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AssigneesSangho Koo, SK Corporation
InventorsSangho Koo, Minkoo Ji
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The present invention provides an intermediate compound used for synthesis of polyene chain structure, that is an important moiety of carotenoid compounds, a process for preparing the same, and carotenoid polyene chain compounds prepared by using the intermediate, and, in particular, a process for preparing lycopene. The process for preparing the carotenoid polyene chain compound employs an allylic sulfone compound as starting material, which is reacted with C-5 sulfide compound to extend the carbon chain. The resultant thio-sulfone compound is oxidized, and the obtained disulfone compound is combined with C-10 di(haloallylic) sulfide compound to form a chain compound containing the desired number of carbon atoms. Then, the diallylic sulfone obtained by oxidation of the diallylic sulfide is subjected to Ramberg-Baklund reaction in order to form the central triene bond. After removal of sulfonyl groups, carotenoid polyene chain compound is obtained.
An allylic sulfide represented by following Chemical Formula 1:
A process for preparing an allylic sulfide of Chemical Formula 1, which comprises the steps of (a-1) oxidizing isoprene to obtain isoprene monoxide;
A process for extending carbon chain by the use of allylic sulfide of Chemical Formula 1, which comprises the steps of (a-2) deprotonating allylic sulfone compound (B), and reacting the resultant compound with allylic sulfide of Chemical Formula 1 to obtain thio-sulfone compound (C);
A process for preparing a carotenoid polyene chain compound represented by Chemical formula 2, which comprises the steps of (a-3) deprotonating the allylic disulfone compound (D), and reacting the resultant compound with not more than 0.5 equivalent of diallylic sulfide (E) (wherein, Y is a halogen atom) on the basis of 1 equivalent of allylic disulfone compound (D) to obtain allylic sulfide compound (F);
An allylic sulfone represented by the following compound (D):
Dependencies are inferred from the claim text.
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Having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton: the carbon skeleton being acyclic and unsaturated
The hetero-atom being a non-metal atom: the hetero-atom being a sulfur atom
Preparation of sulfones; Preparation of sulfoxides: by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of…
Preparation of sulfones; Preparation of sulfoxides: by reactions not involving the formation of sulfone or sulfoxide groups
Term ended 3 Oct 2022 (estimated)
The present invention relates to a process for preparing carotenoid polyene chain compounds. More specifically, it relates to intermediate compounds which are useful for synthesis of carotenoid compounds having polyene chain structure, and a process for preparing the same, and a process for preparing polyene chain compounds, especially lycopene, by using the intermediate compound.
Carotenoid compounds have polyene chain structure. Specific examples of the compounds include beta-carotene, lycopene, astaxanthin, bixin, and the like. The carotenoid compounds have been widely used as natural dyes, and recently, these compounds are reported to have excellent anti-tumor effect, by virtue of their selective reactivity with radicals and singlet oxygen known as carcinogens. In these circumstances, a variety of commercial products containing carotene, including cosmetics or taste food, have been merchandised. However, there still remain conflict opinions on the anti-tumor activity of beta-carotene, since beta-carotene is reported to have a harmful effect on smokers or patients having lung cancer. Thus, people pay more increasing attention to lycopene, having stronger anti-oxidation ability with no conflict opinion on the anti-tumor activity.
To meet such a tendency, the requirement of developing a process for effectively synthesizing polyene chain structures that construct lycopene also increases.
Isoprene monoxide (0.30 ml, 3.1 mmol) was dissolved in N,N-dimethylformamide (DMF) (7 ml), and cuprous iodide (CuI) (15 mg, 0.08 mmol) and benzene thiol (PhSH) (0.33 ml, 3.2 mmol) were added thereto at 0° C. The resultant reaction mixture was stirred at the same temperature for about 6 hours.
When the reaction was completed, the reaction mixture was diluted with ether, washed with 1M-HCl three times (10 ml×3), dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated by evaporation under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 2-methyl-4-phenylthio-2-butene-1-ol (0.52 g, 2.7 mmol) (yield: 87%). According to the analytical data of 1H-NMR and gas chromatography, the ratio of trans- to cis-double bond was not less than 6:1.
1H-NMR: trans δ1.56 (s,3H), 2.38 (br s, 1H),3.55 (d, 2H, J=7.7 Hz), 3.92 (s, 2H), 5.54 (t, 1H, J=7.7 Hz), 7.15˜7.35 (m, 5H); cis δ1.75 (s, 3H), 2.38 (br s, 1H), 3.52 (d, 2H, J=7.9 Hz), 3.90 (s, 2H), 5.41 (t, 1H, J=7.9 Hz), 7.15˜7.35 (m, 5H). 13C-NMR: δ13.6, 31.5, 67.7, 119.9, 126.2, 128.9, 129.8, 136.3, 139.0. HRMS(EI) C11H14OS Calculated: 194.0765, Measured: 194.0771.