Dimethylformamide → Bicyclo[2.2.2]octane-1-carboxylic acid, 4-(chlorocarbonyl)-, methyl ester

HRID 2105682Notes

Reaction equation

HRID 2105682 reaction equation
[CH3:1][O:2][C:3]([C:5]12[CH2:12][CH2:11][C:8]([C:13]([OH:15])=O)([CH2:9][CH2:10]1)[CH2:7][CH2:6]2)=[O:4].CN(C)C=O.C(Cl)(=O)C([Cl:24])=O.CC1C(Br)=C(O)C(Br)=CC=1C1(C2C=C(Br)C(O)=C(Br)C=2C)OS(=O)(=O)C2C=CC=CC1=2>ClCCl.ClCCl.CO>[CH3:1][O:2][C:3]([C:5]12[CH2:12][CH2:11][C:8]([C:13]([Cl:24])=[O:15])([CH2:9][CH2:10]1)[CH2:7][CH2:6]2)=[O:4]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 6451Bromocresol GreenHCID 65578Oxalyl chlorideHCID 110420624-(Methoxycarbonyl)bicyclo[2.2.2]octane-1-carboxylic acid2×

Product 1

HCID 13761775Bicyclo[2.2.2]octane-1-carboxylic acid, 4-(chlorocarbonyl)-, methyl ester

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 21226129Dichloromethane methanolSolvent

Procedure

Bicyclo-[2.2.2]octane-1,4-dicarboxylic acid monomethyl ester (IV, Example 81, 1 wt) is dissolved in dichloromethane (6.25 vol) and dimethylformamide (0.025 vol) is added. Concomitantly oxalyl chloride (0.5125 vol) is dissolved in dichloromethane (0.625 vol) and the resulting mixture is added to the mixture containing the bicyclo [2.2.2]octane-1,4-dicarboxylic acid monomethyl ester (IV) at between 12 to 17° C., tag care for gas evolution. The mixture is stirred at 15 to 25° for 2 to 4 hours which is monitored by (TLC; dichloromethane/methanol: 9/1, visualization Bromocresol green). The solvent is removed under reduced pressure at 40 to 450, dichloromethane (5 vol) is added stirred for 5 to 15 min and removed under reduced pressure at 40 to 45°. The process is repeated by adding dichloromethane (5 vol), stirring for 5 to 15 min and removing under reduced pressure at 40 to 45°. Acetonitrile (6.25 vol) is then added to give the title compound in solution.

Workup

  1. additionthe resulting mixture is added to the mixture
  2. customThe solvent is removed under reduced pressure at 40 to 450, dichloromethane (5 vol)
  3. additionis added
  4. stirringstirred for 5 to 15 min
  5. customremoved under reduced pressure at 40 to 45°
  6. additionby adding dichloromethane (5 vol)
  7. stirringstirring for 5 to 15 min
  8. customremoving under reduced pressure at 40 to 45°
  9. additionAcetonitrile (6.25 vol) is then added

Sources & evidence

ORD record
ord-8a651e1037764b6f81d26cad6b89c61f
Source dataset
uspto-grants-2009_08
Patent number
US07579354B2

Reaction notes

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