19/06/2022

INTERPRETACIÓN DE ESPECTROS
tr í a
o m e
DE MASAS. Métodos GC/MS y LC/MS.

u r s t r o Prof. Dra. Elena E. STASHENKO

C pe as c A
UIS-Bucaramanga, Colombia

I
elena@tucan.uis.edu.co

s
E ma ST s I C
de INJU
1

k o
M e n
s h
CONTENIDOSta
a id a d
l e n s
Introducción: recordando algunos conceptos básicos…

r
E ive al
Ionización en fase gaseosa: ionización electrónica [EI] – GC/MS

n r i e r
Ionización en fase condensada (electronebulización) – LC/MS

U us tand t
Analizadores. Detectores. Calibración.

d
ESPECTRO DE MASAS: análisis general, iones isotópicos, productos

I n a n
Tipos de reacciones de fragmentación:

S
ruptura simple, reordenamientos. Grupos funcionales, isómeros.

de
Patrones de fragmentación y su relación con la estructura química.
Métodos experimentales para establecer el patrón de fragmentación.

2
 19/06/2022

ESPECTROS DE MASAS:

tr í a
Patrones de fragmentación

o m e
u r s t r o
C pe as c I A
s
E ma ST s I C
de INJU
3

k o
M e n
s h
S t a
Esquema nVS a id
Mecanismo a d
l e
E ive al r s
n r i e r
U us tand t
I n d a n
S
4
de
 19/06/2022

Esquema de fragmentación no es lo mismo

que el MECANISMO DE FRAGMENTACIÓN
1. Alta resolución: composición elemental
2. Iones metaestables

tr í a
e
3. Sistemas tándem (espectros de iones precursores,

o
iones-producto, SRM, etc.)

r s r o m
4. Ionización suave (ESI, CI, PI)

u t
5. Potenciales de ionización, potenciales de aparición de

C pe as c I A
iones
6. Marcación isotópica, marcación química

s
E ma ST s I C 7. Cálculos mecano-cuánticos: energías de enlace, estados
de transición, QET, etc.

de INJU
5

k o
M e n
s h
S t a
d
91
100

a id a
92

e n s
50

l
E ive al r
39
51 63
65
89 93

r
27 38 40 45 66
0
20 24 28 32 36 40 44 48 52 56 60 64 68 72 76 80 84 88 92 96 100

i e
(mainlib) Toluene

-H
n
U us C H tand
-C H
CH3

t r .

d n
2 2

n
+

I a
+.
5 5

S
de
M+. m/z 92 (M-H)+. m/z 91 (M-H-C2H2)+. m/z 65

6
 19/06/2022

13C
13C

í a
13C

tr
13C

o
Tolueno: marcado isotópico
m e 92
I%
r s r o 93

Cu c t
C pe C H as
H 12
5 5
I A
13
5 5

C
65 66

s
E ma ST s I m/z

de INJU
7

k o
M e n
s h
S t a
d
91
100

a id a
92

e n s
50

l
E ive al r
39
51 63
65
89 93

r
27 38 40 45 66
0
20 24 28 32 36 40 44 48 52 56 60 64 68 72 76 80 84 88 92 96 100

i e
(mainlib) Toluene

-H
n
U us C H tand
-C H t r
CH3

d n
2 2

n
+

I a
+.
5 5

S
de
M+. m/z 92 (M-H)+. m/z 91 (M-H-C2H2)+. m/z 65

8
 19/06/2022

¿Cómo sé, que esta molécula

tiene enlace(s) doble(s)?
Iones característicos:
tr í a
o C3H5+ m/z 41
m e
u r s t r o
C4H7+ m/z 55
C pe as c A
C5H9+ m/z 69 41, 69, 83, 97…
I
s [C H ] s
E ma ST n 2n-1 I C
+

de INJU
9

k o
M e n
s h
t a
cis- -Ocimeno [(Z)-3,7-Dimethyl-1,3,6-octatriene]

S
a id a d
l e n r s
E ive al r
n
U us tand t r i e
trans- -Ocimeno [(E)-3,7-Dimethyl-1,3,6-octatriene]

I n d a n
S
10
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 19/06/2022

allo- OCIMENO [(E,Z)-2,6-Dimetil-2,4,6-octatrieno]

tr í a
o m e
s o
neo-allo- OCIMENO [(4E,6Z)-2,6-Dimetil-2,4,6-octatrieno]

u r t r
C pe as c I A
s
E ma ST s I C
de INJU
11

k o
M e n
s h
Espectro de masas
S t a
a id a d
1. Ion molecular (paridad de masa, intensidad, aspecto

n
general del espectro de masas)

l e
E ive al r s
2. Masas exactas: composición elemental

r
3. Relación isotópica: composición elemental

n
U us tand t r i e
4. Patrón de fragmentación (esquema): reacciones típicas
de disociación (rupturas α-, β-, alílica, bencílica,

d
transposiciones de McLafferty, RDA, etc.). Relacionar con

n n
la estructura.

I S a
5. Iones típicos (m/z 51, 77, 91, 105, 149, etc.); pérdida de

de
fragmentos característicos (CO, H2O, C2H2, C2H4, CH3OH,
C7H7, etc.). Relacionar con la estructura.

12
 19/06/2022

I%
105
A
100

50 77
Ethyl benzoate 122 M+.
150

a
51

tr í
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

e
m/z

I%

r s o o m
119 B Fragmentation pattern

r
100
in mass spectra

u t
(electron impact, 70

C pe as c A
eV) of some essential

I
M+.
50
Methyl m-methylbenzoate 91 150 oil components.

s s I C
A. Ethyl benzoate

E ma ST
39 65
51 77 135
0
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
B. Methyl
m/z m-methylbenzoate

de INJU
13

k o
M e n
s h
S t a C

a id a d
n
-OR2. -CO

l e s
α-Rupture

r
+. C. α-Rupture and

E ive al
M+. R1 = H, m/z 105 (100%) R1 = H, m/z 77 (45%)
typical benzoyl ions

r
R1 = CH3, m/z 119 (100%) R1 = CH3, m/z 91 (43%)
(m/z 105, 119)

n r i e
formation.

U us tand t H
(2) D D. McLafferty
+. -OCH2CH3.
transposition of ethyl

d
O CH2

n
(1) benzoate molecular ion

I n a
CH2
O -OH. m/z 105 (100%) M+. and formation

S
(1) (2) O -CO
of [M – CH2=CH2] +.
-CH2=CH2 (3)
(m/z 122) fragment.

de
(2)
M+. (3) OH
McLafferty
Ethyl benzoate transposition m/z 122 (30%) m/z 77 (45%)

14
 19/06/2022

I%
108
E
100

p-Methylphenyl acetate
50

a
M+.

í
43 150
E. p-Methylphenyl

tr
77
39 51 65
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 acetate mass spectrum

e
m/z and

s o m
F F. Elimination

r r o
of CH2=C=O neutral

u t
-CH2=C=O fragment, and

C pe as c
formation of [M – 42] +.,

A
1,4-transposition

I
diagnostic ion

s s C
for acetates.

E ma ST
M+. m/z 150
I m/z 108
[M – CH2=C=O]

de INJU
15

k o
M e n
s h
I%

S t a G

d
108
100

a id a
91
G. Benzyl acetate mass

n
spectrum (EI, 70 eV).

e s
M+.

l
50 43

r
Benzyl acetate 79 150
77
H. Methyl 2-

E ive al
51 65
39
phenylacetate mass

r
0

i
spectrum (EI, 70 eV).

e
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

n r
m/z

U us tand t
The formation of
I%
100
91 H tropylium ion (m/z 91),
generated through

d n
benzylic excision.
50

I n a
Methyl 2-phenylacetate

S
M+.
150

de
65
39 51 59 119
105 135
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
m/z 91 tropylium ion
m/z

16
 19/06/2022

Ion benzoilo C6H5CO+ en m/z 105

Benzoato de estradilo

tr í a
o m e
u r s t r o Benzobarbital

C pe as c I A
s
E ma ST s I C
de INJU
17

k o
M e n
s h
S t a
a id a d
Abundance

l e n r s
E ive al
100
59 Dihydroeudesmol

n r i e r 166

U us tand t
109 – CH2=C(OH)CH3

50

n d n
[M – CH3 – H2O]+

I a
151

S
55 81
41 67 123
191 M +.
209 224

de
0
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230
m/z

18
 19/06/2022

Abundance
59
100

tr í a[M – CH3 – H2O]+ [M– H2O]+

o e
93 121

m
136

s
α-Terpineol

r o
50

u r
81

c t
43

C pe as
[M – CH3]+

A
67

I
55
71 107 139

s s I C
0

E ma ST
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
m/z

de INJU
19

k o
M e n
s h
t a
Ocimenol [2,6-Dimethyl-5,7-octadien-2-ol]

S
a id a d
l e n r s
E ive al r
n
U us tand t r i e
allo-Ocimenol [3,7-Dimethyl-1,6-octadien-3-ol]

I n d a n
S
20
de
 19/06/2022

118
-CH3OH

tr í a
o m e
u r s t r o
Efecto “orto”

C pe as c I A
s
E ma ST s I C
de INJU
21

k o
M e n
s h
100

S t a 69
Geraniol

a id a d OH

n
41

l e s
50

E ive al r
r
39 93 123
53 84
29 111 121

i
43 81

e
51 57 65 91 96 107 139
15 19 37 74 117 154

n r
0

U us tand t
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
(mainlib) Geraniol

100
69 Geraniol acetate

n d n
O O

50

I S a 41 43

de
93
121
136
53 80
39 85
27 107
15 31 51 57 61 65 99 113 127 154 196
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210
(mainlib) Geranyl acetate

22
 19/06/2022

100
69
Geraniol
69  41
OH
41

50

29
39
43
53
81
84
93

tr í a 111
123
121

e
51 57 65 91 96 107 139
15 19 37 74 117 154
0

o
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

m
(mainlib) Geraniol

s
69
Nerol

r o
100

u
C pe as c t r 41

I A
50
69  41

s s C
93 HO

E ma ST I
39 84
53 80
43 121
29 91 97 111 139
51 59 65 107 154
15 19 37 117
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
(mainlib) 2,6-Octadien-1-ol, 3,7-dimethyl-, (Z)-

de INJU
23

k o
M e n
s h
S t a
d
Thymol

n a id a
l e
E ive al r s
n r i e r
U us tand t Carvacrol

I n d a n
S
24
de
 19/06/2022

Thymol acetate

tr í a
o m e
s
Carvacrol acetate

u r t r o
C pe as c I A
s
E ma ST s I C
de INJU
25

k o
M e n
s h
S t a
d
Retention indices, average value (90% RI range)
Compound

a id a
Formula
PDMS 5%-Ph-PDMS PEG

e n
(DB-1, HP-1) (DB-5, HP-5) (DB-WAX)

l r s
Thymol C10H14O 1272 1290 2164

E ive al
(1260-1289) (1272-1304) (2100-2205)

r
Thymol acetate 1343 1356 1867

i e
C11H16O2

n r
(1330-1351) (1350-1364) (1783-1945)

U us tand t
Carvacrol C10H14O 1283 1300 2211
(1272-1300) (1291-1314) (2140-2246)

d
Carvacrol acetate C11H16O2 1354 1373 1880

I n n
(1344-1367) (1364-1391) (1868-1890)

S a
Taken from: V.I. Babushok, P.J. Linstrom, and I.G. Zenkevich

de
“Retention Indices for Frequently Reported Compounds of Plant Essential Oils”,
J.Phys.Chem.Ref.Data, Vol. 40, N°4, 2011, 1-47.

26
 19/06/2022

tr í a
o m e
u r s t r o
C pe as c
tR 58.92 min

C I A Compound GUAIOL (M.W. 222)

s s I
Mass range Number of scans

E ma ST
m/z 40-280 16895
m/z 40-550 8549

de INJU
27

k o
M e n
s h
Abundance 41

S t a 67 81

d
2200
Split 1:100

a
121

a id
2000 93
1800
Iny. Vol. 1.0 µm
55

n
1600

e
1400 111

l r s
1200 136
1000

E ive al
800

r
600 154
400

n i e
200

U us tand t r
0
m/z-->
Abundance 67 81
41 121
55000
50000
Splitless

d
55 93
Iny. Vol. 0.2 µm

n
45000

n
40000

I a
35000 111
30000 136

S
25000
20000
154

de
15000
10000
5000
0 m/z-->
40 50 60 70 80 90 100 110 120 130 140 150 160

28
 19/06/2022

NEUROTRANSMISORES

tr í a
Adrenalina (epinefrina)

o m e
u r s r o
Noradrenalina
t
(norepinefrina)

c
C pe Dopamina s I A
s s a I C
E ma ST
de INJU
29

k o
M e n
s h
S t a
a id a d
e n s
Dopamina l r
E ive al r
n
U us tand t r i e
I n d a n
S
de
Feniletilamina Catecol
30
 19/06/2022

Feniletilamina
100
30
+
NH2=CH2

a
NH2

tr í
e
50

o
C7H7+

s m
C5H5 M+.
+

u r t r o
91

65 92 121

c
39 41 51 53 56 59
28 31 63 74 77 79

C pe as
15 18 43 86 89 93 99 103 106 118
0

A
10 20 30 40 50 60 70 80 90 100 110 120 130

I
(mainlib) Benzeneethanamine

Ion molecular M+. de intensidad baja, con masa impar (m/z 121). Ion - pico de

s
E ma ST s I C
base en m/z 30 (ion típico de aminas primarias), producto de la ruptura β
(y ruptura bencílica). Iones complementarios: m/z 30 y m/z 91 65.

de INJU
31

k o
M e n
s h
Catecol
S t a
a id a d
n
M+.
110
100

l e
E ive al r s OH

r
OH

C5H4+. -CO

i e
50

n
U us tand r
-H2O
t
64

63
27 81 92

d
39 53 55
18 26 29 32 51

n
14 40 42 46 62 65 67 69 71 74 77 79 83 91 93

n
0
10 20 30 40 50 60 70 80 90 100 110 120

I a
(mainlib) Catechol

Ion molecular M+. de intensidad alta con masa par (pico de base). Catecol

S
se disocia eliminando sucesivamente molécula de agua y monóxido de carbono,

de
dando origen a los catión-radicales (M – H2O)+. en m/z 92 y
[(M – H2O) – CO]+. en m/z 64; se forma un catión (M – CHO)+ en m/z 81.

32
 19/06/2022

Adrenalina (epinefrina)
100
44
+
CH2-NH=CH2

a
HN

tr í
HO

e
50

r s o o m
HO
M+.

r
139

u t
65
39 42 93 OH

c
53 63 77 81 111 137 183
118 123

C pe as
89 146 152 165
0

A
30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190

I
(mainlib) Epinephrine

Ion molecular M+. de muy baja intensidad con masa impar. Ion - pico de base

s
E ma ST s I C
en m/z 44 (ion típico de aminas secundarias), producto de la ruptura β.
Iones complementarios: m/z 44 y m/z 139.

de INJU
33

k o
M e n
s h
Dopamina
S t a
a id a d
n
+ 124

e s
100

l r
30
NH2=CH2 123 NH2

E ive al r
n i e
30

r
123

U us tand t
50

M+.
HO
153

d
77
51 OH

n n
28 39 53 105
63 89 94 136

I
110

a
15 18 47 116
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
(mainlib) Dopamine

S
Ion molecular M+. de intensidad media baja, con masa impar. Ion - pico de

de
base en m/z 30 (ion típico de aminas primarias), producto de la ruptura β
(y ruptura bencílica). Iones complementarios: m/z 30 y m/z 123.

34
 19/06/2022

Noradrenalina (norepinefrina)
139
100

NH2
93

a
HO

í
-CO

tr
+ 65

e
50

NH2=CH2 -H2O -CO

o m
HO

s o
30 111

r
137
OH

u t r
39 53 63 169
77 81 123 151
28 32 42 46 104 109 133 167
70 160

c
0

C pe as
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180

A
(mainlib) Norepinephrine

I
Ion molecular M+. de baja intensidad con masa impar. Ion típico de aminas primarias
en m/z 30 -producto de la ruptura β-, y su ion complementario [M – CH2= NH2]

s
E ma ST s I C
en m/z 139. La presencia de los tres átomos de oxígeno en la molécula se manifiesta
a través de formación de los iones [(M - NH2=CH2)– CO] en m/z 111,
[(M - NH2=CH2) - CO - H2O] en m/z 93 y [(M - NH2=CH2) - CO - H2O - CO] en m/z 65.

de INJU
35

k o
M e n
s h
S t a
a id a d
MESCALINA

l e n r s
Bernardino de Sahagún
(Sahagún, España, c. 1499 -

E ive al
Tlatelolco, México, 5 de febrero

r
de 1590) - un misionero

n r i e
franciscano, autor de varias obras

U us tand t
en náhuatl y en castellano,
consideradas hoy entre los
documentos más valiosos para la

d
reconstrucción de la historia del

n n
México antiguo antes de la

I a
llegada de los españoles. De

S
entre sus escritos destaca la
Historia general de las cosas de

de
la Nueva España

36
 19/06/2022

Mescalina
100 + 30

NH2=CH2 O

í a
O O

tr
182

e
50
30

s o m
166

M+.

r o
91 181

r
NH2 181 136

u t
39 52 65 80
95 106 121 151
43 139 211

c
33 190 195

C pe as
0
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220

A
(mainlib) Benzeneethanamine, 3,4,5-trimethoxy-

I
Ion molecular M+. de muy baja intensidad con masa impar. Ion - pico de base en

s s I C
m/z 44 (ion típico de aminas secundarias), producto de la ruptura β.

E ma ST
Iones complementarios: m/z 44 y m/z 139.

de INJU
37

k o
M e n
s h
FENILETILAMINAS
S t a MESCALINE (3,4,5-trimethoxyphenethylamine)

a d
DOM (2,5-dimethoxy-4-methylamphetamine

a id
2C-B (2,5-dimethoxy-4-

n
PMA (p-methoxy-amphetamine) bromophenethylamine)

l e s
2,4-DMA (2,4-dimethoxy-amphetamine) 2C-E (2,5-dimethoxy-4-ethylphenethylamine)

E ive al r
2C-T-2 (2,5-dimethoxy-4-
3,4-DMA (3,4-dimethoxy-amphetamine)
ethylthiophenethylamine)

r
MDA (3,4-methylenedioxy-amphetamine)

i
2C-T-7 (2,5-dimethoxy-4-

n r e
propylthiophenethylamine

U us tand t
MMDA (3-methoxy-4,5-methylendioxy-amphetamine)
MMDA-3a (2-methoxy-3,4-methylendioxyamphetamine)
MMDA-2 (2-methoxy-4,5-methylendioxyamphetamine)
TMA
TMA-2
n d n
(3,4,5-trimethoxyamphetamine)

I a
(2,4,5-trimethoxyamphetamine)
DMMDA

S
(2,5-dimethoxy-3,4-methylenedioxyamphetamine) PiHKAL: A Chemical Love Story

de
by Dr. Alexander Shulgin and Ann
DMMDA-2 (2,3-dimethoxy-4,5-methylenedioxyamphetamine) Shulgin (1991). “Phenethylamines I Have
TeMA (2,3,4,5-tetramethoxyamphetamine) Known and Loved".

38
 19/06/2022

44 + Anfetamina
CH2-NH=CH2
100

91 NH2

50
44

a
C7H7 +

í
M+.

tr
91
36 65
39 41 43 45

e
28 51 56 77 92
30 35 53 58 60 63 67 69 71 73 75 79 84 86 89 95 103 115
109 112 135
0

o
20 30 40 50 60 70 80 90 100 110 120 130 140

+
m
(mainlib) Dextroamphetamine

s o
58

r
CH3CH=NH-CH3 Metanfetamina
100

u t r
91

C pe as c
NH

I A
50
58

0
20
s
E ma ST30

30
s I
39 42
40
C 50
51
56

60
65
68 71
70
77
80
84 89
91

90 100
104 111 115 119
110 120
125
130
134

140
M+.
149
150 160

de INJU
(mainlib) Methamphetamine

39

k o
M e n
s hPutrescina
+
t a
30
100

NH2=CH2

a idS a d
n
43 NH2
H2 N

l e s
50

E e r l
(M – NH3)+.
59

i v a r
45 71
28 42

i e
31
70

n
56

r
27 29 39 53 58 60 68 72
18 46 88

t d
0
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

+
U us Cadaverina n
30
100

NH2=CH2

d n t a
I n a
H2 N NH2

S
50

(M – NH3)+.

de
56

18 28 43 45 73 85
31 41 55 57 59
15 17 37 39 46 50 68 70 79 86 98
0
10 20 30 40 50 60 70 80 90 100 110

40
 19/06/2022

No siempre la exactitud alta de medición de

masas es suficiente

tr í a
o m e
u r s t r o
C pe as c
86

A
100

Importantísimo: tener información

I
sobre iones-fragmento

s s C
N

E ma ST I
50

30 58
101
29 42 44 56 87
15 18 70 72
0

de INJU
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110

41

k o
M e n
s h
I%

S t a A

d
105
100

n a id a
e s
50 77

l
Ethyl benzoate M+.

r
122
150

E ive al
51

r
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

n i e
m/z

I%
100

U us tand t r 119 B Fragmentation pattern

in mass spectra

d n
(electron impact, 70

I n a
M+. eV) of some essential

S
50
Methyl m-methylbenzoate 91
150 oil components.

de
39 51
65 A. Ethyl benzoate
77 135
0
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
B. Methyl
m/z m-methylbenzoate

42
 19/06/2022

-OR2. -CO
α-Rupture
C. α-Rupture and

a
+.

í
M+. R1 = H, m/z 105 (100%) R1 = H, m/z 77 (45%) typical benzoyl ions

tr
R1 = CH3, m/z 119 (100%) R1 = CH3, m/z 91 (43%)
(m/z 105, 119)

e
formation.

r s o o
+. H
(2)
-OCH2CH3.

m
D D. McLafferty

r
transposition of ethyl

u t
O CH2
benzoate molecular ion

c
(1)

C pe as
m/z 105 (100%) M+. and formation of
CH2

A
-OH.

I
O
(1) (2) O -CO [M – CH2=CH2] +.

s C
(m/z 122) fragment.

s
-CH2=CH2 (3)

E ma ST I
(2)
M+. (3) OH
McLafferty
Ethyl benzoate transposition m/z 122 (30%) m/z 77 (45%)

de INJU
43

k o
M e n
s h
I%

S t a E

d
108
100

n a id a
p-Methylphenyl acetate

l e s
50

r
E. p-Methylphenyl

E ive al
M+.
43 150
77
acetate mass spectrum

r
39 51 65

i e
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 and

n
U us tand r
m/z

t
F. Elimination
F of CH2=C=O neutral
fragment, and

d n
-CH2=C=O formation of [M – 42] +.,

I n a
1,4-transposition diagnostic ion

S
for acetates.

de
m/z 108
M+. m/z 150
[M – CH2=C=O]

44
 19/06/2022

I% G
108
100

91
G. Benzyl acetate mass
50 43 M+. spectrum (EI, 70 eV).
Benzyl acetate 79 150

a
77
51 65 H. Methyl 2-

í
39

tr
phenylacetate mass
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
spectrum (EI, 70 eV).

e
m/z

o
The formation of

s m
I%
H tropylium ion (m/z 91),

r o
91

r
100
generated through

u t
benzylic excision.
50

C pe as c
Methyl 2-phenylacetate

I A
M+.
150

s s C
+

I
65

E ma ST
39 51 59 119
105 135
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
m/z 91 tropylium ion
m/z

de INJU
45

k o
M e n
s h
t a
Abundance
A

S
limonene

piperitenone
carvone

1800000

d
1600000

a id a
1400000

n
1200000
c
c c20c21 c22 23

e
c17 c18 19

s
1000000 c24

l
A. The use of n-hydrocarbon

r
c16 c25
800000 c15

E ive al
600000 c10
c13
mixture co-injected with
c12 c14

r
400000
c11 the sample for linear

i e
200000
retention indices (LRI)

n
U us tand t r
10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 Time--> calculation.
Abundance
B. Standard compounds
α-Pinene

β-Myrcene

Terpinolene

Linalool
P-Cymene

Limonene

1400000
B
used in the process

d
1300000

n
1200000
of sample components

n
1100000

I a
1000000
900000
800000 identification

S
700000
600000
500000

de
400000
300000
200000
100000
8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 Time-->

Standard compound Sample

46
 19/06/2022

Reacción Retro-DIELS-ALDER (RDA)

tr í a
o m e
u r s t r o
C pe as c I A
3,4-Dihidro-2-fenil-2H-1-benzopirano

s
E ma ST s I C
de INJU
47

k o
M e n
s h
S t a
a id RETRO a d
l e n r s
E iDiels-Alder
v e al r
n
U us tand t r i e
I n d a n
S
48
de
 19/06/2022

Ruptura retro-Diels-Alder
(RDA)
+.
tr í a +.

o m e
u r s t r o - C2H4

C pe as c I A
s
E ma ST s I C
de INJU
49

k o
M e n
s h
S t a
Ruptura retro-Diels-Alder
a id a d
(RDA)

l e n +.

r s
+. +.

E ive al r
O O
C6H5

n
U us tand t r
RDA

i e
C
O
O
M+. m/z 120(100%) m/z 104(42%)

I n d a n
S
de
X

50
 19/06/2022

131
100
RDA
118

146
50
91 105
39
27 51
63 77 128
15
41 53 71 89
29 58

a
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

í
(ma inlib ) Na p htha lene, 1,2,3,4-tetra hyd ro-5-methyl-

tr
104
100 RDA

e
146

o
50

m
91

s
131

r o
115

r
39 51 64 78 128
27 58 72

u t
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

c
(ma inlib ) Na p htha lene, 1,2,3,4-tetra hyd ro-2-methyl-

C pe as
131

A
100

s
50

s I C I RDA

E ma ST
146
91 118
39 51 63 77 104
15 27
58 89
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
(ma inlib ) Na p htha lene, 1,2,3,4-tetra hyd ro-1-methyl-

de INJU
51

k o
M e n
s h
S t a
a id a d
l e n
Reacción Retro-Diels-Alder
r s
(RDA)

E ive al r
n
U us tand t r i e
I n d a n
S
3,4-Dihidro-2-fenil-2H-1-benzopirano

52
de
 19/06/2022

67
100 53

54

50 39
82
41
27
51 53
14 16 26 29 38 40 42 55 65 68 77 79 81
63 74 83

a
0
10 20 30 40 50 60 70 80 90

tr í
79
100

Aromatización

o e
50 77 80

r s o m
39 51
27 78

r
38 40 49 53 63 65 74 81
28

u t
0
10 20 30 40 50 60 70 80 90

C pe as c
78
100

C I A
s s
50

E ma ST I
77
51
39
74 76 79
15 26 28 49 61 63
0
10 20 30 40 50 60 70 80 90
(mainlib) Benzene

de INJU
53

k o
M e n
s h
S t a Ruptura retro-Diels-Alder (RDA)

a id a d 104

n
100

50

l e
E ive al r s 91
- C2H4 132

r
RDA

i e
39 51

n r
27 65 78 117

U us tand t
15 53 58 74 89
41 82
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140
(ma inlib ) Na p htha lene, 1,2,3,4-tetra hyd ro-
131
100

d n
146
118

n
- C2H4

I a
50 RDA

S
105
27 39
91 115

de
51 128
15 63 77
41 53 71
58 89 141
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
(ma inlib ) Nap htha lene, 1,2,3,4-tetra hyd ro-6-methyl-

54
 19/06/2022

131
100
RDA
118

146
50
91 105
39
27 51
63 77 128
15
41 53 71 89
29 58

a
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

í
(ma inlib ) Na p htha lene, 1,2,3,4-tetra hyd ro-5-methyl-

tr
104
100 RDA

e
146

o
50

m
91

s
131

r o
115

r
39 51 64 78 128
27 58 72

u t
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

c
(ma inlib ) Na p htha lene, 1,2,3,4-tetra hyd ro-2-methyl-

C pe as
131

A
100

s
50

s I C I RDA

E ma ST
146
91 118
39 51 63 77 104
15 27
58 89
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
(ma inlib ) Na p htha lene, 1,2,3,4-tetra hyd ro-1-methyl-

de INJU
55

k o
M e n
s h
S t a
Mentofurano
a id a d
l e n r s
E ive al r
Mentol
n
U us tand t r i e
I n d a n
S
56
de
 19/06/2022

Formación de iones ACILO

tr í a
o m e
u r s t r o
C pe as c I A
s
E ma ST s I C
de INJU
57

k o
M e n
s h
100

S t a 43

d
Iones acilo CH3CO+

n a id a
l e s
50

r
. O M+.

E ive al
-CH3 58

r
15 42
27

i e
29 39 44
16 31 57 59

n r
0

U us tand t
10 15 20 25 30 35 40 45 50 55 60 65 70
(mainlib) Acetone

43
100

I n d a n
S
50

-C2H5
. O M+.

de
72
29
27 57
15 39 42 44 71 73
0
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

58
 19/06/2022

2-pentanone
43
100

50

í a
86

tr
41
27 39 58 71
42 44
15 29 31 49 51 53 55 57 59 61 63 65 67 69 72 85 87
0
10 20 30 40 50 60 70 80 90 100

e
(mainlib) 2-Pentanone
2-heptanone

s o m
43
100

u r t r o
58 O

C pe as c
50

I A
57
41
100
27 29 85

C
39

s s
42 71
59
49 51 53 55

I
15 26 30 37 40 44 62 65 67 69 83 86
0

E ma ST
10 20 30 40 50 60 70 80 90 100 110
(mainlib) 2-Hexanone

de INJU
59

k o
M e n
s h
t a
Etil butyl cetona (heptan-3-ona, 3-heptanone)

S a d
m/z 57

a id
100 57

e n
29

l r s
50

E ive al
27 O

m/z 85
85
41

r
72
39 43 114

i
55

e
15 18 31 45 49 62 65 69 73 77 81 87 91 98

n
0

r
10 20 30 40 50 60 70 80 90 100 110 120 130

U us tand t
(mainlib) 3-Heptanone

Formación de iones acilo:

n d n
[M – C4H9]+: CH3CH2CO+ m/z 57 (100%)

I a
S
[M – C2H5]+: CH3(CH2)2CO+ m/z 85 (29%)

de
C2H5CO+  C2H5+ m/z 29 (75%)

60
 19/06/2022

Re-ordenamiento
tr í a
o m e
u r s t r o
McLafferty

C pe as c I A
s
E ma ST s I C
de INJU
61

k o
M e n
s h
S t a
Etil butyl cetona (heptan-3-ona, 3-heptanone)

a id a d
100 57

e n
29

l r s
50

E ive al
27 O
85
41

r
72
39 43 114

i
55

e
15 18 31 45 49 62 65 69 73 77 81 87 91 98

n
0

r
10 20 30 40 50 60 70 80 90 100 110 120 130

U us tand t
(mainlib) 3-Heptanone

Reordenamiento McLafferty:

I n d a n +

S
de
m/z 72 (23%)

62
 19/06/2022

Ciclohexanona
55
100

42 O

a
50 98

í
39 41
69

tr
27
56 83
26 29 38 40 43 51 53 80
71 74 99

e
15 57 61 63 65 67 84
0
10 20 30 40 50 60 70 80 90 100 110

o
(mainlib) Cyclohexanone

s m
O

u r t r o CH2 [ ]

C pe as c
H

C I A m/z 55(100%)

s
E ma ST s I
m/z 98 (53%)

de INJU
63

k o
M e n
s h
S t a
2-Metil-ciclohexanona

a id a d
100 68
41

n
55

l e s
69 O 112

r
39 42
50 27

E ive al
84

r
29 40 43 67
26 53 70 97

i
38 57

e
15 44 79 94
65 85

n
0

r
10 20 30 40 50 60 70 80 90 100 110 120

U us tand t
(mainlib) Cyclohexanone, 2-methyl-

O
CH3

I n d a n
S
64
de
 19/06/2022

2-Propil-ciclohexanona
100 98

50
O

í a
55
41 70

tr
83
27 39 111
81 140
15 45 50 63 91 107 125
0

e
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
(mainlib) Cyclohexanone, 2-propyl-

o
2-Butil-ciclohexanona

r s
100

r o m 98

u c t
O

C pe as I A
50

55

C
83

s s
41
70

I
29
27 39 111

E ma ST
81 93 154
31 37 45 50 63 105 109 113 125 135
0
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
(mainlib) Cyclohexanone, 2-butyl-

de INJU
65

k o
M e n
s h
S t a
a id a d
l e n r s
E ive a+ l r
n
U us tand t r i e
I n d a n
S
66
de
 19/06/2022

84
100

NH
85

Piperidina
50 56

29 44
42

27 41 55 70
39
15 18 26 31 34 37 45 49 51 58 65 67 69 71 78 80 82 86
0
10 20 30 40 50 60 70 80 90 100

84

a
100

tr í
50 NH

42
56
2-Metil-Piperidina

e
28 30 70 99
39
41 44 55 57 85
29 58
15 17 31 37 46 50 53 62 65 67 69 72 77 79 82 93 96
0

o
10 20 30 40 50 60 70 80 90 100 110
(mainlib) 2-Methylpiperidine

s m
100 84

r r o
2-Etil-piperidina

u t
50
NH

c
56

C pe as
28 41 70 85
55 98 112
15 44 50 58 67 77 82 91 94

A
0
10 20 30 40 50 60 70 80 90 100 110 120

I
84
100

s s I C
NH

2-Propil-piperidina

E ma ST
50

82
56
28 43
67 70 79 97 110 126
0
20 30 40 50 60 70 80 90 100 110 120 130 140
(mainlib) Piperidine, 2-propyl-, (S)-

de INJU
67

k o
M e n
s h
S t a
Patrón de fragmentación (Fragmentation pattern)

I,%

a id a d [M – R]+

l e n r s
E ive al
[M – R – CH2=CH2]+ M+.

i e r
-CH2=CH2 -R.

n
U us tand t r
RDA Ruptura β
m/z

d n
-R. -CH2=CH2

I n S a N
Ruptura β
R
RDA

de
H

M+. [M – R]+ [M – R – CH2=CH2]+

68
 19/06/2022

84
100

50

NH

28 41 56 N R
0
50 63 68 77 82 91 98 105 112 120 126 154
H

a
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170
(mainlib) Piperidine, 2-pentyl-

m/z (Intensidad, %)

tr í
e
R

o m
M+. [M-R]+ [M – R –CH2=CH2]+

u r s H
t r o 85 (50%) 84 (100%) 56 (45%)

C pe as cCH3

I A
99 (5%) 84 (100%) 56 (27%)

s s C
C2H3 113 (-) 84 (100%) 56 (15%)

E ma ST
C3H7
I 127 (-) 84 (100%) 56 (7%)

de INJU
69

k o
M e n
s h30
t a
Fragmentos típicos: m/z
S
100

a id a d 30

l e n r s
O

E ive al
50 OH
H2N

n r i e r
U us tand t
28
56
14 16 18 25 31 37 39 41 43 45 47 51 53 58 68 70 73 84 86 103
0
10 20 30 40 50 60 70 80 90 100 110

30
100
Pregabalina (Lyrica)

n d n
O

I S a
50 OH
H2N

de
41 56
103
28 84
39 69
32 58 98 111 141
36 50 53 61 64 73 91 105 116 122 126
0
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170
(mainlib) Pregabalin

70
 19/06/2022

Fragmentos típicos: m/z 44

100 44

a
NH2

í
50
O

e tr
18
42
15 28 30 45

o
17 33 37 39 54 56 58 71 74 88 90
0

m
10 20 30 40 50 60 70 80 90 100

s
(mainlib) 2-Propanamine, 1-methoxy-

r r o
44

u
100

C pe as c t OH

I A
50

s s I C
NH2

E ma ST
36
38 42 51 55 58 62 65 77
15 27 30 74 89 92 103 107 115 119 132
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
(mainlib) Benzenemethanol, α-(1-aminoethyl)-, [R-(R*,R*)]-

de INJU
71

k o
M e n
s h58
t a
Fragmentos típicos: m/z
S
100

a id a d 58

l e n r s
E ive al
50 N

r
O

n
U us tand t r i e
31
42 45 117
32 57 59 70 72
0
30 40 50 60 70 80 90 100 110 120 130

100 58

I n d a n
S
N
50

de
42
30 44
15 54 57 98
26 29 41 52 59
12 17 31 37 66 68 70 72 79 81 95
0
10 20 30 40 50 60 70 80 90 100 110

72
 19/06/2022

Fragmentos típicos: m/z 58

í a
100 58

e tr
NH
O

o m
50

s
O

u r t r o
c
77 135

C pe as
30 51 56
15 39 42 45 63 89 92 96 99 105 118 131 147 161 176 190
0

A
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200

I
(mainlib) N-Methyl-3,4-methylenedioxyamphetamine

s
E ma ST s I C
de INJU
73

k o
M e n
s h
Metilona
S t a
a id a d
e n s
58
100

l
E ive al r
r
O

i e
O

n r
50

U us tand t
HN
O

56 63

d
39 42 91 121 149
50 53 74 77 134 162 176
0

n
30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210

I n S a
74
de
 19/06/2022

psilocibina

tr í a
o m e psilocina

u r s t r o
C pe as c I A
s
E ma ST s I C
de INJU
75

k o
M e n
s h58
t a
Fragmentos típicos: m/z
S
a id a d
n
58
100

l e
E ive al r s
O

r
O
50

i e
HN

n r
O

U us tand t 56 63
39 42 91 121 149
50 53 74 77 134 162 176
0
30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220

d
(mainlib) 3,4-Methylenedioxymethcathinone

n n
Name: 3,4-Methylenedioxymethcathinone

I a
Formula: C11H13NO3
MW: 207 Exact Mass: 207.089543 NIST#: 379125 ID#: 28160 DB: mainlib

S
Contributor: Drug Lab
InChIKey: VKEQBMCRQDSRET-UHFFFAOYSA-N Non-stereo
Synonyms:

de
1.Methylone

Estimated non-polar retention index (n-alkane scale):

Value: 1706 iu
Confidence interval (Diverse functional groups): 89(50%) 382(95%) iu

76
 19/06/2022

DOXEPIN
C19H21NO
Antidepresivo

tr í a
o e
DOSULEPIN

m
r s o
C19H21NS

u t r
Antidepresivo

C pe as c I A
s
E ma ST s I C
de INJU
77

k o
MFragmentos típicos: m/zs72h e n
S t a
100

a id a d 72

n
30

l e r s
NH

E ive al
50 NH

n r i e r 44 58

U us tand t
28 86
15 18 39 70
4 50 64 67 82 129 144
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
(mainlib) N,N'-Diisopropylethylenediamine

72
100

d
30

I n a n
S
O
50 NH

de
43 70 102
28 59
15 56 73 117
18 32 39 50 53 60 68 84 87 100
0
10 20 30 40 50 60 70 80 90 100 110 120 130
(mainlib) N-(2-Methoxyethyl)isopropylamine

78
 19/06/2022

Fragmentos típicos: m/z 72

72
100

50 N

tr í a
o m e
s
86 294

o
57 223

r
29 42 91 165
97 105 115 129 136 149 157 178 193 208 217 227 234 241 250 259 266 279 309

r
0
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310 320

u c t
Name: Methadone

C pe as
Formula: C21H27NO

A
MW: 309 Exact Mass: 309.209265 CAS#: 76-99-3 NIST#: 195723 ID#: 40035 DB: mainlib

I
Other DBs: RTECS, HODOC, EINECS
Contributor: Chemical Concepts

s s C
Related CAS#: 297-88-1

E ma ST I
InChIKey: USSIQXCVUWKGNF-UHFFFAOYSA-N Non-stereo

de INJU
79

k o
M e n
s h
S t a LSD 25
323

d
100

a id a
O
221 LSD

n
N “Delysid”

e s
NH

l r
50
N 207

E ive al
181

r
72
196

i e
154 167

n
44

r
58 76 89 100
128 265 280
235 249

U us tand
295

t
0
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320
(ma inlib ) Lysergid e

d
Análisis confirmatorio:

n n
• HPLC con detector de fluorescencia

I a
(Excitación: = 320 nm; Emisión: = 400 nm) Microscope FT-IR
Spectroscopy

S
• GC-MS
Análisis de LSD in situ
[Columna BP-5, 25 m x 0.25 mm I.D. x 0.33 m;

de
100 C hasta 270 C (30 min) @ 24 C min-1;
t iny. 270 C; ]

80
 19/06/2022

Fragmentos típicos: m/z 86

100 44
86

í a
50 N

tr
58 128

43

e
56
70 72
112 143

o
55 57 59 84 87
45 98 126

m
0
40 50 60 70 80 90 100 110 120 130 140 150

r s r o
100 57 86

u t
43

C pe as c
O

I A
N
50

s s I C
128

E ma ST
41 142

29 185
70 100 170
0
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200
(mainlib) Propanamide, 2,2-dimethyl-N,N-bis(1-methylethyl)-

de INJU
81

k o
M e n
s h31
t a
Fragmentos típicos: m/z
S
a id a d 31

n
100

l e r s
41
N

E ive al
50 HO

n r i e r 26 29 53

U us tand t
15 27 40 42
12 17 19 25 30 32 36 44 54 67 70 72
0
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
(replib) Propanenitrile, 3-hydroxy-

100 31

I n d a n 41
HO Br

S
50
58

de
28
120

39
45 89 93
15 18 53 79 82 99 107 112 137
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150

82
 19/06/2022

Fragmentos típicos: m/z 45

100 45

HO

í a
50

tr
Cl

27 29

e
43
15 55
26

o
39
12 16 19 24 31 33 44 46 48 51 58 63 65 67 70 73 76 79 81 83 86 89 93 95 105 108

m
0
10 20 30 40 50 60 70 80 90 100 110 120

s
(mainlib) 2-Butanol, 3-chloro-, (R*,R*)-

r r o
45

u t
100

C pe as
50

c I A
O
OH

s s I C
O

E ma ST
29
43 75
28 31 41 46 55 58 71 89 103
0
20 30 40 50 60 70 80 90 100 110 120 130
(mainlib) Propanoic acid, 2-hydroxy-, ethyl ester

de INJU
83

k o
M e n
s h59
t a
Fragmentos típicos: m/z
S
a id a d 59

n
100

l e r s
O

E ive al
50
OH

r
31
45
58

n r i e
41 43 47 75

U us tand t
29
15 27 57 60
17 30 33 37 39 42 44 46 48 50 53 55 71 73 76 87 89 103
0
10 20 30 40 50 60 70 80 90 100 110
(mainlib) 2-Butanol, 1-methoxy-

59
100

I n d a n
S
50 HO

de
41
69 73 98
31 55
27 39 51 65 77 80 83 87 91 95 113 123 156
0
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170
(mainlib) 2-Hydroxy-2,4-dimethyl-hept-6-en-3-one

84
 19/06/2022

100 59 Terpineol
OH

93
50
43

í a
81 121
41 67
136

tr
39 68 79
31 55
27 77
95
51 65 71 107
15 139
45 57 60

e
18 89 115 131 154
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
(mainlib) Terpineol

r s o o m
Elemol
59
100

u
C pe as c t r 93

I A
50
41 81
161
107

s s C
121

I
55 67 79 95 135 OH

E ma ST
53 189
29 39 71 149
204
57 65
51 175
89 129
0
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230

de INJU
85

k o
M e n
s h
S t a
d
Mentofurano

n a id a
l e
E ive al r s
n r i e r
U us tand t Mentol

I n d a n
S
86
de
 19/06/2022

Esquema de fragmentación no es lo mismo

que el MECANISMO DE FRAGMENTACIÓN
1. Alta resolución: composición elemental
2. Iones metaestables

tr í a
e
3. Sistemas tándem (espectros de iones precursores,

o
iones-producto, SRM, etc.)

r s o m
4. Ionización suave (ESI, CI, PI)

r
u t
5. Potenciales de ionización, potenciales de aparición de

C pe as c iones

I A
6. Marcación isotópica, marcación química

s
E ma ST s I C
7. Cálculos mecano-cuánticos: energías de enlace, estados
de transición, QET, etc.

de INJU
87

k o
M e n
s h
S t a
Aeróbicos a id a d
l e n
intelectuales.... r s
E ive al r
n
U us tand t r i e
I n d a n
S 18 +
88
de
 19/06/2022

HN

tr í a
e
H3C

o
4

m
5 3 2e, 4e, 5e trans (4e,5e)

s o
6 2

r
1

r
N CH3

u c t
CH3

C pe as I A
s
E ma ST s I C 2e, 4e, 5a cis (4e,5a)

de INJU
89

k o
M e n
s h
S t a .

d
[218 - 203] = 15 = CH3

a id a
70 .

n
I,% [218 - 126] = 92 = C6H5NH

l e
E ive al r s 110 [218 - 125] = 93 = C6H5NH2

r
126 218

n
U us tand r i e
58

t 125
HN

d
H3C

I n a n
84

S
98
119
146
203 N CH3

de
133
CH3
m/z

90
 19/06/2022

HN HN
H3C H3C
CH3.
+.

a
+

í
N CH3
Ruptura  N
RDA

tr
CH3 CH3

o
M+., m/z 218

m e [M - CH3]+, m/z 203

u r s t r o CH2

C pe as c
H2 C +

A
N + HN

I
RDA H3C

s s C
CH3

E ma ST I m/z 70 (100%)

de INJU
91

k o
M e n
s h
S t a
d
.

a
[218 - 203] = 15 = CH3

a id
70
I,%

n
.

e
[218 - 126] = 92 = C6H5NH

l s
110

r
126 [218 - 125] = 93 = C6H5NH2

E ive al
218

i e r
58

n
U us tand t r
125

H3 C
HN

d n
84

I n a
119
98 203

S
146
133 N CH3

de
CH3
m/z

92
 19/06/2022

+
H3C

HN N CH3
H3C CH3

a
+.

í
[M - NHC6H5]+, m/z 126

tr
N CH3
H3C

e
CH3

o
+.

m
M+., m/z 218

s
N CH3

r r o
CH3

u t
CH3.

c
[M - NH2 C6H5]+, m/z 125

C pe as
H3C

I A 125
126

s s C
+

E ma ST I
N
CH3
[M - NH2 C6H5 - CH3]+, m/z 110

de INJU
93

k o
M e n
s h
S t a
.
a
H ?
a d
n i d
[M - NH CH] +

e s
C6H5NHH

l
HN 2 6 5

r
E ive am/zl 125 r
H
CH3 H?
?

i
H H

n e
+.

r
H

U ust tand
H N H CH3
? CH3 ? 218

d
125

I n
M+. m/z 218
a n
S
94
de
 19/06/2022

O O

CH3 CH3 D

CD3OD D D

í a
CH3 CH3

tr
N N

CH3 CH3

o m e
r s o
O

u
CH3

C pe as c t r D
+ NH2 C6H5 HN

A
D D

I
CH3 D

D D

s s C
CH3

I
N

E ma ST
CH3 CH3
N

CH3

de INJU
95

k o
M e n
s h
S t a
2H

a id a d 2H

n
70 72
I,% 112

e
3H

l r s
129

E ive al
110
126 3H

r
127 218 221
HN

i
2H

e
58

n r
58

U us tand t
H3 C D
125
D D

I n d a
84 86

n 3H
N CH3

S
119 134
98
99
121
146
147
203 206 CH3

de
133

m/z

96
 19/06/2022

Ionisation AB AB+.
E M+.

tr í a
e
M

r s o o m
u
C pe as c t r 10-15 - 10-17 seg

C I A
s
E ma ST s I
r

de INJU
97

k o
M e n
s h
S t a
dF +

n a id a
l e
E ive al r s
Ion molecular Fragmento
M
r
+

U n t r i d e
s n
Molecula
M 0PI (EI)
d u PA
n t a
n
I ES ca.a = (PA - PI)

de
a

98
 19/06/2022

NHC6H5
CH3
H 125
H
H
126 WM+ = 7.7%
IP = 7.31 eV

a
CH3 .

í
N I[M - CH3] /IM
+ + = 0.20

tr
CH3 « « I[M - NHPh]+/IM +. = 0.31
trans- I[M - NH2 Ph]+/IM +. = 0.89

o m e
s
NHC6H5

r r o
CH3

u t
H 126 WM+ = 9.0%

c
IP = 7.17 eV

Ccis- pe as
H
I[M - CH3]+/IM +. = 0.20

A
H

I
I[M - NHPh]+/IM +. = 0.43
125

s s C
I[M - NH2 Ph]+/IM +. = 0.26
CH3

I
N

E ma ST
CH3 « «

de INJU
99

k o
M e n
s h
S t a
a id a d
n
Eo  1.44 eV

l e s
H

r
NH CH3

E ive al
H
CH3 CH3
N

r
CH3
H

.
n
U us tand
M+ , IP = 7.31 eV

t r i e +.
N

CH3
CH3

d
[M - NH2 Ph]+, AP trans = 8.75 eV

n n
AP cis = 9.48 eV

I a
H
NH CH3

Eo  2.31 eV

S
H
H CH3
N
CH3

de
.
M+ , IP = 7.17 eV

100
 19/06/2022

NHC6H5
CH3 125
H WM+ = 7.7%
IP = 7.31eV
H H 126 I[M - CH3]+/IM +. = 0.20
I[M - NHPh]+/IM +. = 0.31

a
I[M - NH2Ph]+/IM +.

í
= 0.89

tr
CH3
N « « Eo125  1.44 eV

e
CH3
trans-

r s o
NHC6H5

o m
r
WM+ = 9.0%

u t
CH3
H 126 IP = 7.17eV

c
I[M - CH3]+/IM +. = 0.20

C pe as
H

A
H
I[M - NHPh]+/IM +. = 0.43

I
125
I[M - NH2Ph]+/IM +. = 0.26

s s I C
CH3
N Eo125  2.31 eV

E ma ST
CH3 cis- « «

de INJU
101

k o
M e n
s h
S t a
a id a d
n
H

l e s
NH CH3

E ive al r H
CH3

r
CH3

i e
N

n
U us tand t r
H

I n d
1,4 - cis -Eliminación
a n
S
de
de hidrógeno
102