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Synlett 2006(5): 0795-0797  
DOI: 10.1055/s-2006-933119
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of 1,3- and 1,4-Diacetylamido-Bridged p-tert-Butylcalix[7]arenes

Zhiyang Luo, Shuling Gong, Chunlei Zhang, Qin Zheng, Yuanyin Chen*
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, P. R. of China
Fax: +86(27)87647617; e-Mail: yychen@whu.edu.cn;
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Publication History

Received 29 November 2005
Publication Date:
09 March 2006 (online)

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Abstract

1,3-Oxy-(2′,7′-dioxo-3′,6′-diazaoctamethylene)oxy-bridged p-tert-butylcalix[7]arenes and 1,4-oxy-(2′,8′-dioxo-3′,7′-diazanonamethylene)oxy-bridged p-tert-butylcalix[7]arenes were synthesized regioselectively by a base-promoted alkylation of p-tert-butylcalix[7]arene with dichloro bridging agents [ClCH2CONH(CH2)nNHCOCH2Cl, n = 2, 3], respectively. How­ever, using ClCH2CONH(CH2)6NHCOCH2Cl as a bridging ­reagent, a mixture of 1,3- and 1,4-bridged p-tert-butylcalix[7]arene derivatives were obtained. The bridging pattern and the yields of the products were highly sensitive to the length of bridging reagent and the base employed.

Keywords

calixarene - calix[7]arene - bridging - synthesis - diacetyl­amido bridge

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Typical Procedure for the Preparation of Bridged p - tert -Butylcalix[7]arenes. A mixture of 1 (2.27 g, 2 mmol) and base (anhyd K2CO3 or Cs2CO3, 8 mmol, see Table [1] ) was stirred in refluxing acetone (100 mL) for 1 h. Then the alkylating agent (2.2 mmol) was added. The mixture was stirred under nitrogen for 48 h (K2CO3) or 24 h (Cs2CO3). Progress of the reaction was monitored by TLC. After removal of solvent under vacuum, the residue was dissolved in 80 mL of CHCl3, filtered, and washed with 0.1 mol/L HCl. The organic phase was washed with H2O (2 × 20 mL) and dried over MgSO4. After filtration, the crude product was subjected to column chromatography on silica. Eluent: CHCl3-acetone (30:1, v/v) for 2, CHCl3-acetone (20:1, v/v) for 3, CHCl3-acetone (30:1, v/v) for 4a then CHCl3-acetone (20:1, v/v) for 4b.

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Satisfactory microanalytical and spectral data were obtained for all new compounds. The 1H NMR and 13C NMR spectra were recorded at 300 MHz and 75 MHz, respectively, on Varian Mercury-VX300 spectrometer. The chemical shifts were recorded in parts per million (ppm) with TMS as the internal reference. Melting points (uncorrected) were obtained from XTL-20 microscopic melting point director. ESI mass spectra were determined using Finnigan LCQ Advantage mass spectrometer. Elemental analyses were performed with Yanaco MT-5.
1,3-Oxy-(2′,7′-dioxo-3′,6′-diazaoctamethylene)oxy-Bridged p-tert -Butylcalix[7]arene 2.
White powder (1.33 g, 54% yield, K2CO3; 1.07 g, 42% yield, Cs2CO3, respectively). Mp 273.0-275.2 °C. ESI-MS: m/z = 1275.8 [MH]+. 1H NMR (300 MHz, CDCl3, 298 K): δ = 1.22 (s, t-Bu, 18 H), 1.24 (s, t-Bu, 9 H), 1.26 (s, t-Bu, 18 H), 1.28 (s, t-Bu, 18 H), 3.57 (br, ArCH 2Ar, 2 H), 3.64 (br, NHCH 2, 2 H), 3.72 (br, ArCH 2Ar, 4 H), 3.91 (br, ArCH 2Ar, 4 H), 4.11 (br, NHCH 2, 2 H), 4.27 (s, ArCH 2Ar, 4 H), 4.29 (br, OCH 2CO, 2 H), 4.59 (br, OCH 2CO, 2 H), 6.94 (s, ArH, 2 H), 7.12 (s, ArH, 6 H), 7.16 (s, ArH, 4 H), 7.32 (s, ArH, 2 H), 8.07 (s, ArOH, 1 H), 8.14 (s, CONHCH2, 2 H), 8.53 (s, ArOH, 2 H), 9.45 (s, ArOH, 2 H) ppm. 13C NMR (75 MHz, CDCl3, 298 K): δ = 30.51, 30.79, 31.60 (2 ×), 31.82 (3 ×) [C(CH3)3], 32.76 [C(CH3)3], 34.30 (4 ×), 34.66 (3 ×) (ArCH2Ar), 40.02 (CH2 CH2), 72.40 (OCH2CO), 125.50, 125.82, 126.14, 126.83, 127.10, 127.23, 127.52, 132.74, 132.95 (o-Ar and m-Ar), 143.49 (2 ×), 144.22 (3 ×), 147.38 (2 ×) (p-Ar), 148.29 (2 ×), 148.43 (3 ×), 149.44 (2 ×) (ipso-Ar), 170.20 (CH2 CONH) ppm. Anal. Calcd (%) for C83H106N2O9 (1274.8): C, 78.20; H, 8.38; N, 2.20. Found: C, 78.13; H, 8.42; N, 2.20.
1,4-Oxy-(2′,8′-dioxo-3′,7′-diazanonamethylene)oxy-Bridged p - tert -Butylcalix[7]arene 3.
White powder (0.98 g, 38% yield, K2CO3; 1.16 g, 45% yield, Cs2CO3, respectively). Mp 238.2-240.2 °C. ESI-MS: m/z = 1289.9 [MH]+. 1H NMR (300 MHz, CDCl3, 298 K): δ = 1.22 (s, t-Bu, 18 H), 1.23 (s, t-Bu, 18 H), 1.24 (s, t-Bu, 9 H), 1.28 (s, t-Bu, 18 H), 1.90 (br, CH2CH 2CH2, 2 H), 3.51 (br, NHCH 2 and ArCH 2Ar, 6 H), 3.79 (br, NHCH 2 and ArCH 2Ar, 8 H), 4.25 (br, ArCH 2Ar, 2 H), 4.35 (br, ArCH 2Ar and OCH 2CO, 6 H), 7.06 (s, ArH, 2 H), 7.09 (s, ArH, 4 H), 7.13 (s, ArH, 2 H), 7.15 (s, ArH, 2 H), 7.16 (s, ArH, 2 H), 7.19 (s, ArH, 2 H), 7.91 (s, CONHCH2, 2 H), 8.40 (s, ArOH, 2 H), 8.65 (s, ArOH, 2 H), 9.34 (s, ArOH, 1 H) ppm. 13C NMR (75 MHz, CDCl3, 298 K): δ = 28.76 (CH2 CH2CH2), 31.45 (2 ×), 31.68, 31.72 (2 ×), 31.78 (2 ×) [C(CH3)3], 32.43 (5 ×), 33.34 (2 ×) [C(CH3)3], 34.21 (2 ×), 34.55 (5 ×) (ArCH2Ar), 35.10 (CH2CH2 CH2), 72.68 (OCH2CO), 125.80, 126.06, 126.13, 126.30, 126.51, 126.75, 127.16, 127.43, 127.85, 131.99, 132.75 (o-Ar and m-Ar), 143.60 (3 ×), 144.39 (2 ×), 147.68 (2 ×) (p-Ar), 148.37 (2 ×), 148.79 (3 ×), 149.36 (2 ×) (ipso-Ar), 169.92 (CH2 CONH) ppm. Anal. Calcd (%) for C84H108N2O9 (1288.81): C, 78.28; H, 8.45; N, 2.17. Found: C, 78.21; H, 8.49; N, 2.18.
1,3-Oxy-(2′,11′-dioxo-3′,10′-diazadodecamethylene)oxy-Bridged p - tert -Butylcalix[7]arene 4a. White powder (0.73 g, 31% yield, K2CO3; and 0.47 g, 20% yield, Cs2CO3, respectively).Mp 233.4-235.2 °C. ESI-MS: m/z = 1332.1 [MH]+. 1H NMR (300 MHz, CDCl3, 298 K): δ = 1.13 (s, t-Bu, 18 H), 1.25 (s, t-Bu, 9 H), 1.28 (s, t-Bu, 18 H), 1.31 (s, t-Bu, 18 H), 1.50 [br s, (CH2)2CH 2CH 2(CH2)2, 4 H], 1.69 [br, CH2CH 2(CH2)2CH 2CH2, 4 H], 3.32 (br, NHCH 2, 2 H), 3.65 (m, ArCH 2Ar, 6 H), 3.73 (br, NHCH 2, 2 H), 3.95 (m, ArCH 2Ar, 4 H), 4.30 (m, ArCH 2Ar, 4 H), 4.42 (AX, OCH 2CO, J = 6.9 Hz, 2 H), 4.46 (AX, OCH 2CO, J = 6.6 Hz, 2 H), 6.83 (s, CONHCH2, 2 H), 7.15 (br s, ArH, 8 H), 7.21 (br s, ArH, 6 H), 7.40 (s, ArOH, 1 H), 8.73 (s, ArOH, 2 H), 9.69 (s, ArOH, 2 H) ppm. 13C NMR (75 MHz, CDCl3, 298 K): δ = 25.00 [(CH2)2 CH2 CH2 (CH2)2], 28.71 [CH2 CH2(CH2)2 CH2CH2], 31.13, 31.53 (2 ×), 31.84 (4 ×) [C(CH3)3], 32.75 (5 ×), 32.99 (2 ×) [C(CH3)3], 34.32 (4 ×), 34.55 (3 ×) (ArCH2Ar), 38.02 [CH2(CH2)4 CH2], 72.50 (OCH2CO), 125.19, 125.34, 125.81, 126.07, 126.23, 127.09, 127.69, 132.08, 132.47 (o-Ar and m-Ar), 143.35, 143.66 (2 ×), 144.29 (2 ×), 147.42 (2 ×) (p-Ar), 147.89 (2 ×), 148.72 (2 ×), 150.73 (2 ×) (ipso-Ar), 169.45 (CH2 CONH) ppm. Anal. Calcd (%) for C87H114N2O9 (1330.85): C, 78.52; H, 8.63; N, 2.10. Found: C, 78.47; H, 8.68; N, 2.09.
1,4-Oxy-(2′,11′-dioxo-3′,10′-diazadodecamethylene)oxy-Bridged p - tert -Butylcalix[7]arene 4b. White powder (0.57 g, 24% yield, K2CO3; and 0.83 g, 35% yield, Cs2CO3, respectively). Mp 252.4-254.2 °C. ESI-MS: m/z = 1330.1 [MH]+. 1H NMR (300 MHz, CDCl3, 298 K): δ = 1.17 (s, t-Bu, 18 H), 1.23 (s, t-Bu, 9 H), 1.28 (s, t-Bu, 36 H), 1.57 [br, (CH2)2CH 2CH 2(CH2)2, 4 H], 1.68 [br, CH2CH 2(CH2)2CH 2CH2, 4 H], 3.25 (br, NHCH 2, 2 H), 3.56 (m, ArCH 2Ar, 4 H), 3.65 (br, NHCH 2, 2 H), 3.86 (br, ArCH 2Ar, 6 H), 4.24 (AX, J = 15.9 Hz, ArCH 2Ar, 4 H), 4.50 (AX, J = 15.6 Hz, OCH 2CO, 2 H), 4.56 (AX, J = 15.9 Hz, OCH 2CO, 2 H), 6.92 (s, CONHCH2, 2 H), 7.09 (s, ArH, 2 H),7.12 (s, ArH, 6 H), 7.14 (s, ArH, 2 H), 7.17 (s, ArH, 2 H), 7.20 (s, ArH, 2 H), 8.49 (br s, ArOH, 2 H), 9.40 (br s, ArOH, 2 H), 9.53 (br s, ArOH, 1 H) ppm. 13C NMR (75 MHz, CDCl3, 298 K): δ = 26.23 [(CH2)2 CH2 CH2(CH2)2], 27.68 [CH2 CH2(CH2)2 CH2CH2], 31.24, 31.48 (2 ×), 31.55 (4 ×) [C(CH3)3], 32.24 (3 ×), 32.41 (4 ×) [C(CH3)3], 33.99 (4 ×), 34.37 (3 ×) (ArCH2Ar), 38.55 [CH2(CH2)4 CH2], 71.43 (OCH2CO), 125.00, 125.62, 125.81, 125.95, 126.12, 126.42, 126.91, 127.03, 127.50, 133.25 (o-Ar and m-Ar), 143.41, 144.01 (2 ×), 144.29 (2 ×), 146.86 (2 ×) (p-Ar), 147.52 (3 ×), 147.85, 149.16, 150.33 (2 ×) (ipso-Ar), 169.83 (CH2 CONH) ppm. Anal. Calcd (%) for C87H114N2O9 (1330.85): C, 78.52; H, 8.63; N, 2.10. Found: C, 78.46; H, 8.70; N, 2.10.