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

HRID 613387Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 613387
[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]

Komponenten

8

Edukt 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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 6344DichloromethaneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

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)+.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-2ba5b790ef13472b8450897a962f97ef
Quelldatensatz
uspto-grants-1999_12
Patentnummer
US06008213

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