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Regioselective Synthesis of Calix[4]Arene 1,3-Di- and Monosubstituted Sulfur-Containing Schiff Bases

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Regioselective Synthesis of Calix[4]Arene 1,3-Di- and Monosubstituted Sulfur-Containing Schiff Bases J Incl Phenom Macrocycl Chem DOI 10.1007/s10847-009-9570-5 ORIGINAL ARTICLE Regioselective synthesis of calix[4]arene 1,3-di- and monosubstituted sulfur-containing Schiff bases Jing Sun Æ Dong Mei Liu Æ Jin Xiang Wang Æ Chao Guo Yan Received: 22 December 2008 / Accepted: 12 March 2009 Ó Springer Science+Business Media B.V. 2009 Abstract Regioselective alkylations of p-tert-butylcalix[4] reactions in calix[4]arene chemistry [6, 11, 12], only a few arene with 3-methoxy-4-x-chloroalkoxy-benzaldehydes in the examples of monofunctionalization are known [13, 14]. system of K2CO3/KI/CH3CN efficiently produce 1,3-di- and Direct alkylation of p-tert-butyl calix[4]arene with alkyl monosubstituted aldehydes according to the length of alkyl halides in the presence of one equivalent of the base (Na- chains in alkylating reagent, which provides a versatile protocol OMe [15], K2CO3,CsF[16], NaH [17], (Bu3Sn)2O[18]) is for preparing calixarene 1,3-di- and sulfur-containing Schiff less selective and gives the complicated mixture of mono- bases. alkoxycalixarenes with considerable amounts of deeper alkylation products and unreactive starting p-tert-butylca- Keywords Calixarene Á Alkylation Á Dithiocarbazate Á lixarene. Several indirect synthetic methods of monoalkoxy Schiff base Á Crystal structure p-tert-butylcalixarenes involve preliminary protection of three hydroxyl groups of tetrahydroxycalixarene [19, 20], or selective dealkylation of di- or tetraalkoxycalixarenes with Introduction iodotrimethylsilane [21]. However, these methods are pre- paratively inconvenient. Now we report the selective Calixarenes, which are macrocyclic compounds available in preparation of functional p-tert-calix[4]arene 1,3-di-alde- a variety ring sizes, are of particular interest as inclusion hyde and monoaldehyde derivatives by direct alkylation hosts, selective receptors, molecular sensors, and novel reaction as well as the synthesis of sulfur-containing Schiff building blocks for supramolecular chemistry [1–5]. Owing bases in a very efficient procedure. to its pro-organized structure, calix[4]arene is currently a popular molecular platform for designing highly selective receptors. For these purpose numerous functional groups Experiment section have been introduced on the upper or lower rim of calix[4]arene [6–10]. In spite of numerous efficient methods All reagents and solvents were commercial available with for chemical modification of calixarenes, the region- and analytical grade and used as received. Further purification stereoselective introduction of functional groups, however, and drying by standard method were employed and distilled continues to be a challenge to the synthetic chemist. The prior to use when necessary. All evaporations of organic regioselective substitution of calix[4]arenes at the lower rim solvents were carried out with a rotary evaporator in con- is mainly due to the different acidities of the phenolic junction with a water aspirator. p-tert-Butylcalix[4]arene, hydroxyl groups. While 1,3-bridged or tetrasubstituted [22] S-methyl and S-benzyldithiocarbazate [23–25] were functionalization may be considered as one of the standard prepared according to the published methods. Melting points were taken on a hot-plate microscope apparatus and are uncorrected. 1H NMR and 13C NMR spectra were recorded & J. Sun Á D. M. Liu Á J. X. Wang Á C. G. Yan ( ) with a Bruker AV-600 spectrometer. IR spectra were College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225002, China obtained on a Bruker Tensor27 spectrometer (KBr disc). e-mail: [email protected] Elemental analyses were obtained on PE 2400 instrument. 123 J Incl Phenom Macrocycl Chem X-ray data were collected on a Bruker Smart APEX-2 CCD ArCH2Ar), 4.14 (d, J = 12.0 Hz, 2H, ArCH2Ar), 3.71 (s, diffractometer. 3H, OCH3), 3.44 (d, J = 12.0 Hz, 2H, ArCH2Ar), 3.38 (d, 13 J = 12.0, 2H, ArCH2Ar), 1.20 (s, 36H, CH3); CNMR The general procedure for preparation of calixarene (CDCl3, 150 MHz) d: 191.1, 153.5, 150.4, 149.1, 148.3, aldehydes 3a–b and 4a 147.5, 144.0, 143.4, 133.8, 130.8, 128.3, 128.1, 127.8, 127.6, 126.6, 126.5, 125.9, 125.6, 125.5, 116.4, 112.2, 109.3, 74.0, A suspension of p-tert-butylcalix[4]arene 1 (6.0 mmol, 67.8, 55.8, 34.3, 34.0, 32.7, 31.9, 31.5, 31.3; IR (KBr) t: 2959 4.00 g) and anhydrous potassium carbonate (48.0 mmol, (s), 1692 (s), 1600v (s), 1478 (m), 1307 (m), 1257 (s), 1210 6.6 g), potassium iodide (2.4 g, 14.0 mmol) in dry aceto- (m), 1162 (m), 1114 (w), 1059 (w), 832 (w). Anal Calcd for nitrile (150 mL) was heated to refluxing under nitrogen for C54H66O7: C, 76.56; H, 8.33; Found: C, 76.79; H 8.57. 2 h. Then 3-methoxy-4-(chloroalkoxy)benzaldehyde 2a–b (14.0 mmol) was added. The reaction mixture was refluxed General procedure of preparation of sulfur-containing for 4 days. After removal of larger portion of acetonitrile, Schiff bases 5a–d the residue was put in large portion of water. The resulting precipitates were collected by filtration and recrystallized To a methanol solution (50 mL) of 3a–b (1.0 mmol) was from a mixture of chloroform and ethanol to give pure solid added S-methyldithiocarbazate or S-benzyldithiocarbazate product for analysis. (2.2 mmol) and one drop of concentrated hydrochloric 3a (n = 2, R=CH3, p-CHO): white solid, Yield: 18%, acid. The mixture was stirred at room temperature for 1 m.p. 110–115 °C, H NMR(CDCl3, 600 MHz)d: 9.82 (s, about 2 days. The resulting precipitate was filtrated out and 2H, CHO), 7.39 (br, 2H, ArH), 7.30 (br, 2H, ArOH), 7.06 recrystallized from chloroform and ethanol to give 5a–d: 0 (s, 4H, ArH), 7.03 (br, 2H, ArH), 6.97 (br, 2H, ArH), 6.73 5a (n = 2, R=OCH3, p-CHO, R =H): yellow solid, 69%, 1 (s, 4H, ArH), 4.46 (br, 4H, OCH2), 4.40 (d, J = 13.2 Hz, m.p. 160–168 °C; H NMR (CDCl3, 600 MHz) d: 10.89 (s, 4H, ArCH2Ar), 4.33 (br, 4H, OCH2), 3.64 (s, 6H, OCH3), 2H, NH), 7.77 (s, 2H, CH=N), 7.68 (br, 2H, ArH), 7.37 (s, 3.28 (d, J = 13.2 Hz, 4H, ArCH2Ar), 1.31 (s, 18H, CH3), 2H, ArOH), 7.15 (s, 2H, ArH), 7.06 (s, 2H, ArH), 7.03 (s, -1 0.92 (s, 18H, CH3); IR (KBr, cm ) t: 3449 (m), 2958 (s), 2H, ArH), 6.97 (br, 2H, ArH), 6.86–6.80 (m, 4H, ArH), 2870 (m), 1687 (s), 1591 (s), 1511 (s), 1474 (s), 1271 (vs), 4.36 (br, 4H, OCH2), 4.30 (d, J = 13.2 Hz, 4H, ArCH2Ar), 1201 (s), 1131 (s), 1037 (m). Anal Calcd for C64H76O10:C, 4.21 (br, 4H, OCH2), 3.91 (s, 6H, OCH3), 3.23 (d, 76.46; H, 7.62; Found: C, 76.28; H 7.85. J = 13.2 Hz, 4H, ArCH2Ar), 2.67 (s, 6H, SCH3), 1.14 (s, -1 3b (n = 3, R=CH3, p-CHO): white solid, Yield: 79%, 18H, CH3), 1.03 (s, 18H, CH3); IR (KBr, cm ) m: 3382 (s), 1 m.p. 82–85 °C; H NMR (CDCl3, 600 MHz) d: 9.80 (s, 3415 (s), 2956 (s), 2866 (w), 1617 (vs), 1508 (s), 1454 (s), 2H, CHO), 7.59 (s, 2H, ArH), 7.42 (d, J = 7.8 Hz, 2H, 1404 (vs), 1276 (vs), 1196 (m), 1137 (m), 1032 (m); Anal ArH), 7.35 (s, 2H, ArOH), 7.12 (d, J = 7.8 Hz, 2H, ArH), Calcd for C68H84N4S4O8: C, 67.31; H, 6.98; N, 4.62; 7.03 (s, 4H, ArH), 6.84 (s, 4H, ArH), 4.51 (br, 4H, OCH2), Found: C, 67.05; H 7.22; N, 4.69. 0 4.21 (d, J = 12.0 Hz, 4H, ArCH2Ar), 4.14 (br, 4H, OCH2), 5b (n = 3, R=OCH3, p-CHO, R =H): yellow solid, 65%, 1 3.86 (s, 6H, OCH3), 3.31 (d, J = 12.0 Hz, 4H, ArCH2Ar), m.p. 140–145 °C; H NMR (CDCl3, 600 MHz) d: 10.58 (s, 2.25–2.46 (m, 4H, CH2), 1.27 (s, 18H, CH3), 0.99 (s, 18H, 2H, NH), 7.70 (s, 2H, CH=N), 7.69 (d, J = 7.8 Hz, 2H, 13 CH3); C NMR (CDCl3, 150 MHz) d: 190.9, 154.0, 150.5, ArH), 7.32 (s, 2H, ArOH), 7.06 (s, 2H, ArH), 7.05 (s, 4H, 149.4, 147.3, 141.8, 132.6, 130.1, 127.7, 126.8, 125.6, ArH), 6.94 (d, J = 7.8 Hz, 2H, ArH), 6.86 (s, 4H, ArH), 125.1, 111.9, 109.3, 72.4, 65.8, 55.9, 34.0, 33.9, 31.7, 31.6, 4.36 (s, 4H, OCH2), 4.26 (d, J = 12.0 Hz, 4H, ArCH2Ar), -1 31.0, 29.8; IR (KBr, cm ) t: 2958 (s), 2870 (m), 1687 (s), 4.13 (s, 4H, OCH2), 3.90 (s, 6H, OCH3), 3.34 (d, 1591 (s), 1511 (s), 1474 (s), 1271 (vs), 1201 (s), 1131 (s), J = 12.0 Hz, 4H, ArCH2Ar), 2.66 (s, 6H, SCH3), 2.43 (s, 13 1037 (m). Anal Calcd for C66H80O10: C, 76.71; H, 7.80; 4H, CH2), 1.28 (s, 18H, CH3, 1.00 (s, 18H, CH3); CNMR Found: C, 76.51; H 7.47. (CDCl3, 150 MHz) d: 199.2, 151.2, 150.6, 149.6, 149.4, 4a (n = 2, R=CH3, p-CHO): The same reaction proce- 147.2, 145.8, 141.7, 132.7, 127.7, 125.6, 125.1, 123.5, dure was used by using 1:1.2 ratio of p-tert- 112.2, 108.6, 72.7, 65.7, 56.0, 34.0, 31.7, 31.1, 29.8, 17.7; butylcalix[4]arene (6.0 mmol, 4.00 g) 1 to 3-methoxy-4- IR (KBr, cm-1) t: 3382 (m), 2958 (vs), 2870 (m), 1600 (m), (chloroethoxy)benzaldehyde 2a to give white solid of 4a: 1483 (vs), 1361 (m), 1268 (vs), 1235 (s), 1201 (s), 1133 (m), 1 Yield: 77%, m.p.
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