Ethoxalyl chloride → Ethyl 2-oxoheptanoate

HRID 1062460Notes

Reaction equation

HRID 1062460 reaction equation
[Li+].[I-].[CH2:3]([Mg]Br)[CH2:4][CH2:5][CH2:6][CH3:7].Cl[C:11](=[O:17])[C:12]([O:14][CH2:15][CH3:16])=[O:13]>C1COCC1>[O:17]=[C:11]([CH2:3][CH2:4][CH2:5][CH2:6][CH3:7])[C:12]([O:14][CH2:15][CH3:16])=[O:13]

Participants

5

Reactant 3

HCID 20884Ethoxalyl chlorideHCID 66321Lithium iodideHCID 178445865HCID 178445865, compound

Product 1

HCID 11745091Ethyl 2-oxoheptanoateYield 23.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a suspension of LiI (23.61 g, 176.44 mmol) in THF (200 mL) at rt was slowly added Cu2Br2 (25.30 g, 88.22 mmol). A vigorous exothermic reaction occurred, and the mixture was then cooled to −78° C. Pentylmagnesium bromide (2M, 36.76 mL, 88.22 mmol) was slowly added at −78° C., and followed soon after by ethyl chloro(oxo)acetate (10 g, 73.52 mmol). The resulting solution was stirred 10 minutes at −78° C., then quenched by dropwise addition of water. The mixture was allowed to warm to rt, and then the organic phase was separated, dried (MgSO4), and evaporated. Purification by flash chromatography using 9:1 hexane/EtOAc as eluant gave ethyl 2-oxoheptanoate as a colorless oil (3.0 g, 23%). 1NMR (400 MHz, CDCl3) δ 4.33-4.21 (m, 2 H), 2.82 (m, 2 H), 1.63-1.59 (m, 2 H), 1.63-11.19 (m, p H), 0.9-0.83 (m, 3 H), LC-MS m/z 279.21 (MH+), retention time 2.42 min (method 2).

Workup

  1. customA vigorous exothermic reaction
  2. customquenched by dropwise addition of water
  3. temperatureto warm to rt
  4. customthe organic phase was separated
  5. dry with materialdried (MgSO4)
  6. customevaporated
  7. customPurification by flash chromatography

Sources & evidence

ORD record
ord-312c002125714cd29c73ef6c1858903c
Source dataset
uspto-grants-2005_11
Patent number
US06960601B2

Reaction notes

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