Interactions of new bis-ammonium thiacalix[4]arene derivatives in 1,3-alternatestereoisomeric form with bovine serum albumin.

V.A. Burilov, D.A. Mironova, R.R. Ibragimova, S.E. Solovievaand I.S. Antipin.

Kazan Federal University, 18 Kremlevskayast. Kazan, 420008, Russia.

Correspondence:

Vladimir Burilov

e-mail:

telephone: +7-843-2337344; fax: +7-843-2387901

All reagents were purchased from either Acros or Sigma-Aldrich and used without further purification. TLC was done using “Silufol UV 254” with UV lamp VL-6.LC (6W –254 nm tube). Elemental analysis was performed with automated СHNS/О analyzer «Perkin Elmer PE 2400 series 2». NMR experiments were recorded at BrukerAvance 400 Nanobay with CDCl3 (δ:Н 7.26 ppm) as internal standard. MALDI mass-spectra were recorded at UltraFlex III TOF/TOF with PNA matrix, laser Nd:YAG, λ=355 nm. Cellu Sep H1 dialysis membranes with molecular-weight cutoff (MWCO) limits near 1000 Da were used.

General procedure for synthesis of compounds 1–3

Corresponding alkylazide derivative [1] (0.188 mM), N-propargyl-N,N,N–triethylammonium bromide [2] (0.124 g., 0.566 mM), triethylamine (1 ml), copper(I) iodide (0.0035 g., 0.0188 mM) were dissolved in 10 ml of dry toluene-DMF mixture (1:1). The reaction mixture was stirred at 60 °C for 12 h, and then solvent was evaporated in vacuo. Crude product was dissolved in 10 ml of deionized water and was purified by dialysis for 3 days using Cellu Sep H1 dialysis membrane. Water was evaporated in vacuoand compound was dried in a vacuum desiccator over P2O5 to give 1-3 as white powder.

5,11,17,23-Tetra-tert-butyl-25,27-dibutyloxy-26,28-bis[3-(4-methylene- N,N,N–triethylammonium bromide)-1,2,3-triazol-1-yl)propyloxy]-2,8,14,20-tetrathiacalix[4]arene 1

m = 0.202 g (75 %). Mp: 190°C (decomp.); MALDI TOF(m/z): 1249 [M-Et-2Br-]+; 1463 [M+Na]+ ; IR (KBr) νmax cm -1: 3422 (C-H), 1607 (C-C Ar), 1239 (=C-O), 1133 (C-N).

1H NMR (CDCl3, 298K) δH, ppm: 0.79 (t, J = 7.2 Hz, 6H, CH3), 0.87-0.96 (m, 4H, CH2), 1.01 (s, 18H, CMe3), 1.06-1.16 (m, 4H, CH2), 1.29 (s, 18H, CMe3), 1.48 (t, J = 6.85 Hz, 18H, CH3(CH2)N), 1.67-1.86 (m, 4H, СH2), 3.46 (brq, 12H, CH3(CH2)N), 3.79 (t, J = 7.34 Hz, 4H, -OCH2-), 4.12 (t, J = 5.8 Hz, 4H, -OCH2-), 4.2 (t, J = 6.5 Hz, 4H, NCH2), 4.98 (s, 4H, TrzCH2N), 7.23 (s, 4H, HAr), 7.35 (s, 4H, HAr), 8.71 (s, 2H, TrzH). 13C NMR (101 MHz, CDCl3, 298K) δ: 8.18, 13.92, 18.86, 30.39, 31.3, 34.14, 48.21, 52.14, 53.57, 66.56, 68.37, 126.64, 127.73, 127.86, 128.45, 128.94, 135.5, 145.81, 156.7. Found: С 59.8; Н 7.75; N 7.60 % C72H110 Br2N8О4S4requires: С 60.0; Н 7.64; N 7.77

5,11,17,23-Tetra-tert-butyl-25,27-dioctyloxy-26,28-bis[3-(4-methylene- N,N,N–triethylammonium bromide)-1,2,3-triazol-1-yl)propyloxy]-2,8,14,20-tetrathiacalix[4]arene 2

m = 0.244 g (84 %). Mp: 160°C (decomp.); MALDI TOF(m/z): 1659 [M-Et+PNA]+ ;IR (KBr) νmax cm -1: 3474 (C-H), 1253 (=C-O), 1011 (C-N).

1H NMR (CDCl3, 298K) δH, ppm: 0.88 (t, J = 6.96 Hz, 6H, CH3), 1.03 (s, 18H, CMe3), 1.10-1.24 (m, 24H, CH2), 1.28 (s, 18H, CMe3), 1.45 (t, J = 7.09 Hz, 18H, CH3(CH2)N), 1.67-1.75 (m, 4H, СH2), 3.44 (brq, 12H, CH3(CH2)N), 3.76 (brt, 4H, -OCH2-), 4.03-4.21 (m, 8H, -OCH2-, NCH2), 4.85 (s, 4H, TrzCH2N), 7.25 (s, 4H, HAr), 7.34 (s, 4H, HAr), 8.57 (s, 2H, TrzH). 13C NMR (101 MHz, CDCl3, 298K) δ: 8.23, 14.10, 22.6, 25.84, 28.55, 29.73, 30.58, 31.21, 31.31, 31.87, 34.16, 34.23, 48.13, 52.23, 53.6, 68.67, 126.50, 127.67, 127.88, 128.46, 128.90, 135.63, 145.9, 156.58, 156.79. Found: С 62.05; Н 8.36; N 7.18 % C80H126Br2N8О4S4requires: С 61.90; Н 8.18; N 7.22 .

5,11,17,23-Tetra-tert-butyl-25,27-ditetradecyloxy-26,28-bis[3-(4-methylene-N,N,N–triethylammonium bromide)-1,2,3-triazol-1-yl)propyloxy]-2,8,14,20-tetrathiacalix[4]arene 3

m = 0.237 g (81 %). Mp: 141°C (decomp.); MALDI TOF(m/z): 1609 [M-EtBr]+ , IR (KBr) νmax cm -1: 3474 (C-H),1253 (=C-O), 1011 (C-N).

1H NMR (CDCl3, 298K) δH, ppm: 0.88 (brt, 6H, CH3), 1.02 (brs, 18H, CMe3), 1.17-1.35 (m, 66H, CH2,CMe3), 1.45 (brt, 18H, CH3(CH2)N), 1.68-1.79 (m, 4H, СH2), 3.44 (brq, 12H, CH3(CH2)N), 3.75 (brt, 4H, -OCH2-), 4.13 (brt, 4H, -OCH2-), 4.18 (brt, 4H, NCH2), 4.86 (s, 4H, TrzCH2N), 7.25 (s, 4H, HAr), 7.31 (s, 4H, HAr), 8.56 (s, 2H, TrzH). 13C NMR (101 MHz, CDCl3, 298K) δ: 8.19, 14.13, 22.7, 25.82, 28.56, 29.4, 29.66, 29.71, 30.05, 31.18, 31.32, 31.95, 34.14, 34.23, 48.2, 52.1, 53.56, 66.62, 68.5, 126.54, 127.69, 127.88, 128.46, 128.72, 135.52, 145.85, 156.61, 156.76. Found: С 64.60; Н 8.87; N 6.47 % C92H150Br2N8О4S4requires: С 64.23; Н 8.79; N 6.51.

[1] V.A. Burilov, R.I. Nugmanov, R.R. Ibragimova, S.E. Solovieva, I.S. Antipin, 'Click chemistry' in the synthesis of new amphiphilic 1,3-alternate thiacalixarenes, Mendeleev Communications 25 (2015) 177-179.

[2] H. Sun, J. Han, Ch. Gao, High yield production of high molecular weight poly(ethylene glycol)/α-cyclodextrinpolyrotaxanes by aqueous one-pot approach, Polymer 53 (2012) 2884-2889.