20-4质谱图与结构解析

第二十章质谱分析一、饱合烃alkanes二、芳烃的aromatichydrocarbons三、醇和酚alcoholsandphenols四、醚ethers五、醛、酮aldehydesandketones六、其他化合物othercompounds第四节质谱图与结构解析（电子轰击质谱—EIMS）massspectrometry，MSmassspectrographandstructuredetermination1.直链烷烃1615m/zmethaneM=16一、饱合烃的质谱图alkanesm/z152943578599113142711008090100605030204070020406080100120140160180200%OFBASEPEAK1030507090110130150170190210220230C2C3C4C5C6C7m/z=29m/z=43m/z=57m/z=71m/z=8599113127141155169183197C8C9C10C11C12C13C14C16CH3(CH2)14CH3Mm/z=226n-HexadecaneMW226m/z15294357859911314271正癸烷分子离子：C1(100%)，C10(6%)，C16(小)，C45(0)有m/z：29，43，57，71，……CnH2n+1系列峰(σ—断裂)有m/z：27，41，55，69，……CnH2n-1系列峰C2H5+（m/z=29）→C2H3+（m/z=27）+H2有m/z：28，42，56，70，……CnH2n系列峰(四圆环重排)2.支链烷烃20406080100120140160180200103050709011013015017019021022023010080901006050302040700%OFBASEPEAKC3m/z=43C4m/z=57C5m/z=71C8m/z=85C6m/z=99C7113C9C10C12C16M15M5-MethylpentadecaneCH3(CH2)3CH(CH2)9CH3CH385169141573.环烷烃M=84Cyclohexane84(M)56(C4H8+)41(C3H5+)1008090100605030204070%OFBASEPEAK02040608010010305070901100M=9898(M)1008090100605030204070%OFBASEPEAK02040608010010305070901108369554129MethylCyclohexaneCH3m/z=98m/z=8384(M)0204060801001030507090110695541271008090100605030204070%OFBASEPEAKCHCH3CCH3CH2CH3CHCH3CCH3CHCH3CCH3CH2CH3CH2CH3m/z=69m/z=55134(M)1008090100605030204070%OFBASEPEAK0204060801001030507090110917792513912013014065CH2CH2CH2CH3二、芳烃的质谱图aromatichydrocarbonsCH2CH2CH2CH3CH2m/z=91m/z=91m/z=65m/z=39m/z=134HCCHHCCHCH2CH2CH3H2CCH2CHHCH3CH2HHm/z=92CH2HCCH3CH2CH2CH2CH3m/z=77m/z=134m/z=51HCCHC4H9R2CR1R3OH-R3R2CR1OHm/z:31,59,73,RHCHCH2OHRHCCH2OHH-H2ORHCCH2RHCCH2(CH2)n(CH2)n(CH2)n(CH2)nor三、醇和酚的质谱图alcoholsandphenolsRHCHCH2CH2CH2O+HH2CCH2-H2OM-(Alkene+H2O)M-46H2CCHR-RHCHHCCH2CH2O+HCH3H2CHC-H2O-CH3H2CCHRM-60HCCH2H2CCHHH2CRH2CCH2-CH2CHH2CRM-761008090100605030204070%OFBASEPEAKCH2OHM-(H2OandCH2CH2)M-(H2OandCH3)M-H2OM-11-PenTanolMW88CH3(CH2)3CH2OH314060801001201401030507090110130150020100809010060503020407020406080100120140%OFBASEPEAK1030507090110130150M-(H2OandCH3)M-H2OM-CH3M-1M2-PenTanolMW88OHCH3(CH2)2CH3HC4545M-(H2OandCH2CH2)0100809010060503020407020406080100120140%OFBASEPEAK1030507090110130150M-(H2OandCH2CH2)M-(H2OandCH3)M-CH3M-H2OOHCH3CH2CH3C59CH32-Methyl-2-butanolMW88059CH2OHHOH-m/z=108m/z=107-COHH-H2HHHHHm/z=79m/z=77H2CCH2HOHCH2CH2H2O-H2COHOHCH2OH2O-OHm/z=94OHHHH-COH-CHOm/z=66m/z=65CH2CH3OHCH2OH-CH3m/z107(100%)CHCH3OHm/z121(3.5%)-H1008090100605030204070020406080100120140%OFBASEPEAK1030507090110130150o-Ethylphenol122(M)M-CH3MM-H2OC6H51008090100605030204070020406080100120140%OFBASEPEAK1030507090110130150CH3CH257M-CH3CH2M-CH3MEthylsec-butyletherMW10273298757H3CCHOHCH3CH2HCCH3OCH2CH345297387102四、醚的质谱图ethers02040608010012014016018020050709011013015017019021022023010080901006050302040700%OFBASEPEAKC6H5ClCMM+1M+2M+3M+4p-Chlorobenzophenone216(M)100.0217(M+1)19.28218(M+2)33.99219(M+3)6.21220(M+4)0.98OCOCl1030ClCO五、醛、酮的质谱图aldehydesandketones55M0204060801001030507090422769108090100605030204070%OFBASEPEAK098O1008090100605030204070%OFBASEPEAK57M-CH2CH2M-H2OMMW1424060801001201401030507090110130150020M-1M-44M-43CH3(CH2)7CHO44OCh3(CH2)4CO(small)99CH3(CH2)471CH3(CH)357CH3(CH2)243CH3CH229CH3CH2CH2CH2CH2COH45CO2H59(small)CH2CO2H73(CH2)2CO2H87(CH2)3CO2H1008090100605030204070020406080100120140%OFBASEPEAK1030507090110130150Figure2.14.MethylOcatanoateCOCH3OCH2CH2OCH3O121[M-31]MM+1M+2MethyloctanoateCH3(CH2)6COOCH3158(M)159(M+1)160(M+2)160875974COHOCH3H2C六、其他化合物的质谱图othercompounds129(M)1008090100605030204070%OFBASEPEAK020406080100103050709011086114442912013014058CHNCH2CH3CH2CH2CH3CH3CH3M=85N85(M)1008090100605030204070%OFBASEPEAK02040608010010305070901100H855756444229M=1131008090100605030204070%OFBASEPEAKNH84564127CH2H3C70113(M)2040608010010305070901100120054M412767108090100605030204070%OFBASEPEAK082392040608010010305070900结构未知（C6H12O，酮）解析：1．100，分子离子峰2．85，失去CH3（15）的产物3．57,丰度最大,稳定结构失去CO(28)后的产物内容选择：•第一节基本原理与质谱仪basicprincipleandmassspectrometer•第二节离子峰的主要类型mainkindsofionpeaks•第三节有机分子裂解类型cleavagetypesoforganiccompounds•第四节质谱图与结构解析massspectrographandstructuredetermination•第五节色谱-质谱联用仪hyphenatedmethodsofGC-MS结束