Potassium Carbonate → N-(4-(difluoromethoxy)phenyl)-6-vinylpyridazin-3-amine

HRID 77491

Reaction equation

Cl[C:2]1[N:7]=[N:6][C:5]([NH:8][C:9]2[CH:14]=[CH:13][C:12]([O:15][CH:16]([F:18])[F:17])=[CH:11][CH:10]=2)=[CH:4][CH:3]=1.[CH:19](B1OC(C)(C)C(C)(C)O1)=[CH2:20].C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.O>[F:17][CH:16]([F:18])[O:15][C:12]1[CH:13]=[CH:14][C:9]([NH:8][C:5]2[N:6]=[N:7][C:2]([CH:19]=[CH2:20])=[CH:3][CH:4]=2)=[CH:10][CH:11]=1

Participants

Conditions

Temperature: 80 °C

Procedure

To a solution of 6-chloro-N-(4-(difluoromethoxy)phenyl)pyridazin-3-amine (0.2 g, 0.736 mmol) in dioxane and water mixture were added vinylboronic acid pinacol ester (0.146 mL, 1.104 mmol), and K2CO3 (0.305 g, 2.209 mmol). The mixture was flushed for 15 min with nitrogen. PdCl2 (dppf)-CH2Cl2 adduct (0.060 g, 0.074 mmol) was then added and the reaction mixture heated at 80° C. for 18 h. The reaction mixture was filtered through a pad of celite, washed with ethyl acetate and purified by flash chromatography on silica gel using ethyl acetate in hexane to give N-(4-(difluoromethoxy)phenyl)-6-vinylpyridazin-3-amine as a white solid (0.12 g, 59%). 1HNMR 400 MHz, DMSO-d6: δ ppm 5.47 (d, J=1.20 Hz, 1H), 6.06 (dd, J=0.80, 23.80 Hz, 1H), 6.84-7.38 (m, 5H), 7.75-7.82 (m, 3H), 9.42 (s, 1H).

Workup

customThe mixture was flushed for 15 min with nitrogen
filtrationThe reaction mixture was filtered through a pad of celite
washwashed with ethyl acetate
custompurified by flash chromatography on silica gel

Sources & evidence

ORD record: ord-70a27a3b47514ec89815ce94e3d224e7
Source dataset: uspto-grants-2014_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08841301B2

Linked notes

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