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Water → 2-Bromo-5-[(4-methoxyphenyl)sulfonyl]-6-methyl-5,6-dihydrophenanthridine

HRID 2181788
ノート
印刷プレビュー

反応式

HRID 2181788 の反応式
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([S:9]([N:12]2[CH:25]([CH3:26])[C:24]3[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=3)[C:18]3[CH:17]=[CH:16][CH:15]=[CH:14][C:13]2=3)(=[O:11])=[O:10])=[CH:5][CH:4]=1.[Br:27]Br.O.[Cl-].[Na+]>C(O)(=O)C.C(OCC)(=O)C>[Br:27][C:16]1[CH:15]=[CH:14][C:13]2[N:12]([S:9]([C:6]3[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:8][CH:7]=3)(=[O:11])=[O:10])[CH:25]([CH3:26])[C:24]3[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=3)[C:18]=2[CH:17]=1
参加物実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 962WaterHCID 5234Sodium ChlorideHCID 24408BromineHCID 224823645-[(4-Methoxyphenyl)sulfonyl]-6-methyl-5,6-dihydrophenanthridine

生成物 1

HCID 224823332-Bromo-5-[(4-methoxyphenyl)sulfonyl]-6-methyl-5,6-dihydrophenanthridine収率 48.5%

試薬・触媒・溶媒 2

HCID 176
Acetic Acid
溶媒
HCID 8857Ethyl Acetate溶媒

実験手順

A stirred suspension of 5-[(4-methoxyphenyl)sulfonyl]-6-methyl-5,6-dihydrophenanthridine (0.73 g, 2.0 mmol) was heated to 50° C. in glacial acetic acid 20 mL) and treated drop-wise over seven hours with excess bromine (1.92 g, 12 mmol). After cooling to room temperature, the reaction mixture was diluted with ethyl acetate and the precipitate filtered. The organic phase filtrate was washed sequentially with a saturated, aqueous sodium thiosulfate solution, a 1 N hydrochloric acid solution, and water. The organic phase was further washed sequentially with a 2.5 N aqueous sodium hydroxide solution until a basic extract was obtained, water, and a saturated aqueous sodium chloride solution. The organic phase was dried over anhydrous sodium sulfate, filtered through a short column of silica gel, and the solvent removed in vacuo to afford a crude yellow solid (0.75 g, 1.7 mmol, 85%). The crude solid was purified by preparative chromatography on a Biotage® 40 Mi column of pre-packed silica gel (90 g), eluting with a mixture of methyl tert-butyl ether-hexane (15:85) at a flow rate of 40 mL/min to afford, after evaporation of the solvent, a solid. Crystallization of the solid from a mixture of diethyl ether-hexane yielded the title compound (0.43 g, 0.97 mmol, 48%) as a homogeneous, colorless, crystalline solid, m.p. 192-194° C.;

後処理

  1. filtrationthe precipitate filtered
  2. washThe organic phase filtrate was washed sequentially with a saturated, aqueous sodium thiosulfate solution
  3. washThe organic phase was further washed sequentially with a 2.5 N aqueous sodium hydroxide solution until
  4. extractiona basic extract
  5. customwas obtained
  6. dry with materialThe organic phase was dried over anhydrous sodium sulfate
  7. filtrationfiltered through a short column of silica gel
  8. customthe solvent removed in vacuo
  9. customto afford a crude yellow solid (0.75 g, 1.7 mmol, 85%)
  10. customThe crude solid was purified by preparative chromatography on a Biotage® 40 Mi column of pre-packed silica gel (90 g)
  11. washeluting with a mixture of methyl tert-butyl ether-hexane (15:85) at a flow rate of 40 mL/min
  12. customto afford
  13. customafter evaporation of the solvent
  14. customCrystallization of the solid
  15. additionfrom a mixture of diethyl ether-hexane

出典と根拠

ORDレコード
ord-347bb796ae2e49cab7cae096ec386c53
出典データセット
uspto-grants-2005_05
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US06894061B2

反応ノート

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