Synthesis of homoallylic alcohols by allylation of aldehydes and ketones catalysed by a mesoporous material (mcm-41)-supported cyano palladium complex

Article abstract of DOI:10.3184/030823409X460911

A variety of homoallylic alcohols has been conveniently synthesised in good to high yields by the allylation of aldehydes and ketones with allylic chlorides catalysed by an MCM-41-supported cyano palladium complex in DMF using SnCl2 as reducing agent. This polymeric palladium complex can be recovered and reused with some loss of activity.

Full text of DOI:10.3184/030823409X460911

3
66ꢀ RESEARCH PAPER
JUNE,ꢀ366–369ꢀ
JOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2009
Synthesis of homoallylic alcohols by allylation of aldehydes and ketones
catalysed by a mesoporous material (MCM-41)-supported cyano
palladium complex
a,b
a
a,
Fang Yao , Bin Huang and Mingzhong Cai *
a
Department of Chemistry, Jiangxi Normal University, Nanchang 330022, P. R. China
bDepartment of Chemistry and Pharmaceutical Engineering, West Branch of Zhejiang University of Technology, Quzhou 324000,
P. R. China
Aꢀ varietyꢀ ofꢀ homoallylicꢀ alcoholsꢀ hasꢀ beenꢀ convenientlyꢀ synthesisedꢀ inꢀ goodꢀ toꢀ highꢀ yieldsꢀ byꢀ theꢀ allylationꢀ ofꢀ
aldehydesꢀandꢀketonesꢀwithꢀallylicꢀchloridesꢀcatalysedꢀbyꢀanꢀMCM-41-supportedꢀcyanoꢀpalladiumꢀcomplexꢀinꢀDMFꢀ
usingꢀSnCl ꢀasꢀreducingꢀagent.ꢀThisꢀpolymericꢀpalladiumꢀcomplexꢀcanꢀbeꢀrecoveredꢀandꢀreusedꢀwithꢀsomeꢀlossꢀofꢀ
2
activity.
Keywords: homoallylicꢀalcohol,ꢀallylation,ꢀsupportedꢀcatalyst,ꢀpalladium,ꢀMCM-41
Homoallylicꢀ alcoholsꢀ areꢀ versatileꢀ intermediatesꢀ inꢀ theꢀ
preparationꢀofꢀsomeꢀmaterials,ꢀnaturalꢀproducts,ꢀandꢀbioactiveꢀ
compounds. The utilisation of π-allylpalladium complexes
as nucleophiles has been exemplified by the transformation
highꢀactivityꢀandꢀgoodꢀreusability.ꢀToꢀdate,ꢀaꢀfewꢀpalladiumꢀ
complexesꢀ onꢀ functionalisedꢀ MCM-41ꢀ supportꢀ haveꢀ beenꢀ
2
6-29
preparedꢀ andꢀ usedꢀ inꢀ organicꢀ reactions.
ꢀ However,ꢀ toꢀ
theꢀbestꢀofꢀourꢀknowledge,ꢀthereꢀhasꢀbeenꢀnoꢀgeneralꢀstudyꢀ
ofꢀ carbonylꢀ allylationꢀ reactionsꢀ catalysedꢀ byꢀ anꢀ MCM-41-
supportedꢀ palladiumꢀ complexꢀ catalystꢀ describedꢀ toꢀ date.ꢀ Inꢀ
thisꢀpaper,ꢀweꢀreportꢀtheꢀsynthesisꢀofꢀanꢀMCM-41-supportedꢀ
cyanoꢀpalladiumꢀcomplexꢀcatalystꢀ[MCM-41-CN-Pd(II)]ꢀandꢀ
itsꢀcatalyticꢀbehaviourꢀinꢀtheꢀcarbonylꢀallylationꢀreactionsꢀofꢀ
aldehydesꢀorꢀketones.
ofꢀallylicꢀesters,1 ꢀallylicꢀalcohols ꢀandꢀallylicꢀchlorides
-3
4-7
8-10
ꢀ
withꢀ aꢀ palladium(0)ꢀ catalystꢀ intoꢀ allylicꢀ metalꢀ compounds,ꢀ
whichꢀ haveꢀ thenꢀ beenꢀ appliedꢀ toꢀ carbonylꢀ allylationꢀ toꢀ
prepareꢀhomoallylicꢀalcohols.ꢀSomeꢀotherꢀcarbonylꢀallylationꢀ
reactionsꢀ ofꢀ aldehydesꢀ withꢀ differentꢀ mechanismsꢀ canꢀ alsoꢀ
affordꢀhomoallylicꢀalcohols.1
1-13ꢀ
Masuyamaꢀet al. ꢀreportedꢀ
14
thatꢀ stannousꢀ chlorideꢀ isꢀ moreꢀ effectiveꢀ asꢀ aꢀ reducingꢀ
agentꢀ thanꢀ otherꢀ low-valentꢀ metalsꢀ inꢀ palladium-catalysedꢀ
carbonylꢀallylationꢀbyꢀallylicꢀesters.ꢀHowever,ꢀinꢀmostꢀcases,ꢀ
homogeneousꢀ palladiumꢀ complexesꢀ suchꢀ asꢀ Pd(PPh ) ,ꢀ
Theꢀ startingꢀ MCM-41ꢀ wasꢀ easilyꢀ preparedꢀ accordingꢀ
3
0
toꢀ aꢀ reportedꢀ procedure. ꢀ Theꢀ MCM-41-supportedꢀ cyanoꢀ
palladiumꢀ complexꢀ catalystꢀ [MCM-41-CN-Pd(II)]ꢀ wasꢀ
convenientlyꢀ synthesisedꢀ fromꢀ commerciallyꢀ availableꢀ andꢀ
cheapꢀ g-cyanopropyltriethoxysilaneꢀ byꢀ immobilisationꢀ onꢀ
MCM-41,ꢀ followedꢀ byꢀ reactionꢀ withꢀ palladiumꢀ chlorideꢀ inꢀ
acetoneꢀ (Schemeꢀ 1).ꢀ Theꢀ XRDꢀ analysisꢀ ofꢀ MCM-41-CN-
Pd(II)ꢀindicatedꢀthat,ꢀinꢀadditionꢀtoꢀanꢀintenseꢀdiffractionꢀpeakꢀ
(100),ꢀtwoꢀhigherꢀorderꢀpeaksꢀwithꢀlowerꢀintensitiesꢀwereꢀalsoꢀ
detected,ꢀandꢀthereforeꢀtheꢀchemicalꢀbondingꢀprocedureꢀdidꢀ
notꢀdiminishꢀtheꢀstructuralꢀorderingꢀofꢀtheꢀMCM-41.ꢀNitrogenꢀ
adsorption studies demonstrated that a significant decrease in
poreꢀsizeꢀbyꢀvirtueꢀofꢀsilylationꢀofꢀtheꢀMCM-41ꢀchannelsꢀhadꢀ
occurred. Additionally, upon modification the surface area
andꢀporeꢀvolumeꢀclearlyꢀdecreased.ꢀTheseꢀresultsꢀareꢀinꢀgoodꢀ
agreement with the fact that the surface modification indeed
occurredꢀ insideꢀ theꢀ primaryꢀ mesoporesꢀ ofꢀ theꢀ MCM-41.ꢀ
Elementalꢀ analysesꢀ andꢀ X-rayꢀ photoelectronꢀ spectroscopyꢀ
3
4
Pd(PPh ) Cl ꢀ andꢀ Pd(PhCN) Cl ꢀ areꢀ usedꢀ forꢀ formationꢀ
3
2
2
2
2
of π-allylpalladium complexes. The amount of palladium
catalyst used is about 2 mol% of reactant and it is difficult to
recoverꢀitꢀfromꢀtheꢀproducts.ꢀCarbonylꢀallylationꢀofꢀaldehydesꢀ
catalysedꢀbyꢀhomogeneousꢀpalladiumꢀcomplexesꢀoffersꢀgoodꢀ
toꢀexcellentꢀyieldsꢀofꢀhomoallylicꢀalcohols,1 ꢀbutꢀtheꢀnon-
recoverableꢀ expensiveꢀ palladiumꢀ metalꢀ restrictsꢀ itsꢀ useꢀ inꢀ
industry.ꢀItꢀisꢀhighlyꢀdesirableꢀtoꢀdevelopꢀaꢀnewꢀrecoverableꢀ
andꢀreusableꢀcatalyticꢀsystemꢀwithꢀtheꢀsameꢀorꢀbetterꢀactivityꢀ
thanꢀtheꢀhomogeneousꢀsystem.
5,16
Theꢀ highꢀ costsꢀ ofꢀ transition-metalꢀ catalystsꢀ coupledꢀ withꢀ
toxicꢀ effectsꢀ associatedꢀ withꢀ manyꢀ transitionꢀ metalsꢀ hasꢀ
ledꢀtoꢀanꢀincreasedꢀinterestꢀinꢀimmobilisingꢀcatalystsꢀontoꢀaꢀ
support.ꢀThisꢀclassꢀofꢀsupportedꢀreagentsꢀcanꢀfacilitateꢀbothꢀ
the isolation and recycling of the catalysts by simple filtration,
(
XPS)ꢀwereꢀusedꢀtoꢀcharacteriseꢀtheꢀMCM-41-supportedꢀcyanoꢀ
thusꢀ providingꢀ anꢀ environmentally,ꢀ cleanerꢀ process.1
7,18
ꢀ
palladiumꢀcomplexꢀ[MCM-41-CN-Pd(II)].ꢀTheꢀnitrogenꢀandꢀ
palladiumꢀcontentꢀofꢀtheꢀMCM-41-CN-Pd(II)ꢀwasꢀdeterminedꢀ
Polymer-supportedꢀpalladiumꢀcatalystsꢀhaveꢀsuccessfullyꢀbeenꢀ
usedꢀforꢀaꢀvarietyꢀofꢀorganicꢀreactions.1 Studyꢀofꢀnewꢀtypesꢀ
ofꢀsupportedꢀpalladiumꢀcatalystsꢀwhichꢀmightꢀbeꢀsuitableꢀforꢀ
carbonylꢀallylationꢀofꢀaldehydesꢀorꢀketonesꢀhasꢀtheoreticalꢀandꢀ
practical significance. Recent developments on the mesoporous
materialꢀ MCM-41ꢀ providedꢀ aꢀ newꢀ possibleꢀ candidateꢀ forꢀ aꢀ
9,20ꢀ
-1
toꢀbeꢀ0.73ꢀandꢀ0.23ꢀmmol g,ꢀrespectively,ꢀandꢀtheꢀN:ꢀPdꢀmoleꢀ
ratioꢀofꢀthisꢀcomplexꢀwasꢀ3.17.ꢀTheꢀbindingꢀenergyꢀ(337.5ꢀeV)ꢀ
ofꢀPd3d5/2ꢀofꢀMCM-41-CN-Pd(II)ꢀwasꢀlowerꢀthanꢀtheꢀbindingꢀ
energyꢀ(338.3ꢀeV)ꢀofꢀPd3d5/2ꢀofꢀPdCl ꢀandꢀtheꢀbindingꢀenergyꢀ
2
(
400.2ꢀ eV)ꢀ ofꢀ N ꢀ ofꢀ MCM-41-CN-Pd(II)ꢀ wasꢀ higherꢀ thanꢀ
1s
21
solidꢀsupportꢀforꢀimmobilisationꢀofꢀhomogeneousꢀcatalysts. ꢀ
theꢀ bindingꢀ energyꢀ (399.5ꢀ eV)ꢀ ofꢀ N ꢀ ofꢀ MCM-41-CN.ꢀ
1
s
MCM-41ꢀhasꢀaꢀregularꢀporeꢀdiameterꢀofꢀca50 Å and a specific
TheseꢀresultsꢀsuggestꢀthatꢀaꢀcoordinationꢀbondꢀbetweenꢀNꢀandꢀ
PdꢀwasꢀformedꢀinꢀMCM-41-CN-Pd(II).
2ꢀ -1 22ꢀ
surfaceꢀareaꢀ>ꢀ700ꢀm g . Itsꢀporeꢀsizeꢀallowsꢀpassageꢀofꢀ
largeꢀmoleculesꢀsuchꢀasꢀorganicꢀreactantsꢀandꢀmetalꢀcomplexesꢀ
InꢀorderꢀtoꢀtestꢀtheꢀcatalyticꢀactivityꢀofꢀtheꢀMCM-41-CN-
Pd(II),ꢀtheꢀcarbonylꢀallylationꢀofꢀaldehydesꢀandꢀketonesꢀwithꢀ
allylicꢀchloridesꢀwasꢀinvestigatedꢀ(Schemeꢀ2).ꢀTheꢀreactionsꢀ
wereꢀ carriedꢀ outꢀ underꢀ conditionsꢀ similarꢀ toꢀ thoseꢀ usedꢀ inꢀ
theꢀ correspondingꢀ homogeneousꢀ reactions.ꢀ Theꢀ resultsꢀ areꢀ
summarisedꢀinꢀTableꢀ1.ꢀTheꢀinitialꢀexperimentalꢀwasꢀcarriedꢀ
outꢀ withꢀ benzaldehydeꢀ andꢀ allylꢀ chlorideꢀ usingꢀ 2ꢀ mol%ꢀ
23-25
throughꢀtheꢀporesꢀtoꢀreachꢀtheꢀsurfaceꢀofꢀtheꢀchannel.
ꢀItꢀisꢀ
generallyꢀ believedꢀ thatꢀ highꢀ surfaceꢀ areaꢀ ofꢀ heterogeneousꢀ
catalystsꢀresultsꢀinꢀhighꢀcatalyticꢀactivity.ꢀConsideringꢀtheꢀfactꢀ
thatꢀtheꢀMCM-41ꢀsupportꢀhasꢀanꢀextremelyꢀhighꢀsurfaceꢀareaꢀ
andꢀtheꢀcatalyticꢀpalladiumꢀspeciesꢀisꢀanchoredꢀonꢀtheꢀinnerꢀ
surfaceꢀofꢀtheꢀmesoporeꢀofꢀtheꢀMCM-41ꢀsupport,ꢀweꢀexpectꢀ
thatꢀ anꢀ MCM-41-supportedꢀ palladiumꢀ catalystꢀ willꢀ exhibitꢀ
MCM-41-CN-Pd(II)ꢀ asꢀ catalystꢀ andꢀ 1.5ꢀ equiv.ꢀ SnCl ꢀ asꢀ
2
reducingꢀagentꢀinꢀDMF.ꢀTheꢀallylationꢀreactionꢀatꢀ25°Cꢀrequiredꢀ
*
ꢀCorrespondent.ꢀE-mail:ꢀcaimzhong@163.com
4
8ꢀhꢀtoꢀgoꢀtoꢀcompletionꢀandꢀ1-phenylbut-3-en-1-olꢀ(3a)ꢀwasꢀ

JOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2009ꢀ 367
OEt
O
OH
o
1
2
.Toluene, 100 C, 24 h
SiCH CH CH CN
2 2 2
MCM-41 OH + (EtO) SiCH CH CH CN
MCM-41
O
3
2
2
2
. Me SiCl, rt, 24 h
3
OH
OSiMe3
MCM-41-CN
OEt
O
O
PdCl , CH COCH
3
2
3
SiCH CH CH CN] PdCl
2
2
2
2
2
MCM-41
reflux, 72 h
OSiMe3
MCM-41-CN-Pd(II)
Scheme 1
obtainedꢀinꢀ86%ꢀyield.ꢀWhenꢀ2ꢀmol%ꢀPdCl (PhCN) wasꢀused,ꢀ
correspondingꢀhomoallylicꢀalcoholsꢀinꢀgoodꢀtoꢀhighꢀyieldsꢀafterꢀ
48ꢀh.ꢀTheꢀreactivityꢀofꢀketonesꢀwasꢀlowerꢀthanꢀthatꢀofꢀaldehydes,ꢀ
butꢀtheꢀallylationꢀreactionsꢀofꢀketonesꢀwithꢀallylꢀchlorideꢀcouldꢀ
alsoꢀ proceedꢀ atꢀ 40 ꢀ° Cꢀ andꢀ theꢀ correspondingꢀ homoallylicꢀ
alcoholsꢀwereꢀobtainedꢀinꢀgoodꢀyieldsꢀafterꢀ48ꢀhꢀ(entriesꢀ12–14).ꢀ
Unfortunately,ꢀtheꢀallylationꢀreactionꢀofꢀketonesꢀwithꢀmethallylꢀ
chlorideꢀdidꢀnotꢀoccurꢀatꢀallꢀatꢀ40ꢀorꢀ60 ꢀ° C.
Inꢀ conclusion,ꢀ weꢀ haveꢀ describedꢀ aꢀ MCM-41-supportedꢀ
cyanoꢀpalladiumꢀcomplexꢀcatalystꢀwhoseꢀpreparationꢀisꢀsimpleꢀ
andꢀconvenient.ꢀThisꢀcomplexꢀhasꢀnotꢀonlyꢀhighꢀactivityꢀforꢀ
allylationꢀofꢀaldehydesꢀandꢀketonesꢀwithꢀallylicꢀchlorides,ꢀbutꢀ
alsoꢀoffersꢀpracticalꢀadvantagesꢀsuchꢀasꢀeasyꢀhandling,ꢀeasyꢀ
separationꢀfromꢀtheꢀproductsꢀandꢀreuseꢀforꢀtheꢀpreparationꢀofꢀ
homoallylicꢀalcohols.
2
2ꢀ
1
-phenylbut-3-en-1-olꢀwasꢀobtainedꢀinꢀ81%ꢀyieldꢀunderꢀtheꢀ
sameꢀconditions.ꢀThisꢀpolymericꢀpalladiumꢀcatalystꢀnotꢀonlyꢀ
hasꢀhighꢀcatalyticꢀactivityꢀinꢀtheꢀallylationꢀofꢀbenzaldehyde,ꢀ
but also can be recovered by simple filtration. The activity
ofꢀ theꢀ recoveredꢀ catalystꢀ wasꢀ testedꢀ forꢀ theꢀ allylationꢀ ofꢀ
benzaldehyde with allyl chloride for five recycles and it was
foundꢀthatꢀ1-phenylbut-3-en-1-olꢀ(3a)ꢀwasꢀformedꢀinꢀ85,ꢀ83,ꢀ
7
9,ꢀ72ꢀandꢀ61%ꢀyield,ꢀrespectively.
AsꢀshownꢀinꢀTableꢀ1,ꢀtheꢀallylationꢀreactionꢀcanꢀtolerateꢀaꢀ
rangeꢀ ofꢀ functionalꢀ groupsꢀ onꢀ theꢀ aromaticꢀ aldehydes;ꢀ bothꢀ
stronglyꢀ electronꢀ donatingꢀ andꢀ withdrawingꢀ substituentsꢀ canꢀ
beꢀpresent.ꢀTheꢀallylationꢀofꢀvariousꢀaromaticꢀaldehydesꢀwithꢀ
allylꢀ chlorideꢀ hasꢀ beenꢀ achievedꢀ withꢀ goodꢀ toꢀ highꢀ yields.ꢀ
Theꢀ allylationꢀ ofꢀ aliphaticꢀ aldehydesꢀ withꢀ allylꢀ chlorideꢀ
alsoꢀ proceededꢀ smoothlyꢀ underꢀ theꢀ sameꢀ conditionsꢀ andꢀ theꢀ
correspondingꢀ homoallylicꢀ alcoholsꢀ wereꢀ obtainedꢀ inꢀ goodꢀ
yields.ꢀ Theꢀ allylationꢀ ofꢀ aldehydesꢀ withꢀ methallylꢀ chlorideꢀ
wasꢀ slowꢀ atꢀ 25 ꢀ° Cꢀ underꢀ theꢀ sameꢀ conditionsꢀ andꢀ onlyꢀ traceꢀ
amountsꢀ ofꢀ productsꢀ wereꢀ formedꢀ afterꢀ 48ꢀ h.ꢀ However,ꢀ theꢀ
allylationꢀreactionsꢀcouldꢀproceedꢀsmoothlyꢀatꢀ40 ꢀ° Cꢀtoꢀgiveꢀtheꢀ
Experimental
IRꢀ spectraꢀ wereꢀ obtainedꢀ usingꢀ aꢀ Perkin-Elmerꢀ 683ꢀ instrument.ꢀ
1
HꢀNMRꢀspectraꢀwereꢀrecordedꢀonꢀaꢀBrukerꢀAC-P300ꢀ(300ꢀMHz)ꢀ
spectrometerꢀwithꢀTMSꢀasꢀanꢀinternalꢀstandardꢀusingꢀCDCl asꢀtheꢀ
3
ꢀ
13
solvent.ꢀ Cꢀ NMRꢀ spectraꢀ wereꢀ recordedꢀ onꢀ aꢀ Brukerꢀ AC-P300ꢀ
75ꢀMHz)ꢀspectrometerꢀusingꢀCDCl asꢀtheꢀsolvent.ꢀMicroanalysesꢀ
(
3
ꢀ
wereꢀ obtainedꢀ usingꢀ aꢀ Perkin-Elmerꢀ 240ꢀ elementalꢀ analyser.ꢀ DMFꢀ
Table 1ꢀ AllylationꢀofꢀaldehydesꢀandꢀketonesꢀcatalysedꢀbyꢀMCM-41-CN-Pd(II)a
1
2
b
Entryꢀ
Rꢀ
R ꢀ
R ꢀ
Temp./°Cꢀ
Productꢀ
Yieldꢀ /%
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
1ꢀ
2ꢀ
3ꢀ
4ꢀ
5ꢀ
6ꢀ
7ꢀ
8ꢀ
9ꢀ
Hꢀ
CH3ꢀ
Hꢀ
CH3ꢀ
Hꢀ
Hꢀ
CH3ꢀ
CH3ꢀ
Hꢀ
Hꢀ
CH3ꢀ
Hꢀ
Hꢀ
Hꢀ
Phꢀ
Hꢀ
Hꢀ
25ꢀ
40ꢀ
25ꢀ
40ꢀ
25ꢀ
25ꢀ
40ꢀ
40ꢀ
25ꢀ
25ꢀ
40ꢀ
40ꢀ
40ꢀ
40ꢀ
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
3m
3nꢀ
86
82
90
87
85
74
77
84
89
81
79
73
81
85
Phꢀ
4-ClC H ꢀ
Hꢀ
6
4
4-ClC H ꢀ
Hꢀ
6
4
4-CH OC H ꢀ
Hꢀ
3
6
4
4-O NC H ꢀ
Hꢀ
2
6
4
2-HOC H ꢀ
Hꢀ
6
4
3,4-CH O C H ꢀ
Hꢀ
2
2
6
3
3,4-CH O C H ꢀ
Hꢀ
2
2
6
3
ꢀ
n-C H ꢀ
n-C H13ꢀ
Hꢀ
3
7
ꢀ
Hꢀ
6
ꢀ
Phꢀ
Phꢀ
—(CH ) —ꢀ
CH3ꢀ
ꢀ
CH Clꢀ
2
ꢀ
—ꢀ
2
5
a
Reactionsꢀwereꢀcarriedꢀoutꢀwithꢀ1ꢀmmolꢀofꢀaldehydeꢀorꢀketone,ꢀ2ꢀmmolꢀofꢀallylicꢀchloride,ꢀ1.5ꢀmmolꢀofꢀSnCl ,ꢀ0.02ꢀmmolꢀofꢀ
2
palladiumꢀcatalystꢀinꢀ3ꢀmlꢀofꢀDMFꢀforꢀ48ꢀh.
b
Yieldꢀofꢀisolatedꢀproductꢀ3ꢀbasedꢀonꢀtheꢀaldehydeꢀorꢀketoneꢀused.
R
O
R
OH
Catalyst MCM-41-CN-Pd(II)
Cl
+
R2
o
R1
R2
SnCl , DMF, 25-40 C
2
R1
1
2
3
Scheme 2

3
68ꢀ JOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2009
wasꢀdistilledꢀbeforeꢀuse,ꢀotherꢀreagentsꢀwereꢀusedꢀasꢀreceivedꢀwithoutꢀ
further purification.
Preparation of MCM-41-CN: Aꢀ solutionꢀ ofꢀ g-cyanopropyl-
triethoxysilaneꢀ(1.73ꢀg,ꢀ7.5ꢀmmol)ꢀinꢀdryꢀchloroformꢀ(12ꢀmL)ꢀwasꢀ
addedꢀtoꢀaꢀsuspensionꢀofꢀtheꢀmesoporousꢀsupportꢀMCM-41ꢀ(2.20ꢀg)ꢀ
inꢀdryꢀtolueneꢀ(120ꢀmL).ꢀTheꢀmixtureꢀwasꢀstirredꢀforꢀ24ꢀhꢀatꢀ100ꢀ°C.ꢀ
1-(2-Hydroxyphenyl)-3-methylbut-3-en-1-olꢀ (3g): Oil. IR (film):ꢀ
-1
nꢀ(cm )ꢀ3396,ꢀ3070,ꢀ3026,ꢀ1638,ꢀ1601,ꢀ1495,ꢀ1443,ꢀ1200,ꢀ1030,ꢀ696;ꢀ
1
HꢀNMRꢀ(300ꢀMHz,ꢀCDCl ):ꢀdꢀ8.09ꢀ(s,ꢀ1H),ꢀ7.19–6.82ꢀ(m,ꢀ4H),ꢀ5.01ꢀ
3
(t,ꢀJꢀ=ꢀ1.6ꢀHz,ꢀ1H),ꢀ4.97–4.93ꢀ(m,ꢀ1H),ꢀ4.91ꢀ(d,ꢀJꢀ=ꢀ0.8ꢀHz,ꢀ1H),ꢀ
1
3
2.77ꢀ(s,ꢀ1H),ꢀ2.65–2.59ꢀ(m,ꢀ1H),ꢀ2.48–2.43ꢀ(m,ꢀ1H),ꢀ1.83ꢀ(s,ꢀ3H);ꢀ Cꢀ
NMRꢀ(75ꢀMHz,ꢀCDCl ):ꢀdꢀ155.7,ꢀ141.8,ꢀ129.0,ꢀ127.0,ꢀ126.2,ꢀ119.8,ꢀ
3
Then the solid was filtered off and washed by CHCl ꢀ(2ꢀ¥ꢀ20ꢀmL),ꢀ
117.3,ꢀ115.0,ꢀ72.9,ꢀ46.4,ꢀ22.2;ꢀAnal.ꢀCalcdꢀforꢀC H O :ꢀC,ꢀ74.16;ꢀH,ꢀ
3
11 14
2
andꢀdriedꢀunderꢀreducedꢀpressureꢀatꢀ160ꢀ°Cꢀforꢀ5ꢀh.ꢀTheꢀdriedꢀwhiteꢀ
7.87.ꢀFound:ꢀC,ꢀ73.89;ꢀH,ꢀ7.74%.
1-(3,4-Methylenedioxyphenyl)-3-methylbut-3-en-1-olꢀ (3h):ꢀ Oil.ꢀ
solidꢀwasꢀsoakedꢀinꢀaꢀsolutionꢀofꢀMe SiClꢀ(3.05ꢀg,ꢀ28ꢀmmol)ꢀinꢀdryꢀ
3
-1
tolueneꢀ(100ꢀmL)ꢀatꢀroomꢀtemperatureꢀunderꢀstirringꢀforꢀ24ꢀh.ꢀThenꢀ
the solid was filtered, washed with acetone (3 ¥ꢀ20ꢀmL)ꢀandꢀdiethylꢀ
etherꢀ(3ꢀ¥ꢀ20ꢀmL),ꢀandꢀdriedꢀunderꢀreducedꢀpressureꢀatꢀ160ꢀ°Cꢀforꢀ
IR (film): nꢀ(cm )ꢀ3365,ꢀ3060,ꢀ2881,ꢀ1630,ꢀ1601,ꢀ1489,ꢀ1440,ꢀ1375,ꢀ
1
1243,ꢀ 1040,ꢀ 990,ꢀ 870;ꢀ Hꢀ NMRꢀ (300ꢀ MHz,ꢀ CDCl ):ꢀ dꢀ 6.88ꢀ (d,ꢀ
3
Jꢀ=ꢀ1.6ꢀHz,ꢀ1H),ꢀ6.82–6.75ꢀ(m,ꢀ2H),ꢀ5.94ꢀ(s,ꢀ2H),ꢀ4.90ꢀ(d,ꢀJꢀ=ꢀ1.6ꢀHz,ꢀ
5
ꢀhꢀtoꢀobtainꢀ2.87ꢀgꢀofꢀhybridꢀmaterialꢀMCM-41-CN.ꢀTheꢀnitrogenꢀ
1H),ꢀ4.83ꢀ(s,ꢀ1H),ꢀ4.73–4.70ꢀ(m,ꢀ1H),ꢀ2.44–2.33ꢀ(m,ꢀ2H),ꢀ2.15ꢀ(br,ꢀ
-1
13
contentꢀwasꢀfoundꢀtoꢀbeꢀ0.93ꢀmmol gꢀbyꢀelementalꢀanalysis.
1H),ꢀ1.78ꢀ(s,ꢀ3H);ꢀ CꢀNMRꢀ(75ꢀMHz,ꢀCDCl )ꢀd:ꢀ147.7,ꢀ146.9,ꢀ142.3,ꢀ
3
Synthesis of MCM-41-CN-Pd(II): ToꢀaꢀsolutionꢀofꢀPdCl ꢀ(0.135ꢀg)ꢀ
138.2,ꢀ119.2,ꢀ114.0,ꢀ108.1,ꢀ106.4,ꢀ101.0,ꢀ71.4,ꢀ48.3,ꢀ22.4;ꢀAnal.ꢀCalcdꢀ
forꢀC H O :ꢀC,ꢀ69.90;ꢀH,ꢀ6.80.ꢀFound:ꢀC,ꢀ69.71;ꢀH,ꢀ6.62%.
1-(3,4-Methylenedioxyphenyl)but-3-en-1-olꢀ (3i): Oil. IR (film):ꢀ
2
inꢀacetoneꢀ(50ꢀmL)ꢀwasꢀaddedꢀMCM-41-CNꢀ(2.50ꢀg).ꢀTheꢀmixtureꢀ
was refluxed under an argon atmosphere for 72 h. The product was
allowed to cool and then filtered off. The resulting brown powder
wasꢀwashedꢀwithꢀdistilledꢀwaterꢀ(3ꢀ¥ꢀ10ꢀmL)ꢀandꢀacetoneꢀ(3ꢀ¥ꢀ10ꢀ
mL)ꢀandꢀthenꢀdriedꢀunderꢀreducedꢀpressureꢀtoꢀaffordꢀ2.47ꢀgꢀofꢀMCM-
1
2
14
3
3
1
-1
nꢀ (cm )ꢀ 3360,ꢀ 3070,ꢀ 3024,ꢀ 2880,ꢀ 1640,ꢀ 1600,ꢀ 1490,ꢀ 1440,ꢀ 1240,ꢀ
1
1030,ꢀ990,ꢀ870;ꢀ HꢀNMRꢀ(300ꢀMHz,ꢀCDCl ):ꢀdꢀ6.87ꢀ(d,ꢀJꢀ=ꢀ1.6ꢀHz,ꢀ
3
1H),ꢀ6.81–6.75ꢀ(m,ꢀ2H),ꢀ5.95ꢀ(s,ꢀ2H),ꢀ5.84–5.72ꢀ(m,ꢀ1H),ꢀ5.18–5.12ꢀ
4
0
1-CN-Pd(II).ꢀ Theꢀ nitrogenꢀ andꢀ palladiumꢀ contentꢀ wasꢀ 0.73ꢀ andꢀ
.23ꢀmmol g,ꢀrespectively.
General procedure for the allylation of aldehydes and ketones
(m,ꢀ2H),ꢀ4.65ꢀ(t,ꢀJꢀ=ꢀ6.8ꢀHz,ꢀ1H),ꢀ2.49–2.44ꢀ(m,ꢀ2H),ꢀ1.91ꢀ(br,ꢀ1H);ꢀ
-1
13
Cꢀ NMRꢀ (75ꢀ MHz,ꢀ CDCl )ꢀ d:ꢀ 147.8,ꢀ 146.9,ꢀ 138.0,ꢀ 134.4,ꢀ 119.2,ꢀ
3
118.4,ꢀ108.1,ꢀ106.4,ꢀ101.0,ꢀ73.2,ꢀ43.8;ꢀAnal.ꢀCalcdꢀforꢀC H O :ꢀC,ꢀ
11
12
3
with allylic chlorides: ToꢀaꢀmixtureꢀofꢀSnCl ꢀ(1.5ꢀmmol),ꢀaldehydeꢀorꢀ
68.75;ꢀH,ꢀ6.25.ꢀFound:ꢀC,ꢀ68.51;ꢀH,ꢀ6.30%.
2
3
5
-1
ketoneꢀ(1ꢀmmol),ꢀandꢀallylicꢀchlorideꢀ(2ꢀmmol)ꢀinꢀDMFꢀ(3ꢀmL)ꢀwasꢀ
addedꢀMCM-41-CN-Pd(II)ꢀ(87ꢀmg,ꢀ0.02ꢀmmolꢀPd)ꢀatꢀtheꢀtemperatureꢀ
indicatedꢀinꢀTableꢀ1ꢀunderꢀanꢀargonꢀatmosphere.ꢀAfterꢀbeingꢀstirredꢀforꢀ
1-Propylbut-3-en-1-olꢀ(3j): Oil. IR (film): nꢀ(cm )ꢀ3350,ꢀ2930,ꢀ
1
2854,ꢀ1641,ꢀ1450,ꢀ1375,ꢀ1056,ꢀ1028;ꢀ HꢀNMRꢀ(300ꢀMHz,ꢀCDCl ):ꢀ
3
dꢀ5.89–5.78ꢀ(m,ꢀ1H),ꢀ5.16–5.12ꢀ(m,ꢀ2H),ꢀ3.70–3.62ꢀ(m,ꢀ1H),ꢀ2.36–
4
8 h, the mixture was filtered and the catalyst was washed with DMF
2.27ꢀ(m,ꢀ1H),ꢀ2.19–2.09ꢀ(m,ꢀ1H),ꢀ1.63–1.24ꢀ(m,ꢀ5H),ꢀ0.90ꢀ(t,ꢀJꢀ=ꢀ6.8ꢀ
1
3
(
2ꢀ¥ꢀ10ꢀmL),ꢀdiethylꢀetherꢀ(2ꢀ¥ꢀ10ꢀmL)ꢀandꢀreusedꢀinꢀtheꢀnextꢀrun.ꢀ
Hz,ꢀ 3H);ꢀ CꢀNMRꢀ(75ꢀMHz,ꢀ CDCl ):ꢀdꢀ134.9,ꢀ118.1,ꢀ70.4,ꢀ42.0,ꢀ
3
The filtrate was diluted with 120 ml of a mixed solvent (diethyl ether/
39.0,ꢀ18.9,ꢀ14.1;ꢀAnal.ꢀCalcdꢀforꢀC H O:ꢀC,ꢀ73.68;ꢀH,ꢀ12.28.ꢀFound:ꢀ
7
14
dichloromethaneꢀ=ꢀ2:1)ꢀandꢀwashedꢀsuccessivelyꢀwithꢀaqueousꢀ10%ꢀ
C,ꢀ73.49;ꢀH,ꢀ12.07%.
1-Hexyl-3-methylbut-3-en-1-olꢀ (3k): Oil. IR (film): nꢀ (cm )ꢀ
3358,ꢀ 2930,ꢀ 2857,ꢀ 1641,ꢀ 1442,ꢀ 1375,ꢀ 1054,ꢀ 1025;ꢀ Hꢀ NMRꢀ
3
6
-1
HClꢀsolutionꢀ(2ꢀ¥ꢀ10ꢀmL),ꢀaqueousꢀNaHCO ꢀsolutionꢀ(10ꢀmL),ꢀandꢀ
3
1
waterꢀ(3ꢀ¥ꢀ10ꢀmL).ꢀTheꢀextractsꢀwereꢀdriedꢀoverꢀanhydrousꢀMgSO .
4
ꢀ
Afterꢀ removalꢀ ofꢀ theꢀ solventꢀ underꢀ reducedꢀ pressure,ꢀ theꢀ residueꢀ
(300ꢀMHz,ꢀCDCl ):ꢀdꢀ4.89ꢀ(d,ꢀJꢀ=ꢀ1.6ꢀHz,ꢀ1H),ꢀ4.81ꢀ(d,ꢀJꢀ=ꢀ0.8ꢀHz,ꢀ
3
was purified by preparative TLC on silica gel (light petroleum: ethyl
1H),ꢀ3.75–3.67ꢀ(m,ꢀ1H),ꢀ2.27–2.18ꢀ(m,ꢀ1H),ꢀ2.13–2.04ꢀ(m,ꢀ1H),ꢀ1.77ꢀ
acetateꢀ=ꢀ7:1)ꢀtoꢀaffordꢀaꢀcolourlessꢀoil.
(s,ꢀ3H),ꢀ1.72ꢀ(s,ꢀ1H),ꢀ1.54–1.23ꢀ(m,ꢀ10H),ꢀ0.88ꢀ(t,ꢀJꢀ=ꢀ6.8ꢀHz,ꢀ3H);ꢀ
-Phenylbut-3-en-1-olꢀ (3a):31 Oil. IR (film): nꢀ (cm )ꢀ 3390,ꢀ 3075,ꢀ
-1
13
1
CꢀNMRꢀ(75ꢀMHz,ꢀCDCl ):ꢀdꢀ142.2,ꢀ114.6,ꢀ70.5,ꢀ48.6,ꢀ36.3,ꢀ31.8,ꢀ
3
1
3
030,ꢀ2907,ꢀ1641,ꢀ1603,ꢀ1493,ꢀ1020,ꢀ750,ꢀ690;ꢀ HꢀNMRꢀ(300ꢀMHz,ꢀ
29.2,ꢀ25.7,ꢀ22.5,ꢀ22.3,ꢀ14.1.ꢀAnal.ꢀCalcdꢀforꢀC H O:ꢀC,ꢀ77.65;ꢀH,ꢀ
11
22
CDCl ):ꢀdꢀ7.33–7.25ꢀ(m,ꢀ5H),ꢀ5.86–5.75ꢀ(m,ꢀ1H),ꢀ5.19–5.12ꢀ(m,ꢀ2H),ꢀ
12.94.ꢀFound:ꢀC,ꢀ77.48;ꢀH,ꢀ12.72%.
2-Phenylpent-4-en-2-olꢀ(3l): Oil. IR (film): nꢀ(cm )ꢀ3400,ꢀ3060,ꢀ
2900,ꢀ1640,ꢀ1600,ꢀ1495,ꢀ1450,ꢀ1070,ꢀ760,ꢀ690;ꢀ HꢀNMRꢀ(300ꢀMHz,ꢀ
3
13
31
-1
4
.75–4.72ꢀ (m,ꢀ 1H),ꢀ 2.54–2.47ꢀ (m,ꢀ 2H),ꢀ 2.07ꢀ (br,ꢀ 1H);ꢀ Cꢀ NMRꢀ (75ꢀ
1
MHz,ꢀCDCl ): d 143.9,ꢀ134.5,ꢀ128.4,ꢀ127.6,ꢀ125.8,ꢀ118.4,ꢀ73.3,ꢀ43.8;ꢀ
3
Anal.ꢀCalcdꢀforꢀC H O:ꢀC,ꢀ81.08;ꢀH,ꢀ8.11.ꢀFound:ꢀC,ꢀ80.89;ꢀH,ꢀ7.90%.
CDCl ):ꢀdꢀ7.47–7.24ꢀ(m,ꢀ5H),ꢀ5.68–5.57ꢀ(m,ꢀ1H),ꢀ5.15–5.10ꢀ(m,ꢀ2H),ꢀ
1
0
12
3
32
-1
1
-Phenyl-3-methylbut-3-en-1-olꢀ(3b): Oil. IR (film): nꢀ(cm )ꢀ3399,ꢀ
073,ꢀ3030,ꢀ2936,ꢀ1647,ꢀ1603,ꢀ1493,ꢀ1453,ꢀ1375,ꢀ1054,ꢀ891,ꢀ756,ꢀ699;ꢀ
2.73–2.66ꢀ(m,ꢀ1H),ꢀ2.54–2.47ꢀ(m,ꢀ1H),ꢀ2.06ꢀ(br,ꢀ1H),ꢀ1.55ꢀ(s,ꢀ3H);ꢀ
1
3
3
Cꢀ NMRꢀ (75ꢀ MHz,ꢀ CDCl )ꢀ d:ꢀ 147.6,ꢀ 133.7,ꢀ 128.6,ꢀ 128.2,ꢀ 124.8,ꢀ
3
1
HꢀNMRꢀ(300ꢀMHz,ꢀCDCl ):ꢀdꢀ7.40–7.27ꢀ(m,ꢀ5H),ꢀ4.93ꢀ(d,ꢀJꢀ=ꢀ1.6ꢀHz,ꢀ
119.5,ꢀ73.6,ꢀ48.5,ꢀ15.3;ꢀAnal.ꢀCalcdꢀforꢀC H O:ꢀC,ꢀ81.48;ꢀH,ꢀ8.64.ꢀ
3
11 14
1
H),ꢀ4.87ꢀ(d,ꢀJꢀ=ꢀ0.8ꢀHz,ꢀ1H),ꢀ4.82ꢀ(t,ꢀJꢀ=ꢀ6.8ꢀHz,ꢀ1H),ꢀ2.43ꢀ(d,ꢀJꢀ=ꢀ6.8ꢀHz,ꢀ
Found:ꢀC,ꢀ81.25;ꢀH,ꢀ8.51%.
1-Chloro-2-phenylpent-4-en-2-olꢀ(3m): Oil. IR (film): nꢀ(cm )ꢀ
3450,ꢀ3050,ꢀ2900,ꢀ1640,ꢀ1600,ꢀ1490,ꢀ1440,ꢀ760,ꢀ700;ꢀ HꢀNMRꢀ(300ꢀ
13
37
-1
2
H),ꢀ2.15ꢀ(br,ꢀ1H),ꢀ1.81ꢀ(s,ꢀ3H);ꢀ CꢀNMRꢀ(75ꢀMHz,ꢀCDCl ):ꢀdꢀ144.1,ꢀ
3
1
1
42.4,ꢀ 128.4,ꢀ 127.5,ꢀ 125.8,ꢀ 114.1,ꢀ 71.4,ꢀ 48.4,ꢀ 22.3;ꢀAnal.ꢀ Calcdꢀ forꢀ
C H O:ꢀC,ꢀ81.48;ꢀH,ꢀ8.64.ꢀFound:ꢀC,ꢀ81.22;ꢀH,ꢀ8.48%.
MHz,ꢀCDCl ):ꢀdꢀ7.45–7.27ꢀ(m,ꢀ5H),ꢀ5.64–5.55ꢀ(m,ꢀ1H),ꢀ5.15–5.08ꢀ
11
14
3
3
3
-1
1
-(4-Chlorophenyl)but-3-en-1-olꢀ (3c): Oil. IR (film): nꢀ (cm )ꢀ
(m,ꢀ2H),ꢀ3.87–3.80ꢀ(m,ꢀ2H),ꢀ2.71ꢀ(d,ꢀJꢀ=ꢀ7.6ꢀHz,ꢀ2H),ꢀ2.60ꢀ(s,ꢀ1H);ꢀ
1
3
3
387,ꢀ3078,ꢀ3028,ꢀ2907,ꢀ1641,ꢀ1597,ꢀ1492,ꢀ1411,ꢀ1051,ꢀ919,ꢀ830;ꢀ
HꢀNMRꢀ(300ꢀMHz,ꢀCDCl ):ꢀdꢀ7.32–7.28ꢀ(m,ꢀ4H),ꢀ5.82–5.73ꢀ(m,ꢀ
H),ꢀ5.19–5.14ꢀ(m,ꢀ2H),ꢀ4.74–4.71ꢀ(m,ꢀ1H),ꢀ2.52–2.43ꢀ(m,ꢀ2H),ꢀ2.08ꢀ
br,ꢀ1H);ꢀ CꢀNMRꢀ(75ꢀMHz,ꢀCDCl ):ꢀdꢀ142.3,ꢀ134.0,ꢀ128.5,ꢀ127.5,ꢀ
27.2,ꢀ118.9,ꢀ72.6,ꢀ43.9;ꢀAnal.ꢀCalcdꢀforꢀC H OCl:ꢀC,ꢀ65.75;ꢀH,ꢀ
.03.ꢀFound:ꢀC,ꢀ65.51;ꢀH,ꢀ5.83%.
Cꢀ NMRꢀ (75ꢀ MHz,ꢀ CDCl ):ꢀ dꢀ 142.6,ꢀ 132.4,ꢀ 128.4,ꢀ 127.5,ꢀ 125.5,ꢀ
3
1
3
119.7,ꢀ 75.4,ꢀ 53.8,ꢀ 44.3;ꢀAnal.ꢀ Calcdꢀ forꢀ C H OCl:ꢀ C,ꢀ 67.18;ꢀ H,ꢀ
11 13
1
(
1
6
6.62.ꢀFound:ꢀC,ꢀ66.91;ꢀH,ꢀ6.45%.
13
31
-1
3
1-Allylcyclohexanolꢀ(3n): Oil. IR (film): nꢀ(cm )ꢀ3350,ꢀ3060,ꢀ2870,ꢀ
1
1
0
11
1637,ꢀ1030;ꢀ HꢀNMRꢀ(300ꢀMHz,ꢀCDCl ):ꢀdꢀ5.94–5.84ꢀ(m,ꢀ1H),ꢀ5.16–
3
13
5.08ꢀ(m,ꢀ2H),ꢀ2.22ꢀ(d,ꢀJꢀ=ꢀ7.6ꢀHz,ꢀ2H),ꢀ1.64–1.25ꢀ(m,ꢀ11H);ꢀ CꢀNMRꢀ
34
1-(4-Chlorophenyl)-3-methylbut-3-en-1-olꢀ (3d): Oil. IR (film):ꢀ
(75ꢀMHz,ꢀCDCl ):ꢀdꢀ133.7,ꢀ118.7,ꢀ71.0,ꢀ46.7,ꢀ37.4,ꢀ25.8,ꢀ22.2;ꢀAnal.ꢀ
3
-1
nꢀ(cm )ꢀ3400,ꢀ3076,ꢀ3028,ꢀ2971,ꢀ2936,ꢀ1647,ꢀ1598,ꢀ1491,ꢀ1444,ꢀ1376,ꢀ
CalcdꢀforꢀC H O:ꢀC,ꢀ77.14;ꢀH,ꢀ11.43.ꢀFound:ꢀC,ꢀ76.86;ꢀH,ꢀ11.21%.
9
16
1
1
(
064,ꢀ1014,ꢀ894,ꢀ830;ꢀ HꢀNMRꢀ(300ꢀMHz,ꢀCDCl ):ꢀdꢀ7.31ꢀ(s,ꢀ4H),ꢀ4.94ꢀ
3
t,ꢀJꢀ=ꢀ1.6ꢀHz,ꢀ1H),ꢀ4.85ꢀ(d,ꢀJꢀ=ꢀ0.8ꢀHz,ꢀ1H),ꢀ4.79ꢀ(t,ꢀJꢀ=ꢀ6.8ꢀHz,ꢀ1H),ꢀ
WeꢀthankꢀtheꢀNationalꢀNaturalꢀScienceꢀFoundationꢀofꢀChinaꢀ
ProjectꢀNo.ꢀ20462002)ꢀandꢀtheꢀNaturalꢀScienceꢀFoundationꢀ
of Jiangxi Province in China (2007GZW0172) for financial
13
2.38ꢀ(d,ꢀJꢀ=ꢀ7.2ꢀHz,ꢀ2H),ꢀ2.15ꢀ(br,ꢀ1H),ꢀ1.80ꢀ(s,ꢀ3H);ꢀ CꢀNMRꢀ(75ꢀMHz,ꢀ
(
CDCl ):ꢀdꢀ142.5,ꢀ142.0,ꢀ133.1,ꢀ128.5,ꢀ127.2,ꢀ114.4,ꢀ70.7,ꢀ48.4,ꢀ22.3;ꢀAnal.ꢀ
3
CalcdꢀforꢀC H OCl:ꢀC,ꢀ67.18;ꢀH,ꢀ6.62.ꢀFound:ꢀC,ꢀ67.25;ꢀH,ꢀ6.56%.
11 13
3
3
-1
support.
1
-(4-Methoxyphenyl)but-3-en-1-olꢀ(3e): Oil. IR (film): nꢀ(cm )ꢀ
3
1
386,ꢀ3072,ꢀ3019,ꢀ2930,ꢀ2850,ꢀ1640,ꢀ1600,ꢀ1500,ꢀ1450,ꢀ1380,ꢀ1240,ꢀ
175,ꢀ1030,ꢀ830;ꢀ HꢀNMRꢀ(300ꢀMHz,ꢀCDCl ):ꢀdꢀ7.27ꢀ(d,ꢀJꢀ=ꢀ8.8ꢀHz,ꢀ
1
Received 23 February 2009; accepted 23 April 2009
Paper 09/0459 doi: 10.3184/030823409X460911
Published online: 22 June 2009
3
2
H),ꢀ 6.88ꢀ (d,ꢀ Jꢀ =ꢀ 8.8ꢀ Hz,ꢀ 2H),ꢀ 5.85–5.74ꢀ (m,ꢀ 1H),ꢀ 5.17–5.11ꢀ (m,ꢀ
2
H),ꢀ4.69ꢀ(t,ꢀJꢀ=ꢀ6.8ꢀHz,ꢀ1H),ꢀ3.80ꢀ(s,ꢀ3H),ꢀ2.52–2.48ꢀ(m,ꢀ2H),ꢀ1.99ꢀ
13
(
br,ꢀ1H);ꢀ CꢀNMRꢀ(75ꢀMHz,ꢀCDCl ):ꢀdꢀ159.1,ꢀ136.1,ꢀ134.6,ꢀ127.1,ꢀ
3
1
18.2,ꢀ113.8,ꢀ73.0,ꢀ55.3,ꢀ43.8;ꢀAnal.ꢀCalcdꢀforꢀC H O :ꢀC,ꢀ74.16;ꢀH,ꢀ
11 14 2
References
7
.87.ꢀFound:ꢀC,ꢀ74.27;ꢀH,ꢀ7.78%.
-(4-Nitrophenyl)but-3-en-1-olꢀ(3f): Oil. IR (film): nꢀ(cm )ꢀ3398,ꢀ
-
1
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1
1
3
074,ꢀ 3025,ꢀ 2958,ꢀ 1650,ꢀ 1602,ꢀ 1525,ꢀ 1493,ꢀ 1346,ꢀ 845;ꢀ Hꢀ NMRꢀ
3
702.
(
2
2
300ꢀMHz,ꢀCDCl ):ꢀdꢀ8.21ꢀ(d,ꢀJꢀ=ꢀ8.8ꢀHz,ꢀ2H),ꢀ7.54ꢀ(d,ꢀJꢀ=ꢀ8.8ꢀHz,ꢀ
3
ꢀ
ꢀ
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H),ꢀ 5.84–5.74ꢀ (m,ꢀ 1H),ꢀ 5.22–5.17ꢀ (m,ꢀ 2H),ꢀ 4.89–4.86ꢀ (m,ꢀ 1H),ꢀ
1
3
.60–2.54ꢀ(m,ꢀ1H),ꢀ2.49–2.42ꢀ(m,ꢀ1H),ꢀ2.13ꢀ(br,ꢀ1H);ꢀ CꢀNMRꢀ(75ꢀ
MHz,ꢀCDCl ):ꢀdꢀ151.1,ꢀ147.3,ꢀ133.2,ꢀ126.6,ꢀ123.7,ꢀ119.7,ꢀ72.2,ꢀ43.9;ꢀ
3
Anal.ꢀCalcdꢀforꢀC H NO :ꢀC,ꢀ62.18;ꢀH,ꢀ5.70,ꢀN,ꢀ7.25.ꢀFound:ꢀC,ꢀ
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10
11
3
6
1.89,ꢀH,ꢀ5.52,ꢀN,ꢀ7.08%.
4473.

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