Water → Perfluorophenyl 3-chloroisoquinoline-6-sulfonate

HRID 1473386ノート

反応式

HRID 1473386 の反応式
C([S:8][C:9]1[CH:10]=[C:11]2[C:16](=[CH:17][CH:18]=1)[CH:15]=[N:14][C:13]([Cl:19])=[CH:12]2)C1C=CC=CC=1.ClN1C(C)(C)C(=[O:28])N(Cl)C1=O.[F:31][C:32]1[C:37]([F:38])=[C:36]([F:39])[C:35]([F:40])=[C:34]([F:41])[C:33]=1[OH:42].C(N(CC)CC)C.[OH2:50]>CCOC(C)=O.C(O)(=O)C.C(#N)C>[Cl:19][C:13]1[N:14]=[CH:15][C:16]2[C:11]([CH:12]=1)=[CH:10][C:9]([S:8]([O:42][C:33]1[C:32]([F:31])=[C:37]([F:38])[C:36]([F:39])=[C:35]([F:40])[C:34]=1[F:41])(=[O:28])=[O:50])=[CH:18][CH:17]=2

参加物

9

反応物 5

HCID 962WaterHCID 83601,3-Dichloro-5,5-dimethylhydantoinHCID 8471TriethylamineHCID 13041PentafluorophenolHCID 866874276-(Benzylthio)-3-chloroisoquinoline

生成物 1

HCID 86687428Perfluorophenyl 3-chloroisoquinoline-6-sulfonate収率 87%

試薬・触媒・溶媒 3

HCID 176Acetic Acid溶媒HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A round-bottom flask was charged with 6-(benzylthio)-3-chloroisoquinoline (1.363 g, 4.77 mmol), acetonitrile (44.9 ml), and acetic acid (1.683 ml) to give a suspension. The flask was sonicated for 10 min to give an opaque yellow mixture. Water (1.122 ml) was added, and the mixture became a thin suspension. The flask was cooled in an ice-water bath for 20 min, then 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (1.879 g, 9.54 mmol) was added in one portion, resulting in the formation of a clear solution within 20 sec. After 15 min, 2,3,4,5,6-pentafluorophenol (1.756 g, 9.54 mmol) and triethylamine (2.66 ml, 19.08 mmol) were added in sequence. After another 25 min of stirring, the mixture was diluted with EtOAc (50 mL) and washed with water (2×50 ml), washed with brine, dried over sodium sulfate, filtered, and concentrated. The residue was dissolved in DCM and purified by chromatography on silica gel (40-g column, 25-g silica gel loading column, 0 to 30% EtOAc/Heptane) to give perfluorophenyl 3-chloroisoquinoline-6-sulfonate (1.69522 g, 4.14 mmol, 87% yield) as a clear oil contaminated with some pentafluorophenol: m/z (ESI) 286.2 (M+H)+.

後処理

  1. customto give a suspension
  2. customThe flask was sonicated for 10 min
  3. customto give an opaque yellow mixture
  4. temperatureThe flask was cooled in an ice-water bath for 20 min
  5. customresulting in the formation of a clear solution within 20 sec
  6. washwashed with water (2×50 ml)
  7. washwashed with brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. dissolutionThe residue was dissolved in DCM
  12. custompurified by chromatography on silica gel (40-g column, 25-g silica gel loading column, 0 to 30% EtOAc/Heptane)

出典と根拠

ORDレコード
ord-acd7845b643f457e974c0f939033871f
出典データセット
uspto-grants-2015_04
特許番号
US09012443B2

反応ノート

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