Acetic Acid → 3-Chloro-4,6-dimethylpyridazine

To a mixture of 3-chloro-6-methylpyridazine (0.2 g, 1.55 mmol), acetic acid (0.2 mL, 3.49 mmol), sulphuric acid (0.124 mL, 2.33 mmol) and silver nitrate (0.026 g, 0.16 mmol) in water (4.5 mL) was added dropwise a solution of ammonium persulfate in water (1.5 mL). The mixture was held at 75° C. for 30 minutes, allowed to cool to r.t. and poured onto ice. The mixture was basified to pH 9-10 with ammonium hydroxide and extracted with DCM (50 mL). The organic fraction was washed with aqueous sodium hydroxide (1.0N, 2×15 mL), dried (MgSO4), concentrated in vacuo and purified by preparative HPLC (Method 6). The product was dissolved in DCM (15 mL), washed with aqueous potassium carbonate solution (0.7M) and concentrated in vacuo to give the title compound (0.111 g, 50%) as a pink solid. δH (DMSO-d6) 7.62 (1H, s), 2.57-2.54 (3H, m), 2.33 (3H, s). LCMS (ES+) 142.97 (M+H)+, RT 1.93 minutes (Method 1).

1. additionpoured onto ice
2. extractionextracted with DCM (50 mL)
3. washThe organic fraction was washed with aqueous sodium hydroxide (1.0N, 2×15 mL)
4. dry with materialdried (MgSO4)
5. concentrationconcentrated in vacuo
6. custompurified by preparative HPLC (Method 6)
7. dissolutionThe product was dissolved in DCM (15 mL)
8. washwashed with aqueous potassium carbonate solution (0.7M)
9. concentrationconcentrated in vacuo

ORDレコード

ord-66b6ede1da874660a94383ed581912e5

出典データセット

uspto-grants-2012_08

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US08242116B2