以焦脱镁叶绿酸-a 甲酯为起始原料, 通过对3-位乙烯基的氧化、格氏反应和E-环的空气氧化和重排在二氢卟吩周环的不同位置上构建酰基结构, 利用叶绿素-a 衍生物的烷酰基和叶绿素-b 的原有甲酰基与丙二腈进行Knoevenagel反应, 完成一系列具有长波吸收的β,β-二氰亚甲基叶绿素-a 衍生物的合成, 并对不同取向的共轭取代基团对大环分子的可见光谱所产生的影响进行了相应的讨论. 未见报道的叶绿素-a 衍生物均经UV, IR, 1H NMR 及元素分析证明其结构.
武进
,
殷军港
,
刘冉冉
,
杨泽
,
王振
,
王进军
. β,β-二氰亚甲基取代的叶绿素类二氢卟吩衍生物的合成及其可见光谱[J]. 有机化学, 2012
, 32(01)
: 149
-155
.
DOI: 10.6023/cjoc1106303
Using methyl pyropheophorbide-a as starting material, the carbonyl structures were constructed in different positions of the chlorin periphery by oxidition of the 3-vinyl group, Grignard reaction and air oxidation and rearrangement of E-ring. Then the synthesis of chlorphyll-a derivatives substituted with β,β-dicyanomethylene having long wavelength absorption property was accomplished by Knoevenagel reaction of the carbonyl group on the chromophore with malononitrile. The effect of the peripheral conjugated substitutes oriented in different directions on the visible spectra was also discussed. The structures of all new chlorine derivatives were characterized by elemtntal analysis, UV, IR and 1H NMR spectra.
[1] Bellnier, D. A.; Greco, W. R.; Loewen, G. M.; Nava, H.; Oseroff, A. R.; Pandey, R. K.; Tsuchida, T.; Dougherty, T. J. Cancer Res. 2003, 63, 1806.
[2] Steruberg, E. D.; Dolphin, D. Tetrahedron 1998, 54, 4151.
[3] Chen, Y. H.; Li, G. L.; Pandey, R. K. Curr. Org. Chem. 2004, 8, 1105.
[4] Li, J.-Z.; Liu, W.-H.; Li, F.-G.; Wang, J.-J.; Suo, Y.-R.; Liu, Y.-J. Chin. J. Org. Chem. 2007, 27, 1594 (in Chinese). (李家柱, 刘万卉, 李付国, 王进军, 索有瑞, 刘永军, 有机化学, 2007, 27, 1594.)
[5] Wang, J.-J.; Li, J.-Z.; Yin, J.-G.; Liu, Y.-J. Chin. J. Org. Chem. 2008, 28, 693 (in Chinese). (王进军, 李家柱, 殷军港, 刘永军, 有机化学, 2008, 28, 693.)
[6] Wang, J.-J.; Han, G.-F.; Wu, X.-R.; Wang, L.-M.; Shim, R.-J. Chin. J. Org. Chem. 2004, 24, 537 (in Chinese). (王进军, 韩光范, 邬旭然, 王鲁敏, 沈荣基, 有机化学, 2004, 24, 537.)
[7] Smith, K. M.; Gogg, D. A.; Simpson, D. J. J. Am. Chem. Soc. 1985, 107, 4946.
[8] Schenk, J.; Daessler, H. G. Pharmazie 1969, 24, 419
[9] Li, J.-Z. M.S. Thesis, Yantai University, Yantai, 2007 (in Chinese). (李家柱, 硕士论文, 烟台大学, 烟台, 2007.)
[10] Wang, J.-J.; Zhao, Y.; Wu, X.-R.; Han, G.-F.; Shim, Y.-K. Chin. J. Org. Chem. 2002, 22, 565 (in Chinese). (王进军, 赵岩, 吴旭然, 韩光范, 沈荣基, 有机化学, 2002, 22, 565.)
[11] Linsebigler, A. L.; Lu, G.; Yates, J. T. Chem. Rev. 1995, 95, 735.
