二烯丙氨基对苯醌的合成及表征  

SYNTHESIS AND CHARACTERIZATION OF DIALLYLAMINO p-BENZOQUINONES

作　　者：王建[1,2,3] 刘玮炜[2,4] 孙媛媛[4] 曹志凌[2,4] 王赪胤[3] 王丽[4] 高广林[1] 陶玲[1] 史天智 

机构地区：[1]淮海工学院化工学院,江苏连云港222005 [2]江苏省海洋生物产业技术协同创新中心,江苏连云港222005 [3]江苏省环境材料与环境工程重点实验室,江苏扬州225002 [4]淮海工学院药学院,江苏连云港222005

出　　处：《精细石油化工》2016年第2期80-83,共4页Speciality Petrochemicals

基　　金：江苏省自然科学基金(BK20130404);连云港市科技攻关项目(CG1303);江苏省优势学科建设工程资助项目;海洋公益性行业科研专项经费项目(201505023);江苏省环境材料与环境工程重点实验室开放研究课题(K12029);连云港市科技攻关计划项目-农业攻关(CN1401和CN1304)

摘　　要：对苯二酚、叔丁基对苯二酚、2,5-二叔丁基对苯二醌分别与二烯丙基胺反应,研究不同结构类型对苯醌的二烯丙基氨基衍生物反应活性。结果表明,对苯醌母核上取代基的空间位阻越大,反应活性越差,反应时间越长。对苯二酚与二烯丙基胺物质的量比为1∶2,在60℃下反应15h,得到2,5-二(二烯丙氨基)环己-2,5-二烯-1,4-二酮(a),产率26.8%;叔丁基对苯二酚与二烯丙基胺物质的量比为1∶1,在60℃下反应20h,得到2-(叔丁基)-5-(二烯丙氨基)环己-2,5-二烯-1,4-二酮(b),产率15.2%;(a)和(b)两种产物通过红外、紫外、质谱、核磁等进行了表征。用X射线衍射法测定(a)的晶体结构。(a)属P-1空间群,晶胞参数:a=1.131 45(16)nm,b=1.365 1(2)nm,c=1.580 6(2)nm,α=86.135(2)°,β=69.865(2)°,γ=74.994(2),V=2.213 3(6)nm^3,Z=2,Dc=1.226mg/m^3,μ(Mo Kα)=0.084mm-1,λ=0.071 073nm,F(000)=872.0,R=0.128 4(1 852)。2,5-二叔丁基对苯二醌与二烯丙基胺物质的量比为1∶1,在60℃下反应约100h,仅得到微量2,5-二(叔丁基)-3-(二烯丙氨基)环己-2,5-二烯-1,4-二酮(c),通过质谱进行了初步表征。1,4-Dihydroxybenzene,tert-butylbenzoquionone and 2,5-ditert-butyl-1,4-benzoquinone are reacted with diallylamine respectively.The activity of different types of N-diallylamino quinone structure of the synthesis reaction was explored.The results showed that the bigger steric effect of the substituents on the quinone parent,the more difficult to carry out the reaction and the longer the reaction time.The molar ratio of 1,4-dihydroxybenzene to diallylamine was 1∶2.The reaction temperature was 60 ℃.The reaction time was 15 h.The yield of 2,5-bis（diallylamino）cyclohexyl-2,5-diene-1,4-dione（a）is 26.8%.The molar ratio of tert-butylbenzoquionone to diallylamine was 1∶1.The reaction temperature was 60℃.The reaction time was 20 h.The yield of 2-（tert-butyl）-5-（（diallylamino）cyclohexyla-2,5-diene-1,4-dione（b）can reach 15.2%.The products（a）and（b）were characterized by IR,UV,MS and NMR.Products（a）were investigated with X-ray crystallography.The crystal of（a）belongs to space group P-1with cell parameters：a=1.131 45（16）nm,b=1.365 1（2）nm,c=1.580 6（2）nm,α=86.135（2）°,β=69.865（2）°,γ=74.994（2）,V=2.213 3（6）nm^3,Z=2,Dc=1.226mg/m^3,μ（Mo Kα）=0.084mm^（-1）,λ=0.071 073 nm,F（000）=872.0,R（reflections）=0.128 4（1 852）.The molar ratio of 2,5-di-tert-butyl-benzoquionone to diallylamine was 1∶1.The reaction temperature was 60 ℃in about 100 h.Only to get trace 2,5-bis（t-butyl）-3-（diene propylamino）cyclohexyl-2,5-diene-1,4-dione（c）,it was preliminary characterized by mass spectrometry.

关 键 词：对苯二酚 叔丁基对苯二酚 2 5-二叔丁基对苯二醌 二烯丙基胺 

分 类 号：TQ244.61[化学工程—有机化工]