4-Aryl-5-(pyrimidin-2′-yl)-1,4-dihydropyridines,-1,4-di- and -1,2,3,4-tetrahydropyrimidines

2-Acetonylpyrimidines readily undergo the Hantzsch—Biginelli cyclocondensation. This method was used to obtain derivatives of 1,4-dihydropyridine and 1,4-di- and 1,2,3,4-tetrahydropyrirrzidines, containing the pyrimidine fragment in the 5 position of the heterocycle.Institute of Bioorganic Chemistry and Petroleum Chemistry, Ukrainian Academy of Sciences, Kiev 253660. Translated from Khimiya Geterotsiklcheskikh Soedinenii, No. 5, pp. 679–685, May, 1994. Original article submitted January 20, 1994.     

Synthesis and establishment of the structures of 5-hydroxy-and 8-hydroxy -2-(2-furyl) quinoxaline

Two condensation products — 5-hydroxy-2-(2'-furyl)quinoxaline and 8-hydroxy-2-(2-furyl)-quinoxaline — are formed in the reaction of 2-furylglyoxal or the sodium salt of its aldoxime with 6-hydroxy-1,2-diaminobenzene. Dielcometry was used to establish the position of the substituent in the benzene ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 306–310, March, 1976.Deceased.     

Heterocyclization of 2-allylthiobenzimidazoles into derivatives of benzimidazo[2,1-b]-1,3-thiazines

It was found that bromination of 2-allylthiobenzimiduzoles in organic solvents forms products of addition of bromine to the olefin bond-2, 3-dibromopropylthiobenzimidazoles, which spontaneously or on heating cyclize into 3-bromobenzimidazo[2,1-b]-1, 3-thiazines or cyclodehydrobromination products — 2H- or 4H-benzimidazo[2,1-b]-1, 3-thiazines.Institute of Physical Organic Chemistry and Coal Chemistry, National Academy of Sciences of the Ukraine, Donetsk 340114. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 410–415, March, 1995. Original article submitted December 12, 1994.     

Mass-spectrometric study of 2- and 4-azafluorenones

A mass-spectrometric study of 2- and 4-azafluorenones and their mono- and polymethyl derivatives showed that the presence of a methyl group in the benzene ring leads to a sharp increase in the relative intensity of the [M — H]⁺ ion peak. In contrast to the fragmentation of 2- and 4-azafluorenes, the mass spectra of monomethyl-substituted compounds do not contain an [M — CH₃]⁺ fragment; this is probably associated with expansion of the pyridine or benzene ring to a seven-membered ring in the step involving the formation of the molecular ion due to inclusion of the methyl group. The intensity of the [M — CO]⁺ ion peak in the mass spectra of the 4-azafluorenones is higher by a factor of two with respect to the 2-azafluorenone isomers, and the [M — HCN]⁺ and [M — H, -HCN]⁺ ion peaks observed in the mass spectra of 2-azafluorenones are absent in them.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 89–95, January, 1979.     

Synthesis of 5-(5-R-2-furyl)thiazole derivatives by the reaction of 2-(5-R-furfuryl)thiuronium salts with acetic anhydride

2-Acetamide-4-methyl-5-(5-R-2-furyl)thiazoles were obtained by the reaction of 2-(5-R-furfuryl)thiuronium salts with acetic anhydride. The reaction intermediates — 2-(5-R-furfuryl)-1,3-diacetylthioureas — were isolated and characterized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 557–562, April, 1990.     

Reaction of 3-[N-(2-naphthyl)formimidoyl]pyridine with substituted acetophenones

The reaction of 3-[N-(2-naphthyl)formimidoyl]pyridine with substituted acetophenones in the presence of a proton catalyst leads to 1-aryl-3-(3-pyridyl)benzo[f]quinolines. Noncyclic amino ketones — [1-aryl-3-(3-pyridyl)-3-(2-naphthylamino)]-1-propanones — precede the formation of the cyclic products. The IR, UV, PMR, and mass spectra of the synthesized compounds are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 351–354, March, 1989.     

Alkylation of 2-, 4-, and 8-trialkylsiloxyquinolines by methyl iodide

Trimethyl- and triethylsilyl ethers of 2-, 4-, and 8-hydroxyquinolines have been prepared. The alkylation of these siloxyquinolines by methyl iodide has been studied. In the case of 4-trimethylsiloxyquinoldine, it has been established that both N- and O-alkylation products are formed.Latvian Institute of Organic Chemistry, Riga LV-1006. Translated from Khimiya Geteortsiklicheskikh Soedinenii, No. 9, pp. 1225–1231, September, 1994. Original article submitted September 28, 1994.     

Fragmentation of 2- and 4-(2-furyl) pyridines under the influence of electron impact

The dissociative ionization of 12 compounds of the 2- and 4-(2-furyl)pyridine series that contain methyl, ethyl, and n-propyl groups in various positions of the pyridine ring was investigated. It was established that the intensity of the [M — H]⁺ ion peak depends only slightly on the mutual orientation of the alkyl groups and the furyl grouping, while the probability of cleavage of the furan ring with ejection of CO and HCO particles is very sensitive to these structural factors. Cleavage of the pyridine ring leads to the development of [M — HCN]⁺ and [FuCN]⁺ ions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 769–774, June, 1982.     

Ring-chain isomerism and reactions of 2-(1-anthraquinonecarbonyl)-1,2,3,4-tetrahydrophthalazine

The ring isomer of the corresponding acyl derivative — 5,9-dioxo-17a-hydroxy-9,10,11,16-17,17a-hexahydro-5H-dibenzo[d,e,h]phthalazino[2,3-a]cinnoline — was obtained by acylation of 1,2,3,4-tetrahydrophthalazine with anthraquinone-1-carboxylic acid chloride. Treatment of the product with thionyl chloride or hydrogen chloride gave the deeply colored 5,9-dioxo-9,10,11,16-tetrahydro-5H-dibenzo[d,e,h]phthalazino[2,3-a]cinnolinium chloride. The possibility of charge transfer between the chloride anion and the phthalazinium cation is examined as a reason for the deep coloration. This compound very readily undergoes hydrolytic oxidative cleavage at the C-N bond to give 2-(2-formylbenzyl)-3,7-dioxo-2,3-dihydro-7H-dibenzo[d,e,h]cinnoline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1411–1415, October, 1977.     

Functionally substituted azines. 1. Synthesis and reactions of 2-(N-cyano-N-carbethoxmethylamino)-4,6-dimethylpyrimidine

Treatment of 2-(N-potassium-N-cyanamino)-4,6-dimethylpyrimidine with ethyliodoacetate produces 2-(N-cyano-N-carbethoxymethylamino)-4,6-dimethylpyrimidine. Alkaline hydrolysis of the last gives 2-(3-potassium-2,4-dioxoimidazolidinyl-1)-4,6-dimethylpyrimidine. Ammonolysis and hydrazinolysis give imino- or amino-imidazolidinylpyrimidine, respectively.Armenian Agricultural Institute, Erevan 375009. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1239–1241, September, 1994. Original article submitted August 9, 1994.     

Prototropic isomerization of trans-4-benzamido-3-hydroxy-2-(4-carbomethoxybutylidene)thiophan to cis- and trans-4-benza mido-3-oxo-2-(4-carbomethoxybutyl) thiophan

trans-4-Benzamido-3-hydroxy-2-(4-carbomethoxybutylidene)thiophan (I) was prototropically isomerized in the presence of hydrogen chloride. It is shown that the two possible isomers cis- and trans-4-benzamido-3-oxo-2-(4-carbomethoxybutyl)thiophan — are formed in the process.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 2, pp. 175–177, February, 1973.     

Reaction of 2-(4-alkylpiperazino)-3-chloro-1,4-naphthoquinones with sodium azide

It was shown that 2-(4-alkylpiperazino)-3-chloro-1,4-naphthoquinones react on heating with NaN₃ in DMF to form new heterocyclic quinones — 1,2,3,4-tetrahydro-13-alkyl-3,1-(iminoethano)benzo[g]quinoxaline-5,10-diones as well as the corresponding 2-(4-alkylpiperazino)-3-aminonaphthoquinones and naphthimidazopyrazinediones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2103–2107, September, 1990.     

Spektralphotometrische Bestimmung von Kobalt mit 2-(5-Brom-2-pyridylazo)-5-Diethylaminophenol

Zusammenfassung Eine empfindliche und selektive spektralphotometrische Kobaltbestimmung (<0,9 g ml^–1) ist mit 2-(5-Brom-2-pyridylazo)-5-diethylaminophenol (5-Brom-PADAP) auf Grund des kinetisch stabilen Co(III)L ₂ ^– -Chelates möglich, das nach seiner Bildung bei pH 7 (Ammoniumacetat) in Gegenwart von 0,1% Triton X-100, 5,10^–3 M Ammoniumperoxodisulfat und 10% (v/v) Dimethylformamid (auch nach Zugabe von 1,25 M H₂SO₄, 1,80 M HNO₃ oder auch 0,1–0,01 M EDTA) stabil ist. Eine Reihe von 5-Brom-PADAP-Chelaten störender Ionen werden dabei zersetzt. V(V), Hg²⁺, Ni²⁺, Cu²⁺, Pd²⁺ können stören. Die Kobaltbestimmung in Cyanocobalamin und auch Trinkwasser ist auf diesem Wege möglich. Die Fehler lagen im Bereich von — 3 bis — 7 % (1,8–9 g Co/l).Herrn Prof. Dr. F. Umland, Westfälische Universität, Münster/Westfalen, sind wir für das 5-Brom-PADAP mit herzlichem Dank verpflichtet.     

Complex formation of certain rare earth metals with 1-(2-pyridylazo)-2-naphthol (PAN) in alcohol-water solutions

The formation ofPAN complexes in the systems:Ln(III)—PAN—alcohol—water [whereLn(III) = Pr, Nd, Sm, Eu, Gd, Tb, alcohol - ethanol andLn(III) = Eu, alcohol =n-propanol, isopropanol] was investigated by a spectrophotometric method. Equilibrium constants for the reactionLn ³⁺+HLLnL ²⁺+H⁺ (HL =PAN) and stability constants of complexesLnL ²⁺ are reported.

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Komplexbildung einiger Seltenerdmetalle mit 1-(2-Pyridylazo)-2-naphthol (PAN) in alkoholisch-wäßrigen Lösungen

Zusammenfassung Die Bildung der Komplexe vonPAN in den SystemenLn(III)—PAN—Alkohol—Wasser [Ln(III) = Pr, Nd, Sm, Eu, Gd, Tb, Alkohol = Ethanol undLn(III) = Eu, Alkohol =n-Propanol, Isopropanol] wurde mit einer spektrophotometrischen Methode untersucht. Die Gleichgewichtskonstanten der ReaktionenLn ³⁺+HLLnL ²⁺+H⁺ (HL =PAN) und die Stabilitätskonstanten der KomplexeLnL ²⁺ wurden berechnet.

     

Insect pheromones and their analogs LVI. Chemical-enzymatic synthesis of (S)-(+)-9-hydroxydec-2E-enoic acid, a component of the queen pheromone of the honeybeeApis mellifera

(S,E)-(+)-9-Hydroxydec-2E-enoic acid—a component of the queen pheromones of the honeybeeApis mellifera — has been synthesized by the enzymatic reduction of 9-oxodec-2E-enoic acid with the aid of baker's yeast.Institute of Petrochemistry and Catalysis, Academy of Sciences of the Republic of Bashkortostan, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 877–879, November–December, 1997.     

Synthesis of unsaturated derivatives of 2,5-dimethyl-4-phenylpyridine and 3-methyl-2-azafluorene

A substituted butadiene — 1-phenyl-4-(5-methyl-4-phenyl-2-pyridyl)buta-1,3-diene with a trans, trans configuration — was obtained by condensation of 2,5-dimethyl-4-phenylpyridine with cinnamaldehyde. Two 3-methyl-9-cinnamylidene-2-azafluorene isomers are formed as a result of condensation of the same aldehyde with 3-methyl-2-azafluorene. Data from the PMR and IR spectra were used to prove the configuration of the compounds obtained. It was established that the condensation of 3-methyl-2-azafluorene with salicylaldehyde gives 3-methyl-9-(2-hydroxybenzylidene)-2-azafluorene, which has a zwitterionic structure, and 1,2-bis(3-methyl-2-aza-9-fluorenylidene)ethane. Ideas regarding the chemical mechanism of the formation of the latter are presented. The preparation of an unsaturated alcohol — 3-methyl-9-allyl-2-aza-9-fluorenol — is described.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 82–86, January, 1978.     

2-(Methylthio)pentafluoropropene

2-(Methylthio)pentafluoropropene was obtained by dehydrofluorination of methyl 2H-hexafluoroisopropyl sulfide by the BF₃ · NEt₃ complex. Its reactivity with respect to allyl alcohol and hexamethyldisilazane was studied. The electrophilicity of 2-(methylthio)penta-fluoropropene was compared with the properties of terminal polyfluoroalkenes whose behavior in these reactions has been studied previously.Perfluoroisobutylene also reacts with allyl alcohol in the absence of protophilic agents.3,4Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 80–84, January, 1994.     

Synthesis of 2-(acylmethyl) benzo-1,3-oxathiols from acetylenic ketones

2-(Acylmethyl)benzo-1,3-oxathiols were synthesized by reaction of acetylenic ketones with o-mercaptophenol in alcohol in the presence of a catalyst — triethylamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1328–1329, October, 1975.     

Computation of conformations of 2-(2-hydroxyethoxy)-3,4-dihydropyran with intramolecular hydrogen bonds

The conformations of 2-(2-hydroxyethoxy)-3,4-dihydropyran were calculated by the methods of molecular mechanics and MNDO/H with and without allowance for the formation of intramolecular hydrogen bonds. Two possible centers of the formation of the intramolecular hydrogen bond,viz., the oxygen atoms of the alkoxy radical and of the dihydropyran cycle, have been considered. The results obtained show that 2-(2-hydroxyethoxy)-3,4-dihydropyran does not exist in any preferable conformation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1202–1203, July, 1994.     

Alkaloids ofPetilium eduardi. Petine and petine N-oxide

Two new alkaloids — petine and petine N-oxide — have been isolated from the bulbs of Petilium eduardi. Their structures have been established on the basis of spectral characteristics and chemical transformations.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, FAX (3712) 89-14-75. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 524–528, July–August, 1994.