Ethanol → 4-Chloro-3-(3,5,5,8,7-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl) benzaldehyde

HRID 488843

Reaction equation

HRID 488843 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[Cl:10])[CH:5]=[O:6].[CH3:11][C:12]1[C:13](B(O)O)=[CH:14][C:15]2[C:16](C)([CH3:24])[CH2:17][CH2:18][C:19]([CH3:23])([CH3:22])[C:20]=2[CH:21]=1.[CH2:29](O)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>[Cl:10][C:9]1[CH:8]=[CH:7][C:4]([CH:5]=[O:6])=[CH:3][C:2]=1[C:13]1[C:12]([CH3:11])=[CH:21][C:20]2[C:19]([CH3:22])([CH3:23])[CH2:18][CH:17]([CH3:29])[CH:16]([CH3:24])[C:15]=2[CH:14]=1

Participants

9

Reactant 4

HCID 702EthanolHCID 11430Potassium CarbonateHCID 10037535(3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)boronic acidHCID 140498093-Bromo-4-chlorobenzaldehyde

Product 1

HCID 186722284-Chloro-3-(3,5,5,8,7-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl) benzaldehydeYield 77%

Reagents, catalysts & solvents 4

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

Procedure

To a solution of 3-bromo-4-chlorobenzaldehyde (2.5 g, 11.39 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl) boronic acid (3.1 g, 12.53 mmol) in a mixture of toluene (25 mL), ethanol (5 mL) and water (4 mL) was added potassium carbonate (3.15 g, 22.78 mmol). The solution was degased with argon for 30 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.26 g, 0.23 mmol) was added and the mixture heated at reflux under argon overnight. The solution was cooled to room temperature, diluted with ethyl acetate and washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (biotage: eluant:ethyl acetate/hexane, 5:95) to give 3.0 g of 4-chloro-3-(3,5,5,8,7-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl) benzaldehyde (77%). 1H NMR (300 MHz; DMSO) 1.18 (s, 3H); 1.20 (s, 3H); 1.24 (s, 3H); 1.26 (s, 3H); 1.36 (s, 4H); 1.98 (s, 3H); 7.04 (s, 1H); 7.23 (s, 1H); 7.75 (d, J=7.8 Hz, 1H); 7.80 (d, J=1.8 Hz, 1H); 7.88 (dd, J1=7.8 Hz, J2=1.8 Hz, 1H); 9.99 (s, 1 H).

Workup

  1. customThe solution was degased with argon for 30 minutes
  2. temperaturethe mixture heated
  3. temperatureat reflux under argon overnight
  4. washwashed successively with water and brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue was chromatographed on silica gel (biotage: eluant:ethyl acetate/hexane, 5:95)

Sources & evidence

ORD record
ord-9f28f328602d4766976ed88a3517069e
Source dataset
uspto-grants-2005_12
Patent number
US06974826B2

Linked notes

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