ELEMENTARY ORGANIC SPECTROSCOPY 6. In McLafferty rearrangement, an alkane molecule is lost in a cyclic rearrangement with y-hydrogen, 7. The intensity of M + I peak atoms. In case nitrogen is al dividing the relative intensity of M + 1 peak by 1.1 8. Ina typical case, if M + 2 peak of the parent ion looks larger than the M + 1 peak, the compound may contain Sulphur, Chlorine or bromine atom If a compound contains chlorine atom, then pair of peaks are obtained at two mass units apart in the intensity ratio 1 : 3. But in case, bromine atom is present, then pair of peaks, at two mass unit apart are of equal intensity. 10. The most intense peak in the mass spectrum is called the base peak. Its relative intensity or abundance is taken as 100 and the intensities of other peaks, including the parent peak are expressed as percentage of parent peak IL. Mass to charge ratio (m/z) is a dimensionless ratio of the mass number of the given particle to the number (z) of the charge carried by the particle. Usually the particle is singly charged and the ratio is often expressed as m/e. Doubly charged particle are insignificant in the mass spectra of organic compounds. But the peak corresponding to stable doubly charged ions may be sometimes useful. 12. The relative abundance (RA) of the given ion tells its intensity relative to the base peak which is the most intense peak in the spectrum. 13. Fragmentation of the molecular ion occur by the cleavage of bonds in (wo ways ie., heterolytic or homolytic. Heterolytic cleavage is designated by the arrow (7+) to denote the transfer of a pair of electrons in the direction of the charged site as shown below: a 2 R—CH,“C: ——> RCH, + Hemolytic cleavage is designated by the fishhook arrow (+) to denote the transfer of the single electron as shown below. valuable to know the number of carbon as well as nitrogen nt. the number of carbon atoms can be calculated by RLCH,YCH—CHy —> R' + CH=CH=CH, 14, Metastable ions are generally broader than the normal peaks and also these are of low abundance. Moreover, these ions do not necessarily occur at the integral m/e values. 15. According to Even electron rule, an even electron species will not normally break into two odd electron species because the total energy of this product mixture would be too high. In such a case, an ion degrades to another ion and a neutral molecule. For example. Av ————> B” + N (Most likely) (Even electron species) AT ————> B” + N (Less probable) But the radical ions (odd electron species) fragment by the loss of radicals or even electron molecules. Thus, Av —— B+ BY ———5 C™ + N (Where N stands for any neutral molecule) 16. McLafferty rearrangement involves -cleavage of a bond with 7-hydrogen rearrangement to form a cation radical and a neutral molecule. This rearrangement is meant for compounds, containing y-hydrogen with respect to a multiple bond288 ELEMENTARY ORGANIC SPECTROSCOpy A double MeLatferty rearrangement is a atom originates exclusively fiom the y-position, A secondary hydrogen is preferred (0-4 priinary 10 reported in certain Ketones. ‘The second hydrop jom in this process. The mechanism involves, (2) Ketonisation of the intermediate enol ion by the hydrogen transfer (i) Hydrogen transter to enolic oxygen. Consider the McLalferty rearrangement ig hydroge 4-Heptanone, Hy, neg ou | c " sy > c% ScHw—cu— cn “ asc 2 2 iz a CH, Ch CCH, (MR. Jon!) (Minn) (Enolic 4Hlqatinone Esai “ou Oo: | H c, =(cHy= cH) c. ‘ iN a hC CH, HC CC Lone CH, MR ion tl «Ketonic Form) mic 38 7.7 Metastable lons or Peaks Metastable peaks can be easily determined in a mass spectrum. Some important characteristics of these peaks are: (@ They do not necessarily occur at the integral m/e values (ii) These are much broader than the normal peaks and (iii) These are of relatively low abundance. Formation of metastable ions. Consider that M,* is the parent ion and mj is the daughter ion. If the reaction My > m,* takes place in the source, then the daughter ion, my may travel the whole analyser region and is recorded as m,” ion. On the other hand, if the transition M? 10m) occurs after the source exist and before arrival at the collector, then iis called a metastable ion. We know that in double focussing mass spectrophotometer, there are two field free regions. ‘These are called drift regions. The ions pass through these regions after acceleration. The first field free region refers to the portion of the ion path immediately belore the electrostatic analyser. The second ficld free region lies between electrostatic analyser and magnetic analyser. 8 ‘Second Field < ey) Free Region First Field © Free RegionASS SPECTROMETRY An jon with charge e after being 289 ¥ accelerat 2 cnorty equal toe. Thus, all ions a Ned through a potential, V volts will possess kinetic wriving at A, seay of the ion will be independent oe ‘vit have translational energy equal to eV and thus, Now suppose the reaction, M,* —> mt H Occurs in the second field free region, then the Jaughter fon (m,") will have kinetic energy equal to 2. eV, Also the neutral particle (M, ~ m,) mh will have kinetic energy equal to M eV. It may be noted that the neutral particle is not detected by the mass spectrometer, Mi m Thus, m,” ion formed in the second field free region will have less kinetic energy than it would have possessed if it were formed in the source, Clearly, the peak for the daughter ion (m,") will not appear at the normal position for m,* on the mass scale. Instead, the signal (peak) appears at ‘M). Hence, we conclude that the position of the metastable peak (m*) due to the reaction M," > 1m," occurring in the second field free region is such that m= mM, Important notes. 1. [1 is important to remember that for a reaction M,' —> m,, m* (metastable Peak) has a distance below m, on the mass scale. The distance is approximately similar to the distance that m, lies below M, 2. The relative abundance of the metastable peak (in) is often of the order of 107 or less compared to the abundance of parent or the daughter ions in 70 eV spectrum, (EUR Consider the formation of metastable peaks in the spectrum of p-aminoanisole. The parent (molecular) ion appears at mve 123. Suppose the fragmentation of parent ion into daughter ion, (due to the loss of methyl radical, i.e., loss of 15 mass units) takes place in between the electrostatic and the magnetic analysers, ie. in second field free region. The position of the metastable peak can be calculated as follow: It A NH; NH, ay ? oc, (MD oO Mm) The position of the metastable peak m, _ 108x108 M7 3) 8 We see that the position of metastable peak (94.8) below m,* ion (108) is approximately the same as m, ion is below M," (123) on the mass scale which is linea. j “The position ofthe metastable peak due othe following fragmentation inthe second field free region can also be determined. (108) mt = NH. 25 CaN It (80) aos) g ™ (ms)a ELEMENTARY ORGANIC SPECT ROSCopy 80x 80 able peak m™ = Th The position of meta Consider the mass spectrum of toluene. Two strong peaks «at mde 91 ang ive 63 ore formed. The peak at mde 911s de 10 the formation of ropylam cation (sabe) mg loses a molecule of acetylene (26 mass units) 10 give CoH," (me 65). cu,!" CH, vearangeme “cy arrangement JO oa, ou, MY Gan,'y (Toluene ion Benzyl Cation mk5i eos Suppose the transition C,H," (91) to CsH,* (65) occurs in the second field feee region, then a metastable peak is formed. The position of the broad metastable peak is determined us 65x 65, o1 = 46.4, ji A metastable peak in case of toluene appears at 46.4 in the mass spectrum Importance of metastable peaks. The metastable peaks in the mass spectrum greatly contribute in structure elucidation. From the positions of the parent ion and the daughter ion, the position of the metastable ion is calculated as above and confirmed in the spectrum under examination, In the spectrum of toluene, the formation of less intense metastable peak at 46.4 lends weight to the structure of toluene. It is due to the fragmentation of CH," ion to CH," ion in the second field free region. Similarly, the presence of metastable peaks at the expected positions of the suspected compounds lends weight to its structure, ‘Why metastable peaks are broadened, The most likely reason for the broadening of the metastable peak is the possibility that some of the excitation energy leading to bond capture may be converted into additional kinetic energy. 7.8 The Nitrogen Rule Many signals (peaks) can be ruled out as possible molecular ions simply on the grounds of reasonable structural requirements. The nitrogen rule is often helpful in this regard. It states that a molecule of even numbered molecular mass must contain no nitrogen atom or an even number of nitrogen atoms. An odd numbered molecular mass requires an odd number of nitrogen atoms. This rule holds for all compounds containing carbon, hydrogen, oxygen, nitrogen. sulphur and halogens. An important corollary of this rule states that the fragmentation at a single bond gives an odd! numbered ion fragment from an even numbered molecular ion. Similarly, an even numbered ion fragment results from an odd numbered molecular ion. For this corollary to hold, the fragment ion ‘must contain all the nitrogen atoms of the molecular ion. To explain the nitrogen rule, let us Consider nitro-benzene (CyHsNO,). The signal for molecular ion appears at mle 123; ic. at odd numbered molecular mass sinee the compound contains only one (odd number) nitrogen stom. TW° Important ton fragments which are formed in the mass spectrum of this compound are (i) NO." at me 46 and (ii) NO" at nve 30. Both these fragment ions appear at even mass number. Consider a compound containing two (even number) nitrogen atoms, say 2, 4-dinitrophenol Its molecular ion (M') signal appears at m/e 184. The fragment ions appear at (i) M' ~ H) Le» at m/e 183 and (ii) (M”~ H—CO) i.e., at m/e 155. Thus, we see that the fragment ions comtaining both the nitrogen atoms appear at odd mass number. This proves the validity of the nitrogen rule| From Malojam : nm % sels Assignment 3] {, Que the prdreeple of. Mars Spectroscopy lth, a? { =| da mass a dresceby, a Sample Sn Aha form ef vaber | tel ie hotel dt el ene ore I ~ ht dream. | As a sedutt, cuowatty em atllivon 1 knocked eff es = Bh. molecule | ~ | [This sudut)s tn the Bon if 0: matieubeds Fors -4 [lurbeck Ain a paattere change pe BE ard ons Piece tices | ~ | Excample, . i beam of tlaubreme Ae Aembardid on the vaper | fe Ketone, me f the celckrors From Hh Lore ae | ( Leltrene on athe! Oxygen atom te Leer ay ketone — | Bho perusing a rnélicutor Len (MY ath oT | pest on the omupgern aterm and one ee “yr an || She extro dtsstpats thxce che molustan— | aout kn in fv, ue ces Pevethar ft: ments (FY ERY — | Thi So Utusieated by the! fetter of snap Za + | to: bovedmert 10h of = “se i > - a” a —_— c iI. S . I Ro Rr ; : RY a | cm cay |}000 _—— —————— \ - |pHARMANALY S)¢ we h — Supasna Abraham i | — Rett: No: OL | ——_— — Te ee ! Spectrum: _ om f. CH3OH te” —» cyrou't 4 > p- ——_(m]2 = 32) Molecular tion TOT H. +e CHO cont pay — Mm - cmiz= 31) Tei CH ont — 3 py + "OH > > {ra} 2 =15) 7 CH OH* ——y cHot tH: ., . (m[2=24) : | —t 7 + reark+ it a {oo me tT SASS SPECTRUM OF METHANOL 1 FOR EDUCATIONAL USERetaHve abund. ~The retak Isotope peaks: The isotope pea. lcontains heavies ommuon so tpe: Commonly seen isotope peaks ase (mti" p, or M42)" peaks - : _ EThe inkensihy of an isotope peak ct n yelahve Qhundance of that isatope fn _nahue _ The yelahve abundance of an tsofppe 4 Calulal on the basis of 100 molecules. From the relative -— abundance, the in. ihy of H " ox (M1 ontain ¢? Isotope and 1-108 molecujes contain + c!? iso type ; The relative abundance of common _istop® 3 areas follows: = = a i No | lsohopes— Relative abundance | Peal —= i 4: SH 99-985 50-018 | ema) [ 2 1304 98-992 ¢ 1-10 peel) a 3: ch 7552424 nasa) 3 7 [pr 50:92 149: ug mt) — —} L ——= aS y | eae ete ;—the motectitar ton. Iba 1 a = —hig JD ener SUAUY OE electron yo ea LiectOn beam. As a recut NOOChed off from ane molec | |= This results io the formation Of 9 rotecetar ie has a tive sid ond Top Pattie cnange Yan one free elecwon, . fame seta e0Hy dssgatee trae a endlecatas 19 ef lec i 10 lia) duces £4 rnerits. Olt / lai, ator Pie Ct nw | § 24... ntay Cc ~ € Ir _—_—_ — yf @® we =mle=2t m)e=l05 ; 1 [rs He b= mle = ay mle =43 fk Be i tie ti Th yy 4 FOR EDUCATIONAL USE oy ey — - ——— ai et 54 NE i abet—— _ The most intense pear io the mare spectre ts __catied the se etna 100 FESR SY be the base pea =) aS || > Base pean oe a . Tropytive Lon. Mie = @ Hesie, tropyliue 100 chows base pean