Acetic Acid → 4-(3,4-Dichlorophenyl)-1-oxo-1,2,3,4-tetrahydro-naphthalene-2-carboxylic acid ethyl ester

HRID 556149Notes

Reaction equation

HRID 556149 reaction equation
[H-].[Na+].C(O[C:6](=[O:10])[O:7][CH2:8][CH3:9])C.[Cl:11][C:12]1[CH:13]=[C:14]([CH:19]2[C:28]3[C:23](=[CH:24][CH:25]=[CH:26][CH:27]=3)[C:22](=[O:29])[CH2:21][CH2:20]2)[CH:15]=[CH:16][C:17]=1[Cl:18].C(O)(=O)C>C1COCC1>[CH2:8]([O:7][C:6]([CH:21]1[CH2:20][CH:19]([C:14]2[CH:15]=[CH:16][C:17]([Cl:18])=[C:12]([Cl:11])[CH:13]=2)[C:28]2[C:23](=[CH:24][CH:25]=[CH:26][CH:27]=2)[C:22]1=[O:29])=[O:10])[CH3:9]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 7766Diethyl CarbonateHCID 24758Sodium hydrideHCID 37462514-(3,4-Dichlorophenyl)-3,4-dihydro-1(2H)-naphthalenone

Product 1

HCID 248576724-(3,4-Dichlorophenyl)-1-oxo-1,2,3,4-tetrahydro-naphthalene-2-carboxylic acid ethyl esterYield 80%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a stirred suspension of NaH (60% dispersion in mineral oil, 1.69 g, 42 mmol) in THF (80 ml) under N2 was added dropwise diethylcarbonate (4.85 ml, 40 mmol) at room temperature, followed by 4-(3′,4′-dichlorophenyl)-3,4-dihydro-1-(2H)-naphthalone 1 (5.82 g, 20 mmol) in THF (20 ml). The mixture was refluxed for 48 hours, then cooled to 0° C. Acetic acid (10 ml) was added dropwise, and the mixture was extracted with Et2O. The Et2O extracts were washed with saturated NaHCO3 solution, brine, dried over MgSO4, and evaporated. The residue was purified by chromatography, CombiFlash silica gel column (hexane:CH2Cl2=50:50) to give Compound 9 as a clear oil (5.81 g, 80%). 1H NMR (CDCl3) δ 1.30 (t, J=7.2 Hz, 3H), 2.77 (dd, J=16 Hz, 9.6 Hz, 1H), 2.91 (dd, J=15.6 Hz, 6.4 Hz, 1H), 4.10 (dd, J=12 Hz, 6.4 Hz, 1H), 4.19-4.30 (m, 2H), 6.87 (d, J=6.8 Hz, 1H), 7.00 (dd, J=8.4 Hz, 2.0 Hz, 1H), 7.27-7.36 (m, 5H), 7.89 (dd, J=8.4 Hz, 2.0 Hz, 1H), 12.50 (s, 1H). 13C NMR (CDCl3) δ 14.5, 29.1, 43.4, 61.0, 95.6, 125.0, 127.6, 127.9, 128.1, 130.2, 130.6, 130.7, 131.0, 131.3, 132.8, 140.4, 143.9, 164.8, 172.6.

Workup

  1. temperatureThe mixture was refluxed for 48 hours
  2. extractionthe mixture was extracted with Et2O
  3. washThe Et2O extracts were washed with saturated NaHCO3 solution, brine
  4. dry with materialdried over MgSO4
  5. customevaporated
  6. customThe residue was purified by chromatography, CombiFlash silica gel column (hexane:CH2Cl2=50:50)

Sources & evidence

ORD record
ord-9827a9da11744a1c8ffdd4ed946db3d9
Source dataset
uspto-grants-2011_11
Patent number
US08053603B2

Reaction notes

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