p-Toluenesulfonic acid → 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(1,3-dithiolan-2-yl)-1H-pyrazole-3-carbonitrile ethoxyethylene

HRID 420894Notes

Reaction equation

HRID 420894 reaction equation
[NH2:1][C:2]1[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([C:14]([F:17])([F:16])[F:15])=[CH:9][C:8]=2[Cl:18])[N:5]=[C:4]([C:19]#[N:20])[C:3]=1[CH:21]1[S:25][CH2:24][CH2:23][S:22]1.[CH:26](OCC)([O:30][CH2:31][CH3:32])OCC.[C:36]1(C)C=CC(S(O)(=O)=O)=CC=1>>[NH2:1][C:2]1[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([C:14]([F:17])([F:15])[F:16])=[CH:9][C:8]=2[Cl:18])[N:5]=[C:4]([C:19]#[N:20])[C:3]=1[CH:21]1[S:22][CH2:23][CH2:24][S:25]1.[CH2:26]([O:30][CH:31]=[CH2:32])[CH3:36]

Participants

4

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 31214Ethyl orthoformateHCID 116904045-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(1,3-dithiolan-2-yl)-1H-pyrazole-3-carbonitrile

Product 1

HCID 866204735-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(1,3-dithiolan-2-yl)-1H-pyrazole-3-carbonitrile ethoxyethylene

Procedure

To 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(1,3-dithiolan-2-yl)-1H-pyrazole-3-carbonitrile (0.30 g, 0.71 mmol) in triethyl orthoformate (4.45 g, 29.70 mmol) was added p-toluenesulfonic acid (18 mg). The resulting mixture was heated up to 100 C for 1.5 hr. It was then cooled and then concentrated. The resulting viscous liquid was diluted with dichloromethane (20 mL). The organic layer was washed with saturated sodium bicarbonate, brine, and then dried over sodium sulfate to provide, upon concentration, a yellow oil (0.35 g, 0.72 mmol); 19F-NMR: −63.698.

Workup

  1. temperatureThe resulting mixture was heated up to 100 C for 1.5 hr
  2. temperatureIt was then cooled
  3. concentrationconcentrated
  4. additionThe resulting viscous liquid was diluted with dichloromethane (20 mL)
  5. washThe organic layer was washed with saturated sodium bicarbonate, brine
  6. dry with materialdried over sodium sulfate
  7. customto provide, upon concentration

Sources & evidence

ORD record
ord-0b472f5df1394c52b461dbbec536677f
Source dataset
uspto-grants-2012_01
Patent number
US08097732B2

Reaction notes

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