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

HRID 514105노트

반응식

HRID 514105 반응식
[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]

참가 물질

4

반응물 2

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

생성물 1

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

시약·촉매·용매 1

HCID 10908tert-Butyl acetate용매

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-2aa4599889ad4e8d85862e08074e48e5
출처 데이터셋
uspto-grants-2015_08
특허 번호
US09102614B2

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