Nitrogen → 2-(Thiophen-2-yl)aniline

HRID 1256688

Reaktionsgleichung

Reaktionsgleichung von HRID 1256688
N#N.Br[C:4]1[S:5][CH:6]=[CH:7][CH:8]=1.CC1(C)C(C)(C)OB([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=2[NH2:23])O1.C([O-])(O)=O.[Na+]>COCCOC.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[S:5]1[CH:6]=[CH:7][CH:8]=[C:4]1[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[NH2:23]

Komponenten

7

Edukt 4

HCID 947NitrogenHCID 138512-BromothiopheneHCID 516892Sodium BicarbonateHCID 27346522-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)aniline

Produkt 1

HCID 41160972-(Thiophen-2-yl)anilineAusbeute 92 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumKatalysatorHCID 80711,2-DimethoxyethaneLösungsmittel

Versuchsvorschrift

AB427 (The following reaction is carried out in an N2 atmosphere.) Dissolve Tetrakis-(triphenylphosphine)-palladium(0) (297 mg, 0.26 mmol) and 2-Bromo-thiophene (837 mg, 5.13 mmol) in DME (42 mL), degas the reaction mixture carefully (5 times) and flush with N2. After 10 min stirring add 2-(4,4,5,5-Tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenylamine (1.24 g, 5.64 mmol) and a 1M aqueous NaHCO3 solution (15.4 mL, 15.4 mmol), degas the reaction mixture again carefully (5 times) and flush with N2. Stir the mixture for 3 h at 95° C. Cool mixture to rt, remove solvent under reduced pressure and partition the residue between EtOAc and water. Extract the separated aqueous layer with EtOAc (3 times). Wash combined organic layer with brine and dry it with Na2SO4. Purify the crude product by flash chromatography (silica gel 60, CyH/EtOAc 15+1] to obtain 2-Thiophene-2-yl-phenylamine (55) as a brown solid (825 mg, 92%). 1H NMR (400 MHz, CDCl3): 4.40-6.00 (m, 2H); 6.88 (td, 1H, J1=7.6 Hz, J2=1.0 Hz); 6.93 (dd, 1H, J1=8.0 Hz, J2=1.0 Hz); 7.07 (dd, 1H, J1=5.3 Hz, J2=3.5 Hz); 7.17 (td, 1H, J1=8.0 Hz, J2=1.5 Hz) 7.22 (dd, 1H, J1=3.5 Hz, J2=1.3 Hz); 7.30 (dd, 1H, J1=7.6 Hz, J2=1.5 Hz); 7.33 (dd, 1H, J1=5.3 Hz, J2=1.3 Hz).

Aufarbeitung

  1. customAB427 (The following reaction
  2. customdegas the reaction mixture carefully (5 times)
  3. customflush with N2
  4. customflush with N2
  5. stirringStir the mixture for 3 h at 95° C
  6. customremove solvent under reduced pressure
  7. custompartition the residue between EtOAc and water
  8. extractionExtract the separated aqueous layer with EtOAc (3 times)
  9. washWash
  10. dry with materialdry it with Na2SO4
  11. customPurify the crude product by flash chromatography (silica gel 60, CyH/EtOAc 15+1]

Quellen und Nachweise

ORD-Eintrag
ord-442987a44e8a43ae8e19c1e25e62b911
Quelldatensatz
uspto-grants-2013_06
Patentnummer
US08461207B2

Verknüpfte Notizen

Wird geladen…