tert-Butylsulfinamide, (R)-(+)- → HCID 90373422, Verbindung

HRID 930431Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 930431
[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]

Komponenten

7

Edukt 2

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

Produkt 1

HCID 90373422HCID 90373422, VerbindungAusbeute 82 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 11026Titanium isopropoxideKatalysatorHCID 8028TetrahydrofuranLösungsmittelHCID 8857Ethyl AcetateLösungsmittelHCID 57417360Sodium chloride; waterLösungsmittel

Reaktionsbedingungen

Temperatur
65 °C

Versuchsvorschrift

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.

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-8d3fa49f0dc34e46987988f044b87fe2
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09296734B2

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