Preparation of polyorganoborosiloxanes by heterofunctional condensation

Summary New polymers — polyorganoborosiloxanes, the molecular chain of which contains silicon-oxygen-boron linkages — were prepared by the heterofunctional condensation of alkyl- and aryl-dialkoxysilanes with boron triacetate and of alkyl- and aryl-diacetoxysilanes with tributyl borate.     

Pyrroles from ketoximes and acetylene

2-(2-Furyl)pyrroles and 1-vinyl-2-(2-furyl)pyrroles were obtained in up to 80% yields in the reaction of ketoximes of the furan series with acetylene in MOH—dimethyl sulfoxide (M = Li, K) Superbase media.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1058–1061, August, 1981.     

Some features of formation and dissolution of a series of Pu(IV) and Zr alkyl and butyl alkyl phosphates in the system tBP — N-dodecane — Nitric acid — Water

The formation and composition of salts produced on interaction of a series of alkyl- and butylalkylphosphoric acids having alkyl radical chain lengths from C₄ to C₁₀ with Pu(IV) and Zr in organic and aqueous phases of the system TBP — n-dodecane — nitric acid — water have been studied. The composition of compounds was found to depend on the conditions of their formation, being defined first of all by the HNO₃ concentration in aqueous and organic phases.     

Vanilline Alkanoates in the Synthesis of Hexahydrobenzacridine and Octahydroxanthene Derivatives

Cascade heterocyclization of 1,3-cyclohexanedione and dimedone with 2-naphthylamine and vanilline esters gave derivatives of 2-methoxy-4-(alkyl-11-oxo-7,8,9,10,11,12-hexahydrobenz[a]acridin-12-yl)- and 2-methoxy-4-(alkyl-1,8-dioxo-2,3,4,5,6,7,8,9-octahydro-1H-xanthen-9-yl)phenyl esters of aliphatic (C₁– C₄ ) carboxylic acids.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 654–658.Original Russian Text Copyright © 2005 by Kozlov, Basalaeva.     

Pyrroles from ketoximes and acetylene.

2-Aryl- and 1-viny1-2-pyrroles were synthesized by condensation of p-substituted acetophenone oximes with acetylene under pressure in superalkaline media (KOH/DMSO). The initially formed nitrogen-unsubstituted pyrroles can be vinylated in the presence of acetylene. Lithium hydroxide, which is completely inactive in the vinylation step, was found to be a selective catalyst for the construction of a pyrrole ring from oximes of aliphatic aromatic ketones. In the case of aliphatic and cycloaliphatic ketoximes (for example, cyclohexanone oxime) LiOH has virtually no catalytic effect on the reaction. The yields of 1-viny1-2-ary1-pyrroles depend substantially on the substituent in the phenyl ring. The structures of the synthesized compounds were confirmed by the IR, PMR, UV, and ¹³C NMR spectra.See [1] for communication II.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 489–491, April, 1978.     

Pyrroles from ketoximes and acetylene

The reaction between ketoximes CH₃(RCH₂)C = NOH and acetylene in the presence of KOH and dimethyl sulfoxide at 120°C leads exclusively to 1-vinyl-2-methyl-3-R-pyrroles in 73–87% yields. The regiospecificity of the reaction is disrupted when the temperature is raised, and the fraction of a second isomer (1-vinyl-2-RCH₂-pyrrole) reaches 20–50% at 140°C. Regioselectivity is not observed for R¹CH₂(R²CH₂)C = NOH (R¹ and R² = n-alkyl). The relative shifts of the signals of the ring protons and the vinyl group for a number of 2-alkyl-1-vinyl- and 2,3-dialkyl-1-vinylpyrroles were measured. Alkyl substituents have a distinct effect on the chemical shifts of the protons of the 4–5 bonds. As the volume of the 2-alkyl substituent increases the protons of the N-vinyl group are deshielded by 0.10–0.13 ppm, and the 4-H ring proton is shielded by 0.05–0.16 ppm; this is explained by steric inhibition of the p- conjugation in the N-vinyl group during an s-trans(anti)-gauche conformational transition.This is actually communication XVI. The first publications (for example, see [1–3] and the literature cited in them) were not numbered.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 54–59, January, 1978.     

Pyrroles from ketoximes and acetylene. 45. A new route to 2,2-dipyrroles

The reaction of 1-methyl-2-acetylpyrrole oxime with acetylene at atmospheric and increased pressure can be catalyzed by KOH-DMSO superbase to give 1-methyl-2-(2-pyrrolyl)pyrrole, N-vinyl-2-[1-methyl(2-pyrrolyl)]pyrrole, and the reaction intermediate methyl-2-(1-methylpyrrolyl)-O-vinyloxime.See [1] for Communication 44.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 460–463, April, 1991.     

Alkaloids ofNitraria komarovii. IV. Total synthesis of komarovine and komarovidine

Two alkaloids of a new type — komarovine and komarovidine — have been isolated from the epigeal part of theNitraria komarovii. Their structures — 3-(quinolin-8'-yl)--carboline and 3-(quinolin-8'-yl)-5,6-dihydro--carboline, respectively — have been established by synthesis.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 192–195, March–April, 1981.     

Pyrroles from ketoximes and acetylene. 43. 1,2-Dihaloalkanes and vinyl chloride in the synthesis of 2-(4-alkylthiophenyl)pyrroles

2-(4-Alkylthiophenyl)-3- and 2-(4-alkylthiophenyl)-5-methylpyrroles and their 1-vinyl derivatives were synthesized by the reaction of alkyl(4-alkylthiophenyl)ketoximes with dihaloalkanes or vinyl chloride in the KOH-DMSO system at 120–140C and atmospheric pressure.See [1] for Communication 42.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1, 1337–1340, October, 1990.     

Pyrroles from ketoximes and acetylene. 40. Reaction of alkyl hetaryl ketoximes with 1,2-dichloroethane in superbase media

2-(2-Furyl)- and 2-(2-thienyl)pyrroles and their N-vinyl derivatives were synthesized by the reaction of alkyl furyl (thienyl) ketoximes with 1,2-dichloroethane in superbase media. 2-Chloroethyl and vinyl ethers of alkyl hetaryl ketoximes are intermediates in the reaction.See [1] for Communication 39.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 901–906, July, 1989.     

Synthesis of alkyl- and aryl(o-oxyphenoxymethyl) phosphinic acids

Conclusions Cleavage of 2-oxo-2-chloromethyl-1,3,2-benzodioxaphosphole by Grignard reagents produced pyrocatechol esters of alkyl- and aryl(chloromethyl)phosphinic acids, cyclization of which and subsequent hydrolysis lead to alkyl- and aryl(o-oxyphenoxymethyl)phosphinic acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 943–946, April, 1989.     

Pyrroles from ketoximes and acetylene. 23. 2-(1-naphthyl)- and 2-(2-naphthyl)pyrroles and their 1-vinyl derivatives

2-(1-Naphthyl)- and 2-(2-naphthyl)pyrroles and their 1-vinyl derivatives were synthesized in 22–64% yields by the reaction of 1- and 2-acetylnaphthalene oximes with acetylene at both atmospheric pressure and elevated pressures in an alkali metal hydroxide-dimethyl sulfoxide system.See [1] for communication 22.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1351–1353, October, 1982.     

Saturated heterocycles, 75. Preparation of tetracyclic thiophene derivatives with bridgehead nitrogen. Synthesis of polymethylenethieno[2,3—d]dihydropyrrolo-, tetrahydropyrido- and tetrahydroazepino[1,2—a]pyrimidin-4-ones and -4-thiones

The following tetracyclic ring systems and their derivatives have been synthesized for pharmacological investigations: Trimethylenethieno[2,3—d]dihydropyrrolo[1,2—a]pyrimidin-4-one and -4-thione (1 a, 5 a); Tetramethylenethieno[2,3—d]dihydropyrrolo[1,2—a]pyrimidin-4-one and -4-thione (1 b, 1 j, 5 b); Pentamethylenethieno[2,3—d]dihydropyrrolo[1,2—a]pyrimidin-4-one and-4-thione (1 c, 5 c); Trimethylenethieno[2,3—d]tetrahydropyrido[1,2—a]pyrimidin-4-one and -4-thione (1 d, 5 d); Tetramethylenethieno[2,3—d]tetrahydropyrido[1,2,—a]pyrimidin-4-one and -4-thione (1 e, 5 e); Pentamethylenethieno[2,3—d]tetrahydropyrido[1,2—a]pyrimidin-4-one and -4-thione (1 f, 5 f); Trimethylenethieno[2,3—d]tetrahydroazepino[1,2—a]pyrimidin-4-one and -4-thione (1 g, 5 g); Tetramethylenethieno[2,3—d]tetrahydroazepino[1,2—a]pyrimidin-4-on and -4-thione (1 h, 5 h); Pentamethylenethieno[2,3—d]tetrahydroazepino[1,2—a]pyrimidin-4-one and -4-thione (1 i, 5 i); Tentamethylenethieno[2,3—d]tetrahydroazepino[1,2—a]pyrimidin-4-one (7 b); Pentamethylenethieno-[2,3—d]tetrahydropyrido[1,2—a]pyrimidin-4-one (7 c).Compounds1 a–i were synthesized from 2-amino-3-ethoxycarbonyl-4,5-polymethylenethiophene2 a–c with the corresponding lactim ethers (3 a–c) in chlorobenzene in the presence of polyphosphoric acid (PPA). Compounds7 b and7 c were obtained in the reaction of -amino acid esters2 b and2 c with 2-bromopyridine (6). The thione derivatives (5 a–i) were prepared from compounds1 a–i with phosphorus(V) sulphide.Part 74:Szabó J, Fodor L, Szcs E, Bernáth G, Sohár P (1984) Pharmazie 39: 347.     

Pyrroles from ketoximes and acetylene. 44. Methyl aryl ketoximes with reactive substituents

The Trofimov reaction was extended to methyl aryl ketoximes with substituents in the benzene ring that are unstable with respect to the action of a strongly basic medium. The corresponding pyrroles and their 1-vinyl derivatives were obtained. 4-Nitroacetophenone oxime, from which only 2-phenyl- and 1-vinyl-2-phenylpyrrole were obtained, and 4-bromoacetophenone oxime, the reaction of which leads to the formation of 1-vinyl-2-(4-vinyloxyphenyl)pyrrole in addition to the principal 2-(4-bromophenyl)pyrrole, constituted exceptions.For communication 43, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 187–191, February, 1991.     

Synthesis and transformations of 2,3-dioxo-2,3-dihydroimidazo [1,2-a]-benzimidazole derivatives

9-(H)Alkyl-2,3-dioxo-2,3-dihydroimidazo[1,2-a]benzimidazoles were synthesized by the action of oxalyl chloride on 2-amino-1(H)alkylbenzimidazoles and subsequent cyclization of the resulting 2-amino-1-(H)alkyl-3-chlorooxalylbenzimidazolium chlorides in the presence of triethylamine. The behavior of the synthesized benzimidazoles with respect to the action of alkalis, lithium aluminum hydride, and ethylmagnesium bromide was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1391–1395, October, 1976.     

2-Benzopyrylium salts. 27. Some transformations of 6-oxodibenzo[a,g]-quinolizinium salts

The synthesis of 6-oxodibenzo[a,g]quinolizinium perchlorate — an analog of the alkaloid berberine — and a number of its derivatives, including mesoionic compounds, was accomplished on the basis of a 1-unsubstituted 3-(2-methylenecarboxyaryl)-2-benzopyrylium salt. The interconversions of the compounds obtained in this research were studied.See [1] for communication 26.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1381–1387, October, 1982.     

2,2-Dimethyl-5-(5-R-furfurylidene)-1,3-dioxane-4,6-diones. 3. Selective hydrogenation of the exocyclic double bond and three-dimensional structures of the reaction products

The reaction of 2,2-dimethyl-5-(5-R-furfurylidene)-1,3-dioxane-4,6-diones with sodium borohydride in alcohol leads exclusively to products of hydrogenation of the exocyclic double bond. The three-dimensional structure of one of them — 2,2-dimethyl-5-(5-methyl-furfuryl)-1,3-dioxane-4,6-dioxane — was investigated by x-ray diffraction analysis (XDA).See [1] for Communication 2.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1201–1207, September, 1989.     

Alkynylhalocarbenes. 4. Generation of (alk-1-ynyl)halocarbenes from 3-substituted 1,1,1,3-tetrahalopropanes under the action of bases

When treated with KOH under phase-transfer catalysis or with Bu^tOK, 3-substituted (alkyl or phenyl) 1,1,3-tribromo-1-fluoropropanes 1a—c exclusively generate previously unknown (alk-1-ynyl)fluorocarbenes 5a—c, which react with olefins to give 1-(alk-1-ynyl)-1-fluorocyclopropanes 6a—h in 12—69% yields. Under analogous conditions, 3-alkyl- and 3-aryl-3-bromo-1,1,1-trichloropropanes 2a—c selectively afford (alk-1-ynyl)chlorocarbenes 7a—c, which are trapped by olefins to form the corresponding 1-(alk-1-ynyl)-1-chlorocyclopropanes 8a—k in 35—70% yields. (Phenylethynyl)chlorocarbene 7a is also selectively generated from 1,1,1,3-tetrachloro-3-phenylpropane (3a) upon its treatment with Bu^tOK. With an excess of 2,3-dimethylbut-2-ene or 2-methylpropene, carbene 7a yields 1-chloro-1-(phenylethynyl)cyclopropanes 8a or 8c, respectively. In contrast, 1,1,1,3-tetrachloroheptane 3b and 3-alkyl- and 3-phenyl-1,1,1,3-tetrabromopropanes 4a,c,f react with bases in the presence of olefins to give, along with the corresponding 1-(alk-1-ynyl)-1-halocyclopropanes 8a,c,d and 11a—f, vinylidenecyclopropanes 12a,c—g, which suggests the generation, under these conditions, both (alk-1-ynyl)halocarbenes 7b and 9a—c and vinylidenecarbenes 10 and 11a—c. The composition and structures of intermediate products in the reactions of tetrahalides 1b, 2a, 2b, 3a, and 3b with Bu^tOK were determined and the mechanisms for carbene generation in these reactions were proposed.     

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.     

Studies in the field of pyridazine compounds, 20. 6H-1,2,4-Triazino[4,3—b]1,2,4-triazolo[3,4—f]pyridazine,a novel angular ring system

The novel ring system, 6H-1,2,4-triazino[4,3—b]1,2,4-triazolo[3,4—f]-pyridazine was prepared either by ring closure of1-(1-ethoxycarbonylethylene)-2-(1,2,4-triazolo[4,3—b]pyridazinyl-6)-hydrazine derivatives (4, 5, 7) in polyphosphoric acid or of a hydrazine15 derived from pyridazino-1,2,4-triazine under the action of triethyl orthoformate. Compound8 showed a positive inotropic effect.

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Über Pyridazinring enthaltende Verbindungen, 20. 6H-1,2,4-Triazino[4,3—b]1,2,4-triazolo[3,4—f]pyridazin, ein neues angulares Ringsystem

Zusammenfassung Das neue Ringsystem 6H-1,2,4-Triazino[4,3—b]1,2,4-triazolo[3,4—f]-pyridazin wurde entweder durch Ringschluß der1-(1-Ethoxycarbonylethylen)-2-(1,2,4-triazolo[4,3—b]pyridazinyl-6)-hydrazin-Derivate(4, 5, 7) 4, 5, 7 in Polyphosphorsäure, oder aus einem von Pyridazino-1,2,4-triazin abgeleiteten Hydrazin15 durch Ringschluß mit Orthoameisensäuretriethylester hergestellt. Verbindung8 zeigte einen positiven inotropen Effekt.