Methyl Acrylate → 3-(2-Methyl-pyrimidin-5-yl)-acrylic acid methyl ester

HRID 705973ノート

反応式

HRID 705973 の反応式
Br[C:2]1[CH:3]=[N:4][C:5]([CH3:8])=[N:6][CH:7]=1.[C:9]([O:13][CH3:14])(=[O:12])[CH:10]=[CH2:11].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[CH3:14][O:13][C:9](=[O:12])[CH:10]=[CH:11][C:2]1[CH:3]=[N:4][C:5]([CH3:8])=[N:6][CH:7]=1

参加物

7

反応物 4

HCID 7294Methyl AcrylateHCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 143877445-Bromo-2-methylpyrimidine

生成物 1

HCID 677728483-(2-Methyl-pyrimidin-5-yl)-acrylic acid methyl ester収率 16.8%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒

反応条件

温度
150 °C

実験手順

A sealed mixture of 5-Bromo-2-methyl-pyrimidine (2.6 g, 15.03 mmol, 1 eq), methyl acrylate (1.40 eq, 1.89 ml), palladium(II)-acetate (0.013 eq, 44 mg), triphenylphosphine (0.024 eq, 95 mg), and triethylamine (1.21 eq, 2.54 ml) was heated at 150° C. (temperature on display of heating device) for 16 hours. The mixture was cooled to ambient temperature and was poured into 200 ml of water. Organic substances were extracted with EtOAc (twice, 200 ml was used in total). The gathered EtOAc layers were filtered over celite pad, were dried and the solvent was evaporated. The resulting crude was purified by chromatography on BIOTAGE SP1 purification device using 50 g normal phase silica SNAP column and EtOAc/cyclohexane solvent system (gradient 30-80% of EtOAc in 20 column volumes). Solvent from the gathered fractions of appropriate composition was evaporated and obtained was 3-(2-Methyl-pyrimidin-5-yl)-acrylic acid methyl ester (450 mg, yield=16.80%, purity=95%). MS: [M+H]+=179.13 1H NMR (300 MHz; CDCl3) δ/ppm 2.74 (s, 3H), 3.81 (s, 3H), 6.52 (d, J=16.60 Hz, 1H), 7.58 (d, J=16.60 Hz, 1H), 8.75 (s, 2H)

後処理

  1. temperature(temperature on display of heating device) for 16 hours
  2. temperatureThe mixture was cooled to ambient temperature
  3. extractionOrganic substances were extracted with EtOAc (twice, 200 ml
  4. filtrationThe gathered EtOAc layers were filtered over celite pad
  5. customwere dried
  6. customthe solvent was evaporated
  7. customThe resulting crude was purified by chromatography on BIOTAGE SP1 purification device
  8. customSolvent from the gathered fractions of appropriate composition was evaporated
  9. customobtained

出典と根拠

ORDレコード
ord-4e3e7989914a49bb82a1e93f3823651a
出典データセット
uspto-grants-2015_11
特許番号
US09174968B2

反応ノート

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