JOURNAL OF CHEMICAL RESEARCH 2016 749
Received 12 September 2016; accepted 26 October 2016
Published online: 23 November 2016
CAUTION: Although we did not encounter any problems with
gem-dihydroperoxides and tetraoxanes, peroxides are potentially
explosive and should be handled with extreme care and all necessary
precautions taken. All reactions should be carried out behind a safety
shield inside a fume hood and heating should be avoided.
References
1
2
K. Zmitek, M. Zupan and J. Iskra, Org. Biomol. Chem., 2007, 5, 3895.
R. Oliveira, R.C. Guedes, P. Meireles, I.S. Albuquerque, L.M. Gonçalves, E.
Pires, M.R. Bronze, J. Gut, P.J. Rosenthal, M. Prudêncio, R. Moreira, P.M.
O’Neill and F. Lopes, J. Med. Chem., 2014, 57, 4916.
D. Bonnet-Delpon and J.P. Begue, Tetrahedron Lett., 2003, 44, 6309.
A.O. Terent’ev, A.V. Kutkin, Z.A. Starikova, M.Y. Antipin, Y.N. Ogibin, G.I.
Nikishin and N.D. Zelinsky, Synthesis, 2004, 2356.
R. Amewu, A.V. Stachulski, S.A. Ward, N.G. Berry, P.G. Bray, J. Davies, G.
Labat, L. Vivas and P.M. O’Neill, Org. Biomol. Chem., 2006, 4, 4431.
A.O. Terent’ev, M.M. Platonov, A.I. Tursina, V.V. Chernyshev and Ge.I.
Nikishin, J. Org. Chem., 2008, 73, 3169.
Synthesis of HPA-NaY composite; general procedure
H3PW12O40 (10 g) was mixed with 6 mL zeolite gel (molar composition
16Na2O:Al2O3:15SiO2:320H2O) prepared from mixing 16.13 g sodium
alumina silicate (containing 19.80 wt% SiO2, Merck), 13.20 mL sodium
hydroxide (24 wt%) and 5.20 mL deionised water and aged at 32 °C for
32 h. The mixture was then placed in an autoclave at 100 °C for 24 h. After
cooling the reaction mixture to room temperature, filtering, washing with
water and drying in air, the solid product H3PW12O40/NaY composite was
recovered.36
3
4
5
6
7
8
9
Synthesis of gem-dihydroperoxides; general procedure
P. Ghorai, P.H. Dussault and C. Hu, Org. Lett., 2008, 10, 2401.
10 Q. Zhang, Y. Li and Y.-K. Wu, Chin. J. Chem., 2007, 25, 1304.
11 Y. Hamada, H. Tokuhara, A. Masuyama, M. Nojima, H.-S. Kim, K. Ono, N.
12 H.-S. Kim, Y. Nagai, K. Ono, K. Begum, Y. Wataya, Y. Hamada, K. Tsuchiya, A.
13 A. Masuyama, J.-M. Wu, M. Nojima, H.-S. Kim and Y. Wataya, Mini-Rev. Med.
14 H. Hansma and A. Schroeder, AKZO NV, Belg. Patent 868,681, 1978, Chem.
Abstr., 1979, 90, 153037a.
15 D. Azarifar, K. Khosravi and Z. Najminejad, J. Iran. Chem. Soc., 2013, 10, 979.
16 D. Azarifar and K. Khosravi, Eur. J. Chem., 2010, 1, 15.
17 J.P. Selvam, V. Suresh, K. Rajesh, D. Chanti Babu, N. Suryakiran and Y.
Venkateswarlu, Tetrahedron Lett., 2008, 49, 3463.
To a solution of carbonyl compound (1 mmol) and HPA/NaY (0.01 g)
in CH3CN (3 mL), 30% aqueous H2O2 (1 mL, 9.8 mmol) was added and
the mixture was stirred at room temperature for an appropriate time
(Tables 2–4). After completion of the reaction, as monitored by TLC, the
catalyst was separated by centrifuge and the solvent was evaporated under
reduced pressure. The residue was purified by silica-packed column
chromatography (hexane–EtOAc) to afford pure gem-dihydroperoxides
(Tables 2–4, 60–97% yields). The products were characterised on the basis
of their melting points, elemental analysis and IR, 1H NMR and 13C NMR
spectral analyses. Also, the amount of peroxide in the products was
determined by iodometric titration.
18 K. Jakka, J. Liu and C.G. Zhao, Tetrahedron Lett., 2007, 48, 1395.
19 D. Aarifar and K. Khosravi, Synlett, 2010, 2755.
20 A. Bunge, H.-J. Hamann, E. McCalmont and J. Liebscher, Tetrahedron Lett.,
2009, 50, 4629.
21 K. Khosravi, Res. Chem. Intermed., 2015, 41, 5253.
22 K. Khosravi, A. Mobinikhaledi, S. Kazemi, D. Azarifar and P. Rahmmani,
Iran. J. Catal., 2014, 4, 25.
23 K. Khosravi and S. Kazemi, Chin. Chem. Lett., 2012, 23, 387.
24 T. Ito, T. Tokuyasu, A. Masuyama, M. Nojima and K.J. McCullough,
Tetrahedron, 2003, 59, 525.
Synthesis of 1,2,4,5-tetraoxanes; general procedure
To a mixture of carbonyl compound (1 mmol) and HPA/NaY (0.01 g) in
CH3CN (3 mL), gem-dihydroperoxide (1 mmol) was added and the mixture
stirred at room temperature for the appropriate time (Table 5). After
completion of the reaction, as monitored by TLC, the catalyst was separated
by centrifuge and the solvent was evaporated under reduced pressure. The
residue was purified by silica-packed column chromatography (hexane–
EtOAc) to afford pure 1,2,4,5-tetraoxanes (Table 5, 71–92% yields). All of
the products were characterised on the basis of IR, 1H NMR and 13C NMR
spectral analysis, elemental analysis and by their melting points.
25 A.O. Terent’ev, A.V. Kutkin, N.A. Troizky, Y.N. Ogibin and G.I. Nikishin,
Synthesis, 2005, 13, 2215.
Physical and spectroscopic characterisation data of the catalyst and the
new compounds, including 1e, 3g and 3p, are contained in the Electronic
Supporting Information file and are also shown below.
2,2-dihydroperoxypropane (Table 2, entry 1e, 0.10 g, 95% yield): Oil; IR
(νmax/cm−1, KBr pellet): 3276, 2938, 2908, 2853, 1625, 1450, 1376, 1200,
1167, 829; 1H NMR (CDCl3, 90 MHz): δ = 9.15 (br, s, 2H, OOH), 1.79 (s,
6H); 13C NMR (DMSO-d6, 75 MHz): δ = 107.6, 21.2; Anal. calcd for
C3H8O4: C, 33.34; H, 7.46; found: C, 33.40; H, 7.56%.
26 C.W. Jefford, W. Li, A. Jaber and J. Boukouvalas, Synth. Commun., 1990, 20,
2589.
28 K. Zmitek, K. Zupan, S. Stavber and J. Iskra, Org. Lett., 2006, 8, 2491.
29 B. Das, B. Veeranjaneyulu, M. Krishnaiah, B. Veeranjaneyulu and B. Ravikanth,
Tetrahedron Lett., 2007, 48, 6286.
30 A. Bunge, H.-J. Hamann and J. Liebscher, Tetrahedron Lett., 2009, 50, 524.
31 B. Das, B. Veeranjaneyulu, M. Krishnaiah and P. Balasubramanyam, J. Mol.
Catal. A: Chem., 2008, 284, 116.
1,1,2,2-tetrahydroperoxy-1,2-diphenylethane (Table 4, entry 3g, 0.28
32 P. Ghorai and P.H. Dussault, Org. Lett., 2008, 10, 4577.
33 Y. Li, H.-D. Hao, Q. Zhan and Y. Wu, Org. Lett., 2009, 11, 1615.
34 K.V. Sashidhara, S.R. Avula, L.R. Singh and G.R. Palnati, Tetrahedron Lett.,
2012, 53, 4880.
35 R.S. Varma, Sustainable Chemical Processes, 2014, 2, 11.
36 M. Zendehdel, A. Mobinikhaledi, H. Alikhani and N. Jafari, J. Chin. Chem.
g, 89% yield): White solid, m.p.: 100–102 °C; IR (νmax/cm−1, KBr pellet):
1
3304, 2924, 1614, 1513, 1457, 1375, 1115, 1033, 929; H NMR (CDCl3,
90 MHz): δ = 8.81 (br, s, 4H, OOH), 7.32–7.99 (m, 10H); 13C NMR
(DMSO-d6, 75 MHz): δ = 167.7, 133.3, 131.2, 129.7, 129.02; Anal. calcd for
C14H14O8: C, 54.20; H, 4.55; found: C, 54.15; H, 4.63%.
2,2-dihydroperoxy-1-phenylpropane (Table 4, entry 3p, 0.18 g, 94%
yield): White-brown solid; m.p.: 99–101 °C; IR (νmax/cm−1, KBr pellet):
3427, 2953, 2924, 1633, 1457, 1375, 1212, 1167; 1H NMR (90 MHz, CDCl3),
δ = 9.95 (bs, 2H, OOH), 6.7–7.3 (m, 5H, Ar), 2.2 (s, 2H, CH2), 1.54 (s, 3H,
CH3); 13C NMR (100 MHz, DMSO-d6): δ = 141.9, 128.8, 128.7, 128.5,
126.3, 110.0, 108.4; Anal. calcd for C9H12O4: C, 58.69; H, 6.57; found: C,
58.33; H, 6.81%.
37 F. Zamani, M. Zendehdel, A. Mobinikhaledi and M. Azarkish, Microporous
and Mesoporous Materials, 2015, 212, 18.
38 M. Zendehdel, G. Cruciani, F. Sahra Kar and A. Barati, J. Environ. Health Sci.
& Eng., 2014, 12, 35.
39 M. Zendehdel, F. Hoseini, A. Zendehnam and M. Azarkish, Polym. Bull., 2015,
72, 1281.
40 S.M. Sajadi, M. Maham and S.A. Mahmoud, J. Chem. Res., 2013, 37, 853.
41 K.D. Safa, L. Sarchami, M. Allahvirdinesbat, A. Feyzi and P. Nakhostin Panahi,
J. Chem. Res., 2014, 38, 515.
42 K. Khosravi and S. Kazemi, J. Chin. Chem. Soc., 2012, 59, 641.
43 K. Khosravi, F. Pirbodaghi, S. Kazemi and A. Asgari, J. Iran. Chem. Soc., 2015,
12, 1333.
44 P. Ghorai and P.H. Dussault, Org. Lett., 2009, 11, 213.
45 K. Khosravi and A. Asgari, J. Advanc. Chem., 2015, 11, 3381.
46 D. Azarifar, O. Badalkhani, K. Khosravi and Y. Abbasi, J. Adv. Chem., 2015,
11, 3452.
Acknowledgements
We are grateful to the Arak University Research Councils for
financial support of this work.
Electronic Supplementary Information
Spectrum information for the new compounds available through:
stl.publisher.ingentaconnect.com/content/stl/jcr/supp-data