4-Bromo-3-nitrobenzotrifluoride

clear yellow liquid

Silak reaction tube equipped with a magnetic stirrer was charged with 6.2 mg of silver sulfate, 36.3 mg of copper acetate, and 12.5 mg of 2, 9-dimethyl-1, 10-o-phenanthroline47 mg of 2-nitro-4-trifluoromethylbenzoic acid and 30.9 mg of sodium bromide4 mL of dimethyl sulfoxide. Heat 160 ° C in the presence of oxygenReaction for 24 hours. After the reaction was completed, distilled water was added to quench the reaction, Extraction with ethyl acetate 3 times, each time 10mL, The combined organic phases are concentrated to give16.2 mg of 2-nitro-4-trifluoromethyl bromobenzene, The yield is 30percent.The above reaction was repeated but using acetic acid, acetonitrile or tetrahydrofuran instead of benzonitrile at various concentrations (0.02, 0.04, 0.1 and 1 ml/mmol). Table 14 shows the results, from which it may be seen that the optimal concentration depends upon the solvent, and that the best results were obtained at high concentration.Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Bromide Sources (Process (g)); [0086] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent) and a bromide source (cuprous bromide, cupric bromide, lithium bromide or magnesium bromide) (1 equivalent), or a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) was heated for 6 hours at 160[deg.] C. with benzonitrile, diglyme (diethylene glycol dimethyl ether), acetic acid or N-methylpyrrolidone (1 ml/mmol) to give the title product. Table 11 shows that good selectivity may be obtained using various conditions and that the mixture of cuprous bromide and lithium bromide gives particularly good results. By comparison poor results were obtained in the absence of solvent.Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Bromide Sources (Process (g)); [0086] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent) and a bromide source (cuprous bromide, cupric bromide, lithium bromide or magnesium bromide) (1 equivalent), or a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) was heated for 6 hours at 160[deg.] C. with benzonitrile, diglyme (diethylene glycol dimethyl ether), acetic acid or N-methylpyrrolidone (1 ml/mmol) to give the title product. Table 11 shows that good selectivity may be obtained using various conditions and that the mixture of cuprous bromide and lithium bromide gives particularly good results. By comparison poor results were obtained in the absence of solvent.Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Bromide Sources (Process (g)); [0086] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent) and a bromide source (cuprous bromide, cupric bromide, lithium bromide or magnesium bromide) (1 equivalent), or a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) was heated for 6 hours at 160[deg.] C. with benzonitrile, diglyme (diethylene glycol dimethyl ether), acetic acid or N-methylpyrrolidone (1 ml/mmol) to give the title product. Table 11 shows that good selectivity may be obtained using various conditions and that the mixture of cuprous bromide and lithium bromide gives particularly good results. By comparison poor results were obtained in the absence of solvent.; The above reaction was repeated but using diglyme (diethylene glycol dimethyl ether) instead of benzonitrile at various concentrations (0.01, 0.02, 0.04, 0.08, 0.1, 0.5, 1 or 2 ml/mmol). Table 13 shows that the conversion, yield and selectivity were optimal at the 0.02-0.04 ml/mmol concentration.Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Bromide Sources (Process (g)); [0086] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent) and a bromide source (cuprous bromide, cupric bromide, lithium bromide or magnesium bromide) (1 equivalent), or a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) was heated for 6 hours at 160[deg.] C. with benzonitrile, diglyme (diethylene glycol dimethyl ether), acetic acid or N-methylpyrrolidone (1 ml/mmol) to give the title product. Table 11 shows that good selectivity may be obtained using various conditions and that the mixture of cuprous bromide and lithium bromide gives particularly good results. By comparison poor results were obtained in the absence of solvent.; Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using a Mixture of Cuprous Bromide and Lithium Bromide (Process (g)); [0089] The above procedure of Example 10 was repeated using a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) with various concentrations of benzonitrile (0.02, 0.04, 0.1, 0.5, 1 or 2 ml/mmol). Table 12 shows that good selectivity was obtained using all of these conditions and that when 0.04 ml/mmol of benzonitrile was present the conversion, yield and selectivity were particularly good.; Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Ratios of a Mixture of Cuprous Bromide and Lithium Bromide (Process (g)); [0092] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent), cuprous bromide (1 equivalent) and lithium bromide (2 equivalents) in benzonitrile (4 equivalents) was heated at 180[deg.] C. for 5 hours. The cooled mixture was extracted with toluene, washed with an aqueous solution of sodium bromide and with sodium bisulphite solution, and evaporated to give the title product. The conversion (based on 4-chloro-3-nitrobenzotrifluoride) was 84percent, the yield 78percent, and the selectivity 93percent.[0093] The above reaction was repeated using cuprous bromide (0.1 equivalent) and lithium bromide (2 equivalents) giving a conversion of 83percent and a selectivity of 90percent.Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Bromide Sources (Process (g)); [0086] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent) and a bromide source (cuprous bromide, cupric bromide, lithium bromide or magnesium bromide) (1 equivalent), or a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) was heated for 6 hours at 160[deg.] C. with benzonitrile, diglyme (diethylene glycol dimethyl ether), acetic acid or N-methylpyrrolidone (1 ml/mmol) to give the title product. Table 11 shows that good selectivity may be obtained using various conditions and that the mixture of cuprous bromide and lithium bromide gives particularly good results. By comparison poor results were obtained in the absence of solvent.Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Bromide Sources (Process (g)); [0086] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent) and a bromide source (cuprous bromide, cupric bromide, lithium bromide or magnesium bromide) (1 equivalent), or a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) was heated for 6 hours at 160[deg.] C. with benzonitrile, diglyme (diethylene glycol dimethyl ether), acetic acid or N-methylpyrrolidone (1 ml/mmol) to give the title product. Table 11 shows that good selectivity may be obtained using various conditions and that the mixture of cuprous bromide and lithium bromide gives particularly good results. By comparison poor results were obtained in the absence of solvent.Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Bromide Sources (Process (g)); [0086] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent) and a bromide source (cuprous bromide, cupric bromide, lithium bromide or magnesium bromide) (1 equivalent), or a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) was heated for 6 hours at 160[deg.] C. with benzonitrile, diglyme (diethylene glycol dimethyl ether), acetic acid or N-methylpyrrolidone (1 ml/mmol) to give the title product. Table 11 shows that good selectivity may be obtained using various conditions and that the mixture of cuprous bromide and lithium bromide gives particularly good results. By comparison poor results were obtained in the absence of solvent.The above reaction was repeated but using acetic acid, acetonitrile or tetrahydrofuran instead of benzonitrile at various concentrations (0.02, 0.04, 0.1 and 1 ml/mmol). Table 14 shows the results, from which it may be seen that the optimal concentration depends upon the solvent, and that the best results were obtained at high concentration.Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Bromide Sources (Process (g)); [0086] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent) and a bromide source (cuprous bromide, cupric bromide, lithium bromide or magnesium bromide) (1 equivalent), or a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) was heated for 6 hours at 160[deg.] C. with benzonitrile, diglyme (diethylene glycol dimethyl ether), acetic acid or N-methylpyrrolidone (1 ml/mmol) to give the title product. Table 11 shows that good selectivity may be obtained using various conditions and that the mixture of cuprous bromide and lithium bromide gives particularly good results. By comparison poor results were obtained in the absence of solvent.Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Bromide Sources (Process (g)); [0086] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent) and a bromide source (cuprous bromide, cupric bromide, lithium bromide or magnesium bromide) (1 equivalent), or a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) was heated for 6 hours at 160[deg.] C. with benzonitrile, diglyme (diethylene glycol dimethyl ether), acetic acid or N-methylpyrrolidone (1 ml/mmol) to give the title product. Table 11 shows that good selectivity may be obtained using various conditions and that the mixture of cuprous bromide and lithium bromide gives particularly good results. By comparison poor results were obtained in the absence of solvent.Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Bromide Sources (Process (g)); [0086] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent) and a bromide source (cuprous bromide, cupric bromide, lithium bromide or magnesium bromide) (1 equivalent), or a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) was heated for 6 hours at 160[deg.] C. with benzonitrile, diglyme (diethylene glycol dimethyl ether), acetic acid or N-methylpyrrolidone (1 ml/mmol) to give the title product. Table 11 shows that good selectivity may be obtained using various conditions and that the mixture of cuprous bromide and lithium bromide gives particularly good results. By comparison poor results were obtained in the absence of solvent.Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Bromide Sources (Process (g)); [0086] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent) and a bromide source (cuprous bromide, cupric bromide, lithium bromide or magnesium bromide) (1 equivalent), or a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) was heated for 6 hours at 160[deg.] C. with benzonitrile, diglyme (diethylene glycol dimethyl ether), acetic acid or N-methylpyrrolidone (1 ml/mmol) to give the title product. Table 11 shows that good selectivity may be obtained using various conditions and that the mixture of cuprous bromide and lithium bromide gives particularly good results. By comparison poor results were obtained in the absence of solvent.Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Bromide Sources (Process (g)); [0086] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent) and a bromide source (cuprous bromide, cupric bromide, lithium bromide or magnesium bromide) (1 equivalent), or a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) was heated for 6 hours at 160[deg.] C. with benzonitrile, diglyme (diethylene glycol dimethyl ether), acetic acid or N-methylpyrrolidone (1 ml/mmol) to give the title product. Table 11 shows that good selectivity may be obtained using various conditions and that the mixture of cuprous bromide and lithium bromide gives particularly good results. By comparison poor results were obtained in the absence of solvent.; The above reaction was repeated but using acetic acid, acetonitrile or tetrahydrofuran instead of benzonitrile at various concentrations (0.02, 0.04, 0.1 and 1 ml/mmol). Table 14 shows the results, from which it may be seen that the optimal concentration depends upon the solvent, and that the best results were obtained at high concentration.Preparation of 4-Bromo-3-nitrobenzotrifluoride from 4-Chloro-3-nitrobenzotrifluoride Using Various Bromide Sources (Process (g)); [0086] A mixture of 4-chloro-3-nitrobenzotrifluoride (1 equivalent) and a bromide source (cuprous bromide, cupric bromide, lithium bromide or magnesium bromide) (1 equivalent), or a mixture of cuprous bromide (1 equivalent) and lithium bromide (1 equivalent) was heated for 6 hours at 160[deg.] C. with benzonitrile, diglyme (diethylene glycol dimethyl ether), acetic acid or N-methylpyrrolidone (1 ml/mmol) to give the title product. Table 11 shows that good selectivity may be obtained using various conditions and that the mixture of cuprous bromide and lithium bromide gives particularly good results. By comparison poor results were obtained in the absence of solvent.

Molecular Weight:270.00
XLogP3:2.8
Hydrogen Bond Acceptor Count:5
Exact Mass:268.92993
Monoisotopic Mass:268.92993
Topological Polar Surface Area:45.8
Heavy Atom Count:14
Complexity:228
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes