1,4-Dibromobenzene → 3,3'-(1,4-Phenylene)di(prop-2-yn-1-ol)

HRID 1061588Notes

Reaction equation

HRID 1061588 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5](Br)=[CH:4][CH:3]=1.[CH2:9]([OH:12])[C:10]#[CH:11]>C(N)CC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[OH:12][CH2:9][C:10]#[C:11][C:2]1[CH:7]=[CH:6][C:5]([C:11]#[C:10][CH2:9][OH:12])=[CH:4][CH:3]=1

Participants

6

Reactant 2

HCID 78041,4-DibromobenzeneHCID 7859Propargyl alcohol2×

Product 1

HCID 132529933,3'-(1,4-Phenylene)di(prop-2-yn-1-ol)Yield 90.2%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst2×HCID 178418397HCID 178418397, compoundCatalyst2×HCID 7852PropylamineSolvent

Procedure

A solution of 1,4-dibromobenzene (1.18 g, 5.0 mmol) in n-propylamine (15 ml) is admixed successively with Pd(Ph3P)4 (116 mg, 2%), CuI (28 mg, 3%) and propargyl alcohol (0.9 ml, 15 mmol) and stirred at RT for 1 h and then at reflux for 7 h. More Pd(Ph3P)4 (58 mg, 1%), CuI (14 mg, 1.5%) and propargyl alcohol (0.45 ml, 7.5 mmol) are then added, and the mixture is stirred at reflux for a further 8 h. After cooling, the reaction mixture is filtered off with suction over kieselguhr and the filter cake is washed with ethyl acetate (20 ml). The organic phase is concentrated under reduced pressure. Further purification is carried out by chromatography [Tol/Ac (8:2)] over a silica gel column. This gives the title compound (0.84 g) as a colorless solid. TLC, silica gel (glass plates), [toluene/acetone (8:2)], Rf=0.22.

Workup

  1. temperatureat reflux for 7 h
  2. stirringthe mixture is stirred
  3. temperatureat reflux for a further 8 h
  4. temperatureAfter cooling
  5. filtrationthe reaction mixture is filtered off with suction over kieselguhr
  6. washthe filter cake is washed with ethyl acetate (20 ml)
  7. concentrationThe organic phase is concentrated under reduced pressure
  8. customFurther purification

Sources & evidence

ORD record
ord-2ceb103273aa4ecea55d7e63ae17711d
Source dataset
uspto-grants-2005_11
Patent number
US06960588B1

Reaction notes

Loading…