Oxidation of carotenoids - I. Dihydrooxepin derivatives as products of oxidation of canthaxanthin and β,β-carotene

Tetrahedron Letters

Volumn 38, Issue 45, 1997, Pages 7853-7856

  Zürcher, Marcel ^a   Niggli, Urs A ^a   Steck, Andrea ^a   Pfander, Hanspeter ^a  

^a UNIVERSITY OF BERN   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

11,15' DIHYDROOXEPIN BETA,BETA CAROTENE; 11,16' DIHYDROOXEPIN CANTHAXANTHIN; BETA CAROTENE; CANTHAXANTHIN; CAROTENOID; UNCLASSIFIED DRUG;

ANTINEOPLASTIC ACTIVITY; ANTIOXIDANT ACTIVITY; ARTICLE; CANCER PREVENTION; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL STRUCTURE; MASS SPECTROMETRY; MOLECULAR WEIGHT; OXIDATION; STRUCTURE ANALYSIS;

EID: 0343683308     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)10097-1     Document Type: Article

References (13)

1. Krinsky, N. I. Pure Appl. Chem. 1994, 66, 1003-1010.
2. Bertram, J. S. Pure Appl. Chem. 1994, 66, 1025-1032.
3. Weedon, B. C. L.: Occurrence. In Carotenoids; Isler, O., Ed.; Birkhäuser: Basel, 1971; pp. 29-59.
4. 2O 96:4, and secondly on a 250 x 10 mm Nucleosil® 100-5 CN column with hexane/t-BuOMe 7:3 as mobile phase. The detection was performed at 350 nm by means of a HP 1100® photodiode array detector.
5. 500 mg of crystalline β,β-carotene was dissolved in 400 ml toluene and stirred for 4 hours in darkness at 36-38 °C, with oxygen bubbling through the solution. The reaction was stopped by evaporating the solvent in vacuo. In-chain oxidation products of β,β-carotene were obtained selectively by pre-separating the reaction mixture by open-top CC on MgO/Celite 1:2 as stationary phase and hexane and hexane/ t-BuOMe mixtures as eluents. Isolation and final purification of single in-chain oxidation products were performed in multiple steps by HPLC, on a 250 x 10 mm Nucleosil® 100-5 CN column and hexane or hexane/ethyl acetate mixtures as mobile phases. The detection was performed at 330 nm by means of a Waters 990® photodiode array detector.
6. Hesse, M.; Meier, H; Zeeh, B.: Spektroskopische Methoden in der organischen Chemie; Thieme: Stuttgart, 1995; p. 11.
7. CH couplings C-15'/H-10, C-10/H-15', C-11/H-14', and C-14/H-11
8. 1H decoupled, *: may be interchanged with corresponding signal) δ 12.45* (C-19'), 12.49* (C-19), 12.81 (C-20'), 13.65 (C-18), 13.77 (C-18'), 21.84 (C-20), 27.44 (C-17), 27.54 (C-16), 27.60 (C-16', C-17'), 34.26 (C-3), 34.26 (C-3'), 35.67* (C-1), 35.70* (C-1'), 37.31* (C-2), 37.36* (C-2'), 41.86 (C-11), 42.41 (C-15'), 106.19 (C-12), 108.73 (C-15), 123.05 (C-7), 123.26 (C-11'), 123.66 (C-7'), 129.62* (C-5'), 129.68* (C-5), 132.33 (C-9), 133.23 (C-13'), 133.97 (C-9'), 134.01 (C-10'), 136.96 (C-14'), 137.45 (C-10), 139.32 (C-12'), 140.89 (C-8), 141.23* (C-8'), 141.27 (C-14), 151.29 (C-13), 161.34 (C-6'), 161.53 (C-6), 199.32 (C-4'), 199.39 (C-4) ppm.
9. 1H decoupled; values from HMQC experiment, no quaternary carbons) δ 12.9 (C-19'), 13.0 (C-19), 13.2 (C-20'), 19.5 (C-3, C-3'), 21.9 (C-18), 22.0 (C-18'), 22.2 (C-20), 29.2 (C-16, C-17, C-16', C-17'), 33.2 (C-4), 33.3 (C-4'), 39.9 (C-2, C-2'), 42.4 (C-11), 42.6 (C-15'), 107.3 (C-12), 109.6 (C-15), 125.3 (C-7), 126.4 (C-7'), 130.9 (C-10'), 134.0 (C-10), 136.3 (C-14), 137.9 (C-8), 137.5 (C-12', uncertain), 138.0 (C-8'), 141.3 (C-14) ppm.
10. Chou, W.-N.; White, J. B.; Smith, W. B. J. Am. Chem. Soc. 1992, 114, 4658-4667.
11. Pommelet, J. C.; Manisse, N.; Chuche, J. Tetrahedron, 1972, 28, 3929-3941.
12. Yamauchi, R.; Miyake, N.; Inoue H.; Kato, K. J. Agric. Food Chem. 1993, 41, 708-713.
13. Senda, Y.; Ohno, A.; Ishiyama, J.; Imaizumi, S.; Kamiyama, S. Bull. Chem. Soc. Jpn. 1987, 60, 613-616.