SUPPLEMENTARY INFORMATION
Fluoro functional groups substituted cobalt(II), iron(II) phthalocyanines and their catalytic properties on benzyl alcohol oxidation
Ayşe Aktaş Kamiloğlua, İrfan Acarb[*], Ece Tuğba Sakaa, Zekeriya Biyiklioglua, Halit Kantekina
aDepartment of Chemistry, Faculty of Science, Karadeniz Technical University, 61080 Trabzon, Turkey
bDepartment of Energy Systems Engineering, Of Faculty of Technology, Karadeniz Technical University, 61830 Of, Trabzon, Turkey
1. Experimental
1.1. Materials
4-(2-{2-[3-(Trifluoromethyl)phenoxy]ethoxy}ethoxy)phthalonitrile 1 were synthesized according to the literature [1]. All reagents and solvents were of reagent grade quality and were obtained from commercial suppliers. All solvents were dried and purified as described by Perrin and Armarego [2].
1.2. Equipment
The IR spectra were recorded on a Perkin Elmer 1600 FT-IR spectrophotometer using KBr pellets. 1H-NMR spectra was recorded on a Varian Mercury 400 MHz spectrometer in CDCl3. Chemical shifts were reported (d) relative to Me4Si as internal standard. Mass spectra were measured on a MALDI-MS of complexes were obtained in dihydroxybenzoic acid as MALDI matrix using nitrogen laser accumulating 50 laser shots using Bruker Microflex LT MALDI-TOF mass spectrometer. Optical spectra in the UV-Vis region were recorded with a Perkin Elmer Lambda 25 spectrophotometer. GC Agilent Technologies 7820A equipment (30m x 0.32mm x 0.50 mm DB Wax capillary column, FID detector) was used GC measurements.
1.3. General procedure for the oxidation of benzyl alcohol
Experiments were carried out in a thermostated Schlenk vessel equipped with a condenser and stirrer. The solution of benzyl alcohol and catalyst in solvent was purified with bubbling nitrogen gas to remove the oxygen. A mixture of benzyl alcohol (1.92×10-3 mol), catalyst (3.20×10-6 mol) and solvent (0.01 L) was stirred in a Schlenk vessel for few minutes at room temperature. The oxidant TBHP (1.60×10-3 mol) was then added and the reaction mixture was stirred for the desired time. The samples (0.0005 L) were taken at certain time intervals. Each sample was injected at least twice in the GC, 1 µL each time. Formation of products and consumption of substrates were monitored by GC.
Figure S1. MALDI-TOF spectrum of complex 2
Figure S2. MALDI-TOF spectrum of compex 3
Table S1. Different oxidant effect of benzyl alcohol oxidation with complex 2 and 3
Catalyst / Oxidant / Aldehydea / Quinoneb / Acidc / Tot.Conv.(%) / TONd / TOFe
(h-1) / Selectivity
(%Aldehyde)
2
3 / TBHP / 86
72 / 4.7
8.0 / 6.22
6.0 / 98
90 / 588
540 / 196
180 / 87.7
80
2
3 / H2O2 / 63.2
43.8 / 4.5
7.6 / 5.3
5.6 / 73
57 / 438
342 / 146
114 / 86.5
76.8
2
3 / m-CPBA / 47
59.7 / 9.7
11.5 / 4.3
6.8 / 61
68 / 366
408 / 122
136 / 77.0
87.7
2
3 / Air oxygen / -
- / -
- / -
- / -
- / -
- / -
- / -
-
a Yield of Benzaldehyde
bYield of Benzoquinone
c Yield of Benzoic Acid
dTON = mole of product / mole of catalyst
eTOF= mole of product / mole of catalyst x time
Conversion was determined by GC.
Table S2. Catalytic activities towards the homogeneous oxidation of benzyl alcohol of some previously reported catalyst
Catalyst / Rxn Time(h) / Rxn Temp.
(oC) / Oxidant / Conv.
(%) / Ref.
CuPcb / 30 min / 70 / TBAOX / 25 / [3]
CoPca
PdPca / 5.5
24 / 70
50 / TBHP
m-CPBA / 26.6
31.3 / [4]
Ru(TPP)Clc
Co(TPP)Clc
Mn(TPP)Clc
Fe(TPP)Clc / 30 min / 60 / O2 / 43
42
45
32 / [5]
MnTEPyPd / 4 / 60 / TBHP
NaIO3
NaIO4 / 47
16
84 / [6]
CuTPPe / nrg / 60 / O2 / 40( in toluene)
35( in benzene)
Trace(in acetonitril) / [7]
CoPcf
FePcf / 3 / 70 / TBHP / 94
89 / [8]
aPc=Perfluoroalkylphthalocyanine
bPc=Un-substituted phthalocyanine
c (TPP)Cl= meso-tetraphenylporphyrinchloride
dTEPyP=water soluble metalloporphyrins
eTPP=Copper meso tetraphenylporphyrin
fPc=(2-{2-[3-(dimethylamino)phenoxy]ethoxy}ethoxy) substituted phthalocyanine
References
[1] Aktaş, A., Pişkin, M., Durmuş, M., Bıyıklıoğlu, Z.: Synthesis, photophysical and photochemical properties of zinc phthalocyanines bearing fluoro-functionalized substituents, J Lumines, 145, 899-906 (2014).
[2] Perin, D.D., Armarego, W.L.F.: Purification of laboratory chemicals. 2nd ed. Oxford: Pergamon Press; (1989).
[3] Rezaeifard, A., Jafarpour, M., Naemi, A.: A practical innovative method for highly selective oxidation of alcohols in neat water using water-insoluble iron and manganese porphyrins as reusable heterogeneous catalysts, Catal Commun, 16, 240-244 (2011).
[4] Özer, M., Yılmaz, F., Erer, H., Kani, İ., Bekaroğlu, Ö.: Synthesis, characterization and catalytic activity of novel Co(II) and Pd(II)-perfluoroalkylphthalocyanine in fluorous biphasic system; benzyl alcohol oxidation, Appl Organomet Chem, 23, 55-61 (2009).
[5] Ji, H.B., Yuan, Q.L., Zhou, X.T., Pei, L.X., Wang, L.F.: Highly efficient selective oxidation of alcohols to carbonyl compounds catalyzed by ruthenium (III) meso-tetraphenylporphyrin chloride in the presence of molecular oxygen, Bioorg Med Chem Lett, 17, 6364-6368 (2007).
[6] Ren, Q.G., Chen, S.Y., Zhou, X.T., Ji, H.B.: Highly efficient controllable oxidation of alcohols to aldehydes and acids with sodium periodate catalyzed by water-soluble metalloporphyrins as biomimetic catalyst, Bioorg Med Chem, 18 8144-8149 (2010).
[7] Rahimi, R., Gholamrezapor, E., Naimi-jamal, M.R.: Oxidation of benzyl alcohols to the corresponding carbonyl compounds catalyzed by copper (II) meso-tetra phenyl porphyrin as cytochrome P-450 model reaction, Inorg Chem Commun, 14, 1561-1568 (2011).
[8] Çakır, V., Saka, E.T., Bıyıklıoglu, Z., Kantekin, H.: Highly selective oxidation of benzyl alcohol catalyzed by newperipherally tetra-substituted Fe(II) and Co(II) phthalocyanines, Synth Met, 197, 233-239 (2014).
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