Methyl cyano(oxan-4-ylidene)acetate → HCID 68314247, compound

HRID 76214Notes

Reaction equation

HRID 76214 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([Mg]Br)=[CH:4][CH:3]=1.[C:10]([C:12](=[C:17]1[CH2:22][CH2:21][O:20][CH2:19][CH2:18]1)[C:13]([O:15][CH3:16])=[O:14])#[N:11]>C(OCC)C.[Cu]I>[C:10]([CH:12]([C:17]1([C:5]2[CH:6]=[CH:7][C:2]([F:1])=[CH:3][CH:4]=2)[CH2:22][CH2:21][O:20][CH2:19][CH2:18]1)[C:13]([O:15][CH3:16])=[O:14])#[N:11]

Participants

5

Reactant 2

HCID 11052260Methyl cyano(oxan-4-ylidene)acetateHCID 178418676HCID 178418676, compound

Product 1

HCID 68314247HCID 68314247, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 3283Diethyl EtherSolvent2×

Procedure

A round bottom flask was equipped with a condenser, addition funnel and rubber septum with nitrogen inlet was charged with a solution of p-fluorophenylmagnesium bromide (2.0 M in diethyl ether, 1.99 ml, 3.97 mmol) and CuI (63 mg, 0.331 mmol) in 10 ml dry diethyl ether (10 ml). Methyl 2-cyano-2-(oxan-4-ylidene)acetate (600 mg, 3.31 mmol) in diethyl ether (10 ml) was added drop-wise over 30 min while cooling the reaction flask in an ice bath. The mixture was then stirred for 3 h. The reaction mixture was poured into a 50 g ice/1 N HCl (25 ml) mixture. The product was extracted with Et2O (3×50 ml), washed with brine (50 ml), dried (NA2SO4) and concentrated. Purified by normal phase SiO2 chromatography (7% to 60% EtOAc/hexanes) to give methyl 2-cyano-2-[4-(4-fluorophenyl)oxan-4-yl]acetate as a white solid (730 mg, 80%, m/z: 277.1 [M+Na]+ observed).

Workup

  1. customA round bottom flask was equipped with a condenser, addition funnel
  2. temperaturewhile cooling the reaction flask in an ice bath
  3. extractionThe product was extracted with Et2O (3×50 ml)
  4. washwashed with brine (50 ml)
  5. customdried (NA2SO4)
  6. concentrationconcentrated
  7. customPurified by normal phase SiO2 chromatography (7% to 60% EtOAc/hexanes)

Sources & evidence

ORD record
ord-09d70ac10ab94d9d81eab5dafe0ac242
Source dataset
uspto-grants-2014_09
Patent number
US08835488B2

Reaction notes

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