由酸酐制备酯

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酸酐的酰化能力很强,当加入少量的(几滴)硫酸催化反应能在很短的时间内完成,几乎是定量的。反应中,催化剂硫酸提供质子,酸酐接受质子形成酰基正离子,与醇、酚完成酰化反应后又释出质子。


反应实例

To the aboveflask, containing 3-nitro-4-hexanol (330 g, 2.24 mol) was added a magnetic stirring egg and 1 mL of conc. sulfuric acid.The contents of the flask were stirred in an ice bath and aceticanhydride (240 g, 2.35 mol) was added inportions, keeping the temperature of the reactants below 60℃. After the addition of the acetic anhydride was complete, the contents of the flaskwere stirred for 1 h. The flask was then equipped for vacuum distillation. Thelower boiling components (Ac2O and AcOH) were removed at 25 mm by gently heating the stirredcontents of the flask (≤100℃ bath temperature). After these reagentshave been removed, the system was cooled, attached to a vacuumpump, and carefully heated. The fraction boiling at 105–107℃/10 mmwas collected, affording 4-acetoxy-3-nitrohexane (379 g, 90%).

【 OrganicSyntheses, Coll. Vol. 9, p.242 (1998); Vol. 70, p.68 (1992)】



Ina 1000mL flask, the nitrodiol(52 g, 0.323 mol) were suspended inacetic anhydride (150 mL). Without cooling, 3~6 drops of concentrated sulfuric acid were added. After stirring for 1 h, 500 mLof ice/water was rapidly added and stirring was continued for 60 min. Theresulting colorless crystals were filtered, washed with water, and air-dried togive the product (75.6 g, 95.6%)of colorless crystals .

OrganicSyntheses, Coll. Vol. 8, p.332 (1993); Vol. 69, p.19 (1990)】




5-Hydroxywasophthalic acid (360.56 g, 1.98 mol) was charged to a2000 mL round bottom 3-neck flask with a Friedrich condenser and thermocoupleunder a blanket of nitrogen. Acetic anhydride (808.25 g, 7.96 mol) was addedslowly. The white suspension was stirred and refluxed (~136℃) for 4 h. After cooling the whitesolid was filtered off and washed with toluene to afford 5-acetoxywasophthalicacid (336.95 g, 76%). 

【Patent; Hoechst Celanese Corp.; Publ.: US5777129 A1(1998/07/07), Appl.:  US1995-516853(1995/08/18)】



294 ml of butyric acid anhydride was treated with addition of 2 ml ofconcentrated aqueous sulfuric acid at room temperature, and then 122 g of3,5-dimethyl-phenol was added to the solution at room temperature. The reactiontemperature raised to 40℃ and was then raised to 80℃. The mixture was stirred for 1 h and diluted with 60mL of water and 60 mL of ethanol, poured onto ice water and twice extractedwith 500 mL of hexane each time. The hexane extract was washed with water,aqueous sodium bicarbonate solution, dried over sodium sulfate and evaporatedto give butyryloxy-3, 5-dimethyl-benzene which boils at 123℃.-125℃/11 mm Hg afterrectification.

【Patent; Hoffmann-La Roche Inc.; Publ: US4215215 A1(1980/07/29), Appl.:  US1979-55437  (1979/07/06)】



对于酸不稳定的底物,也可以用碱催化反应,如吡啶,甚至可以用吡啶和酸酐以一定比例混合进行反应。





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