Carbon Dioxide → HCID 10324866, compound

HRID 845900Notes

Reaction equation

HRID 845900 reaction equation
[C:1](=[O:3])=[O:2].[K].[CH3:5][C:6]1[CH:11]=[C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH:9]=[C:8]([CH3:20])[C:7]=1[CH2:21][CH:22]1[C:26](=O)O[CH:24]([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[N:23]1[C:34]([O:36][CH2:37][C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)=[O:35].CI>C1(C)C=CC=CC=1.C1COCC1>[CH3:20][C:8]1[CH:9]=[C:10]([O:12][CH2:13][C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[CH:11]=[C:6]([CH3:5])[C:7]=1[CH2:21][C:22]1([CH3:26])[C:1](=[O:3])[O:2][CH:24]([C:28]2[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=2)[N:23]1[C:34]([O:36][CH2:37][C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)=[O:35]

Participants

7

Reactant 4

HCID 280Carbon DioxideHCID 6328Methyl iodideHCID 5462222PotassiumHCID 10098220HCID 10098220, compound

Product 1

HCID 10324866HCID 10324866, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A 500 ml round bottom flask fitted with a magnetic stirrer, thermometer, dropping funnel, and y-tube (connected to an N2 inlet and a drying tube outlet) was charged with dry THF (150 ml), which was cooled (dry ice bath) to -60°. A solution of potassium hexamethyldislazane in toluene (0.653M, 21.0 ml, Callery Chemical Company, Callery, Pa.) was added all at once. The solution was cooled back to -70°, and a solution of the title compound of Example 53 (5.5 g, 10.6 mmol) in THF (100 ml) was added dropwise rapidly, keeping the reaction temperature at or below -62°. The mixture was then stirred in the cold bath for 30 min, and the cold bath was then removed. Stirring at room temperature for another 30 min elevated the reaction tempature to -12°. The reaction mixture was then re-immersed in the cold bath, and the temperature returned to -70°. Methyl iodide (1.05 ml, 2.40 g, 16.9 mmol) was added al at once, and after another 10 min the cold bath was removed. The reaction mixture was permitted to warm to room temperature, and 3 hr after removal of the cold bath the mixture was partitioned between a mixture of H2 0 (200 ml), 0.5N KHSO4 (50 ml), saturated brine (200 ml) and ether (200 ml). The aqueous phase was washed with ether, the organic fractions were combined, dried (MgSO4), filtered, and stripped to an oil. The oil was applied to silica gel column chromatography on using ethyl acetate-hexane eluent, giving the title compound. NMR: α methyl group at ∫2.71 A, 3 protons.

Workup

  1. customA 500 ml round bottom flask fitted with a magnetic stirrer
  2. temperatureThe solution was cooled back to -70°
  3. custombelow -62°
  4. customthe cold bath was then removed
  5. stirringStirring at room temperature for another 30 min
  6. customto -12°
  7. customreturned to -70°
  8. customwas removed
  9. custom3 hr after removal of the cold bath the mixture
  10. customwas partitioned between a mixture of H2 0 (200 ml), 0.5N KHSO4 (50 ml), saturated brine (200 ml) and ether (200 ml)
  11. washThe aqueous phase was washed with ether
  12. dry with materialdried (MgSO4)
  13. filtrationfiltered

Sources & evidence

ORD record
ord-4e42ecf0ca964bde8d050f1dbba95483
Source dataset
uspto-grants-1988_07
Patent number
US04760180

Reaction notes

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