Synthesis and properties of phenothiazine derivatives. I. Synthesis and properties of bisoxytriazenes containing the phenothiazine fragment

3, 7-Bis(1-phenyl-3-hydroxytriazenyl)phenothiazine has been synthesized from phenothiazine. This compound decomposes to phenyl radicals, nitrogen and 3, 7-bisnitrosophenothiazine under the influence of nitroso compounds and oxidizing agents (PbO₂, Ag₂O). The reaction of bishydroxytriazenylphenothiazene with 2, 4, 6-tribromonitrosobenzene has been studied by EPR spectroscopy.N. P. Ogarev Mordov State University, Saransk 430000. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1284–1287, September, 1996. Original article submitted March 21, 1996.     

Silyl modification of biologically active compounds. 3. organosilicon derivatives of aminoalcohols in the series of tetrahydroquinoline,tetrahydroisoquinoline, and tetrahydrosilaisoquinoline

The N-(2-hydroxyethyl)-1, 2, 3, 4-tetrahydroquinoline, -isoquinoline, and -silaisoquinoline, and their trimethyland triethylsilyl derivatives and the corresponding methiodides were synthesized. The acute toxicity and psychotropic activity of the compounds synthesized were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 793–799, June, 1996. Original article submitted April 25, 1996.     

Synthesis and properties of furan derivatives. 5. Synthesis of 2-substituted benzoxazoles containing furan fragments

The condensation of imidates and imidate hydrochlorides of furan acids with o-aminophenols gives furyl derivatives of 2-substituted benzoxazoles. Such compounds are also formed in the reaction of furan acids with o-aminophenol in the presence of boric acid.Communication 4, see [1].I. M. Gubkin State Petroleum and Gas Academy, 117917 Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 896–901, July, 1996. Original article submitted April 16, 1996.     

Reactions of polyhalogenopyridines. 13. Reaction of isomeric tetrafluorocyanopyridines and pentafluoropyridine with sodium N,N-dimethyldithiocarbamate

The reactions of isomeric tetrafluoropyridines and pentafluoropyridine with sodium N,N-dimethyldithiocarbamate were studied. Substantial differences were found between the nature of their chemical transformations and those of the chlorine analogs. It was shown that tetrafluorocyanopyridines do not undergo heterocyclization with sodium N,N-dimethyldithiocarbarnate to form derivatives of 1,3-dithiolo[4,5-c]pyridine. Instead, extrusion of the CS₂ molecule from the N,N-dimethyldithiocarbanuue substituent at position 2 of the pyridine ring occurs.For communication 12, see [1].Chernogolovka Institute of Chemical Physics, Russian Academy of Sciences, Chernogolovka. Translated from Khimiya Geterotsklicheskikh Soedinenii, No. 8, pp. 1088–1093, August, 1996. Original article submitted June 20, 1996.     

4-Hydroxy-2-quinolones. 31. 3-Amino-ir-2-oxo-4-hydroxyquinolines and their acyl derivatives

Abstarct An alternative method has been developed for preparing and studying the antioxidant activity of 3-acylamino-2-oxo-4-hydroxyquinolones. Results are presented from an investigation of the antithyroid and antimicrobial action of the intermediate 2-oxo-3-(1 pyridinio)quinotin-4-olates and the 3-amino-2-oxo-4-hydroxyquinolines.For communication 30, see [1].Ukrainian Pharmaceutical Academy, Khar'kov 310002. Translated from Khimiya Geterotsklicheskikh Soedinenii, No. 8, pp. 1113–1123, August, 1996. Original article submitted June 10, 1996.     

Berberis alkaloids. XXXVII. Investigation of the alkaloids ofB. oblongata andB. integerrima. Crystal structure of 8-trichloromethyldihydroberberine

Two species of Berberis have yielded 10 isoquinoline alkaloids. In addition to known bases, two artifacts have been isolated — 8-trichloromethyldihydroberberine (I) and 8-trichloromethyldihydropalmatine. An x-ray structural analysis has been made of (1).Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 889–893, November–December, 1996. Original article submitted April 15, 1996.     

Investigations in the area of functionally substituted azines. 5.* Reactions of azines with nucleophiles and hydrogen chloride

It was shown that oxazolopyrimidinium and sym-triazinium chlorides give N₍₃₎-(2-Y-ethyl)-substituted azines with nucleophiles. Oxazolo-sym-triazine also reacts analogously, being converted by hydrogen chloride to the N₍₃₎-(2-chloroethyl) derivative.Armenian Agricultural Academy, Yerevan, 375009. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1417–1420, October, 1996. Original article submitted April 15, 1996.     

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.     

Chemical characterization of the black crust present on the stone central portal of St. Denis abbey

 A black crust sample from the stony central portal of the abbey of St. Denis, France, was analyzed by chromatographic and spectroscopic techniques to determine whether it was due to atmospheric pollution or to the degradation of a past restoration treatment. Stratigraphic surveys by optical microscopy, Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy/energy dispersive X-ray fluorescence (SEM/EDX) and pyrolysis/gas chromatography/mass spectrometry (PY/GC/MS) were consistent in ascribing the bulk of the crust to gypsum (CaSO₄ ⋅ 2H₂O) with inclusion of carbon particulate. The organic fraction was a minor constituent of the black crust. Hence, the deterioration by an organic substance used in the past to restore the building was ruled out. Received: 23 May 1996/Revised: 29 July 1996/Accepted: 1 August 1996     

Chemical characterization of the black crust present on the stone central portal of St. Denis abbey

 A black crust sample from the stony central portal of the abbey of St. Denis, France, was analyzed by chromatographic and spectroscopic techniques to determine whether it was due to atmospheric pollution or to the degradation of a past restoration treatment. Stratigraphic surveys by optical microscopy, Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy/energy dispersive X-ray fluorescence (SEM/EDX) and pyrolysis/gas chromatography/mass spectrometry (PY/GC/MS) were consistent in ascribing the bulk of the crust to gypsum (CaSO₄ ⋅ 2H₂O) with inclusion of carbon particulate. The organic fraction was a minor constituent of the black crust. Hence, the deterioration by an organic substance used in the past to restore the building was ruled out. Received: 23 May 1996/Revised: 29 July 1996/Accepted: 1 August 1996     

Naphthomoles. 7. Synthesis of 4,11-dimethoxynaphtho[2,3-f]indole-5,10-dione and 4-methoxynaphtho[2,3-f]-indole-5,10-dione

4,11-Dimethoxynaphtho[2,3-f]indole-5,10-dione and 4-methoxynaphtho[2,3-f[indole-5,10-dione have been synthesized by the Leimgruber-Batcho reaction from 1,4-dimethoxy-2-methyl-3-nitroanthraquinone.Russian University of Chemical Technology, Moscow 125190. Center for Drug Chemistry, All-Russian Scientific Research Institute for Pharmaceutical Chemistry, Moscow 119815. Translated from Khimiya Geterotsklicheskikh Soedinenii, No. 8, pp. 1050–1054, August, 1996. Original article submitted March 20, 1996.     

4-Hydroxy-2-quinolones. 30 Alkylation of 1H-2-oxo-3-carbethoxy-4-hydroxyquinoline

A study has been made of the alkylation of 1H-2-oxo-3-carbethoxy-4-hydroxyquinoline by alkyl halides in the presence of inorganic bases. New methods for the synthesis of 1-substituted 2-oxo-3-carbethoxy-4-ihydroxyquinolines are examined.For communication 29, see [1].Ukrainian Pharmaceutical Academy, Khar'kov 310002. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1104–1112, August, 1996. Original article submitted June 10, 1996.     

Adamantylazoles. Acid-catalyzed adamantylation of 1,2,4-triazoles

The reaction of 1-adamantanol with 1,2,4-triazole in sulfuric acid forms 1-adamantyl derivatives. In boiling chloroform containing traces of sulfuric acid, a mixture of isomeric N-adamantyl-1, 2, 4-triazoles is obtained. It is shown that 1-adamantyl carbocation is formed at a sulfuric acid concentration above 70%.St. Petersburg State Technological Institute, St. Petersburg 198013. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsklicheskii Soedinenii, No. 8, pp. 1078–1087, August, 1996. Original article submitted June 7, 1996.     

Oxidative reactions of azines. 1. Ketohydroxylation of 4-Phenyl-1,2,5,6-tetrahydropyrines. Synthesis and structure of 3,4-dihydroxy-4-phenylpiperidin-2-ones and their acetoxy derivatives

N-Alkyl substituted 4 phenyl-1.2,5,6-tetrahydropyridines which do not undergo Wagner hydroxylation are converted in good yields to the corresponding 3,4-dihydroxy-2-oxopiperidines under modified conditions for this reaction. The molecular structures of a 3,4-dihydroxy-4-phenylpiperidin-2-one and its diacetatate have been studied by x-ray crystalographic analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 222–226, February, 1996.     

Alkaloids. Plants,structures, properties

For the beginning of the review, see Chemistry of Natural Compounds, No. 1, 102; No. 2, 216 (1996)     

Indolopyridines with a bridging heteroatom. 9. Synthesis,structure, and thermolysis of 5-hydroxy-5-(2-pyridyl)-fluorene and 4-azafluorene

Treatment of fluorenone or 4-azafluoren-9-one with 2-pyridyllithium gives 45-hydroxy-5-(2-pyridyl)fluorene and its aza analog. The structure of the former has been studied by x-ray crystallography. It was found that, in contrast to the non-condensed diaryl-2-pyridylcarbinols, these alcohols do not undergo acid catalyzed dehydration and heterocyclization. Under pyrolytic conditions. 5-pyridylfluorenol undergoes fission to form fluorenone.Russian University of National Friendship, Moscow 117198 and A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow 117813. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 955–959, July, 1996. Original article submitted March 18, 1996.     

The reaction of sulfamic acid derivatives with epoxides. 4. Hydrolysis of 3-chloro-2-hydroxypropylsulfamates

Under basic hydrolysis conditions 3-chloro-2-hydroxypropylsulfamates transform into 2,3-dihydroxypropylsulfamates. Acidic hydrolysis of the latter leads to 3-alkylaminopropane-1,2-diols.For Communication 3 see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2809–2810, November, 1996.     

Berberis Alkaloids XXXVIII. Turcamine — A new isoquinoline alkaloid fromBerberis turcomanica

The new isoquinoline alkaloid turcamine (1) has been isolated from the leaves ofBerberis turcomanica, and its structure has been established as 8-hydroxy-7-methoxy-2-methyltetrahydroisoquinoline. A relationship has been found between a substituent at C-8 and the multiplicities of the signals from C-5 and C-6.Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 894–896, November–December, 1996. Original article submitted April 15, 1996.     

Investigations of unsaturated azoles. 13. Synthesis and some reactions of 1-alkylbenzimidazoles

Methods of direct alkylation of benzimidazoles by haloatkanes in homogeneous medium and under phase transfer catalysis conditions together with cyanoethylation by acrylonitrile are reported. The dealkylation of quaternary benzimidazole salts was also studied.For Communication 12 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 781–792, June, 1996. Original article submitted February 21, 1996.     

Investigations in the area of functionally substituted azines. Synthesis and thermolysis of chlorethoxypyrimidines

The 2-amino-4-(2-chlorethoxy)-6-methyl- and 2-(2-chlorethoxy)-4-methoxy-6-methylpyrimidines were synthesized. Depending on the position of the chlorethoxy group in the ring, their therniolysis results in the formation of the oxazolopyrimidinium chloride or the N₍₁₎-(2-chlorethyl) derivative.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 237–239, February, 1996.