tert-Butylsulfinamide, (R)-(+)- → HCID 90373422、化合物

HRID 930431ノート

反応式

HRID 930431 の反応式
[Cl:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[CH:4][C:3]=1[C:9](=O)[CH3:10].[CH3:12][C:13]([S@:16]([NH2:18])=[O:17])([CH3:15])[CH3:14]>O1CCCC1.[Cl-].[Na+].O.CCOC(C)=O.CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-]>[Cl:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[CH:4][C:3]=1/[C:9](=[N:18]\[S@@:16]([C:13]([CH3:15])([CH3:14])[CH3:12])=[O:17])/[CH3:10]

参加物

7

反応物 2

HCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 149373561-(2-Chloro-3-fluorophenyl)ethan-1-one

生成物 1

HCID 90373422HCID 90373422、化合物収率 82%

試薬・触媒・溶媒 4

HCID 11026Titanium isopropoxide触媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒HCID 57417360Sodium chloride; water溶媒

反応条件

温度
65 °C

実験手順

To a solution of 1-(2-chloro-3-fluorophenyl)ethanone (31.21 g, 181 mmol) in tetrahydrofuran (500 mL) was added (R)-2-methylpropane-2-sulfinamide (32.9 g, 271 mmol) and titanium(IV) isopropoxide (111 mL, 371 mmol). The mixture was heated to 65° C. overnight. LCMS showed 25% starting material remaining. Additional 16 g sulfinamide and 30 mL Ti(OPr)4 was added and the reaction was continued at 70° C. overnight. The mixture was diluted with brine (600 mL), and EtOAc. The solid was filtered through a pad of celite and washed with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by silica gel chromatography (330 g, 0-60% EtOAc-hexane in 20 min) to give (R,Z)-N-(1-(2-chloro-3-fluorophenyl)ethylidene)-2-methylpropane-2-sulfinamide (40.8 g, 82% yield) as yellow oil. MS m/z=276 [M+H]+. Calculated for C12H15ClFOS: 275.8.

後処理

  1. filtrationThe solid was filtered through a pad of celite
  2. washwashed with EtOAc
  3. washThe organic layer was washed with brine
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe crude material was purified by silica gel chromatography (330 g, 0-60% EtOAc-hexane in 20 min)

出典と根拠

ORDレコード
ord-8d3fa49f0dc34e46987988f044b87fe2
出典データセット
uspto-grants-2016_03
特許番号
US09296734B2

反応ノート

読み込み中…