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Carotenoid


DATA No : VCA0004 INFORMANT : Masayoshi Ito

NAME : (3S,5R,6S,3'R)-5,6-Epoxy-3,3'-dihydroxy-7',8'-didehydro-5,6,7,8-tetrahydro-b,b-caroten-8-one

COMMON NAME: Halocynthiaxanthin
SYMBOL:
FORMULA: C40H54O4 MOL.WT (average) : 598.854


Download ChemDraw structure data
BIOLOGICAL ACTIVITY
Anti-neoplastic effect (anti-tumor promotion) (Ref. 0223). Inhibitotory effect on Epstein-Barr virus activation (anti-tumor promotion) (Ref. 0217)
Inhibotor of the reverse transcriptases of HIV type 1 and 2 (Ref. 0224).
Singlet oxygen quenching activity (Ref. 0230).
Suppressing efect of generation of superoxide and nitric oxide (Ref. 1097).
PHYSICAL AND CHEMICAL PROPERTIES
MELTING POINT:158-160degC (Ref. 0035)

BOILING POINT:

REFRACTIVE INDEX:

OPTICAL ROTATION:

DENSITY:

SOLUBILITY:
SPECTRAL DATA
UV SPECTRA:lmax (nm): ethanol 279, 423sh, 453, and 475sh (Ref. 0006); hexane 277, 428sh, 452, 477sh
[Spectrum 0009] (Ref. 0006); ether 430, 452, and 470 (Ref. 0035)

IR SPECTRA:nmax(KBr)/cm-1: 3420 (OH), 2190 (acetylene), 1660 (conj. CO), and 1610 (C=C) (Ref. 0006)
nmax(KBr)/cm-1: 3350 (OH), 2165 (acetylene), 1645 (conj. CO), and 960 (trans CH=CH) (Ref. 0035)

NMR SPECTRA:1H-NMR d(500 MHz, CDCl3): 0.97 (3H, s, 1eq-Me), 1.04 (3H, s, 1ax-Me), 1.15 (3H, s, 1'ax-Me), 1.20, 1.22 (each 3H, s, 1'eq-, 5-Me), 1.35 (1H, dd, J 12.5, 11, 2ax-H), 1.46 (1H, t, J 12.5, 2'ax-H), 1.52 (1H, m, 2eq-H), 1.79 (1H, dd, J 14, 9.5, 4ax-H), 1.84 (1H, ddd, J 12.5, 3.5, 2, 2'eq-H), 1.93 (3H, s, 5'-Me), 1.95 (3H, s, 9-Me), 1.98 (3H, s, 13'-Me), 2.00 (3H, s, 13-Me), 2.02 (3H, s, 9'-Me), 2.07 (1H, ddd-like, J 17.5, 9.5, 1.5, 4'ax-H), 2.32 (1H, br dd, J 14, 4.5, 4eq-H), 2.43 (1H, br dd, J 17.5, 5.5, 4'eq-H), 2.60, 3.65 (each 1H, d, J 18.5, 7-H2), 3.82 (1H, m, 3-H), 3.99 (1H, m, 3'-H), 6.29 (1H, br d, J 12, 14'-H), 6.36 (1H, d, J 15, 12'-H), 6.41 (1H, d, J 11.5, 14-H), 6.46 (1H, dd-like, J 12, 1, 10'-H), 6.57 (1H, dd, J 15, 12, 11'-H), 6.58 (1H, dd, J 15, 11, 11-H), 6.65 (1H, dd, J 14.5, 11.5, 15-H), 6.67 (1H, d, J 15, 12-H), 6.75 (1H, dd, J 14.5, 12, 15'-H), 7.15 (1H, dd-like, J 11, 1, 10-H) (Ref. 0006)

MASS SPECTRA:598 (M), 582 (M-16), 580 (M-18), 565 (M-18-15), 562 (M-18-18), 506 (M-92), 490 (M-92-16), 488 (M-92-18)
[Spectrum 0010] (Ref. 0035)

OTHER SPECTRA:
CHROMATOGRAM DATA
HPLC (column: CHIRALCEL OD; DAICEL IND., LTD., 1.0times25 cm, eluent: EtOH-hexane 15:85, temp.: 37degC, flow: 2.4 ml/min) tR = 14.5 min (Ref. 0006)
SOURCE
Sea squirts (Halocynthia roretzi) (Ref. 0035/0401/0402)
Shell fish (Mytilus edulis) (Ref. 0426)
CHEMICAL SYNTHESIS
Double Wittig condensations of the C10-dialdehyde with the 8-oxo-C15-phosphonium salt and the acetylenic C15-phosphonium salt provided the C40-skeletal compound, which was treated with MCPBA to afford holocynthiaxanthin. These phosphonium salts were derived from the common intermediate, the C15-a-acetytlenic alcohol, which was synthesized via the coupling reaction of protected (4R,6R)-4-hydroxy-2,2,6-trimethylcyclohexanone with the protected (E)-3-methylpent-2-en-4-yn-1-ol. Key step was effective conversion of the C15-a-acetytlenic alcohol into the C15-8-oxo-compound using oxo-metallic catalyst and subsequent iodine-catalysed double-bond shift. (Ref. 0006)
METABOLISM
Sea squirt: fucoxanthin a_right fucoxanthinol a_right halocynthiaxanthin (Ref. 0401)
GENETIC INFORMATION

NOTE

REFERENCES
[0006]
AUTHOR:Yamano,Y.,Tode,C., and Ito,M.
TITLE:Carotenoids and related polyenes. Part 3. First total synthesis of fucoxanthin and halocynthiaxanthin using oxo-metallic catalyst
JOURNAL:J. Chem. Soc., Perkin Trans. 1
VOL: PAGE : 1895 -1904 (1995)
[TOP]

[0035]
AUTHOR:Matsuno,T.,Ookubo,M.,Nishizawa,T., and Shimizu,I.
TITLE:Carotenoids of Sea Squirts. I. New Marine Carotenoids, Halocynthiaxanthin and Mytiloxanthinone from Halocynthia reretzi
JOURNAL:J. Chromatogr.
VOL:32 PAGE : 4309 -4315 (1984)
[TOP]

[0217]
AUTHOR:Tsushima, M., Maoka, T., Katsuyama, M., Kozuka, M., Matsuno, T., Tokuda, H., Nishino, H., and Iwashima, A.
TITLE:Inhibitory effect of natural carotenoids on Epstein-Barr virus activation activity of a tumor promoter in Raji cells. A screening study for anti-tumor promoters PubMed ID:7742789
JOURNAL:Biol Pharm Bull.
VOL:18 PAGE : 227-233 (1995)
[TOP]

[0223]
AUTHOR:Nishino, H., Tsushima, M., Matsuno, T., Tanaka, Y., Okuzumi, J., Murakoshi, M., Satomi, Y., Takayasu, J., Tokuda, H., Nishino, A., et al.
TITLE:Anti-neoplastic effect of halocynthiaxanthin, a metabolite of fucoxanthin PubMed ID:1450444
JOURNAL:Anticancer Drugs.
VOL:3 PAGE : 493-497 (1992)
[TOP]

[0224]
AUTHOR:Loya, S., Kashman, Y., and Hizi, A.
TITLE:The carotenoid halocynthiaxanthin: a novel inhibitor of the reverse transcriptases of human immunodeficiency viruses type 1 and type 2 PubMed ID:1371377
JOURNAL:Arch Biochem Biophys.
VOL:293 PAGE : 208-212 (1992)
[TOP]

[0230]
AUTHOR:Shimidzu,N.,Goto,M., and Miki,W.
TITLE:Carotenooids as Singlet Oxygen Quenchers in Marine Organisms.
JOURNAL:Fisheries Sci.
VOL:62 PAGE : 134 -137 (1996)
[TOP]

[0401]
AUTHOR:Ookubo,M., and Matsuno,T.,
TITLE:Carotenoids of sea squirts - II. Comparative biochemical studies of carotenoids in sea squirts
JOURNAL:Comp. Biochem. Physiol.
VOL:81 PAGE : 137 -141 (1985)
[TOP]

[0402]
AUTHOR:Matsuno,T. and Ookubo,M.
TITLE:A new carotenoid, halocynthiaxanthin from the sea squirt, Halocynthia roretzi
JOURNAL:Tetrahedron Lett.
VOL:22 PAGE : 4659 -4660 (1981)
[TOP]

[0426]
AUTHOR:Hertzberg,S.,Partali,V., and Liaaen-Jensen,S.
TITLE:Animal carotenoids. 32. Carotenoids of Mytilus edulis (Edible mussel)
JOURNAL:Acta Chem. Scand.
VOL:42 PAGE : 495 -503 (1988)
[TOP]

[1097]
AUTHOR:Murakami, A., Nakashima, M., Koshiba, T., Maoka, T., Nishino, H., Yano, M., Sumida, T., Kim, O. K., Koshimizu, K., and Ohigashi, H.
TITLE:Modifying effects of carotenoids on superoxide and nitric oxide generation from stimulated leukocytes PubMed ID:10737715
JOURNAL:Cancer Lett.
VOL:149 PAGE : 115-123 (2000)
[TOP]

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