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Modified synthetic method of dicyclopropyl ketone

A technology of dicyclopropyl ketone and synthesis method, which is applied in the field of improved preparation, can solve the problems of prone to material flushing accidents, unstable yield, poor controllability, etc., and achieve the reduction of water-soluble impurities, high product yield, and environmental protection The effect of pressure reduction

Active Publication Date: 2016-07-06
浜田智子
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0012] The actual actual yield of this synthesis process is generally low, and the yield is unstable, especially when it is used for expanding production.
Moreover, the controllability of the process is poor, and it is prone to punching accidents.

Method used

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  • Modified synthetic method of dicyclopropyl ketone
  • Modified synthetic method of dicyclopropyl ketone
  • Modified synthetic method of dicyclopropyl ketone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] In a 1000mL four-necked bottle, equipped with a thermometer, an electric stirrer, a reflux condenser, and a U-shaped calcium chloride drying tube. 60 g of toluene and 48.8 g of solid sodium methoxide were added under stirring, and the internal temperature was raised to 75°C by heating, and 137.6 g of γ-butyrolactone was added dropwise. After the dropwise addition is completed, the temperature is raised to an internal temperature of 80-90°C and the reaction is carried out for more than 2 hours. Then cool down to room temperature, add 402g of pre-frozen concentrated hydrochloric acid, heat up to 85-90°C to react for more than 1 hour after adding, cool down, filter, and separate phases of the filtrate, and extract the water phase with 20g of toluene for washing the solid. The toluene phases were combined to obtain 182.4 g of the CrDCK / toluene solution in step (2), including 102.4 g of CrDCK and a yield of 70.0% (based on gamma-butyrolactone).

[0039] In a 1000mL four-nec...

Embodiment 2

[0041] In a 1000mL four-necked bottle, equipped with a thermometer, an electric stirrer, a reflux condenser, and a U-shaped calcium chloride drying tube. 80 g of toluene and 101.4 g of solid potassium tert-butoxide were added under stirring, and the internal temperature was raised to 75°C by heating, and 160.0 g of β-methyl-γ-butyrolactone was added dropwise. After the dropwise addition was completed, the temperature was raised to an internal temperature of 80-90°C and the reaction was carried out for 2 hours. Then cool down to room temperature, add pre-frozen concentrated hydrochloric acid 402g, heat up to an internal temperature of 85-90°C for 1 hour, cool down, filter, and separate phases of the filtrate. In the toluene phase, 319.3 g of the β-methyl-CrDCK / toluene solution of step (2) was obtained, including 219.3 g of CrDCK, and the yield was 65.0% (based on γ-butyrolactone).

[0042] Add 200g of water and 65g of solid sodium hydroxide to a 1000mL four-necked bottle, stir...

Embodiment 3

[0044]In a 1000mL four-necked bottle, equipped with a thermometer, an electric stirrer, a reflux condenser, and a U-shaped calcium chloride drying tube. While stirring, 90 g of toluene and 65.3 g of solid sodium ethoxide were added, heated to raise the internal temperature to 75°C, and 137.6 g of γ-butyrolactone was added dropwise. After the dropwise addition is completed, the temperature is raised to an internal temperature of 80-90°C and the reaction is carried out for more than 2 hours. Then cool down to room temperature, add 402g of pre-frozen concentrated hydrochloric acid, heat up to 85-90°C to react for more than 1 hour after adding, cool down, filter, and separate phases of the filtrate, and extract the water phase with 20g of toluene for washing the solid. The toluene phases were combined to obtain 209.5 g of the CrDCK / toluene solution in step (2), of which CrDCK was 99.5 g, and the yield was 68.0% (based on gamma-butyrolactone).

[0045] Add 180g of water and 64g of...

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Abstract

The invention discloses a modified synthetic method of dicyclopropyl ketone, comprising: first, in the presence of reaction inert organic solvent and solid sodium alcoholate, subjecting gamma-butyrrolactone to inter-molecular dehydration condensation to generate an intermediate; second, adding concentrated hydrochloric acid into a reaction system and generating 1,7-dichloro-4-heptanone crude product by decarboxylation; third, closing loop under the action of a strong base to generate the dicyclopropyl ketone. The invention has the advantages that the inert organic solvent and solid sodium alcoholate are used, there is no need for recycling alcohols, reaction controllability is greatly improved, reaction byproducts are decreased, product yield is 15-20% as high as that of a conventional technique, production cost is lowered, environment protection burden is lowered, and product quality is improved.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to a preparation method of a compound, in particular to an improved preparation method of dicyclopropyl ketone and its analogues. Background technique [0002] Dicyclopropylketone (CAS1121-37-5) and its analogues are key basic raw materials for the synthesis of medicines, pesticides, and epoxy resin curing agents. They are widely used and their usage is increasing year by year. [0003] The dicyclopropylmethylamine obtained by the reaction of dicyclopropyl ketone and hydroxylamine hydrochloride followed by hydrogenation reaction is the key intermediate for the synthesis of the antihypertensive α2-receptor agonist drug rilmenidine (Rilmenidine, CAS54187-04-1) body (see formula 1 below). [0004] [0005] The 1,7-dichloro-4-heptanone synthesized by ring-opening of dicyclopropyl ketone and hydrochloric acid is also the basic raw material for the synthesis of 1-azabicyclo[3....

Claims

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Application Information

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IPC IPC(8): C07C49/293C07C45/61
CPCC07C45/59C07C45/61C07D307/58C07C49/293C07C49/16
Inventor 浜田申一浜田智子唐成见
Owner 浜田智子
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