Acetonitrile → HCID 11992473, compound

HRID 2241023Notes

Reaction equation

HRID 2241023 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:15]2[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16]2)[C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[CH:4][CH:3]=1.[C:22]([NH2:26])(=[O:25])[CH:23]=[CH2:24].CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.CC#N>CCOC(C)=O.O.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:15]1(=[C:8]([C:9]2[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=2)[C:5]2[CH:6]=[CH:7][C:2](/[CH:24]=[CH:23]/[C:22]([NH2:26])=[O:25])=[CH:3][CH:4]=2)[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21]1

Participants

8

Reactant 4

HCID 6342AcetonitrileHCID 6579AcrylamideHCID 80271Tri-o-tolylphosphineHCID 68505673HCID 68505673, compound

Product 1

HCID 11992473HCID 11992473, compoundYield 33.7%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

A suspension of [(4-Bromophenyl)(phenyl)methylene]cycloheptane (1) (0.50 g, 1.47 mmol), TEA (1.21 mL, 8.71 mmol), acrylamide (0.62 g, 8.73 mmol), Pd(OAc)2 (0.080 g, 0.36 mmol), P(o-tolyl)3) (0.19 g, 0.63 mmol) and CH3CN was stirred at reflux under N2. After 2 h heating was discontinued and the reaction diluted with EtOAc (50 mL) and water (50 mL). The mixture was filtered through a celite pad and the filtrate transferred to a separatory funnel. The organic fraction was washed with brine (50 mL), dried (MgSO4), filtered and concentrated to an amber oil. This oil was purified by column chromatography on silica gel (50 g) using a hexanes to 25% EtOAc:hexanes to 100% EtOAc gradient to afford a pale yellow solid. Trituration of the solid with EtOAc (25 mL) yielded 164 mg (33%) of the title compound (4) as a white solid. 1H NMR (300 MHz, DMSO-d6): δ 1.54 (s, 8H), 2.24 (br s, 4H), 6.55 (d, J=15.9 Hz, 1H), 7.07 (br, 1H), 7.14-7.20 (m, 7H), 7.25 (d, J=15.9 Hz, 1H), 7.49 (d, J=8.1 Hz, 2H), 7.50 (br, 1H). LRMS (APCI): m/z 332 (M+H)+. Anal. Calcd for C23H25NO.0.1H2O: C, 82.67; H, 7.63; N, 4.19. Found: C, 82.75; H, 7.56; N, 4.20.

Workup

  1. temperatureat reflux under N2
  2. temperatureAfter 2 h heating
  3. filtrationThe mixture was filtered through a celite pad
  4. customthe filtrate transferred to a separatory funnel
  5. washThe organic fraction was washed with brine (50 mL)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated to an amber oil
  9. customThis oil was purified by column chromatography on silica gel (50 g)
  10. customhexanes to 100% EtOAc gradient to afford a pale yellow solid

Sources & evidence

ORD record
ord-e99fafb40b724ff3af99a945d496eaf0
Source dataset
uspto-grants-2010_05
Patent number
US07723393B2

Reaction notes

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