Acetic Acid → Tetraethyl orthocarbonate

HRID 990152Notes

Reaction equation

HRID 990152 reaction equation
[H-].[Na+].[C:3]1(=[O:11])[CH2:10]CCCCCC1.[C:12](=[O:19])([O:16][CH2:17][CH3:18])[O:13][CH2:14][CH3:15].[C:20](O)(=O)[CH3:21]>C1(C)C=CC=CC=1.O>[C:12]([O:11][CH2:3][CH3:10])([O:19][CH2:20][CH3:21])([O:16][CH2:17][CH3:18])[O:13][CH2:14][CH3:15]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 7766Diethyl CarbonateHCID 10403Cyclooctanone3×HCID 24758Sodium hydride3×

Product 1

HCID 66213Tetraethyl orthocarbonateYield 71%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent2×

Conditions

Temperature
80 °C

Procedure

The keto-ester was prepared by the sodium hydride induced acylation of cyclooctanone (1 using diethyl carbonate). A 1-L round bottom flask was charged with NaH (60% dispersion in mineral oil, 17.0 g, 708 mmol). The NaH was washed with three portions of toluene (200 mL), diethyl carbonate (36 mL, 207 mmol) was charged to the flask, and the reaction mixture warmed to 80° C. A solution of cyclooctanone (18.76 g, 149 mmol) in toluene (50 mL) was added dropwise over 1 hr. The temperature was maintained at 80° C. for 1.5 hr after the addition of cyclooctanone. Upon cooling to room temperature, glacial acetic acid (30 mL) was added dropwise, followed by ice water (200 mL). The reaction mixture was stirred until all the solid was in solution (additional water may be necessary). The layers were separated, and the aqueous layer was extracted with toluene (3×100 mL). The organic layer was dried over MgSO4, filtered, and evaporated in vacuo to yield an oil. Purification was achieved by simple high vacuum distillation (91°-93° C. 0.5 to 0.6 mmHg) to yield 20.8 g, 71% of 6; IR (neat) 2950, 2870, 1745, 1710, 1640, 1617, 1468, 1382, 1330, 1250, 1230, 1185, 1100 cm−1; 1H NMR (CDCl3, 300 MHz) δ(keto-enol mix) 1.23 (t), 1.29 (t), 1.33 to 1.58 (m), 1.62 to 1.76 (m), 1.85 to 1.95 (m), 2.32 to 2.68 (m), 3.5 to 3.6 (m), 4.1 to 4.25 (m), 12.6 (s, enol H).

Workup

  1. additionwas charged to the flask
  2. temperatureThe temperature was maintained at 80° C. for 1.5 hr
  3. temperatureUpon cooling to room temperature
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with toluene (3×100 mL)
  6. dry with materialThe organic layer was dried over MgSO4
  7. filtrationfiltered
  8. customevaporated in vacuo
  9. customto yield an oil
  10. customPurification
  11. distillationwas achieved by simple high vacuum distillation (91°-93° C. 0.5 to 0.6 mmHg)

Sources & evidence

ORD record
ord-71c165c3b9af495798909ac8c558b437
Source dataset
uspto-grants-2002_10
Patent number
US06458865B2

Reaction notes

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