Propargyl alcohol → Methyl 3,5-bis-(3-hydroxyprop-1-ynyl)benzoate

HRID 2212324Notes

Reaction equation

HRID 2212324 reaction equation
[CH2:1]([OH:4])[C:2]#[CH:3].Br[C:6]1[CH:7]=[C:8]([CH:16]=[C:17](Br)[CH:18]=1)[C:9]([O:11][C:12](C)(C)C)=[O:10]>C(N(CC)CC)C.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>[OH:4][CH2:1][C:2]#[C:3][C:6]1[CH:7]=[C:8]([CH:16]=[C:17]([C:3]#[C:2][CH2:1][OH:4])[CH:18]=1)[C:9]([O:11][CH3:12])=[O:10]

Participants

5

Reactant 2

HCID 7859Propargyl alcoholHCID 21964570Tert-butyl 3,5-dibromobenzoate

Product 1

HCID 21964565Methyl 3,5-bis-(3-hydroxyprop-1-ynyl)benzoateYield 101.9%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

Pd(Ph3P)4 (1.08 g), CuBrSMe2 (0.41 g) and propargyl alcohol (2.95 g, 50.2 mmol) are added successively to a solution of methyl 3,5-dibromobenzoate (A6, 7.7 g, 22.9 mmol) in triethylamine (130 ml), and the mixture is stirred at RT for 10 min and then under reflux at 80° C. for 3.5 h. After cooling, the reaction mixture is filtered off with suction through kieselguhr, and the filter cake is washed with ethyl acetate (50 ml). The organic phase is concentrated under reduced pressure. Further purification is carried out by chromatography [toluene/acetone (8:2)] on a silica gel column. This gives the title compound (5.7 g) as a colorless solid. TLC, silica gel (glass plates), [toluene/acetone (7.5:2.5)], Rf=0.15.

Workup

  1. temperatureunder reflux at 80° C. for 3.5 h
  2. temperatureAfter cooling
  3. filtrationthe reaction mixture is filtered off with suction through kieselguhr
  4. washthe filter cake is washed with ethyl acetate (50 ml)
  5. concentrationThe organic phase is concentrated under reduced pressure
  6. customFurther purification

Sources & evidence

ORD record
ord-d998a1ca5faf4a27a9121acad545c0e5
Source dataset
uspto-grants-2006_09
Patent number
US07101911B2

Reaction notes

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