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CAS No. : | 97-67-6 | MDL No. : | MFCD00064213 |
Formula : | C4H6O5 | Boiling Point : | - |
Linear Structure Formula : | HOCOCH2CHOHCOOH | InChI Key : | BJEPYKJPYRNKOW-REOHCLBHSA-N |
M.W : | 134.09 | Pubchem ID : | 222656 |
Synonyms : |
(S)-Hydroxybutanedioic acid;(S)-E 296;L-Malic acid;(S)-2-Hydroxysuccinic acid
|
Chemical Name : | (S)-2-hydroxysuccinic acid |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99.9% | EXAMPLE 1 (S)-Dihydro-3-hydroxy-2 (3H)-furanone 10 g of L-(-)-malic acid is stirred in 45 ml of trifluoroacetic acid anhydride for 2 hours at 25 C. Then, it is concentrated by evaporation in a vacuum, 7 ml of methanol is added to the residue, and it is allowed to stir for 12 more hours. Then, it is concentrated by evaporation in a vacuum. The residue that is obtained is dissolved in 150 ml of absolute tetrahydrofuran. It is cooled to 0 C., and 150 ml of borane-tetrahydrofuran complex is added and allowed to stir for 2.5 more hours at 0 C. Then, 150 ml of methanol is added. It is allowed to stir for one more hour at room temperature and then concentrated by evaporation in a vacuum. The crude product that is obtained is dissolved in 80 ml of toluene. 5 g of Dowex(R) (activated, acidic) is added, and it is refluxed for one hour. Then, Dowex(R) is filtered off, and the filtrate is concentrated by evaporation in a vacuum. The crude product that is obtained (7.61 g, 99.9%) is used without purification in the next step. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluoroacetic acid; In tetrahydrofuran; methanol; water; toluene; | EXAMPLE 14 (S)-3-(Acetyloxy)-1-[4-(1-pyrrolidinyl)-2-butynyl]-2-pyrrolidinone A mixture of 60 g of (S)-malic acid, 200 ml of dimethoxypropane and 0.5 g of 4-methylphenyl sulfonic acid was stirred for 30 minutes. Water was added and the mixture was extracted four times with dichloromethane. The extracts were combined, dried and concentrated, giving 48.6 g of solid (mp 107-109 C.). This solid was dissolved in 700 ml of tetrahydrofuran, cooled to -20 C. and 160 ml of a 2.0 M solution of borane methyl sulfide complex in tetrahydrofuran was added dropwise. When the addition was complete the mixture was warmed to room temperature, heated at reflux for 1 hour, and cooled. Methanol was added and the mixture concentrated in vacuo. The residue was concentrated twice from 500 ml of methanol and once from 200 ml of toluene. The residue was diluted with dichloromethane, filtered and concentrated to 200 ml. Trifluoroacetic acid (20 ml) was added and this mixture was stirred overnight. The mixture was evaporated from three 200 ml portions of toluene. The residue was distilled at 1.0 mm, 100 C., giving 27 g of (S)-dihydro-3-hydroxy-2(3H)-furanone as a colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85.2% | Charge 2 -phenyl- 1 -propylamine HCl (317.2 g, 1.85 moles), dry ethanol (2.0 L) and NaOH beads (75.4 g, 1.89 moles) washed with additional ethanol (500 mL) to a dry 3 -L round bottom flask under nitrogen. Stir the mixture for 1.6 hours. Filter and add a solution of L-malic acid (62.0 g, 0.462 mole, 0.25 equivalents) in ethanol (320 mL) dropwise to the yellow filtrate. Heat the solution to 75C, then stir at 75C for 30 minutes. Remove heat and allow the solution to cool slowly. Allow the resulting thick precipitate to stir overnight. Filter the precipitate, rinse with ethanol (325 mL) and dry under reduced pressure to afford (2R)-2-phenylpropylamine malate (147.6 g, 39.5%) as a white crystalline solid. Chiral GC analysis of the free base, 2 -phenyl- 1 -propylamine reveals 83.2% e.e. enriched in the R-isomer. (Configuration is assigned via spectrometric comparison with commercial 2 -phenyl- 1 -propylamine.) IH NMR (CDCI3, 300 MHz) delta 7.32 (m, 2H), 7.21 (m, 3H), 2.86 (m, 2H), 2.75 (m, IH), 1.25 (d, 3H, J=6.9), 1.02 (br s, 2H).Heat a slurry of (2R)-2-phenylpropylamine malate (147.1 g, 83.2% e.e.) in 1325 mL ethanol and 150 mL deionized water to reflux (approximately 79.2 0C) until the solids dissolve. Allow the homogeneous solution to slowly cool with stirring overnight. Cool the precipitate (0 0C to 5 0C) and filter. Collect solids, rinse with ethanol (150 mL), and dry at 35C to afford (2R)-2-phenylpropylamine malate (125.3 g, 85.2% recovery) as a white powder. Chiral GC analysis of the free base, (2R)-2-phenylpropylamine, reveals 96.7% e.e. enriched in the R-isomer. IH NMR (CD3OD, 300 MHz) delta 7.32 (m, 10 H), 4.26 (dd, IH, J=3.6, 9.9), 3.08 (m, 6H), 2.72 (dd, IH, J=9.3, 15.3), 2.38 (dd, IH, J=9.3, 15.6), 1.33 (d, 6H, J=6.6). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63.3% | In water; for 0.5h;Product distribution / selectivity; | Example 13<strong>[173334-57-1]Aliskiren</strong> MalateA solution of 109.8 mg (0. 8192 mmol) L-malic acid in 2 ml water was added to 452 mg (0.819 mmol) <strong>[173334-57-1]Aliskiren</strong> free base and the resulting mixture was shaken well for 30 min resulting in a milky solution. This was frozen, using liquid nitrogen, and was lyophilized for 3 h to yield 356 mg (63.3 %) of a white solid.LCMS purity: 99.51 %. Melting point: 63 C - 69 C.DSC shows a very broad endotherm at 177.6 and 193.8 C.IR: 2959.9, 2874.6, 1720.1 , 1659.3, 1588.7, 1516.1 and 1474.3 cm 1. |
In ethanol; dichloromethane; at 20℃; for 24h; | Example 24: Preparation of aliskiren L-malic acid salt <strong>[173334-57-1]Aliskiren</strong> (1.6 g, 2.9 mmol) was dissolved in dichloromethane (10 mL), and L-malic acid (0.194 g, 1.45 mmol) in ethanol (1 mL) was added while stirring. The solution was stirred at room temperature for 24 h. Then, solvent was evaporated in vacuum, and the product was dried under vacuum at 30C over night. Mp = 79.9-85C XRPD: amorphous |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91.7% | In water; for 0.5h;Product distribution / selectivity; | Example 25<strong>[173334-57-1]Aliskiren</strong> L-Malate 2 : 1A solution of 0.127 g (0.951 mmol) L-malic acid in 15 ml water was added to 1.05 g (1.903 mmol) <strong>[173334-57-1]Aliskiren</strong> free base and stirred slowly for 30 min to obtain a turbid solution. By swirling the flask and freezing at -40C (using a Julabo chiller), the solution was converted into a thin film and subsequently the flask was connected to a freeze drier (conditions: vacuum: 18 mTorr, condenser temperature -104.2 C) for 4 h to obtain solid. Yield = 1 .08 g (91.7 %).DSC showed two merging endothermic peaks at 49.1 , 53.96 (due to water) and a broad endothermic peak at 178.6 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran; at 45℃; | <strong>[500287-72-9]Rilpivirine</strong> base Form II (0.30 g, 0.82 mmol) was dissolved in THF (6 mL) at 45C. L-Malic acid (121 mg, 0.90 mmol, 1.1 eq) was dissolved in THF (3 mL) at room temperature and the resulting solution was then added portion- wise to the solution containing <strong>[500287-72-9]Rilpivirine</strong> base at 45C with stirring. The reaction mixture was removed from the heat source and stirring was continued at room temperature for about 17 h. A precipitate formed and was isolated by filtration to give <strong>[500287-72-9]Rilpivirine</strong> L-malate Form 1. Drying of this material in a vacuum oven at 50C for 18 h afforded the same polymorphic form as was identified prior to drying. |
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