Propargyl alcohol → HCID 58994550, compound

HRID 1190187Notes

Reaction equation

HRID 1190187 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([N+:15]([O-:17])=[O:16])=[C:6]([N:8]2[CH2:13][CH2:12][CH:11]([CH3:14])[CH2:10][CH2:9]2)[CH:7]=1.[CH2:18]([OH:21])[C:19]#[CH:20].C(N(CC)CC)C>O1CCOCC1.CCOC(C)=O.[Cu]I>[CH3:14][CH:11]1[CH2:12][CH2:13][N:8]([C:6]2[CH:7]=[C:2]([C:20]#[C:19][CH2:18][OH:21])[CH:3]=[CH:4][C:5]=2[N+:15]([O-:17])=[O:16])[CH2:9][CH2:10]1

Participants

7

Reactant 3

HCID 7859Propargyl alcoholHCID 8471TriethylamineHCID 59794652HCID 59794652, compound

Product 1

HCID 58994550HCID 58994550, compoundYield 77%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

To a round bottom flask containing 1-(5-bromo-2-nitro-phenyl)-4-methyl-piperidine (as prepared above, 400 mg, 1.33 mmol) in 8 mL of dioxane was added propargyl alcohol (155 μL, 2.64 mmol), bis-dichloro(triphenylphosphinyl)palladium (II) (56.3 mg, 0.0798 mmol), copper (I) iodide (5.0 mg, 0.02 mmol) and triethylamine (741 μL, 5.32 mmol). The result was heated at 80° C. for 16 h. The reaction was then diluted with EtOAc (50 mL), washed with water (2×50 mL), dried (Na2SO4), and concentrated in vacuo. Purification of the crude material by preparative thin layer chromatography (75% EtOAc-hexanes) afforded 280 mg (77%) of the title compound as a reddish oil. 1H-NMR (CDCl3; 400 MHz): δ 7.73 (d, 1H, J=8.6 Hz), 7.17 (d, 1H, J=1.6 Hz), 6.98 (dd, 1H, J=8.6, 1.6 Hz), 3.23-3.26 (m, 2H), 4.53 (s, 2H), 1.73-1.42 (m, 5H), 2.86-2.79 (m, 2H), 1.00 (d, 3H, J=6.4 Hz).

Workup

  1. washwashed with water (2×50 mL)
  2. dry with materialdried (Na2SO4)
  3. concentrationconcentrated in vacuo
  4. customPurification of the crude material by preparative thin layer chromatography (75% EtOAc-hexanes)

Sources & evidence

ORD record
ord-eb534a3d1ce54ed5a274e4d644f97339
Source dataset
uspto-grants-2014_03
Patent number
US08674100B2

Reaction notes

Loading…