Ethanol → HCID 136387801, compound

HRID 2400436Notes

Reaction equation

HRID 2400436 reaction equation
C(O[C:4]([NH:6][C:7]([N:22]1[CH:26]=[C:25]([C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH:24]=[N:23]1)=[N:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([O:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[CH:10]=1)=[O:5])C.CCO>ClC(Cl)C.Cl[Ti](Cl)(Cl)Cl>[O:5]=[C:4]1[C:14]2[C:9](=[CH:10][C:11]([O:15][C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=3)=[CH:12][CH:13]=2)[N:8]=[C:7]([N:22]2[CH:26]=[C:25]([C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH:24]=[N:23]2)[NH:6]1

Participants

5

Reactant 2

HCID 702EthanolHCID 136379415HCID 136379415, compound

Product 1

HCID 136387801HCID 136387801, compoundYield 81.5%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 63651,1-DichloroethaneSolvent

Procedure

To a solution of ethyl 1-(N-(ethoxycarbonyl)-N′-(3-phenoxyphenyl)carbamimidoyl)-1H-pyrazole-4-carboxylate (1.51 g, ca 2.51 mmol) in dichloroethane (DCE) (18 mL), neat TiCl4 (1.18 mL, 10.7 mmol) was added over 2 min. The mixture was then heated to reflux for 2 h, and then cooled in an ice bath. EtOH (50 mL) was added, and the mixture was stirred for 3 h. The resulting precipitate was collected by filtration, washed with cold EtOH, and dried to provide the titled compound (0.77 g, 57%). MS (ESI/CI): mass calcd. for C20H16N4O4, 376.1; m/z found, 377.3 [M+H]+. 1H NMR (400 MHz, DMSO-d6): 12.85 (s, 1H), 9.00 (d, J=0.5 Hz, 1H), 8.31 (s, 1H), 8.13 (d, J=8.8 Hz, 1H), 7.58-7.45 (m, 2H), 7.38-7.27 (m, 1H), 7.26-7.20 (m, 2H), 7.18 (dd, J=8.8, 2.4 Hz, 1H), 6.98 (s, 1H), 4.39-4.13 (m, 2H), 1.42-1.21 (m, 3H).

Workup

  1. temperatureThe mixture was then heated
  2. temperatureto reflux for 2 h
  3. temperaturecooled in an ice bath
  4. filtrationThe resulting precipitate was collected by filtration
  5. washwashed with cold EtOH
  6. customdried

Sources & evidence

ORD record
ord-1166102c7ef6480e8906a8abdb27f229
Source dataset
uspto-grants-2014_08
Patent number
US08796263B2

Reaction notes

Loading…