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由酰氯制备酯

2018/09/06216 作者:佚名
导读:酰氯(点击查看制备方法:酰卤的制备)是强酰化剂和醇、酚作用生成酯的反应很迅速,此方法适用于由空间障碍的酯化。经常是在吡啶或其它叔胺参与下反应。 In an oven-dried, 500-mL, two-necked, round-bot

酰氯(点击查看制备方法:酰卤的制备)是强酰化剂和醇、酚作用生成酯的反应很迅速,此方法适用于由空间障碍的酯化。经常是在吡啶或其它叔胺参与下反应。

In an oven-dried, 500-mL, two-necked, round-bottomed flaskequipped with a magnetic stir bar and a rubber septum was placed 1,3,5-tri-O-benzoyl-α-D-ribofuranose (5.0 g, 10.8 mmol) and 2,6-lutidine (1.4 g, 13.0 mmol) in 200 mL of drydichloromethaneunderan argon atmosphere. The reaction mixture wascooled to 0℃and 3-(trifluoromethyl)benzoylchloride (3.3 g, 16.2 mmol) was addeddropwise to the stirred solution over 30 min. After the addition, the reactionmixture was warmed to room temperature and stirred overnight. The reaction wasquenched with 80 mL of aqueous saturated sodium bicarbonate, the phases wereseparated and the aqueous phase was extracted with dichloromethane (200 mL ×2). The combined organic extracts were washed with brine (100 mL × 2) and driedover anhydrous magnesium sulfate. After filtration, the solvent was removedunder reduced pressure to give yellow oil. Purification by flash columnchromatography (140 g of silica gel) and eluting with 25% ethyl acetate inhexanes gives a white solid that can be recrystallized from EtOAc/hexane toyield 1,3,5-O-tribenzoyl-2-O[(3- trifluoromethyl)benzoyl]- -α-D-ribofuranose(5.62 g, 82%) as white crystals

【Organic Syntheses, Coll. Vol. 10, p.246 (2004); Vol. 77, p.162 (2000)】

A mixture of 28.5 gof 4-nitrobenzoyl chloride, 30.0 g of 3,5-dichlorophenol and 300 mL of pyridinewas heated under reflux for 3 h. Aftercompletion of the reaction, the pyridine was distilled off under reducedpressure, the remaining reaction product was dissolved in ethyl acetate, andthe solution was washed with water and then with a saturated aqueous solutionof sodium chloride and concentrated under reduced pressure to give crudecrystals, which was recrystallized fromethyl acetate to give 3,5-dichlorophenyl-4-nitrobenzoate (44.2 g) as needles

【Patent; Asahi Kasei KogyoKabushiki Kawasha; Publ: EP475531 A1 (1992/03/18), Appl.: EP1991-202310 (1991/09/09)】

To the mixture of 3-Hydroxy-5-pregn-16-en-20-one (10 g) in pyridine (50mL) was added p-methylbenzenesulfonyl chloride (10 g), and the reaction mixturewas stirred at room temperature overnight and then poured into dilutehydrochloric acid. The precipitate was extracted into chloroform, and theextract was washed with dilute hydrochloric acid and with water, dried oversodium sulphate and evaporated to an oil which crystallized on standing. Recrystallisationfrom ethyl acetate/petrol gave 3-p-methylbenzenesulfonyloxy-5-pregn-16-en-20-one(13.3 g) as off-white prisms

【Patent; GlaxoLaboratories Limited; Publ.: US3952031 A1 (1976/04/20), Appl.: US1974-532612(1974/12/13)】

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