ࡱ> `b_a ; jbjbtt ;6666666l  l)++++++,tR W!6a"W66x66)J^6666)66 ('_ 0  6llDllRA UNALNO PROU AVANJE KISELOSTI NEKIH SUPSTITUIRANIH PIRIDINIJEVIH KATIONA COMPUTATIONAL STUDY OF THE ACIDITY OF SOME SUBSTITUTED PYRIDINIUM CATIONS Helena I AK,a Zlatko MIHALI,a Igor PICEK,b Bla~enka FORETIb & Jasna LOVRIb aLaboratory of Organic Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia bLaboratory of Chemistry and Biochemistry, Faculty of Medicine, University of Zagreb, alata 3, 10000 Zagreb, Croatia The aim of this work was to investigate the acidity of the pyridinium cations 16 using high-level quantum-chemical calculations, and to compare the calculated results to the existing experimental ones. The study included the full optimization and vibrational analysis of all of the conformers of keto and enol forms of 16 and all of the conformers of all corresponding deprotonated forms, both in vacuum and water, at B3LYP/6-311+G(d,p) level of theory. The pKa values were calculated within the framework of a continuum solvation model, using IEF-PCM method [1,2,3]. The computational results show that the ketoenol equilibrium is always shifted towards the keto form. Calculated pKa values are in a good agreement with the corresponding experimental values. Based on obtained results it is possible to analyze the influence of structure changes to the studied compounds acidity. [1] Tomasi, J.; Mennucci, B.; Cammi, R., Chem. Rev. 105 (2005) 2999-3093. [2] Kinsella, G. K.; Rodriguez, F. Watson, G. W.; Rozas, I., Bioorg. Med. Chem. 15 (2007) 2850-2855. [3] Sadlej-Sosnowska, N., Theor. Chem. Acc. 118 (2007) 281-293. (*,FHhjlXY ! #     ; ߺyyh}phECJH*h}phE6CJh]bhECJh}phE5CJ!jh}phEUmHnHtHh}phECJh}phECJH*hEmHsHhE hU#hEhU#hEH*h}phEH* h}phE hE5CJh}phE5CJ'*,X  H I ; $V^`Va$gdE $1$7$8$H$a$gdE$a$gdE$m]m^a$gdE$a$gdE; ":pE{. A! " #` $` %$ ,, O L ~g{HH(dh com.apple.print.PageFormat.FormattingPrinter com.apple.print.ticket.creator com.apple.printingmanager com.apple.print.ticket.itemArray com.apple.print.PageFormat.FormattingPrinter _193.198.195.70 com.apple.print.ticket.client com.apple.printingmanager com.apple.print.ticket.modDate 2008-10-17T08:22:23Z com.apple.print.ticket.stateFlag 0 com.apple.print.PageFormat.PMHorizontalRes com.apple.print.ticket.creator com.apple.printingmanager com.apple.print.ticket.itemArray com.apple.print.PageFormat.PMHorizontalRes 300 com.apple.print.ticket.client com.apple.printingmanager com.apple.print.ticket.modDate 2008-10-17T08:22:12Z com.apple.print.ticket.stateFlag 0 com.apple.print.PageFormat.PMOrientation com.apple.print.ticket.creator com.apple.printingmanager com.apple.print.ticket.itemArray com.apple.print.PageFormat.PMOrientation 1 com.apple.print.ticket.client com.apple.printingmanager com.apple.print.ticket.modDate 2008-10-17T08:22:23Z com.apple.print.ticket.stateFlag 0 com.apple.print.PageFormat.PMScaling com.apple.print.ticket.creator com.apple.printingmanager com.apple.print.ticket.itemArray com.apple.print.PageFormat.PMScaling 1 com.apple.print.ticket.client com.apple.printingmanager com.apple.print.ticket.modDate 2008-10-17T08:22:23Z com.apple.print.ticket.stateFlag 0 com.apple.print.PageFormat.PMVerticalRes com.apple.print.ticket.creator com.apple.printingmanager com.apple.print.ticket.itemArray com.apple.print.PageFormat.PMVerticalRes 300 com.apple.print.ticket.client com.apple.printingmanager com.apple.print.ticket.modDate 2008-10-17T08:22:12Z com.apple.print.ticket.stateFlag 0 com.apple.print.PageFormat.PMVerticalScaling com.apple.print.ticket.creator com.apple.printingmanager com.apple.print.ticket.itemArray com.apple.print.PageFormat.PMVerticalScaling 1 com.apple.print.ticket.client com.apple.printingmanager com.apple.print.ticket.modDate 2008-10-17T08:22:23Z com.apple.print.ticket.stateFlag 0 com.apple.print.subTicket.paper_info_ticket com.apple.print.PageFormat.PMAdjustedPageRect com.apple.print.ticket.creator com.apple.printingmanager com.apple.print.ticket.itemArray com.apple.print.PageFormat.PMAdjustedPageRect 0.0 0.0 3406.0000101725263 2379.0000915527344 com.apple.print.ticket.client com.apple.printingmanager com.apple.print.ticket.modDate 2008-10-17T08:22:23Z com.apple.print.ticket.stateFlag 0 com.apple.print.PageFormat.PMAdjustedPaperRect com.apple.print.ticket.creator com.apple.printingmanager com.apple.print.ticket.itemArray com.apple.print.PageFormat.PMAdjustedPaperRect -52.333323160807296 -50 3456.0000101725263 2429.166666666667 com.apple.print.ticket.client com.apple.printingmanager com.apple.print.ticket.modDate 2008-10-17T08:22:23Z com.apple.print.ticket.stateFlag 0 com.apple.print.PaperInfo.PMConstrainedPaper com.apple.print.ticket.creator CUPS_CPL com.apple.print.ticket.itemArray com.apple.print.PaperInfo.PMConstrainedPaper com.apple.print.ticket.client CUPS_CPL com.apple.print.ticket.modDate 2008-10-17T08:22:13Z com.apple.print.ticket.stateFlag 1 com.apple.print.PaperInfo.PMPaperName com.apple.print.ticket.creator CUPS_CPL com.apple.print.ticket.itemArray com.apple.print.PaperInfo.PMPaperName iso-a4 com.apple.print.ticket.client CUPS_CPL com.apple.print.ticket.modDate 2008-10-17T08:22:13Z com.apple.print.ticket.stateFlag 1 com.apple.print.PaperInfo.PMUnadjustedPageRect com.apple.print.ticket.creator CUPS_CPL com.apple.print.ticket.itemArray com.apple.print.PaperInfo.PMUnadjustedPageRect 0.0 0.0 817.44000244140625 570.96002197265625 com.apple.print.ticket.client CUPS_CPL com.apple.print.ticket.modDate 2008-10-17T08:22:13Z com.apple.print.ticket.stateFlag 1 com.apple.print.PaperInfo.PMUnadjustedPaperRect com.apple.print.ticket.creator CUPS_CPL com.apple.print.ticket.itemArray com.apple.print.PaperInfo.PMUnadjustedPaperRect -12.55999755859375 -12 829.44000244140625 583 com.apple.print.ticket.client CUPS_CPL com.apple.print.ticket.modDate 2008-10-17T08:22:13Z com.apple.print.ticket.stateFlag 1 com.apple.print.PaperInfo.ppd.PMPaperName com.apple.print.ticket.creator CUPS_CPL com.apple.print.ticket.itemArray com.apple.print.PaperInfo.ppd.PMPaperName A4 com.apple.print.ticket.client CUPS_CPL com.apple.print.ticket.modDate 2008-10-17T08:22:13Z com.apple.print.ticket.stateFlag 1 com.apple.print.PrintSettings.PMPaperAddedToSubmenu com.apple.print.ticket.creator com.apple.printingmanager com.apple.print.ticket.itemArray com.apple.print.PrintSettings.PMPaperAddedToSubmenu com.apple.print.ticket.client com.apple.printingmanager com.apple.print.ticket.modDate 2008-10-17T08:22:18Z com.apple.print.ticket.stateFlag 0 com.apple.print.ticket.APIVersion 00.20 com.apple.print.ticket.privateLock com.apple.print.ticket.type com.apple.print.PaperInfoTicket com.apple.print.ticket.APIVersion 00.20 com.apple.print.ticket.privateLock com.apple.print.ticket.type com.apple.print.PageFormatTicket TKfZbZJݹh 4]^ MKxZ}$Uchqr,.P>[dw{>ij;-{w6NL=3}ݳsi ɱ DB| $ 1ع$ʇ "qPbbǖ8!ｪُŰ;W^zUu?-3*n=qŵ qbS]w0Kˍ:S3'~\5?(-&2¸COunڏ+[Z;AF7Ik*r[q׈yOy5']!ޜ_g.`-6ֶoZ) '%ꁳ'W ZD^w{$:UKsiovvF wɚub nJj'n2%)z4AHɇЎf Nb yCG`*(G)WNi#^!~a<j7 ]mwѐ6{bG1[ɷw.ztEw;R|580p. 0~nn7%{W;IEֺ?Q#r#<.>=m'R?^`j~_,57rFNi;: s!:)-T6Fmt/[" %nC:tys"<Q^{GG2 |61i3&m.]7̬A=h5!\c+0H9ߺO.J % pXU&:ҜkDk` (6"4Чټݿ4%۠ #KwQAY22\FԸ #ȸPF#"ZH6MY}wG@ -iIxZoǏ. L:{].4rӏF v%vg^༯KBy^wI辶r@n5`{nFkY$-B얁,6zcJoIsd00 @&nSMēեha,0pCɜN7p.O5~-v]L, ?=ICHhKUchWF٥IF |i(9Pwl"1eO" z0p$kUt/$GF %UI.4KLڗs>W$\hviۿ噲P6@j] 3z4!87B@*/֑qj$3I77_ZOCf3-5Vע G-"q4\vd/榗ň\]GZvLÎ\BQ&_'ǴZU.'>jHׂαQ`bƔ5b)pxcpZ'{Yy8p i7&#1ؐK,c:b9LIQzA R5T 9j^"7; BNBG<59N؂R~7k[d{#A=X@3x{ VLc<.<ېrU67mV?3R0j ŢkESā~uqٔld6(;:E )pddɮrINA;ȆuU<8-BҢb}ĢY %$Il{E 4eb8ZMbVYM拵?H ?SNMd Ճ&X=h&/j:Ai!5haWD:v"D84w)LΚąܯmnDmMR)696Tku7BNU-+т+ˆa&=Eޅ;஁{S.`2Gn\uI< -̗,0_.iЪΛ6g.Sǎ c<3[{*q"%l#5(!qAC:5P KꄛI m+XplⴌMS*L1'J,%=q-O=t*M4Vڛ^tlH/ʫARp4nDm{S[;% bJIn]dF%Y.Sx` <#+A9â]I(!MG] .$Nv17^YP`eN Qk]vgZ3i^)4|LǕXLehTک>c(̂TyVaс]}mN-KjMs-]z,ZObz֦ҦhJiCѨ6ڞ 6o)ODYAK ڤS)JA_/:@g8N U ΰIS"Pkp[rS!Y6r-6HeuG#;A38Y`y%,Qd#MoImg Hu=Fc9WB$%d@,SuJRҔTHk:@=GZ8z'>m!D'cC8[P7B's|<6`7Ku x>zޅ38I-*B~ry[nr& (/mzb3~,WKd{*s8=:ޏ7~A Gm&kl:wxfkj@CNXӑǴΓBx2$Oah}%~͐8V舖Uf>P`L؊c9h*m|@6`)~X䍛2f_ƦQt!8>t5dHiX%NMM*oMk1F6! mS]iZDM[1}(1'rcmOo w\]WVXk0hAŢj( *qpS`MhCIpҥ7N$9)Tr:t[S{#7z(`Ipm ӳ|}Bm$sض! ėnKG!M h§BUhU*dLFLj, E= *%̠@YaT"bW˼ K}wqaqxJ~M\oiYV\@8U˿|MQ!PGę̻ŃO BNfQ8;q-Y.Z{˙%pg~N<WQD RϊyT01.^@? Jt=Ao!+SW2|̲I&H3bE\]T+E9qU ̛'=GK6%D1n'>TZ a(,Y@ "CQ.V -iJ :E_:t b^ZZ8vZŅ"j,O5;vTAmҼS\X`c9#kbJ Y_; G.I=nŐDu:݇ط}(h+9ClѽA͂~ٌ-YXQ)=z똪xћrS-9qRżMM8u(nj&{:8OXr% EOL(ʏgp}^"MD89W"[M>u{⎏37\FS qrf9EEObbI}ޟx8>W3'~ZXf:H _^;=2f>/p} _$q| ?򋸞U\_`ڣ^3ЮoWȣ43*ePgFZkWj\j}|1Ȝ?֨Q>s̉L#W̻|3Zbb'~ ۳o=} ({A{pdޛ} W;=H{k\B2\s˽o, ĕܝzm=}1YTNsg+hEZA}Wp\I4P˾0kLqu\}1gD; ]D710pgxB˼KW9QA2vem|%K̟vk;_uM%8^/8'¸|-뀿7sW}N<*j؞MٶέqSX121Uޮ>Ȋ*w#4e~ÐQaTL.cE*whZ(VВvťb>wνtϣ[;{G;"itKaPKJ ڸn5Puad^dL_y\ Fȳu I-KLBKHX!u% sܲ[V1)LWDu >@5jff+$D%&I %$$*2Ƃ̀ BZJ e|P:h%k$Ͼs#FvaH3o"%X ܒ"0[=4 l/t甆$7AIdptJʌKD2X$4 \uDR?$ԉLϞPW*a3ݺD~Vaz+) @#"Fϱf PUi,!a%&ULF=Fm$W+`S#YHTUzPn6J+ے?nw",Vv.S-R$#0Ҙcxl?cFv(?)&ۭw4/InkZ_= 7)ss}4z.ZŠj8֝C|NI`f{.{=k'8_i=Gw۫w[JDak> Ϻxc˵ ( :%i<ݎZNк,8u3~۬N{fOFhr$^(m- q9QkEh!&ќuĺa@ po0=@<}jļikjO3ͼBsW[s%慌{"Z>}zբ`>y+qy!wG,yȾ=Z߉Go|;HߍHoaUOwE$ 3v:+8?X% 0n-Sn^}䰤^YU3$*]ĺ$f9_}Mʼ/Iq, 6(0RߍddNZY/J/a@}$&ǵf GjdtFxx+r{)]b}"~F4n>OR'4laHZ~%|(2ekp@FIUI#$fGj.v:{ gnR?~Jbݤ5y -wuS\YJR)J"i$_Ҙvt¬N6v2m񦴕-f-Oi|!v6oOi=B@ K*Z:op:HeV%ސj4T R_~cbs3ڇWliuDavg _|+ &ciL}S&2J)mYt#|~K{+ }ƽϸy^Z|q8p/E>S^.}ev'nt]I'Ov xAYϸC,"YfXdb1h]nca -}A,͔Ґ|Ǩü)'A$O"^81xҨ?/Pr߾|L}5ZI/5 ce/W"o 3 QK7dÀj`:eTZDi5Kue GYzHW"2)ͣSӹITd,`R"}ChP6D<-WlOQ |R)7LFŒ'=ʋ#?1{b;*EE+O!~K/is, Bf\U*>{vhﻝi^vqۼ2b1M"P3 ry\kRKwX:- TR %L;֫!.pirumDe6wNoZq 8A r&Jf<-!!LWB˘V'ɬs ~j,bu_G^RĐ>.2Və璖t³?fEقnd ꏽZWY fUu5F#b}2Mb+;{ r˝B!fǍvS}]~߸Grkɽ{@كs^=a^˅<*6'ܜV1s^~ٌQK ;ԝ\f_?:-|{U.ơM2)Ms["}ю*_nKiS{wKƸ NˌW@71/N(EoDS[N'H}+&TdLZrdzOт%>GbJ%!7/7J^O_jCr,3{1K/i#Š>H=fR~eWpKT88?)#P!k#JceA aؘCI&^hG4D nȯkn.7j# -H2&Gϝy}D'$RRߒtőا:+DKC4~+7f0^)+z^*!]F1z>@dͼYciBwH:Jt loE/tUuG+2VZYJ|UHK^R2'C 0V ~HO^%3ZQ+C rh%WӨWDʹWEtM"(5~Jo("ItU0Un,r,\jʺ+H-1R ip;bH'Kc7OP->AZdO$c@ SUdU/v;OyO 7RF^(ʹ> j0$, t̶(@ j2x, ʹc!gijbDٳƫD"s=Q0O@</?Z>܊x+pl@$ HcgėX/;[WfA6(!,բAuγk:]8 t~ RvI@ZFL: y=\~;;D^b-MC~q_L+}=ђWZkrֈNt6"uC5gs_b ƅbI,3_ti C?cJN.ό10ƘQv c̪c̪c(1f1 uS.A˧][Lյeȋᦴ 7^ 7pSZ XZ 5J*3FPO K-0=#g3bYC<0F݌XWF }Ed!0g3cf\Ue%XJk FBQ}HF֭wQWcqQl!2,OCY(&է*}+ZK_5nkzoɕ{l?#9D1=?$ٜ^nƏrIyB8|/Gq$9-=Q->~# ?$6?<p8OqfN8x#!=⒳Hׯ8|d-u$ _(,_>GXL!^qz@(>+GXi7+is"Z>}zu!Pu0DaS(LT(pҼRyߜ )VYzNm=?tX𽒛%J>=~} ,|u׀Z^v}eo>JJkMV; 67; ~gW~@cTXO0e_(GJbRz\k=٢p:u1u -u- V1`q(X(V޶&"J(xAYqiqUyYck/؉B@+(R jUg?i? Nd /G?<'xx$DF(Wੌ!LqQ+\C p 3QMX7 I3> 2%E 1 HrkQk2o58.A;GLve2Tԏ|r rPҒ[9Wp+GAtRrJ󜨃AtL OexQN '`e{ bi=0r7{BfAҫlOeuRDzZiL?gJ TA:ߤc4F L@4lqZLH`#Q&1e2)`8hh+yK`C.e[?9<Vw$V'j;˔NDIdJ IcTYS0-r%%YW#˄+ ,| SH/'a3X|}Xظ./Ԓf0` URH7f8~}#d*joaxԲFI 2`_B9c ;Ta>Õ!zK!#i%|>{-X2솛Gzk$bǼqZ+z`%'p 8UaVlCU l7}#iHmwK;4*PqZ( Q7,fMr~&ČUl]Z NETyTTyP;Gvkf[q }N"|c϶6N,WHFOءFH[Qm1ͥx+Y@;sbJwd3%DžAƠ YHVj 0Qr@46McXݓy5˔^:|-q!J>S 'ҏ(L)4:4ya+d,Y=éau z3%(EL)vaPÍ/XLbVh 3eQJR VsVGq: #L Q/2]?˴,b}D)cl]3qf3\\'4p?Ҵn%>Ft ::ä_wa-%t4)+=.n({d'G'[~*:Z;38Q0?ҕAp7E8Bz1|$2.ǧ\|Z q>r +@\r̮85>jh|M96b;6,PfD*۟OABeǏe8N@H:u]U>eNP͍u'pwNR@n8$ө7:j^P*,Vإ/W=Ft϶ÔIY/Xd}LNӤ{ARwbX-()#ɔ. zj zA/Vǐ3h z3eQ0 X0a>Mꮬ5fC:/-/S&Si)gN,q1m>چ0o2|bȃ=j8!`u<}Y@$ŏ). hNZ(z Y5cJ"Q݅A` bu=NΔ M6Soxw|JYM>%:h|cz2 9 If^'R57Y0m0iPVBE)f%x :ZsvHp!iv-3UacOk ^Yj^+Md3:C"`Gft~f^$o&+!i)^gGt"5  3d k}Ws/#Ί+r}ra/Fx3QyiSe~Y`{b51'`63уH':A/")a`BۃSt8p or'k3v$h.\xcY!(Dg͊(ΊWsxH|omdK Gu-REbuz?%*\HR Lo]YʝA޺ky7ct!{c Sf(w`vVg:թZZ%)i. Dc d>gu.X5X|ARǔDIg4-e!Sf).w%񳈻央`u֠)DdJ E $uO2(L Ac sX]5X”ǔ^,e\Lkیj7vq0t%>Grg3oK3|]9.P>g͂moTٙoKB̷p">̷Y0m=!v2|۠ 9,ĉg| 6Cr1qTgdmWHAͷ9m \|[ 8GZ8.Z~wgbTw1yo[ߍʯ8Hj=̳N8ϲI+q/}.븕ՋIڄW,!J3S0h HÔr)]ƾd/ VYWk%S i)_1eQ1S-S$SN淜eeV@S>5)/4Sθ0̍_ |H}՟k ΔD)g]|9߲^G곬>5)rBsk+yEsf25cy]33gq3炶HOvyUT2JTUIWQrf;,i%}:W(ymJ7]r<eTzEq$;;j;qȖ;xB~Jrka®9QhaEQy؏` vN*vET{޵=n=cT%dwUѩ:fl(yz8/TCN 0L YݳKwE%ҥYu٠Yu2ueb}wwևrFba}M܎qGhTox|69([nTJ6[߳}7?S0i?rkہq[4dw0>P›|E ,M>ob^Ǹzί"˻ K_egfK-;rsVFXv`\i=߫*އ0>k٧ sT޼W9Ֆ0l㫖0n4$QRSLQMPk?DOq'8S`H)4Σ2J)2JyԟC"K ԟ2sGu-Cx$EYS?aNg4{qGX"-`c8VeG,n0& xk%qH0N0{P}كIjjdc70E2nC,bu(ߏ&[plcom!muRj[1&{ 8Z `ɝNc&wx!(]3ڍbhϦMr4_o0jHGbZr qX&f&(V&RfH!p.E ^ w d7zY\ӂ߷`| STawjw=~<#AGOq'X:C/Ɲ+֗@WSݰ4tO7`\~/BwK=zׁ/xc7 @Ok |} !b}~Xͳ?s?z.C0C 8B! ^ ^ a֫?\ PTww}IuWW< wTT+4uQG4Է%ZcS 4Il1NMR UJ4fI?g/p=8I*Ϲw=+waka$bO@+x9<;'$8OF[ix@8̈́ D2! ўِȁih/ieŗ#.!h! ډxFvCC.c IP33`&FLhbwpG5tC 0 蟋$ %hO(E{*̃8-߄b[}Bw Ѿ 0NEP+1* m nb=jA B11+TN9mJ"醫:̊`dTROBvv.{b&610)v~X/HQ\++ew(Hmf!)cv LNHNTG#ˑ|BvӁ]=dV f| ñ9;ġ=5 ;f@gwn=~[q}^?>'/|k嚕 #{ rq}-H_2X}b-[koq9`w8N'pJgB@?kqMiAH /J; J;ze\ ۽NlbD?m]!J;>кToCP2_pq,);nJ9ΡXߤ$t9#smxGjiu~wDևۢXwq Χ@<;@}}x[d6֏&6s4+o4+ wDtqvI(l? C#8Drx X.@|W^2q7⍧*JZS5@L Z|Ne58pB]B1zb $dzoƛ{~Br< bsT_&#Zr($ZiZzx|zߺqRzھM7ToI(ҢcbRȝ'yfHGAVtr,[N.ja^I03c[Sޭ5wҪUNUƬR6cڹ 1Sk+K75Y|kU>OC mꎐXqqnI("~c? **$ }W6H.]$g}[4Q* ?ƬY-քûH嶶-P?.V{"3mXSvw;{k> L=ZSWh؝d>9`4I{kDAk<~zkIlHjMZۂ&&P"ǃ ]fKt7DJ_ӈn{5 uE;˯i*n3k6_)¯iDVw[2m֝-֋Q_nnps*f[֝`[C8iQ96r9s w۬ܣ?@ABCEFGHIJKMNOPQRSTUVXYZ[\]^aRoot Entry F2v5c1TableDWordDocumentSummaryInformation(LDocumentSummaryInformation8WCompObjX FMicrosoft Word DocumentNB6WWord.Document.8