Kütle Spektrumları

1
KÜTLE SPEKTRUMLARI
ORGANİK FONKSİYONEL GRUPLARIN
FRAGMANTASYON PATERNLERİ
Enstrümantal Analiz
Organik moleküller, molekülde bulunan fonksiyonel gruplara bağlı olarak çeşitli
parçalanma (fragman) şekilleri gösterirler; fragmanlar pozitif yüklü ise, kütle spektrometresiyle saptanabilir. Spektruma bulunan veya bulunmayan çeşitli kütle pikleri, bileşiğin yapısının aydınlatılmasında kullanılabilen önemli verilerdir. Bu çalışmada temel organik fonksiyonel grupların verebilecekleri fragmanları incelenerek
yapısal formüllerle kütle spektrumlarının bağlantısı gösterilmiştir.
A. ALKANLAR
B. DOYMAMIŞ HİDROKARBONLAR
1. Düz Zincirli Alkanlar
1. Düz Zincirli alkenler
2. Dallanmış Alkanlar
2. Siklik Alkenler
3. Siklik Alkanlar
3. Alkinler
C. AROMATİK BİLEŞİKLER
D. KARBONİL BİLEŞİKLERİ
E. DİĞER ÖNEMLİ GRUPLAR
1. Aldehitler
1. Alkoller
2. Ketonlar
2. Tiyoller
3. Esterler
3. Eterler
4. Karboksilik Asitler
4. Sülfürler
5. Amidler
5. Aminler
6. Anhidritler
6. Nitriller
7. Asit Halojenler
7. Nitro Bileşikleri
8. Halojenli Bileşikler
2
A. ALKANLAR
1. DÜZ ZİNCİRLİ ALKANLAR
Metan, CH4 (16.04)
100
.
16 [CH4] +
M
moleküler iyon
(ana pik)
15 [CH3]+
CH4
Relatif bolluk, %
80
60
40
M+1
17 13CH4
14 [CH2]+
20
12 [C]+
13 [CH]+
0
11
12
13
14
15
16
17
18
m/z
eH
H
H
H
CH4  (CH4)+  CH3+  CH2+  CH+  C+
m/z = 16
moleküler iyon
15
14
13
12
3
Etan, C2H6 (30.07)
100
28
C2H4
H3C CH3
Relatif bolluk, %
80
M+
moleküler
iyon
60
40
30
29
20
0
0
5
10
15
20
25
30
m/z
H H
H C C+• H
m/z = 30
H H
H H
H H
H C C H + eH H
H C C+ +
H
H C+
m/z = 15
H
H•
m/z = 29
H H
H
+ • C H
H
MS ile saptanamaz
35
4
Propan, C3H8 (44.1)
100
H3C
Relatif bolluk, %
80
H2
C
29
temel pik
CH3
28
60
(M+ moleküler iyon)
44
ana pik
40
20
15
0
10
20
30
m/z
40
50
moleküler iyon
H H

H C C
H H
H
+
+C
H H
H
H C C
H
m/z = 15
H
+
H C C
H H
-H
+
H
C H
H H H
44
- CH4
H H
+
H C C
H H
29
H
H H
C H
C C+
H
H H
H
+
C
H
H
5
Pentan, C5H12 (72.15)
100
H3C
Relatif bolluk, %
80
H2
C
C
H2
43
H2
C
CH3
CH3CH2CH2+
42
60
41
40
CH3CH2CH2CH2CH2+
CH3CH2CH2CH2+
CH3CH2+
57
29
CH3+
15
20
72
39
0
10
20
30
40
50
60
70
m/z
H3 C
H2
C
H2
C

+
C
CH3
H2
m/z = 72
H3 C
H2
C
H2
C
C
CH3
H2
m/z = 72
H3C
H2
C
CH2+
m/z = 43
- CH3
M - 15

H2
C
C
H2
m/z = 57
H3 C
+
- CH3CH2
M - 29
H3C
CH2+
H2
C
- C2 H 4
m/z = 29
CH2+
- C2H4
M-1
CH
H3C
CH2+
m/z = 42
CH3+
(M - 29) - 28
m/z = 43
- H
H3 C
(M - 15) - 28
CH2+
m/z = 15
- H
M-2
+
H2C
H
C
CH2
m/z = 41
6
n-Heksan, C6H14 (86.18)
100
H3C
80
Relatif bolluk, %
H2
C
C
H2
H2
C
60
C
H2
CH3
M+ - 29 [M+ - C2H5]
57
+
M - 43
43
M+ - 57
29
M++1
40
M+
86
M+ - 15
71
20
0
10
H3C
20
H2
C
C
H2
H2
C
C
H2
30
40
CH3
- e-
50
m/z
H3C
60
H2
C
C
H2
70
H2
C
80
+
C
H2
CH3
moleküler iyon m/z = 86
H3C
H2
C
H2
C
C
CH2+
H2
m/z = 71
H3C
H2
C
C
H2
57
CH2+
H3C
H2
C
43
CH2+
H3C
CH2+
29
7
2. DALLANMIŞ ALKANLAR
İzobütan, C4H10 (58.12)
100
80
Relatif bolluk, %
43
CH3
H3C CH
CH3
60
40
20
57 58
15
0
10
20
30
40
50
m/z
CH3
H3C CH
CH3
+
- H
M-1
m/z = 58
CH3
H3C CH
CH3
m/z = 58
+
CH3
H3C CH
CH3
+
m/z = 57
- CH3
M - 15
H3C
H2
C
+
CH3
- C3H7
M - 43
CH3+
m/z = 43
m/z = 15
60
8
2,2-Dimetilpropan, C5H12 (72.15)
100
M+ - 15
57
CH3
H3C C CH3
Relatif bolluk, %
80
CH3
60
M+ - 43
29
40
20
M+ - 31
41
M+ 72
M+ - 57
15
0
0
20
CH3
H3C C CH3
CH3
m/z = 72
40
m/z
+
.
60
CH3
H3C C+
+
.CH3
CH3
57
(ters-bütil katyon)
80
9
2-Metilpentan, C6H14 (86.18)
100
CH3
H3C
Relatif bolluk, %
80
CH
C
H2
H2
C
43
M+ - 43
CH3
60
M+ - 15
71
40
M+ - 29
57
20
M+
86
0
10
20
30
40
50
m/z
H3C
H3C
H2
C
CH3
CH
C
H2
CH3
+
H2
C
60
HC+
CH2 +
kolay
kolay
80
CH3
CH3
2-metilpentan
m/z = 86
70
H3C
+
C
H2
CH3
H2
C
C
H+
m/z = 43
CH3
m/z = 71
CH3
çok zor
H3C
CH2
+ H +C CH CH
2
3
m/z = 57
10
3. SİKLİK ALKANLAR
Siklopropan, C3H6 (42.08)
100
80
Relatif bolluk, %
42
H2
C
H2C CH2
41
39
60
40
28
20
0
0
10
20
30
40
50
m/z
H
H C
H C
+
C
H
H
H
H C+

H C
H
C
H
- CH2
H
-H

C C+
H
H
H
m/z = 28
H
moleküler iyon
m/z = 42
H
H
H C
+
H C
C H
H
m/z = 41
-H2
H C C C+
H C+
H C
H
H
C H
m/z = 39
11
Sikloheksan, C6H12 (84.16)
100
H2C
Relatif bolluk, %
80
H2C
60
H2
C
C
H2
56
CH2
M+
84
CH2
40
C3H7+
43
C2H5+
29
20
temel pik
M-28
M+ - CH3.
69
CH3+
15
0
10
20
30
40
50
60
70
80
90
m/z
H2C
H2C
H2
C
CH2
CH2
C
H2
m/z = 84
+
- C2H4
H2C
M - 28
H2C
CH2
CH2
m/z = 56
+
100
12
Metilsikloheksan, C7H14 (98.19)
100
80
Relatif bolluk, %
temel pik
83
H2C CH2
CH CH3
H2C
H2C CH2
M+ - CH3
(98 - 15)
55
60
M+ = 98
C7H14
40
20
0
10
20
30
40
50
60
70
m/z
80
90
100
110
13
B. DOYMAMIŞ HİDROKARBONLAR
1. DÜZ ZİNCİRLİ ALKENLER
1-Büten, C4H8 (56.11)
100
H3C
Relatif bolluk, %
80
H2
C
41
CH2
C
H
60
56
40
27
20
0
0
H3C
H2
C
10
C
H
CH2
1-büten
20
- eH3C
30
m/z
H2
C
- CH3
M - 15
C
H
40
50
H2C
H
C
60
CH2 m/z = 41
CH2+
m/z = 56
- C2H5
m - 29
H
C+
C
H
H
m/z = 27
14
İzopren, C5H8 (68.12)
100
CH2
H2C
Relatif bolluk, %
80
C
H
C
CH3
60
40
20
0
25
50
75
m/z
100
125
15
2-Heksen, C6H12 (84.16)
100
H3C
Relatif bolluk, %
80
H
C
C
H
H2
C
C
H2
55
CH3
60
42
84
40
69
27
20
0
10
20
30
40
H3C
H3C
H
C
C
H
CH2
50
m/z
H
C
C
H
+
H3C
H2
C
H
C+
metallilik katyon m/z = 55
60
70
80
+
C
H2
C
H
CH3
CH2
+ H C CH3
2
16
H3C
H
C
C
H
H2
C
+
C
H2
CH3
H3C
H
C
CH2
H C+
C
H
H
m/z = 27
CH3
H CH
+ C
H2
m/z = 42
CH3
H CH
+ C
+
H2
m/z = 42
H
+
C H
H
2-Hepten, C7H14 (98.19)
100
H3C
Relatif bolluk, %
80
H2
C
C
H2
H2
C
C
H
H
C
CH3
60
40
20
0
10
20
30
40
50
60
70
m/z
80
90
100
110
17
3-Hepten, C7H14 (98.19)
100
H3C
Relatif bolluk, %
80
H2
C
C
H2
H
C
C
H
H2
C
CH3
60
40
20
0
10
20
30
40
50
60
70
m/z
80
90
100
110
18
2. SİKLİK ALKENLER
Siklopenten, C5H8 (68.12)
100
H2C CH
H2C
Relatif bolluk, %
80
C
H2
CH
60
40
20
0
10
20
30
40
50
60
70
m/z
80
90
100
110 120
19
Sikloheksen, C6H10 (82.14)
100
HC
Relatif bolluk, %
80
HC
60
H2
C
C
H2
CH2
54
CH2
82
40
20
0
10
20
30
40
50
60
70
80
m/z

- e-
+

sikloheksen
m/z = 82
- C2H4
+
M - 28
m/z = 54
90
20
3. ALKİNLER
1-Bütin, C4H6 (54.09)
100
80
Relatif bolluk, %
54
H3C
H2C C CH
39
60
53
40
20
0
0
H3C
10
C
H2
C
C
1-bütin
H
20
-e-
30
m/z
40
- H
M-1
H3C
C
H2
C
C+
m/z = 54
50
H3C
H
C
H2
60
C
C+
m/z = 53
-CH3
M - 15
H
H
C C C+
m/z = 39
H
21
1-Pentin, C5H8 (68.12)
100
H3C CH2
H2C C CH
[HC CH2]+
80
Relatif bolluk, %
67
39
60
[CH3CH2]+
40
27
29
68
20
M+ moleküler
iyon
0
10
20
30
40
50
m/z
60
70
80
22
Fenilasetilen, C8H6 (102.13)
100
C CH
Relatif bolluk, %
80
60
40
20
0
20
40
60
80
100
120
m/z
140
160
180
200
23
1-Fenil-1-Pentin, C11H12 (144.21)
100
C C CH2
H2C CH3
Relatif bolluk, %
80
60
40
20
0
20
40
60
80
100
120
140
m/z
160
180
200
220
24
C. AROMATİK BİLEŞİKLER
Benzen, C6H6 (78.11)
100
78
M+.
Relatif bolluk, %
80
60
40
20
51
39
M+1
63
0
10
20
30
40
50
m/z
60
70
80
25
1-Propilbenzen, C9H12 (120.19)
100
H2
C
C
H2
60
40
120
20
0
10
20
30
40
50
60
70
m/z
80
+
- e-

propil benzen
90
100
- C3H7
m/z = 120
+
m/z = 120
- C2H5
M - 29
110
120
+
M - 43
m/z = 77
+

Relatif bolluk, %
80
91
CH3
CH+
+
m/z = 91
tropilyum iyon
26


M -28
H
+
+
+
- C2 H4
m/z = 92
McLafferty düzenlenmesi
- CH3
+
+
M -15
m/z = 105
sübstitüe tropilyum iyon
Toluen, C7H8 (92.14)
100
91
CH3
92
Relatif bolluk, %
80
M+
60
40
20
65
0
10
20
30
40
50
m/z
60
70
80
90
27
CH3
- e-
CH3
+
- H
m/z = 92
+
m/z = 91

+
+
m/z = 91
- C2 H2
tropilyum iyon
+
m/z = 65
28
D. KARBONİL BİLEŞİKLERİ
1. ALDEHİTLER
Heksanal, C6H12O (100.16)
100
44
H3C
Relatif bolluk, %
80
H2
C
C
H2
H2
C
O
C
H2
C
H
60
40
57
29
99 100
20
0
10
20
30
40
50
60
m/z
70
80
90
100
29
H3C
H2
C
C
H2
H2
C


O +
C
C
H2
- H
H
H2
C
H3C
M-1
C
H2
m/z = 100
C
H
- C5H11
C
H2
O  +
-kırılma
O  +
C
-kırılma
m/z = 29


O +
H2
H2C=CHO
C
C
CH2+
-kırılma
H
C
C
H3C
M - 43
H2
H2
m/z = 57
C
H2
C
H
- C5H11
M -56
H2C




H2
H
H3C C CH
O +
H2C
H
M - 71
+
H2
C
C
H2
O 

C
H2
C
H2
H2
C
+
H3C
H2
C
C
m/z = 99

H3C
H2
C
H2
C
OH
C
H
m/z = 44
McLafferty
düzenleme
30
Benzaldehit, C7H6O (106.12)
100
O
CH
Relatif bolluk, %
80
60
40
20
0
10
20
30
40
50
60
70
m/z
80
90
100
110
120
31
2. KETONLAR
2-Bütanon, C4H8O (72.11)
100
H3C
80
C
H2
C
[CH3CO]+
CH3
60
[CH3COCH2CH3]+.
40
[CH3CH2]+
20
72
[COCH2CH3]+
29
57
0
20
30
40
50
60
70
m/z
O
H3C
C
H2
C
- eCH3
O
H3C
C
H2
C
+
10
CH3
m/z = 72

Relatif bolluk, %
43
O
32
C
H2
C
+
H3C

O
- e-
CH3
O
H3C
C
H2
C+
CH3
+
m/z = 57
C
CH3
O
C
H2
C
+
H3C
CH3
O
C+
CH3
m/z = 43

C
H2
+
H3C
- e-

O
- e-
H3C
+
CH2
O
H3C
CH2
m/z = 29
+
C
CH3
33
1-Pentanon, C5H10O (86.13)
100
H3C
C
H2
C
CH3
60
40
M+
86
+
CH3CH2CH2CO:
20
71
0
20
30
40
50
60
70
80
90
m/z


C
H2
C


CH3
O +
C
O+
-C3H7
CH3
M - 43
-kırılma
C
H3C
m/z = 43


H3C
H2
C
C
H2
O


H3C
H2
C
+
10

Relatif bolluk, %
80
+
43 H3CCO:
O
H2
C
-CH3
M - 15
H3C
H2
C
O+
C
C
H2
m/z = 71
-kırılma
100
34
+
C

CH2=C(O)CH3
CH3
H3C
M - 57
CH2+
-kırılma
m/z = 29
C
CH3
H2C=CH2
M - 28
+
C
H2
O +
H2C

H




H2C
C
H2
O


H2C

H3C
H2
C
OH
C
CH3
m/z = 58
McLafferty
düzenlenmesi
35
2-Heptanon, C7H14O (114.19)
100
43
58
O
CH3
H3C C H2C CH2
H2C CH2
Relatif bolluk, %
80
60
40
71
20
99
0
10
20
30
40
50
60
70
80
90
100
110
m/z
CH3
H3C C
H2C CH2
H2C CH2


O
O+
CH3
C
H2C CH2
H2C CH2
-CH3
M - 15
m/z = 114
CH3
H3C C
H2C CH2
H2C CH2
m/z = 114


O
m/z = 99
O+
H3C C
m/z= 43
+
H3C
H2
C
C
H2
H2
C
m/z = 71
CH2+
36
Asetofenon, C8H8O (120.15)
100
105
O
C
Relatif bolluk, %
80
77
CH3
60
40
120
51
20
43
39
0
10
20
30


C
40
50
60
C
M - 15
m/z = 120


80


O + - CH 
3
CH3
70
m/z
O+
90
100
•
C
CH3
+
(M - 15) - 28
O
+ C+
ve
CH3
m/z=43
120
- CO
m/z = 105
O +
110
m/z = 77
O
+
+
•C
CH3
m/z=77
37
ESTERLER
Metil Ester
CH3O· radikal
M - 31
Etil Ester
CH3CH2O· radikal
M - 45
Propil (ve izopropil) Ester
CH3CH2CH2O· radikal
M - 59
Fenil Ester
C6H5O· (PhO·) radikal
M - 93
Benzil Ester
C6H5CH2O· (BzO·) radikal
M - 105
Metil bütirat, C5H10O2 (102.13)
100
H3C
Relatif bolluk, %
80
H2
C
O
C
H2
C
43
O
CH3
74
60
71
15
40
59
20
87
29
102
0
10
20
30
40
50
60
m/z
70
80
90
100
38
H3C
+
H2
C
H3C
M - 31
-kırılma

C
O
H2
m/z = 102
CH3
C
H2
O




C
- CH3O
C
O
H2
C
O+
(M - 31) - 28 H3C
C
H2
m/z = 71
- C3H7
CH3
- CO
C
-kırılma
H2
C
CH2+
m/z = 43
O+


O +


H3C
H2
C
C
O
M - 43
CH3
-kırılma
m/z = 59






H3C
H2
C
C
H2
O +
C
O
C
H2C
CH3
O
O
CH3
H3C
M - 73
CH2+
-kırılma
m/z = 29




H2
C
H3C
O +
C
CH3
C
O
H2
H3C
H2
C


C
H2
O
C
O
CH3+
M - 87
m/z = 15




C
H2
O +
C
O
H2C=CH2
CH3
M - 28
H3C
H2C
-kırılma


H2C
H
M - 15


H2C
O +
C
C
O
H2
m/z = 87
H2
C
-CH3
+
H3C
O +
C
CH3
C
O
H2

H2
C
-kırılma
OH
C
O
m/z = 74
CH3
McLafferty
düzenlenmesi
39
Metil propiyonat, C4H8O2 (88.11)
100
O
C O CH3
H3C CH2
Relatif bolluk, %
80
60
moleküler
88
iyon
40
20
0
10
20
30
40
50
m/z
60
70
80
90
40
Dietil 2-metilmalonat, C8H14O4 (174.19)
100
O
CH3
C CH
H2C O
C O
H3C
O H2C CH3
Relatif bolluk, %
80
60
40
20
M+
174
0
25
50
75
100
m/z
125
150
175
41
Benzil asetat, C9H10O2 (150.17)
100
108
CH2 CH3
O C
O
60
150
40
20
0
50
75
100
120
150
m/z
CH3
CH2
O C
O
m/z = 150
- H2C=C=O
M - 42
CH2
OH
+

+
25
m/z = 108

Relatif bolluk, %
80
42
Fenil asetat, C8H8O2 (136.15)
100
94
O
O
C
CH3
60
40
20
136
0
O
50
75
m/z
O
- H2C=C=O
C

+
m/z = 136
CH3
M - 42
100
125
OH
+
25
m/z = 94

Relatif bolluk, %
80
43
Metil benzoat, C8H8O2 (136.15)
100
C
80
Relatif bolluk, %
105
O
O
CH3
77
60
136
40
20
0
25


50
O
100


O +
C
75
m/z
CH3 - CH O
3
O+
C
- CO
+
M - 28
M - 31
m/z = 136
125
m/z = 105
m/z = 77
44
Metil-2-aminobenzoat, C8H9NO2 (151.16)
100
C
80
Relatif bolluk, %
119
O
O
CH3
NH2
151
60
40
20
0
20
40
60
80
100
120 140
m/z
C
O
NH2
m/z = 151
180
200


O
160
CH3
- CH3OH
M - 32
O
C +
NH
m/z = 119
220
240
45
4. KARBOKSİLİK ASİTLER
Bütirik Asit, C4H8O2 (88.11)
100
H3C
Relatif bolluk, %
80
H2
C
60
O
C
H2
C
O
H
60
40
43
20
71
45
29
87 88
0
10
20
30
40
50
m/z
60
70
80
90
46


O

- HO
H
H3C
M - 17
-kırılma
m/z = 88
H2
C


O +
C
H2
O+
C
m/z = 71
- CO
(M - 17) - 28
-kırılma



+
O
- C3 H 7 
H
M - 43


O
H
O
H3C
H2
C
CH2+
m/z = 43
O+
C
kırılma


m/z = 45


O +
O
H3C
M - 59
CH2+
kırılma
m/z = 29


O +
O
H2
C




O
H
O
H
- H
H
H3C
M-1
H2
C
O +
C
O
C
H2
kırılma
O
CH2=CH2
H
M - 28


+
O +

H


m/z = 87
OH
C
H McLafferty düzenlenmesi
O
H2C
m/z = 60
47
Heksanoik asit, C6H12O2 (116.16)
100
H3C
Relatif bolluk, %
80
H2
C
C
H2
H2
C
O
C
H2
C
OH
60
40
20
0
25
50
75
100
125
150
175
m/z
H3C
C
H2
C
H2
C
+
H2
C

H2
C
H2 H
C
H
H3C
C
O
O
OH
H2C
C
H2
C
m/z = 116
H3C
OH
H2
C
C
H
CH2
O+
+
H2C
H
C
OH
m/z =60
48
O
C
H2
C
H3C
H3C
OH
H2
C
C
H
CH2
H2
C
H O
O
CH2
+
+
H2C
C
H2
C
C+
C
OH
H
m/z = 73
H2C
OH
+
H2C
+
C
H2
H2
C

H3C
H2
C
H
CH
H
+
C
H
CH2
m/z = 41
49
2-Metilbenzoik asit (o-Toluik asit), C8H8O2 (136.15)
O
100
C
118
OH
CH3
136
60
40
20
0
25
50
75
m/z
100
O
C
m/z = 136
C
H2
O
H
H
- H2O
M - 18
C
125


Relatif bolluk, %
80
O
+
m/z = 118
CH2
50
5. AMİDLER
Bütiramid, C4H9ON (87.12)
100
H3C
Relatif bolluk, %
80
H2
C
59
O
C
H2
C
NH2
44
60
43
40
29
86 87
20
71
0
10
20
30
40
50
m/z
60
70
80
90
51
C
NH2
H3C
M - 16
-kırılma
(M - 16) -28
-kırılma
m/z = 71
- C3H7

C
+
C
H2
- CO
H3C
H2
C
NH2
C
O+
-kırılma
H2N
m/z = 44
M - 43






H3C
H2
C
C
H2
O +
C
O
C
H2C
NH2
CH2+
H3C
m/z = 29
NH2
M - 58
-kırılma




C
H2
O +
C
NH2
-H
M-1
CH2=CH2
M - 28
H3C
+
H
NH2

H2C
H2
C
O +
C
C
NH
H2
m/z = 86
-kırılma


H2C
C
H2
C


H2C
O +

H3C
H2
C
OH
C
NH2
m/z = 59
CH2+
m/z = 43

O
C
H2
O+
C

H2
C




m/z = 87
H3C
H2
C
- H2N

C
H2
O +

H3C
H2
C
McLafferty
dönüşümü
52
N,N-Dimetilpropanamid, C5H11ON (101.15)
100
H3C
N CH3
O C
H2C CH3
Relatif bolluk, %
80
60
40
20
0
10
20
30
40
50
60
70
m/z
80
90
100
110
53
6. ANHİDRİTLER
Bütirik anhidrit, C8H14O3 (158.19)
100
O
80
60
M+ = 158
görülmez
43
40
20
0
20
30
40
50
m/z
60
70
80


O
O +

O C
H2
C O
H2C C CH3
H2C CH2
C CH2
H3C
O
H2C CH3
M - 87
m/z = 158 (yok)
-kırılma
O +
C O
H2C CH2
C CH2
H3C
O
H2C CH3


10
+


Relatif bolluk, %
71
C O
H2C CH2 C CH2
O H2C CH3
H3C
-CO
(M - 87) - 28
-kırılma
O
C
H2C CH2
H3C
m/z = 71
H3C
H2
C
CH2+
m/z = 43
90
54
Benzoik anhidrit, C14H10O3 (226.23)
100
O
C
O
105
C
60
77
40
20
226
198
0
20
40
60
80
100
120
m/z
140
160
180
200
220
O + O
C
O
O
C
O+
C
C
m/z = 226


O


Relatif bolluk, %
80
O
-CO
M - 121
M - 121
-kırılma
m/z = 105 -kırılma
+
m/z = 77


55


C
C
O +
O +
C
- CO


O


O
O
m/z = 198
M - 28
O
C
O+
(M - 28) - 93
m/z = 105
p-Toluik anhidrit, C16H14O3 (254.28)
100
O
119
C
Relatif bolluk, %
80
m/z = 118
görülmez
60
O
O
C
H3C
CH3
91
40
20
226
254
0
0
50
100
150
m/z
200
250
300
56
o-Toluik anhidrit, C16H14O3 (254.280)
100
O
C
O
119
CH3
C
CH3
60
40
91 118
20
254
0
0
50
100
150
m/z
O
O +
O
C
C
O
CH3
O
200
250
300
CH3
C


O+
C
M - 135
CH3
CH3
-kırılma
m/z = 254
m/z = 119
- CO
+
(M - 135) - 28
-kırılma
O
O +
O
C
C
O
CH3
CH3
HO
m/z = 91
CH3
CH3
C






Relatif bolluk, %
80
O
O +
C
m/z = 118
M - 136
CH3
57
7. ASİT HALOJENLER
Bütiril Klorür, C4H7OCl (106.55)
100
H3C
Relatif bolluk, %
80
H2
C
43
O
C
H2
C
71
Cl
60
40
78
63 65 70
20
29
106 108
80
0
H2
C


H3C
20
O +
C
30
40
50
- Cl

Cl
C
M - 35
H2
m/z = 106, 108
-kırılma
H3C
60
m/z
H2
C
70


10
C
H2
m/z = 71
80
90
100
O+
C
- CO
(M - 35) - 28
-kırılma
H3C
H2
C
110
CH2+
m/z = 43
58
- C3H7
Cl
H3C
H2
C
O +
C
C
H2


H2C
C
H2
C
H2
C
Cl
O +
C
Cl
H2C
Cl
O
C
CH2+
H3C
-kırılma
m/z = 29
Cl
M -77
CH2=CH2
M - 28


H


H2C


H3C
O +
C
-kırılma
Cl
m/z = 63.65
M -43


H2
C
OH
McLafferty
düzenlenmesi
C
CH2
Cl
m/z = 78.80
- HCl
M - 36
O+
H3C
H2
C


C
+
C
H2



H3 C
O +


H2
C
C
H
m/z = 70
O +
C
McLafferty
düzenlenmesi
59
E. DİĞER ÖNEMLİ FONKSİYONEL GRUPLAR
1. ALKOLLER
Etanol, C2H6O (46.07)
100
HO
Relatif bolluk, %
80
H2
C
31
46 - CH3
CH3
M+ 46 45
C2H5OH+
60
40
20
29
15
0
10
15
20
25
30
m/z
35
40
45
60
1-Propanol, C3H8O (60.1)
100
H3C
Relatif bolluk, %
80
H2
C
31 CH2= OH
C
H2
OH
60
40
42
M+-18
20
60
M+
0
10
20
30
40
50
60
m/z
1-Bütanol, C4H10O (74.12)
31
100
H3C
Relatif bolluk, %
80
H2
C
C
H2
H2
C
56
74 - H2O
41 43
OH
27
60
40
39
20
15
57
0
0
15
30
45
m/z
60
75
90
61
2-Pentanol, C5H12O (88.15)
100
H3C
45
OH
CH
C
CH3
H2
60
40
42
m/z = 88
görülmez
55
20
70
73
0
H3C
H2
C
40
50
m/z
60
OH
CH
C
H2
70
80


30


20
+
10

Relatif bolluk, %
80
H2
C
CH3
m/z = 88 (yok)
- CH3

M - 15
H3C
H2
C
OH+
C
H2
CH
m/z = 73
-kırılma
OH


CH
C
CH3
H2
- H2O
CH
C
CH3 M - 18
H2
dehidrasyon


CH
C
H2
CH3
M - 46
OH+
- C3H7
H3C
M - 43
CH
-kırılma
m/z = 45
H2C CH2

+
- CH3
H2C CH
CH3 (M - 70) - 15
m/z = 70
- H2O
-C2H4
OH
+
H2C
H

H2C


+
OH
+
H2C
H

H2C

H3C
H2
C


62
H2C CH2
H2C CH2
m/z = 55
CH3
H2C
CH+
m/z = 42
dehidrasyon ve ayrılma
+
63
2-Metil-3-pentanol, C6H14O (102.17)
100
H2C
80
Relatif bolluk, %
59
CH3 CH3
CH
CH3
CH
OH
84
(dehidrasyon
piki )
60
73
40
20
0
10
20
30
 kırılmayla C3H7 (M+ - 43)
kaybı
m/z = 59 piki
40
50
60
m/z
CH3
H3C
CH
CH
OH
M+ = 102
H2
C
70
80
90
100
 kırılmayla C2H5 (M+ - 29)
kaybı
CH3
m/z = 73 piki
64
2-Heksanol, C6H14O (102.17)
100
H3C
Relatif bolluk, %
80
C
H2
45
OH
H2
C
CH
C
CH3
H2
60
40
57
31
20
69
27
84 87
102
0
10
20
30
40
50
60
70
80
90
100
m/z
C
H2






H3 C
H2
C
OH
CH
C
CH3
H2
- e-
H3C
C
H2
H2
C


OH
CH
C
CH3
H2


C
H2
+ OH
CH
C
H2
m/z = 102
CH3
-kırılma
H3C
C
H2
H2
C
+
O


H3C
H2
C
CH2
+
HC
CH3
m/z = 45
65
+
O


H2
C
C
H2
CH
C
H2
CH3


H3C
+ OH
H3C
-kırılma
m/z = 102
C
H2
H2
C
C
H2
CH + CH3
m/z = 87


H3C
C
H2
H2
C
+ OH
CH
CH3
C
H2
H3C
m/z = 102

C
H2
CH
C
H2
H+
C
CH3
+ H2O
m/z = 102 - 18 = 84
Fenol, C6H6O (94.11)
100
94
OH
Relatif bolluk, %
80
60
40
66 M - 28
M - 29 65
20
0
10
20
30
40
50
60
m/z
70
80
90
66
2. TİOLLER
Pentantiol, C5H12S (104.21)
100
42
H3C
Relatif bolluk, %
80
60
55
70
C
H2
H2
C
C
H2
H2
C
SH
104
40
106
47
20
0
20
40
60
80
100
120
m/z
140
160
180
200
67
C
H2
SH
C
H2
- H2S
CH2 M - 34
CH
H2C
H
C
H2
H2
C
- C4H9
SH
SH+
-kırılma
CH2
M - 57
m/z = 47
H2C CH2
H2C CH

CH3
m/z = 70
SH
- H2S
- C2H4
CH2
M - 62


H3C
+
H2 C
H
+
CH


H3C
C
H2
H2
C


H3C
-CH3
H2C CH2
(M - 34) - 15
H2C CH2
+
m/z = 55
H2C
H+
C
CH3
m/z = 42
ayrılma
+
68
3. ETERLER
Di-n-bütil eter, C8H18O (130.23)
100
57
H3C
Relatif bolluk, %
80
H2
C
C
H2
H2
C
O
H2
C
C
H2
H2
C
CH3
60
40
31
20
87
130
0
25
50
75
100
125
150
m/z
H2
C
H2
C
- C3H7
CH3
M - 43
-kırılma
H3C
H2
C
H2
C
O+
C
H2
m/z = 87


C
H2
m/z = 130
O


+
C
H2
H2
C

H3C
H2
C
CH2
69
H2
C
H3C
C
H
CH2
HO CH2 m/z = 31
+


(M - 43) - 56
O


H2
C
+
C
H2
H2
C

H3C
H2
C
C
H2
H2
C
- C4H9O
CH3
H3C
M - 73
H2
C
C
H2
CH2+
m/z =57
sek-Bütil izopropil eter, C7H16O (116.2013)
100
H2
O
C
CH3
CH CH
H3C
Relatif bolluk, %
80
CH3
CH3
60
43
40
20
41
87
57
116
101
0
40
60
80
m/z
100
120
70
CH3
CH CH
C
O
CH3
H2
CH3 CH3
H3C
CH + CH
C
O
CH3
H2
- e-


H3C
CH3




CH3
H3C
CH +
C
H2
m/z = 57


H3C
C
H2
CH3
HC
C


CH
CH3
CH3
+


O
+
+
HC
CH3
m/z = 43
CH3
CH
+
CH3
O+


H3C
CH2
-kırılma
m/z = 87
H3C
C
H2
H
C
CH3
CH
+ CH3
CH3
O+




CH3 CH3
H3C
CH + CH
O
CH3
C
H2
m/z = 116
O
CH3


CH3 CH3
H3C
CH + CH
C
O
CH3
H2
m/z = 116




CH3 CH3
H3C
CH + CH
O
CH3
C
H2
m/z = 116
CH3
+


CH3 CH3
H3C
CH + CH
O
CH3
C
H2
m/z = 116
m/z = 101
-kırılma
71
Metil fenil eter, C7H8O (108.14)
100
CH3
O
Relatif bolluk, %
80
60
40
20
0
10
20
30
40
O
+ R
50
60
m/z
70
80
O+
- R
90
- CO
O
+
H
m/z = 65
O
- CH2=CH2
+
H
H m/z = 94
110
C5H5+
-kırılma
m/z = 93
100
O
+
H
yeniden
düzenlenme
72
4. SÜLFÜRLER
Dibütil sülfür C8H18S (146.29)
100
57
61
H3C
Relatif bolluk, %
80
H2
C
C
H2
H2
C
S
H2
C
C
H2
H2
C
CH3
60
146
40
20
103
47
148
0
25
50
75
100
m/z
125
150
175
73
H2
C
S


C
H2
+
C
H2
H2
C

H3C
H2
C
H2
C
CH3
CH3
H2C
H2C
CH
S+
H
CH2


m/z = 103
S


H2
C
+
C
H2
H2
C
M - 43
H3C
CH2
H2
C
C
H
C
H2
+
C
S

H2
m/z = 103
+
SH
CH2
M - 89
CH2
m/z = 47
-C4H9S
CH3
H2
C
CH2
(M - 43) - 56
hidrür transferi
H2
C
H2
C


S+
C
H2
m/z = 103

H3C
H2
C
H2
C


H3C
H3C
-kırılma
m/z = 146
H2
C
-C3H7
H3C
H2
C
C
H2
CH2+
CH2
HC
CH3
(M - 43) - 42
H2C
S+
CH3
m/z = 61
McLafferty
düzenlenmesi
74
Etil fenil sülfür, C8H10S (138.23)
100
H2C CH3
S
Relatif bolluk, %
80
60
40
20
0
20
40
60
80
100
120
m/z
140
160
180
200
220
75
Difenil sülfür, C12H10S (186.27)
100
Relatif bolluk, %
80
S
60
40
20
0
25
50
75
100
m/z
125
150
175
76
5. AMİNLER
Dipropilamin, C6H15N (101.19)
100
30
72
H3C
Relatif bolluk, %
80
H2
C
C
H2
H
N
C
H2
H2
C
CH3
60
40
20
58
100 101
0
10
H3C
20
H2
C
30
40
H2
H
N
C
C + C
CH3
H2
H2
m/x = 101
50
60
70
m/z

- C2H5
M - 29
H3C
80
H2
C
C
H2
90
H+
N
m/z = 72
CH2
100
110
-kırılması
77
H2
C
H3C
H2
H
N
C
C + C
CH3
H2
H2
H3C
C
H2
H+
N
C
H
H2
C
H2C
CH3
H3C
C
H2
H+
N
C
H2
CH3
C
H
+
(M - 1) - 42
-C2H4
CH2
H2
C
C
H
CH3
H
C C CH3
H2N
H2
m/z = 58
H2N CH2
+
(M - 29) - 42
m/z = 72
H+
N
m/z = 100
- H transfer
m/z = 100
H2
C
H3C
M-1
H2
C
-kırılması
m/x = 101
H2
C
- H
- H transfer
m/z = 30
1-Propilamin, C3H9N
100
Relatif bolluk, %
80
H3C
H2
C
C
H2
NH2
30
60
40
20
0
10
59
20
30
40
m/z
50
60
70
78
İzobütilamin, C4H11N (73.14)
100
CH3
Relatif bolluk, %
80
H3C
CH
C
H2
NH2
60
40
20
0
10
20
30
40
50
m/z
60
70
79
6. NİTRİLLER
Pentannitril, C5H9N (83.13)
41
100
H3C
Relatif bolluk, %
80
C
H2
H2
C
C
H2
C
60
40
20
82
83
0
25
C
H2
H2
C
C
H2
C
75
m/z
N +
- H
H3C
M-1
m/z = 83
H3C
CH
H2C
H3C

C
H2
C
H2
H2
C
125
C
H
C
N+
-kırılma
m/z = 82
H
C
100


H3C
50
N+
H
CH
CH2
M - 42
H2C
C
N +
m/z = 41
McLafferty
düzenlenmesi
N
80
Benzonitril, C7H5N (103.12)
100
103
C N
Relatif bolluk, %
80
60
40
20
0
10
20
30
40
50
60
70
m/z
80
90
100
110
120
81
7. NİTRO BİLEŞİKLERİ
1-Nitrobütan, C4H9NO2 (103.12)
100
- NO2.
57
80
Relatif bolluk, %
H3C
C
H2
H2
C
O
C
H2
N+
O-
60
NO+
30
40
NO2+
46
- NO.
73
görülmez
20
103
görülmez
0
0
20
40
60
m/z
80
100
120
82
Nitrobenzen, C6H5NO2 (123.11)
100
O
N+
O
Relatif bolluk, %
80
O-
77
-
+
N
O
77
M+
123
60
40
20
0
10
20
30
40
50
60
70
m/z
80
90
100
110 120
83
8. HALOJENLİ BİLEŞİKLER
1-İyodoheksan, C6H13I (212.07)
100
H3C
Relatif bolluk, %
80
H2
C
C
H2
H2
C
C
H2
H2
C
I
- I.
85
60
40
20
212
0
20
40
60
80
100
120
m/z
140
160
180
200
84
1-Bromopropan, C3H7Br (122.99)
100
43
[M – 79, veya
(M + 2) – 81]
Relatif bolluk, %
80
H3C
H2
C
C
H2
Br
60
40
122 M+
(C3H779Br)
41
27
124 M+2
(C3H781Br)
20
15
0
25
50
75
m/z
1-bromopropan
H3C
H2
C
79
C
H2
Br+
m/z = 122
+
H3C
H3C
H2
C
H2
C
C
H2
81
C
H2
m/z = 124
100
125
Br
Br+
H2
C+
H3C
CH2
m/z = 43
+ Br
85
2-Bromopropan, C3H7Br (122.99)
100
H3C
CH Br
H3C
Relatif bolluk, %
80
60
iki moleküler iyon
yükseklikler oranı: 1/1
40
20
122
124
0
10
20
30
40
H3C
CH Br
H3C
50
- Br
60
70
m/z
H3C
CH2
H3C
80
90
100
- CH3
CH3
H3C
110
120
86
1-Bromoheksan, C6H13Br (165.07)
100
H3C
C
H2
H2
C
C
H2
H2
C
Br
60
40
-Br.
85
20
135 137
164 166
0
25
50
75
100
125
150
m/z
m/z = 164/166
+

C
H2
CH2
H2
C
C
C
H2
H2
m/z = 164/166
M - 29
H2C
Br+
CH2
H2C CH2
-kırılma
m/z = 135/137


H3C
H2
C
Br


CH2
H2C
H2
C
- C2H5


H3C
H2
C


Relatif bolluk, %
80
H2
C
Br

+
- Br
M - 79/81
H3C
H2
C
H2
C
C
C
H2
H2
m/z = 85
CH2+
87
Klorometan, CH3Cl ()
100
50
H3C Cl
Relatif bolluk, %
80
Iki moleküler iyon: m/z = 50 ve 52
yükseklikler oranı: 3/1
60
M+
50 (CH335Cl)
40
M+2
52 (CH337Cl)
52
20
0
10
20
30
40
50
m/z
(35Cl ve 37Cl doğal olarak %67 ve%33 (veya 3/1) oranında bulunurlar.)
60
88
2-Kloropropan, C3H7Cl (78.54)
100
80
Relatif bolluk, %
43
H3C
CH Cl
H3C
m/z: 63/65 = 3/1
m/z: 78/80 = 3/1
60
40
41
20
iki moleküler iyon
63
78
65
80
0
10
20
30
40
50
60
70
80
m/z
H3C
CH Cl
H3C
2-kloroprpan
- e-
H3C
CH
H3C
35
Cl+ +
m/z = 78
H3C
HC
35
m/z = 63
Cl+
H3C
CH
H3C
H3C
37
Cl+
CH+ +
H3C
m/z = 80
+
H3C
HC
37
Cl+ +
m/z = 65
m/z = 43
CH3
Cl
89
1-Kloroheksan, C6H13Cl (120.62)
100
H3C
Relatif bolluk, %
80
H2
C
C
H2
H2
C
C
H2
H2
C
91
Cl
120, 122
görülmez
60
40
93
20
- HCl
84
0
10
20
30
40
50
60
70
80
90
100
m/z
C
H2
H2
C
m/z = 120/122


C
H2
H2
C


H3C
H2
C
Cl

+
- HCl
M -36/38
H3C
H2
C
C
H2
H2
C
m/z = 84
C
H
CH2+
-H transferi
90
1-Fluoroheksan, C6H13F (104.17)
100
H3C
Relatif bolluk, %
80
H2
C
C
H2
H2
C
C
H2
H2
C
F
60
m/z = 104
görülmez
40
20
-HF
84
0
0
10
20
30
40
50
m/z
60
70
80
90
100
91
Bazı Fragmantasyon Paternleri
Alkanlar
Alkenler
Sikloalkanlar
Aromatikler
Halojenürler
Alkoller
Fenoller
Eterler
Aminler
Aldehitler
iyi M+
14-amu fragmanlar
bölgesel M+
m/e = 27
m/e = 41
M-15, M-29, M-43, v.s..
kuvvetli M+
M-28
M-15, M-29, M-43, v.s...
kuvvetli M+
m/e = 105
m/e = 91
m/e = 77
m/e = 65 (zayıf)
M+ ve M+2
m/e = 49 veya 51
m/e = 93 veya 95
M-36, M-38
M-79, M-81
M-127
M+ zayıf veya yok
M-15, M-29, M-43, v.s..
m/e = 31
m/e = 45, 59, 73, ...
m/e = 59, 73, 87, ...
M-18
M-46
kuvvetli M+
kuvvetli M-1
M-28
M+ alkollerden daha kuvvetli
M-15, M-29, M-43, v.s..
M-31, M-45, M-59, v.s..
m/e = 45, 59, 73, ...
M+ zayıf veya yok
m/e = 30
M-15, M-29, M-43, v.s..
zayıf M+
CH2=CH+
CH2=CHCH2+
alkil kaybı
CH2=CH2 kaybı
alkil kaybı
C8H9+
C7H7+
C6H5+
C5H5+
Cl ve Br
CH2=Cl+
CH2=Br+
HCl kaybı
Br·kaybı
I·kaybı
alkil kaybı
CH2=OH+
RCH=OH+
R2C=OH+
H2O kaybı
H2O ve CH2=CH2 kaybı
H·kaybı
CO kaybı
alkil kaybı
OR kaybı
CH2=OR+
Nitrojen kuralı
temel pik
alkil kaybı
92
m/e = 29
M-29
M-43
m/e = 44, 58, 72, 86, ...
kuvvetli M+
M-1
M+ kuvvetli
M-15, M-29, M-43, v.s..
m/e = 43
Ketonlar
m/e = 55
m/e = 42, 83
m/e = 105, 120
M+ zayıf, gözlenebilir
M-17
M-45
Karboksilik asitm/e = 45
ler
m/e = 60
M+ büyük
M-18
M+ zayıf, gözlenebilir
M-31
m/e = 59
m/e = 74
Esterler
M+ zayıf
M-45, M-59, M-73, v.s..
m/e = 73, 87, 101
m/e = 88, 102, 116
m/e = 61, 75, 89
m/e = 108
m/e = 105
M-32, M-46, M-60
HCO+
HCO kaybı
l CH2=CHO kaybı
McLafferty düzenlenmesi
aromatik aldehit
aromatik aldehit H·kaybı
alkil kaybı
CH3CO+
+CH2CH=C=O
siklohensanonda
aril ketonlarda
OH kaybı
CO2H kaybı
CO2H+
·CH2C(OH)2+
aromatik asitler
orto-etkisi
metil esterler
metil esterler OCH3 kaybı
metil esterler CO2CH3+
metil esterler
CH2C(OH)OCH3+
yüksek esterler
OR kaybı
CO2R+
·CH2C(OH)OR+
RC(OH)2+ (uzun alkil ester)
CH2=C=O kaybı (benzil, asetat)
C6H5CO+ (benzoat)
ROH kaybı (orto-etkisi)
Yararlanılan Kaynaklar
http://www.chemistry.ccsu.edu/glagovich/teaching/316/ms%20(old)/ms.html
http://www.chemicalbook.com/ProductIndex_EN.aspx