Ethyl Acetate → HCID 178499654, compound

HRID 480171Notes

Reaction equation

HRID 480171 reaction equation
[CH3:1][O:2][C:3]([CH:5]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)=[O:4].[CH2:25]([O:32][C:33]([C:35]12[CH2:42][CH2:41][C:38](C=O)([CH2:39][CH2:40]1)[CH2:37][CH2:36]2)=[O:34])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.[Cl-].[NH4+].[C:47](OCC)(=O)C>C1COCC1>[CH2:25]([O:32][C:33]([C@:35]12[CH2:42][CH2:41][C@@:38]([CH:47]=[CH:5][C:3]([O:2][CH3:1])=[O:4])([CH2:37][CH2:36]1)[CH2:39][CH2:40]2)=[O:34])[C:26]1[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 17453Acetic acid, 2-(triphenylphosphoranylidene)-, methyl esterHCID 25517Ammonium ChlorideHCID 86591749Benzyl 4-formylbicyclo[2.2.2]octane-1-carboxylate

Product 1

HCID 178499654HCID 178499654, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Methyl (triphenylphosphoranylidene) acetate (60.2 g, 173 mmol) is added to a stirred solution of 4-formylbicyclo[2.2.2]octane-1-carboxylic acid benzyl ester (XIX, Example 94, 33.5 g, 123.2 mmol) in THF (550 ml). This mixture is then heated to gently reflux for 16 hr. The reaction mixture is cooled to 20-25° and to this is added saturated ammonium chloride (75 ml) and stirred for 10 minutes. Ethyl acetate (250 ml) and isomeric hexanes (300 ml) are added and stirred for 10 minutes. The resulting mixture is filtered through a plug of silica gel (850 g) with a thin layer of celite on the top. The solid is washed with ethyl acetate/hexane (1/1, 250 ml). The filtrates are combined and concentrated to give the title compound, NMR (400 MHz, CDCl3) δ 7.24, 6.81, 5.59, 5.01, 3.63, 1.81 and 1.48.

Workup

  1. temperatureThis mixture is then heated
  2. temperatureto gently reflux for 16 hr
  3. temperatureThe reaction mixture is cooled to 20-25°
  4. stirringstirred for 10 minutes
  5. filtrationThe resulting mixture is filtered through a plug of silica gel (850 g) with a thin layer of celite on the top
  6. washThe solid is washed with ethyl acetate/hexane (1/1, 250 ml)
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-c41780ac9cc64e09ae1e3778a86f4ca3
Source dataset
uspto-grants-2003_11
Patent number
US06649600B1

Reaction notes

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