HCID 86700852, compound → HCID 86700854, compound

HRID 881750Notes

Reaction equation

HRID 881750 reaction equation
[Br:1][CH:2]1[C:7]2([C:10]3[CH:15]=[CH:14][C:13]([Cl:16])=[CH:12][CH:11]=3)[CH2:8][CH2:9][C:4]([CH:17]=[CH:18][O:19][CH3:20])([CH2:5][O:6]2)[CH2:3]1.[Cr](Cl)([O-])(=O)=[O:22].[NH+]1C=CC=CC=1>ClCCl.O1CCCC1>[CH3:20][O:19][C:18](=[O:22])[CH2:17][C:4]12[CH2:9][CH2:8][C:7]([C:10]3[CH:15]=[CH:14][C:13]([Cl:16])=[CH:12][CH:11]=3)([CH:2]([Br:1])[CH2:3]1)[O:6][CH2:5]2

Participants

5

Reactant 2

HCID 86700852HCID 86700852, compoundHCID 178418287HCID 178418287, compound2×

Product 1

HCID 86700854HCID 86700854, compoundYield 61%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of the cis and trans mixtures of 6-bromo-1-(4-chloro-phenyl)-4-(2-methoxy-vinyl)-2-oxa-bicyclo[2.2.2]octane (1.7 g, 4.75 mmol) in dichloromethane (12 ml) and tetrahydrofuran (25 ml) at room temperature, was portionally added pyridinium chlorochromate (3.07 g, 14.26 mmol). The reaction mixture was stirred at room temperature for 2 hours. More pyridinium chlorochromate (2.05 g, 9.51 mmol) was added, and the mixture was stirred for another 60 hours at room temperature. The mixture was filtrated and the filtrate was concentrated, and diluted with ethyl acetate (100 ml). The organic phase was washed with water, brine and dried over Na2SO4, and concentrated. The residue was purified by flash chromatography (heptanes/acetone 2/1) to afford [6-bromo-1-(4-chloro-phenyl)-2-oxa-bicyclo[2.2.2]oct-4-yl]-acetic acid methyl ester (1.08 g, 61%) as colorless oil. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.69-1.79 (m, 1H) 1.87-1.98 (m, 1H) 2.01-2.11 (m, 1H) 2.14 (s, 2H) 2.23-2.30 (m, 1H) 2.52-2.63 (m, 1H) 2.75-2.87 (m, 1H) 3.62 (s, 3H) 3.84 (dd, J=10.11, 2.65 Hz, 2H) 4.19-4.29 (m, 1H) 7.23 (d, J=8.80 Hz, 2H) 7.33 (d, J=8.80 Hz, 2H).

Workup

  1. customat room temperature
  2. stirringthe mixture was stirred for another 60 hours at room temperature
  3. filtrationThe mixture was filtrated
  4. concentrationthe filtrate was concentrated
  5. additiondiluted with ethyl acetate (100 ml)
  6. washThe organic phase was washed with water, brine
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated
  9. customThe residue was purified by flash chromatography (heptanes/acetone 2/1)

Sources & evidence

ORD record
ord-a7e6c3352f0c4c0a82a2f07812a55500
Source dataset
uspto-grants-2015_03
Patent number
US08993619B2

Reaction notes

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