‘MASS SPECTROSCOPY Regular Paper Substituent Effects in the Fragmentation of Benzyl Acetates Hisao Nakata*, Kikuko Iwata‘t, Tomiko Kondo*’, Hideo Yoshizumi**, and Akira Tatematsu™* (Received May 23, 1984) Electron ionization mass spectra of substituted benzyl acetates [1] ~[12]] are meas- ured. In general, the spectrum consists of four peaks: M*, [M—42]*, [M—9J*, and ‘mjz 43 peak. A good Bursey-MeLafferty correlation between log (Lmt/z 48]/[M]) and Hammett ¢ constants is found, ‘The Einolf-Munson treatment of m/z 43 and [M—42] ions also gives an expected result, On the other hand, compounds [5] and [7] deviate considerably from the plott of log ((M-42/[MJ) vs. ¢, and the Chin-Harrison analysis Vol. 32, No. 3, August 1984 is applied to explain this discrepancy, 1, Introduction Benzyl acetate is known to undergo a very facile ketene elimination in electron ionization mass spectrometry. t electronic state and fragmentation,” we have selected a set of substituted benzyl acetates and examined their mass spectra under electron ionization. The structure of the benzyl acetates is suitable for our study because the key fragmentation of ketene elimination takes place at the moiety that is remote from the substituted phenyl ring by one satu- In connec- m to our studies on the relation between rated carbon atom. We can therefore remove the direct interaction between substituents and the fragmenting functional group. This structural characteristics would also provide a clue to the concept? of apparent migration of radical site through a saturated carbon chain during the frag- mentation. The Bursey-McLafferty cor Einolf-Munson treatment, and Chi son analysis of the substituent effect are applied to the data obtained. 2, Experimental ‘The compounds used in the present “Department of Chemistry, Aichi Kyoiku University (Kariya, Aichi 448, Japan) ** Faculty of Pharmacy, Meljo University (Tempaku, Nagoya, Aichi 468, Japan) T The present name: Kikuko Taniguchi * The present name: Tomiko Nakajima 297862 — suo! 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[Xzuaq asoy *] A1Qu, UL parst| o18 320m MEIYSOK “A “OPUOY “YZ BIVA] “Y UVLCN “ASubstituent Effects in the Fragment: in most of the compounds but the intensity gradually decreased with the substituent in the order: OCH, > CH, > Cl > H > COCH, > CN > NO, In NO, compound, the M™ peak was scarcely observed. The [M—42] peak was pronounced in all compounds except for m-NO, and pOCH, derivatives, where the intensity of the [M—59] and related [M—60] peaks was extremely large. ‘The m/z 43 peak seems to be significant for compounds that have the electron-with- drawing substituent such as CN or NO,, while the peak was very weak for m- and OCH, compounds. 1) Bursey-McLafferty Correlation It has been empirically demonstrated by the pioneering work of Bursey and MeLafferty” that if a common fragment jon A* is formed from the molecular ion containing a meta or para substituent X for a series of aromatic compounds, then log (CA*]x/CMx*)) —log (LA*Ju/(MaD is a linear function of Hammett o constants for X, where [A*]x and [A*Jx are the observed peak intensities of the common ion At in the spectrum of Mx and Mu, respectively, and [Mx] and [Mu*] are the corresponding molecular ion peak in- tensities. Since a common fragment ion, CH,- C=0*, appeared at m/z 43 for compounds used in the present work, the above Bursey- MeLafferty correlation was first tested for this ion, As is seen from Fig. 1, a rela- tively good correlation was observed. However, the data for compounds [1], [5, and [7] deviated considerably from the correlation line and therefore are not in- cluded in Fig. 1. The very weak intensity Hion of Benzyl Acetates of either the molecular ion peak or the m/z 43 peak would be responsible to scatter. The compound [12] was also ex- cluded, as the m/z 43 ion could be formed from the substituent itself. » Yost ta/2 431,/005)) ~ tostta/2 43,70 0.0 0.5 ry annette & Fig. l. ‘The correlation of relative intensties of ‘m/z 43 ions with Hammett ¢ constants. ‘The numbers 1—12 stand for the com. pounds listed in Table 1. 2) Einolf-Munson Treatment It has been reported by Einolf and Munson” about a decade ago that for two competing fragmentations from the same molecular ion to give products A,* and Ast, the plot of log (CA,*J/TA:*)) vs. sub- stituent constants may give a straight line for a series of aromatic compounds. In our case, both the m/z 43 ion and the [M—42] ion are considered to be derived directly from the molecular ion, and consequently would follow the Einolf-Munson relation- ship. This is actually the case, and a good correlation was obtained (Fig. 2). ‘The result is rather surprising because the formation of the [M—42] ion must — 299 —H, Nakati involve a hydrogen rearrangement, whereas the m/z 43 ion is formed, at least formally, by a simple bond cleavage reaction. One possible explanation is that the fragments which contain the substituent X have the similar structure in these two fragmenta- tions as shown in Scheme 1. Structural, as well as mechanistic similarities are often invoked for the Hammett type cor- relation to be held in mass spectrometry. 0.0 0.5 10 Hansett Fig. 2. The correlation of relative intensities of mja 43 and [M—42] ions with Hammett @ constants. tly Inve 43] : grote 7 GS & Kb OrCetily ff Scheme 1 [e42] 3) Chin-Harrison Analysis ‘As noted previously, the most important fragmentation of these benzyl acetates is the elimination of ketene from the molec- ular ion to afford the [M—42] peak, which K, Iwata, T. Kondo, H. Yoshizumi, and A. Tatematsu is very prominent in the spectrum. The [M—42] fragment ion necessarily contains the substituent and therefore it is of in- terest to see if the similar Hammett type correlation is observed for this ion also, since some complicated situations are usually resulted for the ion that carries the substituent” Although we have used the data of the low energy spectrum (Table 11), they still have some fragment ion peaks due to secondary fragmentation reactions from the [M—42] ion, To evaluate the quantita- tive nature of the substituent effect, these secondary ion abundances should be cor- rected. ka + wha UWS rt, ot, ete. ScHeme 2 For general fragmentation process shown in Scheme 2, Chin and Harrison? have proposed Eq. 1, where the abundances of the initially formed ion and those of the observed ion are represented by [Mo], [A,] and (MJ, CAJ, respectively, fu and fx are the fractions of ions“with insufficient energy to decompose, ie., [M] = fu [Mo], and [A] = {4 [Ac], and ky = Ki + ke. FAY = ta BA Ly 0 cM) kr In the present context, [A]] corresponds to the observed peak intensity of the [M — 42] ion, and [Ao] is the intensity cor- rected by secondary fragmentations, which were identified either by appearance of metastable peaks or by logicel neutral tenesSubstituent Effects in the Fragmentation of Benzyl Acetates losses from the [M—42] ion, CAIMD tion of Fig. 3 was obtained. It is apparent that the correlation was fairly good but the deviation of the compounds [5] and (7) is outstanding. When log plotted against «, a correla- ny 209118) ,/ (0 0.0 0.5 1.0 Hammett Fig. 8. The correlation of relative intensities of [M~42] ions with Hammett ¢ constants, To clarify the possible cause of these deviations, Eq. 1 was modified to Eq. 2, and log (CAs/(Me]) was plotted against Fig. 4). The compounds [5] and (7) again showed an abnormal trend. The term (1—fu) in Eq, 2 is equal to (My~M)/Mo, and this quantity implies the fraction of molecular ions with sufficient energy to decompose in the total ionization. This fraction is often reported™” to be empirically linear function of ionization energies (IE's) of the substrate molecule, Provided that appearance energies (AE's) of the fragment ion in question are almost independent of the substituent. yd Log Lag) /( 0.0 0.5 10 Hammett Fig. 4. ‘The correlation of corrected intensities of [M-42] ions with Hammett ¢ constants. Unfortunately, accurate values of IE and AE for the substituted benzyl acetates are not available to us. However, IE's of disubstituted benzene derivatives, such as those benzyl acetates, can be roughly cal- culated by empirical equations as shown in Table Ill. On the other hand, AE's of the [M~42] ion would not be very much dif- ferent each other, because the data for the same type of fragmentation showed similar AE values for both extremes of ‘Table III, Calculated IE of Substituted Benzyl Acetates* ‘Compound IE (eV) [1] »-0CH, 8.31 [2] mCH, 8.76 [3] cl 8.97 [4] CN 9,60 ‘Compound 1B (eV) [1] p-0CH, 8.39 [8] CH, 8.79 (elec. 8,98 (10) PCN 9.58 [5] m-NO, 9,81 [11] pNO, 9.73 [6] H 9,06) [12] p-COCH, 9.04 The Bentley-Johnstone-Benoit equation®™ has been modified by using the measured IE of unsubstituted benzyl acetate (9,06 eV}: TE (m) = 0.96 Cou:*) + 9.06 TE (p) = 0.86 Corn") + 9,06 **The observed IE.® —301—H. Nakata, K. Iwata, T. Kondo, H, Yoshizumi, and A. Tatematsu Table IV. AE of Related Fragmentations Substrate Molecule Fragmentation Reference x Yracocn, [M—42] 15,15) x Y-ocoen, [M12] 1) X=NO, 11.05 x(t, ,c0008, oan a cH, 11.10 substituents, NO, and OCH, (Table IV). a5 9.0 8.5 10.0 calculated Ionization Energy (eV) Fig. 5. The correlation of calculated IE's fof substituted benzyl acetates with Hammett @ constants, When the quantity (1—fu) was plotted against the calculated IE's, a fair correla- tion including [5] and [7] was obtained (Fig. 5). Since IE’s are known to be linearly proportional to Hammett ¢ constants,” this result indicates that the abnormal behavior of [5] and (7] in Fig. 4 is due to the term ka/kr in Eq. 2 Actually, both [5] and [7] showed very strong [M—59] and related [M60] peaks, which would probably affect a regular tendency of Ks/kx among these benzyl acetates. Finally, it might be pointed out that the appearance of the strong [M — 59] peak for [5] and [7] could be correlated with radical site localization in the molee- ‘As is seen from Scheme 3, a necessary prerequisite for this fragmenta- ular ion, tion to occur is ‘an unpaired electron at the appropriate position of the benzene nucleus. From usual physical organic point of view, the m-NO, or OCH, group appears to be most favored in this respect, ie., the desired distribution of an unpaired electron in the benzene nucleus is achieved effectively by the strongly drawing NO, group and by the strongly electron-conating OCH, group para positions. an effective localization of electron- in, respectively, meta and [r-59] ‘ScHEME 3 —902-Substituent Effects in the Fragmentation of Benzyl Acetates 4, Conclusions As a number of basic factors has been clarified"* for substituent effects in mass spectra of a series of aromatic compounds, it should be important to reveal scope and limitations of these factors for a particular type of compounds. ‘The present work has described only an experimental approach to this aim. The more detailed discussions in terms of electronic state and charge distribution from MO calculations, together with the precise mechanism of the frag- mentation of those benzyl acetates, will be reported shortly. 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Nakata, in “Introduction to Organic Mass Spectrometry,” Kodansha (1981), pp. 125127. 10) See, for example: I, Howe, in "Mass Spectro- metry" (D. H. Williams, ed), A Specialist Periodical Report, The Chemical Society, Vol. 1 (1971), pp. 66-80; Vol. 2 (1973), pp. 15— al. 11) T. W. Bentley, in *Mass Specromelry” (R. A.W. Johnstone, ed.), A Specialist Periodical Report, The Chemical Society, Vol. 3 pp. 72 ~73 (1975). 12) T. W. Bentley and R.A. W. Johnstone, J. Chen, Soc. (B). 1871, 263, 13) F. M. Benoit, Org. Mass Spectrom. 9, 626 cas74). 14) P. Brown, Org. Mass Spectrom, 3, 1173 4970). 15) A.A. Gramble, J.R. Gilbert, and J. G, Tillett, J. Chem. Soc. (B), 1970, 1231. 16) M. A. Baldwin, A.G. Loudon, A. Maccoll, and K. S. Webb, Org. Mass Spectrom., 11, 1180 ast). 31) L Howe and D. H. Wi Soc:, 80, 5161 (1968). 18) A.A. Gamble, J.R. Gilbert, and J. G, Tillett, Org. Mass Spectrom., 5, 1093 (1971). 19) A.Streitwieser, Jr.. Progr. Phys. Org. Chem., 1, 1 (1963). 20) F,W. MeLafferty, Chem. Commuen., 1968, 956; See also for a review: K. Levsen, “Fundamen- tal Aspects of Organic Mass Spectrometry.” Verlag Chemie, pp. 118~124 (1978). Hams, J. Am. Chent, Keywords Electron ionization mass spectra Mass spectra of benzyl acetates Substituent effects Fragmentation mechanisms Bursey-McLafferty correlation jolf-Munson treatment Chin-Harrison analysis Hammett correlations 303 —