Ammonium Chloride → Ethyl 4-(1,1-dimethylethylsulfinamido)-4-(2-fluoro-6-methoxyphenyl)-2-methylbutanoate

HRID 594359노트

반응식

HRID 594359 반응식
Br[C:2]1[C:7]([O:8][CH3:9])=[CH:6][CH:5]=[CH:4][C:3]=1[F:10].[Li]CCCC.[C:16]([S:20]([N:22]=[CH:23][CH2:24][CH:25]([CH3:31])[C:26]([O:28][CH2:29][CH3:30])=[O:27])=[O:21])([CH3:19])([CH3:18])[CH3:17].[NH4+].[Cl-]>C1COCC1.O.CCOCC>[CH3:18][C:16]([CH3:19])([S:20]([NH:22][CH:23]([C:2]1[C:7]([O:8][CH3:9])=[CH:6][CH:5]=[CH:4][C:3]=1[F:10])[CH2:24][CH:25]([CH3:31])[C:26]([O:28][CH2:29][CH3:30])=[O:27])=[O:21])[CH3:17]

참가 물질

8

반응물 4

HCID 25517Ammonium ChlorideHCID 27793182-Bromo-3-fluoroanisoleHCID 86695624Ethyl 4-((tert-butylsulfinyl)imino)-2-methylbutanoateHCID 178418339Butyllithium

생성물 1

HCID 69083866Ethyl 4-(1,1-dimethylethylsulfinamido)-4-(2-fluoro-6-methoxyphenyl)-2-methylbutanoate

시약·촉매·용매 3

HCID 962Water용매HCID 3283Diethyl Ether용매HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
-78 °C

실험 절차

A cooled (−78° C.) solution of commercially available 2-bromo-1-fluoro-3-methoxybenzene (2.642 g; 12.90 mmol) in anh. THF (60 ml), under nitrogen, was treated dropwise with a solution of 1.6 M n-BuLi in hexanes (8.05 ml; 12.90 mmol). The resulting solution was further stirred at −78° C. for 5 min. A solution of ethyl 4-((tert-butylsulfinyl)imino)-2-methylbutanoate (2.550 g; 10.30 mmol) in anh. THF (20 ml) was then added dropwise to the cooled reaction mixture, and stirring at −78° C. was continued for 45 min. The resulting reaction mixture was treated successively with aq. sat. NH4Cl (75 ml), Et2O (250 ml) and water (75 ml). The separated organic layer was then washed with brine (75 ml), dried over anh. MgSO4, filtered, and concentrated to dryness under reduced pressure. Purification by FC (DCM/MeOH=30/1) afforded ethyl 4-(1,1-dimethylethylsulfinamido)-4-(2-fluoro-6-methoxyphenyl)-2-methylbutanoate as a yellow oil. LC-MS (conditions A): tR=0.81 min. and [M+H]+: 374.02 g/mol; tR=0.83 min. and [M+H]+: 374.34 g/mol (mixture of diastereoisomers).

후처리

  1. stirringstirring at −78° C.
  2. waitwas continued for 45 min
  3. customThe resulting reaction mixture
  4. washThe separated organic layer was then washed with brine (75 ml)
  5. dry with materialdried over anh. MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated to dryness under reduced pressure
  8. customPurification by FC (DCM/MeOH=30/1)

출처 및 근거

ORD 기록
ord-2ffc6aca81ad43f49d783b71c6c28723
출처 데이터셋
uspto-grants-2016_01
특허 번호
US09242970B2

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