Jayasree, J

Narayanan, C S

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Indian Journal of ChemistryVol. 36B,January 1997, pp. 9-13Catalytic transformation of (+ )-limonene oxide over binary oxide catal-ysts of alumina-rare earthsJ Jayasree & C S Narayanan*Regional Research Laboratory (CSIR), Thiruvananthapuram-695 019, Kerala INDIAReceived 13 October 1995; revised 10 May 1996The transformation reactions of ( + )-limonene oxide over binary oxides like AI203-Y203, Al203-Sm203, A1203-Eu203, Al203-Pr6011 and Al203-Nd203 at HO°C and 140°C are discussed. The activ-ity of single oxides like Al203, EU203, Nd203 and Y203 used for the transformation r.eaction is stud- ,ied at 110°C. Among the binary oxides, Al203-Eu203 show maximum activity for epoxide transfor-mation. Methyl (3-isopropenyl cyclopentyl) ketone (4) and carvone (5) are the major productsformed over binary oxides at higher reaction temperture.IntroductionCompounds formed from the rearrangement ofepoxides are valuable intermediates in organicsynthesisl-3. The naturally occurring terpene hy-drocarbons can easily be converted to epoxideeconomically and their' further transformation byheterogeneous catalysis can provide compoundsof value. The transformation reactions of limo-nene oxide have been studied over a number ofsolid catalysts" - 8. The decomposition, deoxygena-tion and addition of limonene oxide has been in-vestigated by a number of workers9-11 and itsrearrangements were reported over various typesof alumina I2,13. Alumina contained Bronsted andLewis acid sites as well as basic sites. The presentwork has been undertaken to investigate the var-iation in the activity of alumina by the addition ofrare earth oxides. Binary oxides like Al203-Y203'Al203-Sm203, Al203-Nd203, Al203-Pr6011 andAl203-Eu203 were used as catalysts. For compar-ing the catalytic performance, single oxides likeAl203, Y203, Eu203 and Nd203 were also usedfor transformations at 110°C. Catalyst acidity wascorrelated to the yield of major products formedin the transformation reaction.Materials and MethodsMaterials. (+ )-Limonene oxide (a 1:1 mixtureof cis and trans epoxide) was supplied by AldrichChemical Co., USA. Toluene and xylene wereguaranteed reagents redistilled over sodium metal.Single oxides and binary oxides like Al203-Y203,Al203-Sm203, Al203-Nd203, Al203-Pr60Il andAl203-Eu203 were prepared as hydroxides by co-precipitation from corresponding nitrates usingNH3. The hydroxides were aged for 20h, washed,filtered, dried at 130°C for 24h and calcined at400°C in air for Sh.Methods. The catalysts were completely char-acterised by methods like XRD; TGA, BET, XPSand MAS 27A1NMR and is reported elsewhere."Catalyst acidity was estimated by titration with n-butyl amine and basicity of the catalysts were de-termined by titration with benzoic acid and theresults are summarised in Table p5.16. Acidity ofcatalysts like Al203-Pr6011 and Pr6011 could notbe determined due to the dull green colour of thecatalyst.Reaction procedure and product identification.Catalyst (Lg) and epoxide (1.3 mmole) were ref-luxed in toluene (1OmL) and reaction rate wasTable l+-Acidity and basicity of various catalystsCatalysts Acid amounts in mmole/rn?at various acid strengthsBasicity inmmole/m?at differentbasic strengths+ 6.3 + 4 + 3.3 + 1.5 - 3 + 12.2 + 15Alz03 0.115 0.115 0.103 0.000Y:zOJ 0.089 0.331 0.065Eu20J 0.071 0.001 0.023 0.000NdzOJ 0.031 0.056 0.013 0.001Alz03-Yz03 0.059 0.004 0.002 0.003 0.000 0.023 0.045Al203-EuzOJ 0.1l3 0.499 0.035 0.038 0.008 0.059 0.286A1203-Smz03 0.092 0.437 0.029 0.004 0.007 0.124 0.132Al20J-Ndz03 0.107 0.509 0.012 0.007 0.002 0.121 0.24110 INDIAN J. CHEM. SEC B. JANUARY 1997frequently monitored by TLC. After completionof reaction (12h) reaction mixture was filtered andcatalyst extracted with methylene chloride underreflux. The reaction filtrate and catalyst extractcombined and solvent was removed in vaccuo.Same method Was followed for other catalysts andfor reaction at 140°C. Reaction products wereanalysed by GLC, GC-MS and identified bycomparing relative retention times with authenticsamples. The authentic samples of trans- and cis-exo carveols (2,3) and methyl (3-isopropenyl eye-lopentyl) ketone (4) were prepared by knownmethods-s-!". A standard sample of carvone wassupplied by Fluka and limonene diol was pre-pared by the hydrolysis of limonene oxide. GLCwas carried out on a 5840A model Hewleft Pack-ard gas chromatograph: Column OV17 (10%)1.8m in length, id 3.1mm, column temperature 80to 200°C at a rate of lO°C/min using an FID de-tector injector temperature 250°C FID tempera-ture 250°C.GC-MS analysis was performed on a varion3400 Incos 50 mass spectrometer, Column DB-5,30m in length, i.d. 0.25mm, column temperature60 to 200°C at a rate of 5°C/min. The m/z dataobtained for various compounds are: 2: 41(100),55, 67, 79, 91, 109, 119, 134, 105, 123; 3:41(100), 81, 67, 55, 107, 93, 121, 136, 152; 4: 41(100), 55, 109, 84, 91, 69, 77, 119, 105, 134,123; 5: 82(100), 54, 41, 93, 108, 79, 58, 67; 6:43(100), 71, 67, 55, 82, 108, 88, 137, 152, 119,101. The mass spectral data were compared toNBS mass spectral library and literature-",Results and DiscussionThe XRD data clearly indicated that the singleoxide catalysts used in the present study showedsome crystallinity and binary oxides showed am-orphous nature". Single oxides and binary oxideswere precipitated as hydroxides from correspond-ing nitrates. The hydroxides were used for ther-mal analysis and it is seen that rare earths showeda tendency to bring down the decomposition tem-perature of aluminium hydroxide between 286and 296°C. The hydroxides of yttrium, neodym-ium and europium showed a thermal decomposi-tion resulting in a slow hydroxyl removal fromthem (Figure 1). The activity of single oxides canbe easily explained by the presence of hydroxylswhich act as weak acid sites. Single oxidesshowed weak acidity in the Ho range + 6.8 to+ 1.5 but no basic sites are observed. All binaryoxides showed weak to moderate acidity in theHo range of + 6.8 to - 3.0 and basic strengthvarying between pkBH value 12.2 and 15 and the23o 200 500 800Temperature (Oe)Figure 1- Thermogravimetric curves of (1) hydroxide of yttri-um; (2) hydroxide of neodymium; (3) hydroxide of europiumresults are summarised in Table I. Coprecipitationincreased the number of stronger acidic sites onbinary oxide surface. New basic sites were alsocreated on the surface of binary oxides. Details ofcomplete characterisation of the binary oxide ca-talysts are given elsewhere.".The major compounds obtained from (+) - li-monene oxide (1) in this transformation reactionare trans and cis-exo-carveols (2,3), methyl (3-iso-propenyl cyclopentyl)ketone (4), carvone (5) and8,9-p-menthene-1,2-diol (6). The activity and se-lectivity of various catalysts at 110°C for 12h and140°C for 5h are given in Tables II and III. At140°C the reaction was complete (no significantTable Il+Actjvity and selectivity of catalysts at 110°C (for12h) for the major constituents identifiedCatalyst Conversion(%)2A1203 95 12Y203 60 21Eu203 69 28NdP3 62 28A1203-Y203 65 12A1203-Eu203 78 35A1203-PrfiOll 76 33A1203-Sm203 70 zzA1203-Ndz03 72 30Selectivity(% )3 4 5 620 6030 1849 1043 1710 9 9 3020 20 10 1420 10 205 10 14 2515 15 15 30JAYASREE et al: CATALYTIC TRANSFORMATION OF ( + )-UMONENE OXIDE HTable III-Activity and selectivity of catalysts at 140°C for 5hfor the major constituents identifiedCatalyst Conversion Selectivity(% )%2 3 4 5 6AIP3-Y203 53 24 10 18 20 24Al203-Eu203 81 25 18 16 28 10Al203-Pr6OIl 73 24 9 14 24 8A1203-Sm203 75 19 10 18 22 9AlP3-Nd303 80 17 12 19 24 10increase in the yield of products) but lower reac-tion temperature required more reaction time forcompletion.At HO°C, the percentage transformation ofepoxide varied from 65 and 78 and a rise in reac-tion temperature to 140°C produced a small in-crease in the percentage conversion of epoxide inthe case of Alz03-Euz03, AlZ03-SmZ03 andAlz03-Ndz03• Alz03-Euz03 produced maximumconversion of epoxide and Al203-Y203 producedthe minimum. Trans and cis-exo carveols (2,3) arethe major products formed in the transformationreaction over Alz03-Euz03, Al203-Pr6011 andAl203-Nd203. Single oxides like EU203 andNd203 showed less conversion of epoxide com-pared to Alz03-Eu203 and Alz03-Nd203• Amongthe allyl alcohols formed in the reaction trans-exo-carveol (2) is the major one. The yield of 2varied from 12 to 35% at HO°C and 17 to 25%at 140°C. Al203-Eu203 and Al203-Pr6011 pro-duced maximum yield of allyl alcohol (2).Alumina contains both Lewis and Bronstedacidity on its surface. Removal of hydroxyl groupsby calcination from the catalyst surface leavessome electron deficient centers on' catalyst sur-face. These centers act as adsorption site for theepoxide. The mechanism for the formation of var-ious products from epoxide is illustrated inScheme 1. The epoxide gets attached to an elec-tron deficient centre on catalyst surface throughoxygen atom. The epoxide ring opens up followedby the formation of tertiary carbocation whichrearranges to different products. In Figure 2 thevariation in the. percentage formation of trans-exo-carveol (2) (for reaction at HO°C) with acidityof all catalysts for Ho + 6.8 and + 1.5 is illustrat-ed. The yield of trans-exo carveol (2) increasedwith increase in acidity.Except Al203-Pr6011 all catalysts yielded cis-exo-carveol (3) at HO°C and the yield varied from5% to 20%. Compared to the yield of alcohol (2),SH OH2 tY.~~~Ai,yT-b / <, :r~q+~Hr + ~ 'f,- H..!!- ---rr c-: r~ -H+l0~£O ctA: Acidic site B: Basic siteScheme Ithe yield of 3 is less in all reactions studied. Theepoxide (1) used in the present investigation is a1:1 mixture of cis and trans isomers and the transepoxide may be relatively more reactive and yieldmore trans alcohol (2). Another reason for theformation of trans alcohol is that abstraction of aprimary hydrogen which is more facile than a sec-ondary one. There is no correlation with the yieldof alcohol (3) with acidity.Methyl-(3-isopropenyl cyclopentyl) ketone (4)was formed in the transformation reaction. At110°C. Its percentage yield varied from 9 to 20.As reaction temperature increased to 140°C, theyield increased in the case of Al203-Eu203 andAl203-Pr60U' The variation in the yield of ketone(4) formed at 140°C with catalyst acidity at Hovalues + 3.3 and - 3 is illustrated in Figure 3. At140°C, with increase in acidity at Ho + 3.3 and- 3, the yield of ketone (4) increased.The yield of carvone (5) varied from 9 to 20%at 110°C, the maximum being in the case ofEU203 (30%). At 140°C, Al203-Eu203 producedmaximum yield of carvone (28%). An increase inrection temperature from 110°C to 140°C resultedin an increase in the yield of carvone. In Figure 4the gradual increase in the yield of carvone withacidity of all catalysts at Ho +- 6.8 and + 1.5 isillustrated (140°C). Besides these major productsAl203-Y203, Al203-Sm203, Al203-Pr6011 andY203 yielded some unidentified compounds in mi-nor amounts.12 INDIAN J. CHEM. SEC B, JANUARY 1997.....•~t 40'"0I030"QII'ne: 20'"••~'H 10()~••...•,..;;...0QI>••'" 40oI0"><·f 30..•"'"•• 20~...0 10.."....CD...•>< L-__~~~~~~I~I _o .003 .004.007 .03Acid amount; (mmol/m2) at HO S + 1.5o ·05 .09 ·10 -II..Acid amount (mmol/m2) at HO S + 6.8Figure 2- Variation in the percentage yield of trans-exo-carveol (2) with acid amount of all catalysts in mmole/m? atHo + 6.8 and + 1.5 (reaction at lIO·C).;; 40 40OJc 300.,OJ.>< .z.>...• 200'" 10...OJ..•,..~ ;30o.,OJ:< 20•..o;! 10"...,.I ! '--~-4 ~I-I .J..1__ --I... _o ·0001 '003 ·007 'OOSo ,005 ·01,03 '035Acid amount (mmol/m2) at Ho S + 3.3Acid amount (mmol/m2) at Ho S - 3Figure 3-Variation in the percenage yield of ketone (4) withacid amount of all catalysts in mmole/rn? at Ho + 3.3 and- 3 (reaction at 140·C)...o. 'IJ lO....QI,,'...;;QIC0 30~toU... 250'" 20...••...•...~--~I~--~~~~-o '05' 09 ·10 .11Acid amount (mmol/m2) at HO S + 6.8+~--~--~~~I~ ~'----o -003 -004 ·007 .03Acid amount (mmol/m2) at Ho s + 1.!>Figure 4-Variation in the percentage yield of carvone (5)with acid amount of all catalysts in mmole/m? at Ho + 6.8and + 1.5 (reaction at lIO·C).JAYASREE et al.:CATALYTIC TRANSFORMATION OF ( + )-UMONENE OXIDE 13ConclusionAlumina prepared in the present study yieldeddiol (6) as the. major product. Single oxides likeY203' EU203 and Nd203 mainly yielded carvone(5). The activity and selectivity of binary oxides ofalumina-rare earths are different from single ox-ides. Binary oxides of AlZ03 with oxides likeEU203, Nd203, Nd203 and Pr60U are found to bemore efficient catalysts than single oxides for thetransformation of (+ )-limonene oxide. At 110°Callyl alcohols are the major products obtainedfrom binary oxides and at 140°C carbonyl com-pounds are the major products.References1 Royals E E & Harrell (Jr) L L, J Arn Chern Soc, 77,1955,3405.2 Royals E E & Leffingwell J C, J Org Chern, 29, 1964,2098.3 King L C & Farber H, J Org Chern, 26,1961,326.4 Arata K, Akutagawa & Tanabe K, J Catal, 41,1976,173.5 Arata K, Takahashi & Tanabe K, Rocz Chern, 50, 1976,210.6 Jayasree J & Narayanan C S, Mat Res Bull, 29, 1994,651.7 Jayasree J & Narayanan C S, Mat Res Bull, 30, 1995,637.8 Sindhu P T, Jayasree .T, Sivakumar S, Warrier K G K &Narayanan C S, Indian J Chern, 35A, 1996, 163.9 Massato N & Fujihara Y, Nippon Kagaku Kaishi; 5,1987,883.10 Mitchell & Peter W D, Org Prep Proced Int, 22, 1990,534.11 Comins D L, Guerra L W & Salvador J M, Synth Lett,11, 1994, 972.12 Nigam I C & Levi L, Can J Chern, 46, 1968, 1944.13 Arata K & Tanabe K, Chern Leu, 1976,321.14 Jayasree J & Narayanan C S, Bull Chern Soc, (Japan), 68,1995,84.15 Benesi H, J Arn Chern Soc, 78, 1956, 5490.16 Benesi H, J Phy Chern, 61,1957,970.17 Take J I, Kikuchi N & Yoneda Y, J Catal, 21, 1971, 164.18 Eschinasi E H, Isreal J Chern, 6,1968,713.19 Settine R L, Perks G L & Hunter G L K, J Org Chern,29,1964,616.20 Swigar & Silverstein R M, Hand Book on Monoterpenes(Aldrich Chemical Compo Inco, Wisconsin), 1981.21 Jayasree J, Transformations of terpenyl oxiranes by hetero-geneous catalysis, Ph D Thesis, Kerala University, 1993.

Catalytic transformation of (+)-limonene oxide over binary oxide catalysts of alumina-rare earths

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Catalytic transformation of (+)-limonene oxide over binary oxide catalysts of alumina-rare earths

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