Hydrochloric Acid → HCID 69891638, compound

HRID 1840881Notes

Reaction equation

HRID 1840881 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH:8]=[CH:9][C:10]([C:12]2[CH:13]=[C:14]3[C:19](=[CH:20][CH:21]=2)[N:18]([CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH3:30])[C:17](=[O:31])[CH2:16][C:15]3([CH3:33])[CH3:32])=[O:11])=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[OH-:63].[K+].Cl.CN(C)[CH:68]=[O:69]>C(O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(N(CC)CC)C>[CH2:22]([N:18]1[C:19]2[C:14](=[CH:13][C:12]([C:10](=[O:11])[CH:9]=[CH:8][C:5]3[CH:6]=[CH:7][C:2]([C:68]([OH:69])=[O:63])=[CH:3][CH:4]=3)=[CH:21][CH:20]=2)[C:15]([CH3:33])([CH3:32])[CH2:16][C:17]1=[O:31])[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH3:30]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 14797Potassium HydroxideHCID 812191,3-Bis(diphenylphosphino)propaneHCID 69891409HCID 69891409, compound2×

Product 1

HCID 69891638HCID 69891638, compoundYield 11%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 702EthanolSolvent2×HCID 8471TriethylamineSolvent

Conditions

Temperature
110 °C

Procedure

A solution of 6-[3-(4-bromophenyl)acryloyl]-4,4-dimethyl-1-nonyl-3,4-dihydro-1H-quinolin-2-one (Intermediate 7d, 68 mg, 0.13 mmol), 1,3-bis(diphenylphosphino)propane (20 mg, 0.05 mmol) and palladium acetate (11 mg, 0.05 mmol) in 5 mL of dimethylformamide in a sealed tube was added 1 mL of triethylamine and 2 mL of anhydrous ethanol. Carbon monoxide was bubbled through the solution for 20 min, then the tube was sealed and heated at 110° C. for 12 h. The reaction mixture was then cooled to room temperature and the solvent was removed in vacuo. The residue was dissolved in 10 mL ethyl acetate, washed with 1N HCl (2×20 mL) and brine (2×20 mL). The organic layer was then dried (MgSO4) and concentrated at reduced pressure. Purification by flash chormatography (75:25 hexane/ethyl acetate) afforded a crude ester. The crude ester was dissolved in 5 mL of ethanol, 1 mL of 1 N KOH was added and the mixture was stirred at room temperature for 3 h. The reaction was then acidified with 1N HCl and extracted with ethyl acetate (3×5 mL), washed with brine (1×5 mL), dried (MgSO4) and concentrated at reduced pressure. Purification by flash chormatography (50:49:1 hexane/ethyl acetate/acetic acid) afforded the title compound as a light yellow solid (6.7 mg, 11% yield).

Workup

  1. customCarbon monoxide was bubbled through the solution for 20 min
  2. customthe tube was sealed
  3. temperatureThe reaction mixture was then cooled to room temperature
  4. customthe solvent was removed in vacuo
  5. dissolutionThe residue was dissolved in 10 mL ethyl acetate
  6. washwashed with 1N HCl (2×20 mL) and brine (2×20 mL)
  7. dry with materialThe organic layer was then dried (MgSO4)
  8. concentrationconcentrated at reduced pressure
  9. customPurification by flash chormatography (75:25 hexane/ethyl acetate)
  10. customafforded a crude ester
  11. extractionextracted with ethyl acetate (3×5 mL)
  12. washwashed with brine (1×5 mL)
  13. dry with materialdried (MgSO4)
  14. concentrationconcentrated at reduced pressure
  15. customPurification by flash chormatography (50:49:1 hexane/ethyl acetate/acetic acid)

Sources & evidence

ORD record
ord-4d7d7c7949644b5e80d0c5693cd00712
Source dataset
uspto-grants-2004_01
Patent number
US06683092B1

Reaction notes

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