Milad Kazemnejadi and
Ali Reza Sardarian*
Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71946 84795, Iran. E-mail: sardarian@shirazu.ac.ir; Tel: +98-71-36137109
First published on 12th September 2016
A new heterogeneous and reusable polyvinyl alcohol immobilized copper(II) Schiff base complex (PVA@Cu(II) Schiff base complex) was synthesized in water, characterized and used for the highly efficient environmentally benign one-pot three-component preparation of 5-substituted 1H-tetrazole derivatives through the click reaction of aliphatic and aromatic aldehydes with hydroxylamine hydrochloride and azide salt as inexpensive and commercially available substrates in water with very short reaction times at room temperature.
There are several strategies for the preparation of 5-substituted 1H-tetrazoles, of which the [3 + 2] cycloaddition reaction between nitriles and azide salts has been the popular method.7
Several procedures of this strategy, which have been recently reported in the literature, are: (a) R-CN, NaN3, DMF, I2, 120 °C,8 (b) R-CN, NaN3, Et3N·HCl, PhNO2, MW, 100 °C,9 (c) R-CN, NaN3, Et3N·HCl, DMF, 130 °C, MW,10 (d) R-CN, NaN3, AlCl3, NMP, MW, 200 °C,11 (e) R-CN, NaN3, TMSCl, NMP, MW, 220 °C,12 (f) R-CN, NaN3, water, ZnBr2 or AcOH,13 (g) R-CN, NaN3 tetrabutylammonium hydrogen sulfate in water,14 (h) R-CN, NaN3, NMP, water,15 (i) R-CN, NaN3, isopropanol, water, Sc(OTf)3,16 (j) R-CN, NaN3, immobilized AlCl3 on Al2O3, DMF,17 (k) R-CN, NaN3, immobilized copper(II) complex of 4-phenyl-2,2′:6′,2′′-terpyridine on activated multi-walled carbon nanotubes, DMF,18 and (l) ArCN, NaN3, DMF, Fe3O4@SiO2/salen complex of Cu(II), 120 °C.19a
Due to more availability and less toxicity of aldehydes in compare to nitriles and high efficiency of copper catalysts in [3 + 2]-cycloaddition reactions,19 using copper catalysts for preparation of 5-substituted 1H-tetrazoles through the reaction of a mixture of aldehydes and hydroxylamine hydrochloride or oximes with NaN3 have been drawn attention of organic chemists in last few years. Patil and his co-workers employed Cu(OAc)2 as a catalyst for preparation of 5-substituted 1H-tetrazoles from oximes and NaN3 in DMF at 120 °C.20 Heravi and his co-workers applied also Cu(OAc)2 to synthesize of 5-substituted 1H-tetrazoles via the reaction of aldehydes, hydroxylamine and [bmim]N3 (bmim = 1-butyl-3-methylimidazolium azide), in DMF at 120 °C.21
Recently, Abdollahi-Alibeik and his co-worker have reported a new catalyst, Cu-MCM-41 (MCM = Mobile Composition of Matter) nanoparticles for preparation of this type of tetrazoles from the reaction of aldehydes, hydroxylamine and NaN3 in DMF at 140 °C.22
Majority of methods, which have been above-mentioned, suffer some drawbacks such as need to use high temperature and toxic and expensive solvents.
For sake of notable property of tetrazoles and catalytic activity of copper for the formation of N-containing heterocyclic compounds,23 herein, we wish to introduce, a novel, recoverable and reusable heterogeneous catalyst to overcome some of the above-mentioned impediments by working under mild and green conditions to perform efficiently preparation of 5-substituted 1H-tetrazoles derivatives (Scheme 1).
Scheme 1 Preparation of 5-substituted 1H-tetrazole by using of PVA@Cu(II) Schiff base complex (catalyst). |
The precipitated product 3 by addition of acetone (10 mL) was filtered, washed with cold acetone (2 × 10 mL) and dried to provide the pure product (as a white powder). The product 3 was transferred to a 50 mL round bottom flask along with addition of 20 mL of water:ethanol (1:1) and then salicylaldehyde (1.2 mL, 11.3 mmol) was added to the reaction mixture and stirred for 2 h. To the yellow viscose mixture formed, because of formation the corresponding Schiff base 4, Cu(OAc)2 (0.9 g, 4.9 mmol) was added gradually in 5 min to the reaction mixture to obtain PVA@Cu(II) Schiff base complex 5 (Scheme 2) as a bright green solid. The polymeric copper complex was purified by simple filtration and washing with cold acetone (2 × 10 mL) to provide the pure complex (0.93 g).
It was also possible to prepare PVA@Cu(II) Schiff base complex in DMSO as same procedure as described above.
Formation of the complex 5 was monitoring with UV-Vis instrument at different period of times.
In FT-IR spectrum of the epoxide product of PVA with ECH, the presence of peaks at 848, 948 and 1026 cm−1 was belonged to the epoxy group. The red shift of the peak at 1635 cm−1 to 1612 cm−1 was due to the chelating of copper in polymeric Schiff base ligand 4 that was shown in Fig. 1.
Fig. 1 FT-IR spectrum of PVA epoxidized (a), polymeric Schiff base ligand 4 (b) and its complex 5 (c). |
1H NMR spectrum of the PVA ligand was recorded in DMSO-d6 as solvent and TMS as internal reference. Advent of peak at 9.430 pp m in 1H-NMR demonstrated the preparation of iminium bond in the polymeric Schiff base ligand 4. The chemical shift related to aromatic bonds is setting in 5.6–7.5 ppm (Fig. 2).
Regarding to Zabierowski and co-workers report24 about determination of the structure of salicylidene-2-ethanolamine Schiff bases of copper(II) complex by X-ray, Fig. 3, in which copper(II) atoms are in N2O2 coordination environment of two chelating ligands, the structure of PVA@Cu(II) Schiff base complex 5 might be most likely as it is as shown in Scheme 2.
Fig. 3 Molecular structure of bis{4-chloro-2-[(2-hydroxyethyl)iminomethyl]-phenolato}-copper(II) [Cu(cheimp)2].24 |
Formation of the complex was also investigated with UV-Vis technique in 5 and 45 min after addition of Cu(OAc)2 into solution of polymeric ligand 4 in DMSO (Fig. 4). Appearance of a peak near to 400 nm that was related to electron transfer of Cu (d–d; metal to ligand charge transfer (MLCT)) and also elimination of the absorption at 310–350 nm, which is due to π → π* of nitrogen atom in CN bond in 4, demonstrated the chelation formation of Cu(OAc)2. Also a broad adsorption for polymeric Schiff base ligand 4 at ∼300–350 that assigned to n → π* of imine (CN) have been eliminated due to chelation to Cu(II).
Fig. 4 UV-Vis absorption of 4 (dash line) and the reaction mixture in 5 minutes (dash-dotted line) and 45 minutes (solid line) after addition of Cu(OAc)2. |
Thermal stability of PVA@Cu(II) Schiff base complex 5 was shown in Fig. 5. TGA-DTG spectrum represented three main weight loss stages: first at 110–220 °C corresponds to −9.12% weight loss, which was belong to decomposition of ligand from PVA, second at 238–322 °C that showed decomposition of PVA. Third and final stage, which lasting to 600 °C, could be due to oxidation of copper and formation of CuO and carbonization of polyvinyl alcohol. Furthermore, a low weight loss in the beginning of the spectrum (Fig. 5, −2.27%) showed escaping of humidity and solvent25 trapped in polymeric complex.
Loading amount of copper in catalyst 5 was determined by inductive coupled plasma (ICP) experiment. Catalyst 5 (100 mg) was digested in H2SO4:HNO3 (8:2, 10 mL) mixture (room temperature, 2 h) then diluted as 1:50 with distilled water and along with a blank (water) and four standards ([Cu(OAc)2]; 2.5, 5, 10, 20 mg L−1) were used for measuring of copper content in 5. Experiments showed that 27.30 mg (27.3 wt%) copper was loaded on PVA ligand 4, that was 4.3 mmol g−1 (for 100 mg of 5) (Table 1).
Sample | Conc. (mg L−1) | Int. (C/S) |
---|---|---|
a The analyses were taken at 324.754 nm.b Analysis of residual reaction mixture after 5th run to elucidation of leaching amount of copper from catalyst 5. | ||
Water | 0.00 | 8.93 |
Cu-2.5 | 2.50 | 1672.38 |
Cu-5 | 5.00 | 3916.16 |
Cu-10 | 10.00 | 9191.00 |
Cu-20 | 20.00 | 18757.60 |
Cu-sample | 27.30 | 51941.60 |
Cu-sample-5th runb | 0.50 | 634.40 |
Entry | Solvent | Temperatureb (°C) | Catalyst (mol%) | Timec (min) | Yield (%) |
---|---|---|---|---|---|
a Reaction condition: aldehyde (1 mmol), hydroxylamine hydrochloride (1.5 mmol), sodium azide (1.5 mmol), solvent, temperature.b For optimization, various temperatures were used for each solvent and just some cases were shown.c Completion of the reactions were monitored by TLC.d The reaction was done in the absence of 5 and in the presence of PVA alone.e The reaction was carried out in the presence of Cu(OAc)2 (25 mol%) according to Patil and his co-workers report.26 | |||||
1 | H2O | R. T. | 0.43 | 7 | 98 |
2 | H2O | R. T. | 0.8 | 7 | 98 |
3 | EtOH | R. T. | 0.8 | 60 | 25 |
4 | EtOH | 80 | 0.8 | 60 | 35 |
5 | MeOH | R. T. | 0.8 | 60 | 30 |
6 | DMF | 80 | 0.8 | 30 | 50 |
7 | CH3CN | 80 | 0.8 | 30 | 45 |
8 | Et2O | R. T. | 0.8 | 60 | 20 |
9 | H2O | R. T. | —d | 60 | Trace |
10 | H2O | R. T. | 25e | 240 | 0 |
To elucidation of catalytic activity of PVA@Cu(II) Schiff base complex, the model reaction was carried out in presence of polyvinyl alcohol alone under the optimized conditions that were achieved before. Clearly, the reaction did not show any notable progress for PVA (entry 9). Also the reaction did not proceed at all under the optimized conditions (water medium and room temperature) in the presence of Cu(OAc)2 as a catalyst (Table 2, entry 10).
After implement of optimization steps, the catalyst was employing for determination of scope and versatility of the preparation of 5-substituted 1H-tetrazole derivatives under the optimized conditions. Various aromatic and aliphatic aldehydes served as substrate and the related results showed in Table 3. Aromatic aldehydes bearing whether electron donating or electron withdrawing groups showed excellent results except in the case of 3,4-dihydroxy benzaldehyde and salicylaldehyde that afforded 70% and 80% yields respectively (entries j and h). Aliphatic aldehydes, such as 3-phenyl propionaldehyde and lauraldehyde were also carried out the reaction and provided the desired products in high yields (Table 1, entries n and p) respectively.
Entry | Aldehyde | Product | Time (min) | Yieldb (%) | MP (°C)Lit. |
---|---|---|---|---|---|
a Reaction condition: aldehyde (1 mmol), hydroxylamine hydrochloride (1.5 mmol), sodium azide (1.5 mmol), water, room temperature, catalyst 5 (10 mg, 0.43 mol%).b Isolated yields. | |||||
a | 7 | 98 | 217–21925 | ||
b | 5 | 98 | 132–134 | ||
c | 7 | 98 | 233–23427 | ||
d | 15 | 98 | 220–22228 | ||
e | 15 | 97 | 155–15729 | ||
f | 12 | 98 | 161–163 | ||
g | 7 | 98 | 257–25930 | ||
h | 15 | 80 | 219–22131 | ||
i | 5 | 98 | 154–156 | ||
j | 5 | 70 | 213–215 | ||
k | 7 | 88 | 232–23532 | ||
l | 8 | 95 | 148–150 | ||
m | 8 | 98 | 220–22233 | ||
n | 12 | 80 | 98–10034 | ||
o | 5 | 95 | 205–2078 | ||
p | 3 | 80 | 215–217 |
Therefore, for understanding the mechanism of performance of catalyst 5, three reactions were designed to be studied: (a) in the first reaction, salicylaldehyde reacted with hydroxylamine hydrochloride in the presence of catalyst 5 in water, which immediately provided salicylaldoxime in quantitative yield. In second experiment, conversion of salicylaldoxime to 2-hydroxybenzonitrile was checked in the presence of the Cu(II) catalyst 5, which did not take place at room temperature and even higher temperatures in water. Finally, reaction of salicylaldoxime with sodium azide, which was proceeded rapidly in 11 min towards 5-(2-hydroxyphenyl)-1H-tetrazole in the presence of the catalyst 5 at room temperature in water.
The results of these studies demonstrated that in the present protocol, probably, oxime formation is followed by a [3 + 2] cycloaddition reaction between oxime and hydrazoic acid and then water elimination, on the base of Patil's report,26 to be led to the title tetrazoles (Scheme 4).
Scheme 4 Contingent mechanism for tetrazole synthesis PVA@Cu(II) Schiff base complex 5 as a catalyst. |
On the other hand, due to the presence of both lipophilic (including C–C and C–H bonds) and hydrophilic parts (including polar groups and copper complex) in the structure of catalyst, it may act as a media that is able to dissolve all of the starting materials and keep them close together by hydrogen bonding and coordination with copper(II). Therefore, it provides effective concentrations of the starting materials as higher as possible to help the reaction proceeds without need to large amount of energy and take places at room temperature (Scheme 5).
Run | Catalyst yield (%) | Product yield (%) |
---|---|---|
1 | 98 | 98 |
2 | 98 | 98 |
3 | 97 | 95 |
4 | 95 | 95 |
5 | 82 | 90 |
For comparison among of efficiency of PVA@Cu(II) Schiff base complex with the reported catalysts in the literature for preparation of 5-substituted-1H-tetrazole, the reaction of benzaldehyde with hydroxylamine hydrochloride and azide salt was selected as the model reaction. The results exhibited in Table 5 appeared superiority of PVA@Cu(II) Schiff base complex over the other systems in point of view of environmental and economical aspects.
Because in contrast to the reported catalysts in the literature, which catalyze the preparation of 5-substituted-1H-tetrazoles in DMF as a toxic solvent, long reaction times, under high temperatures (>100 °C), PVA@Cu(II) Schiff base complex works in water as a green solvent, very short reaction times and at room temperature. The other notable advantages of this catalyst are: (a) its preparation in water, and (b) its stability and reusability, so it can be reused five runs without significant reactivity loss.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ra19631d |
This journal is © The Royal Society of Chemistry 2016 |