Ethyl Acetate → HCID 57757233, compound

HRID 2100103Notes

Reaction equation

HRID 2100103 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]([NH:29][C:30]1[CH:35]=[CH:34][C:33](B(O)O)=[CH:32][CH:31]=1)(=[O:28])[CH3:27].C([O-])([O-])=O.[Na+].[Na+].CCOC(C)=O>COCCOC.O.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>[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]([C:33]3[CH:34]=[CH:35][C:30]([NH:29][C:26](=[O:28])[CH3:27])=[CH:31][CH:32]=3)=[CH:7][CH:6]=2)=[CH:14][CH:13]=1

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 27346574-Acetamidophenylboronic acidHCID 686543984-[(4-Bromophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenol

Product 1

HCID 57757233HCID 57757233, compoundYield 44.1%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

To a solution of 4-[(4-bromophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenol (14) (0.1 g, 0.250 mmol) and (4-acetylaminophenyl)boronic acid (0.148, 0.826 mmol) in ethylene glycol dimethyl ether (8 mL) was added tetrakis(triphenylphosphine)palladium (0) (0.026 g, 0.023 mmol) followed by 2 M Na2CO3 (3 mL). The reaction mixture was refluxed for 4 h, cooled to room temperature then diluted with water followed by EtOAc. The layers were separated and the aqueous layer was extracted with EtOAc. The combined organic layers were washed with water followed by brine, dried (MgSO4) filtered and concentrated to an oil. The crude oil was dissolved in DCM, loaded onto silica gel and purified with a gradient of 100% hexanes to 40% hexanes:EtOAc over 60 mins. Pure fractions were combined and concentrated to give 0.05 g (41%) of the title compound 99 as an off white powder. 1H NMR (400 MHz, DMSO-d6): δ 0.89 (s, 12 H), 1.25 (s, 2 H), 1.93 (s, 4 H), 2.03 (s, 3 H), 6.66 (d, J=8.5 Hz, 2 H), 6.94 (d, J=8.4 Hz, 2 H), 7.16 (d, J=8.3 Hz, 2 H) 7.52-7.64 (m, 6 H), 9.27 (s, 1 H), 9.99 (s, 1 H). HRMS (ESI) Calcd for C31H36NO2: 454.2746 (M+H)+. Found 454.2757.

Workup

  1. temperatureThe reaction mixture was refluxed for 4 h
  2. customThe layers were separated
  3. extractionthe aqueous layer was extracted with EtOAc
  4. washThe combined organic layers were washed with water
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated to an oil
  8. dissolutionThe crude oil was dissolved in DCM
  9. custompurified with a gradient of 100% hexanes to 40% hexanes
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-d400c692e1f8488b90ba67e9fcb6ba53
Source dataset
uspto-grants-2009_08
Patent number
US07569601B2

Reaction notes

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