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有机化学 ›› 2008, Vol. 28 ›› Issue (06): 1087-1091. 上一篇    下一篇

研究简报

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

魏荣宝*，倪翔，梁娅

  

  1. (天津理工大学化学化工学院 天津 300191)
  • 收稿日期:2007-09-06 修回日期:2007-11-30 发布日期:2008-06-26
  • 通讯作者: 魏荣宝

</b>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-<br>[5.5]undecyl]}phenyl Porphyrins

WEI Rong-Bao*, NI Xiang, LIANG Ya   

  1. (<I>School of Chemistry & Chemical Engineering</i>, <I>Tianjin University of Technology</i>, <I>Tianjin 300191</i>)<i>
  • Received:2007-09-06 Revised:2007-11-30 Published:2008-06-26
  • Contact: WEI Rong-Bao

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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(<b>3</b>)和<i>α</i>,<i>β</i>,<i>γ</i>,<i>δ</i>-四-(4-甲酰基苯基)卟啉(<b>4</b>).<b> 4</b>与过量的季戊四醇反应, 得到<i>α</i>,<i>β</i>,<i>γ</i>,<i>δ</i>-四-{4-[2-(5,5-二羟甲基-1,3-二噁烷基)]}苯基卟啉(<b>5</b>), <b>5</b>与<b>3</b>的反应产物经10% NaOH 处理后, 再与过量的季戊四醇反应, 得到<i>α</i>,<i>β</i>,<i>γ</i>,<i>δ</i>-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(<b>6</b>), <b>6</b>与乙酐、丙酐、苯甲酰氯反应, 得到<i>α</i>,<i>β</i>,<i>γ</i>,<i>δ</i>-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(<b>7</b>), <i>α</i>,<i>β</i>,<i>γ</i>,<i>δ</i>-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(<b>8</b>)和<i>α</i>,<i>β</i>,<i>γ</i>,<i>δ</i>-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(<b>9</b>)等三种卟啉星形化合物. 中间体<b>1</b>～<b>6</b>和星形化合物<b>7</b>～<b>9</b>均进行了IR, <sup>1</sup>H NMR, 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. <sup>

关键词: 星形化合物, 卟啉, 季戊四醇, 丙二腈, 螺环

The intermediates of 3-[4-(2,2-dicyano)vinyl]phenyl-9-(4-formyl)phenyl-2,4,8,10-tetraoxaspiro- [5.5]undecane (<b>3</b>)<b> </b>and <i>α</i>,<i>β</i>,<i>γ</i>,<i>δ</i>-tetrakis-(4-formylphenyl)porphyrin<b> </b>(<b>4</b>)<b> </b>were prepared using terephthalaldehyde, malononitrile, pentaerythritol, tetrachlorobenzoquinone and pyrrole as starting materials. The compound of <i>α</i>,<i>β</i>,<i>γ</i>,<i>δ</i>-tetrakis-[4-(5,5-dihydroxymethyl-1,3-dioxan-2-yl]phenyl porphy-rin<b> </b>(<b>5</b>)<b> </b>was obtained by a reaction of compound <b>4 </b>with excessive pentae-rythritol. When the products <b>5 </b>and <b>3</b> were treated by 10% NaOH and excessive pentae-rythritol, the compound<b> 6 </b>was produced. The three spiro star of <i>α</i>,<i>β</i>,<i>γ</i>,<i>δ</i>-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<b> 6</b> individually reacting with acetic anhydride, propionic anhydride, ben-zoyl chloride. The products and intermediates were characterized by IR,<sup>1</sup>H NMR, MS spectra and elemental analysis. The effect of vairous parameters were discussed.<b>

Key words: pentaerythritol, porphyrin, spiro compound, malononitrile, star compound