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Synlett 2004(2): 0332-0334  
DOI: 10.1055/s-2003-44975
LETTER
© Georg Thieme Verlag Stuttgart · New York

Diamide Bridged Calix[8]arenes

Jun Li, Wei Wang, Shuling Gong, Yuanyin Chen*, Xiaojun Wu
Department of Chemistry, Wuhan University, Wuhan 430072, P. R. China
Fax: +86(27)87647617; e-Mail: yychen@whu.edu.cn;
Further Information

Publication History

Received 21 October 2003
Publication Date:
04 December 2003 (online)

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Abstract

1,5-Diamide-bridged and 1,3;5,7-doubly diamide-bridged calix[8]arene were obtained by reacting p-tert-butylcalix[8]arene with N,N′-bis(chloroacetyl)alkylenediamine using K2CO3 as a base in acetone.

Key words

calixarenes - macrocycles - amines - regioselectivity

15

General Procedure for Preparation of Compound 2a, 2b and 3: To a suspension of compound 1 (2 mmol) and K2CO3 (6 mmol) in acetone (250 mL) were added appropriate bridging agent (2.76 mmol) and KI (5.52 mmol). The mixture was stirred at 58 °C for 24 h. After concentration under vacuum, the residue was triturated with HCl, collected by filtration, washed with MeOH and dried. Compound 2a, 2b and 3 were isolated by chromatograph on silica gel (eluent: CH2Cl2-MeOH). Compound 2a: Mp >270 °C. 1H NMR (300 MHz, CDCl3, 295 K): δ = 1.22 [s, 18 H, (CH3)3], 1.25 [s, 36 H, (CH3)3], 1.26 [s, 18 H, (CH3)3], 3.56 (s, 4 H, NCH2CH2N), 3.86 (br s, 12 H, ArCH2Ar), 3.96 (br s, 4 H, ArCH2Ar), 4.31 (s, 4 H, OCH2CO), 7.00-7.28 (m, 16 H, ArH), 7.76 (br s, 2 H, NH), 8.40 (br s, 2 H, OH), 8.75 (br s, 4 H, OH). 13C NMR (150 MHz, CDCl3, 295 K): δ = 30.97, 31.49, 31.62, 31.75, 32.52, 34.21, 34.58, 39.39, 72.55, 125.89, 126.17, 126.43, 126.67, 127.10, 127.46, 127.77, 127.85, 132.98, 143.27, 143.73, 144.48, 147.46, 148.49, 149.55, 169.79. MS-FAB: m/z = 1437 [MH+]. Compound 3: Mp >250. 1H NMR (300 MHz, CDCl3, 295K): δ = 1.24 [s, 18 H, (CH3)3], 1.26 [s, 36 H, (CH3)3], 1.27 [s, 18 H (CH3)3], 1.67 (overlapped, 2 H, CH2), 3.65 (br s, 4 H, NCH2), 3.83 [br s, 4 H, ArCH2Ar], 3.90 [br s, 8 H, ArCH2Ar], 4.02 (br s, 4 H, ArCH2Ar, 4 H), 4.38 (s, 4 H, OCH2CO), 7.05-7.27 (m, 16 H, ArH), 7.96 (br s, 2 H, NH), 8.75 (br s, 2 H, OH), 9.42 (br s,4 H, OH). 13C NMR (75 MHz, CDCl3, 295 K): δ = 30.58, 31.73, 31.86, 32.81, 34.37, 34.74, 36.63, 72.22, 125.26, 126.01, 126.74, 127.04, 127.17, 127.41, 128.14, 132.99, 143.12, 143.72, 144.47, 147.24, 148.29, 149.71, 169.82. MS-FAB: m/z = 1451 [MH+]. Compound 2b: mp >250 °C. 1H NMR (300 MHz, CDCl3, 295 K) : δ = 1.16 [s, 36 H, (CH3)3], 1.18 [s, 18 H, (CH3)3], 1.25 [s, 18 H, (CH3)3], 3.64 (br s, 8 H, NCH2CH2N), 3.79 (br s, 8 H, ArCH2Ar), 3.90 (s, 8 H, ArCH2Ar), 4.35 (s, 8 H, OCH2CO), 6.91 [s, 8 H, ArH], 7.16 [s, 4 H, ArH], 7.24 (s, ArH, 4 H), 7.20 (overlapped, 4 H, OH, disappeared after 2 h after the addition of D2O), 8.00 (br s, 4 H, NH, partially disappeared after 2 d after the addition of D2O). 13C NMR (150 MHz, CDCl3, 295 K): δ = 30.55, 30.89, 31.45, 31.72, 31.74, 34.16, 34.52, 39.60, 73.23, 126.02, 126.24, 126.49, 126.77, 126.82, 132.72, 143.09, 143.42, 148.57, 149.12, 149.43, 149.55, 169.22. MS-FAB: m/z = 1577 [MH+].