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Carotenoid


DATA No : VCA0022 INFORMANT : Masayoshi Ito

NAME : 4',5',-Didehydro-4,5'-retro-b,b-carotene-3,3'-dione

COMMON NAME: Rhodoxanthin
SYMBOL:
FORMULA: C40H50O2 MOL.WT (average) : 562.824


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BIOLOGICAL ACTIVITY
Antioxidative activity (Ref. 0460), Inhibitotory effect on Epstein-Barr virus activation (anti-tumor promotion) (Ref. 0217)
PHYSICAL AND CHEMICAL PROPERTIES
MELTING POINT:208-209degC (Ref. 0122)
212-214degC (Ref. 0124)
194degC (Ref. 0121)

BOILING POINT:

REFRACTIVE INDEX:

OPTICAL ROTATION:

DENSITY:

SOLUBILITY:
SPECTRAL DATA
UV SPECTRA:lmax (nm): hexane 505 (E 1%1cm = 2350) (Ref. 0122); CHCl3 493s (E 1%1cm = 2140), 511 (2420) and 533s (2030) (Ref. 0124); cyclohexane 472 (E 1%1cm = 2550), 443 (2530), 417 (1605) (Ref. 0121)

IR SPECTRA:nmax(KBr)/cm-1: 1659s (conj. CO), 1576m, 1536m (conj. C=C), 992m, 978m (CH=CH, trans) (Ref. 0122/0124)

NMR SPECTRA:1H-NMR d(60 MHz, CDCl3)
[Spectrum 0022] (Ref. 0121)
1H-NMR d(400 MHz, CDCl3) all-trans:1.39 (s, 16,17,16',17'-Me), 2.00 (s, 20, 20'-Me), 2.03 (s, 19, 19'-Me), 2.16 (d J 1, 18,18'-Me), 2.39 (s, 2,2'-H2), 5.94 (brs, 4,4'-H), 6.26 (d, J 11.5, 12,12'-H), ca 6.43 (m, 14, 14', 15, 15'-H), 6.46 (d, J 15.5, 10,10'-H), 6.79 (dd, J 14.5, J 12, 11,11'-H), 6.80 (d, J 12.5, 8,8'-H), 6.90 (d, J 12.7, 7,7'-H). 6-cis: 1.25 (s, 16,17-Me), 1.39 (s, 16',17'-Me), 1.99 (s, 20'-Me), 1.993 (s, 20'-Me), 2.016 (s, 19-Me), 2.029 (s, 19'-Me), 2.304 (d, J 1.2, 18-Me), 2.16 (d, J 1, 18'-Me), 2.34 (s, 2-H2), 2.39 (s, 2'-H2), 5.94 (brs, 4,4'-H), 6.24 (d, J 11.5, 12-H), 6.26 (d, J 11.5, 12'-H), ca 6.43 (m, 14, 14', 15, 15'-H), 6.40 (d, J 14.5, 10-H), 6.46 (d, J 14.5, 10'-H), 6.74 (dd, J 15, J 11.5, 11,H), 6.78 (dd, 11'-H), 6.55 (d, J 12.2, 8'-H), 6.80 (d, J 12.3, 8'-H), 6.67 (d, J 12.2, 7'-H), 6.90 (d J 12.3, 7'-H). (Ref. 0474)
all-trans 13C-NMR d(100MHz, CDCl3): 12.41 (19), 12.91 (20), 22.31 (18), 29.87 (16, 17), 38.56 (1), 54.37 (2), 126.05 (4), 129.93 (11), 128.15 (7), 128.32 (8), 129.85 (15), 132.56 (12), 137.51 (13), 137.68 (14), 138.04 (10), 141.32 (9), 142.70 (6), 154.74 (5), 198.95 (3) (Ref. 0474)
6,6'-dicis 13C-NMR d(100MHz, CDCl3): 12.42 (19), 12.88 (20), 25.42 (18), 28.30 (16, 17), 41.26 (1), 52.50 (2), 125.48 (4), 126.40 (11), 128.79 and 128.83 (4) and (8),129.60 (15), 132.47 (12), 137.87, 137.54 and 137.05 (10), (13) and (14), 139.58 (9), 143.83 (6), 155.46 (5), 198.99 (3) (Ref. 0474)

MASS SPECTRA:m/z: 562 (M), 506 (M-56), 470 (M-92), 456 (M-106) (Ref. 0059/0122)

OTHER SPECTRA:
CHROMATOGRAM DATA
TLC (Kieselgel, CH2Cl2-ether 9:1) Rf = 0.33 (Ref. 0124)
HPLC (column: Spherisorb S 5-CN, eluent: n-hexane-isopropyl acetate-acetone (76:17:7), flow rate: 1ml/min (Ref. 0474)
SOURCE
Taxus baccata (berries) (Ref. 0462)
Taxus caspidata (berries) (Ref. 0460)
Ricinus communis (cell cultures) (Ref. 0463)
Aloe vera (leaves) (Ref. 0464)
Cryptomeria japonica (leaves) (Ref. 0465)
Metasequoia glyptostroboides (leaves) (Ref. 0465)
Tilapia nilotica (integuments) (Ref. 0466/0417)
CHEMICAL SYNTHESIS
Rhodoxanthin was synthesized by the Wittig condensation of the C12-dialdehyde with 2 equiv. of the 3-oxo-retro-dehydro-C14-phosphorane, which was prepared in several steps starting from 6-oxoisophorone via 3-oxo-retro-dehydro-C11-aldehyde. (Ref. 0122)
The Wittig condensation of the 2 equiv. of 5-(4,4-ethylenedioxy-2,6,6-trimethyl-1-cyclohexen-1-yl)-3-methyl-2,4-pentadienal (C15) or 5-(2,6,6-trimethyl-4-ethoxy1,3-cyclohexadien-1-yl)-3-methyl-2,4-pentadienal (C15) with 2,7-dimethyl-2,4,6-octatrienylene-bis-(triphenylphosphonium bromide), followed by hydrolysis with acid provided rhodoxanthin. (Ref. 0121)
The key intermediate for the synthesis of rhodoxanthin, [3-methyl-5-(2,6,6-trimethyl-4-oxo-2-cyclohexen-1-yl)-2,4-pentadienyl]triphenylphosphonium bromide was synthesized starting from 6-oxo-isophorone via 3-oxo-cyclocitral and 3-oxo-ionone derivatives. (Ref. 0123)
The key intermediate for the synthesis of rhodoxanthin, [3-methyl-5-(2,6,6-trimethyl-4-oxo-2-cyclohexen-1-yl)-2,4-pentadienyl]triphenylphosphonium bromide was synthesized via the reaction of 6-oxo-isophorone with the protected (E)-methylpent-2-en-4-yn-1-ol, simultaneous elimination of the tertiary hydroxy group and the partial reduction of the triple bond with Zn/acetic acid. This phosphonium salt was reacted with the C10-dialdehyde to give 6,6'-dihydrorhodoxanthin which was dehydrogenatede to provide rhodoxanthin. (Ref. 0019/0124)
METABOLISM
Taxus caspidata (tree) Eschscholtzxanthin a_right eschscholtzxanthone a_right rhodoxanthin(Ref. 0460)
Tilapia nilotica (fish) Zeaxanthin a_right rhodoxanthin <0467>>
GENETIC INFORMATION

NOTE

REFERENCES
[0019]
AUTHOR:Pfander,H. and Bartels,B. (1996) Carotenoids Volume 2: Synthesis Chapter 3: Carotenoid Synthesis Part III: Synthesis of Cyclic Carotenoids (Britton,G.,Liaaen-Jensen,S., and Pfander,H., eds), pp161-200, Birkhäuser Verlag,Basel,Boston,Berlin
TITLE:
JOURNAL:
VOL: PAGE : - ()
[TOP]

[0059]
AUTHOR:Enzell,C.R.,Francis,G.W., and Liaaen-Jensen,S.
TITLE:Mass Spectrometric Studies of Carotenoids 2. A Survey of Fragmentation Reactions
JOURNAL:Acta Chim. Scand.
VOL:23 PAGE : 727 -750 (1969)
[TOP]

[0121]
AUTHOR:Surmatis,J.D.,Walser,A.,Gibas,J.,Schwieter,U., and Thommen,R.
TITLE:New Methods for the Synthesis of Oxygenated Carotenoids
JOURNAL:Helv. Chim. Acta
VOL:53 PAGE : 974 -990 (1976)
[TOP]

[0122]
AUTHOR:Mayer,H.,Montavon,M.,Rüegg,R., and Isler,O.
TITLE:Synthesen in der Carotinoid-Reiche Totalsynthese von Rhodoxanthin
JOURNAL:Helv. Chim. Acta
VOL:50 PAGE : 1606 -1618 (1967)
[TOP]

[0123]
AUTHOR:Widmer,E.,Soukup,M.,Zell,R.,Broger,E.,Lohri,B.,Marbet,R., and Lukác,T.
TITLE:Technische Verfahren zur Synthese von Carotinoiden und verwandten Verbindungen aus 6-Oxo-isophoron. VI. Synthese von Rhodoxanthin und (3RS,3'RS)-Zeaxanthin; Zugänge zur C15-Ringkomponente über 3-Oxo-jonon-Derivate
JOURNAL:Helv. Chim. Acta
VOL:65 PAGE : 944 -957 (1982)
[TOP]

[0124]
AUTHOR:Widmer,E.,Zell,R.,Grass,H., and Marbet,R.
TITLE:Technische Verfahren zur Synthese von Carotinoiden und verwandten Verbindungen aus 6-Oxo-isophoron. VII. Synthese von Rhodoxanthin und (3RS,3'RS)-Zeaxanthin aus der C15-Ringkomponente
JOURNAL:Helv. Chim. Acta
VOL:65 PAGE : 958 -966 (1982)
[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]

[0417]
AUTHOR:Katsuyama,M., and Matsuno,T.
TITLE:Carotenoid and vitanin A, and metabplism of carotenoids, b-carotene, canthaxanthin, astaxanthin, zeaxanthin, lutein and tunaxanthin in tilapia Tilapia nilotica
JOURNAL:Comp. Biochem. Physiol.
VOL:90 PAGE : 131 -139 (1988)
[TOP]

[0460]
AUTHOR:Maoka,T.,Ito,Y.,Fujiwara,Y., and Hashimoto,K.
TITLE:Structures and Antioxidative Activity of retro Carotenoids from the Berries of the Japanese Yew, Taxus cuspidata
JOURNAL:J. Jap. Oil Chem. Soc.
VOL:45 PAGE : 641 -646 (1996)
[TOP]

[0462]
AUTHOR:Kuhn,R., and Brockmann,H.
TITLE:über Rhodoxanthin""
JOURNAL:Ber. Dtsch. Chem. Ges.
VOL:66 PAGE : 828 -834 (1933)
[TOP]

[0463]
AUTHOR:Kayser,H.
TITLE:Hormon Induced Changes in Carotenoid Composition in Ricinus Cell Cultures. I. Identification of Rhodoxanthin
JOURNAL:Z. Naturforsch.
VOL:39 PAGE : 50 -54 (1984)
[TOP]

[0464]
AUTHOR:Diaz,M.,Ball,E., and Luttge,U.
TITLE:Stress-induced accumulation of the xanthophyll rhodoxanthin in leaves of Aloe vera
JOURNAL:Plant Physiol. Biochem.
VOL:28 PAGE : 679 -682 (1990)
[TOP]

[0465]
AUTHOR:Ida,K.,Saito,F., and Takeda,S.
TITLE:Isomers of Rhodoxanthin in Reddish Brown Leaves of Gymnosoerms and Effect of Daylight Intensity on the Contents of Pigments during Autumnal Coloration
JOURNAL:Bot. Mag. Tokyo
VOL:104 PAGE : 157 -169 (1991)
[TOP]

[0466]
AUTHOR:Matsuno,T., and Katsuyama,M.
TITLE:Comparative Biochemical Studies of Carotenoids in Fishes-XIV. Carotenoids of Tilapia-I
JOURNAL:Bull. Jap. Soc. Sci. Fish.
VOL:45 PAGE : 1533 -1538 (1979)
[TOP]

[0474]
AUTHOR:Englert,G., and Vecchi,M.
TITLE:High-performance liquid chromatographic separation and proton nuclear magnetic resonance identification of the 6-mono-cis and 6,6'-di-cis-isomers of rhodoxanthin
JOURNAL:J. Chromatogr.
VOL:235 PAGE : 197 -203 (1982)
[TOP]

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