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

HRID 970006

反応式

HRID 970006 の反応式
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

参加物

7

反応物 5

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 176Acetic Acid溶媒

実験手順

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)+.

後処理

  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%)

出典と根拠

ORDレコード
ord-3035ec7bf2c24e5a8b6dcecf6da847f0
出典データセット
uspto-grants-2007_12
特許番号
US07309699B2

関連ノート

読み込み中…