Triethylamine → 1,1-Dimethylethyl (2E)-3-{4-[cycloheptylidene(4-hydroxyphenyl)methyl]phenyl}-2-propenoate

HRID 1715988Notes

Reaction equation

HRID 1715988 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:16]2[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]2)[C:9]2[CH:14]=[CH:13][C:12]([OH:15])=[CH:11][CH:10]=2)=[CH:4][CH:3]=1.[C:23]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])(=[O:26])[CH:24]=[CH2:25].CCN(CC)CC.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>CC([O-])=O.CC([O-])=O.[Pd+2].O.CCOC(C)=O.CC#N>[C:16]1(=[C:8]([C:9]2[CH:14]=[CH:13][C:12]([OH:15])=[CH:11][CH:10]=2)[C:5]2[CH:4]=[CH:3][C:2](/[CH:25]=[CH:24]/[C:23]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])=[CH:7][CH:6]=2)[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22]1

Participants

9

Reactant 4

HCID 8471TriethylamineHCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 686541254-[(4-Bromophenyl)(cycloheptylidene)methyl]phenol

Product 1

HCID 689772221,1-Dimethylethyl (2E)-3-{4-[cycloheptylidene(4-hydroxyphenyl)methyl]phenyl}-2-propenoateYield 98.4%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
75 °C

Procedure

To a round-bottomeded flask were added 4-[(4-bromophenyl)(cycloheptylidene)methyl]phenol (9) (4.0 g, 11.2 mmol), t-butyl acrylate (7.2 mL, 6.3 g, 49.2 mmol, 4.4 eq), Pd(OAc)2 (0.52 g, 2.3 mmol, 0.21 eq), Et3N (9.5 mL, 6.90 g, 68.2 mmol, 6.1 eq), P(o-tolyl)3 (1.3 g, 4.2 mmol, 0.38 eq), and CH3CN (100 mL). The reaction mixture was heated overnight at 75° C. with stirring under a nitrogen atmosphere. The reaction mixture was allowed to cool to room temperature and then transferred to a separatory funnel with the aid of EtOAc and H2O. The layers were separated, and the organic phase was washed with brine, dried (MgSO4), filtered, and the filtrate was concentrated to give the crude product as a red-orange oil. The crude product was purified by flush chromatography on silica gel with hexanes:EtOAc (9:1 to 4:1) to give 4.46 g (98%) of compound 10 as a yellow solid. 1H NMR (400 MHz, DMSO-d6): δ 1.45 (s, 9H), 1.50 (m, 8H), 2.21 (m, 4H), 6.42 (d, J=16.1 Hz, 1H), 6.65 (d, J=8.4 Hz, 2H), 6.90 (d, J=8.4 Hz, 2H), 7.10 (d, J=8.2 Hz, 2H), 7.48 (d, J=15.9 Hz, 1H), 7.57 (d, J=8.1 Hz, 2H), 9.28 (s, 1H).

Workup

  1. temperatureto cool to room temperature
  2. customThe layers were separated
  3. washthe organic phase was washed with brine
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated
  7. customto give the crude product as a red-orange oil
  8. customThe crude product was purified
  9. customby flush chromatography on silica gel with hexanes:EtOAc (9:1 to 4:1)

Sources & evidence

ORD record
ord-e7250f4984334123bdf919f21c4f6832
Source dataset
uspto-grants-2010_09
Patent number
US07799828B2

Reaction notes

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