Triethylamine → 1,1-Dimethylethyl 3-(3-formylphenyl)-2-propenoate

HRID 322969Notes

Reaction equation

HRID 322969 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH:5]=[O:6].[C:10]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])(=[O:13])[CH:11]=[CH2:12].C(N(CC)CC)C.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>CN(C)C=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH:5]([C:4]1[CH:3]=[C:2]([CH:12]=[CH:11][C:10]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH:9]=[CH:8][CH:7]=1)=[O:6]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 15458tert-Butyl acrylateHCID 765833-BromobenzaldehydeHCID 80271Tri-o-tolylphosphine

Product 1

HCID 543870911,1-Dimethylethyl 3-(3-formylphenyl)-2-propenoate

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

To a stirred mixture of 3-bromobenzaldehyde (20 g), tert butyl acrylate (40 mL), triethylamine (44 mL) and tris(2-methylphenyl)phosphine (3.4 g) in dry dimethylformamide (300 mL) is added palladium (II) acetate in one portion. The resulting dark brown mixture is heated at 100° C. for 18 hours then evaporated in vacuo. The residual semi-solid is partitioned between ethyl acetate (250 mL) and 2 N hydrochloric acid (250 mL). the organic phase is washed three times with water (250 mL), dried over magnesium sulphate and evaporated. The resulting dark brown oil (28.1 g) is purified by flash chromatography on silica eluting initially with a mixture of cyclohexane and dichloromethane (4:1 v/v) then with a mixture of cyclohexane and dichloromethane (1:1 v/v). Fractions homogeneous in the required product are combined and evaporated to give tert-butyl 3-(3-formylphenyl)acrylate as a yellow oil (14.08 g).

Workup

  1. customthen evaporated in vacuo
  2. customThe residual semi-solid is partitioned between ethyl acetate (250 mL) and 2 N hydrochloric acid (250 mL)
  3. washthe organic phase is washed three times with water (250 mL)
  4. dry with materialdried over magnesium sulphate
  5. customevaporated
  6. customThe resulting dark brown oil (28.1 g) is purified by flash chromatography on silica eluting initially with a mixture of cyclohexane and dichloromethane (4:1 v/v)
  7. additionwith a mixture of cyclohexane and dichloromethane (1:1 v/v)
  8. customevaporated

Sources & evidence

ORD record
ord-b1bd759e05b64f5285d7d40c604d2e32
Source dataset
uspto-grants-2001_04
Patent number
US06211234B1

Reaction notes

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