Ammonium Chloride → Ethyl 4-(2,4-dimethoxypyridin-3-yl)-4-(1,1-dimethylethylsulfinamido)-2-methylbutanoate

HRID 594361ノート

反応式

HRID 594361 の反応式
Br[C:2]1[C:3]([O:10][CH3:11])=[N:4][CH:5]=[CH:6][C:7]=1[O:8][CH3:9].[Li]CCCC.[C:17]([S:21]([N:23]=[CH:24][CH2:25][CH:26]([CH3:32])[C:27]([O:29][CH2:30][CH3:31])=[O:28])=[O:22])([CH3:20])([CH3:19])[CH3:18].[NH4+].[Cl-]>C1COCC1.O.CCOCC>[CH3:11][O:10][C:3]1[C:2]([CH:24]([NH:23][S:21]([C:17]([CH3:19])([CH3:18])[CH3:20])=[O:22])[CH2:25][CH:26]([CH3:32])[C:27]([O:29][CH2:30][CH3:31])=[O:28])=[C:7]([O:8][CH3:9])[CH:6]=[CH:5][N:4]=1

参加物

8

反応物 4

HCID 25517Ammonium ChlorideHCID 134797643-Bromo-2,4-dimethoxypyridineHCID 86695624Ethyl 4-((tert-butylsulfinyl)imino)-2-methylbutanoateHCID 178418339Butyllithium

生成物 1

HCID 69082487Ethyl 4-(2,4-dimethoxypyridin-3-yl)-4-(1,1-dimethylethylsulfinamido)-2-methylbutanoate

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

A cooled (−78° C.) solution of commercially available 3-bromo-2,4-dimethoxypyridine (1.390 g; 5.74 mmol) in anh. THF (70 ml), under nitrogen, was treated dropwise with a solution of 1.6 M n-BuLi in hexanes (3.60 ml; 5.74 mmol). The resulting solution was further stirred at −78° C. for 15 min. A solution of ethyl 4-((tert-butylsulfinyl)imino)-2-methylbutanoate (1.290 g; 5.22 mmol) in anh. THF (5 ml) was then added to the cooled reaction mixture, and stirring at −78° C. was continued for 30 min. The resulting reaction mixture was treated successively with aq. sat. NH4Cl (35 ml), Et2O (75 ml) and water (20 ml). The separated organic layer was then washed with brine (30 ml), dried over anh. MgSO4, filtered, and concentrated to dryness under reduced pressure. Purification by FC (DCM/MeOH=30/1) afforded ethyl 4-(2,4-dimethoxypyridin-3-yl)-4-(1,1-dimethylethylsulfinamido)-2-methylbutanoate as a yellow oil. LC-MS (conditions B): tR=0.78 min. and [M+H]+: 386.68 g/mol; tR=0.80 min. and [M+H]+: 386.76 g/mol (mixture of diastereoisomers).

後処理

  1. stirringstirring at −78° C.
  2. waitwas continued for 30 min
  3. customThe resulting reaction mixture
  4. washThe separated organic layer was then washed with brine (30 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)

出典と根拠

ORDレコード
ord-4215c71e68a3464d8800e1014729793f
出典データセット
uspto-grants-2016_01
特許番号
US09242970B2

反応ノート

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