烷烃衍生物第一电离能的自相关拓扑研究

3222005JOURNALOFBEIJINGUNIVERSITYOFCHEMICALTECHNOLOGYVol.32,No.22005(,221116):(fi),fi1(1F):1F=[(1+k)-0125(fifj)-1]015,32(Ip,eV)1FO,N,S(XPL):Ip=1310264-3182081F+011773XPL,R=01992927(F,Cl,Br,I):Ip=812727-2164061F+115168XPL,R=019979Jackknife,,23Ip,,59Ip1F019791,Kier(1Xv)(R014190),2(QSPR):;;;;:O60511;O62511:2004207216:(02KJB150008):,1954,E2mail:[e-mail](Ip),,[122](:RdL,R,,d)(fi),(mF)1(1F),(,L)(XPL,Pauling)[1]32Ip,[2]27Ip,23Ip[3],1FXpL59Ip,0198[4],1,,2/(QSPR/QSAR)[526]Randic[7]Kier[8](mXv),[9],F(t)=f(i)f(j)(1):i,j()t(=0,1,2,),f(i),f(j),[10][10],(RdL):RdLL,L(,k,k=1,2,3,)1,2,3,L,fi=1,,L,fi,,,,,(A)fiCCCCNCCCCCC9611314725108AA,3:,2,342,3,,(fi),fififi=fiXi(2)(2)Xii,Xi=(mcxpc/mixpi)i(tc/ti)i(ni-1)i(3)i=1/ti,i=2ti,i=-(ni-2)012ni,mi,ti,xpii(s)Pauling,mc,tc,xpcn,m,t,xp4,7,1,2196,m,t,xp4,2,2155,(3)XBr=0155745O,S,N,F,Cl,IXi0170298,0140587,0131881,1116447,0192224,0138965LfL=1,fL=XL;,(3),Xc=1,fci=fci,Afi,fi10131881f-1i(1)f(i),CL(k),(mF)mF=[(1+k)(fifj)-1]015,j-i=m,=0125(-1)m(4)m,m=0,1,2,;010F=[(1+k)0125(fi)-2]015(5)1F=[(1+k)-0125(fifj)-1]015(6)0F,1F0F=[(1+2)01250131881-2+2-2+3-2+4-2]015=316571F=[(1+2)-0125(01318812)-1+(1+2)-0125(01318813)-1+(24)-1]015=114530F,1F2Ip1F,XPL[1]32()()Ip1FIp=1316787-2191181F(7)n’=32,R=019913,F=170119,s=011158n’,R,F,sFischer[1](PEI)(qL)Ip,019904,s=011303(8)(O,N,S)(XPL),Ip=1310264-3182081F+011773XPL(8)n=32,R=019929,F=101010,s=011047(8)3IP1F,XPL[2]27Ip1FIp=1511215-5101691F(9)n=27,R=019751,F=48217,s=011878(9)XPL,Ip=812727-2164061F+115168XPL(10)n=27,R=019979,F=282012,s=010551[2]PEIp(Ep)(qL)(aL)Ip,019976,(10)0199794(8),(10),(8)(10)(8),(Leave2one2out)Jackknife[11],,(R)(R2)(8)32,(R)(1)1,(fhi,i),(2)0920051JackknifeFig.1CorrelationcoefficientdistributionofJackknifetestforIpofamines,alcoholsandetherswithremovingonlyonechemicaleachtime(10)21,2,,2JackknifeFig.2CorrelationcoefficientdistributionofJackknifetestforthehaloalkaneswithremovingonlyonechemicaleachtime51F1Xv,:,,1F[122]59Ip1FIp=1415457-4154611F(11)n=59,R=019791,F=131919,s=0121621FIP,Kier[8](vi)(mXv)5911Xv,IpIp=1015875-0149831Xv(12)n=59,R=014190,F=610,s=019649(11)(12),1F(1Xv)Ip,Ip()1FIp,[3]23Ip1F,Ip=1418674-4188091F(13)n=23,R=019893,F=96310,s=011001,6(8),(10)QSPR,,,[12],H(CH2)nLIp,(10)1Iap1Ibp,Icp[2,13],,H(CH2)4ClIp10167eV,[2,13]H(CH2)10Cl,H(CH2)20ClIp,,Ip[14]125Ip9182,9165eV,1H(CH2)nXTable1PredicatedvaluesofIpforSomen2HaloalkanesLn1F/eVXPL/eVIap/eVIbp/eVIcp/eVCl1001930311610161101691017620019533116101551016410174Br1011079219691911010310109201109821969186919810107I1011220216691099115911820112382166910491129112(8)H(CH2)10S(CH2)10HH(CH2)20OHIp,8118,9172eV[1]8116,10107eV;8118eV,192:,Ip()10104eV[13],8108eV,;10123eV,10110eV,[1]5Ip,(8)2Iap,Ibp[1],IcpIp01306eV,[1]01270eV:Icp[1]Ip(Exp.);1F2(Ip)Table2PredictedvaluesofIpforamines,alcoholsandethersN1F/eVXPL/eVInp/eVIbp/eVIcp/eVt2Butanol10019303116101611016910176C4H8O20019533116101551016410174Pyrrodidine1011079219691911010310109C5H10O201109821969186919810107hexylamine10112202166910991159118(8),(10)[3]23Ip,,(8),(10)77111F(fi),KierviA5fi7,8,9,10,11;3fi2,3,4;2fi5,6;vi1,2,3,4,,fifi(6)1F,,951F,21FC2C101491F,Kier1Xv1F,7121FIp,Ip(MO)C,HL,CH,CCCL,LH4,,L()MO,,RdLIpL,L(EL)RdLIp,EL:L(R)71211L,,,L(EL),IpL(XL)LfL=XL,CL1F:1F=[(1+k)-0125(fLfC)-1]015,1FfLCF,CCl,CBr,CI1F(1F)01536,01675,01868,11039,Ip,1F(1F)Ip71212Taft(3)[15],3(3=0),(3),L,EL,Ip3Ip33Ip3,1FTable3Ip,3and1Fofsomeiodoalkanes31F/eVIp/eV1Xv/eVCH3I011039915421535C2H5I-011011116913321500CH3(CH2)2I-011211153912631000H(CH2)4I-011311174912131500(CH3)2CHI-011911171911721619(CH3)3CI-0130112139102217683,L,3Ip()(R=019722)1F,1F3R=-019191,(R018)1F,Ip3a1,,3,Ip,1F;1Xv,015,Ipb1,Ip,3,1Xv(ivi),1Fa,b,1FIp,1XvIpa,b,1FIp2920051Xv7121171212,1FIp,(7)(11)(13)1F,1F,[1].[J].,1999,19(6):616[2],,.[J].,2000,13(3):288[3],.,,[J].(),2003,25(1):55[4],,,.[J].,1998(4):44[5],,,.QSAR[J].,2001,59(6):853[6],.(10)[M].:,2000,401[7]RandicM.Oncharacterizationofmolecularbranching[J].JAmChemSoc,1975,97(25):6609[8]KierLB,HallH.Molecularconnectivityinchemistryanddrugresearch[M].NewYork:AcademicPress,1976,18[9],,.QSAR[J].,1998(10):40[10].[J].,1999,10(3):23[11],.Kovats[J].,2001,19(2):124[12],.[J].(B),1980,3(2):136[13],.[J].,1998,56(3):223[14],.[J].,2000,20:123[15]EfflerJE,GrunwaldE.Ratesandequilibriaoforganicre2actions[M].NewYork:JohnWileySonsInc,1963,178Autocorrelationtopologicalstudyonthefirstionizationpotentialsforaliphaticamines,alcohols,ethersandhaloalkanesFENGChang2jun(DepartmentofChemistry,XuzhouNormalUniversity,JiangsuXuzhou221116,China)Abstract:Anatomiccolouringnumber(fi)wasdefinedinthispaper.Ithasanexcellentselectivityfornon2hy2drogenatomsinalkaneandalkylderivativemolecules.Thefirstorderautocorrelationtopologicalindex(1F)ofthecolouringnumberwasdefinedas:1F=[(1+k)-0125(fiifjj)-1]015,whichshowedagoodstructuralselectivityforalkylderivatives.Thefirstionizationpotentials(Ip,eV)of32compoundsofaliphaticamines,al2cohols,ethers,thio2alcoholsandthio2etherscouldbeexpressedasafunctionof1Fandtheelectronegativity(XPL)ofO,NandSatoms:Ip=1310264-3182081F+011773XPL,R=019929.Asatisfactoryequationfor27compoundsofhal