Ali Hossein Rezayan

Mehdi Shakourian-Fard

Mohammad Mahmoudi Hashemi

Ramin Kheirjou

Somayyeh Kheirjou

Comptes Rendus Chimie

lable at ScienceDirectC. R. Chimie 19 (2016) 314e319Contents lists avaiComptes Rendus Chimiewww.sciencedirect.comFull paper/MemoireSelective aqueous oxidation of alcohols catalyzed by copper(II) phthalocyanine nanoparticlesSomayyeh Kheirjou a, Ramin Kheirjou b, Ali Hossein Rezayan c, **,Mehdi Shakourian-Fard a, Mohammad Mahmoudi Hashemi a, *a Department of Chemistry, Sharif University of Technology, Tehran, Iranb School of Medicine, Tehran University of Medical Sciences, Tehran, Iranc Department of Life Science Engineering, Faculty of New Sciences & Technologies, University of Tehran, P.O. Box 14395-1561, Tehran, Irana r t i c l e i n f oArticle history:Received 2 May 2015Accepted 24 November 2015Available online 28 January 2016Keywords:Phthalocyanine nanoparticlesOxidationAlcoholOxonCarbonyl* Corresponding author.** Corresponding author.E-mail addresses: ahrezayan@ut.ac.ir (A.H. Resharif.edu (M. Mahmoudi Hashemi).http://dx.doi.org/10.1016/j.crci.2015.11.0141631-0748/© 2015 Published by Elsevier Masson SAa b s t r a c tA new catalyst based on metallophthalocyanine nanoparticles has been synthesized andcharacterized by scanning electron microscopy (SEM). The aqueous oxidation of alcohols tothe corresponding carbonyl compounds (aldehydes and ketones) has been studied usingtetra-n-butyl-ammonium-peroxo-monosulfate (n-Bu4NHSO5) as an oxidant and a catalyticsystem consisting of copper (II) phthalocyanine nanoparticles in water. The highly selectiveoxidation gave excellent yields of related aldehydes or ketones without remarkable over-oxidation of the carboxylic acids. Organic co-solvents, surfactants, and co-catalysts werenot used in this catalytic strategy. This strategy was green and time effective. The oxidant'sby-product (TBAHSO4) and catalyst can be efficiently recovered and reused several timeswithout any significant change of catalytic activity.© 2015 Published by Elsevier Masson SAS on behalf of Academie des sciences.1. IntroductionOxidation reactions are among the most importanttransformations in synthetic chemistry and offer animportant methodology for the introduction and modifi-cation of functional groups. Therefore, the oxidation ofalcohols by metal complexes to the correspondingcarbonyl compounds is a worthwhile goal [1,2]. Manydifferent oxidants were used for the oxidation of alcoholssuch as pyridinium chlorochromate (PCC), pyridiniumdichromate (PDC), KMnO4, MnO2, CrO3, H2O2 and so on.Most of these oxidizing reagents which can be used in aresearch laboratory in stoichiometric amounts areexpensive or toxic [1,3]. Thus, offering innovative, “clean”zayan), mhashemi@S on behalf of Academie demethods which use environmentally friendly oxidantssuch as peroxides, molecular oxygen and tetra-n-butyl-ammonium-peroxy-monosulfate and non-toxic solventsin particular aqueous media could be a new challenge inthis regard. Moreover, it has been found that reactions inwater can facilitate access to different reactivity andselectivity patterns compared with those observed incommon organic solvents due to its unique physical andchemical properties. However, the manifestation of a newcatalytic oxidation system which is cost effective, non-toxic and environmentally friendly is receiving a gooddeal of attention.Hydrogen peroxide oxidation is found to be less rela-tively economical because of its cost and poor efficiency[4,5]. Oxone (2KHSO5$KHSO4$K2SO4) has drawn a lot ofattention as amild and operative reagent for various organictransformations in recent years [6e12]. However, oxone ispractically soluble in water. Then, perhaps the most signif-icant drawback in the use of oxone is its application ins sciences.Scheme 1. Oxidation of alcohols with n-Bu4NHSO5 catalyzed by copper (II)phthalocyanine nanoparticles.Fig. 1. SEM images of copper (II) phthalocyanine nanoparticles with averagediameters of 42 nm.S. Kheirjou et al. / C. R. Chimie 19 (2016) 314e319 315aqueous or pH-controlled reactions [13]. Several saltsof oxone have been reported, such as tetra-n-butyl-ammonium-peroxy-monosulfate (n-Bu4NHSO5, TBA-OX),tetra-n-pentyl-ammonium-peroxy-monosulfate, tetra-n-hexyl-ammonium-peroxy-monosulfate and benzyl-triphenyl-phosphonium-peroxy-monosulfate. Recently, Lie et al. [14]have demonstrated TBA-OX as an effective reagent for theoxidation of alcohols in CH2Cl2 or H2O.These tremendous advantages of TBA-OX haveencouraged us to choose it as an oxidant in our study.There are several reagents available for the oxidation ofsulfides and alcohols, but most of them are not satisfac-tory for medium to large scale synthesis due to the lowcontent of effective oxygen, formation of environmentallyunfavorably co-products, and high cost [15]. An aqueoussolution of TBA-OX is an excellent oxidant in terms ofbeing environmentally friendly, safe in storage and oper-ation [14,15].In this work, copper (II) phthalocyanine nanoparticleswere used as a catalytic system. Phthalocyanines (Pcs)constitute a remarkably versatile and robust class of com-pounds with diverse technological applications [16e18].Phthalocyanine transition metal complexes are importantindustrial pigments which have been considered as po-tential oxidation catalysts due to their facile preparation ona large scale, chemical and thermal stabilities. Metal-lophthalocyanines have been used as efficient biomimeticcatalysts for the oxidation, reduction, and other reactions ofdifferent organic compounds. However, the low solubilityof metallophthalocyanine catalysts is the most importantproblem that is often encountered by the catalyst indifferent reactions [8].The extensive use of toxic and volatile organic solventsin these oxidation systems has reduced considerably thepractical importance of biologically inspired oxidationcatalysis. The discarding of harmful organic solvents is aproblem in chemical industries which accounts for about80% of their wastes [13]. Therefore, using non-toxic sol-vents in aqueous media can play a significant role in thesereactions and a new challenge could be done to make sucha process in aqueous solutions or under solvent free con-ditions [19e23].Nanoinorganic materials are an interesting subject ofresearch because of their unique physical and chemicalproperties [24]. Over hundred papers describing inorganicnanoparticle reactions with different materials haveappeared in chemical literature studies in recent years.Nanoparticles have recently emerged as efficient alterna-tives for the immobilization of homogeneous catalysts.Nevertheless, difficulties in recovering the nanoparticlesfrom the reaction mixture result from effective dispersionin solution by forming stable suspensions, which limit theirwide applications [25,26].In continuation of our interest in exploring the oxida-tion of organic compounds [27e30], this study aims toreport a mild and effective heterogeneous strategy for theaqueous oxidation of alcohols by n-Bu4NHSO5 and copper(II) phthalocyanine as catalysts (Scheme 1). However, to thebest of our knowledge, the use of copper (II) phthalocya-nine nanoparticle catalysts for the oxidation of alcohols hasnot been previously reported.2. Experimental1H and 13C spectra were determined on a Varian Mer-cury 300 MHz or a Bruker AM-400. Gas chromatographicanalyses were performed on a Hewlett Packard 6890 in-strument equipped with a FID detector and an HP-1 (eithera 10 m  0.2 mm i.d. or a 25 m  0.2 mm i.d.) capillarycolumn.2.1. Preparation of the nano-CuPcCopper (II) phthalocyanine was synthesized accordingto literature procedures [27e30]. Then, copper phthalocy-anine nanoparticles up to 42 nmwere prepared pursuant tothe following procedures. Briefly, 0.15 g CuPc was firstdissolved in 5 ml 98% concentrated sulfuric acid, and thenthe solution was added drop-by-drop into a 300 mlaqueous solution containing 0.45 g hexadecyltrimethylammonium-bromide in an ultrasonic ice-water bath.Isolation of phthalocyanine nanoparticles from a solutionphase was done by using a simple centrifuge.The obtained nanoparticles were washed immediatelywith hydrochloric acid twice, to remove bromide and thenwashed with deionized water three times. The final prod-uct was dried at 40 C under vacuum.Characterization of copper (II) phthalocyanine nano-particles was performed with a SEM as shown in Fig. 1[31,32]:Confirmation of the catalyst structure was done byelucidating UV (Fig. 2). Fig. 2 shows the absorption spec-trum of CuPc and its related nanoparticles. Other metalphthalocyanines have very similar absorption spectra inthe visible spectral region; these bands were assigned top/p transitions of the macrocyclic p-system [33].Fig. 2. Absorption spectra of CuPc (black) and its related nanosized particles (red) in the ultra-violet and visible (UVeVis) wavelength ranges.Fig. 3. The effect of temperature on the aqueous oxidation of cyclohexanolusing tetra-n-butyl-ammonium-peroxo-monosulfate catalyzed by nano-CuPc.Fig. 4. The reaction profile for aqueous oxidation of cyclohexaS. Kheirjou et al. / C. R. Chimie 19 (2016) 314e319316The oxidant (TBA-OX) was prepared from commerciallyavailable oxone and n-Bu4NHSO4 by a procedure describedin the literature [34].3. Results and discussionCopper (II) phthalocyanine nanoparticles have provideda valuable tool for the synthesis of both aliphatic and aro-matic carbonyl compounds. In a typical reaction, n-Bu4NHSO5 as an oxidant (two equivalents) was added tothe magnetically stirred aqueous solution of a mixture ofalcohol (1 mmol) and copper (II) phthalocyanine. Theoxidation of cyclohexanol with TBA-OX as an oxidant inaqueous media did not proceed in the absence of catalyst.Introductory catalytic experiments were addressed to thenol using n-Bu4NHSO5 catalyzed by nano-CuPc at 85 C.Fig. 5. Recycling of the catalytic system for the oxidation of cyclohexanol.Table 1The oxidation of various alcohols.Entry Alcohol Product Yield% M.P./B.P. ofproduct (C)1 64 562 95 1533 89 1614 87 113e1155 86 205e2086 90 497 94 1158 92 202Table 1 (continued )Entry Alcohol Product Yield% M.P./B.P. ofproduct (C)9 79 17910 85 24911 83 20412 88 4813 92 105S. Kheirjou et al. / C. R. Chimie 19 (2016) 314e319 317oxidation of cyclohexanol (1 mmol) with n-Bu4NHSO5(0.7 g) in the presence of desired copper (II) phthalocyaninenanoparticles (0.5 mol%) in aqueous solution at 25 C underair which led to the formation of cyclohexanone in 55%yield after 8 h according to GC analysis. Then, the temper-ature effect on the aqueous oxidation of cyclohexanol usingn-Bu4NHSO5 catalyzed by nano-CuPc was examined. It canbe concluded from Fig. 3 that an increase in the tempera-ture remarkably increased the effectiveness of the catalyticsystem. The full conversion of cyclohexanol was achieved at85 C within 72 min (Fig. 3).Under these conditions, the oxidation reaction pro-ceeded smoothly and cyclohexanone was secured in 95%yield after a simple extraction from the aqueous phase. It isworth mentioning that blank experiments for the oxidationof cyclohexanol using TBA-OX as an oxidant at 70 C gavejust 10% of cyclohexanone after 1 h. The conversion ofcyclohexanol as a function of temperature is shown in Fig. 3.The yield of oxidation of cyclohexanol to the cyclohex-anone as a function of time is indicated in Fig. 4.It is important to note that using organic co-solventssuch as dichloromethane and n-hexane mitigated the re-action yields; 55, 47 and 6% yields have been obtained forwater, dichloromethane/water and n-hexane/water,respectively.The effect of increasing the amount of catalyst from 0.1to 1 mol% on cyclohexanol oxidation and product selec-tivity was examined. When the catalyst amount wasS. Kheirjou et al. / C. R. Chimie 19 (2016) 314e319318increased, the reaction yield also increased. For instance,34, 71, 100 and 100 have been obtained for the 0.1, 0.2, 0.5and 1 mol% of catalyst, respectively. It is worth mentioningthat the increasing mol percent of catalyst up to 5 does nothave any seminal effect on the reaction yields. However, thefull conversion of cyclohexanol was achieved with a lowcatalyst loading of 0.5 mol %.Recycling of the catalyst has also been studied. Thecatalyst was separated from the product by simpleextraction with ether. n-Bu4NHSO4 can be recycled byremoving the aqueous phase. Tetrabutylammoniumhydrogen sulfate (TBAHS) is a phase transfer catalyst andcan be reused in the preparation of TBA-OX. The proce-dure was repeated 4 times in the oxidation of cyclo-hexanol (Fig. 5) [35].In order to exploit the general applicability of the presentcatalytic system, several primary and secondary aliphaticand aromatic alcohols were selected for oxidation underoptimized conditions in the aqueous solution. Secondaryalcohols gave good yields and these are generally excellentsubstrates for this oxidation system (Table 1, entries1e8).Oxidation of primary alcohols such as benzylic and aliphaticoccurredwith a slow reaction rate and gave low tomoderateyields of the related carbonyl compounds (entries 9e13).Scheme 2. Proposed mechanismTotal aromatic alcohols gave better yields than aliphatic al-cohols in the oxidation reaction by this catalyst.Based on literature studies [36e38], the proposedmechanism for this catalytic oxidation reaction is depictedin Scheme 2. In the first step, copper phthalocyanine (CuPc)reversibly combines with TBA-OX. Apparently, due to theless steric hindrance around the terminal oxygen atom ofthe peroxo residue (HOeOSO3), the attachment of thisspecies to the metal centre through the terminal peroxooxygen atom is more facile relative to the other oxygenatoms of TBA-OX [39]. Cu(III)eOO species induceshydrogen abstraction from the studied alcohols resulting inthe formation of an alcoholic radical. In a rebound processand subsequent cleavage, the corresponding carbonylcompound is produced [40,41].Table 2 shows a comparison between the catalytic effi-ciency of CuPc nanoparticles and other catalysts found inthe literature. As seen in Table 2, the reaction did not pro-ceed without any catalyst at room temperature. The use of12-tungstocobaltate (II), NaCl, and TEMPO-IL/[bmim][PF6]as catalysts at room temperature gave 85, 65, and 90%yields at different times. Our catalyst was more effective interms of yield and reaction time compared to the otherreported catalysts.for the oxidation reaction.Table 2A comparison between the catalytic efficiency of CuPc nanoparticles and other catalysts found in the literature for the oxidation of alcohol.Entry Oxidant catalyst Tempreture Time/min Yield/% [Ref]1 TBOX e 60 180 10<2 TBOX 12-tungstocobaltate (II) 50 180 85 [42]3 TBOX NaCl 25 300 65 [43]4 TBOX TEMPO-IL/[bmim][PF6] 60 30 90 [35]5 TBOX CuPC nanoparticles 85 70 95S. Kheirjou et al. / C. R. Chimie 19 (2016) 314e319 3194. ConclusionIn conclusion, the catalytic performance of nanocopper(II) Phthalocyanine in the oxidation of alcohols using wateras a solvent and n-Bu4NHSO5 as an oxidant was studied.The excellent yieldwas achieved for oxidation of alcohols at85 C with the absence of surfactants and nitrogenousbases. The employment of neat water as a ‘green’ solvent inthis oxidation method gave high yield products as well aseasy and safe work-up which are strong points of this novelmethodology making it more attractive for practical goals.Organic co-solvents, surfactants, and co-catalysts were notused in this catalytic strategy. This system was green andtime effective.AcknowledgementWe gratefully acknowledge the financial support fromthe Research Council of Sharif University of Technology. Wealso thank Vivekanand V. Gobre at Fritz Haber institute derMax Planck for helpful discussions.References[1] Y. He, X. Ma, M. Lu, Arkivoc 8 (2012) 187.[2] A. Rezaeifard, M. Jafarpour, A. Naeimi, S. Mehri, Inorg. Chem. Com-mun. 15 (2012) 230.[3] E. Sandra, M. Garrone, A. Garrone, Tetrahedron Lett. 44 (2003) 549.[4] U.R. Pillai, E. Sahle-Demessie, Appl. Catal. A: Gen. 103 (2003) 245.[5] U.R. Pillai, E. Sahle-Demessie, Green Chem. 6 (2004) 161.[6] N.B. McKeown, Chem. Ind. 3 (1999) 92.[7] B. Meunier, A. 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Selective aqueous oxidation of alcohols catalyzed by copper (II) phthalocyanine nanoparticles

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Selective aqueous oxidation of alcohols catalyzed by copper (II) phthalocyanine nanoparticles

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