Propiolic Acid → 4-Bromo-3,5-dimethylphenyl propiolate

HRID 1483185Notes

Reaction equation

HRID 1483185 reaction equation
[Br:1][C:2]1[C:7]([CH3:8])=[CH:6][C:5]([OH:9])=[CH:4][C:3]=1[CH3:10].[C:11](O)(=[O:14])[C:12]#[CH:13].C1CCC(N=C=NC2CCCCC2)CC1>C(Cl)Cl.CN(C1C=CN=CC=1)C>[C:11]([O:9][C:5]1[CH:6]=[C:7]([CH3:8])[C:2]([Br:1])=[C:3]([CH3:10])[CH:4]=1)(=[O:14])[C:12]#[CH:13]

Participants

6

Reactant 3

HCID 10110Propiolic AcidHCID 10868DicyclohexylcarbodiimideHCID 819704-Bromo-3,5-dimethylphenol

Product 1

HCID 725452334-Bromo-3,5-dimethylphenyl propiolateYield 51%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of 4-bromo-3,5-dimethylphenol (40.87 g, 203.3 mmol) and propiolic acid (20.91 g, 298.5 mmol) in CH2Cl2 (400 mL) was added DCC (50.78 g, 246.1 mmol) in CH2Cl2 (100 mL) and DMAP (0.82 g, 6.7 mmol) at 0° C. The mixture was stirred at room temperature for 3 h and filtered. The filtrate was concentrated and purified by silica gel column chromatography (hexanes:EtOAc:CH2Cl2=20:1:10). The fractions containing the desired compound were concentrated. To the concentrate added hexane and the precipitated solid was collected by filtration. The solid was washed with hexane and dried to give the title compound 6-1 (26.12 g, 51% yield) as a white solid.

Workup

  1. filtrationfiltered
  2. concentrationThe filtrate was concentrated
  3. custompurified by silica gel column chromatography (hexanes:EtOAc:CH2Cl2=20:1:10)
  4. additionThe fractions containing the desired compound
  5. concentrationwere concentrated
  6. additionTo the concentrate added hexane
  7. filtrationthe precipitated solid was collected by filtration
  8. washThe solid was washed with hexane
  9. customdried

Sources & evidence

ORD record
ord-53954c35f7804a46a5de309dfd918267
Source dataset
uspto-grants-2016_08
Patent number
US09416121B2

Reaction notes

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