Triethylamine → Ethyl(2E)-3-{4-[(4-hydroxyphenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenyl}-2-propenoate

HRID 229138Notes

Reaction equation

HRID 229138 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:16]2[CH2:21][C:20]([CH3:23])([CH3:22])[CH2:19][C:18]([CH3:25])([CH3:24])[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:26]([O:30][CH2:31][CH3:32])(=[O:29])[CH:27]=[CH2:28].CCN(CC)CC>CCOCC.CN(C=O)C.CCOC(C)=O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[OH:15][C:12]1[CH:11]=[CH:10][C:9]([C:8](=[C:16]2[CH2:17][C:18]([CH3:25])([CH3:24])[CH2:19][C:20]([CH3:23])([CH3:22])[CH2:21]2)[C:5]2[CH:4]=[CH:3][C:2](/[CH:28]=[CH:27]/[C:26]([O:30][CH2:31][CH3:32])=[O:29])=[CH:7][CH:6]=2)=[CH:14][CH:13]=1

Participants

8

Reactant 3

HCID 8471TriethylamineHCID 8821Ethyl AcrylateHCID 686543984-[(4-Bromophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenol

Product 1

HCID 68977877Ethyl(2E)-3-{4-[(4-hydroxyphenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenyl}-2-propenoateYield 75.1%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

To a round-bottomed flask were added 4-[(4-bromophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenol (14) (10.2 g, 0.0255 mol), ethyl acrylate (28 mL, 0.255 mol.), dichlorobis(triphenylphosphine)palladium(II) (0.895 g, 1.28 mmol, 5 mol %), Et3N (17.6 mL, 0.128 mol), and DMF (50 mL). The stirred reaction mixture was heated to 110° C. for 18 h under a nitrogen atmosphere. The reaction mixture was allowed to cool to room temperature and then diluted with Et2O (200 mL). The reaction mixture was filtered and the filtrate was concentrated under reduced pressure to give crude product. The crude reaction mixture in DMF was diluted with EtOAc (400 mL), washed with water (2×100 mL), brine (1×100 mL), dried (Na2SO4), filtered, and then concentrated under reduced pressure to afford the crude product as an oil. The crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (19:1 to 1:1) as an eluent to give 8.02 g (75%) of compound 15 as a pale yellow solid. 1H NMR (300 MHz, CDCl3): δ 0.88 (s, 6H), 0.91 (s, 6H), 1.31 (s, 2H), 1.35 (t, J=7.2 Hz, 3H), 1.99 (s, 2H), 2.00 (s, 2H), 4.28 (q, J=7.2 Hz, 2H), 5.35 (broad s, 1H), 6.41 (d, J=16.2 Hz, 1H), 6.77 (d, J=8.4 Hz, 2H), 7.04 (d, J=8.4 Hz, 2H), 7.20 (d, J=8.10 Hz, 1H), 7.44 (d, J=8.40 Hz, 2H), 7.68 (d, J=16.2 Hz, 1H). HRMS (EI) Calcd for C28H34O3: 418.57 (M+.). Found: 419.17. Note: Excess ethyl acrylate can be distilled from the reaction mixture before work-up.

Workup

  1. customThe stirred reaction mixture
  2. temperatureto cool to room temperature
  3. filtrationThe reaction mixture was filtered
  4. concentrationthe filtrate was concentrated under reduced pressure
  5. customto give crude product
  6. washwashed with water (2×100 mL), brine (1×100 mL)
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customto afford the crude product as an oil
  11. customThe crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (19:1 to 1:1) as an eluent

Sources & evidence

ORD record
ord-118fba821ac1491787bfaeb2f74b5d6e
Source dataset
uspto-grants-2009_07
Patent number
US07560589B2

Reaction notes

Loading…