Ethoxalyl chloride → HCID 86698438, compound

HRID 527599Notes

Reaction equation

HRID 527599 reaction equation
[CH3:1][C:2]([Si:5]([CH3:19])([CH3:18])[O:6][CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([O:14][CH2:15][O:16][CH3:17])[CH:9]=1)([CH3:4])[CH3:3].[Li]CCCC.Cl[C:26](=[O:32])[C:27]([O:29][CH2:30][CH3:31])=[O:28]>CCCCCC.O1CCCC1>[CH3:4][C:2]([Si:5]([CH3:18])([CH3:19])[O:6][CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([O:14][CH2:15][O:16][CH3:17])[C:9]=1[C:26](=[O:32])[C:27]([O:29][CH2:30][CH3:31])=[O:28])([CH3:1])[CH3:3]

Participants

6

Reactant 3

HCID 20884Ethoxalyl chlorideHCID 67958400HCID 67958400, compound2×HCID 178418339Butyllithium

Product 1

HCID 86698438HCID 86698438, compoundYield 65.7%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent2×

Procedure

To a solution of (1,1-dimethylethyl)(dimethyl){[(3-{[(methyloxy)methyl]oxy}phenyl)methyl]oxy}silane (Intermediate 103, 3 g) in dry n-hexane (30 mL) a solution of BuLi in hexane (1.6M, 7.63 mL, 12.21 mmol) was added and the reaction mixture was stirred for 2 hours at room temperature The reaction mixture was cooled to −78° C. and it was added (via cannulation) to a solution of ethyl chloro(oxo)acetate (1.780 mL, 15.93 mmol) in dry tetrahydrofuran (20 mL) at −78° C. The reaction was quenched with water (20 ml) and extracted with ethyl acetate (2×30 ml). The organic layer was dried over sodium sulphate, filtered and evaporated and the residue was purified by flash chromatography (Biotage system) on silica gel using a 100 g SNAP column and cyclohexane to cyclohexane/ethyl acetate 8:2 as eluents. This afforded the title compound as a yellow pale oil (2.67 g).

Workup

  1. temperaturewas cooled to −78° C.
  2. customThe reaction was quenched with water (20 ml)
  3. extractionextracted with ethyl acetate (2×30 ml)
  4. dry with materialThe organic layer was dried over sodium sulphate
  5. filtrationfiltered
  6. customevaporated
  7. customthe residue was purified by flash chromatography (Biotage system) on silica gel using a 100 g SNAP column and cyclohexane to cyclohexane/ethyl acetate 8:2 as eluents

Sources & evidence

ORD record
ord-97683aa8b269446c9d1270dc510abfdc
Source dataset
uspto-grants-2016_05
Patent number
US09346790B2

Reaction notes

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