Pyridine → 2-(3,4,5-Trimethoxyphenyl)-2,3-dihydro-benzo[H]chromen-4-one

HRID 1869558

反応式

HRID 1869558 の反応式
[CH3:1][C:2]([C:4]1[CH:13]=[CH:12][C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]=1[OH:14])=[O:3].[CH3:15][O:16][C:17]1[CH:18]=[C:19]([CH:22]=[C:23]([O:27][CH3:28])[C:24]=1[O:25][CH3:26])[CH:20]=O.N1CCCCC1.N1C=CC=CC=1>C(O)C>[CH3:28][O:27][C:23]1[CH:22]=[C:19]([CH:20]2[CH2:1][C:2](=[O:3])[C:4]3[C:5](=[C:6]4[CH:7]=[CH:8][CH:9]=[CH:10][C:11]4=[CH:12][CH:13]=3)[O:14]2)[CH:18]=[C:17]([O:16][CH3:15])[C:24]=1[O:25][CH3:26]

参加物

6

反応物 4

HCID 1049PyridineHCID 68583,4,5-TrimethoxybenzaldehydeHCID 8082PiperidineHCID 697331'-Hydroxy-2'-acetonaphthone

生成物 1

HCID 100443052-(3,4,5-Trimethoxyphenyl)-2,3-dihydro-benzo[H]chromen-4-one収率 39%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

実験手順

A mixture of 1-hydroxy-2-acetonaphthone 1 (15 g, 81 mmol) and 3,4,5-trimethoxy-benzaldehyde 2 (17.66 g, 88 mmol) in 600 mL ethanol was treated with piperidine (40 mL) and pyridine (45 mL) and the dark solution was refluxed for 18 h. The reaction mixture was evaporated to dryness and the dark residue was dissolved in methylene chloride (600 mL). The solution was washed with 2×300 mL of water and 2×300 mL brine and dried with anhydrous MgSO4 after which it was filtered and evaporated to afford 60 g of crude material. This was purified via flash chromatography, eluting with methylene chloride (1 L), followed by the solvent mixture CH2Cl2: EtOAc (95:5) to obtain fractions containing pure product. These were evaporated to afford 11.4 g (39% yield) of pure SR 13177 as a yellow solid. TLC: Hexanes/EtOAc (7:3): Rf=0.26; 1H NMR (300 MHz, CDCl3): δ 3.00 (dd, J=16.69, 3.15, 1H, 3-H), 3.22 (dd, J=16.94, 13.28, 1H, 3-H), 3.92 and 3.94 (2s, 9H, OCH3), 5.66 (dd, J=13.31, 3.17, 1H, 2-H), 6.81 (s, 2H, 2′,6′-Ar—H), 7.46-7.95 (m, 5H, Ar—H), 8.36 (d, 1H, Ar—H); 13C (75 MHz, CDCl3): δ 44.27 (C-3), 56.35 (OCH3), 60.89 (OCH3), 80.62 (C-2), 103.49, 115.61, 121.47, 123.61, 124.91, 126.34, 127.94, 129.71, 134.4, 137.67, 153.68, 159.71, 191.42. Anal. calcd. for C22H20O5; C, 72.51; H, 5.53; Found: C, 72.35; H, 5.64.

後処理

  1. temperaturethe dark solution was refluxed for 18 h
  2. customThe reaction mixture was evaporated to dryness
  3. dissolutionthe dark residue was dissolved in methylene chloride (600 mL)
  4. washThe solution was washed with 2×300 mL of water and 2×300 mL brine
  5. dry with materialdried with anhydrous MgSO4 after which it
  6. filtrationwas filtered
  7. customevaporated
  8. customto afford 60 g of crude material
  9. customThis was purified via flash chromatography
  10. washeluting with methylene chloride (1 L)
  11. customto obtain fractions
  12. additioncontaining pure product
  13. customThese were evaporated

出典と根拠

ORDレコード
ord-41e4306fa6a34dcba4eeec399770b780
出典データセット
uspto-grants-2009_12
特許番号
US07638554B2

関連ノート

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