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    • 10. 发明授权
    • Processes for the preparation of 3-bromoanisole and 3-bromonitrobenzene
    • 制备3-溴苯甲醚和3-溴硝基苯的方法
    • US06380440B1
    • 2002-04-30
    • US09680961
    • 2000-10-05
    • Mark GelmontJoseph Zilberman
    • Mark GelmontJoseph Zilberman
    • C07C4100
    • C07C41/01C07C201/12C07C205/12C07C43/225
    • Process for the preparation of 3-bromoanisole comprising methoxydenitrating 3-bromonitrobenzene in the presence of a phase-transfer catalyst (PTC), and the preparation of 3-bromonirtobenzene by the bromination of nitrobenzene with bromine in oleum. The methoxydenitration reagent in an alkali metal methoxide, which is selected from sodium methoxide and potassium methoxide. The amount of methoxide used is 1-1.5 mol per mol of 3-bromonitrobenzene. The alkali methoxide can be a pre-prepared solid or it can be prepared in situ, by the reaction of the corresponding alkali hydroxide and methanol. In the case when pre-prepared solid methoxide is used, the effective amount of alkali hydroxide is between 1.2-1.7 mol per mol of 3-bromonitrobenzebe. The reaction temperatures are between about 40 to 80° C., with preference to reaction temperatures of 50 to 55° C. In the case in which methoxide is prepared in situ, the effective amount of alkali hydroxide is between 2.2-2.4 mol per mol of 3-bromonitrobenzene. The reaction temperatures are between about 50 to 80° C. with preference to reaction temperatures of 55 to 65° C.
    • 在相转移催化剂(PTC)的存在下,制备3-溴苯甲醚的方法,包括在3-溴硝基苯中甲氧基过氧化,通过在发烟硫酸中用溴溴化硝基苯来制备3-溴苯甲腈。 碱金属甲醇盐中的甲氧基浓缩试剂,其选自甲醇钠和甲醇钾。 所用的甲氧化物的量为每摩尔3-溴硝基苯为1-1.5摩尔。 碱金属甲醇盐可以是预制的固体,也可以通过相应的碱金属氢氧化物和甲醇的反应在原位制备。 在使用预制的固体甲醇钠的情况下,碱金属氢氧化物的有效量为每摩尔3-溴硝基苯醚为1.2-1.7摩尔。 反应温度为约40至80℃,优选反应温度为50至55℃。在原位制备甲醇钠的情况下,碱金属氢氧化物的有效量为2.2-2.4摩尔/摩尔 的3-溴硝基苯。 反应温度在约50至80℃之间,优选的反应温度为55至65℃。