Acylation of benzimidazole by the regel-buechel method. 2. Deacylation and dissociation of 1-methyl-3-acyl-2-(1′-methyl-2′-benzimidazolyl)-4-benzimidazolines

With excess acyl halide 1-methyl-3-acyl-2-(1-methyl-2-benzimidazolyl)-4-benzimidazoline is converted to an unstable 1-methyl-3-acyl-2-(1-methyl-3-acyl-4-benzimidazolin-2-yl)benzimidazolium chloride, which undergoes intramolecular redox cleavage with the formation of 1,1-dimethyl-2,2-dibenzimidazolyl and an aldehyde and dissociates at the C-C bond that connects the benzimidazolium and benzimidazoline fragments into a carbene yield and a 1-methyl-3-acylbenzimidazolium chloride.See [1] for communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 339–342, March, 1987.     

Reaction of 1-acyl-2-phenylacetylenes with thiosemicarbazide

Conclusions The reaction of 1-acyl-2-phenylacetylenes with thiosemicarbazide in methanol at 60C gives 2-amino-7-hydroxy-6,7-dihydro-1,3,4-thiadiazepines which, upon heating in -vacuum fragment with the formation of 3,5-disubstituted pyrazoles.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 216–218, January, 1987.     

Synthesis and modification of light-sensitive 3-acyl-2-hetarylchromones containing bromomethyl group in the acyl fragment

A synthesis of photosensitive 3-acyl-2-hetarylchromones containing bromomethyl group in the 3-aroyl fragment and their further modification by the reactions with N-, S- and O-nucleophiles are described. A dependence of spectral properties from the structure of compounds was studied.     

Palladium-catalysed amination of 2-acyl-1-alkyl-5-bromopyrroles

The first intermolecular C-N bond-forming reactions between substituted 2-bromopyrroles and primary and cyclic secondary amines were performed using Pd₂(dba)₃ as catalyst with BINAP as the ligand. The aminations proceeded in the presence of NaO^tBu at 80-100 °C in 31-93% yields.     

Reactions of 1-acyl-2-bromoacetylenes with dithiocarbamic acids

2-Acyl-2-bromoacetylenes react with dithiocarbamic acids in aprotic solvents (acetonitrile, chloroform, or ether) to give 5-acyl-2-diethylamino(heteryl)-1,3-dithiolium bromides, which on reaction with secondary amines (diethylamine or morpholine) undergo cleavage of the 1,3-dithiole ring to give 1-acyl-2-diethyl(morpholyl)dithiocarbamoyl-2-diethylamino(morpholyl)ethylenes. X-ray crystallographic studies on the product from one of these reactions has shown it to be 5-thenoyl-2-diethylamino-1,3-dithiolium bromide.Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 664033 Irkutsk. A. V. Shubnikov Institute of Crystallography, Russian Academy of Sciences, 117331 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1850–1856, August, 1992.     

Chemoselective reductions of 2-acyl-1H-indole-3-carboxaldehydes

A novel procedure for the chemoselective reduction of 2-acyl-1H-indole-3-carboxaldehydes has been developed. Low temperature lithium triethylborohydride reduction affords the indol-2-yl carbinol whilst sodium cyanoborohydride reduction in acetic acid affords the 3-hydroxymethyl analogs. Both processes are high yield, and provide access to intermediates of potential utility for indole alkaloid synthesis.     

Synthesis of 3-acyl-1-alkyl-2-alkylseleno-1-cyclobutene using alkyneselenolate

The reaction of lithium alkyneselenolate with alpha,beta-unsaturated ketone and then alkyl or acyl halide afforded 3-acyl-1-alkyl-2-alkylseleno-1-cyclobutene. The structure of the cyclobutene was elucidated by IR, MS, (1)H, (13)C, and (77)Se NMR, COSY, HMQC, and HMBC data and X-ray analysis.     

Studies on extraction of copper(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone

The extraction of Cu(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone (HA), in different organic solvents has been studied. The extraction mechanism of Cu(II) and the composition of the extracted species has been determined. Cu(II) was extracted as CuA₂, or in the presence of TOPO, as CuA₂TOPO. The extraction constants do not change regularly with increasing the length of acyl chain in the 1-phenyl-3-methyl-4-acyl-5-pyrazolone derivatives. The effect of the temperature on the extraction of Cu(II) has also been investigated.     

C-metallierung an phosphaaromaten - 2-lithio-1-methyl-1,3-benzazaphosphol

1-Methyl-1,3-benzazaphospholes are described; the 2H derivate and t-BuLi give the title compound, characterized by reaction with CO₂ and Me₃SiCl; NMR data confirm the results.     

Thermal decomposition of copper complexes of 1-phenyl-3-methyl-4-acyl-5-pyrazolone in air atmosphere

Copper complexes of some 1-phenyl-3-methyl-4-acyl-5-pyrazolones have been prepared. The complexes were characterized by elemental analyses and thermal analyses. It was shown that the melting points decrease linearly in increasing the molecular weight of the complexes.     

Ethylenic acyl cyanides IV : Intramolecular ene cyclisation of 5-methyl-5-hexenoyl cyanides to 3-methyl-2-cyclohexenones

Condensation of methallyltrimethylsilanes with α,β-ethylenic acyl cyanides leads to 5-methyl-5-hexenoyl cyanides which after thermal cyclisation give 3-methyl-2-cyclohexenones and hydrogen cyanide.     

Studies on extraction of manganese(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone

The extraction of Mn(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone (HA) in MIBK has been studied. Mn(II) is extracted as MnA(2). The extraction constant for each 4-acyl compound was calculated. The effect of temperature on the extraction of Mn(II) has also been investigated.     

Reactions of zinc enolates derived from 1-Aryl-2-bromo-alkanones with 3-acyl-6-bromochromen-2-ones

Zinc enolates derived from 1-aryl-2-bromoalkanones react with 3-acyl-6-bromochromen-2-ones to give 3-acetyl(benzoyl)-6-bromo-4-(2-aryl-2-oxo-1-R-ethyl)chromen-2-ones as a single diastereoisomer.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 10, 2004, pp. 1536–1538.Original Russian Text Copyright © 2004 by Shchepin, Korzun, Shurov, Vakhrin.     

Synthesis of 5H-thiazolo[3,2-a]pyrimidine derivatives from 6-methyl-2-thiouracil and 1-acyl-2-bromoacetylenes. X-ray structural study of 3-benzoyl-7-methyl-5H-thiazolo[3,2-a]pyrimidin-5-one

3-Acyl-7-methyl-5H-thiazolo[3,2-a]pyrimidin-5-ones were synthesized by the reaction of 1-acyl-2-bromoacetylenes with 6-methyl-2-thiouracil, carried out with heating in DMF, dioxane, or acetonitrile in the presence of triethylamine. The structure of 3-benzoyl-7-methyl-5H-thiazolo[3,2-a]pyrimidin-5-one was established by X-ray structural analysis.Deceased in 1995.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2306–2308, September, 1996.     

Synthesis of enzyme-inhibitory phospholipid analogs II. Preparation of chiral 1-acyl-2-acylamido-2-deoxyglycerophosphorycholines from serine

A facile and efficient stereospecific route to the enzyme-inhibitory 2-amide analogs of phosphatidycholine is reported.