摘要
以2,2,2-三溴-1-(4-溴苯基)乙醇的合成为模式反应,通过考察氧化剂种类及用量、反应温度、碱用量对反应收率的影响,成功建立了一种经济、高效、一锅法合成2,2,2-三卤(氯、溴)乙醇类化合物的方法,通过^(1)HNMR对目标化合物进行了表征,并对反应机理进行了探讨。结果表明,以1.0 mmol/1.0 eq.伯醇为原料、DMF为溶剂、1.2 eq.2-碘酰基苯甲酸(IBX)为氧化剂,在N2保护、80℃下反应生成相应醛;无需分离纯化,以回收卤仿为卤化试剂、0.5 eq.KOH/MeOH为碱、-10℃下实现一锅法串联反应获得目标化合物,收率高达96%,在此优化条件下还可以实现克级反应。^(1)HNMR分析表明所有产物均是已知物。该方法具有后处理简单、无金属催化、底物适用范围广、收率高等优点,并为卤仿的回收处理提供了新途径。
Using the synthesis of 2,2,2-tribromo-1-(4-bromophenyl)ethanol as a model reaction,we successfully established an economic and efficient one-pot method for the synthesis of 2,2,2-trihalo(Cl,Br)ethanol compounds by investigating the effects of oxidant type and dosage,reaction temperature,and alkali dosage on yield.Moreover,we characterized the target compounds by ^(1)HNMR,and discussed the possible reaction mechanism.The results show that,when using 1.0 mmol/1.0 eq.primary alcohols as the raw material,DMF as the solvent,and 1.2 eq.2-iodoxybenzoic acid(IBX)as the oxidant,the corresponding aldehydes can be synthesized under N2 protection at 80℃;moreover,without separation and purification,the target compounds with the highest yield of 96%can be obtained by one-pot tandem reactions from the aldehydes at-10℃when recovered haloform is used as the halogenation reagent,and 0.5 eq.KOH/MeOH as the alkali.Under above optimized conditions,the gram order reaction can also be achieved.^(1)HNMR analyses show that all the products are known compounds.This synthetic method has the advantages of simple post-treatment,metal-free,wide application range of substrate,and high yield,etc.,which provides a new way for the recovery and treatment of haloform.
作者
田世颖
吉恒莹
阿布都热西提·阿布力克木
TIAN Shiying;JI Hengying;ABULIKEMU Abudurexiti(School of Chemistry and Chemical Engineering,Xinjiang Normal University,Urumqi 830054,China)
出处
《化学与生物工程》
CAS
2021年第9期19-24,共6页
Chemistry & Bioengineering
基金
新疆维吾尔自治区高校科研计划自然科学重点项目(XJEDU2020I015)
新疆师范大学电化学技术与应用工程研究中心资助项目(XJNUGCZX122018A01)。
