3-(Methoxycarbonyl)benzoic acid → Methyl 3-[({[1,6-diethyl-4-(tetrahydro-2H-pyran-4-ylamino)-1H-pyrazolo[3,4-b]pyridin-5-yl]methyl}amino)carbonyl]benzoate

HRID 564541Notes

Reaction equation

HRID 564541 reaction equation
[NH2:1][CH2:2][C:3]1[C:8]([CH2:9][CH3:10])=[N:7][C:6]2[N:11]([CH2:14][CH3:15])[N:12]=[CH:13][C:5]=2[C:4]=1[NH:16][CH:17]1[CH2:22][CH2:21][O:20][CH2:19][CH2:18]1.[CH3:23][O:24][C:25]([C:27]1[CH:28]=[C:29]([CH:33]=[CH:34][CH:35]=1)[C:30](O)=[O:31])=[O:26].CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F>C(Cl)Cl>[CH2:14]([N:11]1[C:6]2=[N:7][C:8]([CH2:9][CH3:10])=[C:3]([CH2:2][NH:1][C:30]([C:29]3[CH:28]=[C:27]([CH:35]=[CH:34][CH:33]=3)[C:25]([O:24][CH3:23])=[O:26])=[O:31])[C:4]([NH:16][CH:17]3[CH2:18][CH2:19][O:20][CH2:21][CH2:22]3)=[C:5]2[CH:13]=[N:12]1)[CH3:15]

Participants

5

Reactant 3

HCID 6018803-(Methoxycarbonyl)benzoic acidHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 596832145-(Aminomethyl)-1,6-diethyl-N-(tetrahydro-2H-pyran-4-yl)-1H-pyrazolo[3,4-b]pyridin-4-amine

Product 1

HCID 57813262Methyl 3-[({[1,6-diethyl-4-(tetrahydro-2H-pyran-4-ylamino)-1H-pyrazolo[3,4-b]pyridin-5-yl]methyl}amino)carbonyl]benzoateYield 109.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A mixture of 5-(aminomethyl)-1,6-diethyl-N-(tetrahydro-2H-pyran-4-yl)-1H-pyrazolo[3,4-b]pyridin-4-amine (2.0 g, 0.0059 mol) in DCM (60 mL) with 3-[(methyloxy)carbonyl]benzoic acid (1.16 g, 0.00648 mol) and HATU (2.68 g, 0.00706 mol) and TEA (1.19 g, 1.64 mL, 0.0118 mol) gave a yellow solution upon stirring overnight at RT. The solution was washed in turn with sat. aq. NaHCO3, H2O, and sat. aq. NaCl, then dried (Na2SO4), and concentrated to a viscous syrup/foam (3.68 g). This was purified on a ‘CombiFlash’ 40 g silica gel column (hexane-EtOAc) [20-100% EtOAc] to afford the title compound (3.02 g). LC-MS m/z 466.1 (M+H)+.

Workup

  1. customgave a yellow solution
  2. washThe solution was washed in turn with sat. aq. NaHCO3, H2O, and sat. aq. NaCl
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated to a viscous syrup/foam (3.68 g)
  5. customThis was purified on a ‘CombiFlash’ 40 g silica gel column (hexane-EtOAc) [20-100% EtOAc]

Sources & evidence

ORD record
ord-83771cc58eae484eba6e044e2501db0b
Source dataset
uspto-grants-2011_11
Patent number
US08067408B2

Reaction notes

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