Acetate → HCID 89781946, compound

HRID 1055918Notes

Reaction equation

HRID 1055918 reaction equation
C([Sn](CCCC)(CCCC)[C:6]([O:8]CC)=[CH2:7])CCC.Br[C:20]1[CH:21]=[CH:22][CH:23]=[C:24]2[C:29]=1[N:28]=[C:27]([C:30]([O:32][CH3:33])=[O:31])[CH:26]=[CH:25]2.C(OC=C)=C.C([O-])(=O)C>C1COCC1.Cl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCOC(C)=O.C1(C)C=CC=CC=1>[C:6]([C:20]1[CH:21]=[CH:22][CH:23]=[C:24]2[C:29]=1[N:28]=[C:27]([C:30]([O:32][CH3:33])=[O:31])[CH:26]=[CH:25]2)(=[O:8])[CH3:7]

Participants

10

Reactant 4

HCID 175AcetateHCID 8024Vinyl etherHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 58567110HCID 58567110, compound

Product 1

HCID 89781946HCID 89781946, compoundYield 82.1%

Reagents, catalysts & solvents 5

HCID 313Hydrochloric AcidCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of Pd(PPh3)4 (608 mg, 0.53 mmol), tributyl(1-ethoxyvinyl)tin (3.91 mL, 11.57 mmol), methyl 8-bromoquinoline-2-carboxylate (2.80 g, 10.52 mmol), and toluene (50 mL) was heated under argon at 100° C. for 18 h. The mixture was then concentrated under reduced pressure and adsorbed onto silica gel. Column chromatography (silica gel, 10-100% EtOAc in hexanes) afforded a mixture of vinyl ether (M+1=258.0) and the desired acetate. This mixture was dissolved in THF (40 mL), the solution was cooled to 0° C., 10 drops of 1N HCl were added, and the solution was stirred at 0° C. for 5 min. EtOAc (100 mL) was added and the resulting solution was washed successively with 1N NaOH (20 mL), water (40 mL) and brine (40 mL). Significant product remained in the aq. layer and was extracted with 25% IPA in CHCl3. The combined organic layers were dried over MgSO4, filtered, and concentrated to give methyl 8-acetylquinoline-2-carboxylate (1.98 g, 8.64 mmol, 82% yield) as a tan solid: 1H NMR (400 MHz, DMSO-d6) δ ppm 8.69 (d, J=8.4 Hz, 1H), 8.27 (dd, J=8.2, 1.4 Hz, 1H), 8.20 (d, J=8.4 Hz, 1H), 8.00 (dd, J=7.2, 1.4 Hz, 1H), 7.79-7.86 (m, 1H), 3.98 (s, 3H), 2.92 (s, 3H). m/z (ESI, +ve ion) 230.0 (M+H)+.

Workup

  1. concentrationThe mixture was then concentrated under reduced pressure
  2. customColumn chromatography (silica gel, 10-100% EtOAc in hexanes) afforded
  3. temperaturethe solution was cooled to 0° C.
  4. washthe resulting solution was washed successively with 1N NaOH (20 mL), water (40 mL) and brine (40 mL)
  5. extractionwas extracted with 25% IPA in CHCl3
  6. dry with materialThe combined organic layers were dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-cfc5e650ac334339ac860a4b28eda408
Source dataset
uspto-grants-2016_07
Patent number
US09394297B2

Reaction notes

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