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

Zhiyang Luo; Shuling Gong; Chunlei Zhang; Qin Zheng; Yuanyin Chen

doi:10.1055/s-2006-933119

LETTER

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;

Abstract

All articles of this category

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

Full Text

References

References and Notes

For general reviews on calixarenes, see:

<A NAME="RW10005ST-1A">1a</A> Gutsche CD. Calixarenes Stoddart JF. RSC Monographs in Supramolecular Chemistry, Royal Society of Chemistry; Cambridge: 1989.

<A NAME="RW10005ST-1B">1b</A> Gutsche CD. Calixarenes Revisited Stoddart JF. RSC Monographs in Supramolecular Chemistry, Royal Society of Chemistry; Cambridge: 1998.

<A NAME="RW10005ST-1C">1c</A> Calixarenes 2001 Asfari Z. Böhmer V. Harrowfield J. Vicens J. Kluwer Academic; Dordrecht: 2001.

<A NAME="RW10005ST-1D">1d</A> Böhmer V. Angew. Chem., Int. Ed. Engl. 1995, 34: 713

<A NAME="RW10005ST-1E">1e</A> Shinkai S. Tetrahedron 1993, 49: 8933

<A NAME="RW10005ST-2">2</A> Martino M. Gregoli L. Gaeta C. Neri P. Org. Lett. 2002, 4: 1531

<A NAME="RW10005ST-3">3</A> Martino M. Gaeta C. Gregoli L. Neri P. Tetrahedron Lett. 2002, 43: 9521

<A NAME="RW10005ST-4">4</A> Chen YK. Chen YY. Org. Lett. 2000, 2: 743

<A NAME="RW10005ST-5">5</A> Gong SL. Chen YK. Li J. Duan HP. Chen YY. Chin. J. Chem. 2004, 22: 573

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.

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.

<A NAME="RW10005ST-8">8</A> Stewart DR. Gutsche CD. J. Am. Chem. Soc. 1999, 121: 4136

<A NAME="RW10005ST-9">9</A> Cunsolo F. Consoli GML. Piattelli M. Neri P. J. Org. Chem. 1998, 63: 6852

<A NAME="RW10005ST-10A">10a</A> Araki K. Iwamoto K. Shinkai S. Matsuda T. Bull. Chem. Soc. Jpn. 1990, 63: 3480

<A NAME="RW10005ST-10B">10b</A> Groenen L. Steinwender E. Lutz B. van der Maas J. Reinhoudt DN. J. Chem. Soc., Perkin Trans. 2 1992, 1893

<A NAME="RW10005ST-10C">10c</A> Otsuka H. Araki K. Shinkai S. J. Org. Chem. 1994, 59: 1542

<A NAME="RW10005ST-10D">10d</A> Janssen RG. Verboom W. Lutz BG. van der Maas JH. Maczka M. van Duynhoven JPM. Reinhoudt DN. J. Chem. Soc., Perkin Trans. 2 1996, 1869

<A NAME="RW10005ST-10E">10e</A> Geraci C. Piattelli M. Chessari G. Neri P. J. Org. Chem. 2000, 65: 5143