Solid-Phase synthesis of aryl vinyl ethers based on polystyrenesupported aβ-phenylselenoethanol

Article abstract of DOI:10.3184/030823409X447682

A novel facile solid-phase organic synthesis of aryl vinyl ethers by reaction of polystyrene-supported β-phenylselenoethanol with phenols under Mitsunobu conditions and subsequent oxidation-elimination with 30% hydrogen peroxide has been developed. The ad

Full text of DOI:10.3184/030823409X447682

JOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2009
MAY,ꢀ287–289ꢀ
RESEARCH PAPERꢀ 287
Solid-phase synthesis of aryl vinyl ethers based on polystyrene-
supported β-phenylselenoethanol
a
b*
b
b
Jia-Li Zhang , Shou-Ri Sheng , Xue Liu and Shu-Ying Lin
a
Department of Chemistry and Chemical Engineering, East China Jiaotong University, Nanchang 330013, P. R. China
bCollege of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330027, P. R. China
Aꢀ novelꢀ facileꢀ solid-phaseꢀ organicꢀ synthesisꢀ ofꢀ arylꢀ vinylꢀ ethersꢀ byꢀ reactionꢀ ofꢀ polystyrene-supportedꢀ
b-phenylselenoethanolꢀwithꢀphenolsꢀunderꢀMitsunobuꢀconditionsꢀandꢀsubsequentꢀoxidation-eliminationꢀwithꢀ30%ꢀ
hydrogenꢀperoxideꢀhasꢀbeenꢀdeveloped.ꢀTheꢀadvantagesꢀofꢀthisꢀmethodꢀincludeꢀstraightforwardꢀoperation,ꢀlackꢀofꢀ
odour,ꢀgoodꢀyieldꢀandꢀhighꢀpurityꢀofꢀtheꢀproducts.
Keywords: solid-phaseꢀorganicꢀsynthesis,ꢀpolystyrene-supportedꢀb-phenylselenoethanol,ꢀarylꢀvinylꢀether
Vinylꢀethersꢀareꢀvaluableꢀintermediatesꢀthatꢀcanꢀbeꢀusedꢀinꢀaꢀ
wideꢀ arrayꢀ ofꢀ chemicalꢀ transformations. More specifically,
Polymer-supportedꢀ b-phenylselenoethanolꢀ (3)ꢀ wasꢀ readilyꢀ
1
preparedꢀbyꢀtreatmentꢀofꢀaꢀTHF-swollenꢀsuspensionꢀofꢀcross-
1
6
arylꢀ vinylꢀ ethersꢀ withꢀ unsubstitutedꢀ vinylꢀ moiety,ꢀ haveꢀ
wideꢀ syntheticꢀ applicationsꢀ andꢀ areꢀ employedꢀ asꢀ keyꢀ
linkedꢀ(1%)ꢀpolystyrene-boundꢀseleniumꢀbromideꢀ(1) ꢀwithꢀ
LiBH ,ꢀ followedꢀ byꢀ treatmentꢀ withꢀ 2-chloroethanol.ꢀ Theꢀ
4
2
intermediatesꢀforꢀtheꢀgenerationꢀofꢀnewꢀpolymericꢀmaterials, ꢀ
IRꢀspectrumꢀofꢀresinꢀ3 showedꢀaꢀlargeꢀhydroxylꢀabsorptionꢀ
3
-1
-1
asꢀ dienophilesꢀ forꢀ cycloadditionꢀ reactionsꢀ suchꢀ asꢀ [2ꢀ +ꢀ 2], ꢀ
atꢀ3400ꢀcm ,ꢀandꢀbandꢀatꢀ1060ꢀcm ꢀ(C–O).ꢀResinꢀ3ꢀcanꢀbeꢀ
storedꢀatꢀroomꢀtemperatureꢀforꢀaꢀlongꢀtimeꢀwithoutꢀdiminutionꢀ
ofꢀcapacityꢀorꢀtheꢀliberationꢀofꢀdisagreeableꢀodors.ꢀWithꢀtheꢀ
resinꢀ 3 in hand, the etherification reaction was investigated
fromꢀ resinꢀ 3 withꢀ phenolꢀ (4a)ꢀ underꢀ Mitsunobuꢀ reactionꢀ
conditionsꢀ [triphenylphosphine/diethylꢀ azodicarboxylate]ꢀ
inꢀ 4-methylmorpholineꢀ toꢀ affordꢀ polystyrene-supportedꢀ 2-
phenoxyethylꢀ selenide(5a) efficiently, which could not be
reliablyꢀ analysedꢀ withꢀ FT-IR.ꢀ Henceꢀ weꢀ carriedꢀ outꢀ nextꢀ
cleavageꢀ reactionꢀ directlyꢀ afterꢀ washingꢀ theꢀ resinꢀ 5aꢀ usingꢀ
solvents.ꢀTreatmentꢀofꢀresinꢀ5aꢀwithꢀ30%ꢀhydrogenꢀperoxideꢀatꢀ
0ꢀ°Cꢀandꢀthenꢀatꢀroomꢀtemperatureꢀaffordedꢀtheꢀcorrespondingꢀ
phenylꢀ vinylꢀ etherꢀ (6a)ꢀ inꢀ goodꢀ yieldsꢀ (90%)ꢀ andꢀ withꢀ
goodꢀ puritiesꢀ ofꢀ crudeꢀ materialꢀ (95%).ꢀ Theꢀ residualꢀ resin,ꢀ
polystyrene-supportedꢀphenylseleninicꢀacid,ꢀwasꢀobtainedꢀasꢀ
aꢀby-product,ꢀwhoseꢀIRꢀdataꢀwereꢀidenticalꢀtoꢀtheꢀpreviouslyꢀ
4
5
6
[
2ꢀ+ꢀ4] ꢀandꢀ1,3-dipolarꢀcycloadditons, ꢀinꢀcyclopropanations, ꢀ
7
inꢀ hydroformylations, ꢀ andꢀ inꢀ naturalꢀ productꢀ analogueꢀ
synthesis. ꢀArylꢀvinylꢀethersꢀareꢀusuallyꢀpreparedꢀaccordingꢀ
8
toꢀtheꢀfollowingꢀprocedures:ꢀtheꢀdehydrohalogenationꢀofꢀarylꢀ
9
10
2
-haloethylꢀethers, ꢀtheꢀadditionꢀofꢀphenolsꢀtoꢀacetylene ꢀandꢀ
theꢀcopperꢀ(II)-promotedꢀcouplingꢀofꢀarylboronicꢀacidsꢀwithꢀ
11
phenols. ꢀ Recently,ꢀ theꢀ useꢀ ofꢀ vinylꢀ acetateꢀ inꢀ anꢀ iridium-
12
catalysedꢀ reactionꢀ withꢀ phenols, ꢀ andꢀ theꢀ transformationsꢀ
withꢀcopperꢀ(II)ꢀacetateꢀmediatedꢀcouplingꢀofꢀ2,ꢀ4,ꢀ6-trivinyl-
13
cyclotriboroxaneꢀ asꢀ aꢀ vinylboronicꢀ acidꢀ equivalent, ꢀ andꢀ
14
tributy(vinyl)tin ꢀ withꢀ phenolsꢀ haveꢀ alsoꢀ beenꢀ reported.ꢀ
However, most of these methods involved difficulties such
asꢀ harshꢀ reactions,ꢀ laboriousꢀ manipulationꢀ andꢀ lowꢀ overallꢀ
yields,ꢀorꢀinꢀsomeꢀcases,ꢀreactionsꢀareꢀunsuitableꢀforꢀsensitiveꢀ
substrates,ꢀ vigorousꢀ toxicꢀ compoundsꢀ areꢀ usedꢀ orꢀ someꢀ
reagentsꢀ areꢀ notꢀ readilyꢀ available.ꢀ Itꢀ isꢀ wellꢀ knownꢀ thatꢀ
phenylselenoꢀ groupꢀ isꢀ readilyꢀ convertedꢀ toꢀ aꢀ leavingꢀ groupꢀ
givingꢀ accessꢀ toꢀ carbon–carbonꢀ doubleꢀ bondꢀ viaꢀ oxidationꢀ
1
8
reportedꢀ data. ꢀ Theꢀ polystyrene-supportedꢀ phenylseleninicꢀ
acidꢀ couldꢀ beꢀ convertedꢀ toꢀ polymer-supportedꢀ seleniumꢀ
1
9,20
lithium forꢀ recycleꢀ byꢀ treatmentꢀ of it withꢀ KI/Na S O
ꢀ
2
2
3
15
16
followedꢀbyꢀb-eliminationꢀunderꢀextremelyꢀmildꢀconditions. ꢀ
followedꢀbyꢀbromine. ꢀForꢀexample,ꢀphenylꢀvinylꢀetherꢀ(6a)ꢀ
wasꢀobtainedꢀinꢀ88%ꢀyieldꢀunderꢀtheꢀsameꢀreactionꢀconditionꢀ
usingꢀtheꢀrecoveredꢀseleniumꢀlithiumꢀresinꢀ(secondꢀrun),ꢀandꢀ
inꢀ85%ꢀyieldꢀafterꢀsecondꢀrecycleꢀ(i.e.ꢀthirdꢀrun).ꢀItꢀwasꢀshownꢀ
thatꢀrecyclingꢀ2–3ꢀtimesꢀledꢀtoꢀaꢀgradualꢀdeteriorationꢀofꢀtheꢀ
resin.ꢀAfterꢀsuccessfullyꢀpreparationꢀofꢀ6a,ꢀextensionꢀofꢀthisꢀ
methodꢀ toꢀ theꢀ synthesisꢀ ofꢀ otherꢀ analoguesꢀ inꢀ goodꢀ yieldsꢀ
andꢀgoodꢀpuritiesꢀwasꢀinvestigatedꢀ(Tableꢀ1).ꢀAsꢀseenꢀfromꢀ
theꢀ Tableꢀ 1,ꢀ forꢀ substratesꢀ phenols,ꢀ withꢀ substitutionꢀ ofꢀ anꢀ
16
Moreover,ꢀtheꢀpolymericꢀseleniumꢀreagents ꢀhaveꢀbeenꢀnowꢀ
developedꢀ forꢀ solid-phaseꢀ organicꢀ synthesisꢀ (SPOS)ꢀ withꢀ aꢀ
combined advantage of decrease volatility and simplification
ofꢀproductꢀwork-up.ꢀInꢀcontinuationꢀofꢀourꢀinterestꢀinꢀsolid-
17
phaseꢀorganoseleniumꢀchemistry, ꢀdescribeꢀhereꢀaꢀnewꢀsimpleꢀ
and efficient SPOS approach to aryl vinyl ethers based on a
novelꢀ polystyrene-supportedꢀ b-phenylselenoethanolꢀ reagentꢀ
(Schemeꢀ1).
LiBH4
ClCH CH OH
2
2
SeBr
SeLi
SeCH CH OH
2
2
THF, rt
rt
1
2
3
R
OH (4)
R
H O
R
2
2
SeCH CH O
OCH=CH2
2
2
Ph P/DEAD
THF
3
THF/NMM, rt
5
6
Scheme 1
*
ꢀCorrespondent.ꢀE-mail:ꢀshengsr@jxnu.edu.cn

2
88ꢀ JOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2009
Table 1ꢀ Theꢀyieldsꢀandꢀpuritiesꢀofꢀarylꢀvinylꢀethersꢀ(6a–6m)
silicaꢀ gelꢀ usingꢀ chloroform/hexaneꢀ (10:90)ꢀ asꢀ eluentꢀ toꢀ giveꢀ pureꢀ
1
productsꢀ6a–mꢀfor HꢀNMRꢀandꢀIRꢀanalyses.
a
b
Entryꢀ Rꢀ(Phenol)ꢀ
Productꢀ
Yield /%ꢀ Purity /%
14
1
Phenylvinylether(6a):Colourlessꢀoil.ꢀ(lit. ꢀoil);ꢀ HꢀNMR:ꢀdꢀ=ꢀ7.15–ꢀ
7
1
1
1
.02ꢀ(m,ꢀ5ꢀH),ꢀ6.58ꢀ(dd,ꢀJ =ꢀ14.0,ꢀ6.0ꢀHz,ꢀ1ꢀH),ꢀ4.70ꢀ(dd,ꢀJ =ꢀ14.0,ꢀ
1
2
3
4
5
6
7
8
9
Hꢀ(4a)ꢀ
6a
6b
6c
6d
6e
6f
90ꢀ
89ꢀ
90ꢀ
88ꢀ
86ꢀ
83ꢀ
88ꢀ
86ꢀ
90ꢀ
88ꢀ
86ꢀ
88ꢀ
84ꢀ
95
94
97
95
96
95
95
94
96
95
94
96
95
13
.5ꢀHz,ꢀ1ꢀH),ꢀ4.34ꢀ(dd,ꢀJ =ꢀ6.0,ꢀ1.5ꢀHz,ꢀ1ꢀH);ꢀ CꢀNMR:ꢀdꢀ=ꢀ154.0,ꢀ
3-CH (4b)ꢀ
3
ꢀ
44.4,ꢀ133.1,ꢀ120.5,ꢀ115.3,ꢀ95.3;ꢀIRꢀ(neat):ꢀnꢀ=ꢀ3045,ꢀ1640,ꢀ1623,ꢀ
4-CH Oꢀ(4c)ꢀ
-1
3
600,ꢀ1495,ꢀ1230,ꢀ1212,ꢀ1165,ꢀ1155,ꢀ1145,ꢀ956,ꢀ942ꢀcm .
4-t-C H (4d)ꢀ
10
4
9ꢀ
3
-Methylphenyl vinyl ether (6b):ꢀ Colourlessꢀ oilꢀ (lit. ꢀ oil);ꢀ
4-C H (4e)ꢀ
1
6
5ꢀ
HꢀNMR:ꢀdꢀ=ꢀ6.83–7.20ꢀ(m,ꢀ4ꢀH),ꢀ6.50ꢀ(dd,ꢀJ =ꢀ14.2,ꢀ6.5ꢀHz,ꢀ1ꢀH),ꢀ
.32ꢀ(dd,ꢀJ =ꢀ14.2,ꢀ1.8ꢀHz,ꢀ1ꢀH),ꢀ4.04ꢀ(dd,ꢀJ =ꢀ6.5,ꢀ1.8ꢀHz,ꢀ1ꢀH),ꢀ
.30ꢀ(s,ꢀ3ꢀH);ꢀ CꢀNMR:ꢀdꢀ=ꢀ154.6,ꢀ140.4,ꢀ132.1,ꢀ123.7,ꢀ122.6,ꢀ119.5,ꢀ
15.3,ꢀ95.6,ꢀ21.5;ꢀIRꢀ(neat):ꢀnꢀ=ꢀ3050,ꢀ1640,ꢀ1622,ꢀ1600,ꢀ1500,ꢀ1380,ꢀ
4-Cl(4f)ꢀ
4
2
1
1
4-Brꢀ(4g)ꢀ
2-Brꢀ(4h)ꢀ
4-NO (4i)ꢀ
6g
6h
6i
13
2ꢀ
-1
230,ꢀ1160,ꢀ1149,ꢀ960,ꢀ822ꢀcm .
-Methoxyphenyl vinyl ether (6c):ꢀ Colourlessꢀ oilꢀ (lit. ꢀ oil);ꢀ
HꢀNMR:ꢀdꢀ=ꢀ6.95ꢀ(d,ꢀJꢀ=ꢀ8.2ꢀHz,ꢀ2ꢀH),ꢀ6.86ꢀ(d,ꢀJꢀ=ꢀ8.2ꢀHz,ꢀ2ꢀH),ꢀ
.58ꢀ(dd,ꢀJ =ꢀ14.1,ꢀ6.3ꢀHz,ꢀ1ꢀH),ꢀ4.65ꢀ(dd,ꢀJ =ꢀ14.1,ꢀ2.0ꢀHz,ꢀ1ꢀH),ꢀ4.35ꢀ
1
0
1
2
3
4-CNꢀ(4j)ꢀ
6j
2
1
4
1
1
1
4-CO CH ꢀ(4k)ꢀ
6k
6l
2
3
1
4-NHCOCH ꢀ(4l)ꢀ
3
6
(
1
1
1-Naphtholꢀ(4m)ꢀ
6m
1
3
dd,ꢀJ =ꢀ6.3,ꢀ2.0ꢀHz,ꢀ1ꢀH),ꢀ3.78ꢀ(s,ꢀ3ꢀH);ꢀ CꢀNMR:ꢀdꢀ=ꢀ155.4,ꢀ145.8,ꢀ
aOverallꢀ yieldsꢀ basedꢀ onꢀ polystyrene-supportedꢀ seleniumꢀ
34.1,ꢀ 120.5,ꢀ 118.0,ꢀ 115.5,ꢀ 95.5,ꢀ 55.2;ꢀ IRꢀ (neat):ꢀ nꢀ =ꢀ 3045,ꢀ 1638,ꢀ
bromideꢀ1ꢀ(1.18ꢀmmolꢀBr/g).
-1
620,ꢀ1600,ꢀ1495,ꢀ1379,ꢀ1230,ꢀ1162,ꢀ1145,ꢀ958,ꢀ825ꢀcm .
b
DeterminedꢀbyꢀHPLCꢀofꢀcrudeꢀcleavageꢀproductꢀ(lꢀ=ꢀ254ꢀnm).
9
1
4
-t-Butylphenyl vinyl ether (6d):ꢀColourlessꢀoilꢀ(lit. ꢀoil);ꢀ HꢀNMR:ꢀ
dꢀ=ꢀ6.80ꢀ(d,ꢀJ =ꢀ8.2ꢀHz,ꢀ2ꢀH),ꢀ7.18ꢀ(d,ꢀJ =ꢀ8.2ꢀHz,ꢀ2ꢀH),ꢀ6.51ꢀ(dd,ꢀ
electron-withdrawingꢀgroupꢀorꢀanꢀelectron-donatingꢀgroupꢀonꢀ
theꢀaromaticꢀringꢀresultedꢀinꢀnoꢀobviousꢀeffectꢀonꢀtheꢀreactionꢀ
yields.
In summary, we have developed a novel, efficient and
convenientꢀ methodꢀ forꢀ theꢀ SPOSꢀ ofꢀ arylꢀ vinylꢀ ethersꢀ
employingꢀ polymer-supportedꢀ b-phenylselenoethanol.ꢀ Theꢀ
advantagesꢀofꢀthisꢀmethodꢀincludeꢀstraightforwardꢀoperation,ꢀ
lackꢀofꢀodour,ꢀgoodꢀyieldꢀandꢀhighꢀpurityꢀofꢀtheꢀproducts.
J =ꢀ14.0,ꢀ6.2ꢀHz,ꢀ1ꢀH),ꢀ4.28ꢀ(dd,ꢀJ =ꢀ14.0,ꢀ1.6ꢀHz,ꢀ1ꢀH),ꢀ4.24ꢀ(dd,ꢀ
1
3
J =ꢀ6.2,ꢀ1.6ꢀHz,ꢀ1ꢀH),ꢀ1.31ꢀ(s,ꢀ9ꢀH);ꢀ CꢀNMR:ꢀdꢀ=ꢀ157.1,ꢀ145.5,ꢀ
1
1
33.7,ꢀ120.0,ꢀ117.3,ꢀ95.8,ꢀ38.0,ꢀ28.5;ꢀIRꢀ(neat):ꢀnꢀ=ꢀ3045,ꢀ2940,ꢀ1640,ꢀ
-1
600,ꢀ1600,ꢀ1500,ꢀ1378,ꢀ1240,ꢀ1180,ꢀ1149,ꢀ825ꢀcm .
-Phenylphenyl vinyl ether (6e):ꢀWhiteꢀsolid,ꢀm.p.ꢀ72–73ꢀ°C.ꢀ(lit. ꢀ
14
4
1
m.p.ꢀ 71–72ꢀ°C);ꢀ Hꢀ NMR:ꢀ dꢀ =ꢀ 7.66–7.34ꢀ (m,ꢀ 7ꢀ H),ꢀ 7.12–7.06ꢀ (m,ꢀ
2ꢀH),ꢀ6.80ꢀ(dd,ꢀJ =ꢀ13.5,ꢀ6.0ꢀHz,ꢀ1ꢀH),ꢀ4.72ꢀ(dd,ꢀJ =ꢀ13.5,ꢀ1.5ꢀHz,ꢀ
1
3
1ꢀH),ꢀ4.47ꢀ(dd,ꢀJ =ꢀ6.0,ꢀ1.5ꢀHz,ꢀ1ꢀH);ꢀ CꢀNMR:ꢀdꢀ=ꢀ156.6,ꢀ148.2,ꢀ
40.6,ꢀ 136.3,ꢀ 129.0,ꢀ 128.5,ꢀ 127.2,ꢀ 126.8,ꢀ 117.5,ꢀ 95.5;ꢀ IRꢀ (KBr):ꢀ
1
-1
nꢀ=ꢀ3050,ꢀ3021,ꢀ1636,ꢀ1595,ꢀ1509,ꢀ1476,ꢀ1240,ꢀ1136,ꢀ826,ꢀ755ꢀcm .
2
2
1
4
-Chlorophenyl vinyl ether (6f):ꢀColourlessꢀoilꢀ(lit. ꢀoil);ꢀ HꢀNMR:ꢀ
Experimental
dꢀ=ꢀ7.43ꢀ(d,ꢀJ =ꢀ8.4ꢀHz,ꢀ2ꢀH),ꢀ7.01ꢀ(d,ꢀJ =ꢀ8.4ꢀHz,ꢀ2ꢀH),ꢀ6.63ꢀ(dd,ꢀ
Meltingꢀ pointsꢀ wereꢀ uncorrected. Hꢀ NMRꢀ (400ꢀ MHz)ꢀ andꢀ 13Cꢀ
1
J =ꢀ13.7,ꢀ6.1ꢀHz,ꢀ1ꢀH),ꢀ4.80ꢀ(dd,ꢀJ =ꢀ13.7,ꢀ1.8ꢀHz,ꢀ1ꢀH),ꢀ4.51ꢀ(dd,ꢀ
1
3
NMRꢀ (100ꢀ MHz)ꢀ spectraꢀ wereꢀ recordedꢀ onꢀ aꢀ Brukerꢀ Avanceꢀ
J =ꢀ6.1,ꢀ1.8ꢀHz,ꢀ1ꢀH);ꢀ CꢀNMR:ꢀdꢀ=ꢀ156.2,ꢀ148.1,ꢀ132.8,ꢀ119.1,ꢀ116.1,ꢀ
95.8;ꢀIRꢀ(neat):ꢀnꢀ=ꢀ3048,ꢀ1635,ꢀ1595,ꢀ1475,ꢀ1232,ꢀ1165,ꢀ1142,ꢀ1058,ꢀ
(
400ꢀMHz)ꢀspectrometer,ꢀusingꢀCDCl ꢀasꢀtheꢀsolventꢀandꢀTMSꢀasꢀ
3
-1
internalꢀstandard.ꢀFT-IRꢀspectraꢀwereꢀtakenꢀonꢀaꢀPerkin–ElmerꢀSPꢀOneꢀ
FT-IRꢀspectrophotometer.ꢀHPLCꢀanalysisꢀwasꢀperformedꢀonꢀAgilentꢀ
1002,ꢀ955,ꢀ834ꢀcm .
1
4
4-Bromophenyl vinyl ether (6g):ꢀ Colourlessꢀ oilꢀ (lit. ꢀ oil);ꢀ
HꢀNMR:ꢀdꢀ=ꢀ7.40ꢀ(d,ꢀJ =ꢀ8.5ꢀHz,ꢀ2ꢀH),ꢀ6.95ꢀ(d,ꢀJ =ꢀ8.5ꢀHz,ꢀ2ꢀH),ꢀ
1
1
100ꢀautomatedꢀsystemꢀhavingꢀaꢀPDAꢀdetectorꢀusingꢀaꢀgradientꢀwithꢀ
-1
CH CN/H Oꢀ (1ꢀ mLꢀ min )ꢀ onꢀ aꢀ RP-18eꢀ columnꢀ (150ꢀ ¥ꢀ 4.6ꢀ mm).ꢀ
Polystyreneꢀ(Hꢀ1000,ꢀ100–200ꢀmesh,ꢀcross-linkedꢀwithꢀ1%ꢀdivinyl-
benzene)ꢀforꢀpreparationꢀofꢀseleniumꢀbromideꢀresin ꢀwasꢀpurchasedꢀ
fromꢀ Nankaiꢀ University,ꢀ andꢀ theꢀ otherꢀ startingꢀ materialsꢀ wereꢀ
purchasedꢀ fromꢀ commercialꢀ suppliersꢀ andꢀ usedꢀ withoutꢀ furtherꢀ
purification. THF was stilled from sodium benzophenone immediately
priorꢀtoꢀuse.
6.60ꢀ(dd,ꢀJ =ꢀ13.8,ꢀ6.1ꢀHz,ꢀ1ꢀH),ꢀ4.78ꢀ(dd,ꢀJ =ꢀ13.8,ꢀ1.8ꢀHz,ꢀ1ꢀH),ꢀ4.48ꢀ
3
2
1
3
(dd,ꢀJ =ꢀ6.1,ꢀ1.8ꢀHz,ꢀ1ꢀH);ꢀ CꢀNMR:ꢀdꢀ=ꢀ155.9,ꢀ147.7,ꢀ132.6,ꢀ118.5,ꢀ
1
6
115.7,ꢀ96.0;ꢀIRꢀ(neat):ꢀnꢀ=ꢀ3050,ꢀ1636,ꢀ1578,ꢀ1475,ꢀ1230,ꢀ1160,ꢀ1140,ꢀ
-
1
1060,ꢀ1000,ꢀ950,ꢀ820ꢀcm .
1
3
2-Bromophenyl vinyl ether (6h):ꢀ Colourlessꢀ oilꢀ (lit. ꢀ oil);ꢀ
HꢀNMR:ꢀdꢀ=ꢀ7.67–7.65ꢀ(m,ꢀ1ꢀH),ꢀ7.42–7.36ꢀ(m,ꢀ1ꢀH),ꢀ7.21–7.18ꢀ(m,ꢀ
1
1ꢀH),ꢀ7.10–7.06ꢀ(m,ꢀ1ꢀH),ꢀ6.80ꢀ(dd,ꢀJ =ꢀ6.3,ꢀ13.5ꢀHz,ꢀ1ꢀH),ꢀ4.68ꢀ(dd,ꢀ
1
3
J =ꢀ1.8,ꢀ13.5ꢀHz,ꢀ1ꢀH),ꢀ4.53ꢀ(dd,ꢀJ =ꢀ1.8,ꢀ6.3ꢀHz,ꢀ1ꢀH);ꢀ CꢀNMR:ꢀ
dꢀ=ꢀ153.5,ꢀ148.7,ꢀ133.7,ꢀ129.7,ꢀ125.3,ꢀ118.5,ꢀ113.6,ꢀ96.2;ꢀIRꢀ(neat):ꢀ
nꢀ =ꢀ 3043,ꢀ 1640,ꢀ 1595,ꢀ 1472,ꢀ 1232,ꢀ 1164,ꢀ 1142,ꢀ 1063,ꢀ 1005,ꢀ 953,ꢀ
Preparation of polystyrene-supported b-phenylselenoethanolꢀ(3)
Underꢀ aꢀ nitrogenꢀ atmosphere,ꢀ toꢀ deepꢀ redꢀ colouredꢀ polystyrene-
supportedꢀseleniumꢀbromideꢀ1ꢀ(1.0ꢀg,ꢀ1.18ꢀmmolꢀBr/g,ꢀtheꢀloadingꢀofꢀ
functionalꢀBrꢀwasꢀanalysedꢀbyꢀelementaryꢀanalysis)ꢀswollenꢀinꢀTHFꢀ
-
1
765ꢀcm .
1
4
1
4-Nitrophenyl vinyl ether (6i):ꢀColourlessꢀoilꢀ(lit. ꢀoil);ꢀ HꢀNMR:ꢀ
dꢀ=ꢀ8.25ꢀ(d,ꢀJ =ꢀ8.9ꢀHz,ꢀ2ꢀH),ꢀ7.10ꢀ(d,ꢀJ =ꢀ8.9ꢀHz,ꢀ2ꢀH),ꢀ6.68ꢀ(dd,ꢀ
J =ꢀ13.6,ꢀ6.0ꢀHz,ꢀ1ꢀH),ꢀ5.01ꢀ(dd,ꢀJ =ꢀ13.6,ꢀ1.9ꢀHz,ꢀ1ꢀH),ꢀ4.70ꢀ(dd,ꢀ
(
10ꢀmL)ꢀforꢀ30ꢀminꢀwasꢀaddedꢀLiBH ꢀ(3.0ꢀmmol).ꢀAfterꢀ1ꢀhꢀwithꢀ
4
shakingꢀatꢀroomꢀtemperature,ꢀ2-chloroethanolꢀ(3.0ꢀmmol)ꢀinꢀ2ꢀmLꢀ
ofꢀ THFꢀ wasꢀ addedꢀ slowlyꢀ andꢀ theꢀ mixtureꢀ wasꢀ shakenꢀ forꢀ 6ꢀ h.ꢀ
The resin was collected on a filter and washed successively withꢀ
H Oꢀ(2ꢀ¥ꢀ20ꢀmL),ꢀTHFꢀ(3ꢀ¥ꢀ5ꢀmL)ꢀandꢀCH Cl ꢀ(3ꢀ¥ꢀ5ꢀmL),ꢀandꢀthenꢀ
1
3
J =ꢀ 6.0,ꢀ 1.9ꢀ Hz,ꢀ 1ꢀ H);ꢀ Cꢀ NMR:ꢀ dꢀ =ꢀ 161.3,ꢀ 145.5,ꢀ 142.8,ꢀ 125.7,ꢀ
116.3,ꢀ99.1;ꢀIRꢀ(neat):ꢀnꢀ=ꢀ3060,ꢀ1638,ꢀ1600,ꢀ1580,ꢀ1498,ꢀ1481,ꢀ1330,ꢀ
-1
1230,ꢀ1160,ꢀ1120,ꢀ1100,ꢀ945,ꢀ840ꢀcm .
2
2
2
1
4
1
driedꢀunderꢀ vacuumꢀovernightꢀtoꢀaffordꢀ 950ꢀmgꢀofꢀ resinꢀ3,ꢀwhichꢀ
4-Cyanophenyl vinyl ether (6j):ꢀColourlessꢀoilꢀ(lit. ꢀoil);ꢀ HꢀNMR:ꢀ
dꢀ=ꢀ7.70ꢀ(d,ꢀJ =ꢀ8.6ꢀHz,ꢀ2ꢀH),ꢀ7.10ꢀ(d,ꢀJ =ꢀ8.6ꢀHz,ꢀ2ꢀH),ꢀ6.66ꢀ(dd,ꢀ
J =ꢀ13.7,ꢀ6.1ꢀHz,ꢀ1ꢀH),ꢀ4.98ꢀ(dd,ꢀJ =ꢀ13.7,ꢀ2.0ꢀHz,ꢀ1ꢀH),ꢀ4.68ꢀ(dd,ꢀ
-1
wasꢀ calculatedꢀ toꢀ haveꢀ aꢀ loadingꢀ ofꢀ 1.20ꢀ mmolꢀ g ,ꢀ assumingꢀ the
etherification reaction went to completion. IRꢀ(KBr):ꢀnꢀ=ꢀ3400,ꢀ3052,ꢀ
-1
13
2
925,ꢀ1595,ꢀ1475,ꢀ1060,ꢀ940,ꢀ732,ꢀ688ꢀcm .
J =ꢀ6.1,ꢀ2.0ꢀHz,ꢀ1ꢀH);ꢀ CꢀNMR:ꢀdꢀ=ꢀ159.8,ꢀ145.8,ꢀ134.1,ꢀ118.6,ꢀ117.1,ꢀ
1
06.1,ꢀ98.6;ꢀIRꢀ(neat):ꢀnꢀ=ꢀ3050,ꢀ2200,ꢀ1635,ꢀ1595,ꢀ1492,ꢀ1300,ꢀ1235,ꢀ
-1
Preparation of aryl vinyl ethers(6a–m);ꢀgeneral procedure
1160,ꢀ1125,ꢀ950,ꢀ824ꢀcm .
1
4
The resinꢀ3ꢀ(1.0ꢀg,ꢀ1.20ꢀmmol)ꢀwasꢀswollenꢀinꢀTHF (10ꢀmL)ꢀatꢀroomꢀ
4-Methoxycarbonylphenyl vinyl ether (6k):ꢀ Colourlessꢀ oilꢀ (lit. ꢀ
ꢀ
1
temperatureꢀ forꢀ 30ꢀ minꢀ andꢀ thenꢀ aꢀ solutionꢀ ofꢀ triphenylphosphineꢀ
oil);ꢀ HꢀNMR:ꢀdꢀ=ꢀ8.00ꢀ(d,ꢀJ =ꢀ8.3ꢀHz,ꢀ2ꢀH),ꢀ7.15ꢀ(d,ꢀJ =ꢀ8.3ꢀHz,ꢀ
(
1.57ꢀ g,ꢀ 6.0ꢀ mmol)ꢀ andꢀ phenolsꢀ (4a–m)ꢀ (5.0ꢀ mmol)ꢀ inꢀ 4-methyl-
morpholineꢀ (5ꢀ mL)ꢀ wasꢀ added.ꢀ Neatꢀ diethylꢀ azodicarboxylateꢀ
790ꢀμL,ꢀ5.0ꢀmmol)ꢀwasꢀ addedꢀinꢀsmallꢀportionsꢀoverꢀaꢀperiodꢀofꢀ
0ꢀminꢀatꢀroomꢀtempertureꢀAfterꢀtheꢀsuspensionꢀwasꢀshakenꢀforꢀ12ꢀhꢀ
2ꢀH),ꢀ6.88ꢀ(dd,ꢀJ =ꢀ13.6,ꢀ6.0ꢀHz,ꢀ1ꢀH),ꢀ4.85ꢀ(dd,ꢀJ =ꢀ13.6,ꢀ1.6ꢀHz,ꢀ
1
3
1ꢀH),ꢀ4.55ꢀ(dd,ꢀJ =ꢀ6.0,ꢀ1.6ꢀHz,ꢀ1ꢀH),ꢀ3.84ꢀ(s,ꢀ3ꢀH);ꢀ CꢀNMR:ꢀdꢀ=ꢀ166.5,ꢀ
160.2,ꢀ146.6,ꢀ131.5,ꢀ124.5,ꢀ116.1,ꢀ97.3,ꢀ51.8;ꢀIRꢀ(neat):ꢀnꢀ=ꢀ3050,ꢀ
2985,ꢀ2940,ꢀ1710,ꢀ1635,ꢀ1596,ꢀ1498,ꢀ1425,ꢀ1300,ꢀ1272,ꢀ1235,ꢀ1156,ꢀ
(
2
-1
atꢀroomꢀtemperture,ꢀtheꢀresinꢀ(5a–m) was filtered and subsequently
washedꢀwithꢀTHFꢀ(3ꢀ¥ꢀ5ꢀmL),ꢀDMSOꢀ(2ꢀ¥ꢀ10ꢀmL),ꢀTHFꢀ(3ꢀ¥ꢀ5ꢀmL),ꢀ
waterꢀ(2ꢀ¥ꢀ10ꢀmL),ꢀMeOHꢀ(2ꢀ¥ꢀ10ꢀmL)ꢀandꢀCH Cl ꢀ(3ꢀ¥ꢀ5ꢀmL).ꢀ
1132,ꢀ1100,ꢀ840ꢀcm .
4-Acetaminophenyl vinyl ether (6l):ꢀWhiteꢀsolid,ꢀm.p.ꢀ102–103ꢀ°C.ꢀ
1
4
1
(lit. ꢀm.p.ꢀ103–103.5ꢀ°C);ꢀ HꢀNMR:ꢀdꢀ=ꢀ7.40–7.50ꢀ(m,ꢀ2ꢀH),ꢀ7.26ꢀ
(brꢀs,ꢀ1ꢀH),ꢀ6.95–7.05ꢀ(m,ꢀ2ꢀH),ꢀ6.63ꢀ(dd,ꢀJ =ꢀ13.7,ꢀ6.1ꢀHz,ꢀ1ꢀH),ꢀ4.75ꢀ
(dd,ꢀJ =ꢀ13.7,ꢀ1.7ꢀHz,ꢀ1ꢀH),ꢀ4.55ꢀ(dd,ꢀJ =ꢀ6.1,ꢀ1.7ꢀHz,ꢀ1ꢀH),ꢀ2.18ꢀ(s,ꢀ
2
2
Toꢀaꢀsuspensionꢀofꢀtheꢀswollenꢀresinꢀ5a–mꢀinꢀCH Cl ꢀ(10ꢀmL)ꢀandꢀ
2
2
0
.5ꢀmLꢀofꢀ30%ꢀH O (5.8ꢀmmol)ꢀwasꢀaddedꢀatꢀ0ꢀ°C.ꢀTheꢀsuspensionꢀ
2 2ꢀ
1
3
wasꢀshakenꢀatꢀ0ꢀ°Cꢀforꢀ0.5ꢀhꢀandꢀthenꢀatꢀroomꢀtemperatureꢀforꢀ1.0ꢀh,ꢀ
3ꢀH);ꢀ CꢀNMR:ꢀdꢀ=ꢀ169.2,ꢀ153.2,ꢀ148.5,ꢀ133.4,ꢀ122.1,ꢀ117.3,ꢀ94.6,ꢀ
the residual resin was collected by filtration and washed with CH Cl ꢀ
24.1;ꢀIRꢀ(KBr):ꢀnꢀ=ꢀ3258,ꢀ3188,ꢀ3130,ꢀ3055,ꢀ1650,ꢀ1600,ꢀ1495,ꢀ1300,ꢀ
2
2
-1
(
2ꢀ¥ 10 mL). The filtrate was treated with saturated NaHCO ꢀ(20ꢀmL)ꢀ
1235,ꢀ1210,ꢀ1162,ꢀ1145,ꢀ940,ꢀ830ꢀcm .
3
2
3
andꢀwashedꢀwithꢀwater,ꢀdriedꢀoverꢀmagnesiumꢀsulfateꢀandꢀevaporatedꢀ
toꢀ giveꢀ crudeꢀ productsꢀ 6a–m withꢀ 94–97%ꢀ purityꢀ determinedꢀ byꢀ
HPLC, which were further purified by column chromatography on
1-Naphthyl vinyl ether (6m):ꢀWhiteꢀsolid,ꢀm.p.ꢀ31–32ꢀ°C.ꢀ(lit. ꢀm.p.ꢀ
32ꢀ°C);ꢀ HꢀNMR:ꢀdꢀ=ꢀ7.00–7.50ꢀ(m,ꢀ7ꢀH),ꢀ6.71ꢀ(dd,ꢀJ =ꢀ14.1,ꢀ6.0ꢀHz,ꢀ
1ꢀH),ꢀ4.81ꢀ(dd,ꢀJ =ꢀ14.1,ꢀ1.6ꢀHz,ꢀ1ꢀH),ꢀ4.45ꢀ(dd,ꢀJ =ꢀ6.0,ꢀ1.6ꢀHz,ꢀ
1

JOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2009ꢀ 289
1
3
1
1
1
ꢀH);ꢀ CꢀNMR:ꢀdꢀ=ꢀ152.7,ꢀ144.9,ꢀ133.9,ꢀ132.6,ꢀ128.9,ꢀ128.7,ꢀ128.3,ꢀ
5
6
S.N. Savinov and D.J. Austin, J. Chem. Soc., Chem. Commun.,ꢀ 1999,ꢀ
1
813.
26.7,ꢀ125.9,ꢀ123.5,ꢀ115.8,ꢀ95.7;ꢀIRꢀ(KBr):ꢀnꢀ=ꢀ3050,ꢀ1630,ꢀ1600,ꢀ
495,ꢀ1255,ꢀ1226,ꢀ1172,ꢀ1152,ꢀ1142,ꢀ942ꢀcm .
-1
P.E. Maligres, M.M. Waters, J. Lee, R.A. Reamer, D. Askin,ꢀ
M.S. Ashwood and M. Cameron, J. Org. Chem., 2002,ꢀ67,ꢀ1093.
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K. Mizuno, Y. Kimura and Y. Otsuji, Synthesis,ꢀ1979,ꢀ688.
W. Reppe, Liebigs Ann. Chem.,ꢀ1956,ꢀ601,ꢀ8.
D.A. Evans, J.L. Katz and T.R. West, Tetrahedron Lett.,ꢀ1998,ꢀ39,ꢀ2937.
Y. Okimoto, S. Sakaguchi and Y. Ishii, J. Am. Chem. Soc.,ꢀ2002,ꢀ124,ꢀ
1590.
N.F. Mckinley and D.F. O'Shea, J. Org. Chem., 2004,ꢀ69,ꢀ5087.
M. Blouin and R. Frenette, J. Org. Chem., 2001,ꢀ66,ꢀ9043.
H.J. Reich, Acc. Chem. Res.,ꢀ1979,ꢀ12,ꢀ22.
K.C. Nicolaou, J. Pastor, S. Barluenga and N. Winssinger, Chem.
Commun.,ꢀ1998,ꢀ1947.
7
8
9
0
We gratefully acknowledge financial support from the Natural
Science Foundation of Jiangxi Province of P. R. Chinaꢀ
No. 2007GZH839 and No. 2008GZH0029) and the Research
Program of Jiangxi Province Department of Education
GJJ08165).
1
(
1
1
1
2
(
13
14
15
16
Received 26 December 2008; accepted 6 March 2009
Paper 08/0352 doi: 10.3184/030823409X447682
Published online: 20 May 2009
1
7
Q.-S. Hu, S.-R. Sheng, S.-Y. Lin, M.-H. Wei, Q. Xin and X.-L. Liu,ꢀ
J. Chem. Res(S).,ꢀ2007,ꢀ74.
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