1-CHLORO-4-IODO-2-NITROBENZENE

To a jacketed reactor, acetic acid (450 mL) and acetic anhydride (225 mL) is charged at 10° C. To a jacketed reactor, acetic acid (450 mL) and acetic anhydride (225 mL) is charged at 10 °C. Then, to the above mixture, Nal0In a Schlenk reaction tube equipped with a magnetic stirrer, 6.7 mg of palladium trifluoroacetate was added.Cuprous oxide 28.6mg, Potassium phosphate 6.4mg, 4, 5-Difluoro-2-nitrobenzoic acid 40.3mg, Sodium iodide 36mg, Bismuth nitrate pentahydrate 194 mg and 2 mL of dimethyl sulfoxide.The reaction was heated at 170°C for 20 hours in the presence of oxygen. After the reaction is completed, distilled water is added to quench the reaction.Extraction with ethyl acetate 3 times each 10 mL, the combined organic phases were concentrated to give 1-chloro-4-iodo-2-nitrobenzene54.4 mg, 96percent yieldTo a jacketed reactor, acetic acid (450 mL) and acetic anhydride (225 mL) is charged at 10° C. To a jacketed reactor, acetic acid (450 mL) and acetic anhydride (225 mL) is charged at 10 °C. Then, to the above mixture, Nal0In a Schlenk reaction tube equipped with a magnetic stirrer, 6.7 mg of palladium trifluoroacetate was added.Cuprous oxide 28.6mg, Potassium phosphate 6.4mg, 4, 5-Difluoro-2-nitrobenzoic acid 40.3mg, Sodium iodide 36mg, Bismuth nitrate pentahydrate 194 mg and 2 mL of dimethyl sulfoxide.The reaction was heated at 170°C for 20 hours in the presence of oxygen. After the reaction is completed, distilled water is added to quench the reaction.Extraction with ethyl acetate 3 times each 10 mL, the combined organic phases were concentrated to give 1-chloro-4-iodo-2-nitrobenzene54.4 mg, 96percent yieldTo a jacketed reactor, acetic acid (450 mL) and acetic anhydride (225 mL) is charged at 10 C. Then, to the above mixture, NalO4 powder (97.2 g) and Iodine (77.2 g) is added under stirring. While keep internal temperature at below 30 C., conc. H2SO4 (720 mL) is added dropwise. Then, 2-chloro-nitrobenzene (Rt=11.11 min) is added in one portion, and heat the mixture gradually to 64 C. The resulting mixture continues to be stirred for usually at least 2 hours until process monitor shows almost complete conversion. Then, the mixture is cooled down to room temperature, and transferred slowly into another jacketed reactor with pre-cooled cold Na2SO3 solution (250 g Na2SO3 in 2000 mL water). Collect the wet cake by filtration and wash the cake with water (450 mL*2), then purification of the cake with n-heptane crystallization to afford To a jacketed reactor, acetic acid (450 mL) and acetic anhydride (225 mL) is charged at 10 C. Then, to the above mixture, Nal04 powder (97.2 g) and Iodine (77.2 g) is added under stirring. While keep internal temperature at below 30 C, cone. H2S04(720 mL) is added drop- wise. Then, 2-chloro-nitrobenzene (Rt = 1 1 .1 1 min) is added in one portion, and heat the mixture gradually to 64 C. The resulting mixture continues to be stirred for usually at least 2 hours until process monitor shows almost complete conversion. Then, the mixture is cooled down to room temperature, and transferred slowly into another jacketed reactor with pre- cooled cold Na2S03solution (250 g Na2S03in 2000 mL water). Collect the wet cake by filtration and wash the cake with water (450 mL x 2), then purification of the cake with n-heptane crystallization to afford General procedure: A mixture of aryl iodide (5) (1.0 mmol), PdCl2(PPh3)2(5.0 mol%), CuI (10 mol%), and Et3N (2 mmol, 0.3 mL) was stirred in CH3CN (3 mL) at room temperature for 20 minunder an argon atmosphere. 4-Methyl-2-(methylthio)-6-(prop-2-yn-1-yloxy)pyrimidine (3) (1.0 mmol, 0.19 g), wasthen added and the mixture was stirred at room temperature.After completion of the reaction, the crude product was subjected to flash column chromatography (hexane/ethyl acetate = 10:1) to afford the pure product (see Table 2).

Molecular Weight:283.45
XLogP3:3
Hydrogen Bond Acceptor Count:2
Exact Mass:282.88970
Monoisotopic Mass:282.88970
Topological Polar Surface Area:45.8
Heavy Atom Count:11
Complexity:161
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes