulfonic acid (III), 2,2'-dihydroxy-1, 1'-azonaphthalene-3,3', 6,6'-tetrasulfonic acid (IV), 1-(2-hydroxy-3-carboxy-1-naphthylazo)-2-naphthol-3,6-disulfonic acid (V), 1-(2,3-dihydroxy-1-naphthylazo)-2-naphthol-3, 6-disulfonic acid (VI), 1-(2,3-dihydroxy-6-sulfo-1-naphthylazo)-2-naphthol-3,6-disulfonic acid (VII). The acid dissociation constants and the formation constants of the calcium and magnesium chelates of these dyes were determined. The rate of the decomposition of these dyes and their calcium chelates in alkaline solutions was also examined. From the results of photometric and visual titrations of calcium in the presence of magnesium, indicators III and IV provide the sharpest end-points and the best stability in alkaline solutions.     

Diterpenoids ofPulicaria salviifolia IV. Structures of salvicinolide and salvicinolin

Two new clerodanolides — salvicinolide and salvicinolin — have been isolated from the epigeal part ofPulicaria salviifolia Bge inMem (fam. Compositae). Their structures have been established by an investigation of their spectral and physicochemical characteristics. It has been found that salvicinolide is capable of cyclizing at the C-6 and C-19 carbon atoms with the formation of a second lactone ring. The structure of 6-hydroxy-19-carboxy-trans-clero-3,13-dien-15-olide is proposed for salvicinolide, and 6,13-dihydroxy-19-carboxy-rans-cleroda-3,13-diene for salvicinolin.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent fax (3712) 40 64 75. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 594–598, July–August, 1997.     

Oxidation of hydroxyamino- and nitrosopyrimidines. Synthesis of 2- and 4-nitropyrimidines

Oxidation of phenyl- and methyl-substituted 2- and 4-hydroxyamino- and-nitrosopyrimidines has given the azoxy- and nitropyrimidines, respectively. The behavior of the nitropyrimidines obtained towards reduction and nucleophilic substitution is considered.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1100–1105, August, 1989.     

Reaction of 4,5-dihydroxy-2-imidazolidinones with arylsulfinic acids. Synthesis of 4-arylsulfonyl-2-imidazolinones

The reaction of 4,5-dihydroxy-2-imidazolidinones with arylsulfinic acids in water upon heating leads to 4-arylsulfonyl-2-imidazolinones. The formation of such compounds was found to proceed through the loss of a water molecule or sulfinic acid from intermediate 4-hydroxy-5-arylsulfonyl-2-imidazlidinones and 4,5-dihydroxy-2-imidazolidinones. 4-Arylsulfonyl-2-imidazolinones are also formed upon heating glyoxal, urea, and arylsulfinic acids in water.M. V. Lomonosov Moscow State Fine Chemical Technology Institute, 117571 Moscow. Translated from Khimiya Geserotsiklicheskikh Soedinenii, No. 10, pp. 1337–1342, October, 1996. Original article submitted July 17, 1996.     

Clerodane diterpenoids from Microglossa angolensis

Two new diterpenoids, 6β-(2-methylbut-2(Z)-enoyl)-3α,4α,15,16-bis-epoxy-8β,10βH-ent-cleroda-13(16),14-dien-20,12-olide and 10β-hydroxy-6-oxo-3α,4α,15,16-bis-epoxy-8βH-cleroda-13(16),14-dien-20,12-olide, together with the known β-amyrin, spinasterol, 5,7-dihydroxy-3,8,3′,4′-tetramethoxyflavone and 5,7-dihydroxy-3,8,3′,4′,5′-pentamethoxyflavone have been isolated from the aerial parts of Microglossa angolensis Oliv. et Hiern (Compositae). The structures were elucidated on the basis of spectral studies and comparison with published data.     

Contribution à la phytochimie du genre Gentiana. VII. Etude des composés flavoniques et xanthoniques dans les feuilles de Gentiana vernaL. (1ère communication)

A new xanthone-O-glycoside, the 1,7-dihydroxy-3-methoxyxanthone-8-O-β-D-glucopyranoside ( 7 ), has been isolated from the leaves of Gentiana verna L. by means of column chromatography on polyamid. Six known xanthones: 1-hydroxy-3,7,8-trimethoxyxanthone-1-O-primerveroside ( 2 ); 1,7,8-trihydroxy-3-methoxyxanthone ( 3 ); 7-hydroxy-3,8-dimethoxyxanthone-1-O-primeveroside ( 4 ); 7,8-dihydroxy-3-methoxyxanthone-1-O-primeveroside ( 5 ); mangiferin 6 and the flavone C-glycoside isoorientin 8 have also been isolated and identified.