Pyridine → Methyl 2-trifluoromethanesulfonyloxy-1-naphthoate

HRID 430037

反応式

HRID 430037 の反応式
[F:1][C:2]([F:15])([F:14])[S:3]([O:6]S(C(F)(F)F)(=O)=O)(=[O:5])=[O:4].O[C:17]1[CH:26]=[CH:25][C:24]2[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=2)[C:18]=1[C:27]([O:29][CH3:30])=[O:28].N1C=CC=CC=1.C(OC)(C)(C)C>ClCCl>[F:1][C:2]([F:15])([F:14])[S:3]([O:6][C:17]1[CH:26]=[CH:25][C:24]2[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=2)[C:18]=1[C:27]([O:29][CH3:30])=[O:28])(=[O:5])=[O:4]

参加物

6

反応物 4

HCID 1049PyridineHCID 15413tert-Butyl methyl etherHCID 67749Trifluoromethanesulfonic anhydrideHCID 598533Methyl 2-hydroxy-1-naphthoate

生成物 1

HCID 11034997Methyl 2-trifluoromethanesulfonyloxy-1-naphthoate

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

Trifluoromethanesulfonic anhydride (492 g, 1.74 mol, 1.1 eq) in dichloromethane (0.5 L) was added over 1.5 hours to a suspension of methyl 2-hydroxy-1-naphthoate (319 g, 1.58 mol) and pyridine (330 ml, 4.08 mol, 2.6 eq) in dichloromethane (1.7 L) maintained at an internal temperature between −70 and −50° C., under nitrogen. Once the addition was complete, the mixture was allowed to warm to ambient temperature and stirred for 16 hours, after which time all solids had dissolved. Methyl tert-butyl ether (MTBE, 2.5 L) was added, causing precipitation. The solids were removed by filtration and washed with MTBE (0.5 L). The MTBE solutions were combined and washed with 2 N HCl(aq) (0.3 L then 0.2 L), water (2×2.5 L) and brine (2 L). The organic layer was dried (MgSO4), filtered and concentrated under reduced pressure. The residue was dissolved in toluene (2.5 L) and washed with 1 N NaOH (aq) (0.5 L), water (2.5 L) and brine (1 L). The toluene solution was dried (MgSO4), filtered and concentrated under reduced pressure. Initially a slightly brown oil, the product crystallised on standing. Yield 438.5 g, 83%

後処理

  1. temperaturemaintained at an internal temperature between −70 and −50° C., under nitrogen
  2. additionOnce the addition
  3. dissolutionafter which time all solids had dissolved
  4. customprecipitation
  5. customThe solids were removed by filtration
  6. washwashed with MTBE (0.5 L)
  7. washwashed with 2 N HCl(aq) (0.3 L
  8. dry with materialThe organic layer was dried (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. dissolutionThe residue was dissolved in toluene (2.5 L)
  12. washwashed with 1 N NaOH (aq) (0.5 L), water (2.5 L) and brine (1 L)
  13. dry with materialThe toluene solution was dried (MgSO4)
  14. filtrationfiltered
  15. concentrationconcentrated under reduced pressure
  16. customInitially a slightly brown oil, the product crystallised

出典と根拠

ORDレコード
ord-8d1a33fc017a45e8907533a710981894
出典データセット
uspto-grants-2001_11
特許番号
US06320068B1

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