dissolved in ether (50 mL) and water (50 mL) was added. The
aqueous phase was extracted, the organic phase washed with
water (2 Â 50 mL) and dried with MgSO4. Filtration and
evaporation of the solvent made it possible to obtain the
product (2.43 g, 86%) as a yellow oil without further purification.
1H NMR (200 MHz, CDCl3) d (ppm): 7.22 (dd, J = 1.6 Hz and
4.8 Hz, 1H); 6.99–6.95 (m, 2H); 4.00 (s, 2H); 3.65 (t, J = 6.7 Hz,
2H); 2.68 (t, J = 7.0 Hz, 2H); 1.62 (br s, 1H); 1.62–1.50 (m, 4H);
1.42–1.36 (m, 4H). 13C NMR (50 MHz, CDCl3) d (ppm): 144.4;
127.1; 125.4; 124.8; 63.2; 49.4; 48.8; 33.1; 30.3; 27.5; 26.1. HRMS
(ESI): m/z calcd for C11H20NOS [M + H]+: 214.1266; found,
214.1266.
General procedure for the synthesis of monocopper complexes.
Copper(II) chloride (1 eq.) and N-tripodal ligand (1.2 eq.) were
stirred in anhydrous THF for 2 h at room temperature. A solid
was formed or the complex was precipitated by addition of
anhydrous ether or dichloromethane. The precipitate was filtered
under argon, washed with ether or dichloromethane and dried
under vacuum. The anhydrous complex was then dissolved in
MeOH : H2O (95 : 5) and the solvent was evaporated under
reduced pressure to obtain the hydrated form of the complex.
4a. Yield 57% of a blue-green powder. HRMS (ESI): m/z
calcd for C15H23ClCuN5O [M – Cl]+: 387.0887; found, 387.0887.
4b. Yield 52% of a blue powder. HRMS (ESI): m/z calcd for
C16H24ClCuN4O [M – Cl]+: 386.0934; found, 386.0933.
General procedure for the synthesis of N-tripodal ligands
A mixture of 1-hydroxymethylpyrazole (1.1 eq.) and secondary
amine (1 eq.) was stirred without solvent for 3 h at 70 1C. The
product was obtained as a yellow oil in quantitative yield in the
presence of 10% pyrazole.
4c. Yield 55% of a green powder. HRMS (ESI): m/z calcd
for C17H25ClCuN3O [M – Cl]+: 385.0982; found, 385.0981.
4d. Yield 61% of a green powder. Found, C, 39.91; H, 5.92;
N, 9.37; S, 7.06%. Calc. for C15H25N3O2Cl2SCu: C, 40.40; H,
5.65; N, 9.42; S, 7.19%.
6-(((1H-Pyrazol-1-yl)methyl)(pyrazin-2-ylmethyl)amino)hex-
1
an-1-ol (3a). H NMR (200 MHz, CDCl3) d (ppm): 8.73 (s, 1H);
8.56 (d, J = 2.5 Hz, 1H); 8.50 (d, J = 2.5 Hz, 1H); 7.56 (d, J =
2.0 Hz, 1H); 7.52 (d, J = 2.0 Hz, 1H); 6.33–6.30 (m, 1H); 5.57
(s, 2H); 3.93 (s, 2H); 3.64 (t, J = 6.0 Hz, 2H); 2.62 (t, J = 6.0 Hz,
2H); 1.63–1.51 (m, 4H); 1.38–1.31 (m, 4H). 13C NMR (50 MHz,
CDCl3) d (ppm): 155.2; 145.7; 144.3; 143.6; 140.0; 130.1; 106.0;
69.1; 63.2; 56.3; 52.3; 33.1; 27.8; 27.2; 25.9. HRMS (ESI): m/z calcd
for [C15H23N5O]+: 289.1903; found, 289.1889.
Catalysis
The experiments were conducted in air at constant stirring and
temperature of 25 1C, monitored with a contact thermomether
dipped in the solution. 6 mL of a 10À4 mol LÀ1 solution of
copper complex in methanol was added under stirring to a
fresh solution of 10À2 mol LÀ1 of 3,5-di-tert-butylcatechol in
40 mL methanol maintained at 25 1C. The absorbance was
continually monitored at 400 nm for 1 h using a dipping
probe colorimeter (662 photometer from Metrohm) to detect
the o-quinone characteristic signal.
6-(((1H-Pyrazol-1-yl)methyl)(pyridin-2-ylmethyl)amino)hexan-
1
1-ol (3b). H NMR (200 MHz, CDCl3) d (ppm): 8.60 (d, J =
5.0 Hz, 1H); 7.71 (m, 1H); 7.57–7.55 (m, 2H); 7.47 (d, J =
7.0 Hz, 1H); 7.22 (m, 1H); 6.32–6.31 (m, 1H); 5.04 (s, 2H); 3.87
(s, 2H); 3.65 (t, J = 6.7 Hz, 2H); 2.62 (t, J = 7.0 Hz, 2H);
1.63–1.53 (m, 4H); 1.40–1.33 (m, 4H). 13C NMR (50 MHz,
CDCl3) d (ppm): 159.6; 149.7; 139.6; 137.0; 130.5; 123.6; 122.6;
105.8; 69.1; 63.1; 58.3; 52.3; 33.1; 27.8; 27.3; 25.9. HRMS (ESI):
m/z calcd for C16H24N4ONa [M + Na]+: 311.1848; found,
311.1845.
Notes and references
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H. J. Wichers and B. W. Dijkstra, Biochemistry, 2011, 50, 5477.
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2006, 45, 4546.
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6-(((1H-Pyrazol-1-yl)methyl)(benzyl)amino)hexan-1-ol (3c).
1H NMR (200 MHz, CDCl3) d (ppm): 7.56–7.55 (m, 1H);
7.45–7.25 (m, 6H); 6.34–6.26 (m, 1H); 4.97 (s, 2H); 3.69
(s, 2H); 3.62 (t, J = 6.8 Hz, 2H); 2.58 (t, J = 7.0 Hz, 2H);
2.05 (br s, 1H); 1.65–1.46 (m, 4H); 1.42–1.25 (m, 4H).
13C NMR (50 MHz, CDCl3) d (ppm): 139.6; 139.3; 130.3;
129.1; 128.8; 127.6; 105.6; 68.7; 63.2; 56.4; 51.9; 33.1; 27.8;
27.3; 25.9. HRMS (ESI): m/z calcd for C17H25N3ONa [M +
Na]+: 310.1895; found, 310.1896.
6 K. Lerch, C. Longoni and E. Jordi, J. Biol. Chem., 1982, 257, 6408.
7 H. Claus and H. Decker, Syst. Appl. Microbiol., 2006, 29, 3.
8 J. C. Garcia-Borron and F. Solano, Pigm. Cell Res., 2002, 15, 162.
9 C. Gielens, K. Idakieva, M. De Maeyer, V. Van den Bergh,
N. I. Siddiqui and F. Compernolle, Peptides, 2007, 28, 790.
10 K. S. Banu, T. Chattopadhyay, A. Banerjee, S. Bhattacharya,
E. Zangrando and D. Das, J. Mol. Catal. A: Chem., 2009, 310, 34.
11 K. S. Banu, T. Chattopadhyay, A. Banerjee, S. Bhattacharya,
E. Suresh, M. Nethaji, E. Zangrando and D. Das, Inorg. Chem.,
2008, 47, 7083.
6-(((1H-Pyrazol-1-yl)methyl)(thiophen-2-ylmethyl)amino)hexan-
1-ol (3d). 1H NMR (200 MHz, CDCl3) d (ppm): 7.55 (d, J = 2.5
Hz, 1H); 7.44 (d, J = 2.5 Hz, 1H); 7.28–7.27 (m, 1H); 6.98–6.97
(m, 2H); 6.32–6.30 (m, 1H); 5.01 (s, 2H); 3.89 (s, 2H); 3.65 (t, J =
6.7 Hz, 2H); 2.61 (t, J = 7.0 Hz, 2H); 1.63–1.53 (m, 4H);
1.40–1.33 (m, 4H). 13C NMR (50 MHz, CDCl3) d (ppm):
143.4; 139.7; 130.4; 127.0; 126.3; 125.5; 105.8; 68.4; 63.2; 51.7;
51.2; 33.1; 27.8; 27.2; 25.9. HRMS (ESI): m/z calcd for
C15H23N3ONaS [M + Na]+: 316.1459; found, 316.1462.
12 M. Gullotti, L. Santagostini, R. Pagliarin, A. Granata and
L. Casella, J. Mol. Catal. A: Chem., 2005, 235, 271.
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Inorg. Chem., 2002, 41, 3983.
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C. Wiezbicki and E. Schwingel, Inorg. Chem., 2002, 41, 1788.
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c
1834 New J. Chem., 2012, 36, 1828–1835
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012