新型杯[4]芳烃衍生物的合成及其光谱性质研究
摘要
杯芳烃是由4～20个苯酚单元在2，6位与亚甲基相连形成的大环低聚物。随着杯芳烃化学的发展，功能化的杯芳烃已用于分子识别、离子识别、分子探针、医药等各种领域。
本文以对叔丁基苯酚和甲醛为起始原料，通过缩合再通过一步或二步取代反应合成了五种新型对叔丁基杯[4]芳烃衍生物(化合物A、B、C、D、E)，其结构经FT-IR、~1H NMR、FAB-MS表征确认。对化合物D、化合物3与稀土离子Eu~(3+)、Tb~(3+)的配合识别进行了详细的研究，以及将D·Eu~(3+)作为小牛胸腺DNA分子探针作了初步探讨。
Calixarenes are made up of 4-20 phenol units linked by methylene bridges for macrocyclic oligomers. With the development of chemistry of calixarene the functionalized calixarene have been widely used in molecular recognition, ion recognition, molecular fluorescence probe, medicine etc.
Five new p-tert-butylcalix[4]arene derivatives (compounds A,B,C,D,E) were synthesized by condensation, it takes one-step or two-step substitute to react with p-tert-phenol and formaldehyde as starting materials, respectively. The product structures were identified by FT-IR, 1H NMR, FAB-MS spectra. The complex recognition of compound D and compound 3 to Eu3 +, Tb3+ were investigated in details, and a preliminary investigation is tale for the fluorescene probe after adding DNA.
本文以对叔丁基苯酚和甲醛为起始原料，通过缩合再通过一步或二步取代反应合成了五种新型对叔丁基杯[4]芳烃衍生物(化合物A、B、C、D、E)，其结构经FT-IR、~1H NMR、FAB-MS表征确认。对化合物D、化合物3与稀土离子Eu~(3+)、Tb~(3+)的配合识别进行了详细的研究，以及将D·Eu~(3+)作为小牛胸腺DNA分子探针作了初步探讨。
Calixarenes are made up of 4-20 phenol units linked by methylene bridges for macrocyclic oligomers. With the development of chemistry of calixarene the functionalized calixarene have been widely used in molecular recognition, ion recognition, molecular fluorescence probe, medicine etc.
Five new p-tert-butylcalix[4]arene derivatives (compounds A,B,C,D,E) were synthesized by condensation, it takes one-step or two-step substitute to react with p-tert-phenol and formaldehyde as starting materials, respectively. The product structures were identified by FT-IR, 1H NMR, FAB-MS spectra. The complex recognition of compound D and compound 3 to Eu3 +, Tb3+ were investigated in details, and a preliminary investigation is tale for the fluorescene probe after adding DNA.
引文
[1] Gutsche C. D., Muthukrishnan R. J. Org. Chem., 1978, 43: 4905-4907.
[2] Gutsche C. D. Acc. Chem. Res., 1983, 16: 161-170.
[3] IkedaA, ShinkaiS. Chem. Rev., 1997, 97: 1713-1734.
[4] 黄志镗(Huang Z．T．)，杨联明(Yang L．M．)．化学进展(progressin Chemistry), 1994, 6: 173-177.
[5] Bohmer V. Angew. Chem, Int. Ed. Engl., 1995, 34: 713-745.
[6] MarkovskyL, Visotsky M, Pirozhenko V, etal. Chem. Com-mun., 1996: 69-72.
[7] Chawla H. M., SrinivasK, Meena. Tetrahedron, 1995, 51: 2709-2718.
[8] 郑炎松(Zheng YS)．化学进展(Progressin Chemistry)，1999，11：275-285．
[9] 林琳(LinL)，吴采樱(WuCY)．分析化学(ChineseJ．Anal．Chem．)，1997，25：850-856
[10] 陈淑华(Chen S．H．)，李东红(Li D．H．)，袁立华(Yuan L．H．)等．有机化学
(Chin. J. Org. Chem.), 1999, 19: 339-347.
[11] 郑炎松，沈之荃．化学通报(Chem．Bull．)，1998，(4)：27-32．
[12] Andreetti, G. D; Ungaro R.; Pochini, A. J. Chem, Soc., Chem. Commun. 1979. 1005.
[13] Gutsche, C. D.; Dhawan, B.; Levine. J. A.; No. K. H.; Bauer, L, J. Tetrahedron 1983. 39. 409.
[14] Gutsche, C. D.; Bauer, L, J. Tetrahedron Lett. 1981, 22: 4763.
[15] Gutsche, C. D.; Bauer, L, J. J. Am. Chem. Soc. 1985, 107: 6052
[16] Den Otter, W. K.; Briels, W. J. J. Am. Chem. Soc. 1998, 120: 13167
[17] Kusano, T.; Tabatabai, M.; Okamoto, Y.; BOhmer, V. J. Am. Chem. Soc. 1999, 121: 3789.
[18] Coruzzi, M.; Andreetti, G. D., Bocchi, V.; Pochini, A.; Ungaro, R. J. Chem. Soc., Perkin Trans. 2. 1982: 1133.
[19] Andreetti, G. D.; Calestani, G.; Ugozzoli, F.; Arduini, A.; Ghidini, E.; Pochini, A.; Unga ro, R. J. Inclusin Phenom. 1987, 5: 123.
[20] Gutsche, C. D.; Gutsche, A. E.; Karaulov, A. I. J. Inclusion Phenom. 1985, 3: 477.
[21] Danil De Namor A. F., Gill E., Tanc MAL, etal. J. Phys. Chem., 1995, 99: 16776-16780.
[22] BellSEJ, BrowneJK, McKeeV, etal. J. Org. Chem., 1998, 63: 489-501.
[23] GroteGanseyMHB, VerboomW, VeggeIFC, etal. J. Chem. Soc., Perkin Trans. 2, 1998: 2351-2360.
[24] RudkevichDM, VerboomW, VanderToIE, etal. J. Chem. Soc., PerkinTrans. 2, 1995: 131-134.
[25] Jin T, KinjoM, KobayashiY, HirataH. J. Chem. Soc., Faraday Trans., 1998, 94: 3135-3140.
[26] MeierU, Detellier C. Supramol. Chem., 1998, (9): 289-299.
[27] MeierU, DetellierC. J. Phys. Chem. A, 1999, 113: 3825-3829.
[28] BarbosoS, Carrera A G, MatthewsSE, etal. J. Chem. Soc., Perkin Trans. 2, 1999: 719-723.
[29] VanDerVeenNJ, EberinkRJM, EngbersenJFJ, etal. Chem. Commun., 1999: 681-682
[30] Rostaing S P, VainsJBRD, LamartineR.Tetrahedron Lett., 1996, 37: 5889-5892.
[31] DavisJT, TirumalaSK, MarlowA L. J. Am. Chem. Soc., 1997, 119: 5271-5272.
[32] JiHF, BrownG M, DabestaniR. Chem. Commun., 1999: 609-610.
[33] DoneldB, GaryD, Domenico C G. J. Chem. Soc., Chem. Commun., 1995: 675-676.
[34] Talanova G G, NazerSAE, Vladmir S T, RiehardAB. Anal. Chem., 1999, 71: 3106-3109.
[35] James T D, SamankumaruSandanayakeKRA, ShinkaiS. Natrue, 1995, 374: 345-347
[36] ParkerKS, TownsendA, BaleSJ. Anal. Proc., 1995, 32: 183-187.
[37] GradyT, HarrisSJ, SmythMR, DiamondD. Anal. Chem., 1996, 68: 3775-3782.
[38] OhsetoF, MurakamiH, etal. TetrahedronLett, 1992, 33: 1 217-1220.
[39] Aleksiuke O, GrynszpanF, BialiSE, etal. J. Org. Chem., 1993, 58: 1994-1996.
[40] 郑企雨(ZhenQY)，黄志镗(HuangZT)．化学进展(Progressin Chemistry)，1997，9：151-159．
[41] Kim J S, YuI Y, Pong J H, et al. Microchem. J., 1998, 58: 225-228.
[42] KimJS, OhkiA, UekiR, et al. Talanta, 1999, 48: 705-710.
[43] Saiki T, GotoK, TokitohY. J. Org. Chem., 1996, 61: 2924-2925.
[44] NicodL, Rostaing S P, ChitryF, et al. Tetrahedron Lett., 1998, 39: 9443-9446.
[45] Asfari Z, Naumann C, Kaufmann G, VieensJ. Tetrahedron Lett., 1998, 39: 9007-9010.
[46] Arnaud-Neu F, FergusonG, FuangswaadiS, et al. J. Org. Chem., 1998, 63: 7770-7779.
[47] ProdiL, PivariS, BolletteE et al. Eur. J. Inorg. Chem., 1998: 1959-1962.
[48] ChenY Y, Li J S, XinJ, et al. Synth. Commun., 1999, 29: 705-711.
[49] ChenY Y, Li J S, Zhong Z L, Lu X R. Tetrahedron, 1998, 54: 15183-15188.
[50] Arena G, Cotino A, Lombarbo G G, etal.Thermochim. Acta, 1995, 264: 1-11.
[51] Morozumi T, ShinkaiS. J. Chem. Soc., Chem. Commun., 1994: 1219-1220.
[52] Douteau-Guevel N, ColemanAW, Morel J-P, et al. J. Phys. Org. Chem., 1998, 11: 693-696.
[53] Stodeman M, DharN. Thermochim. Acta, 1998, 320: 33-42.
[54] Steemers F J, MeurisHG, V erboomW, Reinhoudt D N. J. Org. Chem., 1997, 62: 4229-4235.
[55] Yeng X, McBranchD, Swanson B, et al. Synthsis, 1994: 185-189.
[56] MatsumotoH, ShinkaiS. Tetrahedron Lett., 1996, 37: 77-80.
[57] Chawla H M, Srinivas K. J. Chem. Soc., Chem. Commun., 1994: 2593-2594.
[58] KuboY, Meade S, TokitaS, et al. Nature, 1996, 382: 522-524.
[59] Gordon J LM, BohmerV, VogtW. Tetrahedron Lett., 1995, 36: 2445-2447.
[60] SharmaSK, Gutsche C D. J. Org. Chem., 1999, 64: 998-1003.
[61] Saadioui M, Shivanyuk A, BohmerV, VogtW. J. Org. Chem., 1999, 64: 3774-3777.
[62] Gonzalaz J J, Prados P, Mendoza J. Angew. Chem. Int. Ed., 1998, 38: 525-528.
[63] David Gutsche, Muzaffer Iqbal, andDONALD Strwart, Calixarenes. 18 Synthesis Procedures for p-tret-Butycalix[4]arene. J. Org. Chem, 1986, 51: 7 42-745.
[64] Araki K, Iwamoto K, Shinkai S, Mastuda T. Bull. Chem. Soc. Jpn., 1990, 63: 3480.
[2] Gutsche C. D. Acc. Chem. Res., 1983, 16: 161-170.
[3] IkedaA, ShinkaiS. Chem. Rev., 1997, 97: 1713-1734.
[4] 黄志镗(Huang Z．T．)，杨联明(Yang L．M．)．化学进展(progressin Chemistry), 1994, 6: 173-177.
[5] Bohmer V. Angew. Chem, Int. Ed. Engl., 1995, 34: 713-745.
[6] MarkovskyL, Visotsky M, Pirozhenko V, etal. Chem. Com-mun., 1996: 69-72.
[7] Chawla H. M., SrinivasK, Meena. Tetrahedron, 1995, 51: 2709-2718.
[8] 郑炎松(Zheng YS)．化学进展(Progressin Chemistry)，1999，11：275-285．
[9] 林琳(LinL)，吴采樱(WuCY)．分析化学(ChineseJ．Anal．Chem．)，1997，25：850-856
[10] 陈淑华(Chen S．H．)，李东红(Li D．H．)，袁立华(Yuan L．H．)等．有机化学
(Chin. J. Org. Chem.), 1999, 19: 339-347.
[11] 郑炎松，沈之荃．化学通报(Chem．Bull．)，1998，(4)：27-32．
[12] Andreetti, G. D; Ungaro R.; Pochini, A. J. Chem, Soc., Chem. Commun. 1979. 1005.
[13] Gutsche, C. D.; Dhawan, B.; Levine. J. A.; No. K. H.; Bauer, L, J. Tetrahedron 1983. 39. 409.
[14] Gutsche, C. D.; Bauer, L, J. Tetrahedron Lett. 1981, 22: 4763.
[15] Gutsche, C. D.; Bauer, L, J. J. Am. Chem. Soc. 1985, 107: 6052
[16] Den Otter, W. K.; Briels, W. J. J. Am. Chem. Soc. 1998, 120: 13167
[17] Kusano, T.; Tabatabai, M.; Okamoto, Y.; BOhmer, V. J. Am. Chem. Soc. 1999, 121: 3789.
[18] Coruzzi, M.; Andreetti, G. D., Bocchi, V.; Pochini, A.; Ungaro, R. J. Chem. Soc., Perkin Trans. 2. 1982: 1133.
[19] Andreetti, G. D.; Calestani, G.; Ugozzoli, F.; Arduini, A.; Ghidini, E.; Pochini, A.; Unga ro, R. J. Inclusin Phenom. 1987, 5: 123.
[20] Gutsche, C. D.; Gutsche, A. E.; Karaulov, A. I. J. Inclusion Phenom. 1985, 3: 477.
[21] Danil De Namor A. F., Gill E., Tanc MAL, etal. J. Phys. Chem., 1995, 99: 16776-16780.
[22] BellSEJ, BrowneJK, McKeeV, etal. J. Org. Chem., 1998, 63: 489-501.
[23] GroteGanseyMHB, VerboomW, VeggeIFC, etal. J. Chem. Soc., Perkin Trans. 2, 1998: 2351-2360.
[24] RudkevichDM, VerboomW, VanderToIE, etal. J. Chem. Soc., PerkinTrans. 2, 1995: 131-134.
[25] Jin T, KinjoM, KobayashiY, HirataH. J. Chem. Soc., Faraday Trans., 1998, 94: 3135-3140.
[26] MeierU, Detellier C. Supramol. Chem., 1998, (9): 289-299.
[27] MeierU, DetellierC. J. Phys. Chem. A, 1999, 113: 3825-3829.
[28] BarbosoS, Carrera A G, MatthewsSE, etal. J. Chem. Soc., Perkin Trans. 2, 1999: 719-723.
[29] VanDerVeenNJ, EberinkRJM, EngbersenJFJ, etal. Chem. Commun., 1999: 681-682
[30] Rostaing S P, VainsJBRD, LamartineR.Tetrahedron Lett., 1996, 37: 5889-5892.
[31] DavisJT, TirumalaSK, MarlowA L. J. Am. Chem. Soc., 1997, 119: 5271-5272.
[32] JiHF, BrownG M, DabestaniR. Chem. Commun., 1999: 609-610.
[33] DoneldB, GaryD, Domenico C G. J. Chem. Soc., Chem. Commun., 1995: 675-676.
[34] Talanova G G, NazerSAE, Vladmir S T, RiehardAB. Anal. Chem., 1999, 71: 3106-3109.
[35] James T D, SamankumaruSandanayakeKRA, ShinkaiS. Natrue, 1995, 374: 345-347
[36] ParkerKS, TownsendA, BaleSJ. Anal. Proc., 1995, 32: 183-187.
[37] GradyT, HarrisSJ, SmythMR, DiamondD. Anal. Chem., 1996, 68: 3775-3782.
[38] OhsetoF, MurakamiH, etal. TetrahedronLett, 1992, 33: 1 217-1220.
[39] Aleksiuke O, GrynszpanF, BialiSE, etal. J. Org. Chem., 1993, 58: 1994-1996.
[40] 郑企雨(ZhenQY)，黄志镗(HuangZT)．化学进展(Progressin Chemistry)，1997，9：151-159．
[41] Kim J S, YuI Y, Pong J H, et al. Microchem. J., 1998, 58: 225-228.
[42] KimJS, OhkiA, UekiR, et al. Talanta, 1999, 48: 705-710.
[43] Saiki T, GotoK, TokitohY. J. Org. Chem., 1996, 61: 2924-2925.
[44] NicodL, Rostaing S P, ChitryF, et al. Tetrahedron Lett., 1998, 39: 9443-9446.
[45] Asfari Z, Naumann C, Kaufmann G, VieensJ. Tetrahedron Lett., 1998, 39: 9007-9010.
[46] Arnaud-Neu F, FergusonG, FuangswaadiS, et al. J. Org. Chem., 1998, 63: 7770-7779.
[47] ProdiL, PivariS, BolletteE et al. Eur. J. Inorg. Chem., 1998: 1959-1962.
[48] ChenY Y, Li J S, XinJ, et al. Synth. Commun., 1999, 29: 705-711.
[49] ChenY Y, Li J S, Zhong Z L, Lu X R. Tetrahedron, 1998, 54: 15183-15188.
[50] Arena G, Cotino A, Lombarbo G G, etal.Thermochim. Acta, 1995, 264: 1-11.
[51] Morozumi T, ShinkaiS. J. Chem. Soc., Chem. Commun., 1994: 1219-1220.
[52] Douteau-Guevel N, ColemanAW, Morel J-P, et al. J. Phys. Org. Chem., 1998, 11: 693-696.
[53] Stodeman M, DharN. Thermochim. Acta, 1998, 320: 33-42.
[54] Steemers F J, MeurisHG, V erboomW, Reinhoudt D N. J. Org. Chem., 1997, 62: 4229-4235.
[55] Yeng X, McBranchD, Swanson B, et al. Synthsis, 1994: 185-189.
[56] MatsumotoH, ShinkaiS. Tetrahedron Lett., 1996, 37: 77-80.
[57] Chawla H M, Srinivas K. J. Chem. Soc., Chem. Commun., 1994: 2593-2594.
[58] KuboY, Meade S, TokitaS, et al. Nature, 1996, 382: 522-524.
[59] Gordon J LM, BohmerV, VogtW. Tetrahedron Lett., 1995, 36: 2445-2447.
[60] SharmaSK, Gutsche C D. J. Org. Chem., 1999, 64: 998-1003.
[61] Saadioui M, Shivanyuk A, BohmerV, VogtW. J. Org. Chem., 1999, 64: 3774-3777.
[62] Gonzalaz J J, Prados P, Mendoza J. Angew. Chem. Int. Ed., 1998, 38: 525-528.
[63] David Gutsche, Muzaffer Iqbal, andDONALD Strwart, Calixarenes. 18 Synthesis Procedures for p-tret-Butycalix[4]arene. J. Org. Chem, 1986, 51: 7 42-745.
[64] Araki K, Iwamoto K, Shinkai S, Mastuda T. Bull. Chem. Soc. Jpn., 1990, 63: 3480.