Optimized structures
Compound 1
N- Benzyl tyrosine amide, [M+H]+ , N protonated
Sum of electronic and thermal Energies=
Sum of electronic and thermal Enthalpies=
Sum of electronic and thermal Free Energies=
-880.581401
-880.580457
-880.650249
N- Benzyl Tyrosine amide, [M+H]+ , O- protonated
Sum of electronic and thermal Energies=
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-880.578900
-880.577956
-880.647906
INC 1(a)
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Benzyl cation
-880.486977
-880.486033
-880.557903
migrated to C ortho to OH group (a)
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1- 2 shift of hydrogen after benzyl shift (a1)
-880.499532
-880.498588
-880.568257
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Sum of electronic and thermal Enthalpies=
Sum of electronic and thermal Free Energies=
-880.496822
-880.495878
-880.565399
Ts for 1 2 hydrogen shift after benzyl shift
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H shifted from ring to N (b)
-880.477366
-880.476422
-880.544915
Sum of electronic and thermal Energies=
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Sum of electronic and thermal Free Energies=
-880.585675
-880.584731
-880.650740
Ts for h shift (a1-b)
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Sum of electronic and thermal Enthalpies=
Sum of electronic and thermal Free Energies=
-880.512650
-880.511706
-880.576970
Fragments
Benzyl cation
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[M+H]-Benzyl cation
-270.549897
-270.548953
-270.584676
Sum of electronic and thermal Energies=
Sum of electronic and thermal Enthalpies=
Sum of electronic and thermal Free Energies=
-609.924005
-609.923061
-609.975394
m/z 197, [M+H-74]+
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Neutral corresponding to m/z 197, [M+H-74]+
-616.054759
-616.053815
-616.107673
Sum of electronic and thermal Energies=
Sum of electronic and thermal Enthalpies=
Sum of electronic and thermal Free Energies=
-264.438608
-264.437664
-264.472432
Scheme 3
INC 1(b)
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-880.511389
-880.510445
-880.583223
Benzyl cation migrated to amide nitrogen (c)
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-880.530373
-880.529428
-880.598708
Proton shifted from NH2 to NH (d)
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-880.555914
-880.554970
-880.622715
TS for H shift from c to d
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-880.553846
-880.552901
-880.620155
Product ions
m/z 226, [M+H-45]+
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-710.704426
-710.703481
-710.764330
Neutral corresponding to ion of m/z 226
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Sum of electronic and thermal Free Energies=
-169.776329
-169.775384
-169.804144
Compound 2
N-[1 –phenylethyl] tyrosine
Sum of electronic and thermal Energies=
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-919.870840
-919.869896
-919.942608
INC 2
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Sum of electronic and thermal Free Energies=
-919.812874
-919.811930
-919.889327
Product ions
m/z 105, 1-phenylethyl cation
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-309.857509
-309.856565
-309.896031
Neutral corresponding to ion of m/z 105
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-609.924004
-609.923060
-609.975396
(INC 3)
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-919.846923
-919.845978
-919.922215
m/z 181(Enol)
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Styrene
-610.315203
-610.314259
-610.366652
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Sum of electronic and thermal Free Energies=
-309.520636
-309.519692
-309.558955
Energy profile of the scan of N-C bond length in [M+H]+ ion of compound 2
Energy profile for the H shift from C to N in INC 2