Malononitrile → 2-Amino-4-benzyl-3-cyano-5-hydroxynaphtho[1,2-b]furan

HRID 5487

反応式

HRID 5487 の反応式
[H-].[K+].CCCCCC.[C:9](#[N:13])[CH2:10][C:11]#[N:12].[CH2:14]([C:21]1[C:22](=[O:32])[C:23]2[C:28]([C:29](=[O:31])[CH:30]=1)=[CH:27][CH:26]=[CH:25][CH:24]=2)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>O1CCCC1.CCCCCC.C(OCC)(=O)C>[NH2:12][C:11]1[O:31][C:29]2[C:28]3[C:23]([C:22]([OH:32])=[C:21]([CH2:14][C:15]4[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=4)[C:30]=2[C:10]=1[C:9]#[N:13])=[CH:24][CH:25]=[CH:26][CH:27]=3

参加物

7

反応物 4

HCID 8010MalononitrileHCID 8058HexaneHCID 82127Potassium hydrideHCID 30156581,4-Naphthalenedione, 2-(phenylmethyl)-

生成物 1

HCID 97968872-Amino-4-benzyl-3-cyano-5-hydroxynaphtho[1,2-b]furan収率 38%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 21226206Ethyl acetate hexane溶媒

実験手順

A mixture of potassium hydride (7.56 g, 63 mmol, 35% oil dispersion) and hexane (250ml) was stirred at room temperature under nitrogen. Solvent was decanted off and substituted with dry tetrahydrofuran (250ml). Malononitrile (4.16 g, 63 mmol), dissolved in tetrahydrofuran (50 ml), was then added to the slurry dropwise. A mixture of 2-benzyl-1,4-naphthoquinone (15.62 g, 63 mmol) and tetrahydrofuran (50 ml) was then added dropwise. The reaction mixture was set at reflux for 2h, allowed to cool to room temperature and quenched with methanol (50 ml). The mixture was poured into water (100 ml) and extracted into ethyl acetate (3 x 250 ml). The organic layer was dried (magnesium sulfate) and evaporated to an oil. Chromatography (silica gel: hexane/ethyl acetate (2 : 1) as eluant) of the oily residue afforded 7.48 g (23 mmol, 38%) of product as green crystals, m.p. 224°-225 ° C.; 1H NMR (d6DMSO): 4.5(s,2H), 7.1-7.6 (m, 7H), 7.9(d, 1H), 9.25(s, 1H); IR (nujol): 3460, 3310, 3240, 3190, 2220; High resolution mass spectrum: calculated 314.1055, measured 314.1061.

後処理

  1. customSolvent was decanted off
  2. additionwas then added to the slurry dropwise
  3. additionwas then added dropwise
  4. temperatureto cool to room temperature
  5. customquenched with methanol (50 ml)
  6. additionThe mixture was poured into water (100 ml)
  7. extractionextracted into ethyl acetate (3 x 250 ml)
  8. dry with materialThe organic layer was dried (magnesium sulfate)
  9. customevaporated to an oil

出典と根拠

ORDレコード
ord-7c77004a91ef499285caec4cc6c25cf0
出典データセット
uspto-grants-1993_09
特許番号
US05244917

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