Diethyl (cyanomethyl)phosphonate → 3-[3-(5-Isopropyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidin-4-yloxy)-5-methyl-phenyl]-acrylonitrile

HRID 426205ノート

反応式

HRID 426205 の反応式
[CH:1]([C:4]1[C:9](=[O:10])[NH:8][C:7](=[O:11])[NH:6][C:5]=1[O:12][C:13]1[CH:14]=[C:15]([CH:18]=[C:19]([CH3:21])[CH:20]=1)[CH:16]=O)([CH3:3])[CH3:2].[C:22]([CH2:24]P(=O)(OCC)OCC)#[N:23].CC(C)([O-])C.[K+]>C1COCC1.CC(=O)OCC>[CH:1]([C:4]1[C:9](=[O:10])[NH:8][C:7](=[O:11])[NH:6][C:5]=1[O:12][C:13]1[CH:14]=[C:15]([CH:16]=[CH:24][C:22]#[N:23])[CH:18]=[C:19]([CH3:21])[CH:20]=1)([CH3:3])[CH3:2]

参加物

6

反応物 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 23665647Potassium tert-butoxideHCID 591848043-(5-Isopropyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidin-4-yloxy)-5-methyl-benzaldehyde

生成物 1

HCID 667053313-[3-(5-Isopropyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidin-4-yloxy)-5-methyl-phenyl]-acrylonitrile収率 40%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a stirred mixture of 3-(5-isopropyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidin-4-yloxy)-5-methyl-benzaldehyde (788 mg, 2.73 mmol) and diethyl cyanomethyl-phosphonate (451 μl, 2.79 mmol) in THF (15 ml) at 0° C. (ice bath) under nitrogen atmosphere, was added potassium t-butoxide (920 mg, 8.2 mmol). After stirring for 1 hr., the mixture was stirred for overnight at room temperature. The mixture was then diluted with EA, washed with aqueous saturated ammonium chloride solution, dried with anhydrous magnesium sulfate, filtered, and evaporated in vacuo. The residue was purified by silica gel column chromatography (eluent, EA: hexanes (from 2:3 to 1:1)) to afford 340 mg (40%) of a white solid. m.p. 279-280° C.; 1H NMR (200 MHz, DMSO-d6) δ 1.05 (6H, d, J=7.0 Hz), 2.33 (3H, s), 2.78 (1H, m), 6.55 (1H, d, J=16.8 Hz), 7.03 (1H, s), 7.21 (1H, s), 7.25 (1H, s), 7.62 (1H, d, J=16.8 Hz), 11.05 (1H, s), 11.31 (1H, s); m/z (LC/Mass, EI) 312 (M+H+).

後処理

  1. stirring, the mixture was stirred for overnight at room temperature
  2. washwashed with aqueous saturated ammonium chloride solution
  3. dry with materialdried with anhydrous magnesium sulfate
  4. filtrationfiltered
  5. customevaporated in vacuo
  6. customThe residue was purified by silica gel column chromatography (eluent, EA: hexanes (from 2:3 to 1:1))

出典と根拠

ORDレコード
ord-7c44d2027ac443f48f09c0c3ee48756a
出典データセット
uspto-grants-2012_01
特許番号
US08106064B2

反応ノート

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