Ethanol → HCID 86588860, compound

HRID 1790183Notes

Reaction equation

HRID 1790183 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[O:10][C:11]([F:14])([F:13])[F:12])C=O.[CH3:15][C:16]1[C:17](B(O)O)=[CH:18][C:19]2[C:20]([CH3:29])([CH3:28])[CH2:21][CH2:22][C:23]([CH3:27])([CH3:26])[C:24]=2[CH:25]=1.[CH2:33]([OH:35])C.C(=O)([O-])[O-].[K+].[K+]>C1(C)C=CC=CC=1.C(OCC)(=O)C.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.O>[F:14][C:11]([F:12])([F:13])[O:10][C:9]1[CH:8]=[C:7]([CH:4]=[CH:3][C:2]=1[C:17]1[C:16]([CH3:15])=[CH:25][C:24]2[C:23]([CH3:27])([CH3:26])[CH2:22][CH2:21][C:20]([CH3:29])([CH3:28])[C:19]=2[CH:18]=1)[CH:33]=[O:35]

Participants

9

Reactant 4

HCID 702EthanolHCID 11430Potassium CarbonateHCID 10037535(3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)boronic acidHCID 131504163-Bromo-4-(trifluoromethoxy)benzaldehyde

Product 1

HCID 86588860HCID 86588860, compoundYield 76%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 3-bromo-4-trifluoromethoxybenzaldehyde (10.0 g, 37.2 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl) boronic acid (11.0 g, 44.68 mmol, 1.2 eq) in a mixture of toluene (100 mL), ethanol (20 mL) and water (15 mL) was added potassium carbonate (10.28 g, 74.4 mmol, 2 eq). The mixture was degased with argon for 40 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.86 g, 0.74 mmol, 0.02 eq) was added and the mixture heated at reflux under argon for 22 hours. The mixture was cooled to room temperature, diluted with ethyl acetate and washed successively with water and brine, dried over MgSO4, filtered and evaporated. The residue was chromatographed on silica gel (eluent: ethyl acetate/hexane 5:95) to give 3-trifluoromethoxy-4-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl) benzaldehyde (11.1 g, 76%), 1H NMR (300 MHz; CDCl3) 1.25 (s, 6 H); 1.32 (s, 6 H); 1.70 (s, 4 H); 2.08 (s, 3 H); 7.06 (s, 1 H); 7.18 (s, 1 H); 7.48 (dd, J1=8.4 Hz, J2=1.5 Hz, 1 H); 7.84 (d, J=2.0 Hz, 1 H); 7.88 (dd, J1=2.0 Hz, J2=8.5 Hz, 1 H), 9.91 (s, 1 H).

Workup

  1. customThe mixture was degased with argon for 40 minutes
  2. temperaturethe mixture heated
  3. temperatureat reflux under argon for 22 hours
  4. washwashed successively with water and brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue was chromatographed on silica gel (eluent: ethyl acetate/hexane 5:95)

Sources & evidence

ORD record
ord-ead6c7a55c0f45819004235a7a0643e8
Source dataset
uspto-grants-2006_07
Patent number
US07071218B2

Reaction notes

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