Acetone → 4-Methyl-2-oxo-6-propyl-1,2-dihydro-3-pyridinecarbonitrile

HRID 516721

반응식

HRID 516721 반응식
C(OC(=O)CCC)C.CC(C)=O.[CH3:13][C:14](=O)[CH2:15][C:16](=O)[CH2:17][CH2:18][CH3:19].[C:22]([CH2:24][C:25]([NH2:27])=[O:26])#[N:23].N1CCCCC1>CCOCC.CCO>[CH3:13][C:14]1[CH:15]=[C:16]([CH2:17][CH2:18][CH3:19])[NH:27][C:25](=[O:26])[C:24]=1[C:22]#[N:23]

참가 물질

8

반응물 5

HCID 180AcetoneHCID 7762Ethyl butyrateHCID 7898CyanoacetamideHCID 8082PiperidineHCID 237322,4-Heptanedione

생성물 1

HCID 138379154-Methyl-2-oxo-6-propyl-1,2-dihydro-3-pyridinecarbonitrile수율 40%

시약·촉매·용매 2

HCID 702Ethanol용매HCID 3283Diethyl Ether용매2회

실험 절차

To a solution of NaNH2 (32.5 g, 862 mmol) in anhydrous ether (500 mL) at 30° C. was added dropwise a mixture of butyric acid ethyl ester (50 g, 431 mmol) and acetone (37.5 g, 646.5 mol). After addition, the reaction mixture was stirred for 4 h. The reaction mixture was poured onto ice water with stirring. Additional ether was added, and the layers were separated. The aqueous layer was acidified to pH 5.0 with 2 N HCl and then to pH 7.5 with Na2CO3. The aqueous layer was then extracted with ether. The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. The crude product, 2,4-heptanedione (20 g, 156 mmol), and 2-cyanoacetamide (13.12 g, 156 mmol) were suspended in EtOH (160 mL) at 75° C., followed by addition of piperidine (13.2 g, 156 mmol). The contents were stirred and heated at reflux for 1 h. The mixture was cooled to room temperature and filtered. The collected solid was suspended in water and stirred for 1 h. The mixture was filtered and dried to give 4-methyl-2-oxo-6-propyl-1,2-dihydro-3-pyridinecarbonitrile (11 g, 40%). LCMS E-S(M+H)=181.1. 1H NMR (400 MHz, DMSO-d6) δ ppm 12.3-12.4 (br s, 1H), 6.25 (s, 1H), 3.64 (s, 3H), 2.50 (t, 2H), 1.63 (m, 2H), 0.94 (t, 3H).

후처리

  1. additionAfter addition
  2. additionThe reaction mixture was poured onto ice water
  3. stirringwith stirring
  4. customthe layers were separated
  5. extractionThe aqueous layer was then extracted with ether
  6. dry with materialThe combined organic layers were dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. stirringThe contents were stirred
  10. temperatureheated
  11. temperatureat reflux for 1 h
  12. filtrationfiltered
  13. stirringstirred for 1 h
  14. filtrationThe mixture was filtered
  15. customdried

출처 및 근거

ORD 기록
ord-4713ef16fb0e4981be92d6a4bd9c67f9
출처 데이터셋
uspto-grants-2015_08
특허 번호
US09114141B2

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