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Thiacalix[4]arene derivatives with proximally bridged lower rim
Tetrahedron 61 (2005) 9990–9995
Thiacalix[4]arene derivatives with proximally bridged lower rim Va´clav Sˇt’astny´,a Ivan Stibor,a Hana Petrˇ´ıcˇkova´,b Jan Sy´korac and Pavel Lhota´ka,* a
Department of Organic Chemistry, Prague Institute of Chemical Technology, Technicka´ 5, 166 28 Prague 6, Czech Republic b Department of Solid State Chemistry, Institute of Chemical Technology, Technicka´ 5, 166 28 Prague 6, Czech Republic c Institute of Chemical Process Fundamentals, Czech Academy of Science, Rozvojova´ 135, 165 02 Prague 6, Czech Republic Received 3 June 2005; revised 22 July 2005; accepted 4 August 2005 Available online 26 August 2005
Abstract—New types of lower rim proximally bridged thiacalix[4]arenes have been prepared by direct aminolysis of starting tetraacetate derivative in the cone conformation using aliphatic a,u-diamines. X-ray crystallography revealed the highly preorganized array of –C(O) NH– bonds resulting in strong intramolecular hydrogen bonding between amide groups of both bridges. The length of the corresponding diamine was found to have an essential influence on the yield of these bridged molecules. q 2005 Elsevier Ltd. All rights reserved.
1. Introduction Thiacalixarenes1 have appeared recently as novel members of the well-known calixarene2 family. The presence of four sulfur atoms results in many novel features3 compared with ‘classical’ calixarenes, such as different complexation ability with sulfur contribution, easy chemical modification, different size and different conformational behaviour. Hence, thiacalix[4]arene exhibits a broad range of interesting functions, which make this compound a good candidate for many applications in supramolecular chemistry. Despite some recently described procedures for thiacalix[4]arene derivatization,4,5 the chemistry of these compounds is still rather undeveloped. In our recent papers, we have described the synthesis of thiacalix[4]arenes bearing amidic functions on the lower rim.4q,r,t These molecules represent potential building blocks suitable, for example, as the cores for dendritic structures or host systems preorganized for the complexation of various guests. The total number of described amidefunctionalized thiacalix[4]arenes, however, still remains relatively low.3 Until now the most frequent way of synthesising amide-functionalized thiacalix[4]arenes has been to use of the corresponding carboxylic acids together with appropriate coupling agents (DCC, CDI, HOBt etc.) or by application of reactive acyl chlorides. During our research connected with syntheses of thiacalix[4]arenebased dendritic cores,4q,r we also investigated the Keywords: Thiocalixarene; Aminolysis; Bridged molecule. * Corresponding author. Tel.: C420 220 445 055; fax: C420 220 444 288; e-mail: [email protected] 0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.tet.2005.08.017
preparation of amide-functionalized thiacalix[4]arenes by means of the ester aminolysis reaction. Several examples of aminolysis of ethyl or methyl esters of ‘classical’ calix[4]arenes have been already reported.6,7 Among them Wu et al. described the formation (unfortunately, without any specification of the yields) of unusual lower rim double 1,2-amide-bridged calix[4]arenes upon treatment of calix[4]arene tetraethyl acetate with an excess of appropriate diamines in ethanol.7b To the best of our knowledge there is no example of aminolysis reaction in the thiacalix[4]arene family so far with only one exception. In our recent paper we have mentioned aminolysis of the known tetraacetate cone 1 with an excess of ethylenediamine in THF at ambient temperature. However, only an intractable mixture containing the corresponding tetraamine derivative 4 (nZ2) as major product together with partly substituted and bridged compounds has been obtained.4r Herein we wish to report the results of aminolysis of readily accessible p-tert-butylthiacalix[4]arene tetraethyl acetate 1 in the cone conformation4e with an excess of different aliphatic a,u-diamines 2a–c in refluxing ethanol.
2. Results and discussion 2.1. Synthesis The aminolysis reaction was accomplished according to Scheme 1. Tetraacetate derivative 1 was refluxed with 10 equiv of appropriate a,u-diamine 2a–c in ethanol overnight to give the corresponding doubly-bridged compounds 3a–3c fixed in the cone conformation in 36, 19 and 8% yields, respectively. These compounds were
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Scheme 1. Aminolysis reaction of p-tert-butylthiacalix[4]arene tetraacetate in cone conformation with aliphatic a,u-diamines.
easily isolated by preparative TLC on silica gel, as their chromatographic behaviour is substantially different (highest Rf values) from the all other components of complicated reaction mixtures. Interestingly, the yield of doubly intramoleculary bridged cone conformers 3a–3c depends on the excess of corresponding diamine. Thus, using less then 5 equiv of diamine led to a rapid decrease in the yield of doubly bridged molecules and the singly bridged compounds 5a and 5b in which two ethyl ester groups remained unreacted were also isolated in low yields (Table 1). However, we did not observe the formation of singly bridged derivatives 6 bearing two free amino groups as described Wu et al. in the case of classical calix[4]arene.7b On the other hand, increasing the excess of diamine over 10 equiv did not have any significant effect on the yield. Another interesting feature of this reaction is the fact that even a high excess of diamines 2a–c did not lead to the formation of tetraamides 4. The same results were obtained using dioxane at 80 8C as solvent instead of ethanol. As indicated in Scheme 1, the yield of doubly-bridged thiacalix[4]arenes 3a–3c rapidly decreases with increasing length of the a,u-diamine’s chain. This clearly point out that an accurate length of the chain of the corresponding diamine is an essential prerequisite for the successful spanning of the two neighbouring (proximal) phenyl rings in p-tert-butylthiacalix[4]arene. Table 1. Aminolysis of thiacalix[4]arene 1 with diamine 2a–c in refluxing ethanol a,u-Diamine
Equiv
Product (yield %)
2a
10 2.5 10 2.5 10 2.5
3a (36) 3a (10)C5a (16) 3b (19) 3b (8)C5b (9) 3c (8) 3c (5), 5c-Not isolated
2b 2c
2.2. 1H NMR and X-ray study Very simple 1H NMR spectra of doubly amide-bridged p-tert-butylthiacalix[4]arenes 3a–3c precisely reflect their C2n symmetry (Fig. 1a). Spanning of two proximal positions on the lower rim with symmetrical bridge causes the nonequivalence of geminal –O–CH2–C(O)– (Hc, Hc 0 ) protons. These protons form an AX spin system and each of them is, in 1H NMR spectrum, represented by a doublet with a typical geminal coupling constant (JZ13.7 Hz). Similarly, the aromatic protons (Hb, Hb 0 ), are represented by two doublets with characteristic meta-splitting (JZ2.2 Hz). On the other hand, the accumulation of signals in 1H NMR spectra of singly amide-bridged derivatives 5a and 5b is caused by the lower symmetry of these molecules. The presence of two singlets belonging to tert-butyl protons (Ha, Ha 0 ) together with signals corresponding to the protons (Hf and Hg) of free ethyl ester groups is in agreement with the above shown structures. As depicted in Figure 1b, four doublets with geminal coupling constants in the range of 15.0–15.5 Hz belonging to reciprocally non-equivalent –O– CH2–C(O)– protons of both amide-bridges (Hc and Hc 0 ) and free acetate groups (Hc 00 and Hc 000 ) can be observed in the region between 4.2 and 5.3 ppm. Four doublets with characteristic meta-splitting (JZ2.4 Hz) patterns in the aromatic region represent further evidence for the singly amide-bridged structure. The structures of the above described doubly-bridged thiacalix[4]arenes 3a, 3b and 3c were unequivocally proven by single crystal X-ray analysis. Suitable single crystals were grown from CH2Cl2/MeOH mixture and were stable in air. As follows from Figure 2, amide-bridges on the lower rim represent a cyclic arrays of binding sites (–NH–C(O)–), potentially suitable for the complexation of selected
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Figure 1. 1H NMR spectra (300 MHz, CDCl3, 25 8C) of derivatives 3a (a) and 5a (b).
substrates by means of hydrogen bonds. Thiacalix[4]arene units adopt the pinched cone conformation with two opposite aromatic rings pointing out of the cavity and the other two tilted towards each other. The conformation of amide-bridging units on the lower rim of derivative 3a is held by three strong intramolecular hydrogen bonds: (S/ ˚ , O/H–N distances 2.07 and 2.25 A ˚ ). H–N distance 2.73 A Similarly, one of the amide –C(O)– groups in molecule 3b is distorted into the cavity, forming strong intramolecular hydrogen bonds with both neighbour and opposite amide ˚ ). –NH– groups: (O/H–N distances 2.30 and 2.46 A Finally, the distortion of one of amide-bridging units in derivative 3c is caused by three intramolecular hydrogen bonds employing both the hydrogen atoms of –NH– amide ˚ , O/H–N distances 1.97 groups: (S/H–N distance 2.28 A ˚ ). and 2.73 A In conclusion, we have demonstrated that the aminolysis of readily accessible thiacalix[4]arene tetraacetate 1 with various a,u-diamines 2 does not lead to the proposed tetraamides 4 but rather gives unusual lower rim doublybridged molecules of type 3. These compounds represent macrocyclic structures possessing well preorganised array of –NH–CO– binding sites on the lower rim. The potential
applications of these compounds in supramolecular chemistry are currently under study.
3. Experimental All moisture sensitive reactions were carried out under nitrogen atmosphere. All dry solvents were prepared according to standard procedures and stored over molecular sieves. Melting points are uncorrected and were determined using a Boetius Block apparatus (Carl Zeiss Jena, Germany). 1 H NMR spectra were recorded at 300 MHz. Elemental analyses were measured on Perkin-Elmer 240 instruments. All samples were dried in the desiccator over P2O5 under vacuum (1 Torr) at 80 8C for 8 h. Mass spectra were measured using FAB technique on ZAB-EQ (VG Analytical) spectrometer. The IR spectra were measured on an FT-IR spectrometer Nicolet 740 in KBr. The purity of the substances and the courses of reactions were monitored by TLC using TLC aluminum sheets with Silica gel 60 F254 (Merck). Preparative TLC chromatography was carried out on 20!20 cm glass plates covered by Silica gel 60 GF254 (Merck). The column chromatography was performed using Silica gel 60 (Merck).
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˚ ). Figure 2. X-ray structures of doubly amide-bridged p-tert-butylthiacalix[4]arene derivatives 3a, 3b and 3c (all distances in A
Compound 14e was prepared according to known procedure. 3.1. Aminolysis of p-tert-butylthiacalix[4]arene tetraethyl acetate 1 (cone) leading to doubly bridged products—general procedure p-tert-Butylthiacalix[4]arene tetraethyl acetate 1 (1.00 g, 0.94 mmol) was suspended in 100 ml of ethanol and 9.4 mmol of the corresponding aliphatic a,u-diamine was added in one portion. The reaction mixture was stirred under reflux for 16 h and then the solvent was evaporated under reduced pressure. The doubly bridged product was isolated by preparative TLC (SiO2, CHCl3/MeOH 10:1). 3.1.1. Doubly amide-bridged p-tert-butylthiacalix[4] arene 3a (cone). Isolated as a white crystalline compound (RfZ0.56, 338 mg, 36% yield). Mp O350 8C (CHCl3– MeOH); 1H NMR (300 MHz, CDCl3) d 1.12 (s, 36H, –C(CH3)3); 3.49–3.52 (m, 4H, –CH2–CH2–NH–C(O)–); 3.72–3.74 (m, 4H, –C(O)–NH–CH2–CH2–); 4.04 (d, 4H, JZ13.7 Hz, –O–CH2–); 5.19 (d, 4H, JZ13.7 Hz, –O–CH2–); 7.37 (d, 4H, JZ2.2 Hz, ArH); 7.40 (d, 4H, JZ2.2 Hz, ArH); 7.79 (m, 4H, –C(O)–NH–); MS (FAB) m/z (rel intensity): 1002 [MHC] (100); IR (KBr) nmax (cmK1): 3341, 1681,
1600, 1550. Calcd for C52H64N4O8S4: C, 62.37; H, 6.44; N, 5.60 S, 12.81. Found: C, 62.47; H, 6.41; N, 5.10; S 12.52. 3.1.2. Doubly amide-bridged p-tert-butylthiacalix[4] arene 3b (cone). Obtained according to the general procedure as a white crystalline compound (RfZ0.62, 184 mg, 19% yield). Mp O350 8C (CHCl3–MeOH); 1H NMR (300 MHz, CDCl3) d 1.14 (s, 36H, –C(CH3)3); 1.98 (m, 2H, –CH2–CH2–CH2–NH–C(O)–); 2.15 (m, 2H, –CH2– CH2–CH2–NH–C(O)–); 3.49–3.56 (m, 4H, –C(O)–NH– CH2–CH2–); 3.68–3.72 (m, 4H, –C(O)–NH–CH2–CH2–); 4.67 (d, 4H, JZ14.6 Hz, –O–CH2–); 4.90 (d, 4H, JZ 14.6 Hz, –O–CH2–); 7.37 (d, 4H, JZ2.5 Hz, ArH); 7.40 (d, 4H, JZ2.5 Hz, ArH); 7.84 (t, 4H, JZ5.2 Hz, –C(O)–NH–); MS (FAB) m/z (rel intensity): 1030 [MHC] (100); IR (KBr) n max (cm K1): 3336, 1682, 1676, 1533. Calcd for C54H68N4O8S4: C, 63.01; H, 6.66; N, 5.44. Found: C, 62.77; H, 6.38; N, 5.41. 3.1.3. Doubly amide-bridged p-tert-butylthiacalix[4] arene 3c (cone). Prepared according to the general procedure and isolated as a beige crystalline compound (RfZ0.56, 79 mg, 8% yield). Mp O350 8C (CHCl3– MeOH); 1H NMR (300 MHz, CDCl3) d 1.14 (s, 36H, –C(CH3)3); 1.87 (br s, 8H, –CH2–CH2–CH2–NH–C(O)–);
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3.51 (br s, 8H, –C(O)–NH–CH2–CH2–); 4.46 (d, 4H, JZ 14.9 Hz, –O–CH2–); 5.19 (d, 4H, JZ15.1 Hz, –O–CH2–); 7.37 (d, 4H, JZ2.5 Hz, ArH); 7.41 (d, 4H, JZ2.2 Hz, ArH); 7.78 (t, 4H, JZ5.1 Hz, –C(O)–NH–); MS (FAB) m/z (rel intensity): 1058 [MHC] (100); IR (KBr) nmax (cmK1): 3387, 1676, 1542. Calcd for C56H72N4O8S4: C, 63.61; H, 6.86; N, 5.30. Found: C, 63.52; H, 6.73; N, 5.21. 3.2. Aminolysis of p-tert-butylthiacalix[4]arene tetraethyl acetate 1 (cone) leading to singly bridged products—general procedure p-tert-Butylthiacalix[4]arene tetraethyl acetate 1 (0.50 g, 0.47 mmol) was suspended in 50 ml of ethanol and 1.18 mmol of the corresponding aliphatic a,u-diamine was added in one portion. The reaction mixture was stirred under reflux for 24 h and then the solvent was evaporated under reduced pressure. The singly bridged product was isolated by preparative TLC (SiO2, CHCl3/MeOH 10:1). 3.2.1. Singly amide-bridged p-tert-butylthiacalix[4]arene diethyl acetate 5a (cone). Obtained as a beige crystalline compound (RfZ0.79, 78 mg, 16% yield). Mp 228–230 8C (CHCl3–MeOH); 1H NMR (300 MHz, CDCl3) d 1.03 (s, 18H, –C(CH3)3); 1.05 (s, 18H, –C(CH3)3); 1.15–1.22 (m, 6H, –O–CH2–CH3); 3.56 (m, 4H, –C(O)–NH–CH2–CH2–); 4.14–4.20 (m, 6H, –O–CH2–CH3 and –O–CH2–); 4.71 (d, 2H, JZ15.1 Hz, –O–CH2–); 4.98 (d, 2H, JZ15.1 Hz, –O– CH2–); 5.22 (d, 2H, JZ14.9 Hz, –O–CH2–); 7.25 (d, 4H, JZ2.4 Hz, ArH); 7.30 (d, 4H, JZ2.4 Hz, ArH); 7.33 (d, 4H, JZ2.4 Hz, ArH); 7.39 (d, 4H, JZ2.4 Hz, ArH); 8.53 (m, 2H, –C(O)–NH–); MS (FAB) m/z (rel intensity): 1033 [MHC] (100); IR (KBr) nmax (cmK1): 3351, 1766, 1733, 1683, 1541. 3.2.2. Singly amide-bridged p-tert-butylthiacalix[4]arene diethyl acetate 5b (cone). Isolated as a beige crystalline compound (RfZ0.71, 44 mg, 9% yield). Mp 292–294 8C (CHCl3–MeOH); 1H NMR (300 MHz, CDCl3) d 1.03 (s, 18H, –C(CH3)3); 1.05 (s, 18H, –C(CH3)3); 1.18 (t, 6H, JZ 7.2 Hz, –O–CH2–CH3); 1.99 (m, 4H, –CH2–CH2–CH2– NH–C(O)–); 3.46 (m, 4H, –C(O)–NH–CH2–CH2–); 3.56 (m, 4H, –C(O)–NH–CH2–CH2–); 4.16 (q, 4H, JZ7.2 Hz, –O–CH2–CH3–); 4.50 (d, 2H, JZ15.4 Hz, –O–CH2–); 4.82 (d, 2H, JZ15.1 Hz, –O–CH2–); 4.93 (d, 2H, JZ15.1 Hz, –O–CH2–); 5.19 (d, 2H, JZ15.4 Hz, –O–CH2–); 7.23–7.27 (m, 8H, ArH); 8.27 (t, 2H, JZ5.9 Hz, –C(O)–NH–); MS (FAB) m/z (rel intensity): 1047 [MHC] (100); IR (KBr) nmax (cmK1): 3405, 1746, 1727, 1680, 1552. 3.3. Crystallographic study X-ray data were collected on an Enraf Nonius CAD4 diffractometer with graphite monochromated Cu Ka radiation at 293 K. The structures were solved by direct methods. Mercury v.1.2.1. available as freeware at http:// www.ccdc.cam.ac.uk/mercury/ was used for visualization. X-ray data for 3a: C52H64N4O8S4, MZ1001.3 g/mol, triclinic system, space group P -1, aZ13.635(1), bZ ˚ , aZ102.09(1), bZ101.54(1), 13.915(1), cZ18.115(2) A ˚ 3, ZZ2, DcZ1.12 g cmK3, gZ112.23(1)8, VZ2959.2(6) A K1 m(Cu Ka)Z1.87 mm , crystal dimensions of 0.2!0.3!
0.8 mm. The structure was solved by direct method8 and anisotropically refined by full matrix least-squares on F values9 to final RZ0.066 and RwZ0.064 using 5880 independent reflections (qmaxZ64.958, 656 parameters). Hydrogen atoms were located from expected geometry and were not refined. j-scan was used for absorption correction. Crystallographic data were deposited in CSD under CCDC registration number 268283. X-ray data for 3b: C54H 68N 4O 8S 4$0.5CH2 Cl 2, MZ 1070.9 g/mol, monoclinic system, space group C 2/c, aZ ˚ , bZ103.23(1)8, 28.993(2), bZ13.9700(9), cZ30.661(2) A 3 ˚ VZ12089(1) A , ZZ8, DcZ1.18 g cmK3, m(Cu Ka)Z 2.26 mmK1, crystal dimensions of 0.1!0.2!0.9 mm. The structure was solved by direct method8 and anisotropically refined by full matrix least-squares on F values9 to final RZ 0.096 and RwZ0.072 using 3076 independent reflections (qmaxZ67.948, 591 parameters). Hydrogen atoms were located from expected geometry and were not refined. Molecule of dichloromethane was not able to refine, the SQUEEZE method was applied. Crystallographic data were deposited in CSD under CCDC registration number 268282. X-ray data for 3c: C56H72N4O8S4, MZ1057.4 g/mol, monoclinic system, space group P 21/c, aZ12.705(3), bZ ˚ , bZ95.00(2)8, VZ6728(2) A ˚ 3, 14.295(3), cZ37.189(3) A K3 K1 ZZ4, DcZ1.04 g cm , m(Cu Ka)Z0.19 mm , crystal dimensions of 0.2!0.3!0.6 mm. The structure was solved by direct method8 and anisotropically refined by full matrix least-squares on F values9 to final RZ0.077 and RwZ0.039 using 5505 independent reflections (qmaxZ59.958, 662 parameters). Hydrogen atoms were located from expected geometry and were not refined. j-scan was used for absorption correction. Crystallographic data were deposited in CSD under CCDC registration number 268284.
Acknowledgements This work was supported by the Grant Agency of the Czech Republic (No. 203/03/0926).
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16, 611–619. (t) Sˇt’astny´, V.; Stibor, I.; Dvorˇa´kova´, H.; Lhota´k, P. Tetrahedron 2004, 60, 3383–3391. (u) Himl, M.; Pojarova´, M.; Stibor, I.; Sy´kora, J.; Lhota´k, P. Tetrahedron Lett. 2005, 46, 461–464. For the upper rim derivatisation of thiacalix[4]arene, see for example: (a) Iki, N.; Fujimoto, T.; Miyano, S. Chem. Lett. 1998, 625. (b) Desroches, C.; Parola, S.; Vocanson, F.; Ehlinger, N.; Miele, P.; Lamartine, R.; Bouix, J.; Eriksson, A.; Lindgren, M.; Lopes, C. J. Mater. Chem. 2001, 11, 3014–3017. (c) Iki, N.; Horiuchi, T.; Oka, H.; Koyama, K.; Morohashi, N.; Kabuto, C.; Miyano, S. J. Chem. Soc., Perkin Trans. 2 2001, 2219–2225. (d) Lhota´k, P.; Himl, M.; Stibor, I.; Sykora, J.; Cisarova, I. Tetrahedron Lett. 2001, 42, 7107–7110. (e) Lhota´k, P.; Mora´vek, J.; Stibor, I. Tetrahedron Lett. 2002, 43, 3665–3668. (f) Lhota´k, P.; Svoboda, J.; Stibor, I.; Sykora, J. Tetrahedron Lett. 2002, 43, 7413–7417. (g) Desroches, C.; Parola, S.; Vocanson, F.; Perrin, M.; Lamartine, R.; Letoffe, J. M.; Bouix, J. New J. Chem. 2002, 26, 651–655. (h) Lhotak, P.; Smejkal, T.; Stibor, I.; Havlicek, J.; Tkadlecova, M.; Petrickova, H. Tetrahedron Lett. 2003, 44, 8093–8097. (i) Parola, S.; Desroches, C. Collect Czech. Chem. Commun. 2004, 69, 966–983. (j) Desroches, C.; Kesslerb, V. G.; Parola, S. Tetrahedron Lett. 2004, 45, 6329–6331. (k) Hu, X.; Shi, H.; Shi, X.; Zhu, Z.; Sun, Q.; Li, Y.; Yang, H. Bull. Chem. Soc. Jpn. 2005, 78, 138–141. Oueslati, I.; Abidi, R.; Thue´ry, P.; Nierlich, M.; Asfari, Z.; Harrowfield, J.; Vicens, J. Tetrahedron Lett. 2000, 41, 8263–8267. (a) Wu, Y.; Liu, H.-B.; Hu, J.; Liu, Y.-J.; Duan, C.-Y.; Xu, Z. Chin. J. Chem. 2000, 18, 94–103. (b) Wu, Y.; Shen, X.-P.; Duan, C.-Y.; Liu, Y.-J.; Xu, Z. Tetrahedron Lett. 1999, 40, 5749–5752. Altomare, A.; Cascarano, G.; Giacovazzo, G.; Guagliardi, A.; Burla, M. C.; Polidori, G.; Camalli, M. J. Appl. Crystallogr. 1994, 27, 435. Watkin, D. J.; Prout, C. K.; Carruthers, R. J.; Betteridge, P. In Crystals, Vol. 10; Chemical Crystallography Laboratory: Oxford, UK, 1996.
Thiacalix[4]arene derivatives with proximally bridged lower rim Va´clav Sˇt’astny´,a Ivan Stibor,a Hana Petrˇ´ıcˇkova´,b Jan Sy´korac and Pavel Lhota´ka,* a
Department of Organic Chemistry, Prague Institute of Chemical Technology, Technicka´ 5, 166 28 Prague 6, Czech Republic b Department of Solid State Chemistry, Institute of Chemical Technology, Technicka´ 5, 166 28 Prague 6, Czech Republic c Institute of Chemical Process Fundamentals, Czech Academy of Science, Rozvojova´ 135, 165 02 Prague 6, Czech Republic Received 3 June 2005; revised 22 July 2005; accepted 4 August 2005 Available online 26 August 2005
Abstract—New types of lower rim proximally bridged thiacalix[4]arenes have been prepared by direct aminolysis of starting tetraacetate derivative in the cone conformation using aliphatic a,u-diamines. X-ray crystallography revealed the highly preorganized array of –C(O) NH– bonds resulting in strong intramolecular hydrogen bonding between amide groups of both bridges. The length of the corresponding diamine was found to have an essential influence on the yield of these bridged molecules. q 2005 Elsevier Ltd. All rights reserved.
1. Introduction Thiacalixarenes1 have appeared recently as novel members of the well-known calixarene2 family. The presence of four sulfur atoms results in many novel features3 compared with ‘classical’ calixarenes, such as different complexation ability with sulfur contribution, easy chemical modification, different size and different conformational behaviour. Hence, thiacalix[4]arene exhibits a broad range of interesting functions, which make this compound a good candidate for many applications in supramolecular chemistry. Despite some recently described procedures for thiacalix[4]arene derivatization,4,5 the chemistry of these compounds is still rather undeveloped. In our recent papers, we have described the synthesis of thiacalix[4]arenes bearing amidic functions on the lower rim.4q,r,t These molecules represent potential building blocks suitable, for example, as the cores for dendritic structures or host systems preorganized for the complexation of various guests. The total number of described amidefunctionalized thiacalix[4]arenes, however, still remains relatively low.3 Until now the most frequent way of synthesising amide-functionalized thiacalix[4]arenes has been to use of the corresponding carboxylic acids together with appropriate coupling agents (DCC, CDI, HOBt etc.) or by application of reactive acyl chlorides. During our research connected with syntheses of thiacalix[4]arenebased dendritic cores,4q,r we also investigated the Keywords: Thiocalixarene; Aminolysis; Bridged molecule. * Corresponding author. Tel.: C420 220 445 055; fax: C420 220 444 288; e-mail: [email protected] 0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.tet.2005.08.017
preparation of amide-functionalized thiacalix[4]arenes by means of the ester aminolysis reaction. Several examples of aminolysis of ethyl or methyl esters of ‘classical’ calix[4]arenes have been already reported.6,7 Among them Wu et al. described the formation (unfortunately, without any specification of the yields) of unusual lower rim double 1,2-amide-bridged calix[4]arenes upon treatment of calix[4]arene tetraethyl acetate with an excess of appropriate diamines in ethanol.7b To the best of our knowledge there is no example of aminolysis reaction in the thiacalix[4]arene family so far with only one exception. In our recent paper we have mentioned aminolysis of the known tetraacetate cone 1 with an excess of ethylenediamine in THF at ambient temperature. However, only an intractable mixture containing the corresponding tetraamine derivative 4 (nZ2) as major product together with partly substituted and bridged compounds has been obtained.4r Herein we wish to report the results of aminolysis of readily accessible p-tert-butylthiacalix[4]arene tetraethyl acetate 1 in the cone conformation4e with an excess of different aliphatic a,u-diamines 2a–c in refluxing ethanol.
2. Results and discussion 2.1. Synthesis The aminolysis reaction was accomplished according to Scheme 1. Tetraacetate derivative 1 was refluxed with 10 equiv of appropriate a,u-diamine 2a–c in ethanol overnight to give the corresponding doubly-bridged compounds 3a–3c fixed in the cone conformation in 36, 19 and 8% yields, respectively. These compounds were
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Scheme 1. Aminolysis reaction of p-tert-butylthiacalix[4]arene tetraacetate in cone conformation with aliphatic a,u-diamines.
easily isolated by preparative TLC on silica gel, as their chromatographic behaviour is substantially different (highest Rf values) from the all other components of complicated reaction mixtures. Interestingly, the yield of doubly intramoleculary bridged cone conformers 3a–3c depends on the excess of corresponding diamine. Thus, using less then 5 equiv of diamine led to a rapid decrease in the yield of doubly bridged molecules and the singly bridged compounds 5a and 5b in which two ethyl ester groups remained unreacted were also isolated in low yields (Table 1). However, we did not observe the formation of singly bridged derivatives 6 bearing two free amino groups as described Wu et al. in the case of classical calix[4]arene.7b On the other hand, increasing the excess of diamine over 10 equiv did not have any significant effect on the yield. Another interesting feature of this reaction is the fact that even a high excess of diamines 2a–c did not lead to the formation of tetraamides 4. The same results were obtained using dioxane at 80 8C as solvent instead of ethanol. As indicated in Scheme 1, the yield of doubly-bridged thiacalix[4]arenes 3a–3c rapidly decreases with increasing length of the a,u-diamine’s chain. This clearly point out that an accurate length of the chain of the corresponding diamine is an essential prerequisite for the successful spanning of the two neighbouring (proximal) phenyl rings in p-tert-butylthiacalix[4]arene. Table 1. Aminolysis of thiacalix[4]arene 1 with diamine 2a–c in refluxing ethanol a,u-Diamine
Equiv
Product (yield %)
2a
10 2.5 10 2.5 10 2.5
3a (36) 3a (10)C5a (16) 3b (19) 3b (8)C5b (9) 3c (8) 3c (5), 5c-Not isolated
2b 2c
2.2. 1H NMR and X-ray study Very simple 1H NMR spectra of doubly amide-bridged p-tert-butylthiacalix[4]arenes 3a–3c precisely reflect their C2n symmetry (Fig. 1a). Spanning of two proximal positions on the lower rim with symmetrical bridge causes the nonequivalence of geminal –O–CH2–C(O)– (Hc, Hc 0 ) protons. These protons form an AX spin system and each of them is, in 1H NMR spectrum, represented by a doublet with a typical geminal coupling constant (JZ13.7 Hz). Similarly, the aromatic protons (Hb, Hb 0 ), are represented by two doublets with characteristic meta-splitting (JZ2.2 Hz). On the other hand, the accumulation of signals in 1H NMR spectra of singly amide-bridged derivatives 5a and 5b is caused by the lower symmetry of these molecules. The presence of two singlets belonging to tert-butyl protons (Ha, Ha 0 ) together with signals corresponding to the protons (Hf and Hg) of free ethyl ester groups is in agreement with the above shown structures. As depicted in Figure 1b, four doublets with geminal coupling constants in the range of 15.0–15.5 Hz belonging to reciprocally non-equivalent –O– CH2–C(O)– protons of both amide-bridges (Hc and Hc 0 ) and free acetate groups (Hc 00 and Hc 000 ) can be observed in the region between 4.2 and 5.3 ppm. Four doublets with characteristic meta-splitting (JZ2.4 Hz) patterns in the aromatic region represent further evidence for the singly amide-bridged structure. The structures of the above described doubly-bridged thiacalix[4]arenes 3a, 3b and 3c were unequivocally proven by single crystal X-ray analysis. Suitable single crystals were grown from CH2Cl2/MeOH mixture and were stable in air. As follows from Figure 2, amide-bridges on the lower rim represent a cyclic arrays of binding sites (–NH–C(O)–), potentially suitable for the complexation of selected
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Figure 1. 1H NMR spectra (300 MHz, CDCl3, 25 8C) of derivatives 3a (a) and 5a (b).
substrates by means of hydrogen bonds. Thiacalix[4]arene units adopt the pinched cone conformation with two opposite aromatic rings pointing out of the cavity and the other two tilted towards each other. The conformation of amide-bridging units on the lower rim of derivative 3a is held by three strong intramolecular hydrogen bonds: (S/ ˚ , O/H–N distances 2.07 and 2.25 A ˚ ). H–N distance 2.73 A Similarly, one of the amide –C(O)– groups in molecule 3b is distorted into the cavity, forming strong intramolecular hydrogen bonds with both neighbour and opposite amide ˚ ). –NH– groups: (O/H–N distances 2.30 and 2.46 A Finally, the distortion of one of amide-bridging units in derivative 3c is caused by three intramolecular hydrogen bonds employing both the hydrogen atoms of –NH– amide ˚ , O/H–N distances 1.97 groups: (S/H–N distance 2.28 A ˚ ). and 2.73 A In conclusion, we have demonstrated that the aminolysis of readily accessible thiacalix[4]arene tetraacetate 1 with various a,u-diamines 2 does not lead to the proposed tetraamides 4 but rather gives unusual lower rim doublybridged molecules of type 3. These compounds represent macrocyclic structures possessing well preorganised array of –NH–CO– binding sites on the lower rim. The potential
applications of these compounds in supramolecular chemistry are currently under study.
3. Experimental All moisture sensitive reactions were carried out under nitrogen atmosphere. All dry solvents were prepared according to standard procedures and stored over molecular sieves. Melting points are uncorrected and were determined using a Boetius Block apparatus (Carl Zeiss Jena, Germany). 1 H NMR spectra were recorded at 300 MHz. Elemental analyses were measured on Perkin-Elmer 240 instruments. All samples were dried in the desiccator over P2O5 under vacuum (1 Torr) at 80 8C for 8 h. Mass spectra were measured using FAB technique on ZAB-EQ (VG Analytical) spectrometer. The IR spectra were measured on an FT-IR spectrometer Nicolet 740 in KBr. The purity of the substances and the courses of reactions were monitored by TLC using TLC aluminum sheets with Silica gel 60 F254 (Merck). Preparative TLC chromatography was carried out on 20!20 cm glass plates covered by Silica gel 60 GF254 (Merck). The column chromatography was performed using Silica gel 60 (Merck).
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˚ ). Figure 2. X-ray structures of doubly amide-bridged p-tert-butylthiacalix[4]arene derivatives 3a, 3b and 3c (all distances in A
Compound 14e was prepared according to known procedure. 3.1. Aminolysis of p-tert-butylthiacalix[4]arene tetraethyl acetate 1 (cone) leading to doubly bridged products—general procedure p-tert-Butylthiacalix[4]arene tetraethyl acetate 1 (1.00 g, 0.94 mmol) was suspended in 100 ml of ethanol and 9.4 mmol of the corresponding aliphatic a,u-diamine was added in one portion. The reaction mixture was stirred under reflux for 16 h and then the solvent was evaporated under reduced pressure. The doubly bridged product was isolated by preparative TLC (SiO2, CHCl3/MeOH 10:1). 3.1.1. Doubly amide-bridged p-tert-butylthiacalix[4] arene 3a (cone). Isolated as a white crystalline compound (RfZ0.56, 338 mg, 36% yield). Mp O350 8C (CHCl3– MeOH); 1H NMR (300 MHz, CDCl3) d 1.12 (s, 36H, –C(CH3)3); 3.49–3.52 (m, 4H, –CH2–CH2–NH–C(O)–); 3.72–3.74 (m, 4H, –C(O)–NH–CH2–CH2–); 4.04 (d, 4H, JZ13.7 Hz, –O–CH2–); 5.19 (d, 4H, JZ13.7 Hz, –O–CH2–); 7.37 (d, 4H, JZ2.2 Hz, ArH); 7.40 (d, 4H, JZ2.2 Hz, ArH); 7.79 (m, 4H, –C(O)–NH–); MS (FAB) m/z (rel intensity): 1002 [MHC] (100); IR (KBr) nmax (cmK1): 3341, 1681,
1600, 1550. Calcd for C52H64N4O8S4: C, 62.37; H, 6.44; N, 5.60 S, 12.81. Found: C, 62.47; H, 6.41; N, 5.10; S 12.52. 3.1.2. Doubly amide-bridged p-tert-butylthiacalix[4] arene 3b (cone). Obtained according to the general procedure as a white crystalline compound (RfZ0.62, 184 mg, 19% yield). Mp O350 8C (CHCl3–MeOH); 1H NMR (300 MHz, CDCl3) d 1.14 (s, 36H, –C(CH3)3); 1.98 (m, 2H, –CH2–CH2–CH2–NH–C(O)–); 2.15 (m, 2H, –CH2– CH2–CH2–NH–C(O)–); 3.49–3.56 (m, 4H, –C(O)–NH– CH2–CH2–); 3.68–3.72 (m, 4H, –C(O)–NH–CH2–CH2–); 4.67 (d, 4H, JZ14.6 Hz, –O–CH2–); 4.90 (d, 4H, JZ 14.6 Hz, –O–CH2–); 7.37 (d, 4H, JZ2.5 Hz, ArH); 7.40 (d, 4H, JZ2.5 Hz, ArH); 7.84 (t, 4H, JZ5.2 Hz, –C(O)–NH–); MS (FAB) m/z (rel intensity): 1030 [MHC] (100); IR (KBr) n max (cm K1): 3336, 1682, 1676, 1533. Calcd for C54H68N4O8S4: C, 63.01; H, 6.66; N, 5.44. Found: C, 62.77; H, 6.38; N, 5.41. 3.1.3. Doubly amide-bridged p-tert-butylthiacalix[4] arene 3c (cone). Prepared according to the general procedure and isolated as a beige crystalline compound (RfZ0.56, 79 mg, 8% yield). Mp O350 8C (CHCl3– MeOH); 1H NMR (300 MHz, CDCl3) d 1.14 (s, 36H, –C(CH3)3); 1.87 (br s, 8H, –CH2–CH2–CH2–NH–C(O)–);
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3.51 (br s, 8H, –C(O)–NH–CH2–CH2–); 4.46 (d, 4H, JZ 14.9 Hz, –O–CH2–); 5.19 (d, 4H, JZ15.1 Hz, –O–CH2–); 7.37 (d, 4H, JZ2.5 Hz, ArH); 7.41 (d, 4H, JZ2.2 Hz, ArH); 7.78 (t, 4H, JZ5.1 Hz, –C(O)–NH–); MS (FAB) m/z (rel intensity): 1058 [MHC] (100); IR (KBr) nmax (cmK1): 3387, 1676, 1542. Calcd for C56H72N4O8S4: C, 63.61; H, 6.86; N, 5.30. Found: C, 63.52; H, 6.73; N, 5.21. 3.2. Aminolysis of p-tert-butylthiacalix[4]arene tetraethyl acetate 1 (cone) leading to singly bridged products—general procedure p-tert-Butylthiacalix[4]arene tetraethyl acetate 1 (0.50 g, 0.47 mmol) was suspended in 50 ml of ethanol and 1.18 mmol of the corresponding aliphatic a,u-diamine was added in one portion. The reaction mixture was stirred under reflux for 24 h and then the solvent was evaporated under reduced pressure. The singly bridged product was isolated by preparative TLC (SiO2, CHCl3/MeOH 10:1). 3.2.1. Singly amide-bridged p-tert-butylthiacalix[4]arene diethyl acetate 5a (cone). Obtained as a beige crystalline compound (RfZ0.79, 78 mg, 16% yield). Mp 228–230 8C (CHCl3–MeOH); 1H NMR (300 MHz, CDCl3) d 1.03 (s, 18H, –C(CH3)3); 1.05 (s, 18H, –C(CH3)3); 1.15–1.22 (m, 6H, –O–CH2–CH3); 3.56 (m, 4H, –C(O)–NH–CH2–CH2–); 4.14–4.20 (m, 6H, –O–CH2–CH3 and –O–CH2–); 4.71 (d, 2H, JZ15.1 Hz, –O–CH2–); 4.98 (d, 2H, JZ15.1 Hz, –O– CH2–); 5.22 (d, 2H, JZ14.9 Hz, –O–CH2–); 7.25 (d, 4H, JZ2.4 Hz, ArH); 7.30 (d, 4H, JZ2.4 Hz, ArH); 7.33 (d, 4H, JZ2.4 Hz, ArH); 7.39 (d, 4H, JZ2.4 Hz, ArH); 8.53 (m, 2H, –C(O)–NH–); MS (FAB) m/z (rel intensity): 1033 [MHC] (100); IR (KBr) nmax (cmK1): 3351, 1766, 1733, 1683, 1541. 3.2.2. Singly amide-bridged p-tert-butylthiacalix[4]arene diethyl acetate 5b (cone). Isolated as a beige crystalline compound (RfZ0.71, 44 mg, 9% yield). Mp 292–294 8C (CHCl3–MeOH); 1H NMR (300 MHz, CDCl3) d 1.03 (s, 18H, –C(CH3)3); 1.05 (s, 18H, –C(CH3)3); 1.18 (t, 6H, JZ 7.2 Hz, –O–CH2–CH3); 1.99 (m, 4H, –CH2–CH2–CH2– NH–C(O)–); 3.46 (m, 4H, –C(O)–NH–CH2–CH2–); 3.56 (m, 4H, –C(O)–NH–CH2–CH2–); 4.16 (q, 4H, JZ7.2 Hz, –O–CH2–CH3–); 4.50 (d, 2H, JZ15.4 Hz, –O–CH2–); 4.82 (d, 2H, JZ15.1 Hz, –O–CH2–); 4.93 (d, 2H, JZ15.1 Hz, –O–CH2–); 5.19 (d, 2H, JZ15.4 Hz, –O–CH2–); 7.23–7.27 (m, 8H, ArH); 8.27 (t, 2H, JZ5.9 Hz, –C(O)–NH–); MS (FAB) m/z (rel intensity): 1047 [MHC] (100); IR (KBr) nmax (cmK1): 3405, 1746, 1727, 1680, 1552. 3.3. Crystallographic study X-ray data were collected on an Enraf Nonius CAD4 diffractometer with graphite monochromated Cu Ka radiation at 293 K. The structures were solved by direct methods. Mercury v.1.2.1. available as freeware at http:// www.ccdc.cam.ac.uk/mercury/ was used for visualization. X-ray data for 3a: C52H64N4O8S4, MZ1001.3 g/mol, triclinic system, space group P -1, aZ13.635(1), bZ ˚ , aZ102.09(1), bZ101.54(1), 13.915(1), cZ18.115(2) A ˚ 3, ZZ2, DcZ1.12 g cmK3, gZ112.23(1)8, VZ2959.2(6) A K1 m(Cu Ka)Z1.87 mm , crystal dimensions of 0.2!0.3!
0.8 mm. The structure was solved by direct method8 and anisotropically refined by full matrix least-squares on F values9 to final RZ0.066 and RwZ0.064 using 5880 independent reflections (qmaxZ64.958, 656 parameters). Hydrogen atoms were located from expected geometry and were not refined. j-scan was used for absorption correction. Crystallographic data were deposited in CSD under CCDC registration number 268283. X-ray data for 3b: C54H 68N 4O 8S 4$0.5CH2 Cl 2, MZ 1070.9 g/mol, monoclinic system, space group C 2/c, aZ ˚ , bZ103.23(1)8, 28.993(2), bZ13.9700(9), cZ30.661(2) A 3 ˚ VZ12089(1) A , ZZ8, DcZ1.18 g cmK3, m(Cu Ka)Z 2.26 mmK1, crystal dimensions of 0.1!0.2!0.9 mm. The structure was solved by direct method8 and anisotropically refined by full matrix least-squares on F values9 to final RZ 0.096 and RwZ0.072 using 3076 independent reflections (qmaxZ67.948, 591 parameters). Hydrogen atoms were located from expected geometry and were not refined. Molecule of dichloromethane was not able to refine, the SQUEEZE method was applied. Crystallographic data were deposited in CSD under CCDC registration number 268282. X-ray data for 3c: C56H72N4O8S4, MZ1057.4 g/mol, monoclinic system, space group P 21/c, aZ12.705(3), bZ ˚ , bZ95.00(2)8, VZ6728(2) A ˚ 3, 14.295(3), cZ37.189(3) A K3 K1 ZZ4, DcZ1.04 g cm , m(Cu Ka)Z0.19 mm , crystal dimensions of 0.2!0.3!0.6 mm. The structure was solved by direct method8 and anisotropically refined by full matrix least-squares on F values9 to final RZ0.077 and RwZ0.039 using 5505 independent reflections (qmaxZ59.958, 662 parameters). Hydrogen atoms were located from expected geometry and were not refined. j-scan was used for absorption correction. Crystallographic data were deposited in CSD under CCDC registration number 268284.
Acknowledgements This work was supported by the Grant Agency of the Czech Republic (No. 203/03/0926).
References and notes 1. Kumagai, H.; Hasegawa, M.; Miyanari, S.; Sugawa, Y.; Sato, Y.; Hori, T.; Ueda, S.; Kamiyama, H.; Miyano, S. Tetrahedron Lett. 1997, 38, 3971–3972. 2. For books on calixarenes see: (a) Asfari, Z., Bo¨hmer, V., Harrowfield, J., Vicens, J., Eds.; Calixarene 2001; Kluwer: Dordrecht, 2001. (b) Mandolini, L.; Ungaro, R. Calixarenes in Action; Imperial College: London, 2000. (c) Gutsche, C. D. In Stoddart, J. F., Ed.; Calixarenes Revisited: Monographs in Supramolecular Chemistry; Royal Society of Chemistry: Cambridge, 1998; Vol. 6. (d) Calixarenes 50th Anniversary: Commemorative Issue; Vicens, J., Asfari, Z., Harrowfield, J. M., Eds.; Kluwer: Dordrecht, 1994. (e) Calixarenes: A Versatile Class of Macrocyclic Compounds; Vicens, J., Bo¨hmer, V., Eds.; Kluwer: Dordrecht, 1991. 3. For recent reviews on thiacalixarenes see: (a) Iki, N.; Miyano, S. J. Inclusion Phenom. Macrocycl. Chem. 2001, 41, 99–105. (b)
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