Diisopropylethylamine → HCID 86638751, compound

HRID 423670Notes

Reaction equation

HRID 423670 reaction equation
CN(C(ON1N=NC2C=CC=CC1=2)=[N+](C)C)C.[B-](F)(F)(F)F.C(N(C(C)C)CC)(C)C.[CH3:32][C:33]([O:36][C:37]([N:39]1[CH2:44][CH2:43][CH:42]([C:45]([OH:47])=O)[CH2:41][CH2:40]1)=[O:38])([CH3:35])[CH3:34].[Br:48][C:49]1[N:54]=[CH:53][C:52]([NH2:55])=[CH:51][CH:50]=1>CN(C=O)C.O>[Br:48][C:49]1[N:54]=[CH:53][C:52]([NH:55][C:45]([CH:42]2[CH2:41][CH2:40][N:39]([C:37]([O:36][C:33]([CH3:32])([CH3:34])[CH3:35])=[O:38])[CH2:44][CH2:43]2)=[O:47])=[CH:51][CH:50]=1

Participants

7

Reactant 4

HCID 81531DiisopropylethylamineHCID 3928711-(tert-Butoxycarbonyl)-4-piperidinecarboxylic acidHCID 6428116-Bromopyridin-3-amineHCID 2733207O-(Benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate

Product 1

HCID 86638751HCID 86638751, compoundYield 77.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

TBTU (2.86 g, 8.9 mmol) and diisopropylethylamine (1.55 mL, 8.9 mmol) were added to a mixture of 1-{[(1,1-dimethylethyl)oxy]carbonyl}-4-piperidinecarboxylic acid (1.35 g, 5.9 mmol) in DMF (20 mL) at ambient temperature. The mixture was stirred at ambient temperature for 1 h, charged with 6-bromo-3-pyridinamine (1.13 g, 6.5 mmol), then stirred at 50° C. overnight. The mixture was cooled to ambient temperature, charged with water (200 mL), and extracted with EtOAc. The organics were dried over MgSO4, filtered, and the filtrate was concentrated. The crude product was purified by chromatography on a silica gel column using 0 to 50% EtOAc/hexanes to give 1.75 g (77%) of 1,1-dimethylethyl 4-{[(6-bromo-3-pyridinyl)amino]carbonyl}-1-piperidinecarboxylate as an off-white solid. 1H NMR (400 MHz, CDCl3): δ 8.32 (d, 1H, J=2.7 Hz), 8.07 (dd, 1H, Ja=8.6 Hz, Jb=2.8 Hz), 7.44-7.39 (m, 2H), 4.16 (bs, 2H), 2.90-2.65 (m, 2H), 2.45-2.35 (m, 1H), 1.95-1.80 (m, 2H), 1.79-1.65 (m, 2H), 1.44 (s, 9H); LRMS (ESI), m/z 384 (M+H).

Workup

  1. stirringstirred at 50° C. overnight
  2. temperatureThe mixture was cooled to ambient temperature
  3. extractionextracted with EtOAc
  4. dry with materialThe organics were dried over MgSO4
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated
  7. customThe crude product was purified by chromatography on a silica gel column

Sources & evidence

ORD record
ord-85f91707568d4bcd9d9ca786fff049ba
Source dataset
uspto-grants-2012_01
Patent number
US08101634B2

Reaction notes

Loading…