Reactions of 3-azido-1,2,4-triazole with electrophiles

Alkylation of 3-azido-1,2,4-triazole with oxiranes, bromoacetone, and methyl vinyl ketone furnished a mixture of N-substituted 3- and 5-azido-1,2,4-triazoles, 3-azido compounds prevailing. The same substrate subjected to heterylation with 3,5-dinitro-1,2,4-triazole derivatives reacted selectively at the N¹ atom, and its bromination afforded 3-azido-5-bromo-1,2,4-triazole..Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 11, 2004, pp. 1699–1704.Original Russian Text Copyright © 2004 by Kofman, Krasnov.     

Acylation of aza crown ethers with N-substituted isophthalimides

Acylated aza crown ethers containing fragments of N-substituted phthalamic acids in the side chain were obtained by the reaction of monoaza-15-crown-5, monoaza-18-crown-6, and diaza-18-crown-6 with N-substituted isophthalimides.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 536–539, April, 1987.     

New path of dissociation of a tetrahedral intermediate during alkaline hydrolysis of benzimidates

A brief review is presented of the authors' studies carried out in recent years on the previously unknown rearrangement in the tetrahedral intermediate formed by alkaline hydrolysis of aryl esters of N-substituted benzimidic acids.Translated from Teoreticheskaya Éksperimental'naya Khimiya, Vol. 28, Nos. 5–6, pp. 400–406, September–December, 1992.     

Synthesis of nonequilibrium Ir<Subscript>x</Subscript>Re<Subscript>1-x</Subscript> solid solutions. Crystal structure of [Ir(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl]<Subscript>2</Subscript>[ReCl<Subscript>6</Subscript>]Cl<Subscript>2</Subscript>

Synthesis of five binary complex salts with an [Ir(NH₃)₅Cl]²⁺ complex cation is described. The counterions are [ReCl₆]^2–, [IrCl₆]^2–, [ReBr₆]^2–, and Cl^–. A polycrystal X-ray diffraction study has been performed for [Ir(NH₃)₅Cl]₂[ReCl₆]Cl₂, and its crystal structure has been determined. A series of Ir _x Re_1–x phases (0.5 x > 1) were obtained by reductive thermolysis. For the Ir-Re system, the history of the V/Z(x) dependence has been refined.Original Russian Text Copyright © 2004 by S. A. Gromilov, S. V. Korenev, I. V. Korolkov, K. V. Yusenko, and I. A. BaidinaTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 508–515, May–June 2004.     

Reformatsky Reaction with N-Substituted 6-Bromo-2-oxochromene-3-carboxamides

Reformatsky reactions of ethyl -bromopropionate, methyl -bromobutyrate, and methyl -bromo-isobutyrate with N-substituted 6-bromo-2-oxochromene-3-carboxamides in the system diethyl ether–benzene– HMPA give N-benzyl-6-bromo-4-(1-alkoxycarbonylalkyl)-2-oxochroman-3-carboxamides, while in the system diethyl ether–benzene–HMPA–THF, 3-R¹-1-R²-1-R³-9-bromo-2,3,4,4a,5,10b-hexahydro-1H-chromeno[3,4-c]-pyridine-2,4,5-triones are obtained.     

Azaindole derivatives. 67. Synthesis of N-substituted 1-benzyl-4-methyl-5-cyano-6-amino-7-azaindoles

N-substituted 1-benzyl-4-methyl-5-cyano-6-amino-7-azaindoles have been synthesized from the respective 1-benzyl-4-methyl-5-cyano-6-chloro(and 6-hydroxy)-7-azaindoles. The effect of the 5-cyano group on the oxidation-reduction processes accompanying nucleophilic replacement of chlorine in 6-chloro-7-azaindoles by primary and secondary amines has been considered. 7-Azaindoline compounds were dehydrogenated by chloranil to N-substituted 1-benzyl-4-methyl-5-cyano-6-amino-7-azaindoles.For communication 66, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 91–96, January, 1986.     

Synthesis of 6-mono- and 5,6-disubstituted 1,2,3-triazolo[4,5-d]pyrimidin-7-ones

The reactions of N-substituted 4-amino-3-benzyl-1,2,3-triazole-5-carboxamides with phosphorus oxochloride and dimethylformamide at 80 °C or with triethyl orthoacetate and acetic anhydride at 160 °C afforded 6-mono- or 5,6-disubstituted 1,2,3-triazolo[4.5-d]pyrimidin-7-ones in 30—85% and 65—90% yields, respectively.     

Cyanoacetylation of 6-aminouracils. Synthesis of 7-aminopyrido[2,3-d]pyrimidine-2,4,5-triones

6-Aminouracils and N-substituted derivatives are cyanoacetylated to give 5-cyanoacetyl-6-aminouracils. In the presence of bases these are converted to pyrido[2,3-d]pyrimidine-2,4,5-triones in high yields.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 971–975, July, 1990.     

Chemical behavior of 5-alkoxy-2-alkylthiophenes under the conditions of the vilsmeier reaction

Dealkylation of the methoxy group and formation of N-substituted 5-alkyl-3-aminomethylene-4-thiolen-2-ones occur during the action of substituted formamides and phosphorus oxychloride on 5-methoxy-2-alkylthiophenes on heating at 50–70 deg C. At 20 deg the major reaction products are 5-alkyl-2-methoxy-3-formylthiophenes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 171–177, February, 1971.     

Kinetik der Diazotierung des Anilins in methanolischer Bromwasserstoff- und Chlorwasserstofflösung, 2. Mitt.

The kinetics of the diazotization of aniline in 0.003n to 0.4n methanolic HBr-and HCl-solution, resp., were determined (HBr at 25 and 15°C, HCl at 25, 15, –10, –20, and –30°C).It was found that the nitrosation reaction is a preceeding advance-back-reaction.The velocity coefficients of the nitrosation from bromide (at 15 and 25°C) and from chloride (at 25, 15, –10, –20, and –30°C) were determined. The decomposition of I (splitting off a proton) is the rate determining reaction. The free enthalpies of activation for the nitrosation reaction above bromide and chloride at the said temperatures are calculated (table 3).     

Pentacyclic triterpenes from <Emphasis Type="Italic">Sarcostemma clausum</Emphasis>

A homologous series of alkanoic acid (C₂–C₅) esters of germanicol was isolated from the methanolic extract of Sarcostemma clausum, of which germanicol-3-propionate and 3-pentanoate have not been previously described in the literature. In addition, taraxasterol, multiflorenol, and bauerenol were also isolated for the first time from the genus Sarcostemma. Structures were elucidated by chemical and spectroscopic methods (NMR, IR, SM) and by comparison with literature data.Published in Khimiya Prirodnykh Soedinenii, No. 6 pp. 464–466, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Nitrogen Trichloride Decomposition in the Presence of Molecular Hydrogen: I. Promotion of Nitrogen Trichloride Decomposition by Molecular Hydrogen Additives Near the Lower Self-Ignition Limit

The promotion of the branched-chain decomposition of nitrogen trichloride by molecular hydrogen additives at room temperature and 20 torr manifests itself in a decrease in the induction period and the acceleration of reactant consumption with an increase in the hydrogen concentration in the NCl₃+ H₂+ He mixtures. The emission spectrum of the H₂+ NCl₃flame contains the intense bands of NCl (b ¹⁺– X ^3–, = 1 – 0, = 0 – 1, and = 0 – 0, where is the vibrational quantum number) and the bands of a hydrogen-free compound. The latter bands can be assigned to electronically excited NCl ₂radicals formed in the H + NCl₃reaction. The calculations restrict the number of elementary reactions favoring promotion. The promotion effect in the system studied should be due to the side reaction of linear branching. The occurrence of the H + NCl₃reaction via two pathways (NHCl + 2Cl and NCl ₂+ HCl) ensures the qualitative agreement between the experimental data and calculation.     

Synthesis and structure of N-substituted 2-amino-3-phenacylidene-3,4-dihydroquinoxalines

N-Substituted 2-imino-5-aryl-2,3-dihydro-3-furanones react with o-phenylenediamine to form N-substituted 2-amino-3-phenacylidene-3,4-dihydroquinoxalines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 528–531, April, 1989.     

Synthesis and mass spectrometric study of α,ω-diallylpermethyloligosilanes

Representatives of the homologous series of α,ω-diallylpermethyloligosilanes were synthesized for the first time by the reaction of α,ω-dichloropermethyloligosilanes Cl(Me₂Si)_nCl (n = 2–6) with allylmagnesium chloride. Fragmentation of α,ω-diallylpermethyloligosilanes under electron impact ionization was studied by mass spectrometry.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2129–2132, October, 2004.     

Reaction of 3-formyl-2-methoxy-1,6-dioxaspiro[4.4]nonanes with 3-amino-1,2,4-triazole: synthesis of 2-(1,2,4-triazolo[1,5-a]pyrimid-6-yl)methylenetetrahydrofurans

The reaction of 3-formyl-2-methoxy-1,6-dioxaspiro[4.4]nonanes with 3-amino-1,2,4-triazole gives 2-(1,2,4-triazolo[1,5-a]pyrimid-6-yl)methylenetetrahydrofurans in 51–65% yields.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2004–2005, November, 1993.     

Synthesis of 4-oxo-3,4,5,6-tetrahydrospiro(benzo[h]quinazoline-5,1-cyclohexane) derivatives

The reaction of4-acylamino-3-cyano-1,2-dihydrospiro(naphthalene-2,1-cyclohexanes) with hydrogen chloride yields 2-substituted 4-oxo-3,4,5,6-tetrahydrospiro(benzo[h]quinazoline-5,1-cyclohexanes). It was found that when the latter are condensed with methyl iodide, N-alkylation takes place exclusively. Alkylation with ethyl iodide in analogous conditions yields a mixture of O- and N-substituted products.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 658–661, May, 1992.     

Synthesis of substituted 2-phenyl-6-hydroxyquinazolines

A method was developed for the synthesis of 2-phenyl-6-hydroxy(methoxy)quinazoline and a number of N-substituted 2-phenyl-4-amino-6-hydroxyquinazolines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 418–420, March, 1971.     

New method of isolating N-substituted 3-aminomethylenethiol-4-en-2-ones

The methods for the synthesis of the little-studied N-substituted 3-aminomethylenethiol-4-en-2-ones (I) — thiophene analogs of aromatic o-hydroxyazomethines — are based on the application of the not readily accessible and labile hydroxy and methoxy derivatives of thiophene [1, 2].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 854–855, June, 1986.     

Quinones

A number of 2-methyl-3-carbethoxy-5-hydroxy-6-arylindole derivatives were obtained by the condensation of aryl-p-benzoquinones with -aminocrotonate esters and N-substituted -aminocrotonate esters. The position of the aryl substituent was established by means of the NMR spectra.See [8] for Communication XLVIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1634–1636, December, 1970.     

Die Kristallstruktur von Ge5O[PO4]6

Zusammenfassung Die Kristallstruktur der Verbindung Ge₅O[PO₄]₆ wurde auf Grund dreidimensionaler Einkristalldaten ausWeissenberg-Aufnahmen ermittelt und nach der Methode der kleinsten Quadrate verfeinert: Raumgruppe ;a=7,994±0,004 undc=24,87±0,01 Å;Z=3; 467 unabhängige Reflexe;R=0,086.Die Kristallstruktur wird aus singulären [GeO₆]-Oktaedern und [Ge₂O₇]-Doppeltetraedern aufgebaut, die über [PO₄]-Tetraeder zu einem dreidimensionalen Strukturverband vernetzt sind. Die mittleren Abstände betragen: Ge^[6]–O=1,863, Ge^[4]–O=1,704 und P–O=1,525 Å.

---

The crystal structure of Ge₅O[PO₄]₆

The crystal structure of Ge₅O[PO₄]₆ has been determined and refined by least-squares, using three-dimensional x-ray data fromWeissenberg-photographs: space group ;a=7.994±0.004 andc=24.87±0.01 Å;Z=3; 467 independent reflections;R=0.086.The crystal structure consists of isolated [GeO₆] octahedra and [Ge₂O₇] double tetrahedra which are linked by [PO₄] groups forming a three-dimensional network. The average interatomic distances are: Ge^[6]–O=1.863, Ge^[4]–O=1.704 and P–O=1.525 Å.

---

---

Mit 2 Abbildungen