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Fragmentation Gugus Fungsi PDF
Fragmentation Gugus Fungsi PDF
+
H3C OH + 1 electron H3C OH + 2 electrons
+
H3C OH CH2 OH+ + H
+
+
H3C OH CH3 + OH
Predicting Fragmentation
2e +
CH3 + H2C O R CH3 CH2+ + Br
Homolytic Heterolytic
Fragmentation Notes
EI + +
R R +
EI
+ +
m/z 91
Fragmentation Guidelines
9. C-C bonds next to heteroatoms often break leaving the
positive charge on the carbon with the heteroatom.
+
O +
O O
+
+
Y
+
CH3
Chem 325
Mass Spectra
of
Various Classes
of
Organic Compounds
1. Saturated Hydrocarbons
General rules 1-3 apply well to hydrocarbons.
Rearrangements are common but usually do not give
intense peaks.
The M+ peak of a straight-chain hydrocarbon is always visible,
but decreases in intensity as the molecule gets larger. The
fragmentation pattern is characterized by peaks separated
by 14 mass units (a CH2 group). The most intense peaks are
the C3 – C5 fragments.
Branched Hydrocarbons
The MS for branched saturated hydrocarbons are similar,
except certain fragments become more prominent.
CI-MS
m/z 91
+
4. Alcohols
Alcohols fragment very easily – secondary and primary alcohols show
very weak M+ peaks, and tertiary alcohols often do not show M+ at
all. MW is often determined by derivatization or CI-MS.
The C-C bond nearest the OH is frequently the first bond to break.
Thus primary alcohols often show a prominent peak at 31 m/z.
+ +
OH OH OH
+
m/z = 60 m/z = 31
Secondary Alcohols
Secondary alcohols cleave in the same way, often showing a
prominent +CHR-OH peak.
+
+ OH OH
OH OH
+ +
m/z = 74 m/z = 59
m/z = 74 m/z = 45
Alcohols
Sometimes the hydrogen R2CH-OH in 1°° and 2°° alcohols
cleaves rather than an alkyl group. The result is an M-1
peak.
+
OH OH
H +
A B
OH OH
+ +
m/z = 59 m/z = 101
More on Alcohols
Alcohols can lose a molecule of water to show a sometimes
prominent M-18 peak. It is especially noticeable for
primary alcohols.
H H + H
O+ HO
+
H
O
+ +
H
OH
94
M-28
M-29
Phenols
If alternative attractive cleavage pathways are available for
phenols, the molecule will often take that path.
m/z = 114
* * *
*
*
Example: 4-methyl-2-hexene
*
m/z = 98
* *
Example: 3-methyl-1-pentanol
OH
m/z = 102
*
*
*
*
*
*
Example: 4-methyl-2-pentanol
* OH
m/z = 102
* *
* * *
*
Example: 2-phenylethanol
OH
m/z = 122
* * *
Example: 1-phenylethanol
OH *
m/z = 122
*
*
*
*
*
5. Ethers
Cleavage happens in two main ways:
1. Breakage of the C-C bond next to O (like alcohols)
OCH3
A +
+
OCH3 m/z = 73
A B
OCH3
B
m/z = 88 + or
+
m/z = 59 m/z = 29
Ethers
Cleavage happens in two main ways:
2. C-O bond cleavage with the charge on the C fragment.
+ +
OCH3 O CH3
m/z = 88 m/z = 57
Aromatic Ethers
M+ is usually strong. MS is similar to phenols – both form
phenoxyl cation (m/z 93) and associated daughters.
6. Ketones
Ketones usually give strong M+ peaks. A major fragmentation
pathway involves α-cleavage to give an acylium ion.
O
+ A +
O
m/z = 71
A B
O
m/z = 100 B
+
m/z = 57
6. Ketones
The carbonyl-containing fragment can also take the radical.
O
+ A +
O
m/z = 29
A B
O
m/z = 100 B
+
m/z = 43
6. Ketones
For ketones with longer chains, the McLafferty
rearrangement often leads to strong peaks.
+ H +
O OH
+ H + +
O H
A B
B
A M-1 m/z = 85 M-R m/z = 29
H C +
OH
M+ m/z = 86
H C
m/z = 44
7. Aromatic Aldehydes …
… are similar to aromatic ketones. M+ is strong, and M-1 (α α-
cleavage to carbonyl) is also strong to give the ArCO+ ion (m/z
105 for Ar = Ph). Loss of CO from this ion is common to give
m/z77 phenyl cation.
+
O O
+ +
H -CO
M+ m/z = 88
OH
O
m/z = 71
+
+ m/z = 43
+
OH
m/z = 60
OH
Aromatic Acids
M+ is very prominent. Common peaks are loss of OH (M-17)
and loss of CO2H (M-45).
+
O O
O O O
O +
+ CO
m/z = 77
Aromatic Esters
The McLafferty rearrangement give the corresponding acid.
A more complicated rearrangement often gives a prominent
acid+1 peak.
+ H +
O O
O OH
OH
+
OH
m/z = 123
10. Amines
Aliphatic monoamines have odd numbered and weak M+
peaks. Most important cleavage is usually breakage of the
C-C bond next to the C-N bond.
+
NH3 NH2 NH2 NH2
2
+ + +
H
m/z = 73 m/z = 72 m/z = 58 m/z = 44
10. Amines
The base peak in nearly all primary amines comes at 30 m/z.
+
+
NH2 NH2
m/z = 101
m/z = 30
Aromatic Amines
M+ is intense (why?). An NH bond can be broken to give a
moderately intense M-1 peak.
H
+
N+ N
H -H H
m/z = 93 m/z = 92
Aromatic Amines
A common fragmentation is loss of HCN and H2CN to give
peaks at 65 and 66 m/z.
H
N+
H
m/z = 93
Aromatic Amines
Alkyl substituted aromatic amines typically show breakage of
the C-C bond next to the C-N to give a strong peak at 106
when Ar = Ph.
H H
N+ N
+
+
O
O
NH2 + +
H
m/z = 69 m/z = 68
Nitriles
Base peak is usually 41 due to a rearrangement like the
McLafferty. This has limited diagnostic value since (C3H5+)
has the same mass.
H +
H H + NH
N
C
C
+
CH2
m/z = 69 m/z = 41
13. Nitro compounds
Aliphatic nitro compounds have weak odd M+. The main
peaks are hydrocarbon fragments up to M-NO2.
+
m/z = 29
NO2
+
m/z = 57
+ m/z = 71
+
m/z = 85
Aromatic Nitro Compounds
M+ is strong. Prominent peaks result from loss of NO2
radical to give an M-46 peak. Also prominent is M-30 from
loss of NO. NO 2 O
-
+
+N
+
O
M-30 m/z = 93
Example: 4-methyl-2-hexene
*
69
m/z = 98
*
41
98
*
29 83
* *
Example: 3-methyl-1-pentanol
OH
m/z = 102
* 56
*
69
31 57
*
* 84
45 *
*
102
*
Example: 4-methyl-2-pentanol
* OH
45
m/z = 102
43 69
* *
57 87
84
* * * 102
*
Example: 2-phenylethanol
OH
* 91
m/z = 122
122
*
31 77 104
* * *
Example: 1-phenylethanol
OH *
107
79
*
m/z = 122
77
*
122
*
43
*
105
91 *
*