Cesium carbonate → HCID 57637316, compound

Participants

Reaction Conditions

Reaction Steps

To N-benzhydrylidene-N′-[1-(5-benzyloxymethyl-3-bromo-thiophen-2-yl)-methylidene]-hydrazine (34 g, 69.5 mmol, Intermediate (88)] in toluene (500 mL) were added hydrazone benzophenone (16.4, 83.4 mmol), cesium carbonate (38.4 g, 118.2 mmol), 1,1′ diphenylphosphinoferrocene (5.8 g, 10.4 mmol), and palladium (II) acetate (1.17 g, 5.2 mmol). The suspension was stirred at 90° C. under nitrogen atmosphere until reaction is complete. The solvent was removed. The residual oil was chromatographed (ethyl acetate/n-heptane, 10/90 as eluant) to product an orange oil. It was dissolved in ethanol (350 mL). Concentrated hydrochloric acid (100 mL) was added. The dark mixture was stirred at 80° C. for 15 hours then diluted with water. It was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated. The residue was chromatographed through silica gel (n-heptane/ethyl acetate, 80/20 then 50/50 as eluant) to afford 5-benzyloxymethyl-1H-thieno[3,2-c]pyrazole [5.2 g, 37%, Intermediate (89)] as an orange powder. LC/MS: 245.1 (M+H), RT=2.83 minutes. 1H NMR [300 Mhz, (CD3)2SO]: tautomer 1: δ 12.97 (s, 1H), 7.73 (s, 1H), 7.40-7.25 (m, 5H), 7.15-7.05 (m, 1H), 4.71 (s, 2H), 4.55 (s, 2H) tautomer 2: δ 13.27 (brs, 1H), 7.98 (s, 1H), 7.40-7.25 (m, 5H), 7.15-7.05 (m, 1H), 4.71 (s, 2H), 4.55 (s, 2H).

Provenance & Evidence