Perchloric Acid → (S)-ethyl 2-tert-butoxy-2-(6-chloro-7-fluoro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

HRID 514105ノート

反応式

HRID 514105 の反応式
[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[F:12])[C:8]([O:13][S:14]([C:17]([F:20])([F:19])[F:18])(=[O:16])=[O:15])=[C:7]([C@H:21]([OH:27])[C:22]([O:24][CH2:25][CH3:26])=[O:23])[C:6]([CH3:28])=[CH:5]2.Cl(O)(=O)(=O)=O>C(OC(=O)C)(C)(C)C>[C:4]([O:27][C@@H:21]([C:7]1[C:6]([CH3:28])=[CH:5][C:4]2[C:9](=[CH:10][C:11]([F:12])=[C:2]([Cl:1])[CH:3]=2)[C:8]=1[O:13][S:14]([C:17]([F:20])([F:19])[F:18])(=[O:15])=[O:16])[C:22]([O:24][CH2:25][CH3:26])=[O:23])([CH3:9])([CH3:5])[CH3:3]

参加物

4

反応物 2

HCID 24247Perchloric AcidHCID 86691554(S)-ethyl 2-(6-chloro-7-fluoro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-hydroxyacetate

生成物 1

HCID 86691553(S)-ethyl 2-tert-butoxy-2-(6-chloro-7-fluoro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate収率 170.3%

試薬・触媒・溶媒 1

HCID 10908tert-Butyl acetate溶媒

実験手順

To a solution of (S)-ethyl 2-(6-chloro-7-fluoro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-hydroxyacetate (4.44 g, 9.99 mmol) in tert-butylacetate (100 mL) was added 70% perchloric acid (1.20 mL, 19.98 mmol). The reaction mixture was stirred for 2.5 hours and quenched with solid sodium bicarbonate and stirred for 45 minutes. Water and solid sodium bicarbonate were carefully added and stirred for another 15 minutes. The mixture was diluted with ethyl acetate, washed with saturated bicarbonate solution (2×), brine, dried (MgSO4), filtered, concentrated and purified by flash column chromatography (silica gel, 0 to 20% ethyl acetate/hexanes) to give an pale orange oil (4.26 g). 1H NMR (400 MHz, CDCl3) δ: 7.86 (d, J=7.2 Hz, 4H), 7.74 (d, J=10.2 Hz, 4H), 7.58 (s, 4H), 7.26 (s, 3H), 5.69 (s, 4H), 4.26-4.08 (m, 9H), 2.53 (s, 12H), 1.20 (s, 34H), 1.17 (t, J=7.1 Hz, 13H).

後処理

  1. customquenched with solid sodium bicarbonate
  2. stirringstirred for 45 minutes
  3. additionWater and solid sodium bicarbonate were carefully added
  4. stirringstirred for another 15 minutes
  5. additionThe mixture was diluted with ethyl acetate
  6. washwashed with saturated bicarbonate solution (2×), brine
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. custompurified by flash column chromatography (silica gel, 0 to 20% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-2aa4599889ad4e8d85862e08074e48e5
出典データセット
uspto-grants-2015_08
特許番号
US09102614B2

反応ノート

読み込み中…