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

HRID 613387Notes

Reaction equation

HRID 613387 reaction equation
[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]

Participants

8

Reactant 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

Product 1

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

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

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)+.

Workup

  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

Sources & evidence

ORD record
ord-2ba5b790ef13472b8450897a962f97ef
Source dataset
uspto-grants-1999_12
Patent number
US06008213

Reaction notes

Loading…