Open Journal of Synthesis Theory and Applications, 2012, 1, 31-35 http://dx.doi.org/10.4236/ojsta.2012.13006 Published Online October 2012 (http://www.SciRP.org/journal/ojsta) Highly Efficient Cobalt (II) Catalyzed O-Acylation of Alcohols and Phenols under Solvent-Free Conditions Shafeek A. R. Mulla*, Suleman M. Inamdar, Mohsinkhan Y. Pathan, Santosh S. Chavan Chemical Engineering and Process Development Division, National Chemical Laboratory, Pune, India Email: *sa.mulla@ncl.res.in Received August 6, 2012; revised September 12, 2012; accepted September 28, 2012 ABSTRACT Solvent free, highly efficient method has been developed using ecofriendly, heterogeneous reusable cobalt chloride catalyst at ambient reaction conditions for the O-acylation of various alcohols and phenols with acetyl chloride in ex- cellent yield in a short reaction time. The catalyst is recycled several times without loss of catalytic activity. Keywords: Acetylation, Alcohol, Phenol, Acetyl Chloride, Cobalt (II) Chloride 1. Introduction An esterification is a key and fundamental step to protect hydroxyl group during functional transformation in vari- ous organic synthesis [1-3]. However, protection and de- protection of hydroxyl functional group of alcohols and phenols being not only prime importance in pharmaceu- tical industries but also in the polymers, cosmetics, per- fumes, plasticizers to achieve excellent yield to potential targeted synthetic compounds. Owing the importance of protection of hydroxyl function al group du ring th e multi- steps organic synthesis, the various methods for the pro- tection of hydroxyl group of alcohols and phenols using varieties of reagent and catalysts such as HgCl2 [4], Montmorillonite [5], TMS-Cl [6], TaCl5-SiO2 [7], ZnCl2 [8], ZnO [9-10], Ru-catalyst [11], Mg(ClO4) [12], SmI2 [13], CeCl3 [14], perchlorates [15], P2O5/Al2O3 [16], CoCl2 [17-18], ZrCl4 [19], NH2SO3H [20], solid sup- ported HBF4-SiO2 [21], lipase enzyme [22], Al(OTf)3 [23], In(OTf)3 [24], Bi(OTf)3 [25], polymer supported Gd(OTf)3 [26], Ce(OTf)3 [27], Ag(OTf)3 [28], molecular Iodine [29], nitro benzeneboronic acid [30], NiCl2 [31], La(NO3).6H2O [32], DCC [33], Co(II)salen-complex [34], Melamine trisulfonic acid (MTSA) [35], ionic liq- uid [36-39], ZnAl2O4 [40], have been reported, however, the most common acetylating reagents used are acetyl chloride, acetic acid, acetic anhydride or any other protic acid [41]. However, all the above methods are badly suffer from one/or other limitations and drawbacks such as drastic reaction conditions, long reaction time, high temperature, use of moisture sensitive, toxic, expensive reagents and catalysts. In addition these limitations, the catalysts are non-recoverable besides the formation of toxic side pro- duct and poor yield for th e desired product in presen ce of organic solvent. Therefore, considering all th e above facts, still there is a need and demand to develop a solvent free, greener and an economical protocol and catalysts for protection of hydroxyl of alcohols and phenols by esterification. Therefore, herein we wish to report a solvent-free, a cheap, mild, rapid and efficient protocol for the O-acyla- tion of alcohols and phenols with acetyl chloride over cobalt (II) chloride catalyst at room temperature (Schemes 1). R-OH 1 mol% CoCl2 room temp R-OAc AcCl (1. 2 eq uiv) - HCl R= P h, Allyl, Benzyl, Nap hthyl, Alip hatic, etc. Scheme 1. Cobalt (II) chloride catalyzed O-acylation of alco- hols and phenols. 2. Experimental Section All chemicals and reagents were procured from suppliers and used without further purification. The products were analyzed by a 5765 NUCON Gas Chromatograph with FID detector using stainless steel column 4 m length x 1/8 inch O.D. x 2 mm I.D., packed with 10% SE-30 on Chromosorb-W with mesh size 80-100 and also charac- terized using 1H NMR, 13C NMR spectra. The NMR spectrums of product were obtained using Bruker AC- 200 MHz spectrometer with TMS as the internal stan- *Corresponding author. C opyright © 2012 SciRes. OJSTA
S. A. R. MULLA ET AL. 32 dard. 2.1 General Experimental Procedure for O-Acetylation of Alcohols and Phenols The alcohol or phenol (5 mmol) in acetyl chloride (6 mmol) was taken in 50 ml round bottom flask. To this reaction mixture 1mol% cobalt (II) chloride catalyst was added and then mixture was stirred at room temperature under solvent free conditions. The influence of acylating agents was investigated using phenol, 4-methyl phenol and chloroethanol as substrate. The completion of the reactions was monitored by GC. After the completion of reaction, the mixture was diluted with ethyl acetate (25 ml) and the catalyst was recovered by filtration. The fil- trate was washed with NaHCO3 and then with water, dried over anhydrous Na2SO4. The dry filtrate was con- centrated under vacuum to obtain the p ure produ ct. 3. Results and Discussion Acylation of phenol (5 mmol) was studied with acetyl chloride (6 mmol) in presence of 1 mol% cobalt (II) chlo- ride catalyst under solvent free condition at room tem- perature to afford phenyl acetate in 99% yield in 20 sec- onds. However, the acetylation reaction of phenol was inefficient in absence of cobalt (II) chloride. After the successful acetylation of phenol with excellent yield to phenyl ester, the influence of acylating agents was invest tigated using phenol, 4-methyl phenol and chloroethanol as substrate and results are summarized in Table 1. The influence of the acylating agent’s study (entries 1 - 3, Table 1) reveals that reactivity of acetyl chloride is ex tremely higher than that of acetic anhydride and acetic acid over the cobalt (II) chloride catalyst under solvent free conditions at room temperature. The results on influence of acylating agents promoted us to evaluate the scope of this methodology for different types of primary, secondary, benzylic, allylic, cyclic al- cohols and phenols using acetyl chloride as acylating agent (Scheme 1). A number of substituted phenols and alcohols such as 4-tert-butyl phenol, 2- tert-butyl, 4-methyl phenol, p- cresol, o-cresol, m-cresol, 2-hydroxy benzaldehyde, 1- naphthol and 2-naphthol (entries 2 - 9, Table 2) and bu- tanol; hexanol; heptanol; 1, 8-octandiol; chloro ethanol; Lauryl alcohol and 2-butanol (entries 1 - 7, Table 3), secondary alcohols (entries 8 - 9, Table 3), allylic alco- hol (entry 10, Table 3) and benzylic alcohols (entry 11 - 12, Table 3) were acetylated respectively, in good to excellent yield without any difficulties. The results (Tables 2 and 3) on the acetylation of alco hols and phenols reveal that the good to excellent yield up to 99% was achieved in very short reaction time Table 1. Influence of acylating agents on various substratea. (%) Yieldb EntrySubstrateProduct Time (s) AcCl Ac2OAcOH 1 OH OAc 20 3600 99 - NR NR NR NR 2 OH Me OAc Me 15 3600 99 - 35 39 NR NR 3 Cl OH Cl OAc 10 3600 99 - 67 99 NR 12 aReaction conditio ns: The s ubstrat e (5 mmol) , acetyl ating agent ( 6 mmol), 1 mol% CoCl2, room temperature; bGC yield. NR: No Reaction. Table 2. Cobalt (II) chloride catalyzed acetylation o f phenols with acetyl chloridea. EntrySubstrate (R) Product Time (s)Yieldb (%) 1 OH OAc 20 99 2 OH OAc 20 99 3 OH Me Me OAc 25 89 4 OH Me OAc Me 15 99 5 OH Me OAc Me 20 99 6 OH Me OAc Me 20 99 7 OH CHO CHO OAc 40 99 8 OH OAc 15 99 9 OH OAc 20 99 aReaction conditions: The substrate (5 mmol), CH3COCl (6 mmol/OH group), 1 mol% CoCl2, room temperature; bGC yield; cwithout CoCl2 cata- lyst. Copyright © 2012 SciRes. OJSTA
S. A. R. MULLA ET AL. 33 Table 3. Cobalt (II) chloride catalyzed acetylation of alco- hols with acetyl chloridea. Entry Substrate (R) Product Time (s) Yieldb (%) 1 OH OAc 10 95 2 OH OAc 10 99 3 OH OAc 15 98 4 OH OH OAc AcO 15 99 5 Cl OH Cl OAc 10 99 6 OH OAc 15 99 7 Me Me OH Me OAc Me 10 98 8 OH OAc 10 99 9 OH OH OH OAc OAc OAc 35 92 10 OH OAc 10 82 11 OH OAc 50 75 12 OH OAc 35 98 aReaction conditions: The substrate (5 mmol), CH3COCl (6 mmol/OH group), 1mol % CoCl2, room temperature; bGC yield. (10 - 50 seconds). Further, the result indicates that the cobalt (II) chloride catalyst shows remarkably high cata- lytic activity and efficiency not only with primary alco- hols and phenols but also with sterically hindered secon- dary, benzylic, allylic, cyclic alcohols and phenols under mild and solvent free reaction conditions at room tem- perature. The catalytic activity and / or recyclability study of 1 mol% cobalt (II) chloride catalyst was performed for the acetylation of phenol (Scheme 2, Table 4). The catalyst was recovered quantitatively four times by simple filtration of the reaction mixture and subse- quently washed with ethyl acetate and water. The recov- ered cobalt (II) chloride catalyst was reused four times (Run 2-5, Table 4) for the acetylation of phenol with acetyl chloride to give the phenyl acetate in 98% - 99% yield, which is almost comparable with fresh catalyst (Run 1, Table 4). This result clearly shows that the recy- cled cobalt (II) chloride gives excellent yield without loss of catalytic activity. As shown in the Scheme 3, the plausible reaction mechanism and/ or catalytic cycle for the acetylation of alcohols and phenols using acetyl chloride as acylating agents over the cob alt (II) chloride under the solvent free room temp AcCl (1.2 equiv) - HCl 1 mol% Rec.CoCl 2 OH O O Scheme 2. Recyclability study of cobalt (II) chloride catalyst for acetylati on of phenols with ac etyl chloride. Table 4. Recyclability study of cobalt (II) chloride for acety - lation of phenol with acetyl chloridea. No. of Run Time (s) Yield (%) Run 1 (Fresh catalyst)20 99 Run 2 20 99 Run 3 25 98 Run 4 25 99 Run 5 30 99 aReaction conditions: phenol (5 mmol) CH3COCl (6 m mol) 1 mol% of Co Cl2 at room temperature Catalyst recovery = 97% ± 2%; bGC yield. R= Ph, Allyl, Benzyl, Naphthyl, Aliphatic, etc. Cl CH3 O OR CoCl 2 H + :: .. _CoCl 2 Cl O CH3 :.. CoCl 2 ROH .. HCl +CH3COCl RO CH3 O (1) (2) (3) (4) (5) Scheme 3. The proposed catalytic cycle for the acetylation reaction over CoCl2 catalyst. condition at room temperature is not clear so far, how- ever, the results obtained in the present study shed some light on these aspects. The carbonyl group of acetyl chloride is known to co- ordinating on Lewis acid sites of the CoCl2 catalyst sur- face via intermediate (2) to activate itself being reactive electrophile. The activation of carbonyl group of acetyl chloride encourage the attack by the oxygen of alcohols and/or phenols as an nucleophile and subsequently stabi- lization intermediate (3) and release of leaving group followed by formation of the corresponding acetate (4) by the loss of hydrochloric acid (5). 4. Conclusions In conclusion, cobalt (II) chloride is an efficient, versatile, ecofriendly, inexpensive, nontoxic, reusable heterogene- ous and green catalyst for the acetylation of alcohols and phenols using acetyl chloride as acetylating reagent. The following features make this methodology attractive: 1) Copyright © 2012 SciRes. OJSTA
S. A. R. MULLA ET AL. 34 its simplicity, clean, efficient, rapid and mild reactions conditions; 2) the protocol is very general and it works well with variety o f alcohols and phenols affording good to excellent yields; 3) the reaction carried out at room temperature in absence of the organic solvent; 4) the relative reactivity of acylating agents over the cobalt (II) chloride catalyst were found to be higher in the order: acetyl chloride > acetic anhydride > acetic acid; 5) the recovered and reused catalyst without further purifica tions gave 98% - 99% yield without loss of catalytic ac- tiveity. 5. Acknowledgements SMI, MYP and SSC thanks to CSIR New Delhi for a SRF and JRF, respectively. The authors also th ank to Dr. V. V. Ranade, Chair, CE-PD for their encouragement and support. REFERENCES [1] S. S. Rana, J. J. Barlow and K. L. Matta, “The Selective Acetylation of Primary Alcohols in the Presence of Sec- ondary Alcohols in Carbohydrates” Tetrahedron Leters, Vol. 22, No. 50, 1981, pp. 5007-5010; doi:10.1016/S0040-4039(01)92405-0 [2] T. S. Li, Y. L. Li a nd X. T. Liang, “Studies of the Synthe- sis of Biomarkers. VII. Synthesis of 5 Alpha-(17R,20R)- 14,15-Secocholestane,” Steroids, Vol. 55, No. 6, 1990, pp. 263-265. [3] P. J. Kocienski, “Protecting Groups,” Theime, Stuttgard, 1994. [4] R. Ghosh, M. Swarupnanda and A. Chakraborty, “Mer- cury Chloride Assisted Cyclisation towards Benzimida- zoles by Focused Microwave Irradiation,” Tetrahedron Leters, Vol. 46, No. 1, 2005, pp. 177-180. [5] A-I. Li, T.-S. Li and T.-H. Ding, “Montmorillonite K-10 and KSF as Remarkable Acetylation Catalysts,” Chemical Communications, No. 15, 1997, pp. 1389-1390. doi:10.1039/a703389c [6] R. Kumareswaran, A. Gupta and Y. D. Vankar, “Chloro- trimethylsilane Catalysed Acetylation of Alcohols” Syn- thetic Communications, Vol. 27, No. 2, 1997, pp. 277-282. doi:10.1080/00397919708005028 [7] S. Chandrashekhar, T. Ramchandar and T. Mohamed, “Acylation of Alcohols with Acetic Anhydride Catalyzed by TaCI5: Some Implications in Kinetic Resolution” Tet- rahedron Letters, Vol. 39, No. 20, 1998, pp. 3263-3266. doi:10.1016/S0040-4039(98)00465-1 [8] P. Yadav, R. Lagarkha and A. Zahoor, “Comparative Study of Acetylation of Alcohols and Phenols with Dif- ferent Acetylating Agents Using Zinc Chloride as Cata- lyst under Solvent Free Conditions at Room Tempera- ture,” Asian Journal of Chemistry, Vol. 22, 2010, pp. 5155-5158. [9] M. H. Sarvari and H. Sharghi, “Zinc Oxide (ZnO) as a New, Highly Efficient, and Reusable Catalyst for Acyla- tion of Alcohols, Phenols and Amines under Solvent Free Conditions,” Tetr a h e dron, Vol. 61, No. 46, 2005, pp. 10903-10907. doi:10.1016/j.tet.2005.09.002 [10] F. Tamaddon, M. A. Amrollahi and L. Sharafat, “A Green Protocol for Chemoselective O-Acylation in the Presence of Zinc Oxide as Heterogeneous, Reusable and Eco-Friendly Catalyst,” Tetrahedron Leters, Vol. 46, No. 45, 2005, pp. 7841-7844. doi:10.1016/j.tetlet.2005.09.005 [11] K. D. Surya, “Ruthenium (III) Chloride Catalysed Acyla- tion of Alcohols, Phenols, Thiols and Amines,” Tetrahe- dron Leters, Vol. 45, No. 14, 2004, pp. 2919-2922. doi:10.1016/j.tetlet.2004.02.071 [12] G. Bartoli, M. Bosco, R. Dalpozzo, E. Marcantoni, M. Massaccesi, S. Rinaldi and L. Sambri, “Mg(ClO4)2 as a Powerful Catalyst for the Acylation of Alcohols under Solvent-Free Conditions,” Synlett, No. 1, 2003, pp. 39-42. [13] Y. Ishii, M. Takeno, Y. Kawasaki, A. Muromachi, Y. Nishiyama and S. Sakaguchi, “Acy lation of Alcohols and Amines with Vinyl Acetates Catalyzed by Cp*2 Sm(OTf)2,” Journal of Organic Chemistry, Vol. 61, No. 9, 1996, pp. 3088-3092. doi:10.1021/jo952168m [14] E. Torregiani, S. Gianfranco, A. Minassi and G. Append- ino, “Cerium (III) Chloride-Promoted Chemoselective Esterification of Phenolic Alcohols,” Tetrahedron Letters, Vol. 46, No. 13, 2005, pp. 2193-2196. doi:10.1016/j.tetlet.2005.02.042 [15] B. P. Bandgar, V. T. Kamble, V. S. Sadavarte and V. S. Uppalla, “Selective Sulfonylation of Arene s and Be n z oy la - tion of Alcohols Using Lithium Perchlorate as a Catalyst Under Neutral Conditions,” Synlett, No. 5, 2002, pp. 735- 738. doi:10.1055/s-2002-25345 [16] A. Zarei, A. R. Hajipour and L. Khazdooz, “P2O5/Al2O3 as an Efficient Heterogeneous Catalyst for the Acetylation of Alcohols, Phenols, Thiols, and Amines under Sol- vent-Free Conditions,” Synthetic Communications, Vol. 41, No. 12, 2011, pp. 1772-1785. doi:10.1080/00397911.2010.492197 [17] S. Velusamy, S. Borpuzari and T. Punniyamurthy, “Co- balt(II)-Catalyzed Direct Acetylation of Alcohols with Acetic Acid,” Tetrahedron, Vol. 61, No. 8, 2005, pp. 2011-2015. doi:10.1016/j.tet.2005.01.006 [18] J. Iqbal and R. R. Srivastva, “Cobalt (II) Chloride Cata- lyzed Acyl ation of Alcohols with Acetic Anhydride: Scope and Mechanism,” Journal of Organic Chemistry, Vol. 57, No. 7, 1992, pp. 2001-2007. doi:10.1021/jo00033a020 [19] A. K. Chakraborty and R. Gulhane, “Zirconium(IV) Chlo- ride as a New, Highly Efficient, and Reusable Catalyst for Acetylation of Phenols, Thiols, Amines, and Alcohols under Solvent-Free Conditions,” Synlett, No. 4, 2004, pp. 627-630. doi:10.1055/s-2004-815442 [20] T.-S. Jin, Y.-R. Ma, Z.-H. Zhang and T.-S. Li, “Salfamic Acid Catalysed Acetylation of Alcohols and Phenols with Acetic Anhydride,” Synthetic Communications, Vol. 28, No. 17, 1998, pp. 3173-3177. doi:10.1080/00397919808004417 [21] A. K. Chakraborty and R. Gulhane, “Fluoroboric Acid Adsorbed on Silica Gel as a New and Efficient Catalyst for Acylation of Phenols, Thiols, Alcohols, and Amines,” Tetrahedron Letters, Vol. 44, No. 17, 2003, pp. 3521- 3525. doi:10.1016/S0040-4039(03)00683-X Copyright © 2012 SciRes. OJSTA
S. A. R. MULLA ET AL. Copyright © 2012 SciRes. OJSTA 35 [22] B. Berger, D. G. Rabiller, K. Konigsberger, K. Faber and H. Griengl, “Enzymatic Acylation Using Acetic Anhy- drides: Crucial Removal of Acid,” Tetrahedron: Asym- metry, Vol. 1, No. 8, 1990, pp. 541-546. doi:10.1016/S0957-4166(00)80545-5 [23] K. Ahmed, A. K. Naseer, R. Srinivasan, Y. V. Srikanth and T. Krishnaji, “Al(OTf)3 as a Highly Efficient Catalyst for the Rapid Acetylation of Alcohols, Phenols and Thio- phenols under Solvent-Free Conditions,” Tetrahedron Letters, Vol. 48, No. 22, 2007, pp. 3813-3818. doi:10.1016/j.tetlet.2007.03.162 [24] K. C. Kamlesh, G. F. Christopher, L. Ian and W. David, “Indium Triflate: An Efficient Catalyst for Acylation Re- actions,” Synlett, No. 11, 1999, pp. 1743-1744. [25] O. Akihiro, T Chiaki, K. Atsushi and O. Junzo, “Highly Powerful and Practical Acylation of Alcohols with Acid Anhydride Catalyzed by Bi(OTf)3,” Journal of Organic Chemistry, Vol. 66, No. 26, 2001, pp. 8926-8934. doi:10.1021/jo0107453 [26] H.-J. Yoon, S.-M. Lee, J.-H. Kim, H.-J. Cho, J.-W. Choi, S.-H. Lee and Y.-S. Lee, “Polymer-Supported Gadolin- ium Triflate as a Convenient and Efficient Lewis Acid Catalyst for Acetylation of Alcohols and Phenols,” Tet- rahedron Letters, Vol. 49, No. 19, 2008, pp. 3165-3171. doi:10.1016/j.tetlet.2008.03.005 [27] R. Dalpozzo, A. D. Nino, L. Maiuolo, A. Proeopio, M. Nardi, G. Bartoli and R. Romeo, “Highly Efficient and Versatile Acetylation of Alcohols Catalyzed by Cerium (III) Triflate,” Tetrahedron Letters, Vol. 44, No. 30, 2003, pp. 5621-5624. doi:10.1016/S0040-4039(03)01358-3 [28] R. Das and D. Chakraborty, “Silver Triflate Catalyzed Acetylation of Alcohols, Thiols, Phenols, and Amines,” Synthesis, Vol. 2011, No. 10, 2011, pp. 1621-1625. [29] J. W. Bosco, A. Aditya and A. K. Saikia, “Molecular Iodine Catalyzed Selective Acetylation of Alcohols with Vinyl Acetate,” Tetrahedron Letters, Vol. 47, No. 24, 2006, pp. 4065-4068. [30] R. H. Tale and R. N. Adude, “A Novel 3-Nitrobenzene- boronic Acid as an Extremely Mild and Environmentally Benign Catalyst for the Acetylation of Alcohols under Solvent-Free Conditions,” Tetrahedron Letters, Vol. 47, No. 40, 2006, pp. 7263-7265. doi:10.1016/j.tetlet.2006.07.046 [31] G. Meshram, G and V. D. Patil, “Simple and Efficient Method for Acetylation of Alcohols, Phenols, Amines, and Thiols Using Anhydrous NiCl2 under Solvent-Free Conditions,” Synthetic Communications, Vol. 39, No. 14, 2009, pp. 4384-4395. doi:10.1080/00397910902906529 [32] T. S. Reddy, M. Narasimhulu, N. Suryakiran, K. C. Mahesh, K. Ashalatha and Y. Venkateswarlu, “A Mild and Efficient Acetylation of Alcohols, Phenols and Amines with Acetic Anhydride Using La(NO3)3·6H2O as a Catalyst under Solvent-Free Conditions,” Tetrahedron Letters, Vol. 47, No. 38, 2006, pp. 6825-6829. doi:10.1016/j.tetlet.2006.07.059 [33] A. Hassner and V. Alexanian, “Direct Room Tempareture Esterification of Carboxylic Acids,” Tetrahedron Letters, Vol. 19, No. 46, 1978, pp. 4475-4478. doi:10.1016/S0040-4039(01)95256-6 [34] R. Fatemeh, “A Heterogeneous Cobalt(II) Salen Complex as an Efficient and Reusable Catalyst for Acetylation of Alcohols and Phenols,” Tetrahedron Letters, Vol. 50, No. 4, 2009, pp. 395-397. doi:10.1016/j.tetlet.2008.11.024 [35] S. Farhad, A. Z. Mohammad and A. Ali-Reza, “Efficient Acetylation of Alcohols, Phenols, and Amines Catalyzed by Melamine Trisulfonic Acid,” Synthetic Communica- tions, Vol. 40, No. 7, 2010, pp. 1022-1028. doi:10.1080/00397910903029941 [36] W. Dong-Sheng, L. Gui-Yun and P. Yan-Qing, “Chloro- ferrate(III) Ionic Liquid as Recyclable Catalyst for the Acetylation of Alcohols and Phenols and for 1,1-Diacy- lation of Aldehydes,” Journal of the Chinese Chemical Society, Vol. 56, 2009, pp. 834-838. [37] I. Lopez, J. L. Bravo, M. Caraballo, J. L. Barneto and G. Silvero, “Task-Oriented Use of Ionic Liquids: Efficient Acetylation of Alcohols and Phenols,” Tetrahedron Let- ters, Vol. 52, No. 26, 2011, pp. 3339-3341. doi:10.1016/j.tetlet.2011.04.079 [38] S. G. Lee and J. H. Park, “Metallic Lewis Acids Catalysed Acetylation of Alcohols with Acetic Anhydride and Ace- tic Acid in Ionic Liquid: Study on Reactivity and Reus- ability of the Catalyst,” Journal of Molecular Catalysis A: Chemical, Vol. 194, No. 1-3, 2003, pp. 49-52. doi:10.1016/S1381-1169(02)00532-0 [39] A. R. Hajipour, L. Khazdooz and A. E. Ruoho, “Bronsted Acidic Ionic Liquid as an Efficient Catalyst for Acetyla- tion of Alcohols and Phenols,” Journal of the Chinese Chemical Society, Vol. 56, No. 2, 2009, pp. 398-403. [40] S. Farhadi, S. Panahandehjoo, “Spinel-Type Zinc Alumi- nate (ZnAl2O4) Nanoparticles Prepared by the Co-Pre- cipitation Method: A Novel, Green and Recyclable Het- erogeneous Catalyst for the Acetylation of Amines, Al- cohols and Phenols under Solvent-Free Conditions,” Ap- plied Catalysis A: General, Vol. 382, No. 2, 2010, pp. 293-302. doi:10.1016/j.apcata.2010.05.005 [41] T. W. Green and P. G. Wuts, “Protective Groups in Or- ganic Synthesis,” 2nd Edition, Wiley, New York, 1991.
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