4-(5-(4-(2,5-Bis(4-nitrophenyl)pyrrolidin-1-yl)phenyl)pyridin-2-yl)morpholine → 4,4'-(1-(4-(6-Morpholinopyridin-3-yl)phenyl)pyrrolidine-2,5-diyl)dianiline

HRID 1470982Notes

Reaction equation

HRID 1470982 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([CH:10]2[CH2:14][CH2:13][CH:12]([C:15]3[CH:20]=[CH:19][C:18]([N+:21]([O-])=O)=[CH:17][CH:16]=3)[N:11]2[C:24]2[CH:29]=[CH:28][C:27]([C:30]3[CH:31]=[CH:32][C:33]([N:36]4[CH2:41][CH2:40][O:39][CH2:38][CH2:37]4)=[N:34][CH:35]=3)=[CH:26][CH:25]=2)=[CH:6][CH:5]=1)([O-])=O.[H][H]>C1COCC1.[Pt](=O)=O>[O:39]1[CH2:40][CH2:41][N:36]([C:33]2[N:34]=[CH:35][C:30]([C:27]3[CH:26]=[CH:25][C:24]([N:11]4[CH:12]([C:15]5[CH:20]=[CH:19][C:18]([NH2:21])=[CH:17][CH:16]=5)[CH2:13][CH2:14][CH:10]4[C:7]4[CH:6]=[CH:5][C:4]([NH2:1])=[CH:9][CH:8]=4)=[CH:29][CH:28]=3)=[CH:31][CH:32]=2)[CH2:37][CH2:38]1

Participants

5

Reactant 2

HCID 867623254-(5-(4-(2,5-Bis(4-nitrophenyl)pyrrolidin-1-yl)phenyl)pyridin-2-yl)morpholineHCID 178418361HCID 178418361, compound2×

Product 1

HCID 672367054,4'-(1-(4-(6-Morpholinopyridin-3-yl)phenyl)pyrrolidine-2,5-diyl)dianilineYield 65%

Reagents, catalysts & solvents 2

HCID 345198Adams' catalystCatalyst3×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
25 °C

Procedure

Charged a 100-mL round bottom flask with the product of Example 108A (174.7 mg, 0.317 mmol), partially dissolved in THF (12.50 mL) and absolute EtOH (2.50 mL), evacuated on house vacuum and filled flask with nitrogen, then added platinum (IV) oxide (14.38 mg, 0.063 mmol), evacuated flask on house vacuum and filled with hydrogen from a balloon, repeated evacuation/filling cycle 3 times, and stirred heterogeneous reaction mixture vigorously under hydrogen (1 atm). After 2 hr, charged reaction with additional platinum (IV) oxide (14.38 mg, 0.063 mmol) and continued to vigorously stir under hydrogen at 25° C. After 5 hr, added additional platinum (IV) oxide (14.38 mg, 0.063 mmol). The reaction mixture was then vacuum filtered through a bed of Celite 545 in a Büchner funnel, the filter pad was washed with CHCl3 (100 mL) and hot CHCl3 (2×50 mL), and the filtrate concentrated by rotary evaporation to give the title compound as a yellow solid (101 mg, 65%) as a mixture of stereoisomers. 1H NMR (400 MHz, DMSO-D6) δ ppm 1.71-1.87 (m, 2H), 2.24-2.31 (m, 1H), 3.37-3.45 (m, 4H), 3.64-3.74 (m, 4H), 4.57 (t, J=4.99 Hz, 2H), 4.95 (s, 4H), 6.42-6.53 (m, 3H), 6.57 (d, J=8.35 Hz, 4H), 6.76-6.89 (m, 2H), 7.15 (d, J=8.35 Hz, 4H), 7.26 (d, J=8.78 Hz, 2H), 7.68 (dd, J=8.84, 2.44 Hz, 1H), 8.29 (d, J=2.39 Hz, 1H); MS (ESI+) m/z 492 (M+H)+.

Workup

  1. customabsolute EtOH (2.50 mL), evacuated on house vacuum
  2. additionfilled flask with nitrogen
  3. additioncharged
  4. waitAfter 5 hr
  5. filtrationvacuum filtered through a bed of Celite 545 in a Büchner funnel
  6. washthe filter pad was washed with CHCl3 (100 mL) and hot CHCl3 (2×50 mL)
  7. concentrationthe filtrate concentrated by rotary evaporation

Sources & evidence

ORD record
ord-d048f752623a48aabf6dabc4660f1136
Source dataset
uspto-grants-2015_04
Patent number
US09006387B2

Reaction notes

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