Improved process for synthesis of per (E)-heptaisopentenol (C35-OH)
By introducing phenylsulfonyl groups into DMF via a simplified synthetic route and then removing them in one step through reduction, the problems of stereoselectivity loss and yield reduction in the synthesis of all-trans polyisoprenol were solved, and efficient synthesis of all-trans polyisoprenol was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SYNERGIA LIFE SCIENCES PVT LTD
- Filing Date
- 2024-10-04
- Publication Date
- 2026-05-12
AI Technical Summary
Existing techniques for synthesizing all-trans polyisoprene alcohol suffer from stereoselectivity loss and reduced yield, especially during the introduction of multiple isopentenyl units.
A second phenylsulfonyl group was introduced by reacting 1-((2E,6E,10E,14E,18E)-1-chloro-3,7,11,15,19,23-hexamethyltetracarbon-2,6,10,14,18,22-hexaen-9-ylsulfonyl)benzene with sodium benzenesulfinate in DMF, followed by reaction with 4-chloroisopentenyl acetate, and then a further reduction in the presence of a superhydrogen compound to remove the two phenylsulfonyl groups. This simplified the synthetic steps and improved the yield.
The process reduces reaction and purification steps, increases the yield of all-trans polyisoprene alcohol, and improves the economics of the process.
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Abstract
Description
Related applications
[0001] This application relates to and claims priority to the full application 202321066937 filed on October 5, 2023 and the full application 202421009595 filed on February 13, 2024, both of which are incorporated herein by reference in their entirety. Technical Field
[0002] This disclosure relates to an improved method for the regio- and stereospecific synthesis of polyprenyl compounds. More specifically, it discloses a regio- and stereospecific synthesis of (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyloctadec-2,6,10,14,18,22,26-heptaen-1-ol, which can be used to synthesize vitamin K2-7. Background Technology
[0003] Polyprenols represent a class of unsaturated, acyclic aliphatic alcohols with at least four isoprene units linked head-to-tail, wherein a hydroxyl group is attached to the head of the chain. These members differ from one another in their chain length and the stereochemistry of their internal isoprene units. Polyprenols are essential components of the biological membranes of living cells and exist as free alcohols and / or their carboxylic acid esters. Three types of natural polyprenols are (a) all-trans-polyprenols, (b) ditrans, polycis-isoprenols or tritrans, polycis-isoprenols, and (c) ditrans, polycis-α-saturated isoprenols. Polyprenols are widely found in bacteria, plants, yeasts, and fungi. Umbreit et al. (J. Bacteriology (1972), 1302-1305) isolated and characterized C5-isoprenol and its derivatives from *Streptococcus faecalis*. Basyuni et al. (Sys Rev Pharm (2020) 11(7):89-97) used two-dimensional thin-layer chromatography to analyze the distribution of polyisoprenol in oil palm seed tissues.
[0004] Polyisoprene alcohols are reported to be non-toxic, non-mutagenic, non-teratogenic, and non-carcinogenic in humans. They exhibit antitumor, anti-hepatitis C virus, and anti-HIV effects and are used as adjuvants in chemotherapy and radiotherapy for leukemia. They are also used as therapeutic agents for hypertension, hypercholesterolemia, diabetes, gout, lupus, and other immune disorders, and have therefore been extensively studied. Substitution of the hydroxyl group has been explored for applications in developing antitumor and anti-anemia effects, as well as for use as antipsychotic drugs. Isoprene acetate exhibits anti-ulcer and antithrombotic activities. EP 0 239 729 B1 discloses methods for enhancing polyisoprene alcohols in... in vivo The use of polyisoprene alcohol-containing injections. Polyisoprene alcohol is supplied by Larodan of Sweden and Indofine of the United States. The drug Ropren (which exhibits neuroprotective and hepatoprotective effects) contains 95% pure polyisoprene alcohol concentrate. (Zhang et al., Fitotereapia [Herbal Therapy] 106 (2015) 184-193).
[0005] Solanesol was the first polyisoprene alcohol isolated from tobacco leaves using methanol and ether. Solanesol has also been isolated from tobacco, mulberry, and unsaponifiable matter from silkworm excrement. In paper mills, polyisoprene alcohol has been isolated from contaminants in cellulose pulp. Extensive research and reviews have been conducted on the isolation, purification, synthesis, structure-functional bioactivity correlations, and pharmacology of polyisoprene alcohol and its derivatives. Yan et al. (Phytochem. Rev. [Reviews of Phytochemistry] (2015) 14(3) 403-417) reviewed the resources, derivatives, bioactivity, pharmaceutical applications, and biosynthesis of solanesol.
[0006] Although polyisoprenol is widely distributed in nature, its content in plants is low, and the yield during separation and purification is low, resulting in high recycling costs.
[0007] Muramatsu et al. (J. Biosci. and Bioengg. 106 (3) 263-267 (2008), J. Biosci. and Bioengg. (108) (1) 52-55, (2009)) described the microbial production of farnesol and related isopentenols.
[0008] Given the wide range of applications of polyisoprenols, their importance in the synthesis of bio-important isoprenoid quinones, and their limited occurrence in nature, efforts have been made to synthesize polyisoprenols, especially all-trans polyisoprenols.
[0009] Cheng and Loh (Pure Appl. Chem., 77, (7)1199-1206, 2005.) disclosed the asymmetric α-isopentenylation of various aldehydes to obtain the corresponding α-isopentenols.
[0010] Sato et al. (J Chem Soc Perkin I (1981) 761) reported the stereoselective synthesis of solanesol and all-trans-decapentenol. Altman et al. (J Am. Chem. Soc., 1972, 94, 3257; Synthesis, 1974, 129) reported the synthesis of all-trans-geraniol.
[0011] Masaki et al. (Tetrahedron Lett. [Tetrahedron Letters] (1978), 4539; J. Chern. Soc., Chern. Comm. [Journal of the British Chemical Society, Chemical Communications], (1979), 855; Tetrahedron Lett. [Tetrahedron Letters], 1978, 5123) discussed the preparation of terminal trans-allyl alcohols from linear isoprene morphologies.
[0012] Turi and Crans (Molecules [Molecules] (2020), 25, 4477-4514) disclosed in a review of naphthoquinone derivative synthesis the Diels-Alder reaction between naphthoquinone and polyprenyl halide for the synthesis of vitamin K.
[0013] Zhou et al. (Chem. Ind. For. Prod. [Forest Products Chemistry and Industry] 33 (2013) 53-56) reported the synthesis of polyisoprene acetate.
[0014] The synthesis of long-chain polyisoprenols involves the coupling of two all-trans polyisoprenyl side chains. While researchers have explored this approach (WO 2011 / 117324 A2 and WO 2010 / 034999 A1), Biellmann chemistry does not always guarantee the preservation of the all-trans character. Coates et al. (Org. Synth. [Organic Synthesis] 2007, 84, 43-57) described the synthesis of polyisoprenols by starting with farnesol and adding one isopentenyl unit at a time, thus maintaining stereoselectivity. However, it has been recognized that adding one unit at a time as the number of isopentenyl units increases may be impractical, as the overall yield of the process decreases at each step.
[0015] US Patent 9,012,693 discloses the ability to prepare polyisoprene compounds using Bierman Chemicals. It discloses a method for synthesizing heptaisoprene alcohol from farnesol.
[0016] U.S. Patent 9,464,021 B2 (2016) points out the loss of stereoselectivity when using Bierman Chemistry to synthesize higher polyisoprene alcohols and discloses the use of polyisoprene side chains with 1,3-dithiane terminal groups for the synthesis of vitamin K2.
[0017] Patent application 20232100851, “Synthesis of polyprenyl alcohols”, discloses that polyisoprenyl (phenylsulfonyl) alcohols with 5 to 10 isopentenyl units can be obtained from commercially available structural units such as isoprene, farnesol, farnesol acetone, and geraniol. These polyisoprenyl alcohols can then be desulfonated in the presence of a catalyst, a reducing agent, and a mixture of solvent and cosolvent to obtain polyisoprenyl alcohols.
[0018] The method for synthesizing (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyloctadec-2,6,10,14,18,22,26-heptaen-1-ol according to patent application 20232100851 involves: introducing a phenylsulfonyl group and removing it by reduction in the presence of a superhydrogen compound, subsequently introducing a second phenylsulfonyl group, reacting it with chloroisopentenyl acetate, followed by hydrolysis and removing the second phenylsulfonyl group by a second reduction in the presence of a superhydrogen compound. Summary of the Invention
[0019] It has now been unexpectedly discovered that (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyloctadec-2,6,10,14,18,22,26-heptaen-1-ol can be synthesized by making 1-((2E,6E,10E,14E,18E)-1-chloro-3,7,11,15,19,23-hexamethyloctadec-2,6,10,14,18,22-hexen-9-ylsulfonyl) The second phenylsulfonyl group is introduced by reacting 1-((2E,6E,10E,14E,18E)-3,7,11,15,19,23-hexamethyl-1-(phenylsulfonyl)tetracos-2,6,10,14,18,22-hexaen-9-ylsulfonyl)benzene with 4-chloroisopentenyl acetate, followed by hydrolysis, and the removal of the two phenylsulfonyl groups by reduction in a single step in the presence of a superhydrogen compound.
[0020] The improved synthetic method has the advantage of eliminating a reduction reaction step in the presence of a superhydrogen compound before the introduction of the second phenylsulfonyl group, and eliminating the need to purify the intermediate compound.
[0021] The improved method has the following advantages: 1) reducing the number of reaction steps, 2) eliminating the need for purification of reaction intermediates, and 3) higher product yield and improved process economy.
[0022] In the embodiments disclosed herein, 1-((2E,6E,10E,14E,18E)-1-chloro-3,7,11,15,19,23-hexamethyltetracarbon-2,6,10,14,18,22-hexaen-9-ylsulfonyl)benzene is reacted with sodium benzenesulfinate in dimethylformamide solvent to obtain 1-((2E,6E,10E,14E,18E)-3,7,11,15,19,23-hexamethyl-1-(phenylsulfonyl)tetracarbon-2,6,10,14,18,22-hexaen-9-ylsulfonyl)benzene.
[0023] In the embodiments disclosed herein, 1-((2E,6E,10E,14E,18E)-3,7,11,15,19,23-hexamethyl-1-(phenylsulfonyl)tetracos-2,6,10,14,18,22-hexaen-9ylsulfonyl)benzene is reacted with 4-chloroisopentenyl acetate in the presence of potassium tert-butoxide, TBAB, and 18-crown-6 to obtain (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyl-5,13-bis(phenylsulfonyl)tetracos-2,6,10,14,18,22,26-heptaenyl acetate.
[0024] In the embodiments disclosed herein, (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyl-5,13-bis(phenylsulfonyl)octadec-2,6,10,14,18,22,26-heptaenyl acetate is hydrolyzed in the presence of potassium hydroxide and methanol to (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyl-5,13-bis(phenylsulfonyl)octadec-2,6,10,14,18,22,26-heptaen-1-ol.
[0025] In the embodiments disclosed herein, in the presence of a superhydrogen compound and tetrahydrofuran, both phenylsulfonyl groups in (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyl-5,13-bis(phenylsulfonyl)octadec-2,6,10,14,18,22,26-heptaen-1-ol are reduced to obtain (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyloctadec-2,6,10,14,18,22,26-heptaen-1-ol.
[0026] In the embodiments disclosed herein, novel compounds having the following formula are disclosed. 1-((2E,6E,10E,14E,18E)-3,7,11,15,19,23-hexamethyl-1-(phenylsulfonyl)tetracocarbon-2,6,10,14,18,22-hexaen-9-ylsulfonyl)benzene.
[0027] In the embodiments disclosed herein, novel compounds having the following formula are disclosed. (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyl-5,13-bis(phenylsulfonyl)octadecano-2,6,10,14,18,22,26-heptaen-1-ol. Detailed Implementation
[0028] The invention will now be described by way of examples, which are representative and do not limit the scope of the invention.
[0029] Example 1 2,6,10,14,18,22-tetradecanohexaeno-1-ol, 3,7,11,15,19,23-hexamethyl-9-(phenylsulfonyl)-, (2 E 6 E 10 E ,14 E 18 E Preparation of )-(C30-SO2Ph-OH) 65.7 g (0.108 mol) of C30-SO2Ph-OAc was dissolved in 197 mL of methanol. The contents were cooled to 0-5 °C. 1.812 g (0.032 mol) of potassium hydroxide dissolved in 9.1 mL of water was slowly added over 10 min. The methanol was distilled off and the residue was extracted with ethyl 20 acetate. The reaction mixture was quenched in water and acidified with 1 M HCl. The ethyl acetate layer was washed with water, then with brine, and dried over anhydrous sodium sulfate. The ethyl acetate was distilled under vacuum to give 61 g of crude C30-SO2Ph-OH as an oil. This was purified by column chromatography to give 40.1 g of pure C30-SO2Ph-OH as a yellow oil.
[0030] C30-SO2Ph-OH 1 H NMR and 13 C NMR characterization 25 1H NMR (400 MHz, CDCl3) δ 7.84 (D 2H), 7.62 (T 1H), 7.52 (T 2H), 5.38 (T 1H), 5.10 (M 4H), 4.91 (D 1H), 4.12 (D 2H), 3.88 (T 1H), 2.89 (D 1H), 2.27 (T 1H), 1.93-2.04 (M 16H), 1.80 (Br 1H), 1.67 (S 3H), 1.62 (S 3H), 1.58 (S 9H), 1.52 (S 3H), 1.15 (S 3H). 13 C NMR (400MHz, CDCI3) δ 145.09, 139.05,137.88, 135.60, 135.02, 133.38, 131.26, 130.17, 129.23,128.69, 127.85,124.35, 124.06, 123.56, 123.45, 117.20, 63.44, 59.24, 39.71, 39.19, 37.32, 3026.73, 26.58, 26.57, 26.32, 25.72, 17.69, 16.34, 16.23, 16.02, 15.98, 15.93.
[0031] Example 2 Preparation of 1-((2E,6E,10E,14E,18E)-1-chloro-3,7,11,15,19,23-hexamethyltetracarbon-2,6,10,14,18,22-hexaen-9-ylsulfonyl)benzene (C30-SO2Ph-Cl).
[0032] 460 mL of N,N-dimethylformamide was cooled to -5 °C. At -5 °C, 36.33 g (0.265 mol) of phosphorus trichloride was slowly added over 10–15 min. The reaction mixture was stirred for another 30 min while maintaining a constant temperature. At 5 °C–10 °C, 200 g (0.353 mol) of C30-SO2Ph-OH dissolved in 240 mL of N,N-dimethylformamide was added to the above solution over 20 min. The reaction mixture was stirred for another 2 h at the same temperature, then quenched with sodium bicarbonate to adjust the pH to 8 and extracted with ethyl acetate. The organic layer was washed with water, then with brine, and dried over anhydrous sodium sulfate. Ethyl acetate was distilled under vacuum to give 215 g of a deep red oily substance, C30-SO2Ph-Cl, in 95% yield.
[0033] Example 3 Preparation of 1-((2E,6E,10E,14E,18E)-3,7,11,15,19,23-hexamethyl-1-(phenylsulfonyl)tetracosano-2,6,10,14,18,22-hexaen-9-ylsulfonyl)benzene (C30-(SO2Ph)2) 79.6 g (0.485 mol) of sodium benzenesulfinate in 473 mL of N,N-dimethylformamide was cooled to 10-15 °C. At 10-15 °C, 215 g (0.367 mol) of C30-SO2Ph-Cl dissolved in 258 mL of N,N-dimethylformamide was added to the above solution over 10 min. The reaction mixture was allowed to reach room temperature and stirred for 15 h. The mixture was then quenched with distilled water and extracted with ethyl acetate. The organic layer was washed with water, followed by brine, and dried over anhydrous sodium sulfate. Ethyl acetate was distilled under vacuum to give 232 g of crude C30-(SO2Ph)2 as a deep red oil, in 84% yield. The crude product was purified by column chromatography in a mixture of hexane and ethyl acetate to obtain a pure product, which was then characterized.
[0034] C30-(SO2Ph)2 1 H NMR and 13C NMR characterization 1 H NMR (400 MHz, CDCl3) δ 7.80 (M 4H), 7.62 (M 2H), 7.54 (M 4H), 5.10 (M 5H), 4.90 (D 1H), 3.90 (M 1H), 3.80 (D 1H), 2.89 (D 1H), 2.26 (T 1H), 1.95-2.05 (M 16H), 1.66 (S 3H), 1.58 (S 9H), 1.50 (S 3H), 1.28 (S 3H), 1.14 (S 3H).
[0035] 13C NMR (400 MHz, CDCI3) δ 146.02, 145.13, 138.65, 137.88, 135.61,133.59, 133.40, 131.22, 130.64, 129.22, 128.99, 128.71, 128.45, 127.29,124.35, 124.05, 123.43, 117.20, 110.42, 63.41, 60.37, 55.99, 39.73, 39.28,29.68, 26.73, 26.40, 25.88, 17.69, 16.35, 16.15, 16.02, 15.99 and 14.20.
[0036] Example 4 Preparation of (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyl-5,13-bis(phenylsulfonyl)octadec-2,6,10,14,18,22,26-heptaenyl acetate (C35-(SO2Ph)2-OAc).
[0037] Under an inert atmosphere, 340 g (0.492 mol) of C30-(SO2Ph)2 was dissolved in 952 mL of tetrahydrofuran. 124 g (0.762 mol) of 4-chloroisopentenyl acetate was added. The reaction mixture was cooled to 0°C to -5°C. 13.07 g of tetrabutylammonium bromide and 2.13 g of 18-crown-6 were added. The reaction mixture was stirred for 5 minutes while maintaining a constant temperature. 82.65 g (0.736 mol) of potassium tert-butoxide in 680 mL of tetrahydrofuran was added to the above solution over 10 minutes, and the reaction mixture was stirred for 2 hours while maintaining a constant temperature, and the reaction was continued overnight. The reaction mixture was quenched in 20% ammonium chloride solution, and the pH was adjusted to 5–6 using 1 M HCl. The tetrahydrofuran was distilled off under vacuum, and the residue was extracted with ethyl acetate. The ethyl acetate layer was washed with water, then with brine, and dried over anhydrous sodium sulfate. Ethyl acetate was distilled under vacuum to give 383 g of crude C35-(SO2Ph)2-OAc in an oily form, with a yield of 75%.
[0038] Example 5 Preparation of (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyl-5,13-bis(phenylsulfonyl)octadec-2,6,10,14,18,22,26-heptaen-1-ol (C35-(SO2Ph)2-OH).
[0039] 18.9 g (0.028 mol) of C35-(SO2Ph)2-OAc was dissolved in 57 mL of methanol. The contents were cooled to 0-5 °C. 0.47 g (0.0084 mol) of potassium hydroxide dissolved in 2.35 mL of water was slowly added over 5 min, and the reaction mixture was stirred overnight. Methanol was distilled off, and the residue was extracted with ethyl acetate. The reaction mixture was quenched in water and acidified with 1 M HCl. The ethyl acetate layer was washed with water, then with brine, and dried over anhydrous sodium sulfate. Ethyl acetate was distilled off under vacuum to give 17.6 g of crude C35-(SO2Ph)2-OH as an oil. The crude product was purified by column chromatography to give 10.4 g of pure C35-(SO2Ph)2-OH as a yellow oil, in 90% yield.
[0040] C35-(SO2Ph)2-OH 1 H NMR and 13C NMR characterization 1 H NMR (400 MHz, CDCl3) δ 7.80 (T 4H), 7.57 (T 2H), 7.48 (T 4H), 5.35(T 1H), 5.05 (M 4H), 4.85 (D 2H), 4.03 (M 3H), 3.88 (M 2H), 2.85 (D 2H), 2.24 (M 4H), 1.84-2.06 (M 18H), 1.63 (S 3H), 1.57 (S 12H), 1.48 (S 3H), 1.20 (S3H).
[0041] 13C NMR (400 MHz, CDCI3) δ 145.19, 137.76, 137.69, 135.56, 134.97,133.51, 133.43, 133.29, 131.16, 129.15, 128.74, 128.70, 127.57, 127.55,127.42, 127.35, 124.33, 124.04, 123.42, 117.17, 117.13, 117.09, 63.45, 63.41,63.09, 60.36, 58.92, 39.71, 39.67, 39.65, 39.21, 37.25, 37.18, 26.70, 26.55, 26.38, 26.09, 25.69, 20.99, 17.67, 16.31, 16.23, 16.14, 15.99, 15.89, 15.83 and 14.16.
[0042] Example 6 Preparation of (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyloctadec-2,6,10,14,18,22,26-heptaen-1-ol (C35-OH).
[0043] Under a nitrogen atmosphere, 100 g (0.129 mol) of C35-(SO2Ph)2-OH was dissolved in 1000 mL of tetrahydrofuran, and 400 mg of (1,3-bis(diphenylphosphine)propane)palladium chloride II was added. The reaction mixture was cooled to -5 °C. 95.72 g (0.903 mol) of superhydrogen compound solution was added over 60 minutes. The reaction mixture was stirred at room temperature for 10–12 hours. After the reaction was complete, it was quenched by dropwise addition of methanol followed by dropwise addition of acetic acid while stirring for 1 hour. THF was distilled off under vacuum, and the residue was extracted twice with ethyl acetate. The ethyl acetate was washed off with water, followed by brine, and the residue was dried over anhydrous sodium sulfate. Ethyl acetate was distilled off under vacuum to give 78 g of crude C35-OH in an oily form, in a yield of 84.47%.
[0044] The crude product was purified by column chromatography in a mixture of hexane and ethyl acetate to recover the pure product. Purity: 90%. Heptapentenol (C35-OH) 1 Characterization by 1H NMR and 13C NMR.
[0045] 1H NMR (400 MHz, CDCl3) δ 5.45 (T 1H), 5.11 (M 6H), 4.17 (D 2H),1.98-2.14 (M 24H), 1.70 (S 6H), 1.62 (S 18H), 1.30 (Br 1H)。
[0046] 13 C NMR (400 MHz, CDCI3) δ 139.57, 135.32, 134.93, 134.85, 134.83,131.15, 124.38, 124.23, 124.14, 123.74, 123.36, 59.28, 39.70, 39.54, 26.73,26.64, 26.63, 26.30, 25.66, 17.64, 16.24, 15.98。
Claims
1. A method for synthesizing (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyloctadec-2,6,10,14,18,22,26-heptaen-1-ol, said method comprising... a) Reaction of (2E,6E,10E,14E,18E)-3,7,11,15,19,23-hexamethyl-9-(phenylsulfonyl)teicocarbamo-2,6,10,14,18,22-hexen-1-ol with PCl3 in dimethylformamide and hexane to obtain 1-((2E,6E,10E,14E,18E)-1-chloro-3,7,11,15,19,23-hexamethylteicocarbamo-2,6,10,14,18,22-hexen-9-ylsulfonyl)benzene b) Reaction of 1-((2E,6E,10E,14E,18E)-1-chloro-3,7,11,15,19,23-hexamethyltetracarbon-2,6,10,14,18,22-hexaen-9-ylsulfonyl)benzene with sodium benzenesulfinate in DMF to give 1-((2E,6E,10E,14E,18E)-3,7,11,15,19,23-hexamethyl-1-(phenylsulfonyl)tetracarbon-2,6,10,14,18,22-hexaen-9-ylsulfonyl)benzene c) Reaction of 1-((2E,6E,10E,14E,18E)-3,7,11,15,19,23-hexamethyl-1-(phenylsulfonyl)tetracos-2,6,10,14,18,22-hexaen-9-ylsulfonyl)benzene with 4-chloroisopentenyl acetate in THF in the presence of potassium tert-butoxide, TBAB, and 18-crown-6 to give (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyl-5,13-bis(phenylsulfonyl)tetracos-2,6,10,14,18,22,26-heptaenyl acetate. d) Hydrolyzing (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyl-5,13-bis(phenylsulfonyl)octadec-2,6,10,14,18,22,26-heptaenyl acetate in the presence of KOH and methanol yields (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyl-5,13-bis(phenylsulfonyl)octadec-2,6,10,14,18,22,26-heptaen-1-ol. e) (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyl-5,13-bis(phenylsulfonyl)octadec-2,6,10,14,18,22,26-heptaen-1-ol) was reduced to (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyloctadec-2,6,10,14,18,22,26-heptaen-1-ol) in THF in the presence of a superhydrogen compound. 。 2. A compound having the following formula 1-((2E,6E,10E,14E,18E)-3,7,11,15,19,23-hexamethyl-1-(phenylsulfonyl)tetracocarbon-2,6,10,14,18,22-hexaen-9-ylsulfonyl)benzene.
3. A compound having the following formula (2E,6E,10E,14E,18E,22E)-3,7,11,15,19,23,27-heptamethyl-5,13-bis(phenylsulfonyl)octadecano-2,6,10,14,18,22,26-heptaen-1-ol.