Benzyl mercaptan → 4-(Benzylthio)-2-nitroaniline

HRID 1504385

Reaktionsgleichung

Reaktionsgleichung von HRID 1504385
Br[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.O1CCOCC1.CCN(C(C)C)C(C)C.[CH2:27]([SH:34])[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1>O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>[CH2:27]([S:34][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1

Komponenten

8

Edukt 4

HCID 7509Benzyl mercaptanHCID 312751,4-DioxaneHCID 701324-Bromo-2-nitroanilineHCID 81531Diisopropylethylamine

Produkt 1

HCID 135509934-(Benzylthio)-2-nitroanilineAusbeute 88,2 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)KatalysatorHCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

A screw cap vial was charged with 4-bromo-2-nitroaniline (7.00 g, 32.3 mmol), xantphos (0.933 g, 1.613 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.738 g, 0.806 mmol), 1,4-Dioxane (32.3 ml), and DIPEA (11.22 ml, 64.5 mmol). The vial was purged with Argon, sealed and heated to 80° C. for 10 minutes. The reaction was cooled to room temperature and benzyl mercaptan (4.01 ml, 33.9 mmol) was added and the reaction heated at 80° C. for 3 hours. The reaction was cooled to room temperature, diluted with water and extracted with DCM (3×). The combined organics were washed with water and brine, dried over magnesium sulfate, filtered and concentrated. The resulting material was concentrated, dissolved in minimal DCM and purified via column chromatography (silica gel 40 g, gradient elution 0 to 50% EtOAc:Heptane) to afford 4-(benzylthio)-2-nitroaniline (7.43 g, 28.5 mmol, 88% yield). m/z (ESI) 261.2 (M+H)+.

Aufarbeitung

  1. customA screw cap vial
  2. customThe vial was purged with Argon
  3. customsealed
  4. temperatureThe reaction was cooled to room temperature
  5. temperaturethe reaction heated at 80° C. for 3 hours
  6. temperatureThe reaction was cooled to room temperature
  7. extractionextracted with DCM (3×)
  8. washThe combined organics were washed with water and brine
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. concentrationThe resulting material was concentrated
  13. dissolutiondissolved in minimal DCM
  14. custompurified via column chromatography (silica gel 40 g, gradient elution 0 to 50% EtOAc:Heptane)

Quellen und Nachweise

ORD-Eintrag
ord-1e006f5cddc94ebfac893136c2591d2d
Quelldatensatz
uspto-grants-2015_12
Patentnummer
US09212182B2

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