Citric Acid → (e)-2-[2-(Tert-butoxy)-2-oxoethyl]-5-cyclohexyl-2-pentenoic acid cyclohexylamine salt

HRID 1281252ノート

反応式

HRID 1281252 の反応式
CC(C)([O-])C.[K+].[C:7]([O:11][C:12](=[O:26])[CH2:13][CH:14](P(OCC)(OCC)=O)[C:15]([OH:17])=[O:16])([CH3:10])([CH3:9])[CH3:8].[CH:27]1([CH2:33][CH2:34][CH:35]=O)[CH2:32][CH2:31][CH2:30][CH2:29][CH2:28]1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O.[CH:50]1([NH2:56])[CH2:55][CH2:54][CH2:53][CH2:52][CH2:51]1>C1COCC1.C(OCC)(=O)C>[CH:50]1([NH2:56])[CH2:55][CH2:54][CH2:53][CH2:52][CH2:51]1.[C:7]([O:11][C:12](=[O:26])[CH2:13]/[C:14](=[CH:35]\[CH2:34][CH2:33][CH:27]1[CH2:32][CH2:31][CH2:30][CH2:29][CH2:28]1)/[C:15]([OH:17])=[O:16])([CH3:8])([CH3:9])[CH3:10]

参加物

8

反応物 5

HCID 311Citric AcidHCID 7965CyclohexylamineHCID 78070CyclohexanepropionaldehydeHCID 111510303-(Diethoxyphosphoryl)succinic acid 1-tert-butyl esterHCID 23665647Potassium tert-butoxide

生成物 1

HCID 69911301(e)-2-[2-(Tert-butoxy)-2-oxoethyl]-5-cyclohexyl-2-pentenoic acid cyclohexylamine salt収率 67%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

Potassium tert-butoxide (20.2 g, 0.18 mol) was added portionwise over 10 minutes to a solution of 3-(diethoxyphosphoryl)succinic acid 1-tert-butyl ester (25.4 g, 82- mmol) in THF (115 ml), at 0° C., under nitrogen. The mixture was stirred at 0° C. for 40 minutes and then cooled to −20° C. A solution of 3-cyclohexylpropan-1 -al (11.5 g, 82 mmol in THF (60 ml) was added dropwise over 10 minutes between −20 and −10° C., under nitrogen. The mixture was stirred between −20 and −5° C. for 3 hours and then aqueous citric acid (10%, 250 ml) and ethyl acetate (200 ml) was added. The organic phase was separated and the aqueous fraction was washed with ethyl acetate (200 ml). The combined organic fractions were washed with saturated sodium bicarbonate solution (2×100 ml), aqueous citric acid solution (10%, 100 ml) and demineralised water (100 ml) and then concentrated in vacuo. The resulting solid was taken up in ethyl acetate (150 ml) and cyclohexylamine (9.4 ml, 82 mmol) was added dropwise over 5 minutes at 20-25° C. The mixture was stirred at 20-25° C. for 16 hours and then filtered. The residue was dried in vacuo at 40° C. for 4 hours to leave the title compound as a colourless solid (21.7 g, 67% yield, 95% pure by NMR).

後処理

  1. temperaturecooled to −20° C
  2. stirringThe mixture was stirred between −20 and −5° C. for 3 hours
  3. customThe organic phase was separated
  4. washthe aqueous fraction was washed with ethyl acetate (200 ml)
  5. washThe combined organic fractions were washed with saturated sodium bicarbonate solution (2×100 ml), aqueous citric acid solution (10%, 100 ml) and demineralised water (100 ml)
  6. concentrationconcentrated in vacuo
  7. stirringThe mixture was stirred at 20-25° C. for 16 hours
  8. filtrationfiltered
  9. customThe residue was dried in vacuo at 40° C. for 4 hours

出典と根拠

ORDレコード
ord-f4665266944c4ae1bbd06e1ce8d7228d
出典データセット
uspto-grants-2002_09
特許番号
US06452041B1

反応ノート

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