Methyl acetoacetate → 4-Hydroxy-6,6-diphenethyl-5,6-dihydro-pyran-2-one

HRID 356522

反応式

HRID 356522 の反応式
[H-].[Na+].[C:3](OC)(=[O:8])[CH2:4][C:5]([CH3:7])=[O:6].C([Li])CCC.[C:16]1([CH2:22][CH2:23][C:24](=[O:33])[CH2:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>C1COCC1.O>[OH:6][C:5]1[CH2:7][C:24]([CH2:23][CH2:22][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)([CH2:25][CH2:26][C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)[O:33][C:3](=[O:8])[CH:4]=1

参加物

7

反応物 4

HCID 7757Methyl acetoacetateHCID 214961,5-Diphenylpentan-3-oneHCID 24758Sodium hydrideHCID 178418339Butyllithium

生成物 1

HCID 547115454-Hydroxy-6,6-diphenethyl-5,6-dihydro-pyran-2-one

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

Freshly distilled THF (25 mL) was cooled in an ice bath under a nitrogen atmosphere, then charged with 660 mg (16.5 mmol) sodium hydride (60% dispersion). This suspension was treated with 1.89 g (16.3 mmol) methyl acetoacetate dropwise, and the reaction was stirred for 10 minutes. n-Butyllithium (10.3 mL of 1.6M in hexanes; 16.5 mmol) was dripped in and the reaction was stirred 30 minutes. At this time 3.10 g (13 mmol) of 1,5-diphenyl-3-pentanone (Ram and Spicer, Tetrahedrom Lett., 1988, 29 (31), 3741) in 20 mL THF was added dropwise over 15 minutes. After 4 hours 100 mL H2O was added and the reaction stirred overnight. The reaction was extracted with diethyl ether, and the organics set aside. The aqueous layer was chilled, treated with 50% HOAc until a precipitate formed, and then extracted with EtOAc. These organics were washed with saturated brine, dried (Na2SO4), and concentrated. 1H NMR (DMSO-d6) δ 2.0 (d of d, 4 H), 2.65 (m, 6 H), 5.0 (s, 1 H), 7.15-7.35 (m, 10 H), 11.4 (bs, 1 H).

後処理

  1. stirringwas stirred 30 minutes
  2. stirringthe reaction stirred overnight
  3. extractionThe reaction was extracted with diethyl ether
  4. temperatureThe aqueous layer was chilled
  5. additiontreated with 50% HOAc until a precipitate
  6. customformed
  7. extractionextracted with EtOAc
  8. washThese organics were washed with saturated brine
  9. dry with materialdried (Na2SO4)
  10. concentrationconcentrated

出典と根拠

ORDレコード
ord-39ad07d5e0ba49a1a03f0075c416c642
出典データセット
uspto-grants-1998_11
特許番号
US05834506

関連ノート

読み込み中…