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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。
Hydroquinone, t-butyl hydroquinone and 2,5-di-tert-butyl-p-benzoquinone were respectively reacted with diallylamine to study the reaction of diallylamino derivatives of p-benzoquinone with different structural types active. The results showed that the larger the steric hindrance of the substituents on the core of p-benzoquinone, the poorer the reactivity and the longer the reaction time. The ratio of hydroquinone to diallylamine was 1: 2, and reacted at 60 ° C for 15 h to give 2,5-bis (diallylamino) cyclohexa-2,5-diene- Dione (a) in a yield of 26.8%; the molar ratio of t-butylhydroquinone to diallylamine was 1: 1 and reacted at 60 ° C for 20 h to give 2- (tert-butyl) Diallylamino) cyclohexane-2,5-diene-1,4-dione (b) in 15.2% yield; the two products of (a) and (b) were characterized by infrared, , NMR and so on were characterized. The crystal structure of (a) was measured by X-ray diffractometry. (a) belongs to the P-1 space group with the unit cell parameters of a = 1.131 45 (16) nm, b = 1.365 1 (2) nm, c = 1.580 6 = 69.865 (2) °, γ = 74.994 (2), V = 2.213 3 (6) nm to 3, Z = 2, Dc = 1.226 mg / m 3, μ (Mo Kα) = 0.084 mm -1, λ = 0.071 073 nm, F (000) = 872.0, R = 0.128 4 (1 852). The molar ratio of 2,5-di-tert-butyl-diphenylquinone to diallylamine was 1: 1 and reacted at 60 ° C for about 100 h to yield only trace amounts of 2,5-di (tert-butyl) - (diallylamino) cyclohexa-2,5-diene-l, 4-dione (c) was initially characterized by mass spectrometry.