Professional Documents
Culture Documents
Journal of Molecular Catalysis A: Chemical: Ali Akbari, Nasser Arsalani, Mojtaba Amini, Esmaiel Jabbari
Journal of Molecular Catalysis A: Chemical: Ali Akbari, Nasser Arsalani, Mojtaba Amini, Esmaiel Jabbari
a r t i c l e i n f o a b s t r a c t
Article history: The azide–alkyne cycloaddition reaction was investigated under catalytic conditions involving a
Received 16 October 2015 copper(II)—polyhedral oligomeric silsesquioxane (POSS)—bridged Schiff base. This material demon-
Received in revised form strated a high catalytic activity in organic synthesis of 1,4-triazoles. No additive such as a base or a
17 December 2015
reductant was required. Finally, recoverability and reusability of the POSS-bridged Schiff base–Cu(II)
Accepted 27 December 2015
Available online 2 January 2016
catalyst was analyzed.
© 2015 Elsevier B.V. All rights reserved.
Dedicated to the memory of Professor Ali
Akbar Entezami who passed away in the
summer of 2015.
Keywords:
Silsesquioxane
Copper
Azide–alkyne cycloaddition
http://dx.doi.org/10.1016/j.molcata.2015.12.022
1381-1169/© 2015 Elsevier B.V. All rights reserved.
48 A. Akbari et al. / Journal of Molecular Catalysis A: Chemical 414 (2016) 47–54
Scheme 1. Synthetic route and the proposed chemical structure for POSS–SAL–Cu complex.
2. Experimental
Fig. 1. FT-IR spectra of POSS (a), POSS–SAL (b) and POSS–SAL–Cu (c).
All chemicals and solvents were purchased from Merck and
Fluka and were used without further purification. Benzyl azides
were prepared according to a previously reported procedure
A. Akbari et al. / Journal of Molecular Catalysis A: Chemical 414 (2016) 47–54 49
Table 1
The effect of reaction conditions on the azide–alkyne cycloaddition.
1 – 70 12 0
2 0.002 70 12 34
3 0.004 70 12 45
4 0.006 70 12 69
5 0.008 70 12 81
6 0.01 70 12 95 (37)b
7 0.008 r.t. 12 8
8 0.008 40 12 16
Fig. 2. (a–d) 1 HNMR (a,c) and 13 CNMR (b,d) spectra of POSS and POSS–SAL.
9 0.008 50 12 33
10 0.008 60 12 87
11 0.008 70 2 29
[41]. Fourier transform infrared (FT-IR) spectra was carried out 12 0.008 70 6 53
on a Bruker FTIR spectrometer (model Tensor 27) over the 13 0.008 70 8 80
range of 500–3500 cm−1 using spectroscopic grade KBr pow- a
Isolated yield.
der at room temperature. 1 HNMR spectra were recorded on a b
In the presence of 0.02 mmol of Cu(OAc)2 ·H2 O as a catalyst.
50 A. Akbari et al. / Journal of Molecular Catalysis A: Chemical 414 (2016) 47–54
Table 2
Cycloaddition of alkyl halides with terminal alkynes in the presence of POSS–SAL–Cu.
1 95
2 95
3 89
4 94
5 91
6 93
7 96
8 92
9 90
10 95
11 95
12 96
13 91
14 93
a
Isolated yield.
A. Akbari et al. / Journal of Molecular Catalysis A: Chemical 414 (2016) 47–54 51
(100 MHz, DMSO): ı 165.68 (s, phenolic OH), 161.01 (s, CH NH), 2.4. Synthesis of POSS–SAL–Cu, compound 3
132.44–116.75 (s, Aromatic carbons), 39.57 (s, CH2 NH3 ), 24.39 (s,
SiCH2 CH2 ), 9.53 (s, SiCH2 ). A solution of Cu(OAc)2 ·H2 O (8 mmol) in 10 mL C2 H5 OH was
added to a solution of 1.0 mmol POSS–SAL in 10 mL CH2 Cl2 . The
52 A. Akbari et al. / Journal of Molecular Catalysis A: Chemical 414 (2016) 47–54
mixture was stirred for 24 h at ambient condition to form a green 2.5. General procedure for Cu(II) POSS-bridged Schiff base
solid. The solid was filtered off, washed with ethanol and finally azide–alkyne cycloaddition
with diethyl ether and dried in vacuum. Elemental analysis for
POSS–SAL–Cu (by the weight percentage): C 51.48%, N 5.57%, and Alkyne (0.5 mmol), the organic halide (0.55 mmol), and NaN3
H 5.47%, and the loading amount of Cu in the catalyst POSS–SAL–Cu (0.55 mmol) were added to a suspension of POSS–SAL–Cu (5 mg)
is calculated to be about 16.7%. in H2 O (2 mL). The reaction mixture was heated to 70 ◦ C
and monitored by TLC until total conversion of the starting
A. Akbari et al. / Journal of Molecular Catalysis A: Chemical 414 (2016) 47–54 53
The two step synthetic pathway for POSS–SAL–Cu is depicted in To optimize the reaction conditions, a series of experiments
Scheme 1. POSS–NH3 + was prepared via hydrolyses and conden- were carried out with varying catalyst loading, temperature and
sation reaction by using 3-aminopropyltriethoxysilane (ATPES) as time for representative reaction of benzyl chloride, phenyl acety-
the sol–gel precursor in acidic condition [43]. The reaction was car- lene and NaN3 to synthesize 1-benzyl-4-phenyl-1,2,3-traizole with
ried out at 90 ◦ C to reduce the reaction time (one week at ambient POSS–SAL–Cu as the catalyst (Scheme 2). Water was used as the
condition) to 16 h [42]. Imine bonds were readily formed via con- standard “green” solvent. All reactions were performed in air with-
densation of salicylaldehyde with POSS–NH3 + in the presence of out any additive. In a typical reaction, alkyne, organic halide and
triethylamine in methanol and produced the POSS–SAL, compound NaN3 in a ratio of 1:1.1:1.1 were mixed in a flask, followed by the
2, in nearly quantitative yield. Finally POSS–SAL–Cu, compound addition of water and catalyst. The mixture was heated to 70 ◦ C
3, was prepared as a green solid. All compounds were character- for a certain period (Table 1). The organic product was isolated by
ized by 1 HNMR, 13 CNMR, FT-IR, MOLDI-TOF, SEM and TEM. The extraction and analyzed by elemental analysis and 1 H NMR. Results
resulting solid catalyst was insoluble in common organic solvents, are summarized in Table 1.
such as THF, DMF, ethanol, acetonitrile, and chloroform, thus the When the amount of catalyst was increased from 0 to 5 mg, the
synthesized catalyst is a good candidate with respect to solubility product yield increased sharply from 0 to 95%. No product was
for heterogeneous catalysis. FT-IR was used for structure eluci- obtained in the absence of catalyst. As indicated in Table 1, the reac-
dation. Fig. 1 illustrates the FT-IR spectra of POSS (a), POSS–SAL tion did not initiate at ambient temperature with magnetic stirring
(b) and POSS–SAL–Cu (c). Fig. 1a shows the most prominent for 12 h, but the product yield increased significantly at higher tem-
bands of the POSS cage, Si O Si asymmetric stretching absorption peratures. Also, the yield increased significantly from 29% to 95%
between 1107 and 1125 cm−1 and deformation of Si O Si bridges with increasing reaction time from 2 to 12 h. Catalytic activity of
at 705 cm−1 [44]. In addition, the peaks at 2893 and 2955 cm−1 in the reaction system decreased dramatically when POSS–SAL–Cu
the FT-IR spectra confirmed the presence of propyl chains in POSS. was replaced by Cu(OAc)2 , as shown in Table 1 (entry 6).
After the reaction of POSS with salicylaldehyde, the structure of the A wide range substituted phenyl acetylenes were reacted with
new compound, POSS–SAL, as a free ligand exhibited many new the mixture of benzyl bromides/chlorides and sodium azide using
absorption peaks including those at 1630 and 1277 cm−1 which this procedure to produce the corresponding 1,4-disubstituted-
were attributed to C N azomethine and C O phenolic vibrations, 1,2,3-triazoles. The results are summarized in Table 2. The
respectively. After complexation with copper, the azomethine substitution of electron withdrawing or electron donating groups
vibration of the free ligand at 1630 cm−1 was moved to a lower fre- on the phenyl ring of benzyl halides and phenyl acetylenes did not
quency, i.e., 1620 cm−1 . Additionally, the C O phenolic vibration have an appreciable effect on the reaction outcome (entries 2–6).
at 1277 cm−1 in the free ligand was shifted to a higher frequency Furthermore, steric hindrance of the ortho substituents on benzyl
by 47 cm−1 after complexation. These shifts confirmed the forma- chlorides affected progress of the reaction. The benzyl chloride sub-
tion of POSS–SAL–Cu by coordination of azomethine nitrogen and stituted with methyl group at the ortho position was less reactive
phenolic oxygen with copper ions. toward the cycloaddition reaction than the para derivative (entries
We have characterized the POSS–NH3 + and POSS–SAL by NMR 2 and 3). However, the cycloaddition of benzyl bromide had a lower
spectroscopy (1 HNMR and 13 CNMR) as shown in Fig. 2a–d. Based yield under similar reaction conditions (entries 7–9). The results
on the 1 HNMR spectrum in Fig. 2c, the ratio of the peaks for methy- of Cu(II)-catalyzed cycloaddition of various terminal alkynes with
lene groups of POSS, as the base with integral value of 8 protons, to benzyl azide are summarized in Table 2. The reactions of substi-
that of the imine protons (8.45 ppm, 3.95 H) was 2.02. As a result, 8 tuted phenyl acetylenes and benzyl azides in water with 5 mg of
ammonium groups of POSS were successfully reacted with salicy- POSS–SAL–Cu resulted in 91–96% products (entries 10–14), while
laldehyde and converted to imine groups. a blank experiment under similar conditions provided no product.
54 A. Akbari et al. / Journal of Molecular Catalysis A: Chemical 414 (2016) 47–54
Higher reaction conversions compared to the blank experiments [3] E. Haldón, M.C. Nicasio, P. Pérez, Org. Biomol. Chem. 13 (2015) 9528–9550.
clearly demonstrated the activity of POSS–SAL–Cu catalyst in the [4] J.E. Hein, V.V. Fokin, Chem. Soc. Rev. 39 (2010) 1302–1315.
[5] D. Bock, H. Hiemstra, J.H. van Maarseveen, Eur. J. Org. Chem. (2006) 51–68.
reactions. [6] M. Meldal, C.W. Tornøe, Chem. Rev. 108 (2008) 2952–3015.
Finally, a set of experiments were carried out to test the [7] C.O. Kappe, E. Van der Eycken, Chem. Soc. Rev. 39 (2010) 1280–1290.
heterogeneity and reusability of POSS–SAL–Cu catalyst in the [8] S. Park, M.S. Kwon, Y. Kim, J.S. Lee, J. Park, Org. Lett. 10 (2008) 497–500.
[9] B.S. Lee, M. Yi, S.Y. Chu, J.Y. Lee, H.R. Kwon, K.R. Lee, D. Kang, W.S. Kim, H.B.
azide–alkyne cycloaddition reaction of benzyl chloride, phenyl Lim, J. Lee, H.-J. Youn, D.Y. Chi, N.H. Hur, Chem. Commun. 46 (2010)
acetylene and NaN3 at 70 ◦ C for 12 h. For each cycle, the catalyst 3935–3937.
was recovered from the reaction mixture by filtration, washed with [10] L. Liang, D. Astruc, Coord. Chem. Rev. 255 (2011) 2933–2945.
[11] F. Alonso, Y. Moglie, G. Radivoy, Acc. Chem. Res. 48 (2015) 2516–2528.
distilled water and ethyl ether repeatedly, dried at 50 ◦ C for 1/2 h,
[12] F. Alonso, Y. Moglie, G. Radivoyand, M. Yus, Org. Biomol. Chem. 9 (2011)
and reused in the next cycle. As shown in Fig. 5, the reaction yield 6385–6395.
slightly decreased due to the loss of catalyst activity after recycling [13] Y. Monguchi, K. Nozaki, T. Maejima, Y. Shimoda, Y. Sawama, Y. Kitamura, Y.
Kitade, H. Sajiki, Green Chem. 15 (2013) 490–495.
the catalyst three times. A comparison of the IR data for the fresh
[14] I. Luz, F.X.L. i Xamena, A. Corma, J. Catal. 276 (2010) 134–140.
and recycled catalyst (Fig. 6) revealed changes in the spectra for the [15] R.H. Baney, M. Itoh, A. Sabakibara, T. Suzuki, Chem. Rev. 95 (1995) 1409–1430.
two materials. Thus, structural changes maybe responsible for the [16] E.A. Quadrelli, J.-M. Basset, Coord. Chem. Rev. 254 (2010) 707–728.
reduction in catalytic activity of the catalyst upon repeated use. [17] D.B. Cordes, P.D. Lickiss, F. Rataboul, Chem. Rev. 110 (2010) 2081–2173.
[18] C. Marcolli, G. Calzaferri, Appl. Organomet. Chem. 13 (1999) 213–226.
To address the leaching of copper species into solution, the cat- [19] H.C.L. Abbenhuis, Chem. Eur. J. 6 (2000) 25–32.
alyst was removed by ultracentrifugation at half the reaction time [20] G. Li, L. Wang, H. Ni, C.U. Pittman Jr., J. Inorg. Organomet. Polym. 11 (2002)
(6 h) in a separate experiment. The reaction did not proceed signifi- 123–154.
[21] G. Calzaferri, R. Imhof, K.W. Törnroos, J. Chem. Soc. Dalton Trans. (1993)
cantly upon further treatment of the residual mixture under similar 3741–3748.
reaction conditions for 6 h (second half of the reaction). There- [22] P.G. Harrison, R. Kannengiesser, J. Chem. Soc. Chem. Commun. (1995)
fore, it can be concluded that the leaching of the copper catalyst 2065–2066.
[23] M. Rattay, D. Fenske, P. Jutzi, Organometallics 17 (1998) 2930–2932.
was negligible. The Cu content of the residual mixture, measured [24] A.R. Bassindale, T. Gentle, J. Organomet. Chem. 521 (1996) 391–393.
by atomic absorption spectroscopy, was below the detection limit [25] S.G. Kim, J. Choi, R. Tamaki, R.M. Laine, Polymer 46 (2005) 4514–4524.
which confirmed negligible leaching of the catalyst. [26] E.A. Bijpost, M.A. Zuideveld, A. Meetsma, J.H. Teuben, J. Organomet. Chem. 551
(1998) 159–164.
[27] M. Moraı́n, C.M. Casado, I. Cuadrado, J. Losada, Organometallics 12 (1993)
4. Conclusions 4327–4333.
[28] N.L. Dias Filho, F.C.M. Portugal, J.M.F. Nogueira, P. Branda˜o, V. Feı́lix, P.D. Vaz,
C.D. Nunes, L.F. Veiros, M.J. Villa de Brito, M. Joseı́Calhorda, Organometallics
All eight propylammonium side chains of POSS 1 reacted with
31 (2012) 4495–4503.
salicylaldehyde, producing the new compound 2 (POSS–SAL) with [29] K. Wada, D. Izuhara, M. Shiotsuki, T. Kondo, T. Mitsudo, Chem. Lett. 30 (2001)
eight salicylaldehyde arms. Further, the reaction of compound 2 734–735.
[30] G. Hornyak, M. Kroll, R. Pugin, T. Sawitowski, G. Schmid, J.O. Bovin, G. Karsson,
with the metal precursor Cu(OAc)2 produced the new derivative
H. Hofmeister, S. Hopfe, Chem. Eur. J. 3 (1997) 1951–1956.
POSS–SAL–Cu (3). Based on the SEM and TEM images, the derivative [31] G. Schmid, R. Pugin, J.O. Malm, J.O. Bovin, Eur. J. Inorg. Chem. (1998) 813–817.
3 contained an aggregate of spherical nanoparticles. The synthe- [32] K. Naka, H. Itoh, Y. Chujo, Nano Lett. 2 (2002) 1183–1186.
sized POSS-bridged copper Schiff base was a highly efficient catalyst [33] X. Wang, K. Naka, H. Itoh, Y. Chujo, Chem. Lett. 33 (2004) 216–217.
[34] K. Naka, H. Itoh, Y. Chujo, Bull. Chem. Soc. Jpn. 77 (2004) 1767–1771.
for azide–alkyne cycloaddition in aqueous media. Superior cat- [35] E.G. Vieira, I.V. Soares, G. Pires, R.A.V. Ramos, D.R. Do Carmo, N.L. Dias Filho,
alytic activity, easy recovery and reusability are the advantages of Chem. Eng. J. 264 (2015) 77–88.
compound 3. To our knowledge, this is the first POSS cage function- [36] N.L. Dias Filho, F. Marangoni, R.M. Costa, J. Colloid Interface Sci. 313 (2007)
34–40.
alized with eight salicylaldehydes as a ligand for coordination with [37] V. Soares, E.G. Vieira, N.L. Dias Filho, A.C. Bastos, N.C. da Silva, E.F. Garcia, L.J.A.
copper metal to produce model nano-platforms in heterogeneous Lima, Chem. Eng. J. 218 (2013) 405–414.
catalysis. The application of POSS–SAL as a Schiff base free ligand [38] E.G. Vieira, I.V. Soares, N.L. Dias Filho, N.C. da Silva, S.D. Perujo, A.C. Bastos, E.F.
Garciaa, T.T. Ferreira, L.F. Fraceto, A.H. Rosa, J. Hazard. Mater. 237–238 (2012)
catalyst in coordination with other metals for organic synthesis is 215–222.
in progress. [39] M.C. Gravel, C. Zhang, M. Dinderman, R.M. Laine, Appl. Organomet. Chem. 13
(1999) 329–336.
[40] Y.J. Pu, H. Yuan, M. Yang, B. He, Z.W. Gu, Chin. Chem. Lett. 24 (2013) 917–920.
Acknowledgments [41] S.G. Alvarez, M.T. Alvarez, Synthesis 4 (1997) 413–414.
[42] Y.-J. Pu, H. Yuan, M. Yang, B. He, Z.-W. Gu, Chin. Chem. Lett. 24 (2013)
Partial funding support was provided by the Research Council 917–920.
[43] T. Fouquet, T.N.T. Phan, L. Charles, Rapid Commun. Mass Spectrom. 26 (2012)
of University of Tabriz (N.A.) and University of Maragheh (M.A.).
765–774.
[44] H. Mori, M.G. Lanzendörfer, A.H.E. Müller, J.E. Klee, Macromolecules 37 (2004)
References 5228–5238.
[45] X. Wu, G. Yu, C. Luo, A. Maeda, N. Zhang, D. Sun, Z. Zhou, A. Puntel, K.
Palczewski, Z.R. Lu, ACS Nano 8 (2014) 153–161.
[1] C.W. Tornøe, C. Christensen, M. Meldal, J. Org. Chem. 67 (2002) 3057–3064.
[2] V. Rostovtsev, L.G. Green, V.V. Fokin, K.B. Sharpless, Angew. Chem. Int. Ed. 41
(2002) 2596–2599.