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

HRID 5487

반응식

HRID 5487 반응식
[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

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매2회HCID 21226206Ethyl acetate hexane용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-7c77004a91ef499285caec4cc6c25cf0
출처 데이터셋
uspto-grants-1993_09
특허 번호
US05244917

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