2,6-Lutidine → HCID 71086828, compound

HRID 571864Notes

Reaction equation

HRID 571864 reaction equation
[N:1]([C:4]1[CH:9]=[CH:8][C:7]([O:10][CH:11]([F:13])[F:12])=[CH:6][CH:5]=1)=[N+:2]=[N-:3].C1COCC1.[C:19]([O:23][CH2:24][CH3:25])(=[O:22])[C:20]#[CH:21].N1C(C)=CC=CC=1C>[Cu]I.C(OCC)(=O)C.O.CS(C)=O>[F:13][CH:11]([F:12])[O:10][C:7]1[CH:8]=[CH:9][C:4]([N:1]2[CH:21]=[C:20]([C:19]([O:23][CH2:24][CH3:25])=[O:22])[N:3]=[N:2]2)=[CH:5][CH:6]=1

Participants

9

Reactant 4

HCID 79372,6-LutidineHCID 8028TetrahydrofuranHCID 12182Ethyl propiolateHCID 86674694HCID 86674694, compound

Product 1

HCID 71086828HCID 71086828, compoundYield 84.4%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 679Dimethyl SulfoxideSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

In a 50 ml round-bottomed flask, 1-azido-4-(difluoromethoxy)benzene (540 mg, 2.92 mmol) was combined with THF (10 ml) and dimethylsulfoxide (0.16 ml) to give an orange solution. Then ethyl propiolate (858 mg, 0.89 ml, 8.75 mmol), copper (I) iodide (556 mg, 2.92 mmol) and 2,6-lutidine (625 mg, 0.68 ml, 5.83 mmol) were added and the reaction mixture was stirred for 2 hours at room temperature. Water and ethyl acetate were added and the layers were separated. The organic layer was washed with 1 N hydrochloric acid and brine, dried over MgSO4 and filtered. The filtrate was concentrated under vacuum to yield a brown solid, which was adsorbed on silica gel and purified by flash chromatography (20 g Silica gel, 20% ethyl acetate in heptane) yielding 698 mg (84%) of a light yellow solid. MS (ISP): 284.2 ([M+H]+).

Workup

  1. customto give an orange solution
  2. customthe layers were separated
  3. washThe organic layer was washed with 1 N hydrochloric acid and brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationThe filtrate was concentrated under vacuum
  7. customto yield a brown solid, which
  8. custompurified by flash chromatography (20 g Silica gel, 20% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-70a887f71950460695a74afbf7e09c95
Source dataset
uspto-grants-2015_05
Patent number
US09029370B2

Reaction notes

Loading…