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ChemicalBook CAS DataBase List Mildronate
76144-81-5

Mildronate synthesis

2synthesis methods
Hydrazinium,2-(3-methoxy-3-oxopropyl)-1,1,1-trimethyl-, chloride (1:1)

76144-82-6

Mildronate

76144-81-5

The general procedure for the synthesis of Mildronate from 3-(2,2,2-trimethylhydrazine)-propionic acid methyl ester chloride is as follows: 1. 24 g of sodium hydroxide was suspended in 450 mL of ethanol, maintaining the temperature at 18-20 °C, and 136 g of methyl 3-(2,2,2-trimethylhydrazine)-propionate chloride was slowly added under stirring for 5-10 minutes. 2. the reaction mixture was stirred continuously at 18-20 °C until the saponification of the ester was complete (the progress of the reaction was monitored by thin layer chromatography TLC). 3. the reaction mixture is cooled to 2-4 °C and saturated with carbon dioxide gas until a pH of 8.1-8.5 is reached. 4. The precipitate formed was collected by filtration and the precipitate was washed with 3 x 10 mL of ethanol. 5. The filtrates were combined and concentrated by evaporation to give 91 g (95% yield) of a semi-crystalline solid product containing 95% of 3-(2,2,2-trimethylhydrazine) propionate. 6. recrystallizing the product using ethanol, isopropanol or other suitable solvent to obtain 3-(2,2,2-trimethylhydrazine) propionate dihydrate with a melting point of 85-87 °C (purity >99.5%).

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Yield:76144-81-5 95%

Reaction Conditions:

Stage #1:methyl 3-(2,2,2-trimethylhydrazinium)propionate chloride with ethanol;sodium hydroxide at 18 - 20;
Stage #2: with carbon dioxide; pH=8.1 - 8.5Product distribution / selectivity;

Steps:

5
Example 5; 24 g of NaOH were suspended in 450 ml of ethanol and, at 18-20° C., 136 g of methyl-3-(2,2,2-trimethylhydrazinium)propionate chloride during 5-10 min were added under stirring. The stirring was continued at 18-20° C. until ester saponification was completed (controlled by TLC). The mixture was then cooled to 2-4° C. and saturated with CO2 to pH 8.1-8.5. Precipitate thus formed was filtered off, washed with 3×10 ml of ethanol and the combined filtrates were evaporated. 91 g (95%) of semi-crystalline solid were obtained (3-(2,2,2-trimethylhydrazinium)propionate content 95%). Crystallization from ethanol or propanol-2 or another appropriate solvent gave 3-(2,2,2-trimethylhydrazinium)propionate dihydrate with m.p. 85-87° C. (purity >99.5%).

References:

Silva, Jorge US2009/318731, 2009, A1 Location in patent:Page/Page column 3

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