Heterocyclization of 2-chloro-1-cyano-1-diethoxyphosphoryl-2-trifluoromethylethylene and 2-chloro-2-chlorodifluoromethyl-1-cyano-1-diethoxyphosphorylethylene

The reactions of 2-chloro-1-cyano-1-diethoxyphosphoryl-2-trifluoromethylethylene (2a) and 2-chloro-2-chlorodifluoromethyl-1-cyano-1-diethoxyphosphorylethylene (2b) with arylamines, arylhydrazines, amidines, 2-aminopyridines, and 5-aminopyrazoles were studied. Alkenes 2a, b can serve as precursors of aminopyrazoles, pyrimidines, pyrido[1,2-a]pyrimidines, and pyrazolo[1,5-a]pyrimidines modified with the fluoroalkyl and diethoxyphosphoryl groups. Intermediates of some heterocyclization reactions were detected by NMR spectroscopy. The structures of the compounds were confirmed by X ray diffraction analysis.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1977–1986, September, 2004.     

Synthese von 1-Aryl-2-azido-2-alken-1-onen

Zusammenfassung Durch Kondensation von -Azidoacetophenonen mit aliphatischen Aldehyden wurden 1-Aryl-2-azido-2-alken-1-one erhalten. Die Thermolyse dieser Verbindungen gab Azirine, die sich mit Cyclopentadien in 2-Azatricyclo[3.2.1.0^2.4]-6-octene überführen lassen.

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Synthesis of 1-aryl-2-azido-2-alken-1-ones (ene-azides, V)

1-Aryl-2-azido-2-alken-1-ones were obtained by condensing -azidoacetophenones with aliphatic aldehydes. Thermolysis of these compounds gave azirines, which can be converted to 2-azatricyclo[3.2.1.0^2.4]-6-octenes by reaction with cyclopentadiene.

     

Relativistic calculation of autoionization widths of 1s2s2pjJ, 1s2s2 2S1/2, and 1s2pJ 2pj′J levels

The autoionization widths of levels 1s 2s 2p_jJ, 1s2s^{2 2}S_1/2, and 1s2p_j2p_j′ J have been calculated for ions with Z = 6–30. The calculation has been carried out in intermediate coupling. The decay amplitudes have been calculated in a relativistic approximation.     

1,1,1-三氟-2-甲基-2-丙醇合成工艺研究

以氯甲烷(2)为原料制备甲基氯化镁格氏试剂;以三氯化镓为催化剂,甲基氯化镁与1,1,1-三氟丙酮(3)反应,经水解制得1,1,1-三氟-2-甲基-2-丙醇(1).产物结构经1 H-NMR、13 C-NMR、19 F-NMR及MS表征;通过单因素、正交实验和放大重复性实验确定了最佳反应条件:溶剂为正丁醚、格氏试剂浓度3 ...     

Synthesis of 2, 2 -dimethyl-1-p-tolyl-1-hydroxypropane and 2,2-dimethyl-1-p-tolyl-1-oxopropane

Conclusions 2,2-Dimethyl-1-p-tolyl-1-hydroxypropane and 2,2-dimethyl-1-p-tolyl-1-oxopropane were obtained for the first time.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 149–150, January, 1973.     

2 1 1At-tellurium colloid and Na2 1 1At injections,and their radiobiological effects

Na^{2 1 1}At and^{2 1 1}At–Te colloid injections were prepared. By comparison with tissue distribution of Na^{2 1 1}At and^{2 1 1}At–Te colloid injections it has been demonstrated that the^{2 1 1}At–Te colloid is stable in vivo. It has been shown that the radiohalogen,^{2 1 1}At, has huge and extensive radiobiological effects in studying on the changes in histopathology, enzyme histochemistry, chromosome aberration, micronucleus frequency of bone-marrow polychromatic erythrocytes and the injury effect of^{2 1 1}At on experimental Ehrlich ascites cells.     

Improved Synthesis of 1-Aryl-2, 2-Dichloro-1-Alkanones

Recently¹ we described a convenient synthesis of 1-aryl-2, 2-dichloro-1-alkanones 1 by a reaction sequence involving conversion of the parent alkylarylketones into the corresponding N-cyclohexylketimines, followed by chlorination with N-chlorosuccinimide in carbon tetrachloride to afford N-cyclo-hexyl α,α-dichloroketimines, the latter compounds being hydrolyzed in acidic medium to yield the title compounds 1. The relative inaccessibility of compounds of type 1 in the literature was striking. α,α-Dichloroacetophenones 1 (R=H) are     

Reaction of 1, 1-Di-p-methoxyphenyl-2, 2-dinitroethylene and 1, 1-Di-O-methoxyphenyl-2, 2-dinitroethylene with 1-Benzyl-1, 4-dihydronicotinamide： Evidence for Concerted Electron-hydrogen Atom Transfer Mechanism

1,1-Di-p-methoxyphenyl-2, 2-dinitroethylene reacts with 1-benzyl-1, 4-dihydronicotinamide (BNAH) in deaerated acetonitrile to give 1,1-di-p-methoxyphenyl-2, 2-dinitroethane,while 1,1-di-O-methoxyphenyl-2, 2-dinitroethylene fails to react with BNAH under the same conditions, which provides evidence for a concerted electron-hydrogen atom transfer mechanism.     

Synthesis of substituted 1-(2-arylvinyl)-2-azolyl-1-pyridylethanols-1

A series of new 1-(2-arylvinyl)-2-azolyl-1-pyridylethanols-1 has been obtained with various positions of the nitrogen atom in the pyridine fragment and with substituents in the benzene ring, by the reaction of (2-arylvinyloxiran-2-yl)pyridines with triazole and imidazole, for agrochemical screening. The compounds mentioned displayed high fungicidal activity. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1167–1174, August, 2007.     

Stereoselective epoxidation of 2-arylidene-1-indanones and 2-arylidene-1-benzosuberones

Summary Oxidation of the (E) and (Z) isomers of 2-arylidene-1-indanones (1) and 2-arylidene-1-benzosuberones (4) by alkaline hydrogen peroxide (methodi) afforded the spiroepoxidestrans-2a–g andtrans-5a–g from both isomers as sole products in high yields. On the other hand, dimethyldioxirane epoxidation(methodii) of the (E) isomers1a–g and4a–g gave the correspondingtrans spiroepoxides in good yields, whereas the (Z) isomers1a,c,e and4a,c,e led to thecis spiroepoxides in moderate yields. Dimethyldioxirane oxidation (methodii) of (Z)-1c and (Z)-4c,e gave diones3c and6c,e as by-products as well. Epoxidation of (Z)-1a,c,e and (Z)-4a,c,e bym-chloroperoxybenzoic acid (methodiii) resulted inca. 6:1 mixtures ofcis-2a,c,e andtrans-2a,c,e orcis-5a,c,e andtrans-5a,c,e spiroepoxides.Dedicated to Prof.W. Fleischhacker on the occasion of his 65^th birthday     

1-Fluoro-2-hydrostibatrane

1-Fluoro-2-hydrostibatrane was synthesized by the reaction of antimony trifluoride with triethanolamine. The molecular structure of the compound was studied by X-ray diffraction and multinuclear magnetic resonance. The coordination polyhedron of the Sb atom is intermediate between a distorted tetrahedron (AX₄E type of molecule) and a tetrahedral pyramid (AX₄DE type of molecule). Diastereotopism of the geminal protons of each methylene group in the half-rings of the heterocycle, observed in the NMR spectra, vanishes at 65°C because of reversible cleavage of the N → Sb coordination bond and inversion of the nitrogen atom. The chemical environment of the OCH₂ and NCH₂ protons of the heterocycle and 2-hydroxyethyl protons is averaged due to the fast prototropic tautomerism at 75–120°C (in DMSO-d ₆).     

1-Amino-2-hydrazinopyrimidin-N-ylides. Unusual tautomers of 1-aminopyrimidin-2-hydrazones

Summary 1-Amino-2-methylthiopyrimidinium iodides3 have been synthesized by reaction of 3-isothiocyanato-2-propeniminium perchlorates1 with hydrazines and subsequent methylation of the resulting 1-amino-2(1H)-pyrimidinthiones2. Reaction of3 with hydrazine causes substitution of the methylthio group and results in the formation of deeply coloured 1-amino-2-hydrazinopyrimidin-N-ylides5 as unusual tautomers of the commonly expected 1-amino-2(1H)-pyrimidinhydrazones4. The structure of these N-ylides has been proved by spectroscopic methods as well as by subsequent transformation to 3-amino-1,2,4-triazolo[2,3-a]pyrimidinium salts9 by dehydration or to pyrimidotriazinium salt10 c by oxidation. Reaction of N,N-disubstituted 1-amino-2-methylthiopyrimidinium salt7 a with hydrazine also causes substitution of methylthiol, the resulting orange N,N-disubstituted 1-amino-2(1H)-pyrimidinhydrazone8 a, however, cannot tautomerize to N-ylides.

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1-Amino-2-hydrazinopyrimidin-N-ylide. Ungewöhnliche Tautomere von 1-Aminopyrimidin-2-hydrazonen

Zusammenfassung Es wurden 1-Amino-2-methylthiopyrimidiniumjodide3 ausgehend von 3-Isothiocyanato-2-propeniminiumperchloraten1 und Hydrazinen durch Methylierung der primär gebildeten 1-Amino-2(1H)-pyrimidinthione2 hergestellt. Die Reaktion dieser Pyrimidiniumsalze3 mit Hydrazin verläuft unter Substitution der Methylthiogruppe unter Bildung violett gefärbter 1-Amino-2-hydrazinopyrimidin-N-ylide5 als ungewöhnliche Tautomere der allgemein erwarteten 1-Amino-2(1H)-pyrimidinhydrazone4. Die Struktur dieser Ylide5 wird durch spektroskopische Methoden sowie durch nachfolgende Dehydratisierung zu 3-Amino-1,2,4-triazolo[2,3-a]pyrimidiniumsalzen9 bzw. Oxydation zum Pyrimidotriaziniumsalz10 c bewiesen. Die Reaktion des N,N-disubstituierten 1-Amino-2-methylthiopyrimidiniumsalzes7 a mit Hydrazin verläuft ebenfalls unter Substitution der Methylthiogruppe. Jedoch kann das gebildete orange gefärbte, N,N-disubstituierte 1-Amino-2(1H)-pyrimidinhydrazon8 a nicht zu einem N-Ylid tautomerisieren.

     

A concise synthesis of 2-benzoyl-1-indanones and 1-indanones from 2-aryl-1-tetralones

Abstract

Methyl-2-(3-oxo-3-aryl) benzoates derived from acid catalyzed air oxidative fragmentation of 2-aryl-1-tetralones were efficiently undergone intramolecular-Claisen condensation in the presence of potassium tertiary butoxide. The resulting 2-benzoyl-1-indanones formed in two-step ring contractions were further subjected to indium triflate mediated retro-Claisen condensation to get 1-indanones.