Diethyl Oxalate → ethyl 4-(adamantan-1-yl)-2,4-dioxobutanoate

HRID 2225164Notes

Reaction equation

HRID 2225164 reaction equation
[C:1]([O:8][CH2:9][CH3:10])(=[O:7])[C:2]([O:4]CC)=O.[H-].[Na+].[CH3:13][C:14]([C:16]12[CH2:25][CH:20]3[CH2:21][CH:22]([CH2:24][CH:18]([CH2:19]3)[CH2:17]1)[CH2:23]2)=[O:15]>C1COCC1>[CH2:9]([O:8][C:1](=[O:7])[C:2](=[O:4])[CH2:13][C:14]([C:16]12[CH2:25][CH:20]3[CH2:21][CH:22]([CH2:24][CH:18]([CH2:19]3)[CH2:17]1)[CH2:23]2)=[O:15])[CH3:10]

Participants

5

Reactant 3

HCID 7268Diethyl OxalateHCID 24758Sodium hydrideHCID 123126Methyl tricyclo(3.3.1.13,7)dec-1-yl ketone

Product 1

HCID 28397220ethyl 4-(adamantan-1-yl)-2,4-dioxobutanoateYield 100.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Preparation C13, Step 1: Diethyl oxalate (3.81 mL, 28 mmol, 1 eq.) was dissolved in THF (25 mL) at RT under nitrogen then taken to near-reflux. Sodium hydride (1.18 g, 29 mmol, 1.05 eq.) was added in 5 portions carefully. A solution of 1-adamantyl methyl ketone (5.00 g, 28 mmol, 1 eq.), in THF (10 mL) was added dropwise via an addition funnel. After the addition was complete, the mixture was refluxed for 1 hour. Cooled to RT and very carefully quenched with saturated NH4Cl (50 mL) then extracted 3 times with methylene chloride. The organic layers were combined, dried and stripped in vacuo to give 7.80 g of 4-adamantan-1-yl-2,4-dioxo-butyric acid ethyl ester as an amber oil. MS found: (M+H)+=279.

Workup

  1. customPreparation C13, Step 1
  2. temperatureto near-reflux
  3. additionAfter the addition
  4. temperaturethe mixture was refluxed for 1 hour
  5. customvery carefully quenched with saturated NH4Cl (50 mL)
  6. extractionthen extracted 3 times with methylene chloride
  7. customdried

Sources & evidence

ORD record
ord-f6e95ff32c96453fa685ced1dae191b5
Source dataset
uspto-grants-2008_05
Patent number
US07378409B2

Reaction notes

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