A method for preparing 4,10-dioxatricyclo[5.2.1.0(2,6)]dec-8-en-3-one
A dioxane, 10- technology, applied in the direction of organic chemistry, can solve the problems of excessive reduction of impurities, difficult to control, affecting the performance of downstream polymerization products, etc., to achieve the effect of good reproducibility and easy operation
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Embodiment 1
[0019] The first step, into a 1L reaction flask, add potassium borohydride (53.9g, 1.0mol), 18-crown-6 (5.3g, 0.02mol) and 200.0g of tetrahydrofuran, cool to 0°C, dropwise add maleic anhydride (98.1g, 1.0mol) and 500g of tetrahydrofuran, the temperature was controlled not to exceed 25°C, it took 1h to finish dropping, and the temperature was kept stirring for 2h.
[0020] The temperature was controlled not to exceed 25° C., and 10% hydrochloric acid (500 g) was added dropwise to quench the reaction, which took 1.5 hours to finish dropping, and the stirring was continued for 0.5 hours. Extraction with ethyl acetate 300g×3, the obtained oil layers were combined and washed with water 300g×3. After washing, an ethyl acetate solution of intermediate 2 (HPLC purity 98%) is obtained. After collecting 200-300 g of ethyl acetate under negative pressure not higher than 35°C, the remaining solution is directly used in the next step.
[0021] In the second step, the ethyl acetate solutio...
Embodiment 2
[0030] first step:
[0031] Referring to the operation of the first step in Example 1, the reaction conditions were changed to obtain the results in Table 1.
[0032] Table 1
[0033]
[0034] Step 2:
[0035] Referring to the operation of the second step in Example 1, the reaction conditions were changed to obtain the results in Table 2.
[0036] Table 2
[0037]
[0038]
Embodiment 3
[0040] The first step, in the 50L reaction flask, add potassium borohydride (1.08Kg, 20.0mol), 18-crown-6 (106g, 0.4mol) and tetrahydrofuran 4.00Kg, cool to 0 ° C, dropwise add maleic anhydride ( 1.96Kg, 20.0mol) and 10.0Kg of tetrahydrofuran, the temperature was controlled not to exceed 25°C, it took 2h to finish dropping, and the stirring was continued for 3h.
[0041] The temperature was controlled not to exceed 25°C, and 10% hydrochloric acid (10.0Kg) was added dropwise to quench the reaction, which took 1.5h to finish dropping, and the stirring was continued for 0.5h. Extraction with ethyl acetate 6.00Kg×3, the obtained oil layers were combined and washed with water 6.00Kg×3. After washing, an ethyl acetate solution of intermediate 2 (HPLC purity 97%) is obtained. After 4-6 Kg of ethyl acetate is harvested under negative pressure not higher than 35° C., the remaining solution is directly used in the next step.
[0042] In the second step, the ethyl acetate solution of th...
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