ELECTRONIC EFFECTS IN MULTICENTER REARRANGEMENTS OF COMPOUNDS WITH NITROGEN-NITROGEN BONDS
ELECTRONIC EFFECTS IN MULTICENTER REARRANGEMENTS OF COMPOUNDS WITH NITROGEN-NITROGEN BONDS
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DOI：
10.1021/jo00438a032
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发表时间：
1977-01-01
影响因子：
3.6
通讯作者：
OGURI, H
中科院分区：
文献类型：
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作者：
COOLEY, JH;STONE, DM;OGURI, H
实验部分6 1-[（氯甲基）硫基]-4-（1，1-二甲基乙基）苯。向6.50 g（0.10 mol）细粉状85%氢氧化钾在300 mL溴氯甲烷中的淤浆中加入12.5 g（0.10 mol）4-（1，1-二甲基乙基）苯乙烷。向该混合物中加入0.125g（0.00055mol）苄基三乙基溴化铵，并将反应混合物在25-30 ℃下搅拌0.5小时。反应混合物为琥珀色，并且沉淀出浅黄色固体。过滤反应混合物，真空除去溴氯甲烷，留下浅琥珀色油状物。将油状物溶解在100 mL乙醚中，并将所得溶液通过无水硫酸镁过滤。在真空下从滤液中除去乙醚，留下16.5g几乎无色的油状物。减压蒸馏油状物，得到12.30克（产率60%）标题化合物，为无色液体，沸点100-106 ℃（3 mm）。1-[（氯甲基）硫代]-2，4，6-三溴苯。向1.63 g（0.025 mol）细粉状85%氢氧化钾在150 mL溴氯甲烷中的淤浆中加入8.70 g（0.025 mol）2，4，6-三溴苯乙胺。向该混合物中加入0.30g苄基三乙基溴化铵，温度在几分钟内从26 ℃升至28 ℃.将反应混合物搅拌2小时，然后过滤除去溴化钠，溴化钠分离。在真空中从滤液中除去溴氯甲烷，留下浅红棕色油。用75 mL乙醚处理油状物，溶解大部分物质，留下少量红棕色油状物。将醚溶液用无水硫酸镁干燥并过滤。用等量己烷稀释乙醚，真空浓缩所得溶液，得到4.20
Experimental Section6 1-[(Chloromethyl) thio]-4-(l, l-dimethy le thy 1) benzene. To a slurry of 6.50 g (0.10 mol) of finely powdered 85% potassium hydroxide in 300 mL of bromochloromethane were added 12.5 g (0.10 mol) of 4-(1, 1-dimethylethyl) benzenethiol. To this mixture, 0.125 g (0.00055 mol) of benzyltriethylammonium bromide was added, and the reac-tion mixture was stirred at 25-30 C for 0.5 h. The reaction mixture was amber in color, and a pale yellow solid had precipitated. The re-action mixture was filtered, and the bromochloromethane removed in vacuo leaving a light amber oil. The oil was dissolved in 100 mL of ether, and the resulting solutionfiltered through anhydrousmagnesium sulfate. The ether was removed in vacuo from the filtrate leaving 16.5 g of nearly colorless oil. Theoil was distilled under reduced pressure to give 12.30 g (60% yield) of the title compound as a colorless liquid, bp 100-106 C (3 mm).1-[(Chloromethyl) thio]-2, 4, 6-tribromobenzene. To a slurry of 1.63 g (0.025 mol) of finely powdered 85% potassium hydroxide in 150 mL of bromochloromethane was added 8.70 g (0.025 mol) of 2, 4, 6-tribromobenzenethiol. To this mixture, 0.30 g of benzyltriethylammonium bromide was added, and the temperature rose from 26 to 28 C in several minutes. The reaction mixture was stirred for 2 h and then filtered to remove the sodium bromide which separated. The bromochloromethane was removed in vacuo from the filtrate leaving a light, red-brown oil. The oil was treated with 75 mL of ether dissolving most of the material and leaving a small amount of red-brown oil. The ether solution was dried over anhydrous magnesium sulfate and filtered. The ether was diluted with an equivalent amount of hexane, and the resulting solution concentrated in vacuo to give 4.20