Cesium carbonate → 4-Benzyloxy-3-[(4-(methoxycarbonylmethyl)thio-3,5,6-trifluoropyridin-2-yl)oxy]benzonitrile

HRID 324992

反応式

HRID 324992 の反応式
F[C:2]1[N:7]=[C:6]([F:8])[C:5]([F:9])=[C:4](F)[C:3]=1[F:11].[C:12]([O:16][CH3:17])(=[O:15])[CH2:13][SH:14].C(=O)([O-])[O-].[Cs+].[Cs+].[CH2:24]([O:31][C:32]1[CH:37]=[CH:36][C:35]([C:38]#[N:39])=[CH:34][C:33]=1[OH:40])[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.[OH-].[K+]>C(#N)C.C(OCC)(=O)C>[CH2:24]([O:31][C:32]1[CH:37]=[CH:36][C:35]([C:38]#[N:39])=[CH:34][C:33]=1[O:40][C:2]1[C:3]([F:11])=[C:4]([S:14][CH2:13][C:12]([O:16][CH3:17])=[O:15])[C:5]([F:9])=[C:6]([F:8])[N:7]=1)[C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1

参加物

8

反応物 5

HCID 10796Cesium carbonate2 回HCID 14797Potassium HydroxideHCID 16907Methyl ThioglycolateHCID 69690PentafluoropyridineHCID 154534514-(Benzyloxy)-3-hydroxybenzonitrile

生成物 1

HCID 220017604-Benzyloxy-3-[(4-(methoxycarbonylmethyl)thio-3,5,6-trifluoropyridin-2-yl)oxy]benzonitrile収率 56.2%

試薬・触媒・溶媒 2

HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a solution of pentafluoropyridine (1.9 g, 11.2 mmol) in acetonitrile (25 mL) at 0° C. was added methyl thioglycolate (1.0 mL, 11.2 mmol) and cesium carbonate (4.4 g, 13.5 mmol). The resultant mixture was allowed to warm slowly to ambient temperature and stirred for 16 hours. To the mixture was added 2-benzyloxy-5-cyanophenol (2.6 g, 11.5 mmol) and cesium carbonate (4.4 g, 13.5 mmol). The resultant mixture was stirred at 40° C. for 16 hours. The mixture was then cooled to ambient temperature and poured into 150 mL of 0.5 M aqueous KOH solution and 150 mL of ethyl acetate. The organic layer was separated and washed further with 150 mL of 0.5 M aqueous KOH solution, then brine (150 mL), dried over MgSO4, filtered, and concentrated in vacuo to afford a yellow oil. Purification by flash chromatography on silica gel afforded 2.9 g (56% yield) of 4-benzyloxy-3-[(4-(methoxycarbonylmethyl)thio-3,5,6-trifluoropyridin-2-yl)oxy]benzonitrile, a compound of formula (E), as a pale yellow oil: NMR (CDCl3) 7.5-7.0 (m, 8), 5.1 (s, 2), 3.8 (s, 2), 3.7 (s, 3) ppm.

後処理

  1. temperatureThe mixture was then cooled to ambient temperature
  2. customThe organic layer was separated
  3. washwashed further with 150 mL of 0.5 M aqueous KOH solution
  4. dry with materialbrine (150 mL), dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto afford a yellow oil
  8. customPurification by flash chromatography on silica gel

出典と根拠

ORDレコード
ord-55d63ad679ef40f896e7fd7627d542ae
出典データセット
uspto-grants-2001_04
特許番号
US06221886B1

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