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New synthetic “tricks” One-pot preparation of N-substituted phthalimides from azides and phthalic anhydride
Tetrahedron Letters, Vo1.27, Printed in Great Britain
No.5,
NEW
pp 639-640,
1986
0040-4039/86 $3.00 + .OO 81986 Pergamon Press Ltd.
SYNTHETIC "TRICKS'!
CNE-POT PREPARATION OF N-SUBSTIWI'ED PHTHALIMIDES FRCMAZIDES AND PHIWALICANHWRIDE Jordi Garcia and Jaume Vilarrasa Departament
de Q&mica
Org$nica, Facultat de Quimica, Universitat 08028 Barcelona, Catalonia, Spain
of Organic
Chemistry.
de Barcelona,
XavierBordas and AnnaEanaszek Institute
Polish Academy
of Sciences.
Warsaw, Poland
N-Substituted pbthalimidescan beobtained in verygoA yields, underessentially neutral conditions, byor heating an alkyl(orary1) azide, triphenylphosphine, and phtblic anhydride in benzene or toluene,inthe presence of a catalytic pranisC-q+
munt
of tetrabutylamronim cyanide. Application of tke reaction into the damin of carbchydrates ia
7be@haloylgnxpisa
amzmprotectirggrcupforanines: thea7rineisalla4sdtorextwithphthalic8J?r
dri&(orwitharelat&canparrd)aoi
theresultingintennsdiateis thenheated tocause theintrz3mlecularaXXkl-
sstiao to the cbnsircdphthazimide~l the phtklolyl groupmt
only blccks the amine but may ckmge the reectivityof
either the vicinalcarixn atans or shstituents (hysteric hirrirance. byancMmaric assistanon...)rfinsllyrits ofh~~ne.Whslmilderconditionsthanthasejustindicat~arere3uired.
clesvageisnommllyaconipliahedbymeans ~@h&mi~grcupcanbe~teredvia
theMitsunobureacticnr2frcm thealcohol ardphthalimide.3kw3er.
unsatis-
factoryyiebisaresmet.imesoh~.
sincedabydratian-a reacticnal.sopranXedby the Et@ZO-N=N-COOEt/phgp
reagent-instead ofsubstituticn&es
often place.
Lproposehereanaw,altemstiveuayfor
theprepsratianof~~imidoderivatives,
(L) and convertsthenintothemr~~phasphazenesorphasphineimides(~),4
khichstartsfmnazides
thesecaqx&sreactirg
in situ
with pVhalicanhydride.Inprel iminvyevperimntsrreobservedthatmnpollnds1resc~gui~ylyithphthalicanhyorif& togive inter-a&&&s that uerem3reslowlyconvertadintomixturesof
the@halimido
derivat.ives(~)~ their
Ph3p R-i?-N=N-hPh3-j
R-N=PPh3 t
T N2
2
thewrkup. lheovemZ1 yieldswere ccrmqmtlylow.
Wereporthere tit thepresence of 0.1 quiv. of tetrabuty1-
~vnc~de~izasquantitatively4intothedesired,~~callyfavcured'~(~~tterlvfiether~JVf ~isaddEdatthe@irmingorattheerdofthen33ction). ikresultsCanbe
summrizedasfollcwa:
639
640
0
$,R=H, C&j, rt,L?.h,81% 0X&
&R=&,C+&j,A,&,85Z &Ra$IMs2,Q,Q#,=,
l3, C&,A,42h,81%7
lkmlly, 1.0 mwls of the azide, 283 q (1.1 mmls) ofPh9, 163ng (1.1 mmls) of $tinlicaohqdridejust p-ifiedbysublimtim,azdca. P~ofanh. EQV& were dismlved in 5-1Oml ofa&. bmzezeor toluene,wxkr N2. In the case of -5. 6,'andl3stirring overnightat rem tenpratore WB sufficientto obtain a practicallyquantitative anversim (XV). (3 the other hand, for the nwre hkdered azides hsating in tolueneat reflex km.3nxeisxy toenhame tkreactivit ofthephosphazene tithphthalican+dride.Aftem~3r&. theorganicsolutims kere concmtratsdt and @zhalimidss 8 w+reeaaily.sqaratedbycolum chramtcgraphy(either with ~$l2orC@l4/AdXt) cmailica gel. .Sxeadvantaggareinkrent
to thisnew"vi~"forprotect~arrdnogroups:i)~~ygoodyielcLsare
abtained~-~t,quitesrmthormlitigns:ii)chiralcentres~ involvedinrhereactia,andsince,even~in~~e~ aregsenti~ly~tralr
izmpmk 2-mim
iii)application
tim orr&timmight-,tkaxditiak3
tonatural prc&Yssemsprmisingespciallyin
with piXhalimic.k3gmpatC-2lilce~and~are sugars, ofdkauharides
lm.lter~,as~ted,sincetheyaremt
carbdqdratecbmistry:lo
veryeffective for thesynthe3i.9, fmnderivativesof
(oroligosaccharides)with &gl~~clinkag~.~l
l.-A.K.E!ase, inOrg.S_@~.Ml. Vol.V, Wiley,NewYork,1973. E.HoffmnnandH.Schiff-Shenhav, J.Org.Ckmr27, 46%(1%2). D.A.&o@&er, D.N.Reinhmdt, T.S.Lie, J.J.Gunneweg, andH.C.Eeyemm.Rec.lkav.Chim.fay+Bas,~,819 (1973).Fora review, seeT.W.Greene, '!Protective Groupsin Organic Synthesis", Wiley,NewYork,1981. 2.-Review: O.Mitsunobu, S~thesis,l(l%1). 3.-See,e.g.,M.&niel&, J.Jur&, andA.Zumjski, Tetra&lrm,34,2977(1978) andref.therein. 4.-Fora recentreviewon theStaudinger reaction (i.e.1-2) seeYu.G.Gololobov, I.N.Zlnurova, andL.F.&mkhin, Tetrahedrm,37,437(1%1). to thecorresponding imidesat hightemperature. SeeG.V.Poyd andR.L. 5.-Itisla~mmthatn~stiso~desrearrange Mmteil,J.Qlem.soC.,pT-1,133!3(1978), W.R.Rcdericj andP.L.Bhatia, J.Org.Qm&28,2018(1%3), and ref.therein. 6.-Wnenthereection~perfo~without~~,inretl.benzene for lob,separationby columchxcmtqraphy afforded 11 in 37%yieldandthecorresponding isoirrride in 35%yield. 7.-lhereacZonhw actually carried outwithamixtureof anawrs (BX of anmra, 12%of amm- 0). 8.-Inthiscase,ti-e Pmsphineinddewsgenemtedfranethylleucim te hydrochloride, Phw2 (1.05quiv.),ami NEt3(3.3qliv.). 9.-'Ihestnrtureswereconfirmedbyl~,l~, and IR spectrascopy,and also,in saw cases,bycaquismwith lamm,aut.hentic samples.Satisfactorymicrcmalyseswereobtained forthenewproducts. lo.-Several phosphazenes arising franazidosugarshavebeenformerly reported to affordeithercarbodiinn'des or cyclic carbamtes(withC%) andaziridine derivatives (e.g., fransme 3-N~2-0Tsderivatives).SeeA.Elessner,I.Pint&r,and v&s,I.Pint&,A.E,andG.T&h, Car&+dr.Res..141,57(1%5),.+ ref.th. F.Szeg~,Aqgew.&em.Int.Ed.r3,ZB(1%2),J.Ko ll.-Review: H.Paulsen, &gew.Ckm.Int.Ed.,21.155(1982). A&m&dgmznt.- J.G.andJ.V.thanktheirfriends GaborJ&acs andSergioCastill6n (XX, Gif-sur-Yvette) forsmples of saw protected sugars. (Received
in UK 15 November 1985)
No.5,
NEW
pp 639-640,
1986
0040-4039/86 $3.00 + .OO 81986 Pergamon Press Ltd.
SYNTHETIC "TRICKS'!
CNE-POT PREPARATION OF N-SUBSTIWI'ED PHTHALIMIDES FRCMAZIDES AND PHIWALICANHWRIDE Jordi Garcia and Jaume Vilarrasa Departament
de Q&mica
Org$nica, Facultat de Quimica, Universitat 08028 Barcelona, Catalonia, Spain
of Organic
Chemistry.
de Barcelona,
XavierBordas and AnnaEanaszek Institute
Polish Academy
of Sciences.
Warsaw, Poland
N-Substituted pbthalimidescan beobtained in verygoA yields, underessentially neutral conditions, byor heating an alkyl(orary1) azide, triphenylphosphine, and phtblic anhydride in benzene or toluene,inthe presence of a catalytic pranisC-q+
munt
of tetrabutylamronim cyanide. Application of tke reaction into the damin of carbchydrates ia
7be@haloylgnxpisa
amzmprotectirggrcupforanines: thea7rineisalla4sdtorextwithphthalic8J?r
dri&(orwitharelat&canparrd)aoi
theresultingintennsdiateis thenheated tocause theintrz3mlecularaXXkl-
sstiao to the cbnsircdphthazimide~l the phtklolyl groupmt
only blccks the amine but may ckmge the reectivityof
either the vicinalcarixn atans or shstituents (hysteric hirrirance. byancMmaric assistanon...)rfinsllyrits ofh~~ne.Whslmilderconditionsthanthasejustindicat~arere3uired.
clesvageisnommllyaconipliahedbymeans ~@h&mi~grcupcanbe~teredvia
theMitsunobureacticnr2frcm thealcohol ardphthalimide.3kw3er.
unsatis-
factoryyiebisaresmet.imesoh~.
sincedabydratian-a reacticnal.sopranXedby the Et@ZO-N=N-COOEt/phgp
reagent-instead ofsubstituticn&es
often place.
Lproposehereanaw,altemstiveuayfor
theprepsratianof~~imidoderivatives,
(L) and convertsthenintothemr~~phasphazenesorphasphineimides(~),4
khichstartsfmnazides
thesecaqx&sreactirg
in situ
with pVhalicanhydride.Inprel iminvyevperimntsrreobservedthatmnpollnds1resc~gui~ylyithphthalicanhyorif& togive inter-a&&&s that uerem3reslowlyconvertadintomixturesof
the@halimido
derivat.ives(~)~ their
Ph3p R-i?-N=N-hPh3-j
R-N=PPh3 t
T N2
2
thewrkup. lheovemZ1 yieldswere ccrmqmtlylow.
Wereporthere tit thepresence of 0.1 quiv. of tetrabuty1-
~vnc~de~izasquantitatively4intothedesired,~~callyfavcured'~(~~tterlvfiether~JVf ~isaddEdatthe@irmingorattheerdofthen33ction). ikresultsCanbe
summrizedasfollcwa:
639
640
0
$,R=H, C&j, rt,L?.h,81% 0X&
&R=&,C+&j,A,&,85Z &Ra$IMs2,Q,Q#,=,
l3, C&,A,42h,81%7
lkmlly, 1.0 mwls of the azide, 283 q (1.1 mmls) ofPh9, 163ng (1.1 mmls) of $tinlicaohqdridejust p-ifiedbysublimtim,azdca. P~ofanh. EQV& were dismlved in 5-1Oml ofa&. bmzezeor toluene,wxkr N2. In the case of -5. 6,'andl3stirring overnightat rem tenpratore WB sufficientto obtain a practicallyquantitative anversim (XV). (3 the other hand, for the nwre hkdered azides hsating in tolueneat reflex km.3nxeisxy toenhame tkreactivit ofthephosphazene tithphthalican+dride.Aftem~3r&. theorganicsolutims kere concmtratsdt and @zhalimidss 8 w+reeaaily.sqaratedbycolum chramtcgraphy(either with ~$l2orC@l4/AdXt) cmailica gel. .Sxeadvantaggareinkrent
to thisnew"vi~"forprotect~arrdnogroups:i)~~ygoodyielcLsare
abtained~-~t,quitesrmthormlitigns:ii)chiralcentres~ involvedinrhereactia,andsince,even~in~~e~ aregsenti~ly~tralr
izmpmk 2-mim
iii)application
tim orr&timmight-,tkaxditiak3
tonatural prc&Yssemsprmisingespciallyin
with piXhalimic.k3gmpatC-2lilce~and~are sugars, ofdkauharides
lm.lter~,as~ted,sincetheyaremt
carbdqdratecbmistry:lo
veryeffective for thesynthe3i.9, fmnderivativesof
(oroligosaccharides)with &gl~~clinkag~.~l
l.-A.K.E!ase, inOrg.S_@~.Ml. Vol.V, Wiley,NewYork,1973. E.HoffmnnandH.Schiff-Shenhav, J.Org.Ckmr27, 46%(1%2). D.A.&o@&er, D.N.Reinhmdt, T.S.Lie, J.J.Gunneweg, andH.C.Eeyemm.Rec.lkav.Chim.fay+Bas,~,819 (1973).Fora review, seeT.W.Greene, '!Protective Groupsin Organic Synthesis", Wiley,NewYork,1981. 2.-Review: O.Mitsunobu, S~thesis,l(l%1). 3.-See,e.g.,M.&niel&, J.Jur&, andA.Zumjski, Tetra&lrm,34,2977(1978) andref.therein. 4.-Fora recentreviewon theStaudinger reaction (i.e.1-2) seeYu.G.Gololobov, I.N.Zlnurova, andL.F.&mkhin, Tetrahedrm,37,437(1%1). to thecorresponding imidesat hightemperature. SeeG.V.Poyd andR.L. 5.-Itisla~mmthatn~stiso~desrearrange Mmteil,J.Qlem.soC.,pT-1,133!3(1978), W.R.Rcdericj andP.L.Bhatia, J.Org.Qm&28,2018(1%3), and ref.therein. 6.-Wnenthereection~perfo~without~~,inretl.benzene for lob,separationby columchxcmtqraphy afforded 11 in 37%yieldandthecorresponding isoirrride in 35%yield. 7.-lhereacZonhw actually carried outwithamixtureof anawrs (BX of anmra, 12%of amm- 0). 8.-Inthiscase,ti-e Pmsphineinddewsgenemtedfranethylleucim te hydrochloride, Phw2 (1.05quiv.),ami NEt3(3.3qliv.). 9.-'Ihestnrtureswereconfirmedbyl~,l~, and IR spectrascopy,and also,in saw cases,bycaquismwith lamm,aut.hentic samples.Satisfactorymicrcmalyseswereobtained forthenewproducts. lo.-Several phosphazenes arising franazidosugarshavebeenformerly reported to affordeithercarbodiinn'des or cyclic carbamtes(withC%) andaziridine derivatives (e.g., fransme 3-N~2-0Tsderivatives).SeeA.Elessner,I.Pint&r,and v&s,I.Pint&,A.E,andG.T&h, Car&+dr.Res..141,57(1%5),.+ ref.th. F.Szeg~,Aqgew.&em.Int.Ed.r3,ZB(1%2),J.Ko ll.-Review: H.Paulsen, &gew.Ckm.Int.Ed.,21.155(1982). A&m&dgmznt.- J.G.andJ.V.thanktheirfriends GaborJ&acs andSergioCastill6n (XX, Gif-sur-Yvette) forsmples of saw protected sugars. (Received
in UK 15 November 1985)