Acetylinic ketones. Part II.. Reaction of acetylenic ketones with nucleophilic nitrogen compounds

Aroylphenylacetylenes (I) reacted with ethyl and phenyl hydrazinecarboxylates (II) to give ω-aroylacetophenone-N-ethoxycarbonyl-(Vla-f) and N-phenoxycarbonyl-(VIg-l) hydrazones, respectively. When these were healed with acetic anhydride they were converted to 5-aryl-1-ethoxycarbonyl-and 1-phenoxycarbonyl-3-phenylpyrazoles (VII), respectively, which on hydrolysis with rnethanolic potassium hydroxide gave the corresponding 5(3)aryl-3(5)phenylpyrazoles (VIII). Reaction of the above acetylenic ketones with guanidine hydrochloride in the presence of sodium carbonate gave the corresponding 2-amino-6-aryl-4-phenylpyrimidines (XII). Similarly, reaction of benzoylphenylacetylene with thiourea and with urea in the presence of sodium ethoxide gave rise to 2,4-diphenylpyrimidine-2-thione (XVIII) and 2,4-diphenyl-2(1H)pyrimidin-one (XV), respectively.     

Acetylenic ketones. Part IV. Reaction of p-nitrobenzoylphenylacetylene with nucleophilic nitrogen compounds

p-Nitrobenzoylphenylacetylene (I) reacted with acylhydrazines (IIa-d) to give the corresponding hydrazones (VIa-d), which when treated with acetic anhydride, gave the same substituted pyrazole (VII). Hydrolysis of the latter with methanolic potassium hydroxide gave the pyrazole derivative (IX). The reaction of I with ethyl and phenyl hydrazinecarboxylates (IIe,f) led to the formation of the hydrazones (VIe) and (VIf), respectively, whereas with methyl- and phenylhydrazines it produced the pyrazoles (X) and (XI), respectively. However, guanidine hydrochloride gave with acetylenic ketone (I), the pyrimidine (XV).     

Acetylenic ketones. Part V. Reaction of acetylenic ketones with thiourea and some of its derivatives

Aroylphenylacetylenes (I) reacted with thiourea and S-benzylisothiourea to give 4,6-diaryl-pyrimidine-2(1H)thiones (IV) and α-aroyl-β-benzylmercaptostyrenes (X), respectively. Methyla-tion and acetylation of the thiones (IV) gave the corresponding S-methyl- (V) and S-acetyl- (VI) derivatives, respectively. The oxidation of these thiones gave the corresponding disulfide derivatives (VII). Reaction of α-aroyl-β-benzylmercaptostyrenes (X) with hydrazine hydrate and phenylhydrazine gave 3(5)-aryl-5(3)-phenylpyrazoles (XI) and 3-aryl-1,5-diphenylpyrazoles (XIII), respectively. Reaction of aroylphenylacetylenes (1) with N-allylthiourea gave 1-allyl-4,6-diaryl-pyrimidine-2-thiones (XVI).     

Acetylenic ketones. VII—Structural analyses by mass spectrometry of the products obtained from the reaction of acetylenic ketones with nucleophilic sulphur compounds

The mass spectra of β-hydroxy-α-thiobenzoylstyrene derivatives and (E, Z)- or (E, E)-β,β-di(α-aroylstyryl)sulphides as well as β,β′di(α-aroylstyryl)disulphides are discussed. The fragmentation patterns support their proposed structure and configuration.     

Acetylenic ketones. Part VI. Reaction of aroylphenylacetylenes with hydrazine derivatives

The reaction of aroylphenylacetylenes (I) with acyl- or aroylhydrazines (II) gave ω-aroyl-acetophenone-N-acyl or N-aroylhydrazones (IV). The latter gave upon treatment with methanolic potassium hydroxide and with acetic anhydride in the presence of sodium acetate, the corresponding pyrazoles (V) and the N-acetylpyrazoles (VII and VIII), respectively. The acetylenic ketones ( 1 ) also reacted with methylhydrazine and 1,1-dimethylhydrazine to give 5-aryl-1-methyl-3-phenylpyrazoles (XII), and 1,1-dimethylhydrazine derivatives (XIII), respectively. When the latter compounds were heated with acetic anhydride, they gave the N-methylpyrazoles (XII).     

Acetylenic ketones. I. Reaction of aroylphenylacetylenes with compounds containing an active methylene group

Aroylphenylacetylenes reacted with ethyl phenylacetate and benzyl cyanide in the presence of sodium ethoxide to give 6-aryl-3,4-diphenyl-2H-pyran-2-ones (2) and 4-aroyl-2,3-cis-diphenyl-crotonitriles (11) , respectively. The structure and configuration of the products are based on chemical and spectroscopic evidence.     

Reaction of acetylenic ketones with hydrazine derivatives. Synthesis of hydroxypyrazoles

Aroylphenylacetylenes Ia-c react with (-butyl hydrazinecarboxylate (IIa) and 2-furylhydrazide (IIb) to give the corresponding hydroxydihydropyrazole derivatives IVa-f. This cyclic structure is supported by chemical transformations. Thus, when compounds IVa-c are heated with acetic anhydride, they yield the corresponding 5-aryl-1-(t-butoxycarbonyl)-3-phenylpyrazoles Va-c which, upon hydrolysis with methanolic potassium hydroxide, produce the corresponding 5(3)aryl-3(5)phenylpyrazoles VI. Spectroscopic data also confirm the suggested cyclic structure IV.     

Reaction of dithiomalonic acid dianilide with substituted acetylenic ketones

The reaction of dithiomalonic acid dianilide with 1-benzoyl(2-thienyl, 2-furoyl)-2-phenylacetylenes in glacial acetic acid in the presence of equimolar amount of perchloric acid under heating (90–115°C) was used to prepare 6-anilino-2-(acylmethyl)-2-phenyl-4-(phenylimino)-4H-1,3-dithiinium perchlorates in good yields.     

Reaction of sulfur with organic compounds

Catalytic reaction of sulfur with the appropriate ethers and esters of p-isopropylphenol has given several previously unknown 4-p-alkoxyphenyl-, 4-p-aryloxyphenyl-, and 4-p-aroyl-oxyphenyl-1,2-dithiole-3-thiones.For part XVIII, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 5, pp. 592–594, May, 1970.     

Reaction of sulfur with organic compounds

The effect of the number and position of phenyl groups in a four-carbon chain on the yields of di- and triphenylthiophenes in the reaction of sulfur with phenylbutanes was investigated. New, simple methods were developed for the synthesis of 2,3-diphenylthiophene (from 1,2-diphenylbutane), 3,4-diphenylthiophene (from 2,3-diphenylbutane), 2,5-diphenylthiophene (from 1,4-diphenylbutane), and 2,3,5-triphenylthiophene (from 1,3,4-triphenyl-1-butanone). Di-, tri-, and tetrasubstituted butanes, butenes, and butadienes that contain two aromatic substituents attached to the same carbon atom do not react with sulfur under the investigated conditions.See [1] for communication XXI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 755–758, June, 1971.     

Gas-phase thermolysis of sulfur compounds. Part III: n-butyl 2-propenyl sulfide

The pyrolysis of n-butyl 2-propenyl sulfide has been investigated in a static system in the initial pressure range of 50–350 torr. The reaction was found to be homogeneous and first order. The rate coefficients are given by the Arrhenius equation between 262 and 293°C. The rate of the reaction remains unchanged in the presence of cyclohexene as radical inhibitor. The main reaction products were propene and a trimer of n-butyl thioaldehyde. The results are interpreted in terms of a molecular mechanism involving a cyclic six-centered transition state. This mechanism is supported by the pyrolysis of 1,1-dideutero-n-butyl 2-propenyl sulfide at 281°C. The kinetic deuterium isotope effect had a value of 2.7 ± 0.2. Nuclear magnetic resonance and mass spectroscopic analysis of the reaction products showed the deuterium to be distributed as expected from the proposed reaction mechanism.     

Condensation of acetylenic acetals with ketones

Summary A study was made of the reaction of propargylaldehyde acetal with a number of ketones under the influence of BF₃ etherate. With acetone and methyl ethyl ketone the reaction goes with the cleavage of 1 mole of alcohol and the formation of the corresponding ethoxyacetylenic ketones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1070–1072, June, 1965     

Reaction of sulfur halides with unsaturated compounds

Conclusions Oxidation of 2,9-dichloro-13-thiabicyclo[8.2.1]cis-5-tridecene with tert-amyl hydroperoxide leads to the respective exo-sulfoxide and also to a derivative of 13-thiabicyclo[7.3.1]cis-5-tridecene, which is a product from rearrangement with enlargement of the thiacyclopentane ring to a thiacyclohexane ring.See [1] for Communication 11.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 384–389, February, 1976.     

Synthesis of acetylenic ketones

A general preparative method of synthesis of acetylenic ketones was developed based on acylation of terminal acetylenes with acid chlorides in the presence of Cu(I) chloride.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2551–2555, November, 1990.     

Reaction of organic sulfur compounds with superoxide anion—III : Oxidation of organic sulfur compounds to sulf1nic and sulfonic acids

Organic sulfur compounds such as disulfide, thiolsulfinate, thiolsulfonate, thiol, sodium thiolate, and sodium sultinale were readily oxidized to both sulfinic and sulfonic acids with superoxide anion generated from potassium superoxide and 18-crown-6-ether under mild conditions. However, both sulfide and sulfoxide did not react with superoxide anion, O₂^-. Although thiol was easily oxidized to disulfide with O₂^? at room temperature, it was oxidized further with O₂^? at 60° to the corresponding sulfinic and sulfonic acids. Symmetrical disulfide was obtained in the reaction of unsymmetrical thiolsulfinate or thiolsulfonate along with both sulfinic and sulfonic acids. Most reactive was thiolsulfinate which reacted at lower temperature ranging between ?40 and 0° to afford the products within 30 min. Relative reactivities fall in the following order: thiolsulfinate > thiolsulfonate > disulfide ? sodium thiolate ? sodium sulfinate. Polar solvents such as pyridine and acetonitrile were more effective than such a less polar solvent as benzene in the oxidation of the substrate, and increased amount of the crown ether shortened the reaction time. Nucleophilic attack of O₂^? and electron transfer processes are believed to be involved in these oxidations.