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Preparation method of cyclopropyl fenpropathin derivative

A technology of bromocyclopropylmethyl cyanide and derivatives, which is applied in the field of preparation of cyclopropylmethyl cyanide derivatives, can solve problems such as unfavorable industrial production, influence on reaction yield, cumbersome operation, etc., achieve method safety and increase reaction temperature , the effect of improving production efficiency

Active Publication Date: 2013-12-18
DALIAN QIKAI MEDICAL TECH +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the process of synthesizing the intermediate product cyclopropyl formamide derivatives, when ammonia water is used as ammoniation reagent, a part of acid chloride will be hydrolyzed into carboxylic acid unavoidably, while using anhydrous solvent tetrahydrofuran and liquid ammonia as ammoniation reagent, the yield High, but because the liquid ammonia is easy to volatilize from the organic solvent during the post-treatment, the pollution to the environment is relatively large, and the operation is cumbersome, which is not conducive to industrial production
The dehydration reaction of the intermediate product cyclopropyl formamide derivatives to prepare the product cyclopropyl methyl cyanide derivatives, almost all of the literature uses strong acidic dehydration reagents, and the dehydration reaction process with these reagents is very classic, and the technology is also very advanced. Mature, but these acidic dehydrating reagents will inevitably cause some side reactions, affecting the reaction yield

Method used

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  • Preparation method of cyclopropyl fenpropathin derivative
  • Preparation method of cyclopropyl fenpropathin derivative
  • Preparation method of cyclopropyl fenpropathin derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Embodiment 1 prepares 1-bromocyclopropyl methyl cyanide

[0044] The process route is as follows:

[0045]

[0046] (1) Synthesis of methyl 2.4-dibromobutyrate

[0047] Put 17kg of γ-butyrolactone and 21.6kg of phosphorus tribromide into the glass-lined reactor, lower the temperature to -10°C under the protection of nitrogen, slowly add 58kg of bromine, and absorb the tail gas with a three-stage absorption tower, and control the reaction temperature to 40 ~50°C; heat up for 1 hour after adding, then raise the temperature to 80°C and hold for 3 hours. After the reaction, the temperature was lowered to -5°C, 14.2 kg of methanol was added dropwise, and the reaction was kept at -5 to 5°C for 1 hour after the addition was completed.

[0048] Add 100kg methyl tert-butyl ether, 15kg tap water in the above-mentioned product, use 10%Na 2 CO 3 The pH of the solution was adjusted to 7, the layers were allowed to stand, and the oil layer was washed once with 10 kg of tap wat...

Embodiment 2

[0062] Embodiment 2 prepares 1-bromocyclopropyl methyl cyanide

[0063] (1) Synthesis of methyl 2.4-dibromobutyrate

[0064] Put 86g of γ-butyrolactone and 11.8g of red phosphorus into the four-necked reaction bottle, lower the temperature to -10°C under the protection of nitrogen, slowly add 665g of bromine dropwise, absorb the tail gas with liquid alkali, and keep the temperature in the bottle at 40-50°C ; Add and keep warm for 1 hour, heat up to 80°C and keep warm for 3 hours. Cool down to -2°C, add 80 g of methanol dropwise, and keep the reaction at -5 to 5°C for 1 hour after the addition.

[0065] Add 400g of chloroform, 70g of tap water to the above product, and then use 10%Na 2 CO 3 The pH value of the aqueous solution was adjusted to 7, and the layers were allowed to stand. The oil layer was washed once with 70 g of tap water, and all the water layers were treated as wastewater. The oil layer was distilled to remove the solvent to obtain 2.4-dibromobutyric acid meth...

Embodiment 3

[0076] Embodiment 3 prepares 1-bromocyclopropyl methyl cyanide

[0077] The preparation method is the same as in Example 2, but step (3) synthesizes 1-bromocyclopropyl carboxylic acid and proceeds as follows: in a four-necked glass reaction flask, add 120 g of methanol, 50 g of 1-bromocyclopropyl formate methyl ester, 82% Potassium hydroxide 17g, react at 0-10°C for 15 hours, distill off the solvent, add 100g tap water to the remaining solid, adjust the pH to 1-2 with concentrated hydrochloric acid, add methyl tert-butyl ether for extraction 3 times, combine the oil layers with After washing with tap water once, the oil layer was distilled off under reduced pressure to remove the solvent to obtain 41.2 g of solid 1-bromocyclopropylcarboxylic acid with a yield of 90%.

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Abstract

The invention relates to a preparation method of a cyclopropyl fenpropathin derivative. The preparation method comprises the following steps: synthesizing a cyclopropyl carboxylic acid derivative by taking gamma-butylrolactone as a raw material; and then carrying out acylation, amination and dewatering reactions so as to prepare the cyclopropyl fenpropathin derivative. The method provided by the invention can be used for large-scale industrial production, has the advantages of low energy consumption, less side reactions, high yield, high product purity and the like, and is an ideal safe and efficient energy-saving consumption-reducing process for preparing the cyclopropyl fenpropathin derivative.

Description

technical field [0001] The invention relates to a preparation method of cyclopropylmethyl cyanide derivatives, in particular to a method for synthesizing cyclopropylmethyl cyanide derivatives with gamma-butyrolactone as raw material. Background technique [0002] Cyclopropylmethyl cyanide derivative is an important highly active compound, as a pharmaceutical intermediate, widely used in drug synthesis, but there is no literature report on the synthesis of this compound. [0003] The preparation of cyclopropylmethyl cyanide derivatives first needs to synthesize cyclopropylcarboxylic acid derivatives, and there are some shortcomings and drawbacks in the preparation methods of cyclopropylcarboxylic acid derivatives introduced in the literature at present. Document J.Org.Chem 54,6100 (1989) and J.M.Synthesis 1983, 915 reported the synthetic method of 1-bromo-1-carboxycyclopropane. The starting material γ-butyrolactone used in J.Org.Chem 54,6100 (1989) is cheap, easy to get, and...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C255/46C07C253/20
Inventor 姜殿平苑峰蒋斌李成斌
Owner DALIAN QIKAI MEDICAL TECH
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