Triethyl phosphite → (E)-Ethyl 3-(dimethylamino)-5-(4-(methoxymethoxy)-3,5-dimethylstyryl)benzoate

HRID 2368875ノート

反応式

HRID 2368875 の反応式
Cl[CH2:2][C:3]1[CH:4]=[C:5]([CH:11]=[C:12]([N:14]([CH3:16])[CH3:15])[CH:13]=1)[C:6]([O:8][CH2:9][CH3:10])=[O:7].C(OP(OCC)OCC)C.C[O-].[Na+].[CH3:30][O:31][CH2:32][O:33][C:34]1[C:41]([CH3:42])=[CH:40][C:37]([CH:38]=O)=[CH:36][C:35]=1[CH3:43]>CCOC(C)=O.CCO.CN(C=O)C>[CH3:15][N:14]([CH3:16])[C:12]1[CH:11]=[C:5]([CH:4]=[C:3](/[CH:2]=[CH:38]/[C:37]2[CH:40]=[C:41]([CH3:42])[C:34]([O:33][CH2:32][O:31][CH3:30])=[C:35]([CH3:43])[CH:36]=2)[CH:13]=1)[C:6]([O:8][CH2:9][CH3:10])=[O:7]

参加物

8

反応物 4

HCID 31215Triethyl phosphiteHCID 10942334Sodium MethoxideHCID 199197474-(Methoxymethoxy)-3,5-dimethylbenzaldehydeHCID 68335175Ethyl 3-(chloromethyl)-5-(dimethylamino)benzoate

生成物 1

HCID 68335176(E)-Ethyl 3-(dimethylamino)-5-(4-(methoxymethoxy)-3,5-dimethylstyryl)benzoate収率 67.1%

試薬・触媒・溶媒 3

HCID 702Ethanol溶媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

Compound 3 (1.224 g, 4.277 mmol) and triethylphosphite (1.512 mL, 8.555 mmol) were heated to 150° C. for 3 hours. The reaction mixture was cooled to 0° C. and then 6 mL of DMF and 6 mL of EtOH were added. NaOMe (486 mg, 8.554 mmol) and 4-(methoxymethoxy)-3,5-dimethylbenzaldehyde (0.831 g, 4.277 mmol) were added to the solution. After 18 hours, the mixture was diluted with EtOAc and the solution was washed with brine. After drying on Na2SO4, the organic layer was filtered and concentrated under reduced pressure. The residue was subjected to chromatography over silica gel (Hexanes/EtOAc=9/1) to give Compound 4 (1.10 g, 67%). 1H-NMR (500 MHz, CDCl3) δ 7.56 (s, 1H), 7.30 (m, 1H), 7.20 (s, 2H), 7.06 (d, J=16.3 Hz, 1H), 6.99 (d, J=16.3 Hz, 1H), 6.97 (s, 1H), 4.96 (s, 2H), 4.39 (q, J=7.1 Hz, 2H), 3.62 (s, 3H), 3.03 (s, 6H), 2.32 (s, 6H), 1.42 (t, J=7.1 Hz, 3H); 13C-NMR (125 MHz, CDCl3) δ 167.23, 154.65, 150.72, 138.36, 133.12, 131.48, 131.24, 128.70, 127.78, 127.07, 115.70, 114.53, 112.47, 99.11, 60.92, 57.39, 40.65, 16.99, 14.40; ESI-MS: m/z (MH+): 384.2169 (calc'd), 384.2173 (found).

後処理

  1. washthe solution was washed with brine
  2. customAfter drying on Na2SO4
  3. filtrationthe organic layer was filtered
  4. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-ef0868bad66a4a21addde9927a991964
出典データセット
uspto-grants-2014_04
特許番号
US08703815B2

反応ノート

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