腈类化合物的新法合成  

New method for synthesis of nitriles

作　　者：朱周静 仝红娟 唐文强 唐初 刘斌[1] ZHU Zhou-jing;TONG Hong-juan;TANG Wen-qiang;TANG Chu;LIU Bin(Xianyang Key Laboratory of Molecular Imaging and Drug Synthesis,School of Pharmacy,Shaanxi Institute of International Trade&Commerce,Xianyang 712046,China;School of Life Science and Technology,Xidian University,Xi􀆳an 710126,China)

机构地区：[1]咸阳市分子影像与药物合成重点实验室陕西国际商贸学院医药学院,陕西咸阳712046 [2]西安电子科技大学生命科学与技术学院,陕西西安710126

出　　处：《化学研究与应用》2022年第8期1912-1919,共8页Chemical Research and Application

基　　金：陕西省自然科学基础研究计划项目(2021JM-540)资助;陕西省自然科学基础研究计划项目(2021JQ-883,2021JQ-885)资助;陕西省中药绿色制造技术协同创新中心重点培育项目(2019XT-1-05,2019XT-2-05)资助;咸阳市分子影像与药物合成重点实验室项目(2021QXNL-PT-0008)资助。

摘　　要：本文报道腈类化合物的一种新合成方法。以各种醛(2a~2q)为原料,分别与盐酸羟胺反应得到一系列醛肟中间体(3a~3q),然后在叠氮磷酸二苯酯(DPPA)和1,8-二氮杂二环十一碳-7-烯(DBU)作用下,得到一系列腈类化合物(1a~1q)。中间体及产物结构均经过~1H NMR和ESI-MS表征。其中,中间体3i、3l及产物1q结构进一步通过X-单晶衍射确证。并以2-硝基苯甲醛肟(3a)和2-硝基苯腈(1a)的合成为模型,考察反应的主要影响因素。确定产物腈的合成条件为:DPPA用量为n(DPPA)∶n(化合物3a)=1.1∶1,DBU用量为n(DBU)∶n(3a)=1.2∶1,在25℃反应30 min,产物2-硝基苯腈(1a)收率为68.5%。该合成方法工艺简单、反应时间短、产物收率高、底物适用性广、原料廉价易得,为腈类化合物的合成提供了一种高效的新方法。A new synthetic method of nitriles was reported.A series of aldoxime intermediates(3a~3q)were synthesized from aldehydes(2a~2q)with hydroxylamine hydrochloride,then a series of nitriles(1a~1q)were synthesized by the reaction of aldoxime with DPPA and DBU.The structure of intermediates and products were characterized by 1H NMR and ESI-MS.The structure of 3i,3l and 1q were further confirmed by X-ray single crystal diffraction.Also,the effect of reaction conditions on the yield of 2-nitrobenzonitrile(1a)was investigated as model reaction.The synthetic conditions of the product nitrile were determined as follows:The amount of DPPA:n(DPPA)∶n(3a)=1.1∶1,the dosage of DBU:n(DBU)∶n(3a)=1.2∶1,the yield of 2-nitrobenzonitrile(1a)was 68.5%at 25℃ for 30 min.The method had the advantages of simple process,short reaction time,high yield,wide tolerance of substrates and low cost of raw materials.It provided a new and efficient method for the synthesis of nitriles.

关 键 词：腈类化合物 醛肟 晶体结构 合成方法 

分 类 号：O623.76[理学—有机化学]