Dimethylformamide → HCID 22591692, compound

HRID 2079829Notes

Reaction equation

HRID 2079829 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].C(Cl)(=O)C(Cl)=O.[CH3:22][N:23](C=O)C.CN>C(Cl)Cl>[CH3:22][NH:23][C:13]([C:8]12[CH2:11][CH2:12][C:5]([C:3]([O:2][CH3:1])=[O:4])([CH2:10][CH2:9]1)[CH2:6][CH2:7]2)=[O:15]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 6329MethylamineHCID 65578Oxalyl chlorideHCID 110420624-(Methoxycarbonyl)bicyclo[2.2.2]octane-1-carboxylic acid

Product 1

HCID 22591692HCID 22591692, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

4-(Methoxycarbonyl)bicyclo[2.2.2]octane-1-carboxylic acid 1-A (Chapman, N. B. et al. J. Org. Chem., 1970, 35, 917) (4.0 g, 18.9 mmol) was dissolved in 12 mL of anhydrous methylene chloride under a nitrogen atmosphere, treated with oxalyl chloride (2M in methylene chloride, 28 mL, 56 mmol) and subsequently with 0.5 ml of DMF. The reaction was stirred at room temperature under a nitrogen atmosphere for 90 min, then evaporated and placed under vacuum for 20 min. The reaction was concentrated and stripped from toluene 3 times. The acid chloride was dissolved in anhydrous methylene chloride (75 mL), cooled in an ice-bath, and then treated dropwise with a solution of methylamine (2M in THF, 57 mL, 113 mmol). Upon addition of the amine, the cooling bath was removed and the reaction stirred at ambient temperature for 30 min. The mixture was diluted with 1000 mL of methylene chloride and washed with 1N aqueous HCl, saturated aqueous sodium bicarbonate, and brine. The organic layer was dried over anhydrous sodium sulfate and evaporated. Product was purified by flash silica gel chromatography, eluting with a 0-5% MeOH/CH2Cl2 gradient to yield 1-B as a white solid. MS (ESI+)=226.2 (M+1).

Workup

  1. customevaporated
  2. waitplaced under vacuum for 20 min
  3. concentrationThe reaction was concentrated
  4. dissolutionThe acid chloride was dissolved in anhydrous methylene chloride (75 mL)
  5. temperaturecooled in an ice-bath
  6. customthe cooling bath was removed
  7. stirringthe reaction stirred at ambient temperature for 30 min
  8. additionThe mixture was diluted with 1000 mL of methylene chloride
  9. washwashed with 1N aqueous HCl, saturated aqueous sodium bicarbonate, and brine
  10. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  11. customevaporated
  12. customProduct was purified by flash silica gel chromatography
  13. washeluting with a 0-5% MeOH/CH2Cl2 gradient

Sources & evidence

ORD record
ord-2dfe7f3a6b1e4bcb9e62fb1aa366ccbf
Source dataset
uspto-grants-2011_04
Patent number
US07932280B2

Reaction notes

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