Propargyl alcohol → HCID 11435374, compound

HRID 1061587Notes

Reaction equation

HRID 1061587 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4](Br)[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:4]1[CH:3]=[C:2]([C:11]#[C:10][CH2:9][OH:12])[CH:7]=[CH:6][CH:5]=1

Participants

6

Reactant 2

HCID 7859Propargyl alcohol2×HCID 79271,3-Dibromobenzene

Product 1

HCID 11435374HCID 11435374, compoundYield 64.4%

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 1,3-dibromobenzene (0.6 ml, 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 20 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 6.5 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 (0.6 g) as a colorless oil. TLC, silica gel (glass plates), [toluene/acetone (8:2)], Rf=0.22.

Workup

  1. stirringthe mixture is stirred
  2. temperatureat reflux for a further 6.5 h
  3. temperatureAfter cooling
  4. filtrationthe reaction mixture is filtered off with suction over kieselguhr
  5. washthe filter cake is washed with ethyl acetate (20 ml)
  6. concentrationThe organic phase is concentrated under reduced pressure
  7. customFurther purification

Sources & evidence

ORD record
ord-a2bdc70c0bce4acca0f4cae57e86b69e
Source dataset
uspto-grants-2005_11
Patent number
US06960588B1

Reaction notes

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