Potassium Carbonate → methyl 5-(methyloxy)-4-(1-methyl-1H-pyrazol-5-yl)-2-thiophenecarboxylate

HRID 2392210Notes

Reaction equation

Br[C:2]1[CH:3]=[C:4]([C:9]([O:11][CH3:12])=[O:10])[S:5][C:6]=1[O:7][CH3:8].[CH3:13][N:14]1[C:18](B2OC(C)(C)C(C)(C)O2)=[CH:17][CH:16]=[N:15]1.C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.O.CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[CH3:8][O:7][C:6]1[S:5][C:4]([C:9]([O:11][CH3:12])=[O:10])=[CH:3][C:2]=1[C:18]1[N:14]([CH3:13])[N:15]=[CH:16][CH:17]=1

Participants

Conditions

Temperature: 85 °C

Procedure

To a 350 mL sealed flask reactor was added methyl 4-bromo-5-(methyloxy)-2-thiophenecarboxylate (772 mg, 3.07 mmol), 1-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (773 mg, 3.72 mmol) [prepared according to the procedure of Preparation 7], K2CO3 (1.419 g, 10.27 mmol) and Pd(Pt—Bu3)2 (103 mg, 0.20 mmol) in 1,4-Dioxane (12 mL) and Water (3 mL). The reaction was heated at 85° C. for 2 hours. The mixture was partitioned between CHCl3/H2O and the aqueous layer made acidic with 6N HCl. The separated organic layer was dried over Na2SO4 and evaporated. The resulting material was adsorbed onto silica and purified via column chromatography (0-50% EtOAc/Hexane) affording the title compound (967 mg, 4.39 mmol, 85%): LC-MS (ES) m/z=253 (M+H)+.

Workup

customTo a 350 mL sealed flask reactor
customprepared
customThe mixture was partitioned between CHCl3/H2O
dry with materialThe separated organic layer was dried over Na2SO4
customevaporated
custompurified via column chromatography (0-50% EtOAc/Hexane)

Sources & evidence

ORD record: ord-8c1c8fa8b13b4e7295de6cd68e7d6e7d
Source dataset: uspto-grants-2012_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08273782B2

Reaction notes

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