2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 3-Ethyl-6-(methyloxy)-2-phenyl-1-naphthalenyl acetate

HRID 1992851Notes

Reaction equation

HRID 1992851 reaction equation
[CH2:1]([CH:3]1[CH2:12][C:11]2[C:6](=[CH:7][CH:8]=[C:9]([O:13][CH3:14])[CH:10]=2)[C:5](=[O:15])[CH:4]1[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[CH3:2].ClC1C(=O)C(C#N)=[C:26](C#N)[C:27](=[O:30])C=1Cl>C(OC(C)=C)(=O)C.C(Cl)Cl>[C:27]([O:15][C:5]1[C:6]2[C:11](=[CH:10][C:9]([O:13][CH3:14])=[CH:8][CH:7]=2)[CH:12]=[C:3]([CH2:1][CH3:2])[C:4]=1[C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)(=[O:30])[CH3:26]

Participants

5

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 685413613-Ethyl-6-(methyloxy)-2-phenyl-3,4-dihydro-1(2H)-naphthalenone

Product 1

HCID 685362503-Ethyl-6-(methyloxy)-2-phenyl-1-naphthalenyl acetateYield 64%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 7916Isopropenyl acetateSolvent

Procedure

3-Ethyl-6-(methyloxy)-2-phenyl-3,4-dihydro-1(2H)-naphthalenone (55) (0.84 g, 3.00 mmol) was dissolved in isopropenyl acetate (30 mL). pTsOH monohydrate (100 mg) was added. The mixture was refluxed under nitrogen for 3 days. Cooled to room temperature, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (1.74 g, 7.50 mmol) was added. The resulting mixture was refluxed under nitrogen overnight. Cooled to room temperature and diluted with CH2Cl2 (150 mL). The mixture was washed with 0.2 N NaOH (4×20 mL), water (2×20 mL), brine (30 mL), dried over Na2SO4, filtered, and the filtrate was concentrated to give the crude product as a dark brown tar. The crude product was purified by flash chromatography over SiO2 with hexanes:acetone (50:1) to give 0.61 g (64%) of the title compound (56) as a white solid. 1H NMR (400 MHz, CDCl3): δ 1.11 (t, J=7.5 Hz, 3H), 1.97 (s, 3H), 2.55 (q, J=7.5 Hz, 2H), 3.93 (s, 3H), 7.10-7.16 (m, 2H), 7.20-7.25 (m, 2H), 7.30-7.45 (m, 3H), 7.57 (s, 1H), 7.62 (d, J=8.9 Hz, 1H).

Workup

  1. temperatureThe mixture was refluxed under nitrogen for 3 days
  2. temperatureThe resulting mixture was refluxed under nitrogen overnight
  3. temperatureCooled to room temperature
  4. washThe mixture was washed with 0.2 N NaOH (4×20 mL), water (2×20 mL), brine (30 mL)
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationthe filtrate was concentrated
  8. customto give the crude product as a dark brown tar
  9. customThe crude product was purified by flash chromatography over SiO2 with hexanes:acetone (50:1)

Sources & evidence

ORD record
ord-726360292c9d4e7cb423249c60297b37
Source dataset
uspto-grants-2010_01
Patent number
US07649093B2

Reaction notes

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