2-Methyl-2-butene → Ethyl (+/-)-3-[3-carboxy-1-propyl]-5H-dibenzo [a,d]cycloheptene-10-acetate

HRID 613387노트

반응식

HRID 613387 반응식
[OH:1][CH2:2][CH2:3][CH2:4][CH2:5][C:6]1[CH:7]=[CH:8][C:9]2[CH:15]=[C:14]([CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:13]3[CH:22]=[CH:23][CH:24]=[CH:25][C:12]=3[CH2:11][C:10]=2[CH:26]=1.[Cl-].CC1(C)CCCC(C)(C)[N+]1=[O:37].CC(=CC)C.[O-]Cl=O.[Na+]>C(Cl)Cl.O.CCOC(C)=O>[C:2]([CH2:3][CH2:4][CH2:5][C:6]1[CH:7]=[CH:8][C:9]2[CH:15]=[C:14]([CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:13]3[CH:22]=[CH:23][CH:24]=[CH:25][C:12]=3[CH2:11][C:10]=2[CH:26]=1)([OH:37])=[O:1]

참가 물질

8

반응물 4

HCID 105532-Methyl-2-buteneHCID 10954377Piperidinium, 2,2,6,6-tetramethyl-1-oxo-, chlorideHCID 23668197Sodium ChloriteHCID 53688679Ethyl (+/-)-3-[4-hydroxy-1-butyl]-5H-dibenzo[a,d]cycloheptene-10-acetate

생성물 1

HCID 54111116Ethyl (+/-)-3-[3-carboxy-1-propyl]-5H-dibenzo [a,d]cycloheptene-10-acetate

시약·촉매·용매 3

HCID 962Water용매HCID 6344Dichloromethane용매HCID 8857Ethyl Acetate용매

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온도
0 °C

실험 절차

A solution of ethyl (±)-3-[4-hydroxy-1-butyl]-5H-dibenzo[a,d]cycloheptene-10-acetate (342.4 mg, 0.97 mmole) in anhydrous CH2Cl2 (19 mL) was cooled to 0° C. under argon, and 2,2,6,6-tetramethyloxopiperidinium chloride (J. Org. Chem. 1985, 50, 1332-1334; 260 mg, 1.36 mmole) was added in one portion. The reaction was stirred at 0° C. for 1 hr, then 2-methyl-2-butene (1.2 mL, 11 64 mmole) was added, followed by a cold (0° C.) solution of NaClO2 (0.88 g, 7.76 mmole) and NaH2PO4 (0.90 g, 6.50 mmole) in H2O (26 mL). After 10 min, the reaction was diluted with EtOAc (100 mL) and the layers were separated. The organic layer was washed sequentially with cold 1.0 N HCl (10 mL) and saturated brine (20 mL), dried (MgSO4), and concentrated. Silica gel chromatography (gradient: 1:1 EtOAc/CHCl3 then 9:9:2 EtOAc/CHCl3 /EtOH) gave impure title compound. Rechromatography on silica gel (7:3:0.1 toluene/EtOAc/AcOH) gave the pure title compound (233.7 mg, 66%): TLC (1:1 EtOAc/CHCl3) Rf 0.46; 1H NMR (400 MHz, CDCl3) δ 7.05-7.22 (m, 4 H), 6.92-7.05 (m, 3 H), 4.34 (d, J=15.0 Hz, 1 H), 4.10-4.25 (m, 2 H), 3.80-3.90 (m, 2 H), 3.33 (dd, J=15.1, 4.1 Hz, 1 H), 2.95 (dd, J=15.1, 9.4 Hz, 1 H), 2.48-2.60 (m, 4 H), 2.48-2.60 (m, 4 H), 2.37 (t, J=7.4 Hz, 2 H), 1.87-2.00 (m, 2 H), 1.27 (t, J=7.2 Hz, 3 H); MS (ES) m/e 389 (M+Na)+, 367 (M+H)+.

후처리

  1. waitAfter 10 min
  2. customthe layers were separated
  3. washThe organic layer was washed sequentially with cold 1.0 N HCl (10 mL) and saturated brine (20 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated

출처 및 근거

ORD 기록
ord-2ba5b790ef13472b8450897a962f97ef
출처 데이터셋
uspto-grants-1999_12
특허 번호
US06008213

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