Biologically Active Compounds. II. The Synthesis of β-CarboxY-γ-butyrolactone Derivatives

Amide derivatives of γ-substituted paraconic and aconic　acids have been　synthesized. Ultraviolet spectra of the aconic acid derivatives showed characteristic　fine structure in the region of 245 to 280 mμ

Reaction of γ,γ-Dimethyl-α, β-dicarbethoxybutyrolactone with Acetyl Chloride

Acetylation of γ,γ-dimethyl-α,β-dicarbethoxybutyrolactone in benzene in the presence of sodium hydride was attempted. The structure of the condensation product was assigned to O-acetyl derivative, which was converted into γ,γ-dimethyl-β-carbethoxy-α-carboxybutyrolactone whose structure is also discussed by IR spectrum

Synthesis of Ethyl dl-Jasmonate and Ethyl dl-2-Epi-jasmonate

Ethyl dl-jasmonate (1a) and ethyl dl-2-epi-jasmonate (1b), novel constitutents in jasmin absolute from Italian Jasminum grandiflorum L, were prepared from 8-endo-(2'-cis-pentenyl)-3-oxo-2-oxa-bicyclo [3.2.1] octane, jasmine acid δ-lactone(2). Improvement of the preparation of the intermediate (9), a key precursor of (2), was made by different route via lactonization of (7) and/or (8). NMR and IR spectra (la) and (1b) are given

Lactone Carboxylic Acids. II. Synthesis of α-Benzylideneparaconic Acids

The reaction of ethyl γ,γ-dialkylparaconate with aromatic aldehydes, i.e., benzaldehyde, anisaldehyde, p-chlorobenzaldehyde, and piperonal, has been investigated. The condensation took place at the α-position of the lactone ring. As the acidic components, α-benzylideneparaconic acids and α-benzylidene-β-alkylidensuccinic acids were obtained in 25-48% and 7-15% yields, respectively. From the neutral portions small amount of ethyl benzylideneparaconates were separated. During the course of distillation ethyl α-benzylideneparaconate was partially converted into α-benzylidene-γ-methy-γ-ethylbutyrolactone

New Stable Sulfonium Ylides. 1-Dimethylsulfuranylidene-l-phenylsulfonyl-2-propanone and Related Compounds

The preparation of the title compounds as a new type of stable S-ylides has been described. The reaction of 1-dimethylsulfuranylidene-1-phenylsulfonyl-2-propanone (IIb) with lithium aluminium hydride was found to result in the formation of trans-phenylpropenylsulfone (IV), phenylsulfonyl-2-propanone (Ib), and an unidentified paraffin as major products

Lactone Carboxylic Acids. III. Reaction of Ethyl β-Alkylglycidates with Ethyl Malonate

The ring opening of epoxide group in the reaction of ethyl ,β-alkylglycidates with sodiomalonate was observed mostly at the α-position of the glycidates. Ethyl β-ethylglycidate, however, on treatment with sodiomalonate gave ten percent of β-fission product, elucidated by NMR spectra. The reaction sequence provides a general preparative route to γ-alkylparaconic acids and their derivatives

Biologically Active Compounds. I. The Synthesis of 5-Substituted 4-Methy1-3-carboxy-3(or 4)-alkenamides

Monoamides of 5-substituted 4-methyl-3-carboxy-3(or 4)-alkenoic acids have been synthesized, starting with substituted itaconic anhydrides. The anhydride ring was opened by amines to afford N-aryl(or alkyl)-4-alkyl(or aryl)-3carboxy- 3(or 4}-alkenamides. The structure of the amide was elucidated by the comparison with the reference compound prepared from the corresponding Stobbe half-esters

The Anodic Oxidation of trans-Cinnamic Acid. I. The Formation of Ketone and Aldehyde Derivatives

The electrochemical oxidation of trans-cinnamic acid in a mixed aqueous solution of acetic acid and methanol containing potassium hydroxide was studied. The separation of ketones and aldehydes from the neutral materials using Girard reagent P gave benzaldehyde, tolualdehydes, acetophenone, methylacetophenones, propiophenone, phenacyl acetate, and phenacyl alcohol. The mechanism of the anodic reaction of trans-cinnamic acid has been discussed

Mass Fragmentations. II. Some Aspects of Mass Spectra from a Series of Compounds Related to Methyl dl-Jasmonate Syntheses

This paper deals with graphical mass spectral data of the twentyfive compounds related to the preparation of methyl dl-jasmonate and its related materials. The fragmentations from the substituted cyclopentanones and norbornane derivatives can serve basic data for both characterization and elucidation of the structures of complex compounds referring to the preparation of principal components of jasmine flower

Mass Spectral Fragmentations. I. Mass Spectral Date on the Synthetic Intermediates Related to the Preparation of Linaloyl Oxide

This paper describes mass spectral data from synthetic intermediates of linaloyl oxide. The fragmentation of sulfur functional groups including compounds l-8 would provide fruitful evidences for structural assignment of acyclic and alicyclic monoterpenoid precursors. Since, 1,3-dithianyl group in l,2, and 3 can provide a base peak and the elimination of the sulfinyl group from 7 and 8 is considered to occur at the initial stage of the fragmentation