o-D-mannoplrannside `
Transkrypt
o-D-mannoplrannside `
]oL^Nl,\MĄsLlŃsK]\ sollclf ' sYLl,! I^ Dg}.łh:!lt.IfhFi.il ch!)islry rdT.|] KLKol!(A .log]. 01 |o]ynos synth€sis of ma.rocvclic and linear olisorners of methyl o-D-mannoplrannside ' s!nna!} Tjt Pol|.ond.xłtjoI oI thlL! D mnNf]lar!ia! lI) rutl] r'!hśL1.ń]mrI]rh.l|1! tł6 (|')u'dg ]]ooU\ i(i]..]hjrśs .idsr.ihI .l5ll+ll t2+ż] hn.il.oPolyn.I diildlhydl Iho. !( d i]]t fuóLył'1a.L llt nolil l]ho ot.ihLl* io in|d.hyd.' sh.l'a Y.:y !.o' |łhola. nountli łI&! Dn )dd ÓIlhe;eJl 'lg|'i..łl]4 i]ł rłan! l]] Jrh n{!'i, j hrs,,i rononinilris,fro!,dN Ii !iiin lii (r. (o,ro d].nn.il' :h1sjń] r1 |]:olog]sl P1]TdLś ihł !l.]] I', 19l2 n:g!:, l !lł(!..]'.lc uMd .Didil:olT lllr:lh !!.l. lii.r slhc "n:sgh 7i.!hr dlLlhon TłhoJ' lltzD\o ]ll Thb an.lPo]lDdś nńy r'! alL:l'!.Lri| ,L,i.|r,iLlu L:nn.id,.ns.' dddrnB.fid,otrs) l".oiort, r.:s LrB trlFnriÓl .i jm.Lo.!d$ ThjsDr pd i.adion his thc tgn!i. ,r! r.f,.s.ir th. rb(nod!Nrl b rl'! {L'rhq. d ainihoi 1 o]igoDcĘ is bl|Iod!d .f {j]. ''b].L L']hIg .t|] ]b k]ntraL]J.l}r! .l.Lłł]o| o d j fudtal d!]i'rŃ oJ r||! ll $ ]rLgh.|.i:gon.E hil. l1l EtśLll v ! rf. J Ho]rI.l, thEiPp:oi.h E omfel! d .ło] PoL|.ondaxalion Protigahon llP.nsif il.s jl d:'ńfl]]i \1 l) fu].]o.|.in t.Lt.ilE :v$.ń\ li|.b..l|l! rh. m|orbut (1. or q.l12 m m polr.on.i!)si !rn1 5i{. F.d.]s.n!.J L:.] sl ł] dDr| ł]]q l9]' TIL! lEilĄlą)]1rt5 spoibtr.oLs s!L. no|bL|otb.ł..'o|śFtdu kIilddul '! i1 t]] Ijj.h..]iśl-llh.oĘ o' Po]l.on sscnblv oi rhc sub*tstr. rh tr :! ls airr Frory 16,71 rń Ńln.nt lj.n.lG), oi ]egE JrLl Joorb.DśEv Ń .vdiŻ idr lt..iLinśd. mtPlar inflole,ina nod]'t.' df o(urDs rtues$ r!,ih ihe s fś',!Lł.n:IIgLh. (Tc|] r!is n{ntiL]! 1olłl]jled F.lIotr!!nn.ons nide I!] 1950 ]iÓ5l .)i sb.lNYcI t3] modltBl ałti.l]ar b.!:n,.n *at6 lllL1rD]jen boIdng, hPo' .hir. fu |udoqo lt't-....'.ro'"...r', '' 'a!] iśq1i.;.jlI i i soLcoLl!l.iu p..rr1r t.li.pir n6ign eflołs tÓ.onfÓl iselró!.t]b:1 t]r]l r.s).iłr.!; st|. hrdr !a!lv studi.s m our labonr the Ęadlon o' meńyl 0 D nannoF]'tnosidc (I] on s.hem.A]w llnmlla h dńjJeh],des llclePhihaIildehyde n1] oI l,x bis(z.lorm],lFhenory).lk3n.s tF.ń!la 0D on tr2 r5lllcads to thc Iorm ,on ormx o._v s.hen,eAl s (Le\aod l,ne nu..onoho Th.presentP3perdeals nih sfodies Ón płańłss lhat. rnr ormrtroq,dE.oDpou.ds +r6?:3c (. = r 5 ń (rS).1+)..rmphor r0 H,o)' trellinc Pojnt 29o surloni..lid ( =2r H:o 3o0 t' =!cl'L _solvenb toli bcM.l.'djń*hykllfold!(DN{so), !hl'on'nr, i.done' py!dń. Jl vdrÓus 99 -r !! (Pocl.' clŃrc, u]itv.aL gEd? pmd!.łn jn thc FolycondcnsrLior A F'xtun.r u) (005 mohr iNi I lnlhon 0]enz€ne/DN'so) .onh .ahlls ta5 subF.Ed ro aŻ.oEoPr dEh Tn. rolloHirE mattuls n.r. usRl: Meihyl n D mannopyrrnosidc FlL,ka, Bi. chcn]Li fo] mbobloloEy>99 0 9l Glh oIł3nilońssl HPLC)' ldli'= |i9i2'(. - r0 ]n llro), ńdbng to]nt ],x-BB(2lolńvlphenÓiv)alkanes rde (rlura) w r!,rh.Dson dh.nfi.a.on w h l 3]krlatjoiof 2 hvd roxybe i2al deh cablysś _ f To]uencs]|aon. iod nonohydnle łdod.łid (ilcD,ljluta], t1]; = (| TsoH; Fluta), B Óia ([ Evas.\brł.d llith extił wł5 N6hed włh i solLłjon o' Niilcor }!ter (3 r tincs), dn.d ovo inhrdr.or .hlolofom Th. Mgso], Iilt{ed olf ind !.h]orÓIÓ.ń \aŚ Ęmorcd und.: ledtr.elF.e$ulc Th. |joLl!ł M Tl]. Ilałion DsoLuD]c !] tłÓm l|olńula o!) o| sdĘn]eAw}s. x = 1, 5' ]j, s] Ras p!.ned bv.:j'9.]l]/ ]on fronr ethyl a.łate.hLorofom (3l)' Th. łrU. tur oI IIII) was ideihń.dby rHNMR,ircNMRsFT L tt tixj ,r\) sct?w A Prl|djtttn lnł ń nlhll a D L'hon 1Dc r shrk) A'tu ih! Fadnń' the Ghlvś}?s fiLend dead,v cd l{kh cacot.nd th. s ł'fłd;il,'!snl r]) l'ił ]/ liJ(2 lnnqj|n vłkl|jnć nI) Ii,nuli irv)] i!: dri.r u,d.r!i.uuo \l ])d '. r\rlR sP..ti "'.l. j..o;.jŃ lsj)g i sP!łr.D!t: (]_r0 vH2 aIJ r'i:].n]'|n]tr,lJ]]oYi g M^T T9Q 70ir !+n. ,(. rl n!r,, s {ig. qMdr:p.r.,ms sp.dnl n\., cA. r ,.r.I0!mBD,L s oiru I c,u .li\:) ofrl }]n \JiśsPt!uD r itrs( oi{/]:Ll 2iiil nl t.Ś tn'ci.! .d i |r: e!ENptus .r noL1. T]t !A|is D F]!|]| : .J 0lh) r!l.m \ = ó) .l]. i-r h Llnlr mr-!onh\r Lirng.rlit6 6! fp'n srhrir ltu.l. r! : r't i, ,c l,rt.\ r rng ir.ln,id(rh.10 i tr i: .rri .otrnnn or), .h(N,dr F(:-r! rJlfum.r:!pnn.tr.a!rnno5!r. nłh.\)' |nlons' Po!]qil llni) t.\ś!ih[..!j L{ a.1, o l:2 (r,\ nio\r)lrl,(r)ll ]h. r! :!llIi T.dnLn] iFjg 2)..']i]mŃr]r!N.o linŻ |1(H.,,J.ld H 2 di.\::] 2 yl (Hl) ind c' f, : ]r. NvR li:r Mi:, .]D.]1]) lP/ł] ł]Jlr ł.jtrlil.!lD.lli'llrrłr J, F.!iio. conj Js lłh cHo ' ń dl in.l|] i PÓ:iL]D|sl'1h to rcj,nih.i or ne1. r efuNl{J L! !nr1 lr rl SrDuPserisr lI) iudl r, ol ih.,lilkorv nr.!r xr 1r) ri r p.nr LrI rrc,l .o'nPonid m| adoPi] hL8h nLń'! 1\hef t.. Nb.L orrix:bl...nro From rhc llporeu..n a telble drjn ot l]!r.: n dn:d. mu|(d.f'cno|trr..l'|j]Ż ]oI ą]!! łJ'ljiry 'irt. Jł].nr] k .li !.f h]] I irł wh.n tt illoil +I.0 b.t{.|:] ł.!]atf, Ll]!s |?s shoi,.! olcH:)P rnlL oraH:):o bi]jir lleł1}) ol 1]trxFLd\]:r.o,n]llI! to|Li.o|toL ńc ionn.hoi oi.Il:o.]dt.oDP.u.ns Pouds lel nLrl.t th.x rfrour( d!łs ('lbh r) Th]: aPProa.h .llols Dnfo]lig .$]ńal r3 e|. eli]e]menh:dł L].ń!:. homo!.n.!! and :.i on Ń| ń|o!(ilś -ifs .r r!u.nanr f d toshud ,]drld.: i!. l].\: on ot aHo Elolps n th. i1mł]! o| ]''eId oI iI'c :.nLl1in3 ń..l..-vdc A Ę(hrrisr ot ti! to:n ro| oi.' I]is ?ic th! ]ł]B1]] o!.|]loxr s]! n :u((e\\nLL śrith.sisoa milIÓ.ld!!.an i.i]i.vĆd ll.nr (!) r.j dildlI'\ds bP !] \']n.h ;fm]'L hr Piłi.uLi| th! ahlons]nP li ra 'jt. ob PkL5]LnP /Fi" '"ę} .^ó \l sLhtt a hre& "J 11 IlolłńiD (II)? Tioll FĘ'4 rful D| !}tnl]t |p,;! ł 1.3 bkl2J nglphlnrlykc laft ł1l) rĄd łTsoH rn llrt liu rl ń |i.!tks (b!n tn attltFtl tn) (l {th r '8.bElr'for. lrt lplenoxv)odane (1,&o'dial) h ']']rc lca.noĄ WcIc jn a Fclao!ńcd Th! Predomimme ol mado$de t1+]l wth 53'ó L |Fld $łs obse ed when ihe.ondo[ io| o1(I] wjth rń o dlal w35 .ablyued b], ł H olĘvei pyrid hE p blLene! ulfonab 3 nd .af phÓl ]o{ullonl. acd (csA) denon*IŃe ].lahvc]y lowcI . alyti. 3dilitils in .onparison with P TśoH i'' tIE .y clnihon proes' contaĄ' to ou .XP€ckhons' jt was found thłt Pol|.ÓndensatjÓn t' lrne .ł d iv !!,lbeńŻenlreal sbuńtr?. Th€ yPld sńall (2 ? '/'l iosulfnje iD t(s ol of rh e liR s tsrMsśP(ni(di l.5il'/.fo'l lrfu) af n|pn !|bs t1t1] (r) rld Iz+2] (b),' = ThLc'ń.t.]. b..\Dlr]n.d ing th.r..dlon Tl]|s ]] T.oH on dr.b is oilon.or' iśn acbl]z*(n bui tr(o cłr].|: rd.oop.Fhl. sdf'i} ęfibjr hmPlii.li lhe:]:oNśoiI (Tłjq!.]el) i]d snrp!o: ll] s!Lionlr i.ids hI. ]c]łhvclr Lij6.j glo!|s tr' .o'nPł!]sÓl wiih r TsoH QiPouLl: sItNn i] oll |jl.\ (.ul fiP.ls lr2 ]j] ł ihs yt:l^s ih. FDlv(.n1]!.shon oI ń!i!!ln D T n]opr]] lx]dP (]) łrd d:i]d.hvdś(],r h \l].i.rinD]t\.\vnL rancs III) Lrr nuudradihsn.dr ś.tgIori]] !livm.riŻ on !rii]] a Ao5e:lĄ. ri, ric,niclido.i b. Tlle j''IlLre|.P oa ihe Mt[. ]ioune. idńl&.i}Jł D il]:\ r. so!.d I l! Ihc .ś]lilh ESr rIihc]TilP of no]a] Dl.aMlIł aid o lŃlo of (I]) n1-{a i! lsellrnonbir tn(.,.) i only t]t. ilrł oi xd']Ż ] Lo\i ( !n!]$oP.]łine fLt ilj.nbla (.Dtlai! D i]t Pr].c$ oi iid!asi''B.ID.n.m: (di])/mbl!{ nr rvlstrDPor n bornllErrd rl]Lrńo l]]i]] llLr ńr(](l(]]l l]ń;utrll r L]7] LdnrJ !r,Ahrlit J,Di\!sl LD !r(\riD nul.l]Prii.l.].lr!]],r2'j92,9: rroqP 3 lJll j,J !'łl: l,l lI lfułi.lr]lDiJłł!l.'ł]T5oir' /]|l /ill..,rrJ.]fut ol ll] Dr pr.dL lrl { h r/rr J fnf..plroifdErq.io,.rr".onrr: ]4q]b{a lJ ' , fąl.r.] c l] r] sLo.(fł'ł!r J / /lrlIiJ|]lr]ł'j r4!,',!1 \6!l]:is|i solL.h] \J.]{]ńjLi5o !]]l,kll ! \Ln:th ]1 5D]!:: l\,Kubr[]ll'xuli!r J' kul|łl'i ! lJ !i 'ij ril .soi510Ldr!224, d.h.'laLurot silld id,rud nślnh ł/:sLls Tl,a! ralu!s r.d!.p.fd b l]I i'rdivnLLal inado.tda i..ł.]ś 1F:g 6) ]om3:c duto3 ihc Pol!ond.]liłii'l lc:dlng lln RtLtrl,biun or.f s{hii, it v.:v hrsh.onr.aror NlałLd5li 5oL.h l ' ]ńr3 ]' coD)oc F a xs E, Ir(ol'L] s lJi Jl]