摘要
以天然产物丹皮酚和对位芳香醛为原料来合成丹皮酚类衍生物,探讨丹皮酚和对位芳香醛反应的机理,为其利用提供科学依据。方法:室温下用丹皮酚分别与对硝基苯甲醛、对甲基苯甲醛和对氟苯甲醛在碱性介质中反应,合成对位取代的丹皮酚类衍生物,对产物利用红外光谱(IR)、紫外(UV)、质谱(MS)、核磁共振谱(NMR)、X-衍射结构分析以及元素分析等技术来表征其结构。并对3-羟基-1-(2-羟基-4-甲氧基苯)-3-(4'-硝基苯)-1-丙酮和2-羟基-4-甲氧基-4'-甲基查尔酮的晶体采用单晶X-衍射技术确定其分子结构。结果:丹皮酚与对硝基苯甲醛发生羟醛缩合反应,丹皮酚与对甲基苯甲醛、对氟苯甲醛发生Claisen-Schmidt反应生成了丹皮酚类的查尔酮衍生物,3-羟基-1-(2-羟基-4-甲氧基苯)-3-(4'-硝基苯)-1-丙酮为单斜晶系,p_1_21/c_1空点群,a=0.875 0(15)nm,b=1.137 8(2)nm,c=1.554 0(3)nm,α=90.0(8)°,β=106.5(8)°,γ=90(8)°,V=1.483 5(5)nm3,Dc=1.416 mg.m-3,μ=0.110 mm-1,F(000)=660,Z=4,R1=0.059 5,ωR2=0.185 3,R(int)=0.021 9。2-羟基-4-甲氧基-4'-甲基查尔酮为单斜晶系,P2(1)/n空点群,a=1.137 7(3)nm,b=0.683 7(17)nm,c=2.043 0(4)nm,α=90.0(10)°,β=117.7(10)°,γ=90(10)°,V=1.406 4(6)nm3,Dc=1.416 mg.m-3,μ=0.086 mm-1,F(000)=568,Z=4,R1=0.045 2,ωR2=0.122 5,R(int)=0.021 5。结论:常温下丹皮酚和对位芳香醛在碱性介质中反应经过不同的反应机理生成不同类型的衍生物。
Novel paeonol para-substitution derivatives were synthesized with the natural resources paeonol and p-nitro-benzaldehyde,p-methyl benzaldehyde,p-fluorobenzaldehyde,and discussed those reaction mechanisms,This research will provide scientific proof.Methods：Novel paeonol para-substitution derivatives were synthesized in alkaline medium with the natural resources paeonol and p-nitro-benzaldehyde,p-methyl benzaldehyde,p-fluorobenzaldehyde respectively at room temperature,three novel compounds structures were characterized by IR,UV,MS,1H-NMR,13C-NMR,135° DEPT,X-ray structure analysis.and elemental analysis.Those crystal structures of 3-hydroxy-1-（2-hydroxy-4-methoxy phenyl）-3-（4 ＇-nitrobenzene）-1-acetone and 2-hydroxy-4-methoxy-4＇-methylchalcone were also characterized by X-ray structure analysis.Results： The reaction of paeonol and p-nitro-benzaldehyde is by aldol condensation reaction,and paeonol and p-methyl benzaldehyde,or p-fluorobenzaldehyde is by Claisen-Schmidt condensation reaction.The crystal of 3-hydroxy-1-（2-hydroxy-4-methoxy phenyl）-3-（4 ＇-nitrobenzene）-1-acetone belongs to triclinic crystallographic system,space group p_1_21 /c_1 and cell parameters： a = 0.875 0（15）nm,b = 1.137 8（2） nm,c = 1.554 0（3）nm,α = 90.0（8） °,β = 106.5（8） °,γ = 90（8） °,V = 1.483 5（5） nm3,Dc = 1.41 6mg.m-3,μ = 0.110 mm-1,F（000） = 660,Z = 4,R1 = 0.059 5,ωR2= 0.185 3,R（int） = 0.021 9.The crystal 2-hydroxy-4-methoxy-4＇-methylchalcone belongs to triclinic crystallographic system,space group P2（1） /n and its cell parameters： a = 1.137 7（3） nm,b = 0.683 7（17） nm,c = 2.043 0（4） nm,α = 90.0（10）°,β = 117.7（10）°,γ = 90（10） °,V = 1.406 4（6） nm3,Dc = 1.416 mg.m-3,μ = 0.086 mm-1,F（000） = 568,Z = 4,R1 = 0.045 2,ωR2 = 0.122 5,R（int） = 0.021 5.Conclusion： Different type paeonol derivatives were synthesized in alkaline medium with the natural resources paeonol and p-nitro-benzaldehyde,p-methyl benzaldehyde,p-fluorobenzaldeh
出处
《中国实验方剂学杂志》
CAS
北大核心
2011年第9期95-100,共6页
Chinese Journal of Experimental Traditional Medical Formulae
基金
陕西省科技厅社发项目(2009K11-03)
陕西省教育厅专项科研计划项目
