Diethyl (cyanomethyl)phosphonate → tert-Butyl 4-(cyanomethylidene)piperidine-1-carboxylate

HRID 500280노트

반응식

HRID 500280 반응식
CC(C)([O-])C.[K+].[C:7]([CH2:9]P(=O)(OCC)OCC)#[N:8].O=[C:19]1[CH2:24][CH2:23][N:22]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH2:21][CH2:20]1>C1COCC1>[C:7]([CH:9]=[C:19]1[CH2:24][CH2:23][N:22]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH2:21][CH2:20]1)#[N:8]

참가 물질

5

반응물 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 23665647Potassium tert-butoxide

생성물 1

HCID 15326949tert-Butyl 4-(cyanomethylidene)piperidine-1-carboxylate수율 97.2%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매3회

실험 절차

To a solution of 1.0 M of potassium tert-butoxide in THF (26.3 mL) at 0° C. was added drop wise a solution of diethyl cyanomethylphosphonate (4.47 mL, 0.0276 mol) in THF (33.6 mL). The reaction was warmed to RT and then cooled at 0° C. again. To the reaction mixture was then added a solution of tert-butyl 4-oxo-1-piperidinecarboxylate (5.0 g, 0.025 mol) in THF (6.72 mL). The reaction was allowed to warm up to RT and stirred overnight. After being quenched with water, the mixture was extracted with EtOAc. The combined organic layers were washed with brine, dried, and concentrated. The crude mixture was purified on silica gel eluting with EtOAc in hexanes (0-60%) to give the desired product (5.4 g, 96.81%). LCMS: (M+Na)=244.9, (M-56+H)=167.0.

후처리

  1. temperaturecooled at 0° C. again
  2. temperatureto warm up to RT
  3. customAfter being quenched with water
  4. extractionthe mixture was extracted with EtOAc
  5. washThe combined organic layers were washed with brine
  6. customdried
  7. concentrationconcentrated
  8. customThe crude mixture was purified on silica gel eluting with EtOAc in hexanes (0-60%)

출처 및 근거

ORD 기록
ord-3c76746be00f41c4990bb200bd33ec3f
출처 데이터셋
uspto-grants-2010_08
특허 번호
US07767675B2

반응 노트

불러오는 중…