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Beta-Lapachone → 5-(acetyloxy)-2,2-dimethyl-3,4-dihydro-2H-benzo[h]chromen-6-yl N-(tert-butoxycarbonyl)glycinate

HRID 1914987
ノート
印刷プレビュー

反応式

HRID 1914987 の反応式
[CH3:1][C:2]1([CH3:18])[CH2:11][CH2:10][C:9]2[C:8](=[O:12])[C:7](=[O:13])[C:6]3[CH:14]=[CH:15][CH:16]=[CH:17][C:5]=3[C:4]=2[O:3]1.[O-]S(S([O-])=O)=O.[Na+].[Na+].[C:27]([O:31][C:32]([NH:34][CH2:35][C:36]([OH:38])=O)=[O:33])([CH3:30])([CH3:29])[CH3:28].C(N([CH2:44][CH3:45])CC)C.CN(C([O:53]N1N=NC2C=CC=CC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F>[Zn].CCOC(C)=O.CN(C=O)C>[C:27]([O:31][C:32]([NH:34][CH2:35][C:36]([O:13][C:7]1[C:8]([O:12][C:44](=[O:53])[CH3:45])=[C:9]2[C:4](=[C:5]3[CH:17]=[CH:16][CH:15]=[CH:14][C:6]=13)[O:3][C:2]([CH3:18])([CH3:1])[CH2:11][CH2:10]2)=[O:38])=[O:33])([CH3:28])([CH3:29])[CH3:30]
参加物実験手順後処理出典と根拠反応ノート

参加物

9

反応物 5

HCID 3885Beta-LapachoneHCID 8471TriethylamineHCID 24489Sodium DithioniteHCID 78288N-(tert-butoxycarbonyl)glycineHCID 2733084Methanaminium, N-((1H-benzotriazol-1-yloxy)(dimethylamino)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)

生成物 1

HCID 59514379
5-(acetyloxy)-2,2-dimethyl-3,4-dihydro-2H-benzo[h]chromen-6-yl N-(tert-butoxycarbonyl)glycinate
収率 60%

試薬・触媒・溶媒 3

HCID 23994Zinc触媒2 回HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A mixture of zinc dust (6.0 g, 91.7 mmol), 2,2-dimethyl-3,4-dihydro-2H-benzo[h]chromene-5,6-dione (6.0 g, 24.8 mmol), Na2S2O4 (17.26 g, 99.1 mmol), N-(tert-butoxycarbonyl)glycine (8.77 g, 49.6 mmol), triethylamine (3.1 mL, 22.3 mmol), HBTU (18.79 g, 49.6 mmol) and DMF (100 mL) is stirred for 16 hours at room temperature. To the reaction mixture is then added EtOAc (300 mL). The reaction is filtered and the filtrate washed with H2O (4×200 mL). The organic extract is dried with Na2SO4 and concentrated under reduced pressure. The residue is dissolved in acetic anhydride (30 mL) followed by the addition of zinc dust (3.0 g, 45.9 mmol) and thriethylamine (3.35 mL, 24.0 mmol). The reaction is heated at 90° C. with vigorous stirring and held for 2 hours. The reaction is allowed to cool and the solvent removed under reduced pressure. The residue is dissolved in EtOAc (200 mL) and washed with water (2×100 mL). The organic extract is dried with Na2SO4 and concentrated under reduced pressure. The crude product is purified by flash column chromatography (SiO2, 2% EtOAc in dichloromethane) to afford about 60% pure final product. Crystallization of the partly pure solid from EtOAc/Hexane gives the desired product as pure white solid (3.2 g, 31%). M.p.=177° C.; 400 MHz 1H NMR (CDCl3) δ: 8.21 (d, J=8.4 Hz, 1H), 7.67 (d, J=8.4 Hz, 1H), 7.46 (m, 2H), 5.13 (br. s, 1H), 4.30 (d, J=5.6 Hz, 2H), 2.68 (t, J=6.6 Hz, 2H), 2.38 (s, 3H), 1.87 (t, J=6.6 Hz, 2H), 1.48 (s, 9H), 1.42 (s, 6H); LCMS: 444 [M+H]; Calc. for C24H29NO7: C, 64.94; H, 6.59; N, 3.16; Found C 64.98, H 6.51, N 3.15.

後処理

  1. filtrationThe reaction is filtered
  2. washthe filtrate washed with H2O (4×200 mL)
  3. extractionThe organic extract
  4. dry with materialis dried with Na2SO4
  5. concentrationconcentrated under reduced pressure
  6. dissolutionThe residue is dissolved in acetic anhydride (30 mL)
  7. temperatureThe reaction is heated at 90° C.
  8. stirringwith vigorous stirring
  9. waitheld for 2 hours
  10. temperatureto cool
  11. customthe solvent removed under reduced pressure
  12. dissolutionThe residue is dissolved in EtOAc (200 mL)
  13. washwashed with water (2×100 mL)
  14. extractionThe organic extract
  15. dry with materialis dried with Na2SO4
  16. concentrationconcentrated under reduced pressure
  17. customThe crude product is purified by flash column chromatography (SiO2, 2% EtOAc in dichloromethane)

出典と根拠

ORDレコード
ord-4b8987146a4f41d2af4325c7ea2369ca
出典データセット
uspto-grants-2013_12
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08614228B2

反応ノート

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