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With 1,2-diphenyl-1,1,2,2-tetrahydroperoxyethane; hydrogen bromide In water; acetonitrile at 20℃; for 2.5 h;
General procedure: To a solution of aniline/phenol (1 mmol) in CH3CN (4 mL), HBr and THPDPE (depending on the substrate as shown in Table 7) were added and the solution was stirred at room temperature. After the reaction was completed, Na2SO3 (3M, 1mL) was added to the stirring mixture followed by the addition of H2O (10 mL). The solution was stirred until the desired precipitates appeared. The products were filtered and more purification was carried out using silica- packed column chromatography (Hexane–EtOAc). All of the products were characterized on the basis of their melting points, IR, 1H NMR, and 13C NMR spectral analysis and compared with those reported
74%
With bromine In 1,4-dioxane; sodium hydroxide
EXAMPLE 25 PREPARATION OF 4-AMINO-3,5-DIBROMOBENZONITRILE STR37 To a stirred solution of 100 mg (0.847 mmoles) of p-aminobenzonitrile in 3.6 mL dioxane chilled in an ice-bath was added sequentially 356 μL (1.78 moles) of 5N sodium hydroxide solution and mg (1.78 mmoles) of bromine. The ice-water bath was removed and the reaction mixture was stirred further for 1.5 hours. After this time, 21.8 μL (0.423 mmoles) of bromine was added to drive the reaction to completion and stirring was continued for 10 minutes. The mixture was partitioned between ethyl acetate and ice-water and the organic phase was separated. It was washed with brine, dried over anhydrous sodium sulfate, filtered, and evaporated. Purification by plate layer chromatography using hexane-ethyl acetate (7:3) as the eluant provided 175 mg (74percent) of the entitled product. NMR(CDCl3) δ5.1 (bs, 2H), 7.66 (s, 2H).
Reference：
[1] RSC Advances, 2016, vol. 6, # 93, p. 90184 - 90187
[2] Journal fuer Praktische Chemie (Leipzig), 1986, vol. 328, # 4, p. 497 - 514
[3] Tetrahedron, 2018, vol. 74, # 45, p. 6584 - 6592
[4] Journal of Organic Chemistry, 1998, vol. 63, # 5, p. 1555 - 1565
[5] Journal of the American Chemical Society, 1960, vol. 82, p. 3454 - 3456
[6] Synthesis (Germany), 2013, vol. 45, # 11, p. 1497 - 1504
[7] Patent: US5455239, 1995, A,
2
[ 873-74-5 ]
[ 58633-04-8 ]
Yield
Reaction Conditions
Operation in experiment
74%
With bromine In 1,4-dioxane; sodium hydroxide
EXAMPLE 1 Preparation of 4-Amino-3,5-dibromobenzonitrile STR15 To a stirred solution of 100 mg (0.847 mmoles) of p-aminobenzonitrile in 3.6 mL dioxane chilled in an ice-bath was added sequentially 356 μL (1.78 mmoles) of 5 N sodium hydroxide solution and 284 mg (1.78 mmoles) of bromine. The ice-water bath was removed and the reaction mixture was stirred further for 1.5 hours. After this time, 21.8 μL (0.423 mmoles) of bromine was added to drive the reaction to completion and stirring was continued for 10 minutes. The mixture was partitioned between ethyl acetate and ice-water and the organic phase was separated. It was washed with brine, dried over anhydrous sodium sulfate, filtered, and evaporated. Purification by plate layer chromatography using hexane-ethyl acetate (7:3) as eluant provided 175 mg (74percent) of the entitled product. NMR(CDCl3) δ: 5.1 (bs, 2H), 7.66 (s, 2H).
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