Diisopropylamine → 1-Methyl-3-(phenylselanyl)piperidin-2-one

HRID 473721노트

반응식

HRID 473721 반응식
C(NC(C)C)(C)C.C([Li])CCC.[CH3:13][N:14]1[CH2:19][CH2:18][CH2:17][CH2:16][C:15]1=[O:20].[C:21]1([Se:27]Cl)[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>O1CCCC1>[CH3:13][N:14]1[CH2:19][CH2:18][CH2:17][CH:16]([Se:27][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:15]1=[O:20]

참가 물질

6

반응물 4

HCID 7912DiisopropylamineHCID 13603N-Methyl-2-piperidoneHCID 21928ChloroselenobenzeneHCID 178418339Butyllithium

생성물 1

HCID 866418121-Methyl-3-(phenylselanyl)piperidin-2-one

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매3회

실험 절차

A solution of diisopropylamine (3 mL, 21.2 mmol) in tetrahydrofuran (44 mL) under argon was cooled to −78° C. and added butyllithium solution, 2.5 M in hexanes (8 mL, 21.2 mmol). After 5 min, a solution of 1-methylpiperidin-2-one (2 g, 17.6 mmol) in tetrahydrofuran (2 mL) was added dropwise. After stirring for 10 min, a solution of phenylselenenyl chloride (4.0 g, 21.2 mmol) in 16 mL of tetrahydrofuran was added, and the reaction was stirred at −78° C. for 2 h. The reaction was quenched with aqueous saturated NH4Cl solution and diluted with CH2Cl2; the aqueous layer was back-extracted with CH2Cl2 (1×). The combined organic extracts were dried (MgSO4), filtered, and concentrated in vacuo to afford a crude crop of 1-methyl-3-(phenylselanyl)piperidin-2-one in dichloromethane. To the crude 1-methyl-3-(phenylselanyl)piperidin-2-one in dichloromethane (50 mL) at 0° C. under argon was added 3-chlorobenzoperoxoic acid (7.92 g, 35.3 mmol). The resulting mixture was allowed to gradually warm to room temperature overnight. The orange suspension was filtered, and the filtrate was concentrated in vacuo and partitioned between CH2Cl2 and aqueous saturated NaHCO3 solution; the aqueous layer was back-extracted with CH2Cl2 (5×). The combined organic extracts were dried (MgSO4), filtered, and concentrated in vacuo. Flash column chromatography (20% EtOAc/Hexanes to 100% EtOAc) afforded 1-methyl-5,6-dihydropyridin-2(1H)-one as a brown oil. MS (ESI, pos. ion) m/z: 112.2 (M+1).

후처리

  1. stirringthe reaction was stirred at −78° C. for 2 h
  2. customThe reaction was quenched with aqueous saturated NH4Cl solution
  3. additiondiluted with CH2Cl2
  4. extractionthe aqueous layer was back-extracted with CH2Cl2 (1×)
  5. dry with materialThe combined organic extracts were dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

출처 및 근거

ORD 기록
ord-1f8f5eec4ad64af59c4476598f195112
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08637500B2

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