Triethylamine → (E)-3-(1-Methyl-7-oxo-3-n-propyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-5-yl)-4-n-propoxycinnamic acid t-butyl ester

HRID 21927ノート

反応式

HRID 21927 の反応式
Br[C:2]1[CH:3]=[CH:4][C:5]([O:22][CH2:23][CH2:24][CH3:25])=[C:6]([C:8]2[NH:9][C:10](=[O:21])[C:11]3[N:16]([CH3:17])[N:15]=[C:14]([CH2:18][CH2:19][CH3:20])[C:12]=3[N:13]=2)[CH:7]=1.C(N(CC)CC)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[C:55]([O:59][C:60]([CH3:63])([CH3:62])[CH3:61])(=[O:58])[CH:56]=[CH2:57]>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:60]([O:59][C:55](=[O:58])/[CH:56]=[CH:57]/[C:2]1[CH:3]=[CH:4][C:5]([O:22][CH2:23][CH2:24][CH3:25])=[C:6]([C:8]2[NH:9][C:10](=[O:21])[C:11]3[N:16]([CH3:17])[N:15]=[C:14]([CH2:18][CH2:19][CH3:20])[C:12]=3[N:13]=2)[CH:7]=1)([CH3:63])([CH3:62])[CH3:61]

参加物

7

反応物 4

HCID 8471TriethylamineHCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 1361515895-(5-Bromo-2-propoxyphenyl)-1,6-dihydro-1-methyl-3-propyl-7H-pyrazolo[4,3-d]pyrimidin-7-one

生成物 1

HCID 136331508(E)-3-(1-Methyl-7-oxo-3-n-propyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-5-yl)-4-n-propoxycinnamic acid t-butyl ester収率 378%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 6342Acetonitrile溶媒

実験手順

To a solution of 5-(5-bromo-2-n-propoxyphenyl)-1-methyl-3-n-propyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one (1.0 g, 0.0025 mol) and triethylamine (0.38 g, 0.0038 mol) in acetonitrile (2 ml), was added palladium(II) acetate (0.03 g, 0.00013 mol), tri-o-tolylphosphine (0.076 g, 0.00025 mol) and t-butyl acrylate (0.48 g, 0.00038 mol). The mixture was heated under reflux for 4 hours, then cooled and evaporated under vacuum. The residue was suspended in water (30 ml) and extraction with dichloromethane (3×20 ml) effected. The organic extracts were combined, dried (Na2SO4) and evaporated under vacuum to give a yellow-green solid. Chromatography on silica gel (12 g), using a methanol in dichloromethane elution gradient (0-2% methanol), followed by crystallisation from ethyl acetate-hexane gave the title compound as a white solid (0.65 g, 58%), m.p. 167°-168° C. Found: C,66.47; H,7.00; N,12.31. C25H32N4O4 requires C,66.35; H,7.13; N,12.38%.

後処理

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 4 hours
  3. temperaturecooled
  4. customevaporated under vacuum
  5. extractionextraction with dichloromethane (3×20 ml)
  6. dry with materialdried (Na2SO4)
  7. customevaporated under vacuum
  8. customto give a yellow-green solid
  9. washa methanol in dichloromethane elution gradient (0-2% methanol)
  10. customfollowed by crystallisation from ethyl acetate-hexane

出典と根拠

ORDレコード
ord-06040810ef7e4c14b7ad4f50910b2b76
出典データセット
uspto-grants-1995_06
特許番号
US05426107

反応ノート

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