Chlorovinyl Ketones Research Articles

Reaction of quinoline and isoquinoline with nucleophilic organic compounds in the presence of?-chlorovinyl ketones

Reaction of quinoline and isoquinoline with nucleophilic organic compounds in the presence of?-chlorovinyl ketones

Synthesis of pyrazoles by condensation of unsymmetrical dialkylhydrazines with?-chlorovinyl ketones

1,3-Dialkylpyrazoles (in yields up to 70%), dialkylhydrazones of saturated ketones (CH3COR), and salts of formic acid are obtained by the alkali-induced decomposition of the products of condensation of salts of unsymmetrical dialkylhydrazines with chlorovinyl ketones (ClCH = CHCOR). Schemes for the formation of these compounds are proposed.

Ketovinylation of barenide ions

1. For the ketovinylation of barenide ions those 2-chlorovinyl ketones can be used in which the approach to the carbonyl group is sterically hindered (phenyl and t-butyl 2-chlorovinyl ketones). 2. Attack by nucleophiles which are strong bases (−OCH3, amines) is directed not on the double bond of anα, β-unsaturated ketone of the barenyl series, but on the barene nucleus.

Reaction of Phosphorylides with 2‐Chlorovinyl Ketones

Reaction of Phosphorylides with 2‐Chlorovinyl Ketones

Reactions of (2-acylvinyl)trialkylammonium salts with nucleophilic reagents

1. (2-Acylvinyl)trialkylammonium salts are more convenient acylvinylating agents than 2-chlorovinyl ketones. 2. Methods were developed for O- and N-acylvinylation on the basis of reactions of these salts with sodium or potassium acetate, glycine, and potassiophthalimide.

Synthesis and rearrangements of 2-azidovinyl ketones

1. A method was developed for the synthesis of the previously unknown 2-azidovinyl ketones from 2-chlorovinyl ketones. 2. Under the action of hydrochloric acid 2-azidovinyl phenyl ketone undergoes rearrangement with the liberation of nitrogen; as a result benzoylacetonitrile and 5-phenylisoxazole were prepared and identified.

Synthesis of arylpyrazoles

1. A method was developed for the synthesis of arylpyrazoles by reaction of aryl 2-chlorovinyl ketones with hydrazine and substituted hydrazines (yields: 60–90%). 2. It was shown that aryl 2-chlorovinyl ketones react with substituted hydrazines in one way only with formation of 1,3-substituted pyrazoles. 3. It was shown that the p-nitrophenylhydrazone of 4-chloro-3-buten-2-one is very readily cyclized to a pyrazole derivative, which confirms the view that the condensation of aryl 2-chlorovinyl ketones with substituted hydrazines passes through the stage of hydrazone formation.

Cyclic acetals of ?-keto aldehydes and their use in synthesis of alkylnaphthalenes

1. A general method was developed for the synthesis of cyclic acetals of β -keto aldehydes by reaction of β -chlorovinyl ketones with ethylene glycol in presence of alkaline agents. Yields of 50–85% were obtained. 2. It was shown that heating of open-chain β -keto acetals with ethylene glycol in presence of alkali results in transacetalization with formation of the corresponding cyclic acetals. 3. It was shown that the use of cyclic acetals for the synthesis of alkylnaphthalenes by the method that we developed previously [8] makes it possible to obtain these naphthalenes in higher yield.

Condensation of 2-Chlorovinyl ketones with benzene and its homologs

1. A new method was developed for the synthesis of styryl ketones. It consists in the condensation of 2-chlorovinyl ketones with aromatic hydrocarbons in presence of aluminum chloride and moist hydrogen chloride. 2. It was shown that 1,4-dichloro-3-buten-2-one is extremely reactive in this reaction.

2-Aminovinyl ketones Communication 4. Synthesis of ketones of the pyridine series

1. The reaction of alkyl 2-aminovinyl ketones with alkyl 2-chlorovinyl ketones was investigated. It provides a method for the synthesis of 5-acyl-2-alkylpyridines. 2. The structure of the products was confirmed by the oxidation of one of them to isocinchomeromic acid. 3. It was shown that the condensation of 2-aminovinyl methyl ketone with acetonacetaldehyde diemthyl acetal yields 5-acetyl-2-methylpyridine.

Some reactions of alkyl 2-phenoxyvinyl ketones

1. Hydrogenation of alkyl 2-phenoxyvinyl ketones over a palladium catalyst yields alkyl 2-phenoxyethyl ketones, but in their hydrogenation over a platinum catalyst hydrogenolysis of the carbon-oxygen bond occurs, so that phenol and the corresponding saturated ketones are formed. 2. Reaction of alkyl 2-phenoxyvinyl ketones with cyclopentadiene yields derivatives of bicyclo[2,2,1]hept-2-ene. This reaction, however, goes only under severe conditions, and the yields are not high. 3. Reaction of methyl 2-phenoxyvinyl ketone with methylmagnesium bromide results in the formation of 2-methyl-1,3-pentadiene and 2-methyl-3-penten-2-ol. 4. When methyl 2-phenoxyvinyl ketone is heated with aqueous alkali, it undergoes hydrolytic decomposition to acetone, phenol and formic acid. 5. The results indicate that, with respect to the reactivities of the double bond and carbonyl group, 2-phenoxylvinyl ketones occupy an intermediate position between 2-chlorovinyl ketones and 2-aminovinyl ketones.

2-Aminovinyl ketones

1. A study was tirade of the reaction of alkyl 2-dimethylaminovinyl ketones with methyl iodide; after hydrolysis of the reaction mixture, hydroxymethylcne ketone are obtained. This reaction provides a new method for the synthesis of hydroxymethylene ketones. 2. It was shown that, with increase in the size of the alkyl radical of the alkylating agent, the alkylation of dirnethylaininovinyl ketones becomes more difficult and the yields of hydroxymethylene ketones diminish. 3. The structure of the compounds obtained was proved by hydrolysis. 4. The method of synthesizing 2-dialkylaminovinyl ketones from 2-chlorovinyl ketones was extended to the synthesis of aryl 2-dialkylaminovinyl ketones.