A kind of preparation method of 2,2-difluoro-5-chloromethyl piperonyl ring
The technology of chloromethyl piperonyl ring and difluoro piperonyl ring is applied in the field of preparation of 2,2-difluoro-5-chloromethyl piperonyl ring, can solve the problems of serious reaction pollution, difficult operation and high reaction cost, and achieves The effect of low reaction cost, simple post-processing and high yield
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[0021] The present invention provides a kind of preparation method of 2,2-difluoro-5-chloromethyl piperonyl ring, comprising the following steps:
[0022] 2,2-Difluoropiperone ring (Ⅰ) (English name: 2,2-difluorobenzo[d][1,3]dioxole) and chloromethyl ether undergo chloromethylation under the catalysis of Lewis acid to obtain 2,2-Difluoro-5-chloromethyl piperonyl ring (Ⅱ) (English name, 5-(chloromethyl)-2,2-difluorobenzo[d][1,3]dioxole), its reaction equation is as follows:
[0023]
[0024] The specific method of the reaction is as follows: adding 2,2-difluoropiperonyl, chloromethyl ether and Lewis acid into a reaction vessel for reaction.
[0025] The catalyst Lewis acid can be added to the reaction vessel at one time or in batches. Lewis acids that can be used include, but are not limited to, anhydrous zinc dichloride, anhydrous aluminum trichloride, anhydrous ferric chloride, tin tetrachloride, titanium tetrachloride or boron trifluoride etherate or multiple combinatio...
Embodiment 1
[0034] Add 2,2-difluoro-5-chloromethyl piperonyl (10g, 0.063mol), chloromethyl methyl ether (105ml, 1.386mol), 100ml dichloromethane, anhydrous zinc dichloride to the reaction flask respectively (17.2g, 0.126mol), reacted at room temperature for 3 hours, and the reaction was complete by TLC monitoring. Pour the reaction solution into 500ml of ice water, stir for 10 minutes, extract 100ml x 3 times with dichloromethane, combine the organic phases, wash with 200ml x 3 of water, wash with 350ml of saturated saline, dry, and spin dry to obtain 2,2-difluoro - 15 grams of light yellow oily substance of 5-chloromethyl piperonylcycline. Distilled under reduced pressure and received the fraction at 70-74°C under 0.5mmHg to obtain 11.7g of product with an isolated yield of 90%. The purity of the product before distillation: the purity detected by TLC is more than 90%, and the purity detected by lcms is: 90.41% (Agilent 1200).
[0035] 1 H NMR (400 MHz, DMSO) δ 7.42 (s, 1H), 7.32 (d, ...
Embodiment 2
[0037] Example 2: Preparation of 2,2-difluoro-5-chloromethyl piperonyl ring
[0038] With embodiment 1, just catalyzer is anhydrous aluminum trichloride, and the isolated yield of product is 70%.
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