Benzidine → N-1-azabicyclo[2.2.2]oct-3-yl-1,1'-biphenyl-4,4'-diamine

HRID 970006

Reaktionsgleichung

Reaktionsgleichung von HRID 970006
Cl.[N:2]12[CH2:9][CH2:8][CH:5]([CH2:6][CH2:7]1)[C:4](=O)[CH2:3]2.[C:11]1([C:18]2[CH:23]=[CH:22][C:21]([NH2:24])=[CH:20][CH:19]=2)[CH:16]=[CH:15][C:14]([NH2:17])=[CH:13][CH:12]=1.[O-]S([O-])(=O)=O.[Na+].[Na+].[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+].C([O-])(O)=O.[Na+]>C(O)(=O)C>[N:2]12[CH2:9][CH2:8][CH:5]([CH2:6][CH2:7]1)[CH:4]([NH:17][C:14]1[CH:13]=[CH:12][C:11]([C:18]3[CH:23]=[CH:22][C:21]([NH2:24])=[CH:20][CH:19]=3)=[CH:16][CH:15]=1)[CH2:3]2

Komponenten

7

Edukt 5

HCID 7111BenzidineHCID 24436Sodium SulfateHCID 1020191-Azabicyclo(2.2.2)octan-3-one, hydrochloride (1:1)HCID 516892Sodium BicarbonateHCID 5049666Sodium triacetoxyborohydride

Produkt 1

HCID 11380826N-1-azabicyclo[2.2.2]oct-3-yl-1,1'-biphenyl-4,4'-diamine

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 176Acetic AcidLösungsmittel

Versuchsvorschrift

3-Quinuclidinone hydrochloride (Aldrich, 1.61 g, 10 mmol) in acetic acid (25 mL) was treated with biphenyl-4,4′-diamine (Aldrich, 0.92 g, 5.0 mmol), Na2SO4 (anhydrous, Aldrich, 7.40 g, 50 mmol) and NaBH(OAc)3 (Aldrich, 3.16 g, 15 mmol) at ambient temperature for 15 hours. The reaction mixture was slowly poured into a flask containing 75 mL of saturated NaHCO3, stirred for 20 minutes, and extracted with ethyl acetate (3×100 mL). The extracts were combined and washed with brine (2×20 mL). The organic phase was concentrated under reduced pressure and the title compound was purified by chromatography (SiO2, CH2Cl2:MeOH:NH3.H2O, 80:20:4, Rf. 0.10) as a solid (0.98 g, yield, 67%). 1H NMR (MeOH-d4, 300 MHz) δ 1.40-1.52 (m, 1H), 1.64-1.84 (m, 2H), 1.89-2.04 (m, 2H), 2.57 (ddd, J=13.9, 5.2, 2.1 Hz, 1H) 2.75-3.00 (m, 4H), 3.27-3.35 (m, 1H), 3.50-3.60 (m, 1H), 6.61-6.69 (m, 2H), 6.80-6.86 (m, 2H), 6.92-6.97 (m, 2H), 7.06-7.13 (m, 2H) ppm. MS (DCl/NH3) m/z 294 (M+H)+.

Aufarbeitung

  1. additionThe reaction mixture was slowly poured into a flask
  2. extractionextracted with ethyl acetate (3×100 mL)
  3. washwashed with brine (2×20 mL)
  4. concentrationThe organic phase was concentrated under reduced pressure
  5. customthe title compound was purified by chromatography (SiO2, CH2Cl2:MeOH:NH3.H2O, 80:20:4, Rf. 0.10) as a solid (0.98 g, yield, 67%)

Quellen und Nachweise

ORD-Eintrag
ord-3035ec7bf2c24e5a8b6dcecf6da847f0
Quelldatensatz
uspto-grants-2007_12
Patentnummer
US07309699B2

Verknüpfte Notizen

Wird geladen…