Propargyl alcohol → HCID 11672832, compound

HRID 1061591Notes

Reaction equation

HRID 1061591 reaction equation
[CH2:1]([OH:4])[C:2]#[CH:3].Br[C:6]1[C:10](Br)=[CH:9][S:8][CH:7]=1>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:4][CH2:1][C:2]#[C:3][C:6]1[C:10]([C:3]#[C:2][CH2:1][OH:4])=[CH:9][S:8][CH:7]=1

Participants

6

Reactant 2

HCID 7859Propargyl alcohol2×HCID 184523,4-Dibromothiophene

Product 1

HCID 11672832HCID 11672832, compoundYield 87.4%

Reagents, catalysts & solvents 3

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

Procedure

Pd(Ph3P)4 (116 mg, 2%), CuI (28 mg, 3%) and propargyl alcohol (0.9 ml, 15 mmol) are added successively to a solution of 3,4-dibromothiophene (1.18 g, 5.0 mmol) in n-propylamine (15 ml), and the reaction mixture is stirred at RT for 1 h and then under 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 under reflux for another 8 h. After cooling, the reaction mixture is filtered off through kieselguhr and 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. temperatureunder reflux for 7 h
  2. stirringthe mixture is stirred
  3. temperatureunder reflux for another 8 h
  4. temperatureAfter cooling
  5. filtrationthe reaction mixture is filtered off through kieselguhr
  6. washwashed with ethyl acetate (20 ml)
  7. concentrationThe organic phase is concentrated under reduced pressure
  8. customFurther purification

Sources & evidence

ORD record
ord-600e136ea1304ba4969fa00fb432e449
Source dataset
uspto-grants-2005_11
Patent number
US06960588B1

Reaction notes

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