Compound as well as preparation and application thereof
A technology for compounds and pharmaceutical preparations, applied in the field of new optical isomers and their preparations, can solve problems such as unreported
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Embodiment 1
[0043] Preparation (3 S ,9 R ,10 R )-9,10-epoxy-1-heptadecen-4,6-diyn-3-ol
[0044] 0.0118g (0.12 mmol) cuprous chloride, 0.16mL n-butylamine, 0.37mL water, 0.108 g (0.6mmol) (4 R ,5 R )-4,5-epoxy-1-dodecyne in dichloromethane (9mL) solution was slowly added 0.144g (0.9mmol) ( S )-5-bromo-1-penten-4-yn-3-ol, 0.2081g (3mmol) hydroxylamine hydrochloride aqueous solution 2mL, keep the system light yellow, after the dropwise addition, continue to react for 1h. After the reaction, extract with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter, concentrate, and perform silica gel column chromatography (petroleum ether: ether, 5:1) to obtain 0.13 g of light yellow oily liquid (yield: 85 %). [α] D 20 = 45.6 (c = 1.2, CHCl 3 ); 1 H NMR (300 MHz, CDCl 3 ): δ 5.95 (ddd, J = 17.03, 10.12, 5.33 Hz 1H), 5.43-5.50 (m, 1H), 5.23-5.27 (m, 1H), 4.90-4.94 (m, 1H), 2.81-2.88 (m, 2H), 2.67-2.75 ( m, 1H), 2.48-2.56 (m,1H), 1.97-1.99 (m, 1H), 1.25–...
Embodiment 2
[0047] Preparation (3 S ,9 R ,10 R )-9,10-epoxy-1-heptadecen-4,6-diyn-3-ol
[0048] 0.0177g (0.12 mmol) cuprous bromide, 0.16mL ethylamine, 0.37mL water, 0.108g (0.6mmol) (4 R ,5 R )-4,5-epoxy-1-dodecyne in chloroform (9mL) solution was slowly added 0.144g (0.9mmol) ( S )-5-bromo-1-penten-4-yn-3-ol, 0.2081g (3mmol) hydroxylamine hydrochloride aqueous solution 2mL, keep the system light yellow, after the dropwise addition, continue to react for 1h. After the reaction, extract with chloroform, combine the organic phases, dry over anhydrous sodium sulfate, filter, concentrate, and perform silica gel column chromatography (petroleum ether: ether, 5:1) to obtain 0.13 g of light yellow oily liquid (85% yield) . [α] D 20 = 45.6 (c = 1.2, CHCl 3 ); 1 H NMR (300 MHz, CDCl 3 ): δ 5.95 (ddd, J = 17.03, 10.12, 5.33 Hz 1H), 5.43-5.50 (m, 1H), 5.23-5.27 (m, 1H), 4.90-4.94 (m, 1H), 2.81-2.88 (m, 2H), 2.67-2.75 ( m, 1H), 2.48-2.56 (m,1H), 1.97-1.99 (m, 1H), 1.25–1.60 (m, 12H), ...
Embodiment 3
[0061] (4 R ,5 R The synthetic method of )-4,5-epoxy-1-dodecyne is
[0062] (1) Preparation of 2-decyn-1-alcohol (compound 2 )
[0063] Add 50mL tetrahydrofuran, 5.32mL (90mmol) propynyl alcohol, 39.5mL (225mmol) hexamethylphosphoric triamide to a 250mL reaction flask successively under nitrogen protection, and slowly add 72mL (180mmol) n-butyl at -78°C Lithium solution. After 0.5 h of dropwise addition, the temperature was raised to -30°C and stirred for 3 h, and 7.07 mL (45 mmol) of n-bromoheptane was added, stirred for 20 min, then raised to room temperature and continued to react for 21 h. After the reaction was completed, 30 mL of saturated ammonium chloride aqueous solution was added, extracted with ether (30 mL'3), and the organic phases were combined. The organic phase was washed with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was subjected to silica gel (200-300 mesh) column chrom...
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