Spektra Massa MS
Spektra Massa MS
15
N (0.37%) and
33
S (0.76%) harus dipertimbangkan
2
H (0.015%) and
17
O (0.037%) dapat diabaikan
7
Formula from Mass Spectrum
M+2 Contributors
Sesuatu yang berguna dari intensitas M+2?
32
S :
34
S
Isotopes Natural abundances Intensity M : M+2
100 : 4.4 95.0 : 4.2
35
Cl :
37
Cl 75.8 : 24.2
100 : 31.9
79
Br :
81
Br 50.7 : 49.3 100 : 97.2
Kesimpulan: Spektrum massa molekul dengan S, Cl, Br atau memiliki signifikan M+2 puncak
8
m/z
C
CH
3
Cl
CH
3
H
C
3
H
7
Cl
80
Formula from Mass Spectrum
M+2 Contributors
M+2: 36 + 7 + 37 = 80
C H Cl
M: 36 + 7 + 35 = 78
M:M+2
abundance
~3:1
78
9
122
R
e
l
a
t
i
v
e
a
b
u
n
d
a
n
c
e
(
%
)
m/z
Br
C
3
H
7
Br
Formula from Mass Spectrum
M+2 Contributors
M+2: 36 + 7 + 81 = 124
C H Br
M: 36 + 7 + 79 = 122
M:M+2
abundance
~1:1
124
10
Identifying the Molecular Ions
Which peaks are molecular ions?
Highest m/z not always M
M+1 has m/z one more than m/z of M
Br
C
7
H
7
Br
M: m/z = 170
11
Formula from Mass Spectrum
M: Menyatakan massa molekul terdiri dari isotop massa terendah
M+1: Intensitas of M+1 / 1.1% = number of carbons
M+2: Intensitas mengungkapkan adanya sulfur, klorin, dan bromin
Summary of Information from Mass Spectrum
kuliah mendatang : Prosedur untuk menurunkan rumus dari spektrum massa
12
B. Determination of Molecular Mass
5. Aturan Nitrogen adalah cara lain untuk mengkonfirmasi ketaatan dari
puncak ion molekul
6. Jika molekul berisi bahkan jumlah atom nitrogen (hanya 'umum' atom
organik dengan valensi ganjil) atau atom nitrogen tidak ion molekul
akan memiliki nilai yang lebih massa
7. Jika molekul mengandung ganjil atom nitrogen, ion molekul akan
memiliki nilai massa ganjil
8. Jika molekul mengandung klorin atau bromin, masing-masing dengan
dua isotop umum, penentuan M + dapat dibuat lebih mudah, atau
jauh lebih kompleks seperti yang akan kita lihat.
13
1. Simple cleavage
Radical Remote Fragmentation (a-cleavage)
i. Compounds containing saturated heteroatoms
ii. Compounds containing unsaturated heteroatoms
R' CR
2
Y R'
+
CR
2
Y
R' CR
2
Y R''
R'
+
CR
2
YR''
iii. Compounds containing unsaturated carbon-carbon bonds
R
+
R CH
2
CH CH
2
- e
R CH
2
CH
CH
2
CH
3
CH CH
2
CH
2
CH CH
3
14
Charge Remote Fragmentation ( i-cleavage)
R'
R
OH
i
R
+
OR
C
R
R'
O
i
R +
R'
C O
-Cleavage and i-cleavage are competitive reactions.
The sequence of -cleavage tendency:
N > S, O, p bond, R > Cl > Br > I
The sequence of i-cleavage tendency:
halogen > O, S >> N, C
15
Compounds without heteroatoms ( s-cleavage)
R
+
R R'
- e
R'
s
R
+
R'
R
CH
R'
OH
R
+
CHR'
OH
R
C
O
NH CH
2
R'
R
C
O
NH CH
3
+
R'
R
C
O
NH CH
2
R'
R C NH CH
2
R +
O
Examples:
-cleavage
R
R R' + S
+
SR'
i-cleavage
16
Examples:
O
71
45
59
73
87
CH
3
CH
2
CH
2
CH
2
CH
2
C OH
57
43
29
17
Loss of small molecules, such as H
2
O, CO, C
2
H
4
H
HO
C
6
H
13
H
2
O + C
6
H
13
- CO
O
O
O
- CO
+
O
H
O
H
O
H
2
O
H
OH
CH
3
H
2
C CHCH
3
CH
2
=CH
2
H
2
O + +
18
G. Patterns of different organic compounds fragmentation
Saturated hydrocarbons
1. Alkanes
Figure 1 Mass spectrum of dodecane.
Dodecane
19
2. Branched Alkanes
20 40 60 80 100 120 140 160 180 200
10 30 50 70 90 110 130 150 170 190 210220230
10
0
80
90
100
60
50
30
20
40
70
0
%
O
F
B
A
S
E
P
E
A
K
C
3
m/z=43
C
4
m/z=57
C
5
m/z=71
C
8
m/z=85
C
6
m/z=99
C
7
113
C
9
C
10
C
12
C
16
M
15
M
5-Methylpentadecane
CH
3
(CH
2
)
3
CH (CH
2
)
9
CH
3
CH
3
85
169
141
57
Figure 2 Mass spectrum of 5-methylpentadecane.
20
Figure 3 Mass spectrum of 4-methylundecane.
4-methylundecane
Figure 4 Mass spectrum of 2,2,4,6,6-pentamethylheptane.
21
3. Cycloalkanes
M=84
Cyclohexane
84(M )
56(C
4
H
8
+
)
41(C
3
H
5
+
)
10
0
80
90
100
60
50
30
20
40
70
%
O
F
B
A
S
E
P
E
A
K
0 20 40
60 80 100
10
30 50
70 90 110
0
Figure 5 Mass spectrum of cyclohexane.
22
Figure 6 Mass spectrum of 1-methyl-3-pentylcyclohexane.
1-methyl-3-pentylcyclohexane
23
Aromatic hydrocarbons
Figure 7 Mass spectrum of 1-phenylhexane
24
CH
2
m/z=91
m/z=91
m/z=65
m/z=39
HC CH HC CH
m/z = 162
I.
H
2
C
CH
2
CH
H
CH
2
H
H
m/z=92 m/z = 162
II.
m/z=77 m/z=51
HC CH
C
6
H
9
m/z = 162
III.
Process of fragmentations:
25
Alcohols, Phenol and Ether
1. Alcohol
Figure 8 Mass spectrum of 1-dodecanol
26
R
2
C
R
1
R
3
OH
- R
3
R
2
C
R
1
OH
m/z: 31,59,73,
......
I.
RHC
H
CH
2
CH
2
CH
2
O+
H
H
2
C CH
2
- H
2
O
M - (Alkene + H
2
O)
H
2
C CH R
-
III.
Process of fragmentations:
- H
2
O
RHC CH
2 RHC CH
2
(CH
2
)
n
(CH
2
)
n
or
H
RHC
C
H
2
CH
2
OH
n
RHC
C
H
2
CH
2
OH
n
H
II.
C
H
CH
2
H
2
C
C
H
H
H
2
C R
H
2
C CH
2
-
CH
2
CH
H
2
C R
27
2. Phenol
H
2
C
C
H
2
H
OH
CH
2
CH
2
H
2
O
-
H
2
C
O
H
OH
CH
2
O
H
2
O
-
28
3. Ether
Figure 9 Mass spectrum of hexyl ether.
29
Ketone and Aldehyde
Figure 10 Mass spectrum of 2-dodecanone.
30
10
0
80
90
100
60
50
30
20
40
70
%
O
F
B
A
S
E
P
E
A
K
57
M-CH
2
CH
2
M-H
2
O
M
MW 142
40 60 80 100 120 140 10 30 50 70 90 110 130 150 0
20
M-1
M-44
M-43
CH
3
(CH
2
)
7
CHO
44
Figure 11 Mass spectrum of octanal .
31
Carboxylic acid
O
Ch
3
(CH
2
)
4
CO (small) 99
CH
3
(CH
2
)
4
71
CH
3
(CH)
3
57
CH
3
(CH
2
)
2
43
CH
3
CH
2
29
CH
3
CH
2
CH
2
CH
2
CH
2
C OH
45 CO
2
H
59(small) CH
2
CO
2
H
73 (CH
2
)
2
CO
2
H
87 (CH
2
)
3
CO
2
H
32
Ester
Figure 12 Mass spectrum of hexyl benzoate.
33
Other compounds
Figure 13 Mass spectrum of 1-chlorododecane.
34
Figure 14 Mass spectrum of 1-bromododecane.
35
129(M )
10
0
80
90
100
60
50
30
20
40
70
%
O
F
B
A
S
E
P
E
A
K
0
20 40
60 80 100 10
30 50
70 90 110
86
114
44
29
120 130
140
58
CH N CH
2
CH
3
CH
2
CH
2
CH
3
CH
3
CH
3
Figure 15 Mass spectrum of N-isopropyl-N-methylbutan-1-amine
36
M=113
10
0
80
90
100
60
50
30
20
40
70
%
O
F
B
A
S
E
P
E
A
K
NH
84
56
41
27
CH
2
H
3
C
70
113(M )
20
40 60
80 100
10 30
50 70
90
110
0
120
0
Figure 16 Mass spectrum of N-ethylcyclopentamine.
37
Figure 17 Mass spectrum of methyl octanoate.
10
0
80
90
100
60
50
30
20
40
70
0
20 40 60 80 100 120 140
%
O
F
B
A
S
E
P
E
A
K
10 30 50 70 90 110 130 150
COCH
3
O
CH
2
CH
2
OCH
3
O
121[M-31]
M
Methyl octanoate
CH
3
(CH
2
)
6
COOCH
3
158(M)
159(M+1)
160(M+2)
160
87
59
74
C
OH
OCH
3
H
2
C
M+1
M+2
38
%
O
F
B
A
S
E
P
E
A
K
0 20 40 60 80
100 120 140 160
100
50
39
41
51
77
79
107
118
136
Exercise 1:
HRMS menunjukkan massa tepat senyawa A adalah 136.0886 dan rumus ini
senyawa C
9
H
12
O, silahkan konfirmasi struktur senyawa A.
Answer
DEB: = (2*9+2-12)/2 = 4
m/z: 118 M-18 M-H
2
O
-OH
39, 51, 77
107 M-29 M-C
2
H
5
-C
2
H
5
CH
H
2
C
OH
CH
3
39
Exercise 2:
Please confirm the structure of compound A.
%
O
F
B
A
S
E
P
E
A
K
0
20 40 60 80
100 120 140 160
100
50
156
158
107
94
77
65
51
39
27
157
I
158
= 13%
I
157
= 3.7%
I
156
= 41%
40
Answer
1. I
156
/I
158
= 3/1 Containing one Cl atom
2. N
c
= 3.7/411.1%8
Containing eight C atoms
3. m/z: 39, 51, 77
; 94
OH
107 O CH
2
4. 156-35-77-16-14 = 14
CH
2
O
H
2
C
H
2
C Cl
Cl O
H O
Cl
O
H
H
O
94
77 65
51
39
O
CH
2
107
41
Exercise 3:
%
O
F
B
A
S
E
P
E
A
K
0
20 40 60 80
100 120 140 160
100
50
150
104
93
77
65
76
121
134
Berdasarkan spektrum massa EI senyawa A, silakan menulis
proses fragmentasi
42
Answer
H
O
N
OH
NO
2
NO
OH
H
O
H
OH
O
O
OH
O
O
NO
O
O
O
93
121
121
134 150
65
-H
-OH
-NO
-CO