Diethyl Carbonate → ethyl 1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate

HRID 254275Notes

Reaction equation

HRID 254275 reaction equation
[H-].[Na+].[C:3]1(=[O:13])[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[CH2:6][CH2:5][CH2:4]1.[CH2:14]([O:16][C:17](=O)[O:18]CC)[CH3:15]>C1(C)C=CC=CC=1>[CH2:14]([O:16][C:17]([CH:4]1[CH2:5][CH2:6][C:7]2[C:12](=[CH:11][CH:10]=[CH:9][CH:8]=2)[C:3]1=[O:13])=[O:18])[CH3:15]

Participants

5

Reactant 3

HCID 7766Diethyl CarbonateHCID 107241-TetraloneHCID 24758Sodium hydride

Product 1

HCID 251472ethyl 1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylateYield 64%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

To a stirred suspension of NaH (11 g, 274 mmol, 60% in oil) in toluene was added dropwise 1-tetralone (20 g, 137 mmol) in toluene (50 mL). After the complete addition, the mixture was heated at reflux for 1 h. Then at 60° C. diethylcarbonate was added (24 g, 137 mmol) dropwise and the mixture was again heated at reflux for 2 h. The reaction was quenched with aqueous HCl (4N, 100 mL) and dilute with H2O. Ether (200 mL) was added for the extraction, the organics were dried and concentrated to oil. Distillation (100° C. at 0.1 mm Hg) gave the title compound (19.1 g, 64%). 1H NMR (CDCl3, 200 MHz): δ 1.34 (t, 3H, J 7.0 Hz), 1.38 (t, 3H, J 7.0 Hz), 2.20-3.10 (m, 4H), 3.59 (1H, dd, J 7.0 Hz J 10.0 Hz), 4.24 (1H, q, J 7.0 Hz), 4.28 (q, 1H, J 7.0 Hz), 7.29 (m, 3H), 7.78 (m, 1H), 8.01 (m, 1H), 12.5 (s, 1H). 13C NMR (CDCl3, 50 MHz): δ 14.1, 14.2, 20.5, 26.36, 27.5, 27.7, 54.5. 60.4; 61.1; 96.9. 124.2, 126.5, 126.7, 127.2, 127.6; 128.7, 130.0, 130.4. 131.8. 133.7, 139.3, 143.6. 165.0, 170.1, 172.6, 193.0.

Workup

  1. additionAfter the complete addition
  2. temperaturethe mixture was heated
  3. temperatureat reflux for 1 h
  4. temperaturethe mixture was again heated
  5. temperatureat reflux for 2 h
  6. customThe reaction was quenched with aqueous HCl (4N, 100 mL)
  7. additiondilute with H2O
  8. additionEther (200 mL) was added for the extraction
  9. customthe organics were dried
  10. concentrationconcentrated to oil
  11. distillationDistillation (100° C. at 0.1 mm Hg)

Sources & evidence

ORD record
ord-0ba10904c0ce4553a86f118d3d0ec9ec
Source dataset
uspto-grants-2011_01
Patent number
US07875617B2

Reaction notes

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