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酰胺硒取代
TETRAHEDRON
LETTERS
Pergamon
TetrahedronLetters44(2003)6911–6913
SynthesisofN,N-disubstitutedselenoamidesbyO/Se-exchange
withselenium–Lawesson’sreagent
JohnBethke,aKonstantinKaraghiosoffb,*andLudgerA.Wessjohanna,*
b
Leibniz-InstituteofPlantBiochemistry,Weinberg3,06120Halle(Saale),Germany
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DepartmentofChemistry,Ludwig-Maximilians-UniversityMunich,Butenandtstra?e5-13(D)
,81377Munich,Germany
Received28May2003;revised4July2003;accepted5July2003
a
Abstract—TheseleniumanalogueofLawesson’sreagent,[PhP(Se)(m-Se)]2isaneffectiver
eagentforsynthesizingN,N-disubsti-tutedselenoamides.Thereactioniscarriedoutunder
mildconditions(roomtemperature)andaffordstheselenoamideinhigheryieldthanusingoth
erselenationreagents.?2003ElsevierLtd.Allrightsreserved.
Selenoamidesarewellknowninpreparativeorganicchemistry.Publicationsonthistopicrea
chbacktothebeginningofthelastcenturyandmanydifferentreagentsfortheintroductionof
seleniumwereused.1Incontrasttothehomologousthioamides,however,thesynthesisofsele
noamidesisstillachallenge,duetothelackofsuitable,readilyobtainable,andeasytohand
leselenatingreagents.HerewereportageneralandhighlyeffecientsynthesisofN,N-disubs
titutedselenoamidesusingthenovelselenatingreagent1,3-di-selena-2,4-diphosphetane
-2,4-diselenide(2,Fig.1).2,3Compound2representsaseleniumanalogueofthewell-knowns
ulfurtransferreagent1(Lawesson’sreagent)andiseasilypreparedbyreactionof(PhP)5wi
th10equiv.ofgreyselenium.4ItsabilitytoactasaseleniumtransferreagentbymeansofanO/
Se-exchangewasinitiallyreportedbyoneofus,5andthegroupofJ.D.Woollins.6
Reactionoftheformamides3–7withtheselenide2ina4:1molarratioinbenzeneatambienttem
peratureresultsinanO/Se-exchangeatthecarbonylcarbonatomwithformationoftheselenof
ormamides17–21(Scheme1).Thereactionproceedssmoothlyandiscompletewithinamaximumo
f20h.Theselenoform-
amides17–21areisolatedinyieldsupto85%(Table1).Thismethodisofgeneralapplicabilit
yandcanbeextendedtothesynthesisofvariousN,N-dialkylsubsti-tutedselenoamides(22–
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28)havinganalkylorarylsubstituentattheselenocarbonylgroup.Asexpected,thereactivi
tyoftheamidesdecreaseswithincreasingchainlengthandbulkinessofthesubstituentsatni
tro-
Figure1.Lawesson’sreagent1andtheseleniumanalogue2.
Keywords:selenoamides;O/Se-exchange;selenium–Lawesson’sreagent;selenium-NMR.
*Correspondingauthor.Tel.:
49-345-5582-1301;fax:
49-345-5582-1309;e-mail:wessjohann@ipb-halle.de
0040-4039/$-seefrontmatter?2003ElsevierLtd.Allrightsreserved.doi:10.1016/S0040-4
039(03)01690-3
Scheme1.Synthesesofselenoamidesusing2.
6912J.Bethkeetal./TetrahedronLetters44(2003)6911–6913
Table1.SelenoamidespreparedbyO/Se-exchangewithreagent219
Carboxamide345678910111213141516
a
Selenoamide1710181119102012211222132314242526132715281629173018
R
HHHHHMeMeMeMeEtPh
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4-MeOC6H4n=1n=2
R1MeEtiPrMePhMeEtiPrMeMeEtMeMeMe
R2MeEtiPrPhPhMeEtiPrPhMeEtMe––
Yield(%)8277758559662921485772667461
Mp(°C,uncorr.)l
77
Se20
87–88–10570–
3045
609.5a568.8a586.3a768.8a879.4a627.4b592.9c597.9c659.3c578.2c771.0a718.4a376.4b53
8.9c
MeasuredinC6D6.MeasuredinCD2Cl2.c
MeasuredinCDCl3.
b
gen,whichresultsinlongerreactiontimesandsome-whatloweryields.Cyclicselenoamides,
e.g.29and30,canbepreparedstartingfromthecorrespondinglac-tams15and16bythesamepro
cedure.
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Inallinvestigatedreactions,allfourseleniumatomsofthediselenide2aretransferredtot
heorganiccom-pound.Thus,initsselenium-transferability2ismoreeffectivethanLawesso
n’sreagentinitssulfur-transferability,whereonlyhalfofthesulfuratomsareusedtogen
eratethethioamide.Themainphosphoruscon-tainingby-product(>80%)isthe2,4,6-triphen
yl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide,whichisreadilyidenti?edbyits3
1PNMRspectrum(A2Btypespectrum,lA=1.6,lB=3.5,2JAB=39.9Hz).
Theisolatedselenoamidesareidenti?edandcharacter-izedby1H,13C,77SeNMRspectroscopy
,IRspec-troscopy,andmassspectrometry.Characteristicisthelow?eldchemicalshiftofth
eselenocarbonylcarbonatom(l=188.6–194.1fortheformamides,and200.8–209.7forother
carboxamides)inthe13CNMRspec-trumandthelargevalueof1JSeC(210.4–219.2Hz).7,8Inth
e77SeNMRspectrum,thesignaloftheone-coordi-natedseleniumatomappearsatlow?eld(l=53
9–880)inarangetypicalforl77Seofselenoamides.8,9Itisworthnotingthewellresolved77
Se-satellitesobservedforthesignaloftheformamideproton(l=10.3–11.7)inthe1HNMRspe
ctrumwith2JSeHintherangeof7–10Hz.Thea-CH-protonsofthehigherselenoamidessynthesi
zedappearbetween2.4and3.1ppm.
Inconclusion,theselenationofamidesusingaseleniumanalogueofLawesson’sreagent,the
1,3-diselena-2,4-diphosphetane-2,4-diselenide2,providesageneralandstraightforwar
droutetoN,N-disubstitutedselenoform-amidesandselenoamides.Theeasyavailabilityofs
elenoamidesbythisroutestimulatesasystematicstudyoftheirchemicalproperties.Furthe
rchemistryof2andofotheranaloguesofLawesson’sreagentisundercurrentinvestigation.
Acknowledgements
WethanktheDeutscheForschungsgemeinschaftfor?nancialsupport.
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19.Generalprocedure:Toasuspensionofreagent2(0.53g,
1mmol)in3–5mlbenzenethecorrespondingcarbox-amide(4mmol)isadded.Theresultingmixt
ureisstirredfor12–20hatroomtemperature,while2dissolvescom-pletely.Fromtheresult
ingclearyellow–greensolutionthesolventisevaporatedinvacuoandtheresidueissubject
edtovacuumdistillation[10?1mbarand90–150°CKugelrohrapparatustemperature(Bu¨ch
i)]orchro-matographedondried(!)silicagelwithCH2Cl2.
20.Spectraldataforsometypicalselenoamides:17:1HNMR
(C6D6,270.17MHz):10.32(s,1H,CH??Se),2.73(s,3H,CH3),2.07(s,3H,CH3)ppm.13C1HNMR(C6
D6,67.94MHz):191.3(CH??Se),47.9(CH3),40.9(CH3)ppm.77SeNMR(C6D6,51.39MHz):609.5pp
m.22:1H
NMR(CDCl3,300MHz):3.62(s,3H,CH3),3.26(s,3H,CH3),2.69(s,3H,CH3)ppm.13CNMR(CDCl3,7
5.5MHz):202.7(C??Se),48.7(CH3),42.7(CH3),37.2(CH3)ppm.77SeNMR(CD2Cl2,95.4MHz):62
7.4ppm.GC–MS(70eV):m/z151(M ??,100%),107(32%),MS(ESI):151.99662.Anal.calcdforC4
H9NSe(150.08):C,32.01;H,6.04;N,9.33.Found:C,31.98;H,5.91;N,8.93%.24:1
HNMR(CDCl3,300MHz):6.35–6.16(m,1H),4.24–4.04(m,1H),2.89(s,3H,CH3),1.46(d,J=6.6
Hz,6H,CH3),1.27(d,J=5.9Hz,6H,CH3)ppm.13CNMR(CDCl3,75.5MHz):202.8(C??Se),60.4(NCH
),50.1(NCH),37.4(CH3),22.0(CH3),19.1(CH3)ppm.77SeNMR(CDCl3,95.4MHz):597.9ppm.GC
–MS(70eV):m/z207(M ??,46%),123(43%),58(100%).MS(ESI):208.05959;calcd:208.0599.2
5:1HNMR(CDCl3,300MHz):7.51–7.37(m,3H,arom.H),7.22–7.16(m,2H,arom.H),3.85(s,3H,
CH3),2.43(s,3H,CH3)ppm.13CNMR(CDCl3,75.5MHz):205.1(C??Se),145.6(C-i),129.9(C-m),
128.6(C-p),124.3(C-o),49.9(NCH3),38.4(CH3)ppm.77SeNMR(CDCl3,95.4MHz):659.3ppm.GC
–MS(70eV):m/z213(M ??,31%),91(38%),56(100%).MS(ESI):214.01217;calcd:214.0129.30
:1HNMR(CDCl3,300MHz):3.58(s,3H,NCH3),3.42(t,J=6.2Hz,2H,NCH2),3.04(t,J=6.2Hz,2H,C
H2),1.96(quint,J=6.2Hz,2H,CH2),1.70(quint,J=6.2Hz,2H,CH2)ppm.13CNMR(CDCl3,75.5MH
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z):202.4(C??Se),53.8(NCH2),47.5(NCH3),45.1(CH2),22.9(CH2),20.4(CH2)ppm.77SeNMR(C
DCl3,95.4MHz):538.9ppm.GC–MS(70eV):m/z177(M ??,91%),68(100%).MS(ESI):178.01214.
Anal.calcdforC6H11NSe(176.12):C,40.92;H,6.30;N,7.95.Found:C,40.88;H,6.21;N,7.63%
.
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