Reaction of cyclopropenoid fatty acid derivatives with hydrogen halides

Bailey, A. V.; Magne, Frank C.; Boudreaux, G. J.; Skau, Evald L.

doi:10.1007/bf02654746

Cited by 14 publications

(5 citation statements)

References 3 publications

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“…The following reactions were thought to occur with the products obtained depending upon the severity of the method used for the decomposition (100). Iodine values and infrared absorption measurements indicated to other workers (8) that the reaction of cyclopropenoid fatty acids with hydrogen halides involved the formation of four isomeric monounsaturated monohalo moieties as shown. The mechanism Nunn (196) suggested that sterculic acid polymerized by the addition of the carboxyl group across the double bond.…”

Section: Oxidationsupporting

confidence: 53%

Review of the Chemistry of Cyclopropene Compounds

Carter¹,

Frampton²

1964

Chem. Rev.

151

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Section: Oxidationsupporting

confidence: 53%

Review of the Chemistry of Cyclopropene Compounds

Carter¹,

Frampton²

1964

Chem. Rev.

151

View full text Add to dashboard Cite

“…The present report deals with an analytical method based upon the measurement of the absorptivity at 11.05 microns after treatment with aqueous hydrochloric acid. The development of the absorption maximum at 11.05 microns is attributable entirely to the unsymmetrically disubstituted olefinic group CH2 || -CH2-C-CHCl-, resulting from the opening of the cycloprcpene ring (1).…”

Section: Infrared Absorption Methodsmentioning

confidence: 96%

“…The hydrochlorination of the cyclopropenoid moiety results in four isomers, only two of which have an absorption band at 11.05 microns (1). The proportion of the products responsible for the absorption maximum at this wavelength is, however, always the same.…”

Section: Infrared Absorption Methodsmentioning

confidence: 99%

“…The absorptivities plotted against the calculated sterculic acid contents of the samples fell on a straight line represented by the equation x =518.56 a -5.186 (1) where x is the percentage of cyclopropenoid moiety as sterculic acid and a is the corrected absorptivity at the 11.05micron absorption maximum. This absorptivity may of course vary with the particular spectrophotometer used.…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Methods for Determination of Cyclopropenoid Fatty Acids. Infrared Absorption Method.

Magne¹,

Bailey²,

McCall³

et al. 1964

Anal. Chem.

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“…Subsequent hydrogenation reactions of this alcohol using Pd and Pt catalysts revealed that the cyclopropene ring was kept intact during reduction [20]. Halogenation reactions of CPEFA with concentrated aqueous hydrogen halides in acetic acid for 1 h gave isomeric mono-unsaturated monohalo compounds [21] (Eq. 3).…”

Section: Introductionmentioning

confidence: 99%

Chemical modifications of Sterculia foetida L. oil to branched ester derivatives

Manurung

Daniel

Bovenkamp

et al. 2011

Euro J Lipid Sci & Tech

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An experimental study to modify Sterculia foetida L. oil (STO) or the corresponding methyl esters (STO FAME) to branched ester derivatives is reported. The transformations involve conversion of the cyclopropene rings in the fatty acid chains of STO through various catalytic as well as stoichiometric reactions. Full conversion of the cyclopropene rings was obtained using Diels-Alder chemistry involving cyclopentadiene in water at 408C without the need for a catalyst. Olefin metathesis reactions were performed using a Grubbs 2nd generation catalyst and cyclopropene ring conversion was !99 and 54 mol% with 2,3-dimethyl-2-butene and 1-octene, respectively. Oxidation reactions were performed using established epoxidation (Sharpless) and dihydroxylation (Prilezhaev) protocols using aqueous hydrogen peroxide as the oxidant. For both reactions, full conversion of the cyclopropene rings was obtained at RT to yield the corresponding a,b-unsaturated ketone in good selectivities. Rearrangement reactions of the cyclopropene rings to the corresponding conjugated diene were successfully performed using homogeneous and heterogeneous palladium catalysts. Excellent conversions (!99%) were obtained using homogeneous palladium catalyst in a biphasic cyclohexane-water mixture (1:1) at 908C. Relevant cold flow properties of all products were determined and compared to crude STO and STO FAME. Best results were obtained for the metathesis products of STO with 1-octene, with a cloud point (CP) and pour point (PP) of À128C.Practical applications: The S. foetida L. tree produces a tropical oil with high potential to be converted to various oleochemical products. The oil contains cyclopropene rings in the fatty acid chains which are known to be very reactive and as such excellent starting materials for various chemical modification reactions. We here report an experimental study on the modifications of STO into novel branched ester derivatives which are prospective products for a range of applications. Examples are the use as cold-flow improvers for biodiesel or biolubricants (ester derivatives with long, aliphatic branches), as reactive building block material for resin, coatings and/or packaging application (derivatives containing unsaturated (cyclic) structures in the fatty acid chains). Abbreviations: APT, attached proton test; 1, methyl esters of STO; 2, methyl esters of Diels-Alder reaction products; 3a, product of metathesis reaction of STO with 2,3-dimethyl-2-butene; 3b, product of metathesis reaction of STO with 1-octene; 4a, methyl esters of 3a; 4b, methyl esters of 3b; 5, product of epoxidation reaction; 6, product of hydroxylation reaction; 7, product of 1,4-addition reaction of STO with noctylMgBr; 8, methyl esters of 7; 9, methyl esters of rearrangement

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Reaction of cyclopropenoid fatty acid derivatives with hydrogen halides

Cited by 14 publications

References 3 publications

Review of the Chemistry of Cyclopropene Compounds

Review of the Chemistry of Cyclopropene Compounds

Methods for Determination of Cyclopropenoid Fatty Acids. Infrared Absorption Method.

Chemical modifications of Sterculia foetida L. oil to branched ester derivatives

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