α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉星形化合物的合成  

Synthesis of Star Compound of α,β,γ,δ-Tetrakis-{4-[3-(9-(4-(3-(9-(4-(5,5-diacyloxamethyl-1,3-dioxan-2-yl)))phenyl-2,4,8,10-tetraoxaspiro-[5.5]undecyl)))phenyl-2,4,8,10-tetraoxaspiro- [5.5]undecyl]}phenyl Porphyrins

作　　者：魏荣宝[1] 倪翔[1] 梁娅[1] 

机构地区：[1]天津理工大学化学化工学院,天津300191

出　　处：《有机化学》2008年第6期1087-1091,共5页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No20472064);天津市自然科学基金(No040884311)资助项目

摘　　要：以对苯二甲醛、丙二腈、季戊四醇和吡咯为原料,合成了含有螺环结构单元的中间体3-[4-(2,2-二氰基)乙烯基]苯基-9-(4-甲酰基)苯基-2,4,8,10-四氧杂螺[5.5]十一烷(3)和α,β,γ,δ-四-(4-甲酰基苯基)卟啉(4).4与过量的季戊四醇反应,得到α,β,γ,δ-四-{4-[2-(5,5-二羟甲基-1,3-二噁烷基)]}苯基卟啉(5),5与3的反应产物经10%NaOH处理后,再与过量的季戊四醇反应,得到α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二羟甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(6),6与乙酐、丙酐、苯甲酰氯反应,得到α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二乙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(7),α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二丙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(8)和α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二苯甲酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(9)等三种卟啉星形化合物.中间体1～6和星形化合物7～9均进行了IR,1HNMR,MS和元素分析等结构表征.对影响反应的诸因素进行了讨论.The intermediates of 3-[4-（2,2-dicyano）vinyl]phenyl-9-（4-formyl）phenyl-2,4,8,10-tetraoxaspiro- [5.5]undecane （3） and α,β, γ,δ-tetrakis-（4-formylphenyl）porphyrin （4） were prepared using terephthalaldehyde, malononitrile, pentaerythritol, tetrachlorobenzoquinone and pyrrole as starting materials. The compound of α,β, γ,δ-tetralds-[4-（5,5-dihydroxymethyl-1,3-dioxan-2-yl]phenyl porphyrin （5） was obtained by a reaction of compound 4 with excessive pentaerythritol. When the products 5 and 3 were treated by 10% NaOH and excessive pentaerythritol, the compound 6 was produced. The three spiro star of α,β, γ,δ- tetrakis- { 4-[3-（9-（4-（3-（9-（4-（5,5-diacyloxamethyl- 1,3-dioxan-2-yl）））phenyl-2,4,8,10-tetraoxaspiro[5.5]- undecyl）））phenyl-2,4,8,10-tetraoxaspiro[5.5]undecyl]}phenyl porphyrins were synthsized through 6 individually reacting with acetic anhydride, propionic anhydride, benzoyl chloride. The products and intermediates were characterized by IR,^1H NMR, MS spectra and elemental analysis. The effect of vairous parameters were discussed.

关 键 词：星形化合物 季戊四醇 螺环 丙二腈 卟啉 

分 类 号：O626[理学—有机化学]