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Synthesis of Aldehydes and Ketones by the Dehydrogenation of Alcohols in the Presence of a Raney Nickel/Aluminium Isopropoxide/A

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Synthesis of Aldehydes and Ketones by the Dehydrogenation of Alcohols in the Presence of a Raney Nickel/Aluminium Isopropoxide/A CEJC 2(1)2004 214{219 Communication Synthesisof Aldehydes and Ketones by the Dehydrogenationof Alcohols in the Presence ofa RaneyNickel/ AluminiumIsoprop oxide/Alumina Catalyst 1 1;2 2 1;2 Ilie Ciocan Tarta ,Ioan A.Silberg ,Mircea Vlassa ¤,Ioan Oprean 1 \RalucaRipan "University, Institute ofChemistry, 30F^ ant^aneleStr., RO-3400Cluj-Napoca, Romania 2 \Babes-Bolyai"University, Departmentof Chemistry, 11Arany Janos Str., RO-3400Cluj-Napoca, Romania Received 24June 2003; accepted 13October 2003 Abstract: Thesynthesis ofaldehydes andketones by the dehydrogenationof allylic and secondaryalcohols using aRaney-Ni-Al( i-OPr)3-Al2O3 catalyst without hydrogenacceptors is presented. c Central EuropeanScience Journals. All rights reserved. ® Keywords: dehydrogenation, alcohols, heterogeneous catalysis Raney nickel, aluminium isopropoxide, alumina 1Introduction The oxidation of alcoholsto carbonyl compounds isa fundamental reaction in organic synthesis [1].A number of transition metal-catalyzedprocedures havebeen developed, such as those using ruthenium [2]or palladium[3].A Raney-Nicatalyst isused frequently for the dehydrogenation of secondary alcoholsto ketones because of the high yields. However,this later method has the disadvantage of requiring either high temperatures[4] or largeamounts of hydrogen acceptors ( i:e.cyclohexanone),which are required for completeconversion[5]. Sometimes, noncatalytic quantities of Raney-Nihave been used for the dehydrogenation ofprimary and secondary alcohols[6]. ¤ E-mail:[email protected] I.C.T artaet al. / CentralEuropean Journal of Chemistry 2(1)2004 214{219 215 Our studies show that the dehydrogenation ofthe secondary and allylicalcohols can be achievedwith acatalyticmixture of Raney-Ni:Al( i-OPr)3:Al2O3:substrate (3:5:5:100 weight) without hydrogen acceptors and at temperatures between 120-170 0C (see Table 1). The reaction isselective, producing ketones,and the yieldsobtained are quiteim- pressive.This procedure has industrial signi¯cance, as the reaction could potentially be conducted inasemi-continuous mode. 2Resultsand Discussion The experimentalresults are shown in Table1. Secondary saturated alcoholsare oxidized to the corresponding ketones in high yields(90-98%; seeT able1: entry 1-4,7.). Primary and secondary allylicalcohols produce the corresponding saturated carbonyl compounds by redox isomerization (Table1: entry 6,7) [7].T ertiary alcohols(see T able1: entry 9) and primary alcoholsdo not react. The dehydrogenation reaction of secondary alcoholsto ketones does not occur when either Raney-Ni, Al( i-ORr)3,or alumina are absent from the catalyticmixture. No reaction isobserved if the Raney-Niis substituted with other Ni(II) salts ( i:e. NiCl2) or complexes( i:e. Ni(PPh3)2Cl2).Wealso observe that using octeneas ahydrogen acceptor has no in°uence on the yieldor the reaction time,but if air isbubbled through the reaction mixture, the reaction does not proceed atall. This mechanism issupported by the following observations: a) The formation of complex3 ispossible knowing the tendency of Alcompounds to form four-coordinate complexes( i.e.Meerwein-Pondorf-Verleyreaction). b) The transition state isfavored by Raney-Nidue to the great a±nity of Nifor hy- drogen. c) The elimination of one hydride ion from the alkoxidecarbon and one proton from the oxonium ion inthe presence of Ni-Raneyvia a six-atom concerted ring transfer, leads to the formation ofthe ketone,4. d) The inductive e®ect (+I) or conjugation e®ects (+E) of the substituents stabilize the carbocation obtained by elimination of hydride ion.This can beexplainedbased on the high reactivityof allylicand secondary alcohols. 3Conclusions In conclusion,our studies show that the mixture of Raney-Ni-Al( i-OPr)3-Al2O3is an excellentcatalyst for the preparation of ketones and aldehydes from secondary and allylic alcoholsin good yields. 4Experimental 1 H-NMRspectra were recorded on aGemini 300MHzspectrometer using CDCl 3 as the solvent and TMS (tetramethylsilane) as the internal standard. IRspectra were recorded 216 I.C.T artaet al. / CentralEuropean Journal of Chemistry 2(1)2004 214{219 on aPerkin Elmer 700 spectrophotometer. GCand MS analyseswere performed on aHewlett Packard 5890(GCL)-5872(MSD) using aHP-5MS 30m x0.25 ¹mcapillary. The reactions were carried out under anitrogen atmosphere. Aluminium oxidegranules, about 1-5 mm,were obtained from Merck.All alcohols were obtained commercially. General oxidation procedure Toadegassed alcohol(0.1 mol), 3%( weight mass) offreshly prepared Raney-Ni[8], 5% (w/w) of Al(i-OPr)3,and 5%(w/w) of Al 2O3 were added. This mixture was magnetically stirred under nitrogen and heated for 6-50 hrs (seeT able1). The catalyst was removed by ¯ltration under an inert atmosphere and washed with petroleum ether. Subsequently, the ¯ltrate was puri¯ed by fractional distillation in vacuo,yielding52-95% of the pure carbonyl compounds (seeT able1). The catalyst removed by ¯ltration (a mixture of Ni and alumina) was reused. The mass, 1H,and IRspectra of the products corresponded with those reported inliterature. References [1](a) G. Cainelli,G. Cardilo: ChromiumOxidation in OrganicChemistry , Springer- Verlag,Berlin, 1984. (b) R.C.Larock: ComprehensiveOrganic Transformations ,VCH Publishers Inc., New-York,1989, pp. 604{614. [2](a) C.Bilgrein,S. Davis,R.S. Drago :\The selectiveoxidation of primary alcoholsto aldehydes by O 2 employinga trinuclear ruthenium carboxylatecatalyst", J.Am.Chem.Soc. ,Vol.109,(1987), pp. 3786{3787. (b) G.Z.W ang, J.E. BÄackvall:\Ruthenium-catalyzed oxidation of alcoholsby acetone", J. Chem.Soc.Commun. ,Vol.4, (1992), pp. 337{339. (c) J.E. BÄackvall,U. Andreasson: \Ruthenium-catalyzed isomerization of allylic alcoholsto saturated ketones", TetrahedronLett. ,Vol.34, (1993), pp. 5459{5462. [3](a) K.P.Peterson, R.C.Larock: \Palladium-catalyzed oxidation of primary and secondary allylicand benzilicalcohols", J.Org. Chem. ,Vol.63, (1998), pp. 3185{ 3189. (b) Y.Shivo, A.H.I.Arisha: \Regioselectivecatalytic dehydrogenation of aldehydes and ketones", J.Org.Chem. ,Vol.63, (1998), pp. 5640{5642. (c) J.H.Kim, R.J. Kulawiec: \Synthesis of 2-phenyl-2-cycloalkenonesvia palladium catalyzedtandem epoxideisomerization-intramolecular aldolcondensation", TetrahedronLett. ,Vol.39, (1998), pp. 3107{3110. (d) N.S.Wilson, B.A. Keay: \A desilylationand one-pot desilylation- oxidation of aliphatic tert- butyldimethylsilylethers using catalyticquantities of PdCl2(CH3CN)2", J.Org.Chem. ,Vol.61, (1996), pp. 2918{2919. (e) K.Kaneda, M.F ujii,K. Morioka: \Highly selective oxidation of allylicalcohols to ®,¯-unsaturated aldehydes using Pdcluster catalyst in the presence ofmolecular oxygen", J.Org.Chem. ,Vol.61, (1996), pp. 4502{4503. (f)S.A.Mohand, F.Henin,J.Muzart: \Palladium(II)-mediated oxidation ofalcohols using 1,2-dichloroethane as Pd(0) reoxidant", TetrahedronLett. ,Vol.36, (1995), pp. 2473{2476. [4](a) M.R.Sander, D.J. Trecker:\Raney nickel catalyzed decarboxylation of formate esters", J.Org. Chem. ,Vol.38, (1973), pp. 3954{3956. I.C.T artaet al. / CentralEuropean Journal of Chemistry 2(1)2004 214{219 217 (d) E.J. Badiu: \Catalytic dehydrogenation I.Catalytic conversion of alcoholsinto aldehyde,para± ns and ole¯ns", J. Am. Chem.Soc. ,Vol.45, (1943), pp. 1809{1813. [5](b) M.Botta, F.De Angeles,R. Nicoletti:\A new, facileN-alkylation of amines and alcohols", Synthesis,(1977), pp. 722{723. (c) E.C. Kleidere,E.C. Korn¯eld: \Raney nickel as an organic oxidation-reduction catalyst", J. Org. Chem. ,Vol.13, (1946), pp. 455{458. (d)S.B. Mahato, S.K.Banerjce, R.N.Chakravarti: \Reactionin high boiling solvent II.E® ect of Raneynickel on triterpenoids", Tetrahedron ,Vol.27, (1971), pp. 177{ 186. (e) J.Forsek:\Conversion of the allylicand homoallylicsteroidal alcoholsto the corresponding saturated ketones by means ofthe activated Ra/Ni", TetrahedronLett. , Vol.21, (1980), pp. 1071{1074. (f)F.C.Changm: \Potential bileacid metabolites II.3,7,12-T risubstituted 5- ¯- cholanicacids", J.Org. Chem. ,Vol.44, (1979), pp. 4567{4572. [6]M.E. Kraft, W.I.Crooks, B.Zorc, S.E. Milczanowski:\Reaction of Raneynickel with alcohols\, J.Org. Chem. ,Vol.53, (1988), pp. 3158{3163. [7]B. M. T rost: \On investigation reactions for atom economy", Acc. Chem.Res. , Vol. 35,(2002), pp. 695{705. [8]H. Becker, W. Berger, G. Domschke,E. Franghanel, J.Faust, M.,Fischer, F. Gentz, K.Gewald, R.Gluch, R.Mayer, K. MÄ uller,D. Pavel,H. Schmidt, K. Scholbergf, K.ScÄuhwetlick,E. Seiler,G. Zeeppenfeld: Organicum,Editura Stiinti¯ca siEnciclopedica,Bucuresti, 1982,pp. 707. 218 Entry Alcohol Temperature (0C) Reaction product Yields (%) /Reaction time (h) 1 C4H9-CH(OH)-CH3 137/30 C4H9-C(O)-CH3 98 I.C. T 2 C4H9-CH(OH)-C2H5 150/40 C4H9-C(O)-C2H5 98 arta 3 C8H17-CH(OH)-CH3 170/16 C8H17-CH(O)-C3 94 et l al. 4 CH3-CH=CH-CH(OH)-CH3 120/30 CH3-CH2-CH2-C(O)-CH3 90 / eta Central 5 170/19 80 European ora Journal 6 170/19 54 7 C4H9-CH=CH-CH2-OH 170/14 CH3-(CH2)5-CH=O 92 of hmsr Chemistry 8 Ph-CH(OH)-Ph 170/6 Ph-C(O)-Ph 52 9 CH3(CH2)7-C(OH) (CH3)-CH3 160/50 CH3(CH2)7-C (OH) (CH)3-CH3 0 ()2(1) Table 1 Carbonyl compounds prepared in the presence of a Raney-Ni-Al(i-OPr)3/Al2O3 cata- lyst. 2004 214{219 I.C.T artaet al. / CentralEuropean Journal of Chemistry 2(1)2004 214{219 219 Scheme 1. Dehydrogenationmechanism of alcoholsin the presenceof Raney-Ni-Al(-OPr) 3/Al2O3 catalyst..
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