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

反応式

[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]

参加物

反応物 3

HCID 6101p-Toluenesulfonic acid

HCID 31214Ethyl orthoformate

HCID 116904045-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(1,3-dithiolan-2-yl)-1H-pyrazole-3-carbonitrile

生成物 1

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

実験手順

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.