电化学传感阴离子受体的合成和性质研究
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摘要
分子识别是超分子化学研究的重要内容之一，它包括对中性分子、阳离子和阴离子的识别。其中阴离子识别较前两者发展相对迟缓，亟待丰富和发展新型识别体系。近年来，由于阴离子在生物学和环境中的重要地位，采用电化学方法进行分子识别作为传感技术的发展的一个重要组成部分，更引起了人们的广泛关注。阴离子受体一般含有阴离子的结合基团和表达阴离子结合的信号报告基团，两者可直接或通过连接臂相连。因此，信息报告基团、结合基团和连接臂的设计成为阴离子识别研究的关键。
首先，从4，5-二丁硫基-1，3-二硫杂环戊二烯-2-酮和N-对苯磺酰基-2-硫代-1，3-二硫杂环戊二烯并[4，5-c]吡咯出发，经交叉偶联、去保护得2，3-二丁硫基四硫富瓦烯并[6，7-c]吡咯11。11在碱存在下与甲醛水溶液(37％)反应生成N-羟甲基化的产物。并用~1H NMR，~(13)C NMR，IR，MALDI-TOF-MS和元素分析进行了结构表征。用核磁共振氢谱研究了12在不同极性溶剂中的偶合行为。
其次，设计并合成了三个带有单吡咯并四硫富瓦烯基团的阴离子受体，并用~1H NMR，~(13)C NMR，MS(EI)进行了结构表征。从目标化合物14c与F~-离子络合物的紫外吸收可以观察到分子内电荷转移的发生。并通过核磁共振、紫外、循环伏安法研究了化合物14b，14c与F~-，AcO~-，H_2PO_4~-等阴离子的结合能力。我们发现化合物14c对F~-离子具有高效的电化学传感和选择性，并且伴随着明显的颜色变化，核磁滴定更进一步证明了此结论。
Molecular recognition is an important research area in supramolecular chemistry.The development of anion coordination chemistry is delayed compared with neutralmolecules and cations. It is necessary to construct novel anion receptors. Recently, thesignificant role of anionic species in biology and the environment has led to increasedinvestigation into designing molecules suited to their analytical determination byelectrochemical methods. The anion receptor generally includes two groups, whichare the group that binds anion and the group that expresses the anion binding signal,which connect directly or through a connect arm. Therefore, the design of theinformation reporting groups, the anion binding groups and the connect arm is veryimportant in the study of anion recognition.
In this paper, first, by means of cross-coupling and deprotection to obtain2,3-dibutylthiotetrathiafulvaleno [6,7-c]pyrrole 13 from 4,5-dibutylthio-1,3-Dithiole-2-one and N-tosyl-2-thiono-1,3-dithiolo[4,5-c] pyrrole. Under base condition, 13 reactwith formalin(37%) to give N-hydroxymethyl product 14. The target compounds werecharacterized by ~1H NMR, ~(13)C NMR, IR, MALDI-TOF-MS and elemental analysis.The coupling behavior of 14 was studied with ~1H NMR in different polar solvents.
Secondly, we have designed and synthesized three anion receptors whichcombined with monopyrrole-TTF unit. The target compounds were characterized by~1H NMR, ~(13)C NMR, IR, MS(EI). From UV-vis spectra of the complex of targetcompound 14c and F, the intramolecular charge-transfer (CT) absorption band wasobserved clearly. We have studied the binding ability between the receptor 14b, 14cand F~-, AcO~-, H_2PO_4~- through ~1H NMR, UV-vis, and Cyclic voltammetry method. Wefind compound 14c have remarkable electrochemical sensitivity and selectivity towards F~-, which combined with visible colour change. The NMR also exhibits thisresult.
首先，从4，5-二丁硫基-1，3-二硫杂环戊二烯-2-酮和N-对苯磺酰基-2-硫代-1，3-二硫杂环戊二烯并[4，5-c]吡咯出发，经交叉偶联、去保护得2，3-二丁硫基四硫富瓦烯并[6，7-c]吡咯11。11在碱存在下与甲醛水溶液(37％)反应生成N-羟甲基化的产物。并用~1H NMR，~(13)C NMR，IR，MALDI-TOF-MS和元素分析进行了结构表征。用核磁共振氢谱研究了12在不同极性溶剂中的偶合行为。
其次，设计并合成了三个带有单吡咯并四硫富瓦烯基团的阴离子受体，并用~1H NMR，~(13)C NMR，MS(EI)进行了结构表征。从目标化合物14c与F~-离子络合物的紫外吸收可以观察到分子内电荷转移的发生。并通过核磁共振、紫外、循环伏安法研究了化合物14b，14c与F~-，AcO~-，H_2PO_4~-等阴离子的结合能力。我们发现化合物14c对F~-离子具有高效的电化学传感和选择性，并且伴随着明显的颜色变化，核磁滴定更进一步证明了此结论。
Molecular recognition is an important research area in supramolecular chemistry.The development of anion coordination chemistry is delayed compared with neutralmolecules and cations. It is necessary to construct novel anion receptors. Recently, thesignificant role of anionic species in biology and the environment has led to increasedinvestigation into designing molecules suited to their analytical determination byelectrochemical methods. The anion receptor generally includes two groups, whichare the group that binds anion and the group that expresses the anion binding signal,which connect directly or through a connect arm. Therefore, the design of theinformation reporting groups, the anion binding groups and the connect arm is veryimportant in the study of anion recognition.
In this paper, first, by means of cross-coupling and deprotection to obtain2,3-dibutylthiotetrathiafulvaleno [6,7-c]pyrrole 13 from 4,5-dibutylthio-1,3-Dithiole-2-one and N-tosyl-2-thiono-1,3-dithiolo[4,5-c] pyrrole. Under base condition, 13 reactwith formalin(37%) to give N-hydroxymethyl product 14. The target compounds werecharacterized by ~1H NMR, ~(13)C NMR, IR, MALDI-TOF-MS and elemental analysis.The coupling behavior of 14 was studied with ~1H NMR in different polar solvents.
Secondly, we have designed and synthesized three anion receptors whichcombined with monopyrrole-TTF unit. The target compounds were characterized by~1H NMR, ~(13)C NMR, IR, MS(EI). From UV-vis spectra of the complex of targetcompound 14c and F, the intramolecular charge-transfer (CT) absorption band wasobserved clearly. We have studied the binding ability between the receptor 14b, 14cand F~-, AcO~-, H_2PO_4~- through ~1H NMR, UV-vis, and Cyclic voltammetry method. Wefind compound 14c have remarkable electrochemical sensitivity and selectivity towards F~-, which combined with visible colour change. The NMR also exhibits thisresult.
引文
[1] Pedersen C.J.,Angew. Chem. Int. Ed. Engl. 1988, 27, 1021.
[2] Schmidtchen F. P, Berger, M., Chem. Rev. 1997, 97, 1609.
[3] Beer P D., Gale P A., Angew. Chem. Int. Ed. 2001, 40, 486.
[4] Shannon R. D., Acta Crystallogr. Sect. A, 1976, 32, 751.
[5] Schmidtchen F P., Muller G.,J. Chem. Soc. Chem. Commun. 1984, 1115.
[6] Worm K., Schmidtchen F.P, Angew. Chem. Int. Ed. Engl.1995, 34, 65.
[7] Pascal R. A., Spergel J., Engbersen D. V., Tetrahedron Lett. 1986, 27, 4099.
[8] S Valiyaveettil, J. F.J. Engbersen, W Verboom, D. N. Reinhoudt, Angew. Chem. 1993, 105, 942.
[9] Raposo C., Perez N., Almaraz M. L., Caballero M. C., Moran J. R., Tetrahedron Lett. 1995, 36, 3255.
[10] Kelley T. R., Kim M. H., J. Am. Chem. Soc. 1994, 116, 7072.
[11] Bulmann P., Nishizawa S., Xiao K. P., Umezawa Y., Tetrahedron 1997, 3, 1647.
[12] Gale P. A., Sessler J. L., Kra I V., V. Lynch, J. Am. Chem. Soc. 1996, 118, 5140.
[13] Sessler J. L., Gale P.A., Genge J. W., Chem. Enr. J. 1998, 4, 1095.
[14] V. Kral, J. L. Sessler, T. V. Shishkanova, P. A. Gale, R. Volf, J. Am. Chem. Soc. 1999, 121, 8771.
[15] H. Miyaji, P. Anzenbacher, Jr, J. L. Sessler, E. R. Bleasdale, P. A.Gale, Chem. Commun. 1999, 1723.
[16] A. Andrievsky, F. Ahuis, J. L. Sessler, F. V6gtle, D. Gudat, M. Moini, J. Am. Chem. Soc. 1998, 120, 9712.
[17] C. H. Park, H. E. Simmons, J. Am. Chem. Soc. 1968, 90, 2431.
[18] E. Graf, J.-M. Lehn, J. Am. Chem. Soc. 1976, 98, 6403.
[19] B. Metz, J. M. Rosalky, R. Weiss, J. Chem. Soc. Chem. Commun. 1976, 533.
[20] J.-M. Lehn, E. Sonveaux, A. K.Willard, J. Am. Chem. Soc. 1978, 100, 4914.
[21] M. W. Hosseini, J.-M. Lehn, J. Am. Chem. Soc. 1982, 104, 3525.
[22] J. A. Aguilar, E. Garcia-Espana, J. A. Guerrero, S. V. Luis, J. M. Linares, J. F. Miravet, J. A. Ramirez, C. Soriano, J. Chem. Soc. Chem. Commun. 1995, 2237.
[23] J. L. Sessler, M. J. Cyr, V. Lynch, E. McGhee, J. A. Ibers, J. Am. Chem. Soc. 1990, 112, 2810.
[24] M. Shionoya, H. Furuta, V. Lynch, A. Harriman, J. L. Sessler, J. Am. Chem. Soc. 1992, 114, 5714.
[25] M. M. G. Antonisse, D. N. Reinhoudt, Chem. Commun. 1998, 443.
[26] P. D. Beer, Chem. Commun. 1996, 689.
[27] P. D. Beer, P. A. Gale, G. Z. Chen, J. Chem. Soc. Dalton Trans. 1999, 1897.
[28] P. L. Boulas, M. GomeAz-Kaifer, L. Echegoyen, Angew. Chem. Int. Ed. 1998, 37, 216.
[29] P. D. Beer, D. Hesek, J. Hodacova, S. E. Stokes, J. Chem. Soc. Chem. Commun. 1992, 270.
[30] P. D. Beer, C. Hazlewood, D. Hesek, J. Hodacova, S. E. Stokes, J. Chem. Soc. Dalton Trans. 1993, 1327.
[31] P. D. Beer, M. G. B. Drew, A. R. Graydon, D. K. Smith, J. Chem. Soc. Dalton Trans. 1995, 403.
[32] P. D. Beer, M. G. B. Drew, J. Hodacova, S. E. Stokes, J. Chem. Soc. Dalton Trans. 1995, 3447.
[33] P. D. Beer, A. R. Graydon, A.O. M. Johnson, D. K. Smith, Inorg. Chem. 1997, 36, 2112.
[34] A. P. de Silva, H. Q. N. Gunaratne, T. Gunnlaugsson, A. J. M. Huxley, C. P. McCoy, J. T. Rademacher, T. E. Rice, Chem. Rev. 1997, 97, 1515.
[35] (a) Nielsen,M. B., Lomholt, C., Becher, Jr. Chem. Soc. Rev. 2000, 29, 153; (b) Segura, J. L., Martin, N. Angew. Chem. Int. Ed. 2001, 40, 1372; (c) Jeppesen, J. O., Becher, J. Eur. J. Org. Chem. 2003, 3245
[36] (a)Liu, H. L., Liu, S., Echegoyen, L. Chem. Commun. 1999,1493; (b)Fletcher, R. J., Lampard, C., Murphy, J. A., Lewis, N.J. Chem. Soc. Perkin Trans. 1 1995, 623. (c) Jeppesen J. O., Levillain E., Becher J., Chem. Commun. 2003, 846.
[37] Kent A. Nielsen, Jan O. Jeppesen, Eric Levillain et al, Angew. Chem. Int. Ed. 2003, 42. No. 2, 187-190.
[38] a) Chelintzev V.V. and Maksorov B.V., J. Russ. Phys. Chem. Soc., 1916, 48, 746-79. b)Silverstein R.M., Ryskiewicz E.E., and Chikin S.W., J. Am. Chem. Soc., 1954, 76, 4485-4486; c) Taniguchi S., Hasegawa H. et al., Tetrahedron, 2001, 57, 2103-2108.
[39] Jeppesen J.O., Becher J. et al., J. Org. Chem.,2000, 65, 5794-5805.
[40] Chen T., Wang C.L., Cong Z.Q., and Yin B.Z., Heterocycles, 2005, 65(1), 187-193.
[41] F.P. Schmidtchen, M. Berger. Chem. Rev. 1997, 97, 1609.
[42] T. S. Snowden, E. V. Anslyn, Curr. Opin. Chem. Biol. 1999, 3, 740.
[43] P.D. Beer and G. Z.J. Chem. Soc. Dalton Trans. 2001, 1428-1431.
[44] Paul V. Bernhardt, Nicol L. Creevey, J. Chem. Soc. Dalton Trans. 2004, 914-920.
[45] L. Nie, Z. Li, J. Han, X. Zhang, R. Yang, W.-X. Liu, E-Y. Wu, J.-W. Xie, Y.-E Zhao and Y.-B. Jiang, J. Org. Chem. 2004, 69, 6499.
[46] Z.-Y. Zeng, Y.-B. He, J.-L. Wu et al, Eur. J. Org. Chem. 2004, 2888.
[47] C. Suksai and T. Tuntulani, Chem. Soc. Rev. 2003, 32, 192.
[48] (a)S. Camiolo, P. A. Gale, M. B. Hursthouse, M. E. Light and A. J. Shi, Chem. Commun. 2002, 758; (b)P. A. Gale, K. Navakhun, S. Camiolo, M. E. Light et al, J. Am. Chem. Soc. 2002, 124, 11228.
[49] S. Camiolo, P.A. Gale, M. B. Hursthouse and M. E. Light, Org. Biomol. Chem. 2003, 1,741.
[50] T. Gunnlaugasson, P. E. Kruger, P. Jensen, F.M. Pfeffer and G. M. Hussey, Tetrahedron lett. 2003, 44, 8909.
[51] A. M. Costero, M. J. Banuls, M. J. Aurell et al., Tetreahedron 2004, 60, 9471.
[52] (a) B. M. Petersen, J. O. Jeppesen, J. Becher, Synthesis 2004, No.15, pp 2555-2559; (b)Jeppesen J. O., Takimiya K., Jensen E et al., J. Org. Lett. 1999, 1, 1291.
[53] Fumio Toda, S. J. Hyoda, K. G. Okada et al., J. Chem. Soc. Chem. Commun. 1995, 1531-1532.
[54] Louise S. E., Philip A. Gale, Mark E. L. et al., Q. Chem. Commun. 2006, 965-967.
[55] F.-Y. Wu, Z. Li, Z.-C. Wen et al., Org. Lett. 2002, Vol. 4 No. 19, 3203-3205.
[2] Schmidtchen F. P, Berger, M., Chem. Rev. 1997, 97, 1609.
[3] Beer P D., Gale P A., Angew. Chem. Int. Ed. 2001, 40, 486.
[4] Shannon R. D., Acta Crystallogr. Sect. A, 1976, 32, 751.
[5] Schmidtchen F P., Muller G.,J. Chem. Soc. Chem. Commun. 1984, 1115.
[6] Worm K., Schmidtchen F.P, Angew. Chem. Int. Ed. Engl.1995, 34, 65.
[7] Pascal R. A., Spergel J., Engbersen D. V., Tetrahedron Lett. 1986, 27, 4099.
[8] S Valiyaveettil, J. F.J. Engbersen, W Verboom, D. N. Reinhoudt, Angew. Chem. 1993, 105, 942.
[9] Raposo C., Perez N., Almaraz M. L., Caballero M. C., Moran J. R., Tetrahedron Lett. 1995, 36, 3255.
[10] Kelley T. R., Kim M. H., J. Am. Chem. Soc. 1994, 116, 7072.
[11] Bulmann P., Nishizawa S., Xiao K. P., Umezawa Y., Tetrahedron 1997, 3, 1647.
[12] Gale P. A., Sessler J. L., Kra I V., V. Lynch, J. Am. Chem. Soc. 1996, 118, 5140.
[13] Sessler J. L., Gale P.A., Genge J. W., Chem. Enr. J. 1998, 4, 1095.
[14] V. Kral, J. L. Sessler, T. V. Shishkanova, P. A. Gale, R. Volf, J. Am. Chem. Soc. 1999, 121, 8771.
[15] H. Miyaji, P. Anzenbacher, Jr, J. L. Sessler, E. R. Bleasdale, P. A.Gale, Chem. Commun. 1999, 1723.
[16] A. Andrievsky, F. Ahuis, J. L. Sessler, F. V6gtle, D. Gudat, M. Moini, J. Am. Chem. Soc. 1998, 120, 9712.
[17] C. H. Park, H. E. Simmons, J. Am. Chem. Soc. 1968, 90, 2431.
[18] E. Graf, J.-M. Lehn, J. Am. Chem. Soc. 1976, 98, 6403.
[19] B. Metz, J. M. Rosalky, R. Weiss, J. Chem. Soc. Chem. Commun. 1976, 533.
[20] J.-M. Lehn, E. Sonveaux, A. K.Willard, J. Am. Chem. Soc. 1978, 100, 4914.
[21] M. W. Hosseini, J.-M. Lehn, J. Am. Chem. Soc. 1982, 104, 3525.
[22] J. A. Aguilar, E. Garcia-Espana, J. A. Guerrero, S. V. Luis, J. M. Linares, J. F. Miravet, J. A. Ramirez, C. Soriano, J. Chem. Soc. Chem. Commun. 1995, 2237.
[23] J. L. Sessler, M. J. Cyr, V. Lynch, E. McGhee, J. A. Ibers, J. Am. Chem. Soc. 1990, 112, 2810.
[24] M. Shionoya, H. Furuta, V. Lynch, A. Harriman, J. L. Sessler, J. Am. Chem. Soc. 1992, 114, 5714.
[25] M. M. G. Antonisse, D. N. Reinhoudt, Chem. Commun. 1998, 443.
[26] P. D. Beer, Chem. Commun. 1996, 689.
[27] P. D. Beer, P. A. Gale, G. Z. Chen, J. Chem. Soc. Dalton Trans. 1999, 1897.
[28] P. L. Boulas, M. GomeAz-Kaifer, L. Echegoyen, Angew. Chem. Int. Ed. 1998, 37, 216.
[29] P. D. Beer, D. Hesek, J. Hodacova, S. E. Stokes, J. Chem. Soc. Chem. Commun. 1992, 270.
[30] P. D. Beer, C. Hazlewood, D. Hesek, J. Hodacova, S. E. Stokes, J. Chem. Soc. Dalton Trans. 1993, 1327.
[31] P. D. Beer, M. G. B. Drew, A. R. Graydon, D. K. Smith, J. Chem. Soc. Dalton Trans. 1995, 403.
[32] P. D. Beer, M. G. B. Drew, J. Hodacova, S. E. Stokes, J. Chem. Soc. Dalton Trans. 1995, 3447.
[33] P. D. Beer, A. R. Graydon, A.O. M. Johnson, D. K. Smith, Inorg. Chem. 1997, 36, 2112.
[34] A. P. de Silva, H. Q. N. Gunaratne, T. Gunnlaugsson, A. J. M. Huxley, C. P. McCoy, J. T. Rademacher, T. E. Rice, Chem. Rev. 1997, 97, 1515.
[35] (a) Nielsen,M. B., Lomholt, C., Becher, Jr. Chem. Soc. Rev. 2000, 29, 153; (b) Segura, J. L., Martin, N. Angew. Chem. Int. Ed. 2001, 40, 1372; (c) Jeppesen, J. O., Becher, J. Eur. J. Org. Chem. 2003, 3245
[36] (a)Liu, H. L., Liu, S., Echegoyen, L. Chem. Commun. 1999,1493; (b)Fletcher, R. J., Lampard, C., Murphy, J. A., Lewis, N.J. Chem. Soc. Perkin Trans. 1 1995, 623. (c) Jeppesen J. O., Levillain E., Becher J., Chem. Commun. 2003, 846.
[37] Kent A. Nielsen, Jan O. Jeppesen, Eric Levillain et al, Angew. Chem. Int. Ed. 2003, 42. No. 2, 187-190.
[38] a) Chelintzev V.V. and Maksorov B.V., J. Russ. Phys. Chem. Soc., 1916, 48, 746-79. b)Silverstein R.M., Ryskiewicz E.E., and Chikin S.W., J. Am. Chem. Soc., 1954, 76, 4485-4486; c) Taniguchi S., Hasegawa H. et al., Tetrahedron, 2001, 57, 2103-2108.
[39] Jeppesen J.O., Becher J. et al., J. Org. Chem.,2000, 65, 5794-5805.
[40] Chen T., Wang C.L., Cong Z.Q., and Yin B.Z., Heterocycles, 2005, 65(1), 187-193.
[41] F.P. Schmidtchen, M. Berger. Chem. Rev. 1997, 97, 1609.
[42] T. S. Snowden, E. V. Anslyn, Curr. Opin. Chem. Biol. 1999, 3, 740.
[43] P.D. Beer and G. Z.J. Chem. Soc. Dalton Trans. 2001, 1428-1431.
[44] Paul V. Bernhardt, Nicol L. Creevey, J. Chem. Soc. Dalton Trans. 2004, 914-920.
[45] L. Nie, Z. Li, J. Han, X. Zhang, R. Yang, W.-X. Liu, E-Y. Wu, J.-W. Xie, Y.-E Zhao and Y.-B. Jiang, J. Org. Chem. 2004, 69, 6499.
[46] Z.-Y. Zeng, Y.-B. He, J.-L. Wu et al, Eur. J. Org. Chem. 2004, 2888.
[47] C. Suksai and T. Tuntulani, Chem. Soc. Rev. 2003, 32, 192.
[48] (a)S. Camiolo, P. A. Gale, M. B. Hursthouse, M. E. Light and A. J. Shi, Chem. Commun. 2002, 758; (b)P. A. Gale, K. Navakhun, S. Camiolo, M. E. Light et al, J. Am. Chem. Soc. 2002, 124, 11228.
[49] S. Camiolo, P.A. Gale, M. B. Hursthouse and M. E. Light, Org. Biomol. Chem. 2003, 1,741.
[50] T. Gunnlaugasson, P. E. Kruger, P. Jensen, F.M. Pfeffer and G. M. Hussey, Tetrahedron lett. 2003, 44, 8909.
[51] A. M. Costero, M. J. Banuls, M. J. Aurell et al., Tetreahedron 2004, 60, 9471.
[52] (a) B. M. Petersen, J. O. Jeppesen, J. Becher, Synthesis 2004, No.15, pp 2555-2559; (b)Jeppesen J. O., Takimiya K., Jensen E et al., J. Org. Lett. 1999, 1, 1291.
[53] Fumio Toda, S. J. Hyoda, K. G. Okada et al., J. Chem. Soc. Chem. Commun. 1995, 1531-1532.
[54] Louise S. E., Philip A. Gale, Mark E. L. et al., Q. Chem. Commun. 2006, 965-967.
[55] F.-Y. Wu, Z. Li, Z.-C. Wen et al., Org. Lett. 2002, Vol. 4 No. 19, 3203-3205.