Chinese Journal of Organic Chemistry >
Synthesis of 3,4-Ethylenedioxythiophene Substituted with Hydroxymethyl and Iodomethyl Groups and Their Selective Esterification and Etherification
Received date: 2012-08-18
Revised date: 2012-09-10
Online published: 2012-09-12
Supported by
Project supported by the National Natural Science Foundation of China (Nos. 21076078, 20872035, 20676036).
3,4-Ethylenedioxythiophene (EDOT) and its derivatives contained hydroxyl groups are good blocks for the synthesis of the functional molecules based on EDOT. However, the products of the reaction between dimethyl 3,4-dihydroxy-thiophene-2,5-dicarboxylate (1) and epibromohydrin via Williamson etherification were a mixture of dimethyl 2'-hydroxymethyl-3,4-ethylendioxy-thiophene-2,5-dicarboxylate (2) and dimethyl 2'-hydroxypropyl-3,4-dioxythiophene- 2,5-dicarboxylate (2'), which is difficult to separate. Dimethyl 2'-iodomethyl-3,4-ethylendioxy-thiophene-2,5-dicarboxylate (3) and dimethyl 2'-iodopropyl-3,4-dioxythiophene-2,5-dicarboxylate (3') as well as 3,4-ethylendioxy-2'-hydroxymethyl-thio- phene (4) and 3,4-dioxy-2'-hydroxypropyl-thiophene (4') were synthesized by using the mixture. They are still mixtures and difficult to separate. It is very surprising that when an etherification reaction between the mixture (3+3') and cyanoethyl-carried tetrathiafulvalene (TTF-1) was conducted, the reaction showed highly selectivity, i.e., only 3 could react with TTF-1. The same situation happened when an esterification between the mixture (4+4') and carboxylic acid carried tetrathiafulvalene (TTF-3) was made, only 4 could react with TTF-3. Both the reactions afforded a single product, i.e., EDOT-TTF 1 and EDOT-TTF 2, respectively, whose chemical structures were characterized by 1H NMR, 13C NMR, MS, and HRMS.
Zuo Hujin , Zhang Lei , Wu Changzhi , Wang Chengyun , Shen Yongjia . Synthesis of 3,4-Ethylenedioxythiophene Substituted with Hydroxymethyl and Iodomethyl Groups and Their Selective Esterification and Etherification[J]. Chinese Journal of Organic Chemistry, 2013 , 33(01) : 148 -153 . DOI: 10.6023/cjoc201208017
[1] Roncali, J. Chem. Rev. 1992, 92, 711.
[2] Roncali, J. Chem. Rev. 1997, 97, 173.
[3] Groenendaal, L. B.; Zotti, G.; Aubert, P. H.; Waybright, S. M.; Reynolds, J. R. Adv. Mater. 2003, 115, 855.
[4] Groenendaal, L. B.; Jonas, F.; Freitag, D.; Pielarzik, H.; Reynolds, J. R. Adv. Mater. 2000, 12, 481.
[5] Wang, F.; Wilson, M. S.; Rauh, D.; Schottland, P.; Thompson, B. C.; Reynolds, J. R. Macromolecules 2000, 33, 2083.
[6] Bao, Z.; Chan, W.; Yu, L. Chem. Mater 1993, 5, 2.
[7] Aubert, P. H.; Knipper, M.; Groenendaal, L.; Lutsen, L.; Manca, J.; Vanderzande, D. Macromolecules 2004, 37, 4087.
[8] Segura, J. L.; Martín, M. Angew. Chem., Int. Ed. 2001, 40, 1372.
[9] Inagi, S.; Naka, K,; Chujo, Y. J. Mater. Chem. 2007, 17, 4122.
[10] Skabara, P. J.; Roberts, D. M.; Serebryakov, I. M.; Pozo-Gonzalo, C. Chem. Commun. 2000, 1005.
[11] Liu, Y. B.; Wang, C. Y.; Li, M. J.; Lai G. Q.; Shen, Y. J. Macromolecules 2008, 41, 2045.
[12] Liu, Y. B.; Wang, C. Y.; Li, M. J.; Lai G. Q.; Shen, Y. J. New J. Chem. 2008, 32, 505.
[13] Huchet, L.; Akoudad, S.; Roncali, J. Adv. Mater. 1998, 10, 541.
[14] Lima, A.; Schottland, P.; Sadki, S.; Chevrot, C. Synth. Met. 1998, 93, 33.
[15] Binet, L.; Fabre, J. M. Synthesis 1997, 1179.
[16] Zhang, L.; Wu, C. Z.; Zuo, H. J.; Wang, C. Y.; Shen, Y. J. J. Heterocycl. Chem. 2012, in press.
/
| 〈 |
|
〉 |
