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Synthesis of 1,3,5-triaryl benzene catalyzed by CuCl2

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  • Save International Journal of M aterials and Chemistry 2012, 2(4): 128-131 DOI: 10.5923/j.ijmc.20120204.02 Synthesis of 1, 3, 5-Triarylbenzenes, Using CuCl2 as a New Catalyst Sohrab Abdollahi*, Fate me h Mostaghni Chemistry department, Payame Noor University, I. R. of Iran, PO BOX 19395-3697, Tehran , Iran Abstract Among the aromatic ketones, aceto phenone and its various substituted derivatives have been studied since early 20th century. This ketone can perform the self condensation reaction and produces trimmer having an aro mat ic ring of 1,3,5-triphenyl benzene (T.P.B) with general fo rmula of C24H18. In this research, the compounds 1,3,5-triphenyl benzene and 1,3,5-tris (2-naphthyl) benzene are synthesized via self condensation of acetophenone and 2-aceto naphthalene respectively, using Cu2+(CuCl2) as a new catalyst. Catalyst of copper(II) chlo ride is a very suitable catalyst and comparing to the other ones is cheaper, abundant and very facile to use in these condensation reactions for the synthesis of trimmers. Since Cu2+ has empty p and d orbitals, therefo re, Cu Cl2 acts as a good Lewis acid. Further, the catalyst is a good electron transfer oxidative reagent, therefore it is very useful catalyst for self-condensation of ketones. This method seems to be general for the synthesis of other derivatives of 1,3,5-triarylben zene using various ketone derivatives. These trigonal molecu les may be converted to flexib le clathrates or nano cage molecules, wh ich are h ighly pro mising for the separation and chemical transformation. Keywords Trimerization, Tri Aryl Ben zene, Clathrate Inclusion Co mpounds 1. Introduction mo lecules[3]. Therefore, in the crystalline structure the units of host-gust are arranged such as stack form in Figure 1. The synthesis of 1,3,5-t ris ary lbenzene co mpounds due to self-condensation of acetophenone were reported for the first time in 1874[1]. The years later, these co mpounds with different substituted phenolic rings using various reagents were prepared. In 1991, the synthesis of different derivatives of this co mpound were conducted with h igh y ield , using catalyst of tetrachloro silane in ethanol as a solvent at room temperature and molar ratio of 1:1 (acetophenone:catalyst) [2]. In these reactions, the central benzene ring is c reated by condensation of three mo lecu les of ketones via releasing three mo lecules of water to produce expected trimer[3-8]. Bis hop and Danc e, fo r the firs t t ime , s how that 1,3,5-t riary lb en zen e co mp oun d reacts with water and benzene to produce solvated crystalline molecules[9]. Later on, Weber et al. prepared these inclusion compounds with a number of molecules of different sizes fro m methanol to mo rp h o line hav in g p rop ert ies o f alicy clic, aro mat ic, h et ero cyclic an d d ip o lar mo lecu les with and with out proton[10]. X-ray studies on the single crystal of inclusion compounds such as 1,3,5-Tris (4-carbo xyl phenyl) ben zenedimethy l fo rmamid e (1:3) sho w t hat th e host mo lecu le has a p ropeller con fo rmat ion with co mp lete th ree-fo ld symmetry providing hydrogen bond as a donor to three DMF * Corresponding author: (Sohrab Abdollahi) Published online at Copyright © 2012 Scientific & Academic Publishing. All Rights Reserved Figure 1. Inclusion molecule made of two triarylbenzene planes connected by hydrocarbon bridge and having cavity to hold different molecules In order to study this inclusion behaviour in more detail, preparation of double-decker phanes having a cavity to include other organic molecules were attempted[3, 7, 11-17]. Other researchers reported the synthesis and characterizat ion of a new family of star-shaped molecules and dendrimers. In these dendrimers, the structural unit of 1,3,5-triphenylbenzene acts as a fluorescent core[18]. This fluorescence core mo lecule, 1,3,5-triphenylbenzene, is a class of C3 symmetry mo lecule wh ich is important for electrolu minescent devices and electrodes. Even fo r the developing of organic light emitt ing diodes (OLEDS)[19], the 1,3,5-t riphenylbenzene core, and synthesis of dendrimers and fullerene frag ments(20-24]) have been used. 129 International Journal of M aterials and Chemistry 2012, 2(4): 128-131 Fro m substituted acetophenones, the synthesis of 1,3,5-triary lbenzene is possible using Suzu ki cross-coupling of cyclocondensation reactions[25]. The synthesis of many chemical species, such as mult imetallic p incer, star-shaped thiophenes and organic-inorganic hybrid mesoporous materials can be carried out by cyclocondensation reactions. These reactions can be conducted by triflic acid, sulfuric acid-sodium pyrosulfate, perfluorinated resins and tetrachlorosilane in ethanol (26-29). In different syntheses, various CuCl2 catalysts have been used. In most reactions, CuCl2 either is supported by a solid med ia such as alumina[30] or is bonded to an organic groups or ligands[31-33]. Co mmercial catalysts are produced by impregnation of γ-alu mina with Cu Cl (4-8 wt% Cu) following the incip ient wetness method. Other ch lorides, (main ly alkaline or alkaline earth chlorides) in a variab le concentration are also added in order to improve the catalyt ic performance; making the catalyst more suitable fo r use in the industrial reactors[34,35]. A type of polymer- supported CuCl2 catalyst for synthesis of dimethyl carbonate (DMC) was obtained by using π− conjugated poly (2,2'-bipyriding-5,5-diy l) as the supporting ligand. The high catalytic activity is associated with the π-conjugated conductive properties of the supporting ligand, PBpy[32]. Another type of homogeneous catalyst for dimethyl carbonate synthesis by oxidative carbonylation of methanol in the liquid-phase reaction was investigated by Jun-cheng Hu[36]. The poly mer-bond monometallic PVP-Cu Cl catalyst (PVP, poly(N-vinyl-2-pyrolidone) prepared by the combination of an alcoholic solution of PVP and CuCl2, exhibits excellent catalytic performance for the o xidative carbonylation of methanol with carbon mono xide and oxygen to DM C under 3.0 MPa pressure at temperature around 140-160℃ [36]. 2. Experimental Yields refer to isolated pure center cut fro m colu mn chromatography or to the main band scratched from preparative TLC p late. Products were characterized by comparison with authentic sample through IR, NM R,TLC, and mp methods. Due to the experimental limitat ion, the melting points are not fully accurate and determined by Metller FP5 melting point apparatus. IR spectra were obtained on a Shimad zu IR-470. 1HNM R data were recorded in CDCl3 on Brucker 80 MHz and 13CNMR on Brucker Advance 500-MHz spectrometer. All reagents were analytical grade and used without further purification. 2.1. Preparati on of 1,3,5-tris(2-naphthyl) Benzene For the synthesis of 1,3,5-tris(2-naphthyl) benzene, 2-acetonaphthalene and CuCl2 are used with mo lar ratio of (1:15). CuCl2(0.03 gr, 0.19 mmole) was added to a mixtu re of 2-acetonaphthalene(0.4 gr 2.3 mmo l) and toluene(5ml) in a 25 ml round bottom flask equipped by magnetic stirrer and reflu x condenser. The mixture was reflu xed in o il bath for 6 hours at temperature of 180-220℃. After co mplet ion of the reaction, the mixture was ext racted by ether (3 x 10ml) and dried by magnesium sulfate. Then, the mixture co mponents were separated by column chro matography (mp = 115-120℃). The structure of the product was analyzed by spectroscopic method such as IR, 1H NM R and 13C NM R. IR(KBr): 3050(W), 3250(m), 1418(m), 1180(s), 1145(m), 1120(s), 720(vs), 695(s) cm-1.1HNM R(CDCl3): δ; 6.8-7.7 (m, 24H)pp m.13CNM R(CDCl3):δ;131.7(s),131.6 (s),128.1(s), 128 (s). Anal. Calcd For C36H24 (456.396):C, 94.7; H,5.3 Found:C,94.7; H,5.5. 2.2. Preparati on of 1,3,5-tri phenyl Benzene For the synthesis of 1,3,5-t riphenylbenzene, CuCl2 and acetophenone are used with molar ratio of (1:15). Cu Cl2(0.03 gr, 0.19 mmo le) was added to a mixture of acetophenone (0.34 gr 2.9 mmo l) and toluene(5ml) in a 25 ml round bottom flask equipped by magnetic stirrer and reflu x condenser. The mixtu re was reflu xed in oil bath for 6 hours at temperature of 180-220℃. After co mplet ion of the reaction, the mixtu re was extracted by ether (3 x 10ml) and dried by magnesium sulfate. Then, the mixture co mponents were separated by column chro matography (mp = 173-174℃). The structure of the product was analyzed by spectroscopic method such as 1H NMR and 13C NMR , as shown in the Figure 2 for 1H NMR and Figure 3 for 13C NM R . 1H NM R(CDCl3): δA = 7.77 ppm, δB = 7.68, δC = 7.46, δD = 7.37. D C C B B A A B C B C A D B C B D C Figure 2. 1H NMR of 1,3,5-triphenyl benzene molecule in which hydrogens are labled by letters of A, B, C and D 13CNMR(CDCl3): δ1 = 142.31, δ2 = 141.13, δ3 = 128.78, δ4 = 127.47, δ5 = 127.30, δ6 = 125.11. 4 3 3 5 5 2 1 6 6 5 3 1 5 1 2 3 2 6 4 5 5 4 3 3 Figure 3. 13C NMR of 1,3,5-triphenyl benzene molecule in which carbons are labeled with numbers 1,2,3,4,5,6 Sohrab Abdollahi et al.: Synthesis of 1, 3, 5-Triarylbenzenes, Using CuCl2 as a New Catalyst 130 3. Results and Discussion 4. Conclusions The goal of this research is an investigation on the self condensation reaction of aromatic ketones via CuCl2 catalyst, considering the fact that the trisanulated benzenes, and 1,3,5-tris(2-thienyl) co mpound have been synthesized previously by our group using the same catalyst[37]. Now, in this paper, Cu Cl2 catalyst is used to conduct self condensation reaction of 2-aceto naphthalene to produce1,3,5-tris(2-naphthyl)benzene. this molecule is a new one with bulky structure and trigonal symmetry that can behave as a clatherat. Substituted benzene of 1,3,5-triary l is considered as a rich source of porous crystalline host which can provide inclusion compounds[38]. Wide spread application, specific properties of these type of compounds and also the fact that the porosity of the compounds depends on the nature, type and position of these substituents linked to it, have caused an incentive for our group to prepare 1,3,5-tris(2-naphthyl)benzene, which is shown in Figure 4. Contrary to previous syntheses by other researcher that use ligand bonded Cu Cl2 catalysts, in this research the pure unhydrated powder of Cu Cl2 was used as a catalyst for condensation reaction. In condensation process, CuCl2 reduces to CuCl (Cu2+ to Cu1+). On the other hand the produced water during reaction can o xidize in acid ic solution. This oxidation reaction in turn produces more H+ and helps the solution become more acidic. Cooper cation, Cu2+, contains empty orbitals such as p and d orbitals and therefore acts as a Lewis acid and attacks to free loan pairs of o xygen in carbonyl group; producing coordination bond. As a result, the oxygen of carbonyl g roup achieves positive charge. The positive charge at high temperature can be neutralized by α hydrogen via chloride ion which acts as a bridge in this mechanis m. In this case enolate is formed and immed iately attaches to protonated carbonyl group of second molecule of 2-aceto naphthalene and produces keto alcohol. At the reflux temperature, the keto alcohol releases a molecu le of water. At acidic condition this ketone is protonated and reacts with third molecule of 2-aceto naphthalene via releasing two mo lecules of water and forms a central aro matic ring. This synthesis and related product, 1,3,5- t ris(2-naphthyl) benzene, can provide extensive research for the future. For example, substitution of different kinds of functional group on naphthalene ring can obtain various kinds of inclusion compounds with different sizes and inclusion behavior which may be essentially useful for the various syntheses as shown in Figure 5. The synthesis of star like mo lecules such as 1,3,5-triaryl benzene ((1,3,5-t riphenylebenzene and 1,3,5-tris(2-naphthyl) benzene) can be used for designing and synthesis of binary crystals via hydrogen bonds[39], halogen bonds[40], π...π [41]or van der Walls forces[42]. Even, the construction of ternary and higher-order cocrystals will be under considerations[43, 44]. One possible challenge to make three-co mponent solids is host-gust design in which the host is a crystalline lattice assembled using two mo lecular species[45]. Usually, inclusion compounds have been synthesized by crystallizing the host and guest compounds fro m a solution[46]. The choice of co mponents available for the construction of such a system is limited by the solubility of the host and the guest compounds. This limitation become mo re serious in mu ltico mponent systems that require balancing the solubility of several molecu lar species. By using these cyclization condensation reactions, via CuCl2 as catalyst, and using heteroaromatic rings such as thiophene, pyrole and furan, one may synthesis various mo lecules of star like structures with different physical and chemical properties. Many of hetero atoms such as oxygen and nitrogen that contain free loan pairs of electrons can provide an inclusion compounds with interesting electrical properties in addition to separation abilities. These kinds of properties make star like molecu les a good precursor for making nano cage-like co mpounds. By selecting proper derivatives of ketones, the cavity of the inclusion co mpounds can be controlled for the separation of specific mo lecule. Figure 5. Proposed stack form of two molecules of 1,3,5-tris(2-naphthyl) benzene which can be used to make an inclusion compound ACKNOWLEDGEMENTS Figure 4. Molecule of 1,3,5-tris(2-naphthyl)benzene precursor of inclusion compounds I would like to acknowledge the Gilan University and University of Payame Noor of lamerd, fo r their financial support and the opportunities that were provided for our 131 International Journal of M aterials and Chemistry 2012, 2(4): 128-131 research. 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