Cyanoethylation of alcohols and amines by cesium-modified zeolite y

Article abstract of DOI:10.1016/S1872-2067(12)60751-7

Zeolite Y modified by cesium and magnesium ions was prepared by ion-exchange and impregnation methods, and its activity in the cyanoethylation of aliphatic and aromatic alcohols and amines was investigated. During the preparation of some samples, the transformation of zeolite Y into a pollucite-type phase occurred. This phase exhibited good activity in the cyanoethylation of aliphatic alcohols. The prepared solids modified by the impregnation method were more active than the ion-exchanged solids. The activities of the catalysts, in contrast to other basic solids, were scarcely affected by the presence of air or moisture. A correlation between catalyst basicity and catalytic activity is discussed. The catalysts were characterized by X-ray diffraction, volumetric nitrogen adsorption surface area measurement, and CO₂ temperature-programmed desorption. Scanning electron microscopy revealed that the particles of the modified nanocatalysts were < 40 nm. The reaction of acrylonitrile with linear alcohols in the presence of the catalysts was accelerated by microwave irradiation.

Full text of DOI:10.1016/S1872-2067(12)60751-7

ChineseꢀJournalꢀofꢀCatalysisꢀ35ꢀ(2014)ꢀ264–269
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ꢀ ꢀ ꢀ
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ava i l a b l e a t w w w. s c i e n c ed i r e c t . c o m
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j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e /c h n j c
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ꢀ
Article
Cyanoethylationꢀofꢀalcoholsꢀandꢀaminesꢀbyꢀcesium‐modifiedꢀ ꢀ
zeoliteꢀYꢀ
SaraꢀZamanian,ꢀAliꢀNematiꢀKharatꢀ*
ꢀ
SchoolꢀofꢀChemistry,ꢀUniversityꢀCollegeꢀofꢀScience,ꢀUniversityꢀofꢀTehran,ꢀTehran,ꢀIranꢀ
A R T I C L E ꢀ I N F O ꢀ
A B S T R A C T ꢀ
Articleꢀhistory:ꢀ
ZeoliteꢀYꢀmodifiedꢀbyꢀcesiumꢀandꢀmagnesiumꢀionsꢀwasꢀpreparedꢀbyꢀion‐exchangeꢀandꢀimpregnationꢀ
methods,ꢀandꢀitsꢀactivityꢀinꢀtheꢀcyanoethylationꢀofꢀaliphaticꢀandꢀaromaticꢀalcoholsꢀandꢀaminesꢀwasꢀ
investigated.ꢀDuringꢀtheꢀpreparationꢀofꢀsomeꢀsamples,ꢀtheꢀtransformationꢀofꢀzeoliteꢀYꢀintoꢀaꢀpollu‐
cite‐typeꢀ phaseꢀ occurred.ꢀ Thisꢀ phaseꢀ exhibitedꢀ goodꢀ activityꢀ inꢀ theꢀ cyanoethylationꢀ ofꢀ aliphaticꢀ
alcohols.ꢀ Theꢀ preparedꢀ solidsꢀ modifiedꢀ byꢀ theꢀ impregnationꢀ methodꢀ wereꢀ moreꢀ activeꢀ thanꢀ theꢀ
ion‐exchangedꢀsolids.ꢀTheꢀactivitiesꢀofꢀtheꢀcatalysts,ꢀinꢀcontrastꢀtoꢀotherꢀbasicꢀsolids,ꢀwereꢀscarcelyꢀ
affectedꢀbyꢀtheꢀpresenceꢀofꢀairꢀorꢀmoisture.ꢀAꢀcorrelationꢀbetweenꢀcatalystꢀbasicityꢀandꢀcatalyticꢀ
activityꢀ isꢀ discussed.ꢀ Theꢀ catalystsꢀ wereꢀ characterizedꢀ byꢀ X‐rayꢀ diffraction,ꢀ volumetricꢀ nitrogenꢀ
adsorptionꢀ surfaceꢀ areaꢀ measurement,ꢀ andꢀ CO2ꢀ temperature‐programmedꢀ desorption.ꢀ Scanningꢀ
electronꢀmicroscopyꢀrevealedꢀthatꢀtheꢀparticlesꢀofꢀtheꢀmodifiedꢀnanocatalystsꢀwereꢀ<ꢀ40ꢀnm.ꢀTheꢀ
reactionꢀ ofꢀ acrylonitrileꢀ withꢀ linearꢀ alcoholsꢀ inꢀ theꢀ presenceꢀ ofꢀtheꢀcatalystsꢀwasꢀ acceleratedꢀbyꢀ
microwaveꢀirradiation.ꢀ
Receivedꢀ22ꢀAugustꢀ2013ꢀ
Acceptedꢀ13ꢀNovemberꢀ2013ꢀ
Publishedꢀ20ꢀFebruaryꢀ2014ꢀ
Keywords:ꢀ
ModifiedꢀYꢀzeoliteꢀ
Basicꢀcatalystꢀ
Cyanoethylationꢀ
Nano‐particle
©
ꢀ2014,ꢀDalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences.
PublishedꢀbyꢀElsevierꢀB.V.ꢀAllꢀrightsꢀreserved.
1
.ꢀ ꢀ Introductionꢀ
priorꢀtoꢀpurificationꢀofꢀtheꢀproductꢀgeneratesꢀwasteꢀandꢀreduc‐
esꢀtheꢀproductꢀyields.ꢀInꢀmostꢀcases,ꢀbleachingꢀstepsꢀareꢀneces‐
saryꢀforꢀtheꢀremovalꢀofꢀcolorꢀarisingꢀfromꢀimpurities.ꢀLowꢀse‐
lectivityꢀisꢀanꢀadditionalꢀproblem.ꢀ ꢀ
Theꢀ catalyticꢀ additionꢀ ofꢀ alcoholsꢀ orꢀ aminesꢀ toꢀ aꢀ car‐
bon‐carbonꢀ doubleꢀ bondꢀ providesꢀ aꢀ usefulꢀ methodꢀ forꢀ theꢀ
preparationꢀ ofꢀ ethersꢀ andꢀ aminesꢀ [1].ꢀ Cyanoethylation,ꢀ theꢀ
additionꢀofꢀalcoholsꢀorꢀaminesꢀwithꢀactiveꢀhydrogenꢀtoꢀacrylo‐
nitrile,ꢀ hasꢀ attractedꢀ significantꢀ interestꢀ forꢀ theꢀ synthesisꢀ ofꢀ
drugꢀintermediates,ꢀplasticizers,ꢀinsecticides,ꢀemulsifiers,ꢀaddi‐
tivesꢀ forꢀ syntheticꢀ rubber,ꢀ andꢀ physiologicallyꢀ activeꢀ com‐
poundsꢀ[2].ꢀTheꢀresultingꢀnitrilesꢀcanꢀbeꢀconvertedꢀtoꢀdifferentꢀ
typesꢀ ofꢀ aminesꢀ afterꢀ hydrogenationꢀ orꢀ canꢀ formꢀ theꢀ relatedꢀ
carboxylicꢀ acid.ꢀ Usually,ꢀ cyanoethylationꢀ canꢀ beꢀ promotedꢀ inꢀ
theꢀpresenceꢀofꢀaꢀbaseꢀ[2,3].ꢀTheꢀhomogeneousꢀbasicꢀcatalystsꢀ
Anionꢀ exchangeꢀ resinsꢀ haveꢀ beenꢀ usedꢀ asꢀ heterogeneousꢀ
catalystsꢀ forꢀ cyanoethylationꢀ reactionsꢀ [7–9].ꢀ Theꢀ problemꢀ
associatedꢀwithꢀuseꢀofꢀtheseꢀresinsꢀisꢀtheirꢀdeactivationꢀafterꢀaꢀ
fewꢀ runsꢀ probablyꢀ dueꢀ toꢀ theꢀ formationꢀ ofꢀ polyacrylonitrileꢀ
layersꢀonꢀtheꢀsurface.ꢀHattoriꢀandꢀKabashimaꢀ[10]ꢀstudiedꢀtheꢀ
cyanoethylationꢀ ofꢀ alcoholsꢀ overꢀ alkaliꢀ metalꢀ oxides,ꢀ hydrox‐
ides,ꢀcarbonates,ꢀandꢀalumina‐supportedꢀKFꢀasꢀbasicꢀcatalysts.ꢀ
Theyꢀfoundꢀthatꢀmagnesiumꢀoxideꢀisꢀaꢀveryꢀactiveꢀcatalystꢀforꢀ
theꢀ cyanoethylationꢀ ofꢀ alcohols.ꢀ Inꢀ theꢀ lastꢀ decade,ꢀ modifiedꢀ
layeredꢀ doubleꢀ hydroxidesꢀ (LDHs)ꢀ haveꢀ beenꢀ usedꢀ andꢀ showꢀ
highꢀcatalyticꢀactivityꢀinꢀseveralꢀreactions.ꢀTheꢀhydroxylꢀgroupsꢀ
onꢀsurfaceꢀofꢀMg–Al–OHꢀlayeredꢀdoubleꢀhydroxidesꢀareꢀcapableꢀ
ofꢀactingꢀasꢀBrönstedꢀbasicꢀsitesꢀinꢀcatalyticꢀreactionsꢀsuchꢀasꢀ
[2,4]ꢀ soꢀ farꢀ reportedꢀ forꢀ theꢀ cyanoethylationꢀ ofꢀ alcoholsꢀ areꢀ
alkaliꢀhydroxidesꢀ[3],ꢀalkaliꢀalkoxidesꢀ[4],ꢀtetraalkylammoniumꢀ
hydroxidesꢀ [5],ꢀ alkylꢀ mercaptans,ꢀ cresols,ꢀ andꢀ partialꢀ pyro‐
phosphateꢀestersꢀ[6].ꢀNeutralizationꢀofꢀtheseꢀsolubleꢀcatalystsꢀ
*ꢀCorrespondingꢀauthor.ꢀTel:ꢀ+98‐21‐61112499;ꢀE‐mail:ꢀalnema@khayam.ut.ac.irꢀ
DOI:ꢀ10.1016/S1872‐2067(12)60751‐7ꢀ|ꢀhttp://www.sciencedirect.com/science/journal/18722067ꢀ|ꢀChin.ꢀJ.ꢀCatal.,ꢀVol.ꢀ35,ꢀNo.ꢀ2,ꢀFebruaryꢀ2014ꢀ

ꢀ
SaraꢀZamanianꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ35ꢀ(2014)ꢀ264–269ꢀ
ꢀ
cyanoethylationꢀ[11–16].ꢀ
Subsequentlyꢀ theꢀ mixtureꢀ wasꢀ allowedꢀ toꢀ dryꢀ onꢀ theꢀ steamꢀ
bath.ꢀ Thisꢀ sampleꢀ wasꢀ washedꢀ withꢀ aꢀ solutionꢀ ofꢀ metha‐
nol‐waterꢀ(1:1),ꢀthenꢀdriedꢀovernightꢀatꢀ100ꢀ°Cꢀandꢀcalcinedꢀatꢀ
600ꢀ°Cꢀforꢀ4ꢀh.ꢀAꢀportionꢀofꢀcatalystꢀBꢀ(0.5ꢀg)ꢀwasꢀimpregnatedꢀ
withꢀaꢀmixtureꢀofꢀMgOꢀ(0.2ꢀg)ꢀinꢀethanolꢀ(25ꢀmL)ꢀforꢀ15ꢀminꢀinꢀ
anꢀultrasonicꢀbathꢀatꢀ25ꢀ°C.ꢀTheꢀsolventꢀwasꢀremovedꢀbyꢀevap‐
orationꢀunderꢀvacuum,ꢀandꢀthenꢀdriedꢀovernightꢀatꢀ100ꢀ°Cꢀandꢀ
calcinedꢀatꢀ600ꢀ°Cꢀforꢀ4ꢀhꢀ(catalystꢀC).ꢀForꢀpreparationꢀofꢀcata‐
lystꢀD,ꢀtheꢀporesꢀofꢀcatalystꢀAꢀ(0.5ꢀg)ꢀwereꢀimpregnatedꢀwithꢀaꢀ
mixtureꢀofꢀMgOꢀ(0.2ꢀg)ꢀinꢀethanolꢀ(25ꢀmL)ꢀforꢀ15ꢀminꢀinꢀanꢀul‐
trasonicꢀbathꢀatꢀ25ꢀ°C.ꢀTheꢀsolventꢀwasꢀremovedꢀbyꢀevapora‐
tionꢀunderꢀvacuum,ꢀafterꢀwhichꢀtheꢀsolidꢀwasꢀdriedꢀovernightꢀatꢀ
100ꢀ°Cꢀandꢀthenꢀcalcinedꢀatꢀ600ꢀ°Cꢀforꢀ4ꢀh.ꢀ
ZeolitesꢀareꢀaluminosilicatesꢀconstructedꢀfromꢀTO ꢀtetrahe‐
4
draꢀ (T:ꢀaꢀtetrahedralꢀunitꢀbuiltꢀaroundꢀ Siꢀ andꢀAl)ꢀwithꢀ apicalꢀ
oxygenꢀ atomsꢀ sharedꢀ withꢀ neighboringꢀ tetrahedra,ꢀ andꢀ theseꢀ
materialsꢀ haveꢀ greatꢀ potentialꢀ asꢀ basicꢀ catalystsꢀ andꢀ catalystꢀ
supports.ꢀWhileꢀtetrahedraꢀcontainingꢀSi4+ꢀandꢀAl areꢀattachedꢀ
toꢀformꢀaꢀthree‐dimensionalꢀzeoliteꢀframework,ꢀthereꢀisꢀaꢀnega‐
tiveꢀ chargeꢀ associatedꢀ withꢀ eachꢀ Al3+ꢀ atom.ꢀ Theꢀ negativeꢀ
frameworkꢀ chargeꢀ isꢀ balancedꢀ byꢀ anꢀ exchangeableꢀ cation,ꢀ
achievingꢀ electricalꢀ neutrality.ꢀ Theꢀ basicityꢀ ofꢀ ion‐exchangedꢀ
zeolitesꢀarisesꢀfromꢀtheꢀnegativeꢀchargeꢀonꢀtheꢀframeworkꢀ[17].ꢀ
Twoꢀapproachesꢀhaveꢀbeenꢀusedꢀtoꢀcreateꢀbasicityꢀinꢀzeo‐
lites.ꢀTheꢀfirstꢀmethodꢀusesꢀion‐exchangeꢀwithꢀalkaliꢀmetalꢀions.ꢀ
Inꢀthisꢀmethod,ꢀtheꢀnatureꢀofꢀtheꢀalkaliꢀmetalꢀaffectsꢀtheꢀbasicꢀ
strengthꢀofꢀtheꢀmodifiedꢀzeolites.ꢀTheꢀsecondꢀmethodꢀemploysꢀ
impregnationꢀofꢀtheꢀzeoliteꢀporesꢀwithꢀentitiesꢀthatꢀcanꢀactꢀasꢀ
basesꢀ[18,19].ꢀ
Inꢀthisꢀresearch,ꢀweꢀmodifiedꢀzeoliteꢀYꢀwithꢀalkaliꢀmetalꢀionsꢀ
byꢀ ion‐exchangeꢀ andꢀ impregnationꢀ methods.ꢀ Zeoliteꢀ Yꢀ isꢀ aꢀ
three‐dimensionalꢀ zeoliteꢀ withꢀ largeꢀ cavitiesꢀ presentꢀ inꢀ theꢀ
structureꢀthatꢀareꢀinterconnectedꢀbyꢀ12ꢀmemberꢀringꢀchannels,ꢀ
whichꢀmeansꢀthatꢀthereꢀareꢀ12ꢀcationsꢀ(Si ꢀandꢀAl )ꢀandꢀ12ꢀO ꢀ
anionsꢀpresentꢀinꢀtheꢀring.ꢀTheseꢀstructuralꢀpropertiesꢀmadeꢀitꢀ
suitableꢀasꢀaꢀselectiveꢀheterogeneousꢀcatalystꢀ[20].ꢀ ꢀ
3+ꢀ
Theꢀcesiumꢀandꢀmagnesiumꢀcontentsꢀofꢀtheꢀcatalystsꢀwereꢀ
determinedꢀ usingꢀ anꢀ ICP‐OESꢀ (Varianꢀ Vista‐MPX)ꢀ spectrome‐
ter.ꢀCatalystsꢀA,ꢀB,ꢀC,ꢀandꢀDꢀcontainedꢀ13%,ꢀ40.2%,ꢀ35.3%,ꢀandꢀ
8.5%ꢀcesium,ꢀrespectively.ꢀTheꢀcontentsꢀofꢀmagnesiumꢀinꢀcata‐
lystsꢀCꢀandꢀDꢀwereꢀ9.1%ꢀandꢀ11%,ꢀrespectively.ꢀ
2.2.ꢀ ꢀ Catalystꢀcharacterization
4+
3+
2–
Theꢀ structureꢀ andꢀ phaseꢀ purityꢀ ofꢀ allꢀ synthesizedꢀ zeolitesꢀ
wereꢀ monitoredꢀ byꢀ powderꢀ X‐rayꢀ diffractionꢀ (XRD)ꢀ usingꢀ aꢀ
α
BrukerꢀD8ꢀADVANCEꢀdiffractometerꢀusingꢀCuꢀK ꢀradiation.ꢀTheꢀ
Preparedꢀ catalystsꢀ wereꢀ studiedꢀ inꢀ theꢀ cyanoethylationꢀ ofꢀ
aliphaticꢀ andꢀ aromaticꢀ alcoholsꢀ andꢀ amines.ꢀ Allꢀ theꢀ reactionsꢀ
wereꢀcarriedꢀoutꢀatꢀambientꢀtemperatureꢀorꢀunderꢀrefluxꢀcon‐
ditions.ꢀCorrelationꢀofꢀtheꢀcatalyticꢀperformanceꢀwithꢀtheꢀphys‐
icochemicalꢀstructureꢀofꢀtheꢀcatalystsꢀhasꢀbeenꢀcarriedꢀout.ꢀ ꢀ
Theꢀuseꢀofꢀmicrowaveꢀovensꢀinꢀsyntheticꢀchemistryꢀhasꢀre‐
centlyꢀshownꢀ rapidꢀ growthꢀ[21–33].ꢀ Afterꢀtheꢀ firstꢀreportsꢀ ofꢀ
microwave‐assistedꢀ synthesisꢀ inꢀ 1986ꢀ [34,35],ꢀ thisꢀ techniqueꢀ
hasꢀbeenꢀwidelyꢀacceptedꢀasꢀaꢀmeansꢀofꢀreducingꢀreactionꢀtimesꢀ
scanningꢀrangeꢀofꢀ2θꢀwasꢀsetꢀbetweenꢀ5°ꢀandꢀ50°.ꢀN
2
ꢀadsorp‐
tion/desorptionꢀ isothermsꢀ wereꢀ obtainedꢀ atꢀ −196ꢀ °Cꢀ usingꢀ aꢀ
BELSORP‐miniꢀ IIꢀ surfaceꢀ areaꢀ measurementꢀ systemꢀ afterꢀ de‐
gassingꢀ theꢀ samplesꢀ underꢀ vacuumꢀ atꢀ 300ꢀ °Cꢀ overnight.ꢀ Theꢀ
surfaceꢀ areasꢀ ofꢀ allꢀ samplesꢀ wereꢀ calculatedꢀ usingꢀ theꢀ BETꢀ
methodology.ꢀ Theꢀ surfaceꢀ morphologyꢀ ofꢀ theꢀ catalystsꢀ wasꢀ
obtainedꢀ onꢀ aꢀ Zeissꢀ DSM‐960Aꢀ scanningꢀ electronꢀ microscopeꢀ
(SEM)ꢀwithꢀanꢀaccelerationꢀvoltageꢀofꢀ10ꢀkV.ꢀ
Temperature‐programmedꢀ desorptionꢀ (TPD)ꢀ studiesꢀ ofꢀ
synthesizedꢀcatalystsꢀwereꢀcarriedꢀoutꢀusingꢀCO2ꢀasꢀaꢀprobeꢀforꢀ
determiningꢀ theꢀ numberꢀ andꢀ strengthꢀ ofꢀ activeꢀ basicꢀ sites.ꢀ
[36–40].ꢀToꢀreduceꢀtheꢀreactionꢀtimeꢀinꢀourꢀcase,ꢀweꢀcarriedꢀoutꢀ
theꢀcyanoethylationꢀofꢀaliphaticꢀalcoholsꢀwithꢀacrylonitrileꢀun‐
derꢀmicrowaveꢀirradiationꢀinꢀtheꢀpresenceꢀofꢀtheꢀvariousꢀcata‐
lysts.ꢀ
CO
(Quantachrome)ꢀinstrument.ꢀTheꢀTPDꢀdesorptionꢀrampꢀofꢀtheꢀ
chemicallyꢀ adsorbedꢀ CO ꢀ wasꢀ runꢀ fromꢀ 50ꢀ toꢀ 1000ꢀ °Cꢀ withꢀ aꢀ
2
‐TPDꢀ analysisꢀ wasꢀ performedꢀ onꢀ aꢀ ChemBET‐3000ꢀ
2
2
.ꢀ ꢀ Experimentalꢀ
heatingꢀrateꢀofꢀ10ꢀ°C/minꢀusingꢀheliumꢀasꢀtheꢀcarrierꢀgas.ꢀTheꢀ
catalystꢀsampleꢀ(0.103ꢀg)ꢀwithꢀaꢀparticleꢀsizeꢀofꢀ60–80ꢀμmꢀwasꢀ
heldꢀinꢀaꢀplugꢀflowꢀquartzꢀreactorꢀthatꢀwasꢀcoupledꢀtoꢀaꢀthermalꢀ
conductivityꢀ detectorꢀ (TCD).ꢀ Theꢀ catalystꢀ samplesꢀ wereꢀ de‐
gassedꢀunderꢀaꢀnitrogenꢀflowꢀ(10ꢀmL/min)ꢀatꢀconstantꢀheatingꢀ
rateꢀ(10ꢀ°C/min)ꢀtoꢀ500ꢀ°Cꢀandꢀheldꢀatꢀtheꢀfinalꢀtemperatureꢀforꢀ
1ꢀh.ꢀThen,ꢀaꢀstreamꢀofꢀHe/CO2ꢀwithꢀaꢀ19/1ꢀfeedꢀratioꢀwasꢀpassedꢀ
overꢀ theꢀ catalystꢀ bedꢀ forꢀ 20ꢀ minꢀ atꢀ 50ꢀ °Cꢀ andꢀ finallyꢀ flushedꢀ
withꢀheliumꢀforꢀ1ꢀhꢀatꢀ50ꢀ°C.ꢀForꢀtheꢀdeterminationꢀofꢀtheꢀiden‐
tityꢀandꢀpurityꢀofꢀreactionꢀproducts,ꢀaꢀmassꢀspectrometerꢀandꢀaꢀ
gasꢀ chromatographꢀ (GC‐MS),ꢀ Agilentꢀ modelꢀ 7890Aꢀ withꢀ anꢀ
HP‐5ꢀcapillaryꢀcolumnꢀandꢀanꢀFIDꢀdetectorꢀwereꢀused.ꢀ
2.1.ꢀ ꢀ Catalystꢀpreparation
Allꢀtheꢀreagentsꢀwereꢀusedꢀwithoutꢀfurtherꢀpurification.ꢀNaYꢀ
zeoliteꢀ withꢀ aꢀ SiO
cordingꢀ toꢀ publishedꢀ methodsꢀ [41,42].ꢀ Cs
Mg(CH CO ꢀwereꢀobtainedꢀfromꢀMerck.ꢀMagnesiumꢀoxideꢀwasꢀ
preparedꢀ byꢀ theꢀ decompositionꢀ ofꢀ magnesiumꢀ acetateꢀ atꢀ ele‐
vatedꢀtemperaturesꢀunderꢀvacuum.ꢀCs‐exchangedꢀzeoliteꢀYꢀwasꢀ
preparedꢀ fromꢀ theꢀ synthesizedꢀ NaYꢀ usingꢀ ion‐exchangeꢀ withꢀ
cesiumꢀ carbonateꢀ solution.ꢀ Aꢀ totalꢀ ofꢀ 5ꢀ gꢀ zeoliteꢀ Yꢀ wasꢀ sus‐
2
/Al
2 3
O
ꢀ molarꢀ ratioꢀ ofꢀ 5ꢀ wasꢀ preparedꢀ ac‐
2
CO andꢀ
3
ꢀ
3
)
2 2
pendedꢀinꢀ100ꢀmLꢀofꢀ0.05ꢀmol/LꢀCs
2
CO
3
ꢀaqueousꢀsolutionꢀandꢀ
MicrowaveꢀreactionsꢀwereꢀcarriedꢀoutꢀusingꢀaꢀSamsungꢀdo‐
mesticꢀ microwaveꢀ ovenꢀ operatingꢀ atꢀ 2.45ꢀ GHzꢀ withꢀ aꢀ PTFEꢀ
closedꢀcontainerꢀofꢀ15ꢀmLꢀcapacityꢀasꢀtheꢀreactionꢀvessel.ꢀ
stirredꢀforꢀ24ꢀhꢀatꢀ70–80ꢀ°C.ꢀAfterꢀfiltrationꢀandꢀwashingꢀtwiceꢀ
withꢀdistilledꢀwater,ꢀtheꢀsolidꢀwasꢀdriedꢀovernightꢀatꢀ100ꢀ°Cꢀandꢀ
thenꢀcalcinedꢀatꢀ600ꢀ°Cꢀforꢀ4ꢀhꢀ(catalystꢀA).ꢀCatalystꢀBꢀwasꢀpre‐
paredꢀinꢀaꢀdifferentꢀwayꢀbyꢀmixingꢀNaYꢀzeoliteꢀwithꢀCs
2 3
CO ꢀinꢀaꢀ
2.3.ꢀ ꢀ Reactionꢀprocedure
minimumꢀamountꢀofꢀwaterꢀonꢀaꢀsteamꢀbath.ꢀTheꢀmixtureꢀwasꢀ
stirredꢀ forꢀ 2ꢀ hꢀ whilstꢀ theꢀ waterꢀ contentꢀ remainedꢀ constant.ꢀ
Differentꢀalcoholsꢀorꢀaminesꢀ(76ꢀmmol,ꢀexcessꢀamount),ꢀac‐

ꢀ
SaraꢀZamanianꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ35ꢀ(2014)ꢀ264–269ꢀ
rylonitrileꢀ (19ꢀ mmol),ꢀ andꢀ catalystꢀ (0.06ꢀ g)ꢀ wereꢀ addedꢀ toꢀ aꢀ
roundꢀ bottomedꢀ flaskꢀ andꢀ wereꢀ stirredꢀ underꢀ argonꢀ atꢀ roomꢀ
temperatureꢀ forꢀ 24ꢀ h.ꢀ Thisꢀ reactionꢀ wasꢀ performedꢀ inꢀ theꢀ
presenceꢀofꢀ1ꢀmLꢀofꢀtolueneꢀasꢀsolventꢀunderꢀrefluxꢀconditionꢀ
forꢀ6ꢀh.ꢀ ꢀ
Cs
MgO
(a)
Catalyst D
Toꢀaꢀmicrowaveꢀvesselꢀcontainingꢀtheꢀrequiredꢀquantitiesꢀofꢀ
aliphaticꢀ alcoholsꢀ andꢀ acrylonitrile,ꢀ 0.06ꢀ gꢀ ofꢀ catalystꢀ Cꢀ wasꢀ
added.ꢀTheꢀvesselꢀwasꢀsealedꢀandꢀirradiatedꢀforꢀ5ꢀandꢀ15ꢀminꢀ
usingꢀaꢀpowerꢀlevelꢀofꢀ900ꢀW.ꢀAfterꢀseparationꢀofꢀtheꢀcatalystꢀbyꢀ
centrifuging,ꢀ theꢀ productsꢀ wereꢀ analyzedꢀ byꢀ GC‐MS.ꢀ Conver‐
sionsꢀ wereꢀ periodicallyꢀ determinedꢀ usingꢀ n‐decaneꢀ asꢀ anꢀ in‐
ternalꢀstandard.
Theꢀseparatedꢀcatalystꢀwasꢀwashedꢀwithꢀethanolꢀandꢀwaterꢀ
andꢀdriedꢀatꢀ100ꢀ°Cꢀovernightꢀthenꢀcalcinedꢀatꢀ300ꢀ°Cꢀforꢀ4ꢀh.ꢀAllꢀ
reactionsꢀ wereꢀ carriedꢀ outꢀ onꢀ theꢀ recoveredꢀ catalyst,ꢀ whichꢀ
showedꢀ onlyꢀ aꢀ smallꢀ lossꢀ ofꢀ activityꢀ afterꢀ beingꢀ reusedꢀ fourꢀ
times.
Catalyst A
NaY
(b)
Cs
MgO
Catalyst C
3
.ꢀ ꢀ Resultsꢀandꢀdiscussion
Catalyst B
Pollucite
Theꢀgeneralꢀreactionꢀschemeꢀforꢀtheꢀcyanoethylationꢀofꢀal‐
coholsꢀandꢀaminesꢀisꢀshownꢀinꢀSchemeꢀ1.ꢀThisꢀtypeꢀofꢀreactionꢀ
requiresꢀ aꢀ basicꢀ catalyst,ꢀ andꢀ soꢀ activitiesꢀ reflectꢀ theꢀ basicꢀ
characterꢀofꢀtheꢀpreparedꢀcatalysts.ꢀTheꢀresultsꢀofꢀcyanoethyla‐
tionꢀreactionsꢀofꢀalcoholsꢀandꢀaminesꢀareꢀsummarizedꢀinꢀTableꢀ
1
0
20
2
30
40
50
o
/( )
Fig.ꢀ1.ꢀComparisonꢀofꢀpowderꢀXRDꢀpatternsꢀofꢀ(a)ꢀsynthesizedꢀcata‐
lystsꢀAꢀandꢀDꢀbasedꢀonꢀzeoliteꢀNaYꢀandꢀ(b)ꢀsynthesizedꢀcatalystsꢀBꢀandꢀ
Cꢀwithꢀpollucite.ꢀ
1.ꢀ
Noꢀappreciableꢀactivityꢀwasꢀseenꢀatꢀroomꢀtemperatureꢀafterꢀ
4ꢀhꢀandꢀunderꢀrefluxꢀafterꢀ6ꢀhꢀforꢀlinearꢀaliphaticꢀalcohols,ꢀorꢀ
2
ComparisonꢀofꢀacrylonitrileꢀconversionsꢀonꢀcatalystsꢀAꢀandꢀ
Bꢀ showedꢀ that,ꢀ withꢀ impregnationꢀ ofꢀ NaYꢀ zeoliteꢀ byꢀ cesiumꢀ
carbonate,ꢀaꢀmoreꢀbasicꢀcatalystꢀwasꢀobtainedꢀcomparedꢀwithꢀ
theꢀion‐exchangedꢀsolid.ꢀItꢀwouldꢀappearꢀthatꢀtheꢀhighꢀalkalinityꢀ
ofꢀcesiumꢀcarbonateꢀtransformedꢀtheꢀframeworkꢀofꢀYꢀzeolite,ꢀaꢀ
FAUꢀ typeꢀ structureꢀ withꢀ 12‐memberedꢀ ringsꢀ intoꢀ aꢀ pollu‐
cite‐typeꢀ phase,ꢀ anꢀ ANAꢀ typeꢀ zeoliteꢀ withꢀ distortedꢀ 8‐ringꢀ
pores.ꢀXRDꢀdiffractionꢀtracesꢀinꢀFig.ꢀ1ꢀshowꢀthatꢀuponꢀimpreg‐
nationꢀ ofꢀ theꢀ zeoliteꢀ withꢀ cesiumꢀ carbonateꢀ (catalystꢀ B),ꢀ theꢀ
zeoliteꢀYꢀstructureꢀisꢀdestroyedꢀandꢀtheꢀpeaksꢀrelatedꢀtoꢀpollu‐
citeꢀphaseꢀappearꢀ(PowderꢀDiffractionꢀFileꢀNo.ꢀ29‐0407,ꢀInter‐
nationalꢀ Centreꢀ forꢀ Diffractionꢀ Dataꢀ (ICDD),ꢀ Newtonꢀ Square,ꢀ
forꢀphenolꢀasꢀanꢀaromaticꢀalcoholꢀinꢀtheꢀpresenceꢀofꢀcatalystꢀA,ꢀ
butꢀanilineꢀshowedꢀaꢀlowꢀconversionꢀatꢀambientꢀtemperatureꢀ
andꢀmoderateꢀconversionꢀunderꢀreflux.ꢀTheꢀconversionꢀofꢀ ac‐
rylonitrileꢀ inꢀ theꢀ reactionꢀ withꢀ hexylamineꢀ andꢀ diethylamineꢀ
increasedꢀupꢀtoꢀ100%ꢀinꢀtheꢀpresenceꢀofꢀtheꢀpreparedꢀcatalystsꢀ
eitherꢀ atꢀ theꢀ roomꢀ temperatureꢀ orꢀ underꢀ reflux,ꢀ whichꢀ wasꢀ
expectedꢀbecauseꢀofꢀtheꢀhigherꢀbasicityꢀofꢀaminesꢀwithꢀrespectꢀ
toꢀ alcohols.ꢀ Catalystꢀ B,ꢀ whichꢀ isꢀ activeꢀ forꢀ cyanoethylationꢀ ofꢀ
linearꢀaliphaticꢀalcohols,ꢀshowedꢀnoꢀactivityꢀforꢀtheꢀreactionꢀofꢀ
phenolꢀwithꢀaniline.ꢀ ꢀ
Base
catalyst
PA).ꢀ Polluciteꢀ isꢀ aꢀ cesiumꢀ aluminosilicateꢀ (CsAlSi
2
O )ꢀ andꢀ isꢀ
6
H2 H2
R XH +H C CH CN
R X
CN
2
C
C
commerciallyꢀ theꢀ mostꢀ importantꢀ cesium‐bearingꢀ ore.ꢀ Peaksꢀ
aroundꢀ 2θꢀ =ꢀ 26°ꢀ inꢀ Fig.ꢀ 1(b)ꢀ indicateꢀ theꢀ presenceꢀ ofꢀ excessꢀ
cesiumꢀionsꢀinꢀcatalystꢀB.ꢀTheꢀeffectꢀofꢀtheꢀcesiumꢀionꢀinꢀim‐
X = O, NH
Schemeꢀ1.ꢀCyanoethylationꢀofꢀalcoholsꢀandꢀaminesꢀtoꢀrelatedꢀnitriles.
Tableꢀ1ꢀ
Conversionꢀofꢀacrylonitrileꢀinꢀtheꢀpresenceꢀofꢀpreparedꢀcatalystsꢀforꢀvariousꢀreactants.ꢀ
Conversionꢀ(%)ꢀ
Catalystꢀ ꢀ
Noneꢀ
Aꢀ
Aꢀaꢀ
Methanolꢀ
Ethanolꢀ
Propanolꢀ
Butanolꢀ
Phenolꢀ
Anilineꢀ
Hexylamineꢀ
Diethylamineꢀ
0ꢀ
0ꢀ
0ꢀ
0ꢀ
0ꢀ
0ꢀ
0ꢀ
0ꢀ
0ꢀ
0ꢀ
0ꢀ
62.2ꢀ
95.9ꢀ
ꢀ 8.5ꢀ
95.7ꢀ
0ꢀ
ꢀ 0ꢀ
ꢀ 0ꢀ
ꢀ 0ꢀ
ꢀ 0ꢀ
75ꢀ
ꢀ 0ꢀ
46ꢀ
ꢀ 0ꢀ
ꢀ 0ꢀ
ꢀ 0ꢀ
ꢀ ꢀ 8.4ꢀ
40ꢀ
ꢀ 0ꢀ
ꢀ ꢀ 5.3ꢀ
ꢀ 0ꢀ
ꢀ 91ꢀ
ꢀ 98ꢀ
100ꢀ
ꢀ 92ꢀ
100ꢀ
ꢀ 90ꢀ
100ꢀ
ꢀ 95ꢀ
100ꢀ
ꢀ 65ꢀ
ꢀ 87ꢀ
100ꢀ
ꢀ 75ꢀ
100ꢀ
ꢀ 70ꢀ
100ꢀ
ꢀ 95ꢀ
100ꢀ
0ꢀ
Bꢀ
Bꢀaꢀ
ꢀ
ꢀ
ꢀ
ꢀ
87.4ꢀ
99.7ꢀ
96.1ꢀ
99.4ꢀ
0ꢀ
85.2ꢀ
99.3ꢀ
89.7ꢀ
98.5ꢀ
0ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
77.3ꢀ
99.5ꢀ
17.1ꢀ
97.6ꢀ
0ꢀ
ꢀ
ꢀ
Cꢀ
Cꢀaꢀ
ꢀ
ꢀ
ꢀ ꢀ 0.8ꢀ
ꢀ
Dꢀ
Dꢀaꢀ
ꢀ 17.8ꢀ
92ꢀ
0ꢀ
0ꢀ
0ꢀ
0ꢀ
aꢀUnderꢀrefluxꢀforꢀ6ꢀh.

ꢀ
SaraꢀZamanianꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ35ꢀ(2014)ꢀ264–269ꢀ
ꢀ
provingꢀ theꢀ basicꢀ characterꢀ ofꢀ solidꢀ catalystsꢀ hasꢀ beenꢀ men‐
tionedꢀ elsewhereꢀ[43].ꢀ Theꢀ effectꢀisꢀrelatedꢀtoꢀtheꢀlargeꢀionicꢀ
radius,ꢀ lowꢀ chargeꢀ density,ꢀ andꢀ theꢀ highꢀ polarizabilityꢀ ofꢀ theꢀ
cesiumꢀcation.ꢀ
Anꢀinterestingꢀpointꢀconcernsꢀtheꢀcyanoethylationꢀactivityꢀofꢀ
theꢀ preparedꢀ catalystsꢀ forꢀ anilineꢀ andꢀ phenolꢀ (Tableꢀ 1).ꢀ Theꢀ
heterogeneouslyꢀcatalyzedꢀcyanoethylationꢀreactionꢀofꢀalcoholsꢀ
andꢀaminesꢀproceededꢀbyꢀtwoꢀdifferentꢀmechanismsꢀ(Schemeꢀ
Tableꢀ2ꢀ
Comparisonꢀofꢀtheꢀsurfaceꢀareaꢀandꢀporeꢀvolumeꢀofꢀsynthesizedꢀcata‐
lysts.ꢀ
2
3
Catalystꢀ
NaYꢀ
Aꢀ
Bꢀ
Cꢀ
Surfaceꢀareaꢀ(m
/g)ꢀ
Poreꢀvolumeꢀ(cm
0.30ꢀ
/g)ꢀ
720ꢀ
583ꢀ
194ꢀ
182ꢀ
436ꢀ
0.25ꢀ
0.02ꢀ
0.08ꢀ
Dꢀ
0.02ꢀ
2).ꢀ ꢀ
Inꢀ theꢀ firstꢀ mechanism,ꢀ alcoholsꢀareꢀactivatedꢀbyꢀtheꢀsolidꢀ
catalystꢀ producingꢀ alkoxideꢀ species,ꢀ whereasꢀ inꢀ theꢀ secondꢀ
mechanism,ꢀinꢀtheꢀreactionꢀwithꢀamines,ꢀacrylonitrileꢀwasꢀad‐
sorbedꢀ andꢀ activatedꢀ onꢀ theꢀ catalystꢀ surface.ꢀ Theꢀ basicityꢀ ofꢀ
catalystꢀBꢀisꢀprobablyꢀ sufficientꢀ forꢀdeprotonationꢀofꢀ alcoholsꢀ
withꢀ subsequentꢀ attackꢀ ofꢀ theꢀ alkoxideꢀ toꢀ formꢀ acrylonitrile,ꢀ
whichꢀthenꢀformsꢀtheꢀ3‐alkoxypropanenitrileꢀanionꢀfollowedꢀbyꢀ
adsorptionꢀatꢀsurfaceꢀprotonꢀcentersꢀtoꢀproduceꢀtheꢀfinalꢀprod‐
uctꢀ (mechanismꢀ 1)ꢀ [10].ꢀ Forꢀ reactionꢀ withꢀ amines,ꢀ adsorbedꢀ
acrylonitrileꢀwasꢀaffectedꢀbyꢀtheꢀhighꢀelectrostaticꢀfieldꢀofꢀtheꢀ
alkaliꢀ ionsꢀ onꢀ theꢀ surfaceꢀ ofꢀ theꢀ ion‐exchangedꢀ zeolite.ꢀ Thisꢀ
producedꢀanꢀelectron‐deficientꢀcenterꢀatꢀtheꢀβ‐carbonꢀofꢀacry‐
lonitrile,ꢀandꢀevenꢀanilineꢀwithꢀitsꢀrelativelyꢀlowꢀnucleophilicityꢀ
couldꢀattackꢀtheꢀdoubleꢀbondꢀ(mechanismꢀ2)ꢀ[44].ꢀ
alystꢀB,ꢀcesiumꢀionsꢀenteredꢀtheꢀporesꢀofꢀtheꢀzeoliteꢀandꢀsignifi‐
cantlyꢀ reducedꢀ theꢀ surfaceꢀ areaꢀ andꢀ poreꢀ volume.ꢀ Catalystꢀ Bꢀ
hadꢀaꢀhigherꢀbasicityꢀthanꢀcatalystꢀAꢀandꢀshowedꢀhigherꢀactivityꢀ
inꢀtheꢀcyanoethylationꢀofꢀalcohols,ꢀevenꢀforꢀphenolꢀ(underꢀre‐
fluxꢀconditions).ꢀ
TheꢀhigherꢀbasicityꢀofꢀcatalystꢀC,ꢀassociatedꢀwithꢀitsꢀhigherꢀ
catalyticꢀactivity,ꢀwasꢀconfirmedꢀbyꢀCO
‐TPD.ꢀThisꢀtechniqueꢀisꢀ
2
aꢀsuitableꢀtoolꢀforꢀobtainingꢀinformationꢀaboutꢀtheꢀactivityꢀandꢀ
distributionꢀofꢀactiveꢀsitesꢀinꢀzeolites.ꢀInꢀFig.ꢀ2,ꢀTPDꢀprofilesꢀforꢀ
allꢀ samplesꢀareꢀshown.ꢀTheꢀ firstꢀmaximaꢀofꢀcatalystsꢀBꢀ andꢀ Cꢀ
appearedꢀ atꢀ 580ꢀ andꢀ 690ꢀ °C,ꢀ respectively,ꢀ whichꢀ areꢀ muchꢀ
higherꢀ thanꢀ forꢀ catalystꢀ Aꢀ (390ꢀ °C)ꢀ andꢀ catalystꢀ Dꢀ (440ꢀ °C).ꢀ
Higherꢀ maximaꢀ forꢀ theꢀ CO ꢀ desorptionꢀ temperatureꢀ andꢀ theꢀ
2
Theꢀsurfaceꢀareasꢀandꢀporeꢀvolumesꢀofꢀallꢀsamplesꢀareꢀlistedꢀ
peakꢀ areasꢀ ofꢀ catalystsꢀ Bꢀ andꢀ Cꢀ confirmꢀ thatꢀ theseꢀ catalystsꢀ
haveꢀaꢀhigherꢀbasicityꢀandꢀaꢀhigherꢀconcentrationꢀofꢀbasicꢀsitesꢀ
inꢀTableꢀ2.ꢀSurfaceꢀareasꢀofꢀNaYꢀzeoliteꢀdecreasedꢀfromꢀ720ꢀtoꢀ
2
5
83ꢀ andꢀ toꢀ 194ꢀ m /gꢀforꢀcatalystsꢀAꢀandꢀB,ꢀrespectively.ꢀTheꢀ
withꢀrespectꢀtoꢀtheꢀotherꢀcatalysts.ꢀTheꢀCO ‐TPDꢀprofileꢀofꢀcat‐
2
3
totalꢀporeꢀvolumesꢀfellꢀfromꢀ0.3ꢀtoꢀ0.25ꢀcm /gꢀforꢀcatalystꢀAꢀandꢀ
alystꢀ Cꢀ showsꢀ thatꢀ byꢀ introducingꢀ theꢀ MgOꢀ speciesꢀ intoꢀ theꢀ
poresꢀofꢀcatalystꢀB,ꢀanꢀincreaseꢀinꢀbasicityꢀwasꢀobserved,ꢀbutꢀ
theꢀconcentrationꢀofꢀtheꢀbasicꢀsitesꢀremainedꢀconstant.ꢀ ꢀ
Forꢀ catalystꢀ C,ꢀ acrylonitrileꢀ conversionꢀ decreasedꢀ withꢀ anꢀ
increasingꢀnumberꢀofꢀcarbonsꢀinꢀtheꢀmoleculeꢀfromꢀmethanolꢀtoꢀ
butanol,ꢀinꢀlineꢀwithꢀtheꢀrelativeꢀalcoholꢀacidities.ꢀTheꢀeaseꢀofꢀ
protonꢀ abstractionꢀ withꢀ aꢀ baseꢀ catalystꢀ dependsꢀ onꢀ alcoholꢀ
acidity,ꢀ implyingꢀ thatꢀ aꢀ higherꢀ acidityꢀ wasꢀ associatedꢀ withꢀ
higherꢀ conversionꢀ levels.ꢀ Withꢀ catalystꢀ B,ꢀ noꢀ productsꢀ wereꢀ
foundꢀ fromꢀ attemptsꢀ toꢀ affectꢀ theꢀ cyanoethylationꢀ ofꢀ phenolꢀ
andꢀanilineꢀwhenꢀtheꢀreactionsꢀwereꢀcarriedꢀoutꢀatꢀroomꢀtem‐
perature.ꢀAcceptableꢀconversionsꢀwereꢀachievedꢀwithꢀphenolꢀinꢀ
theꢀ presenceꢀ ofꢀ catalystꢀ Cꢀ underꢀ reflux,ꢀ butꢀ anilineꢀ wasꢀ stillꢀ
unreactiveꢀunderꢀtheseꢀconditions.ꢀ
3
toꢀ 0.02ꢀ cm /gꢀ forꢀ catalystꢀ B,ꢀ whichꢀ confirmsꢀ theꢀ presenceꢀ ofꢀ
moreꢀbasicꢀsitesꢀonꢀtheꢀinternalꢀandꢀexternalꢀsurfaceꢀofꢀcatalystꢀ
BꢀandꢀtheꢀphaseꢀtransformationꢀofꢀzeoliteꢀYꢀtoꢀpollucite.ꢀInꢀcat‐
Cs+
RO CH2 CH2 CN
O
O
ROH
O
Si
Al
RO
HC C
Mechanism 1
N
H
O
H2C
RO
Cs+
Al
H
O
O
Cs+
Si
O
O
HC C
N
HC
O
Si
Al
H2C CH CN
H
O
Cs+
Theꢀadditionꢀofꢀaminesꢀtoꢀα,β‐unsaturatedꢀcompoundsꢀhasꢀ
O
O
RO
Si
Al
1
0
8
6
4
2
0
Catalyst A
Catalyst B
Catalyst C
Catalyst D
Cs+
Al
O
O
H2C CH CN
O
Si
HN CH2 CH2 CN
Mechanism 2
HC C
N
H
HC C
H2C
N
N
H2C
Cs+
Al
H
Cs+
O
O
O
O
O
O
Si
Si
Al
H N
0
200
400
600
800
1000
2
o
Temperature ( C)
Schemeꢀ2.ꢀAꢀplausibleꢀmechanismꢀforꢀtheꢀcyanoethylationꢀofꢀalcohols
andꢀaminesꢀoverꢀtheꢀcatalysts.ꢀ
Fig.ꢀ2.ꢀTPDꢀprofilesꢀofꢀCO
2
ꢀadsorbedꢀonꢀtheꢀcatalysts.ꢀ

ꢀ
SaraꢀZamanianꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ35ꢀ(2014)ꢀ264–269ꢀ
beenꢀextensivelyꢀstudiedꢀ[45,46],ꢀbutꢀanilineꢀhasꢀbeenꢀlessꢀusedꢀ
asꢀ theꢀ substrateꢀ inꢀ theꢀ reactionꢀ withꢀ α,β‐unsaturatedꢀ com‐
poundsꢀ [47,48].ꢀ Homogenousꢀ catalystsꢀ andꢀ someꢀ Lewisꢀ acidꢀ
catalystsꢀhaveꢀbeenꢀusedꢀforꢀthisꢀtypeꢀofꢀreaction,ꢀgivingꢀyieldsꢀ
inꢀ theꢀ rangeꢀ 33%–50%ꢀ [49,50],ꢀ butꢀ heterogeneousꢀ systemsꢀ
basedꢀonꢀzeolitesꢀhaveꢀattractedꢀmuchꢀlessꢀattention.ꢀOurꢀpre‐
paredꢀ zeolite‐basedꢀ catalystsꢀ showedꢀ conversionsꢀ upꢀ toꢀ 90%ꢀ
forꢀtheꢀcyanoethylationꢀreactionꢀwithꢀaniline.ꢀ ꢀ
Tableꢀ3ꢀ
Conversionꢀ (%)ꢀ ofꢀ acrylonitrileꢀ inꢀ theꢀ presenceꢀ ofꢀ catalystꢀ Cꢀ underꢀ
microwaveꢀirradiationꢀforꢀdifferentꢀreactionꢀdurationꢀandꢀmicrowaveꢀ
powerꢀlevel.ꢀ
Powerꢀ ꢀ
W)ꢀ
Methanolꢀ
5ꢀmin 15ꢀmin
Ethanolꢀ
ꢀ
Propanolꢀ
(
5ꢀminꢀ 15ꢀminꢀ ꢀ 5ꢀmin 15ꢀmin
9
6
3
00ꢀ
00ꢀ
00ꢀ
83ꢀ
47ꢀ
13ꢀ
98ꢀ
78ꢀ
42ꢀ
34ꢀ
12ꢀ
ꢀ 0ꢀ
77ꢀ
38ꢀ
23ꢀ
ꢀ
ꢀ
ꢀ
0ꢀ
0ꢀ
0ꢀ
0ꢀ
0ꢀ
0ꢀ
Accordingꢀtoꢀmechanismꢀ1ꢀ(Schemeꢀ2),ꢀgoodꢀreactivityꢀwithꢀ
phenolꢀneedsꢀhighꢀbasicity.ꢀTheꢀlowꢀsurfaceꢀareaꢀandꢀlowꢀtotalꢀ
poreꢀvolumeꢀofꢀcatalystꢀCꢀconfirmedꢀaꢀhighꢀlevelꢀofꢀmagnesiumꢀ
oxideꢀloadingꢀintoꢀtheꢀ catalystꢀ poresꢀandꢀonꢀitsꢀsurface.ꢀ Newꢀ
peaksꢀappearingꢀatꢀ2θꢀ=ꢀ43.1°ꢀinꢀtheꢀXRDꢀpatternsꢀofꢀcatalystꢀCꢀ
ꢀ
powerꢀ andꢀ irradiationꢀ timeꢀ mightꢀ improveꢀ theꢀ conversions.ꢀ
Theꢀdielectricꢀconstantꢀ(є)ꢀofꢀmethanol,ꢀethanol,ꢀandꢀpropanolꢀ
wereꢀ extractedꢀ fromꢀ theꢀ Dortmundꢀ Dataꢀ Bankꢀ (www.ddbst.ꢀ
com/en/EED/PCP/DEC_C95.php).ꢀ
Theꢀ higherꢀ dielectricꢀ constantꢀ ofꢀ methanolꢀ (єꢀ =ꢀ 32.7)ꢀ inꢀ
comparisonꢀ withꢀ ethanolꢀ (єꢀ =ꢀ 24.3)ꢀ andꢀ propanolꢀ (єꢀ =ꢀ 20.1)ꢀ
leadsꢀtoꢀaꢀhigherꢀreactivityꢀunderꢀmicrowaveꢀirradiation.ꢀ
(
Fig.ꢀ 1(b))ꢀ indicateꢀ theꢀ existenceꢀ ofꢀ magnesiumꢀ oxideꢀ inꢀ theꢀ
framework.ꢀ
Interestingly,ꢀcatalystꢀD,ꢀwhichꢀhadꢀnoꢀactivityꢀforꢀcyanoeth‐
ylationꢀofꢀalcohols,ꢀshowedꢀaꢀlowꢀconversionꢀatꢀroomꢀtempera‐
tureꢀ andꢀ aꢀ veryꢀ highꢀ conversionꢀ underꢀ refluxꢀ conditionsꢀ forꢀ
aniline.ꢀ Inꢀ thisꢀ case,ꢀ precipitatedꢀ Mg(OH)2ꢀ couldꢀ increaseꢀ theꢀ
basicityꢀofꢀtheꢀcatalyst,ꢀbutꢀtheꢀbasicityꢀpresentꢀisꢀinsufficientꢀtoꢀ
catalyzeꢀ theꢀ cyanoethylationꢀ ofꢀ alcohols.ꢀ Catalystꢀ Dꢀ wasꢀ theꢀ
bestꢀ sampleꢀ forꢀ cyanoethylationꢀ ofꢀ theꢀ lessꢀ reactiveꢀ aniline,ꢀ
withꢀconversionsꢀofꢀupꢀtoꢀ90%.ꢀItꢀseemsꢀthatꢀcatalystꢀDꢀshowedꢀ
someꢀsimilarityꢀinꢀreactivityꢀforꢀcyanoethylationꢀwithꢀcatalystꢀ
A.ꢀXRDꢀpatternsꢀofꢀcatalystsꢀAꢀandꢀDꢀconfirmedꢀthatꢀtheꢀstruc‐
tureꢀofꢀzeoliteꢀYꢀwasꢀpreserved.ꢀNewꢀpeaksꢀatꢀ2θꢀ=ꢀ25.7°ꢀandꢀ
4.ꢀ ꢀ Conclusions
CesiumꢀandꢀmagnesiumꢀmodifiedꢀzeoliteꢀYꢀareꢀactiveꢀcata‐
lystsꢀforꢀtheꢀcyanoethylationꢀofꢀaliphaticꢀandꢀaromaticꢀalcoholsꢀ
andꢀ amines.ꢀ Modifiedꢀ heterogeneousꢀ basicꢀ solidsꢀ withꢀ bothꢀ
cesiumꢀ andꢀ magnesiumꢀ showedꢀ higherꢀ activityꢀ thanꢀ singlyꢀ
ion‐exchangedꢀcatalysts.ꢀOwingꢀtoꢀtheꢀstronglyꢀbasicꢀconditionsꢀ
obtainedꢀbyꢀtheꢀimpregnationꢀprocedureꢀleadingꢀtoꢀcatalystꢀB,ꢀ
theꢀtransformationꢀofꢀzeoliteꢀYꢀintoꢀaꢀpollucite‐typeꢀphaseꢀoc‐
curred,ꢀandꢀtheꢀsolidꢀshowedꢀgoodꢀactivityꢀinꢀtheꢀcyanoethyla‐
tionꢀofꢀaliphaticꢀalcohols.ꢀTheꢀactivitiesꢀofꢀtheꢀcatalysts,ꢀunlikeꢀ
theꢀotherꢀbasicꢀsolids,ꢀwereꢀscarcelyꢀaffectedꢀbyꢀtheꢀpresenceꢀofꢀ
airꢀ orꢀ moisture.ꢀ Itꢀ seemsꢀ thatꢀ theꢀ cyanoethylationꢀ ofꢀ aniline,ꢀ
whichꢀfollowedꢀaꢀdifferentꢀmechanism,ꢀwasꢀwellꢀcatalyzedꢀbyꢀ
catalystsꢀAꢀandꢀD.ꢀTheꢀSEMꢀimagesꢀofꢀallꢀcatalystsꢀshowedꢀpar‐
ticlesꢀwithꢀsizesꢀ<ꢀ40ꢀnm.ꢀUsingꢀmicrowaveꢀirradiation,ꢀtheꢀre‐
actionꢀtimesꢀofꢀacrylonitrileꢀwithꢀlinearꢀalcoholsꢀwereꢀreducedꢀ
toꢀ15ꢀminꢀwithꢀgoodꢀyieldsꢀinꢀtheꢀpresenceꢀofꢀbasicꢀheteroge‐
neousꢀcatalysts.ꢀ
42.5°ꢀinꢀtheꢀXRDꢀpatternꢀofꢀcatalystꢀA,ꢀinꢀcomparisonꢀwithꢀzeo‐
liteꢀ Y,ꢀ showedꢀ theꢀ presenceꢀ ofꢀ cesiumꢀ inꢀ catalystꢀ A.ꢀ Theꢀ lowꢀ
surfaceꢀareaꢀofꢀcatalystꢀD,ꢀrelatedꢀtoꢀtheꢀpresenceꢀMgOꢀinꢀtheꢀ
pores,ꢀ exhibitedꢀ confirmatoryꢀ newꢀ peaksꢀ atꢀ 2θꢀ =ꢀ 35.8°ꢀ (Fig.ꢀ
1(a)).ꢀ
SEMꢀimagesꢀofꢀallꢀcatalystsꢀstudiedꢀshowedꢀtheꢀpresenceꢀofꢀ
nanoparticlesꢀforꢀallꢀsamplesꢀ(Fig.ꢀ3).ꢀTheꢀhighestꢀconversionꢀofꢀ
acrylonitrileꢀ inꢀ reactingꢀ withꢀ linearꢀ alcoholsꢀ wasꢀ observedꢀ inꢀ
theꢀ presenceꢀ ofꢀ catalystsꢀ Bꢀ orꢀ Cꢀ underꢀ refluxꢀ conditions.ꢀ Toꢀ
reduceꢀ theꢀ reactionꢀ timesꢀ further,ꢀ theꢀ microwave‐assistedꢀ
techniqueꢀ wasꢀ employedꢀ forꢀ theꢀ reactionꢀ inꢀ theꢀ presenceꢀ ofꢀ
catalystꢀC.ꢀMethanolꢀandꢀethanolꢀreactedꢀwithꢀacrylonitrileꢀwithꢀ
goodꢀ yieldsꢀ underꢀ microwaveꢀ irradiationꢀ (Tableꢀ 3),ꢀ butꢀ noꢀ
productsꢀwereꢀ foundꢀ forꢀpropanol.ꢀIncreasingꢀtheꢀmicrowaveꢀ
Acknowledgments
Theꢀ authorsꢀ gratefullyꢀ acknowledgeꢀ theꢀ financialꢀ supportꢀ
fromꢀtheꢀUniversityꢀofꢀTehran.ꢀ
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