Propanoic acid, 2-bromo-2-methyl-, ethyl ester → HCID 21451949, compound

HRID 596336Notes

Reaction equation

HRID 596336 reaction equation
[H-].[Na+].[Cl:3][C:4]1[CH:5]=[CH:6][C:7]([O:27][CH3:28])=[C:8]([CH:26]=1)[NH:9][C:10]([CH2:12][C:13]1[CH:18]=[CH:17][C:16]([C:19]2[CH:24]=[CH:23][C:22]([OH:25])=[CH:21][CH:20]=2)=[CH:15][CH:14]=1)=[O:11].Br[C:30]([CH3:37])([CH3:36])[C:31]([O:33][CH2:34][CH3:35])=[O:32]>CCOCC.CN(C)C=O>[CH3:36][C:30]([O:25][C:22]1[CH:23]=[CH:24][C:19]([C:16]2[CH:15]=[CH:14][C:13]([CH2:12][C:10]([NH:9][C:8]3[CH:26]=[C:4]([Cl:3])[CH:5]=[CH:6][C:7]=3[O:27][CH3:28])=[O:11])=[CH:18][CH:17]=2)=[CH:20][CH:21]=1)([CH3:37])[C:31]([O:33][CH2:34][CH3:35])=[O:32]

Participants

6

Reactant 3

HCID 11745Propanoic acid, 2-bromo-2-methyl-, ethyl esterHCID 24758Sodium hydride2×HCID 21451921HCID 21451921, compound

Product 1

HCID 21451949HCID 21451949, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
20 °C

Procedure

A 55% suspension of 2.57 gm (58.8 millimols) of sodium hydride in oil was washed free of oil with absolute ether, and the residual sodium hydride was suspended in 60 ml of absolute dimethylformamide. While stirring the resulting suspension at 20° C in an atmosphere of nitrogen, a solution of 10.8 gm (about 29.4 millimols) of raw 4-(5-chloro-2-methoxyanilinocarbonyl-methyl)-4'-hydroxy-biphenyl in 40 ml of dimethylformamide was added dropwise thereto. The resulting mixture was stirred on a bath at 80° C for 11/2 hours more, and then 11.5 gm (58.8 millimols) of ethyl 2-bromo-2-methylpropionate were added and the mixture was stirred at 100° C for 3 hours. After evaporation in vacuo, water was added, and the mixture was extracted with ethyl acetate/ether (2:1). The organic extract was washed with water, dried over sodium sulfate, filtered and evaporated to dryness in vacuo. The dark brown, viscous evaporation residue was purified by chromatography on silicagel with toluene/ethyl acetate (4:1). The combined uniform fractions were evaporated and dried at 80° C/1 mm Hg, yielding 1.7 gm (12% of theory) of a bright red, viscous substance, m.p. < 20° C, which was identified to be the compound of the formula ##STR14##

Workup

  1. stirringThe resulting mixture was stirred on a bath at 80° C for 11/2 hours more
  2. stirringthe mixture was stirred at 100° C for 3 hours
  3. customAfter evaporation in vacuo, water
  4. additionwas added
  5. extractionthe mixture was extracted with ethyl acetate/ether (2:1)
  6. extractionThe organic extract
  7. washwas washed with water
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. customevaporated to dryness in vacuo
  11. customThe dark brown, viscous evaporation residue was purified by chromatography on silicagel with toluene/ethyl acetate (4:1)
  12. customThe combined uniform fractions were evaporated
  13. customdried at 80° C/1 mm Hg
  14. customyielding 1.7 gm (12% of theory) of a bright red, viscous substance, m.p. < 20° C, which

Sources & evidence

ORD record
ord-0f9a1aa4cf6a4fd18e053896e2cb4731
Source dataset
uspto-grants-1977_03
Patent number
US04010279

Reaction notes

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