* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With chromium(VI) oxide; sulfuric acid In acetic acid at 0 - 20℃;
To an ice-cooled mixture of 6 (20.00 g, 0.08 mol) in glacial acetic acid (150 mL) was added sulfuric acid (28 mL) slowly to keep the temperature below 5 °C. Chromium oxide (28.00 g, 0.28 mol) was added in small portions at such a rate that the temperature did not exceed 10 °C. The reaction solution was stirred at room temperature overnight, then ice water (20 mL) was added. The precipitated solid was filtered, washed with water and dried to afford 7 22.0 g (85percent) of a white powder. mp 254-256 °C.
60%
for 4 h; Reflux
A mixture of (4-nitrophenyl)(4-tolyl)methanone (12c) (0.50 g, 2.0 mmol) and Jones reagent (0.7 ml) in glacial acetic acid (4 ml) was heated under reflux for 4 h. The reaction mixture was then poured on crushed ice, and extracted with ethyl acetate (10 ml) three times. The organic layer was washed with water until the washings became neutral and was extracted with 10percent NaHCO3 (2 .x. 20 ml). The aqueous extract was acidified with concentrated HCl to pH 3. The solid that formed was filtered off and dried. Yield (0.337 g, 60percent), m.p. 256-257 °C (lit.24 m.p. 255 °C). 1H NMR (300 MHz, (CD3)2SO): d 8.37 (d, J = 8.8 Hz, 2H), 8.05 (d, J = 8.4 Hz, 2H), 7.96 (d, J = 8.8 Hz, 2H), 7.78 (d, J = 8.4 Hz, 2H). 13C NMR (75 MHz, (CD3)2SO): d 194.42, 167.43, 149.47, 142.43, 137.48, 130.75, 129.58, 129.28, 129.03, 123.69.
Reference:
[1] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 2, p. 1036 - 1039
[2] Journal of Medicinal Chemistry, 2006, vol. 49, # 2, p. 748 - 759
[3] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 1, p. 380 - 386
[4] Justus Liebigs Annalen der Chemie, 1895, vol. 286, p. 329
[5] Molecular crystals and liquid crystals, 1984, vol. 111, # 3-4, p. 255 - 266
[6] Medicinal Chemistry, 2013, vol. 9, # 2, p. 294 - 302
With sodium hydroxide In toluene at 100℃; for 2h; Schlenk technique;
2. General Procedure for the Preparation of Dissymmetric Ketones
General procedure: An oven-dried Schlenk flask, equipped with a magnetic stir bar, septum and a condenser was charged with acyl chloride (1.0 mmol), arylboronic acid (1.0 mmol), NaOH (4 mmol) and 5.0 mL of toluene. The flask was immersed and stirred in an oil bath at 100 °C. Upon complete consumption of starting materials as determined by GC analysis, the water (10.0 mL) was added. The reaction mixture was extracted with diethyl ether (3 × 5.0 mL). The combined organic layer was collected, dried over anhydrous Na2SO4 and concentrated in vacuum to afford product which was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate = 9:1 or 8:2).
85%
Stage #1: 4-methylphenylboronic acid; 4-nitro-benzoyl chloride With p-xylene-2-sulphonic acid sodium salt In water at 28℃; for 0.0833333h;
Stage #2: With palladium 10% on activated carbon; potassium carbonate In water at 60℃; for 3h;
66%
With C32H28N6Pd(2+)*2Br(1-); potassium carbonate In toluene at 60℃; for 6h; Inert atmosphere; Schlenk technique;
60%
With caesium carbonate In toluene for 0.166667h; microwave irradiation;
With potassium fluoride; potassium phosphate; copper; Trimethylacetic acid at 100℃; for 9h;
92%
With potassium fluoride; potassium phosphate; copper; Trimethylacetic acid at 100℃; for 9h;
3
General procedure: A 25 mL reaction flask was charged with copper nanoparticles (0.1 mmol)Aryl diiodonium (0.5 mmol),Benzene boronic acid (1.5 mmol),Potassium phosphate (1.0 mmol),Potassium fluoride (0.5 mmol), pivalic acid (0.5 mmol) and polyethylene glycol-400 (2.0 g)And introducedAn atmospheric pressureCarbon monoxide.The reaction mixture was reacted at 100 ° C until the reaction was complete and cooled to room temperature,The product was isolated by column chromatography after evaporation of the solvent under reduced pressure.
90%
With potassium phosphate; nickel dichloride; Trimethylacetic acid at 80℃; for 5h;
90%
With potassium phosphate; nickel dichloride; Trimethylacetic acid at 80℃; for 5h; Green chemistry;
2 Example 2
General procedure: Into a 25 ml reaction flask was successively added nickel chloride (0.01 mmol), R2 substituted aryl iodide (table 2) (0.5 mmol), R3 substituted arylboronic acid (0.75 mmol), potassium phosphate (1.0 mmol), pivalic acid (0.25 mmol) and polyethylene glycol 400 (2.0 g), and introduce one atmospheric pressure carbon monoxide. The reaction mixture at 80 °C react until starting material reaction complete and cool to room temperature, pressure reducing evaporate the solvent column chromatography separation to obtain the product. The experimental results are set out in table 2.
85%
With potassium carbonate In methoxybenzene at 80℃; for 5h;
83%
With potassium carbonate In methoxybenzene at 80℃; for 5h;