Citrus Carotenoids. II. The Structure of Citranaxanthin, a New Carotenoid Ketone

The Journal of Organic Chemistry
1965.0

Abstract

During the course of recent investigations of the carotenoid constituents of the peel of the trigeneric hybrid, Sinton citrangequat (Citrus sinensis × Poncirus trifoliata × Fortunella margarita), we isolated a small amount of a new carotenoid ketone, C33H44O, which we propose to call citranaxanthin. The visible spectra of citranaxanthin, recorded in petroleum ether and ethanol, were very similar to those of β-apo-8'-carotenal though somewhat longer in wave length, strongly indicating the presence of a conjugated carbonyl group and a decaenone chromophore similar to that of kryptocapsin. The infrared spectrum showed a band at 1662 cm.⁻¹ characteristic of a conjugated carbonyl grouping. Reduction with sodium borohydride gave a product with a hypsochromic shift. The n.m.r. spectrum exhibited singlets at τ 7.72 (end-of-chain methyl group α to a carbonyl group), 8.02 (in-chain olefinic methyl group), 8.25 (methyl group attached to C=C in the cyclohexene ring), and 8.92 (gem-dimethyl group), and a doublet at τ 2.50 (J = 16 c.P.s.) indicating the trans configuration of the double bond to which the vinyl proton β to the carbonyl is attached. On treatment with aqueous alcoholic potassium hydroxide, citranaxanthin underwent retroaldol cleavage to yield acetone (identified as its 2,4-dinitrophenylhydrazone) and β-apo-8'-carotenal. Condensation of β-apo-8'-carotenal with acetone in the presence of alcoholic potassium hydroxide afforded a compound that did not separate from natural citranaxanthin on thin layer chromatography and had identical infrared and n.m.r. spectra. These facts lead unambiguously to structure I as the structure of citranaxanthin, which is the first known naturally occurring carotenoid with a methyl ketone grouping in the side chain. Isolation involved extracting 8 kg of Sinton citrangequat peel with acetone, partitioning carotenoids between petroleum ether and 90% methanol, column chromatography on magnesium oxide-Hyflo Supercel, yielding 90 mg of citranaxanthin with m.p. 156-156°, λmax in petroleum ether 463 and 495 mp, in ethanol 475 mp, and infrared bands including 1662 cm.⁻¹ (conjugated carbonyl). Reduction with sodium borohydride gave citranaxanthol with a hypsochromic shift.

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