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Synthetic method of 2-diester methylmalonate compounds

A methylmalonate diester and synthetic method technology, applied in the preparation of organic compounds, chemical instruments and methods, and carboxylate preparation, can solve the problems of increasing the difficulty of separation and purification, the difficulty of product separation, and the high cost of raw materials. Achieve the effect of unique method, simple post-processing and low cost

Active Publication Date: 2015-11-18
HEBEI JIUTIAN MEDICINE CHEM CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The first two methods not only cause waste of raw materials, generate a large number of by-products, but also increase the difficulty of separation and purification, while the third method has the disadvantages of high raw material cost and difficult product separation.

Method used

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  • Synthetic method of 2-diester methylmalonate compounds
  • Synthetic method of 2-diester methylmalonate compounds
  • Synthetic method of 2-diester methylmalonate compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Synthesis of A, 2-hydroxypropionitrile:

[0035]

[0036] Add acetaldehyde (44.05g, 1mol) to the four-neck flask, cool down to 0-10°C, then add hydrocyanic acid (32.43g, 1.2mol) dropwise, stir the reaction, add triethylamine dropwise to control the pH at 2~ 3. Insulation reaction for 1-2h. The reaction system makes free HCN escape from the reaction solution under vacuum conditions, and the tail gas of 30% NaOH solution is absorbed. After removing HCN, 70.75 g of 2-hydroxypropionitrile was obtained, with a yield of 99.54%. 1 HNMR (300MHz, CDCl 3 ): 1.56~1.60 (m,3H,CH 3 ), 4.43~4.49 (m, H, CH).

[0037] B, the synthesis of 2-cyanoethyl methanesulfonate:

[0038]

[0039] Add 2-hydroxypropionitrile (71.08g, 1mol), triethylamine (101.19g, 1mol) and 100mL of dichloromethane into a four-neck flask, cool down to 0-10°C, and slowly add methanesulfonyl chloride (114.55g , 1mol), and reacted at 20-25°C for 24h after dropping. Add 30 mL of saturated sodium carbonate s...

Embodiment 2

[0047] Synthesis of A, 2-hydroxypropionitrile:

[0048] Add acetaldehyde (44.05g, 1mol) to the four-neck flask, cool down to 0-10°C, then add hydrocyanic acid (54.06, 2.0mol) dropwise, stir the reaction, add dropwise 50% sodium hydroxide solution to control the pH at 8-9, heat preservation reaction for 3-4h. The reaction system makes free HCN escape from the reaction solution under vacuum conditions, and the tail gas of 30% NaOH solution is absorbed. After removing HCN, 70.60 g of 2-hydroxypropionitrile was obtained, with a yield of 99.32%.

[0049] B, the synthesis of 2-cyanoethyl trifluoromethanesulfonate:

[0050]

[0051] Add 2-hydroxypropionitrile (71.08g, 1mol), potassium carbonate (276.42g, 2mol) and 150mL dichloroethane into the four-neck flask, cool down to 0-10°C, and slowly add trifluoromethanesulfonyl chloride ( 219.08g, 1.3mol), reacted at 20~25℃ for 20h after dropping. After filtering to remove salt, add 80 mL of saturated sodium carbonate solution to rins...

Embodiment 3

[0058] Synthesis of A, 2-hydroxypropionitrile:

[0059] Add acetaldehyde (44.05g, 1mol) to the four-neck flask, cool down to 0-10°C, then add hydrocyanic acid (27.03, 1.0mol) dropwise, stir the reaction, add pyridine dropwise to control the pH at 4-5, keep warm Reaction 2-3h. The reaction system makes free HCN escape from the reaction solution under vacuum conditions, and the tail gas of 30% NaOH solution is absorbed. After removing HCN, 70.05 g of 2-hydroxypropionitrile was obtained, with a yield of 98.55%.

[0060] B, the synthesis of 2-cyanoethyl ethyl sulfonate:

[0061]

[0062] Add 2-hydroxypropionitrile (71.08g, 1mol), diisopropylethylamine (258.48g, 2mol) and 100mL toluene into a four-necked flask, cool down to 0-10°C, and slowly add ethylsulfonyl chloride dropwise (192.87g, 1.5mol), react at 0~10℃ for 24h after dropping. After filtering to remove salt, add 80 mL of saturated sodium carbonate solution to rinse the reaction solution, dry it with anhydrous magnesi...

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Abstract

The invention discloses a synthetic method of 2-diester methylmalonate compounds, and relates to the technical field of carboxylic ester preparation. The synthetic method comprises steps as follows: C, sulfonic acid 2-ethyl N-cyanoethanimideate IV and cyanide react under the action of a solvent and a catalyst, and 2-methyl malononitrile V is obtained; D, 2-methyl malononitrile V and ROH react under the action of the solvent and concentrated sulfuric acid, and products of 2-diester methylmalonate compounds I are obtained, wherein MCN is cyanide, M is Na or K, ROH is alkyl alcohol, alkenyl alcohol or a fluoride group containing alcohol, is benzyl alcohol or benzyl alkyl, halogen or nitro substituted benzyl alcohol, or is phenol or C1-C5 containing alkyl, halogen or nitro substituted phenol. The method is unique, the reaction conditions are mild, the reaction process is basically free of by-products, the yield is high, adopted raw materials have extensive sources, and acetaldehyde can be used as the raw material; the synthetic method is applicable to industrial production.

Description

technical field [0001] The invention relates to the technical field of preparation of carboxylic acid esters. Background technique [0002] 2-Methylmalonate diester compounds are important pharmaceutical industry intermediates, such as dimethyl 2-methylmalonate is an important intermediate of medical muscone. [0003] At present, the main methods for preparing 2-methylmalonate diesters are: (1) "Iodomethane" method (Hosokawa, Takahiro, etc., Journal of Organic Chemistry, 1995, 60, 6159), that is, using malonate as raw material , Prepared by reacting with methyl iodide under the action of sodium methoxide. Since iodomethane is a highly active methylating reagent, it is difficult to control the reaction to monomethylated products, resulting in a large number of dimethylated by-products. (2) "2-chloropropionic acid" method (Franchimont et al., Recueildes Travaux Chimiques des Pays-Bas, 1889, 8, 285), which uses 2-chloropropionic acid as raw material, after alkalization, react...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/40C07C67/22C07C69/63
CPCC07C67/22C07C253/16C07C255/04C07C69/40C07C69/63
Inventor 刘少华石会王金花郭亚运王金金董璞程丽华彭艳丽
Owner HEBEI JIUTIAN MEDICINE CHEM CO LTD
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