Methyl Acrylate → 3-(4-Formyl-2,6-dimethyl-phenyl)-acrylic acid methyl ester

HRID 1665905ノート

反応式

HRID 1665905 の反応式
[CH:1]([C:3]1[CH:8]=[C:7]([CH3:9])[C:6](OS(C(F)(F)F)(=O)=O)=[C:5]([CH3:18])[CH:4]=1)=[O:2].C(N(CC)CC)C.[C:26]([O:30][CH3:31])(=[O:29])[CH:27]=[CH2:28]>CN(C=O)C.C(OCC)C.CC([O-])=O.CC([O-])=O.[Pd+2].C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:31][O:30][C:26](=[O:29])[CH:27]=[CH:28][C:6]1[C:7]([CH3:9])=[CH:8][C:3]([CH:1]=[O:2])=[CH:4][C:5]=1[CH3:18]

参加物

8

反応物 3

HCID 7294Methyl AcrylateHCID 8471TriethylamineHCID 544771104-Formyl-2,6-dimethylphenyl trifluoromethanesulfonate

生成物 1

HCID 765393073-(4-Formyl-2,6-dimethyl-phenyl)-acrylic acid methyl ester収率 79.6%

試薬・触媒・溶媒 4

HCID 812191,3-Bis(diphenylphosphino)propane触媒HCID 167845palladium(II) acetate触媒HCID 3283Diethyl Ether溶媒HCID 6228Dimethylformamide溶媒

反応条件

温度
115 °C

実験手順

To a stirred solution of trifluoro-methanesulfonic acid 4-formyl-2,6-dimethyl-phenyl ester (4.7 g, 16.7 mmol) in dry DMF (75 mL) under argon is sequentially added at rt triethylamine (3.4 g, 33.3 mmol), methyl acrylate (14.3 g, 167 mmol), 1,3-bis-(diphenylphosphino)-propane (378 mg, 0.92 mmol) and Pd(OAc)2 (187 mg, 0.83 mmol). The mixture is heated to 115° C. and stirred for 5 h. The mixture is diluted with diethyl ether (350 mL) and washed twice with aq. 1 N HCl and once with sat. aq. NaHCO3. The organic extract is dried over MgSO4, filtered and evaporated. The residue is purified by CC on silica gel eluting with heptane:EA 5:1 to give 3-(4-formyl-2,6-dimethyl-phenyl)-acrylic acid methyl ester (2.9 g) as a slightly yellow solid; LC-MS: tR=0.96 min.

後処理

  1. washwashed twice with aq. 1 N HCl and once with sat. aq. NaHCO3
  2. extractionThe organic extract
  3. dry with materialis dried over MgSO4
  4. filtrationfiltered
  5. customevaporated
  6. customThe residue is purified by CC on silica gel eluting with heptane:EA 5:1

出典と根拠

ORDレコード
ord-62028ba17af4459d848031701abf3eac
出典データセット
uspto-grants-2011_10
特許番号
US08039644B2

反応ノート

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