Propargyl alcohol → 5-Chloro-2-(2-chlorophenyl)-7-(3-hydroxy-1-propynyl)-benzoxazole

HRID 842128Notes

Reaction equation

HRID 842128 reaction equation
Br[C:2]1[C:10]2[O:9][C:8]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=3[Cl:17])=[N:7][C:6]=2[CH:5]=[C:4]([Cl:18])[CH:3]=1.[CH2:19]([OH:22])[C:20]#[CH:21]>C1(C)C=CC=CC=1.C(N(CC)CC)C.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu]I>[Cl:18][C:4]1[CH:3]=[C:2]([C:21]#[C:20][CH2:19][OH:22])[C:10]2[O:9][C:8]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=3[Cl:17])=[N:7][C:6]=2[CH:5]=1

Participants

7

Reactant 2

HCID 7859Propargyl alcoholHCID 46392547-Bromo-5-chloro-2-(2-chlorophenyl)-1,3-benzoxazole

Product 1

HCID 226182815-Chloro-2-(2-chlorophenyl)-7-(3-hydroxy-1-propynyl)-benzoxazoleYield 85.8%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolventHCID 8471TriethylamineSolvent

Procedure

A solution of 17.15 g (50 mmol) of 7-bromo-5-chloro-2-(2-chlorophenyl)-benzoxazole and 4.40 ml (75 mmol) of propargylalcohol in 32 ml of toluene and 64 ml of triethylamine was heated under nitrogen to 80-5° C. with 175.4 mg (250 μM) of bis(triphenylphosphine)palladium (II) chloride and 8.6 mg (4.5 μM) of copper (1) iodide. After 6 hours, the solid was filtered off and washed with dichloromethane. The solution was evaporated in vacuo. The residue was dissolved in ethyl acetate, washed with 1 N HCl, sodium bicarbonate solution, and water. The ethyl acetate was removed in vacuo, the residue (15.46 g) was dissolved in dichloromethane and filtered through 60 g of silica gel to give the title compound (13.64 g, 85.8%), mp 165-9° C.

Workup

  1. filtrationthe solid was filtered off
  2. washwashed with dichloromethane
  3. customThe solution was evaporated in vacuo
  4. dissolutionThe residue was dissolved in ethyl acetate
  5. washwashed with 1 N HCl, sodium bicarbonate solution, and water
  6. customThe ethyl acetate was removed in vacuo
  7. dissolutionthe residue (15.46 g) was dissolved in dichloromethane
  8. filtrationfiltered through 60 g of silica gel

Sources & evidence

ORD record
ord-aee9e3d6108e4747bb00479c6329acf7
Source dataset
uspto-grants-2002_04
Patent number
US06372770B1

Reaction notes

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