Citric Acid → Benzyl 4-formylpiperidine-1-carboxylate

HRID 23528ノート

反応式

HRID 23528 の反応式
CN(OC)[C:3]([CH:5]1[CH2:10][CH2:9][N:8]([C:11]([O:13][CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[O:12])[CH2:7][CH2:6]1)=[O:4].C1(C)C=CC=CC=1.[H-].[Al+3].[Li+].[H-].[H-].[H-].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>CCOCC.C(OCC)(=O)C>[CH2:14]([O:13][C:11]([N:8]1[CH2:9][CH2:10][CH:5]([CH:3]=[O:4])[CH2:6][CH2:7]1)=[O:12])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

参加物

7

反応物 4

HCID 311Citric AcidHCID 1140TolueneHCID 21226445Aluminium lithium hydrideHCID 22574154Benzyl 4-(methoxy(methyl)carbamoyl)piperidine-1-carboxylate

生成物 1

HCID 2776272Benzyl 4-formylpiperidine-1-carboxylate

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

N-Methyl-N-methoxy 1-benzyloxycarbonylpiperidin-4-carboxamide (79.9 g, 261 mmol) was azeotroped with toluene (2×200 mL) to remove any water and dissolved in THF (700 mL). The solution was cooled to −60° C., before dropwise addition of a solution of lithium aluminum hydride in TBF (1 M, 100 mL, 100 mmol). The temperature of the reaction mixture was allowed to rise slowly to −30° C. over approx. 1 h. The mixture was transferred by cannula into a rapidly stirred mixture of ethyl acetate (200 mL) and 10% aqueous citric acid (500 mL), cooled to 0° C. After addition was complete, ether (500 mL) was added and the phases separated. The organic layer was washed with 1M HCl, water, saturated sodium bicarbonate solution and brine. After drying over anhydrous sodium sulfate, the solvent was evaporated in vacuo to afford the crude product, used without further purification (59 g).

後処理

  1. customto remove any water
  2. dissolutiondissolved in THF (700 mL)
  3. additionAfter addition
  4. customthe phases separated
  5. washThe organic layer was washed with 1M HCl, water, saturated sodium bicarbonate solution and brine
  6. dry with materialAfter drying over anhydrous sodium sulfate
  7. customthe solvent was evaporated in vacuo

出典と根拠

ORDレコード
ord-4478315ab52b4a3a91abaa2a6be1cf39
出典データセット
uspto-grants-2005_02
特許番号
US06852727B2

反応ノート

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