金属次卟啉二甲酯对空气氧化环己烷的催化作用

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (4): 723.

金属次卟啉二甲酯对空气氧化环己烷的催化作用

周维友, 胡炳成, 徐士超, 孙呈郭, 刘祖亮

南京理工大学化工学院, 南京 210094

收稿日期:2009-05-14 出版日期:2010-04-10 发布日期:2010-04-10
通讯作者: 胡炳成, 男, 博士, 副研究员, 主要从事卟啉类化合物的合成及应用研究. E-mail: hubingcheng@yahoo.com
基金资助:
江苏省自然科学基金(批准号: 2009386)和南京理工大学科技发展基金(批准号: XKF09008)资助.

Catalysis of Metallo-deuteroporphyrins for Cyclohexane Oxidation with Air

ZHOU Wei-You, HU Bing-Cheng*, XU Shi-Chao, SUN Cheng-Guo, LIU Zu-Liang

College of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

Received:2009-05-14 Online:2010-04-10 Published:2010-04-10
Contact: HU Bing-Cheng. E-mail: hubingcheng@yahoo.com
Supported by:
江苏省自然科学基金(批准号: 2009386)和南京理工大学科技发展基金(批准号: XKF09008)资助.

摘要/Abstract

摘要：

在无任何外加溶剂及共还原剂的条件下, 将金属次卟啉二甲酯应用于催化空气氧化环己烷的氧化反应. 结果表明, 金属次卟啉二甲酯能够很好地催化环己烷的氧化反应, 与简单的金属四苯基卟啉相比, 金属次卟啉二甲酯催化剂具有更高的催化活性. 进而研究了络合金属对其催化性能的影响.

关键词: 金属次卟啉二甲酯; 环己烷氧化; 仿生催化

Abstract:

The efficient and selective oxidation of hydrocarbon catalyzed by metalloporphyrins has attracted much attention from the organic and industrial chemists. During the last decades of years, a huge amount of work has shown that substituted metalloporphyrins are efficient catalysts for the oxidation of hydrocarbons at unprecedented rates under very mild conditions. However, nearly all of the metalloporphyrins used as oxidation catalysts were based on the system of synthetic meso-tetraphenylporphyrin(TPP). The high accessibility of deuteroporphyrin together with its excellent stability and close relationship to the naturally occurring heme make it an ideal compound to mimic enzymatic systems based on heme. Therefore, to investigate the catalytic activity of the deuteroporphyrins complex and search more efficient biomimetic catalysts for hydrocarbon oxidation under mild conditions, the metallo-deuteroporphyrin dimethyl esters[M(DPDME)] were used as the catalysts for cyclohexane oxidation by air without any coreductant or solvent. The results indicated that the metallo-deuteroporphyrins could smoothly catalyze the oxidation of cyclohexane under the selected conditions; and they exhibited markedly higher catalytic activity than simple metallo-tetraphenylporphyrins. The effect of central metals was discussed.

Key words: Metallo-deuteroporphyrin dimethyl ester; Cyclohexane oxidation; Biomimetic catalysis

TrendMD:

周维友, 胡炳成, 徐士超, 孙呈郭, 刘祖亮. 金属次卟啉二甲酯对空气氧化环己烷的催化作用. 高等学校化学学报, 2010, 31(4): 723.

ZHOU Wei-You, HU Bing-Cheng*, XU Shi-Chao, SUN Cheng-Guo, LIU Zu-Liang. Catalysis of Metallo-deuteroporphyrins for Cyclohexane Oxidation with Air. Chem. J. Chinese Universities, 2010, 31(4): 723.

参考文献

[1]Mansuy D.. C. R. Chim.[J], 2007, 10: 392—413
[2]ZHOU Wei-You(周维友), HU Bing-Cheng(胡炳成), LIU Zu-Liang(刘祖亮). Chemistry Online(化学通报)[J], 2008, 71(3): 179—186
[3]LIU Ye(刘晔), ZHANG Hong-Jiao(张红娇), WU Hai-Hong(吴海虹), et al.. Chem. J. Chinese Universities(高等学校化学学报)[J], 2007, 28(8): 1523—1527
[4]Guo C. C., Liu X. Q., Liu Y., et al.. J. Mol. Catal. A: Chem.[J], 2003, 192: 289—194
[5]WANG Ai-Qin(王爱琴), REN Qi-Zhi(任奇志), LIU Shuang-Yan(刘双艳), et al.. Chem. J. Chinese Universities(高等学校化学学报)[J], 2009, 30(4): 752—756
[6]Cojocaru V., Winn P. J., Wade R. C.. Biochim. Biophys. Acta[J], 2007, 1770: 390—401
[7]GUO Can-Cheng(郭灿城), ZHANG Xiao-Bing(张晓兵), OUYANG Yu-Zhu(欧阳玉祝), et al.. Chem. J. Chinese Universities(高等学校化学学报)[J], 2000, 21(2): 227—232
[8]Ji H. B., Yuan Q. L., Zhou X. T., et al.. Bioorgan. Med. Chem. Lett.[J], 2007, 17: 6364—6368
[9]WANG Xu-Tao(王旭涛), CHU Ming-Fu(褚明福), GUO Can-Cheng(郭灿城). Chem. J. Chinese Universities(高等学校化学学报)[J], 2005, 26(1): 64—67
[10]Cosnier S., Walter A., Montforts F. P.. J. Porph. Phthal.[J], 1998, 2: 39—43
[11]CHEN Liang(陈亮), LI Du-Xin(李笃信), ZHAI Mi-Lin(翟密林). J. Shanxi University(山西大学学报)[J], 1992, 15(3): 281—285
[12]Zbik D. R., Witko M.. J. Mol. Catal. A: Chem.[J], 2006, 258: 376—380
[13]Serra A. C., Marcalo E. C., Gonsalves A. M. A. R.. J. Mol. Catal. A: Chem.[J], 2004, 215:17—21
[14]MA Deng-Sheng(马登生), HU Bing-Cheng(胡炳成), L Cun-Xu(吕春绪), et al.. Chinese Appl. Chem.(应用化学)[J], 2006, 23: 848—853
[15]Geier G. R., Lindsay J. S.. J. Org. Chem.[J], 1999, 64: 1596—1603
[16]Alder A. D., Longo F. R.. J. Inorg. Nucl. Chem.[J], 1970, 32: 2443—2445
[17]Guo C. C., Chu M. F., Liu Q.. Appl. Catal. A: Gen.[J], 2003, 246: 303—309
[18]Grinstaff M. W., Hill M. G., Labinger J. A.. Science[J], 1994, 264: 1311—1313
[19]GUO Can-Cheng(郭灿城), LI Zhi-Peng(李枝蓬), LIANG Ben-Xi(梁本熹). Chem. J. Chinese Universities(高等学校化学学报)[J], 1997, 18(2): 242—246
[20]Groves J. T.. J. Inorg. Biochem.[J], 2006, 100: 434—447
[21]Groves J. T., Lee J., Marla S. S.. J. Am. Chem. Soc.[J], 1997, 119: 6269—6273
[22]Stephenson N. A., Bell A. T.. Inorg. Chem.[J], 2007, 46: 2278—2285
[23]Lyons J. E., Ellis P. E., Myers H. K.. J. Catal.[J], 1995, 155: 59—73
[24]Groves J. T.. Inorg. Chem.[J], 1987, 26: 785—786
[25]Poltowicz J., Tabor E., Pamin K., et al.. Inorg. Chem. Commun.[J], 2005, 8: 1125—1127
[26]Haber J., Matachowski L., Pamin K., et al.. J. Mol. Catal. A: Chem.[J], 2000, 162: 105—109