1,1'-Thiocarbonyldi-2(1H)-pyridone → 5,6-Dichloro-3-isothiocyanatoisoquinoline

HRID 1875985Notes

Reaction equation

[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[Cl:12])[CH:8]=[N:7][C:6]([NH2:13])=[CH:5]2.[Cl:14][C:15]1[C:24]([Cl:25])=[CH:23][CH:22]=[C:21]2[C:16]=1[CH:17]=[C:18]([NH2:26])[N:19]=[CH:20]2.[C:27](N1C=CC=CC1=O)(N1C=CC=CC1=O)=[S:28]>ClCCl>[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[Cl:12])[CH:8]=[N:7][C:6]([N:13]=[C:27]=[S:28])=[CH:5]2.[Cl:14][C:15]1[C:24]([Cl:25])=[CH:23][CH:22]=[C:21]2[C:16]=1[CH:17]=[C:18]([N:26]=[C:27]=[S:28])[N:19]=[CH:20]2

Participants

Conditions

Temperature: 40 °C

Procedure

To 6,7-dichloroisoquinolin-3-amine and 5,6-dichloroisoquinolin-3-amine (0.410 g, 1.924 mmol) in dichloromethane (20 mL) was added 1,1′-thiocarbonyldipyridin-2(1H)-one (0.469 g, 2.021 mmol) and the reaction mixture was stirred at 40° C. for 4 hours. The reaction was cooled to room temperature and chromatographed (Biotage: 10-100% ethyl acetate/hexanes) to yield the separated regioisomers, 6,7-dichloro-3-isothiocyanatoisoquinoline (0.2 g, 0.784 mmol, 40.7% yield) and 5,6-dichloro-3-isothiocyanatoisoquinoline (0.23 g, 0.902 mmol, 46.8% yield) as yellow solids. 5,6-dichloro-3-isothiocyanatoisoquinoline: 1H NMR (500 MHz, CDCl3) δ ppm 9.10 (s, 1H), 7.87 (d, J=8.85 Hz, 1H), 7.82 (s, 1H), 7.66 (d, J=8.55 Hz, 1H). MS (LC/MS) R.T.=3.63; [M+H]+=255.0. 6,7-dichloro-3-isothiocyanatoisoquinoline: 1H NMR (500 MHz, CDCl3) δ ppm 9.04 (s, 1H), 8.11 (s, 1H), 7.94 (s, 1H), 7.37 (s, 1H). MS (LC/MS) R.T.=3.42; [M+H]+=255.0.

Workup

temperatureThe reaction was cooled to room temperature
customchromatographed (Biotage: 10-100% ethyl acetate/hexanes)

Sources & evidence

ORD record: ord-86d0c5eda0c147b798f14b8310089c7a
Source dataset: uspto-grants-2012_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08309577B2

Reaction notes

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