Appendix Q - Ions For Determining Unknown Structures

A P P E N D I X Q
IONS FOR DETERMINING UNKNOWN
STRUCTURES
[M + 1]+ Possible Precursor Compounds

13
C isotope (present at 1.1% for each 12C)
Aliphatic nitriles also usually exhibit an [M – 1]+ peak
Ethers
Sulfides
Aliphatic amines
Alcohols
Esters
Increasing the sample size or decreasing the repeller voltage may
increase the relative abundance of the [M + 1]+ ion. If the
sample pressure is very high, dimers may also be produced.
M+•
In general, the relative intensity of the M+• peak decreases in
the following order.
1. Aromatics
2. Conjugated olefins
3. Alicyclics
4. Sulfides
5. Unbranched hydrocarbons
6. Ketones
7. Amines
8. Esters
9. Ethers
10. Carboxylic acids
11. Branched hydrocarbons
12. Alcohols
[M – 1]+ Possible Precursor Compounds and Functionalities
Dioxolanes
Some amines
Aldehydes*
*
The mass spectra of aldehydes also exhibit [M – 18]+, [M – 28]+, and [M – 44]+ peaks. The
mass spectra of aromatic aldehydes exhibit [M – 1]+ and [M – 18]+ peaks.
Gas Chromatography and Mass Spectrometry � 2010 by Academic Press. Inc.
DOI: 10.1016/B978-0-12-373628-4.00053-8 All rights reserved.
519
520 Appendix Q
Some fluorinated compounds (e.g., C6F5–CH2OCH2C≡CH)
Acetals
Segmented fluoroalcohols (some even lose •H and HF)
(e.g., CF3CF2CF2CH2CH2OH)*.
Aryl–CH3 groups
N–CH3 groups
Aliphatic nitriles (also may have [M + 1]+ peak)**
Aromatic isocyanates
Aromatic phenols
Certain butenols
Certain fluorinated amines***
e.g., C8F17CH2CH2CH2NH2
or
CF3(CF2)2CH2CH2CH2NH2
[M – 2]+ Possible Precursor Compounds
Polynuclear aromatics (e.g., dihydroxyphenanthrene)
Ethylsilanes (dimers to heptamers)
2 Structural Significance
H2
[M – 3]+
ions must be fragments from a higher-mass molecular
ion (e.g., [M – CH3]+ and [M – H2O]+)
[M – 10]+
Add 18 to the higher mass and 28 to the next lower mass to
determine M. Look for an [M – 44]+ peak to see if it is an
aldehyde.
[M – 13]+
Not from a molecular ion, but could be the loss of a •CH3
(radical) and the loss of a •C2H4 (radical) or CO from the
molecular ion.
Not observed from a molecular ion; however, a mixture of
two different compounds may be present where the
higher mass ion is MH.
The apparent loss of 14 could also be the loss of 15 from the
molecular ion.
CH2 in ketene
*
Also lose HF
**
The [M – 1]+ peak is larger than the [M + 1]+ peak, especially in n-nitriles.
***
May not observe the M+• peak, just the [M – H]+.
Ions for Determining Unknown Structures 521

Methyl derivatives
tert-Butyl and isopropyl compounds
Trimethylsilyl derivatives
Acetals
Compounds with NC2H5 groups
Compounds with aryl–C2H5 groups
Saturated hydrocarbons do not lose CH3 from a straight-chain
compound.
CH3 as in CH3F, CH3N=NCH3, CH3OC(O)OCH3,
CH3OC(O)(CH2)4C(O)OCH3
CH3OCH = CH2, CH3OCF = CF2, H3C S CH3

O O
O
CH3O(CO)CH2(CO)OCH3
NH
Aromatic nitro compounds*
N-Oxides
Oximes
Aromatic hydroxylamines
Aromatic amides (loss of NH2)
Sulfonamides
Sulfoxides
Epoxides
Quinones
Certain diamines (e.g., hexamethylenediamine)
O, NH2, CH4
Carboxylic acids (loss of OH)
Aromatic compounds with a functional group containing
oxygen
Ortho to a group containing hydrogen
Diamino compounds (loss of NH3)
*
Nitro compounds show peaks representing [R – O]+ and [R – NO]+ and should have a
large m/z 30.
522 Appendix Q
Simple aromatic acids

Some amino acid esters
Loss of NH3 (amines having a four-carbon chain or longer)
OH, NH3
Primary straight-chain and aromatic alcohols (also look for
a large m/z 31)*
Alcohol derivatives of saturated cyclic hydrocarbons
Steroid alcohols (e.g., cholesterol)
Straight-chain aldehydes (C6 and upward)**
Steroid ketones (peak generally <10%)
Carboxylic acids, particularly aromatic acids with a methyl
group ortho to the carboxyl group
Aliphatic ethers with one alkyl group containing more than
eight carbons
Loss of CD3 from deuterated TMS derivatives
A highly characteristic peak for amines (NH4)
H2O
Fluorocarbons
Alcohols, [M – (H2O + H)]+
Fluorine compounds (m/z 19, 31, 50, and 69)
Rearrangement ion characteristic of hydroxyl compounds
Glycols
Acetals
Diols
Aliphatic alcohols
Alkyl fluorides and fluoroethers***
Fluorosteroids
Fluoroalcohols
Compounds such as C8F17CH2CH3 may not show a M+• peak
but an [M – F]+ peak as the highest m/z value.
n-Alkyl fluorides
*
Primary alcohols: [M – 18]+, [M – 33]+, and [M – 46]+.
**
Aldehydes observe [M – 28]+ and [M – 44]+ ions.
M+• is usually not observed. In CI, the highest mass observed is [M + H – HF]+.
***

[M – (H2F)]+
from segmented fluoroalcohols
e.g.,
OH
F17C8 C C
H
H 3C
[M – (H + HF)]+
from: CF3CH2CH2CF2CF2CF3
Segmented fluoroalcohols are represented by
CF3CH2CH2OH, CF3CF2CH2CH2OH,
CF3CF2CF2CH2CH2OH, etc.
Acetylene
Acetylene (strong ion observed in spectrum)
Maleic acid
Acrolein
Fluoroacetylene
Loss of C2H2 from thiophene
Aromatic compounds
Pyrrole
Bicyclic compounds:
for example,
Isocyanides (R–N≡C)
Aliphatic nitriles and dinitriles
HCN
Acrylonitrile
Propanenitrile
Pyrazines
Pyrroles
Acetylene
Maleic acid
Maleic anhydride
Succinic anhydride
Vinyl group (look for m/z 40 and 54)
524 Appendix Q

N-containing heterocyclics (see pyridine, etc.)
Simple aromatic amines
Loss of C2H3 by double-H rearrangement in ethyl-containing
phosphites* and phosphonates*
HCN for unsaturated nitriles
Aliphatic nitriles and dinitriles
Alkenes and compounds with unsaturated R groups
CH2=CH–R
CH2=CHC(O)R
CH2=CHC(O)OR, etc.
HCN, CH2=CH–
Phenols
Diaryl ethers (especially ethyl ethers)
Quinones
Anthraquinones
Aldehydes (look for [M – 1]+, [M – 18]+, [M – 28]+, and [M – 44]+
ions)
Cyclic ketones
Anhydrides
Naphthols
O-containing heterocyclics
[M – (HCN + H)]+ (low-molecular-weight aliphatic nitriles) and
isocyanides**
Phenylisocyanate ([M – CH2N]+)
Phenylenediisocyanate
Chlorophenylisocyanate
N-containing heterocyclic compounds
Ethyl esters
Cycloalkanes
Acid fluorides (e.g., benzoyl fluoride)
Lactones
Ethyleneimines
Alkyl amines
*
Phosphite (C2H5O)2POH; *phosphonate (C2H5O)2P(O)–H; *ethyl phosphonate
(RO)2P(O)–C2H5.
**
Isocyanides lose HCN + H2CN more readily; this may help differentiate cyanides from
isocyanides.
Saturated hydrocarbons
Dialkyl aromatic hydrocarbons
Dioxanes
Cyclobutane
Butyrolactone
Butyraldehyde
Succinic acid
1-Tetralone
Carbonyls
Aromatic aldehydes (should observe [M – H]+ as well as
[M – CHO]+)
Simple phenols
Quinones
Ethyl groups or alicyclic compounds
Cyclic ketones and cyclic amino ketones such as pyrilidone,
piperidone, and caprilactam
Phenols
Naphthols
Polyhydroxybenzenes
Diaryl ethers
Aliphatic nitriles
Purines [M – (CH2 = NH)]+ and imines
Propanals
Indicates an alkyl group (may not be ethyl)
Loss of CHO from compounds such as
CH3C(O)OCH2OC(O)CH3
Alkanes or compounds with an alkyl groups (m/z 43, 57,
71, etc. may also be present)*
Aldehydes
Propionates
Cyclic polyethers
α-Amino acids
Hydroperoxides
C2H5, CHO
Aromatic nitro compounds
Loss of CH2O from simple aromatic ethers
Lactones**
*
For branched alkanes such as tert-butyl, m/z 43 is the dominant ion.
**
Produces [M + H]+ using isobutane CI.
526 Appendix Q
Loss of CH2O from

O
R C
(usually do not see the
C O molecular ion peak)
R CH2
(see dioxane, dioxolanes, and epichlorohydrin)

Morpholine
Cyclic amines unsubstituted on the nitrogen
Primary amines*
Nitro compounds and aliphatic nitrites (should observe
[M – 16]+ and [M – 30]+)
Secondary amides
Formamides
Nitrosamines
Ureas
Caprolactam
NO (aliphatic and aromatic nitro compounds)
N2H2, CH2O, CH4N, CH2NH2, C2H6, etc.
Note: In the absence of rearrangement, fragment ions
containing an odd number of nitrogen atoms have an
even m/z value.
Methyl esters—the simultaneous presence of peaks at m/z
74 and 87, and [M – 31]+ strongly indicates a methyl ester
Methoxy derivatives, including methoximes
Primary aliphatic alcohols and glycols
Loss of •CH2OH radical
Loss of SiH3
A peak occurs at m/z 31 in almost all alcohols and ethyl
ethers, as well as in some ketones; m/z 31 in the absence of
fluorine indicates oxygenated compounds.
Fluorocarbons (with m/z 19, 31, 50, and 69)
Ethers and alcohols (m/z 31, 45, and 59)**
*
Amines show a powerful tendency to break beta to the nitrogen atom. This mass is not
characteristic only of primary compounds because the ion is formed from other amines by
rearrangement.
**
If the spectrum is of an alcohol, to identify the molecular weight, it may be necessary to
add 18 or 46 to the highest m/z value peak observed.
Primary straight-chain alcohols

Primary alcohols bonded at the γ-carbon
Formates
Aliphatic carboxylic acids
Alkyl ethyl ethers
Cyclic polyethers
Phosphorus compounds
Rearrangement peak in dioxanes
o-Methyl benzoates
Loss of methanol
Ortho substituent of methyl esters of aromatic acids
Loss of 31 also should be present.
[M – (CH3OH)]+ from methyl esters and ethers
[M – (O + NH2)]+ from sulfonamides
Loss of sulfur from thiophenols and disulfides
Hydrazine
Methanol
Fluoroethylene
Deutero compounds
Oxygen
Methyl formate
Carbonyl sulfide

Alcohol derivatives of cyclic hydrocarbons
Thio compounds
Thiocyanates
Short-chain unbranched primary alcohols
[M – (H2O + CH3)]+ from hydroxy steroids
Loss of –SH
Glycols
Diols
Alcohols
Acetals
CH2F
Mercaptans (usually aliphatic)
CH3F, H2S, PH3 (see triethyl phosphine, etc.)
Chloro compounds
528 Appendix Q
[M – (H2O + OH)]+ from certain dihydroxy and polyhydroxy

compounds
[M – (CH3 + HF)]+ from compounds such as
F
(CH3)3Si O
O CF2 C CF3
Thioethers
Sulfides
Chloro compounds
n-Alkyl chlorides
(Some alkyl chlorides lose HCl and appear to be butenes;
for example, 1,2,3,4-tetrachlorobutane appears to be
trichlorobutene)
[M – (H2O + H2O)]+ from certain polyhydroxy compounds
HCl
[M – 37Cl]+from alkyl chlorides
(H2O + F) from certain fluoroalcohols
HC–C≡C–
[M – 2F]+
from fluorocarbons
C2N, –CH2C≡C–
Diallyl sulfide
Malononitrile
Dicyanoacetylene
Furan
(HF + F) (e.g., fluoroalcohols)
H
HO
H3C CF2 C CF2 CH3
O CF2 CF2 O
Furans
Alkenes
Dienes
Cyclic alkenes
Acetylenes
Aromatic compounds, particularly di- and tetrasubstituted
compounds
(m/z 39, 50, 51, 52, 63, and 65)
C3H3, CH3C≡C–, –CH=C=CH2, –CH2C≡CH
Aliphatic dinitriles (loss of CH2CN)*
Aromatic compounds
Cyclic carbonate compounds
Segmented fluoroalcohols such as (loss of H2F2)
F17C8 CHOH
C
H3C
[M – (HF + HF)]+
Butanol
Dinitriles (may have m/z 41, 54, and 68)
C3H4, CN2, C2O, CH3C≡CH, CH2=C=CH2, C2H2N, – CH2C≡N

Nitriles
Suggests a propyl ester
N-influenced fragmentation, for example,
H3C N CH3
H 3C N CH3
Nitriles and dinitriles (m/z 54 also may be present)**
Esters of aliphatic dibasic carboxylic acids
Thioethers
*
The highest mass may be [M – 28]+ and/or [M – 40]+. (Usually the M+• is not observed.)
Large m/z 41, 55, and 54 peaks also should be present.
**
CH3CN exists in lower aliphatic nitriles. Higher nitriles have (CH2)nCN (e.g., m/z 54, 68, etc.).
530 Appendix Q
Isothiocyanates
Primary aliphatic alcohols
Alkenes and compounds with an alkenyl group
Cyclohexyl (m/z 41, 55, 67, 81, and 82)
Methacrylates (also look for m/z 69)*
C3H5, C2HO, C2H3N, CH3CN, –CH2CH=CH2,
H3C–CH=CH– and
CH3
C
CH2
m/z 69, 41, and 86 suggest segmented fluoromethacrylates**

[M – 42] +
Possible Precursor Compounds
Acetates (loss of ketene, see if m/z 43 is also present)
N-Acetylated compounds (acetamides)
Enol acetates
Simple purines (loss of cyanamide)
2-Tetralone
Loss of ketene from bicyclic structures (e.g., for camphor)
CH3
H3C
C CH3
O
C
Cycloalkanes
Alkenes (<C6); peaks at m/z 42 and 56 suggest alkenes
Ethyleneimines (H2C=C=NH)
Pteridines
Cyclic ketones (saturated)
THF
Butanediol
Simple purines
*
May have to add 86 Da to the m/z value of the last peak observed to deduce the molecular
weight.
O
** CH3
F2n+1Cn
O C C
CH2
C3H6, C2H2O, CNO, CH2N2, C2H4N, CH3N=CH–
H 2C H
N
N N
, H3CCH N , , H C CH2
2
H2C C CH2
H
(CH3)2N– also should observe m/z 44

Uracils: [M – (C(O)NH)]+
Cyclic amides
Propyl derivatives (particularly isopropyl)
Cyclic peptides
Dioxopiperazines
Tertiary amides
Aliphatic nitriles (>C6)
Common loss from cyclohexane rings
Terpenes
Alkanes (m/z 43, 57, 71, 85, etc. characterize the spectra
of alkanes)
Compounds with an alkyl group
Acetates (also observe m/z 61)
Alditol acetates (Check for the presence of m/z 145, 217,
289, etc.)
Methyl ketones (when looking for larger than methylethyl
ketone, look for m/z 58 as well).
Cyclic ethers
Vinyl alkyl ethers
N-Alkylacetamides
Isothiocyanates
Aliphatic nitriles
With m/z 87 suggests triethyleneglycol diacetate
C3H7, CH3C≡O, (CH3)2CH, H2C=CHO, C2H5N, CH3N2, C(O)NH,
C3H7C(O)OR, C3H7C(O)NR2, C3H7C(O)R, C3H7SR, C3H7OR,
C3H7OC(O)R, C3H7X, C3H7NO2

Aliphatic aldehydes (look for [M – 1]+, [M – 18]+, [M – 28]+, and
[M – 44]+ ions.)
Compounds with (CH3)2N–
Aromatic amides
Anhydrides (e.g., phthalic acid anhydride)
532 Appendix Q
Aliphatic aldehydes unbranched on the α-carbon (is the base
peak for C4–C7). (Look for [M – 1]+, [M – 18]+,
[M – 28]+, and [M – 44]+ ions.)
Primary amines with α-methyl groups
Secondary amines unbranched on the α-carbon
Tertiary amides*
C R2
R1 N
R3
Vinyl alkyl ethers

Caprolactam derivatives
Cyclic alcohols
Piperazines (C2H6N)
CO2, N2O, CF ≡ CH, CH3CHO, C2FH, C3H8, OC–NH2, C2H4O,
CH2NHCH3, (CH3)2N, CH2NO, CH2CHO + H, CH3CHNH2, CH4N2,
HC=NOH, C2H5NH, –CH2CH2NH2
Ethoxy derivatives
Ethyl esters
Carboxylic acids (may lose 17, 18, and 45)
Cyanoacetic acid, 8-cyano-1-octanoic acid
Aliphatic carboxylic acids
2° alcohols (e.g., sec-butyl alcohol, m/z 45, 59, and 31)**
Propylene glycol
Di- and triethylene glycols
Isopropyl and sec-butyl ethers
*
Will produce
O
C R2
H3C N
R3
via McLafferty rearrangement if R1 contains a hydrogen on carbon 4.
** R2
H C OH 2° alcohol
R1
Butyrates
Methylalkyl ethers unbranched on the α-carbon
–C(O)–OH, H2C=CF–, C2H5O, CH3OCH2, CH2CH2OH, C2H2F, CH3NO,
*
C2H7N, CH3SiH2, CH2=P+, CH3CHO + H, CHS
Oxygenated compounds can be disregarded if peaks are
absent at m/z 31, 45, 59, etc.
Nitro compounds (NO2)
Loss of C2H5OH from ethyl esters
Aromatic acids with methyl groups ortho to the carboxyl
groups
Long-chain unbranched primary alcohols
Loss of C2H3F
Straight-chain high-molecular-weight primary alcohols
Loss of water plus C2H4
Possibly loss of formic acid (e.g., C6H5CH2CH2C(O)OH)
Cyano acids
Nitrates
CH2=CHF, CH3CH2OH, HC(O)OH
CH3OCH3, NO2, C2FH3, CH3NH=NH2
Alkylnitro compounds
Acid fluorides
Sulfur compounds (loss of CH3S)
Loss of CH3OH + CH3
Thiols (m/z 61 and 89 also suggest sulfur-containing
compounds)
Acid fluorides
Thioethers (sulfides)
Fluorosilanes such as FC6H4SiH3
Acetals (generally containing the ethoxy group)
Fluoroethane
C, O, and F compounds (peak may be small)
Formates (small peak)
CH3S, –C(O)–F, SiF, PO
CH3CHF, CH2SH, CH3PH, CH2CH2F
Methyl thioethers
(COH + F) from pentafluorophenol
*
Is characteristic of certain sulfur compounds such as thiophenes.
534 Appendix Q
(CHO + F) from fluoroaldehydes

Aromatic sulfoxides
Methyl thioethers
CH3SH from mercaptans
SO, CH3SH, –CHCl, C2H5F, CH3S, +H, C4
Tetraborane
Chlorinated compounds (loss of CH2Cl)
(e.g., β-chloroisopropylbenzene)
Halogenated compounds containing CH2Cl
Methyl thioethers
CH2Cl, –C≡C–C≡CH
Fluorocarbons (loss of CF2)
Methyl esters of unsaturated acids (loss of CH3OH + H2O)
Methyl esters of straight-chain hydroxycarboxylic acids
except 2-hydroxy acids
CF compounds
Compound containing phenyl or pyridyl groups
Chloromethyl derivatives
CF2
Loss of CHF2
HC≡CCN from α,β-unsaturated nitriles
Acetylenes
Compounds containing phenyl or pyridyl groups
Compounds containing CHF2
Small m/z 51 peak indicates compounds containing C, H, and F
CHF2, C4H3 (aromatics), SF
Butadienes
Acetylenes
Compounds containing phenyl or pyridyl groups
Nitrogen trifluoride
C2N2, –CH=CHCN, CH2=CH–C≡CH, C2H4, NF2
Chromium
Cyanogen, C2N2
Furans
Cyclobutenes
Dienes
Acetylenes
Pyrazine
Aminophenol
Acrylonitrile
Chloroprene
Hydroquinone
C3H3N, C4H5, C2HN2, C3HO, NF2H, etc.
The mass spectra of pyrrole derivatives usually contain
prominent ions at m/z 53 and 80, and sometimes the
m/z 67 rearrangement ion.
CH
CH
C
O
H3C
NC
(from branched dinitriles)

Unsaturated cyclic hydrocarbons (e.g., vinyl-cyclohexene)
Butadienes
Dinitriles (C2H4CN) (dinitriles lose 40 Da and 28 Da and
generally give m/z 41, 55, and 54 ions.)
Acetylenes
Cyclohexanes
Nitriles (m/z 41 also may be present)
Maleic acid
Maleic anhydride
Quinone
–CH2CH2CN, C(O)–CN, C3H2O, C4H6, C2H2N2
A loss of 55 is possibly the loss of C4H7 from esters (double
hydrogen rearrangement). The loss suggests a butyl or
isobutyl group, especially when m/z 56 is also present.
Loss of (CO + HCN) from aromatic isocynate
Loss of H2C=CH–C(O)
Cyclic ketones
Cycloalkanes
536 Appendix Q
Indicates a cyclohexyl ring (m/z 55, 83, and 41)

Aliphatic nitriles and dinitriles (see m/z 54)
Thioethers
Alkenes
Primary aliphatic alcohols
Olefins have fragment ions at m/z 55, 69, 83, etc.
Cyclohexanones
(CH3)2C=CH, CH2=CH–C(O)–
Acrylates (m/z 55 and 99 suggest glycol diacrylates)
Base Next Most Compound Highest m/z

Peak Intense Peaks Peak >1%
55 82 54 67 27 1,6-Hexanediol diacrylate 113

(MW = 226 Da)
55 196 82 127 126 Pentaerythnitol triacrylate 225
(MW = 298 Da)
55 54 27 71 85 1,4-Butylene glycol diacrylate 126
(MW = 198 Da)
55 54 71 126 85 1,4-Butylene glycol diacrylate 126
(MW = 198 Da)
55 56 70 41 43 n-Octyl acrylate 112
(MW = 184 Da)
55 27 70 41 56 n-Heptyl acrylate 113
(MW = 170 Da)
55 56 73 27 41 Butyl acrylate 99
(MW = 128 Da)
55 56 73 84 43 n-Hexyl acrylate 99
(MW = 156 Da)
55 72 59 27 31 2-Ethoxyethyl acrylate 99, 100, 101
(MW = 144 Da)
55 82 67 73 54 Cyclohexyl acrylate 111
(MW = 154 Da)
55 84 27 69 43 2-Ethylbutyl acrylate 98
(MW = 156 Da)
55 45 45 27 29 2-Methoxyethyl acrylate 87
(MW = 130 Da)
55 27 85 42 58 Methyl acrylate (MW = 86 Da) 86
55 69 70 43 97 Ethylene glycol diacrylate 14, 141
(MW = 170 Da)
55 91 79 107 162 Benzyl acrylate (MW = 162 Da) 162
55 127 56 27 68 2,2-Dimethyl propane 140, 152
diacrylate (MW = 212 Da)

Aromatic diisocyanates
Quinones
Ketals of cyclohexanone
Anthraquinones
C4H8 from carbonyl compounds
Butyl compounds (e.g., C6H5OC4H9)
Butyl esters
Cyclohexylamines
Isocyanates (n-alkyl). Peaks associated with M – CO,
M – (H + CO), M – (HCN + CO) are generally observed. Also look
for a peak at m/z 99.
Cycloalkanes
Some n-chain alcohols (butanol, hexanol, heptanol, octanol,
nonanol, etc.)
Aliphatic nitriles (see m/z 54)
–CH2–N=C=O, C4H8, C3H6N, (CH3)2N=CH2,
CH3N=CHCH2–,
H2C
NCH2
H2C

Isocyanates (M–CH3N=C=O)
Loss of F3 in perfluorotributylamine
C4H9 from TBDMS derivatives
Compounds containing alkyl groups, particularly tertiary
butyl group
Ethyl ketones
Propionates
Aliphatic nitriles
Isobutylene trimers and tetramers (also observe m/z 41 and 97)
Alkanes (m/z 29, 43, 57, 71, etc. are also observed)
C4H9; C2H5CHCH3, (CH3)3C, etc.
C3H5O; C2H5C(O)–, CH3C(O)CH2–, etc.
C2H5N=N
Aliphatic methyl ketones (CH3C(O)CH3
Simple aromatic nitro compounds (NO + CO)
Straight-chain mercaptans
538 Appendix Q
Thiocyanates and isothiocyanates

Methyl alkyl ketones unbranched at the α-carbon (43 + 58)
+
OH
H 2C C
Rearrangement ion of 2-methylaldehydes

n-Propyl-, butyl-, amyl-, and hexylketones
Primary amines with a 2-ethyl group
Tertiary amines with at least one N-methyl group
Thiocyanates
Isothiocyanates
H
O NH
N H
CH3
C C C
H HON C
H H3CO
(CH3)2CNH2, (CH3)3CH, C3H8N
(CH3)2NCH2– (sometimes an m/z 42 peak also is present),
C2H5NHCH2–
CH3C(O)NH– (generally observe an m/z 60 rearrangement ion)
CH3C(O)CH2 + H, C3H6O, C2H2O2, C2H4NO, C2H6N2, C3H8N,
–C(O)–NHCH3, CNO2, C3H3F, CH2N2O, C4H10, HC(O)NHCH2–
Peaks at m/z 58, 72, and 86 suggest that a C=O group is
present (also look for M – CO).
Loss of (C(O)OCH3) from methyl esters
Loss of OC3H7 from propyl esters
Methyl esters of 2-hydroxycarboxylic acids
Loss of CH3C(O)O from sugar acetates
Tertiary aliphatic alcohols
Methyl esters of carboxylic acids
Esters of n-chain carboxylic acids
Silanes
Ethers (C2H5OCH2–)
m/z 59, 45, 31, and 103 suggest di- or tri-propylene glycol
Primary straight-chain amides (greater than propionamide)
Amides
OH
H2C
NH2
(look for m/z 59, 44, and 72)
(CH3)2COH (tertiary alcohols)
Largest peak in the mass spectrum of propylene glycol ethers
CH3OCH2CH2– (diethylene glycol dimethyl ether)
CH3CHOHCH2–, C2H5OCH2–, (CH3)2COH
CH3OC(O)–, CH3CHCH2OH, C3FH4
Peaks at m/z 31, 45, and 59 reveal oxygen in alcohols, ethers,

and ketones.
Acetates
Methyl esters of short-chain dicarboxylic acids
Loss of –OCH2CH2NH2
–C6H10(CO2CH3)2
O-Methyl toluates
A characteristic rearrangement ion of monobasic carboxylic
acids above C4 (also see m/z 73)
Cyano acids (observe [M – 46]+ and large m/z 41, 54, and 55
peaks)
Esters of nitrous acids
Sugars
Aliphatic nitriles unbranched at the α-carbon
Ethyl valerate has m/z 60 and 73 (these ions are normally
associated with carboxylic acids)
Cyclic sulfides
H2C CH2
m/z 60 with an m/z 58 peak suggests CH3C(O)NH + 2H C3H5F

C3H8O, CH6N3, –CH2ONO, CH4N2O, CH2NO2, C2H6NO, C2H4S,
–NHCH2CH2OH, ClC≡CH, COS, C2H4O2, C2H8N2,
Suggests CH3N•OCH3 and CH3NHOCH3
Loss of (Si2H5) from
540 Appendix Q
Ph
Ph
Si Ph
H Si
Si
Ph H
Ph Ph
m/z 61 is a characteristic rearrangement ion in acetates other
than methyl acetate (should observe [M – 42]+ as well as a
large m/z 43)
Esters of high-molecular-weight alcohols (CH3CO2H2)
Base peak in 1,2-difluorobutanes
Acetals
Primary thiols (CH2CH2SH)
Thioethers (CH3SCH2–)
N-TFA of n-butylmethionine
m/z 61 and 89 suggest sulfur-containing compounds (RSR′)
TMS derivatives; for example,
H3C
Si
HO
CH3CH2CHF–, CH3C(O)C + 2H, CH3CFCH3

–CHOHCH2OH, –CH2CH2SH, CH3CHSH
CH3NOCH3 + H
Thiols
Ethyl thioethers
F2C=C–, –CHCH2Cl, –CF=CF–, PH2C2H5,
(see triethylphosphine and tributylphosphine)
CH3CH2SH, (CH3)2S
Methyl esters of dibasic carboxylic acids
Acid chlorides (C(O)Cl)
Ethyl thioethers
CF2=CH–, –CH2CH2Cl, CH3CHCl, CH3S(O), SiCl, C2F2H, CH3P–OH,
CF2=CH–
CF3CH2CH2– structure also provides a large m/z 63 peak
C2H5OC(O) (e.g., diethyl carbonate)
–CH2CH2Cl, –OCH2CH2Cl

Loss of OCH2Cl
–SO2CH2–
Certain sulfones (HSO2)
Aromatic compounds (C5H5)
Aromatic alcohols
Vinyl furans
CH3CF2–, C2F2H3
Unsaturated nitriles
Dicyanobutones
Methyl pyridines
Ethyl disulfides (HSSH)
Acrylonitrile dimers
CFCl, N2F2, C2F2H4, C5H6
CH3
NH
Perfluoro acids
Cycloalkyl compounds
Alkadienes (also may have an intense m/z 81 ion)
Alkynes
CHClF (in Freon-21), CF2OH, SOF–, C5H7, C4H5N,
C CH2
H2C C
CH3
m/z 67, 81, 95, 109, etc. suggest 1-acetylenes

Dinitriles
Cyclopentanes
Cyclohexenes
Cyclohexanols
Aliphatic nitriles (m/z 41 and 54 also may be present), C4H6N
542 Appendix Q
C5H8 (cyclopentane derivatives), –CH2CH2CH2CN, NCCH2C(O)

CH2CIF
Fluorocarbons (loss of CF3)
Fluorocarbons
Cycloparaffins (e.g., cyclopentyl)
Aliphatic nitriles
Isothiocyanates (>C7)
Methacrylates (m/z 41 is also present)*
C(O)C(CH3)=CH2, CH3CH=CHC(O)–, (CH3)2C=CH–CH2–, CF3, C5H9,
PF2, –CH=CHCH(CH3)2,
A series of peaks at m/z 69, 83, 97, 111, etc. (two mass units
less than the corresponding paraffins) suggest olefins
m/z 69, 41, and 86 suggest segmented fluoromethacrylates
m/z 69, 77, 65, and 51 are characteristic of segmented
fluoroiodides (e.g., C8F17CH2CH2I, etc.)
Abundant Ions Compound MW
69 41 87 39 Ethylene glycol monomethacrylate 30

69 41 113 112 Ethylene glycol dimethacrylate 198
69 113 41 86 Diethylene glycol dimethacrylate 242
69 41 113 45 Triethylene glycol dimethacrylate 286
69 41 55 43 Trimethylolpropane trimethacrylate 338
69 41 54 55 1,6-Hexanediol dimethacrylate 254

(CHF2 + F) loss observed in 1-H perfluoro compounds
(e.g., CF3(CF2)7H, CF(CF2)8H, –C4H8N)
Pyrrolidines
NH CH3
Aliphatic nitriles
Amyl esters
*
To postulate the mass of the molecular ion, add 86 Da to the even-mass ion of a doublet in
the high-mass region.
If the mass spectrum has a large peak at m/z 42, check

1-pentanol
C4H8N, CH3N=CHCH2CH–
CH3
C
CH3
C
O
Hexamethyleneimine
Isocyanates (–CH2CH2NCO)
m/z 70 and 43 suggest a diacetoxybutene
Loss of (CH3)3CCH2
H3C CH3
H3C H
C C OH
H3C C
H CH3
THF derivatives
Butyrates
Methyl cyclohexanols
Propyl ketones
Terminal aliphatic epoxides:
H
H2C C CH2
C
O H H
H 3C H H
C C H2C C O
HO CH2 CH2
CH2
O
CH3CH(OH)CH = CH–, C3H7C(O)
(CH3)2CHC(O), –C (O) OCH = CH2,
H 3C H CH3
O
C H
C H2C C OCH3 C
H3C HO C CH
CH H H
C5H11, C4H9N, NF3, (C2H5)2CH
544 Appendix Q

Loss of –NHCH2CH(CH3)2
Acrylates (loss of acrylic acid)
Loss of C2O3 from compounds such as cyclohexane
dicarboxylic acid anhydride
Amides
Secondary and tertiary amines (C3H10N)
Ethyl ketones
Thiocyanates (CH2SCN)
Isothiocyanates (–CH2–N=C=S)
Rearrangement ion of 2-ethylaldehydes
CH3C(O)NHCH2, C2H5NHCH2CH2–,
*
CH3C(O)CHCH3 + H
*
(CH3)2C–NHCH3, C3H7CHNH2, C2H5C(O)CH2 + H
(C2H5)2N, (CH3)2NC(O)–, CH3NCH2–,
H
H C CH3
N
H3C H
H

Alditol acetates
Loss of (C(O)C2H5)
Methyl esters of aliphatic dibasic carboxylic acids
(–CH2C(O)OCH3)
n-Butyl esters (loss of C4H9O)**
Sugars
Aliphatic acids (m/z 73 with a peak at m/z 60 suggests acids)
Alcohols (C3H7CHOH–)
Ethers (C3H7OCH2–)
Ethyl esters (–C(O)OC2H5)
Methyl esters of dibasic carboxylic acids (CH2C(O)OCH3)
1,3-Dioxolanes
H2C O
H2C C
O H
(m/z 73 and 45 suggest dioxolanes)
*
By γ-hydrogen shift-induced β-cleavage rearrangement (McLafferty rearrangement).
**
See dibutyl azelate (MW = 300 Da) and dibutyl oleate (MW = 338 Da).
TBDMS and trimethylsilyl derivatives, (CH3)3Si–

H H O H CH3
C OCH3 H5C2 C
H3C , , C ,
CH3 H3C OCH3
H
– CH2CH2C(O)OH
O O , C H Cl
CH2OC(O)CH3, 3 2
C

Some butyl esters (C4H9OH by rearrangement)
(CH2CHSCH3) loss from N-TFA, n-butyl methionine
m/z 74 is a characteristic rearrangement ion of methyl esters
of long-chain carboxylic acids in the C4–C26 range. Also
look for an m/z 87 peak.
Monobasic carboxylic acids with an α-methyl group
Cyclic sulfides
Aliphatic nitriles with an α-methyl group
H OCH3
C N , CH3NHCH2CHOH–, HOC2H4NHCH2–,
H CH3
CH3CHONO, –CH2NHCH2CH2OH, CH2=C(OH)–OCH3,
CH2OCH3*
*
C3F2, H2NCHC(O)OH , N
CH3

Loss of –CH2OCH2CH2OH
Dimethyl acetals [(CH3O)2CH–]
Disubstituted benzene derivatives containing electrophilic
substituents C6H3
*
Also observe m/z 74, 73, and 72.
546 Appendix Q
Dichlorobutenes, CH2ClCH=CH–, CH2CH=CHCl
Propionates (generally small)
Sulfides (C2H5SCH2–)
(CH3)2SiOH, –CF=CHCH2OH, C2H5OC(O) + 2H, (CH3)2CH–S–,
CH3OCH(OH)CH2–
TMS derivatives of all aliphatic alcohols [HO+=Si(CH3)2]
Loss of C2H4SO from ethyl sulfones
Loss of CF2CN
Benzene derivatives (C6H4)
Aliphatic nitrates (–CH2ONO2)
Propyl thioethers (C3H7SH)
*
–CF2CN, C6H4, CS2, C3H5Cl, N(OCH3)2, (CH3)2NS
Monosubstituted benzene derivatives containing an electrophilic
substituent
(CH3)2SiF, –CF2CH=CH2
C3F2H3 (e.g., –CHFCF=CH2, –CH2CH=CF2, CH3CF=CF–,
–CH=CHCHF2), C6H5–, (CH3)2P(O), CH2ClC(O),
CH3
C2H5Si(H)F Cl C H3CCH2CHCl–
H3C
Alkylbenzene (m/z 39, 50, 51, 52, 63, 65, 76, 77, and 91)
CnF2n+1CH2CH2I
Loss of benzene from compounds such as (C6H5)2 and
CHOCH(C6H5)2
Phenyl tolyl ethers
Compounds containing the pyridyl group
C2F2O, C3F2H4, N
C O
C CF2
C O
C2H7PO
*
m/z 76, 42, and 61 suggest (CH3)2NS–

Bromides
Cycloalkadienes
Bromides
Pyridines
–CH=CClF, CH3SS–, –CF2C2H5, H3CC5H4, Br
N O
H OH
, , H3CS , Cl C C
O H H
N
CHF2C(O), HOP(O)OCH3
Alkyl bromides (loss of HBr)
Alkyl pyrroles
Substituted cyclohexenes (C6H8)
Methyl disulfides (CH3SS + H)
C5H6N, C2H2ClF,
, C5H6N (m/z 80)

NH CH2 N
O2N NH2 C5H6N (m/z 80)
Hexadienes (C6H9)
Alkyl furans
N-TFA, n-butyl histidine
CH3OCF2–, CH3SiF2, CF2=CF–, –CH=CH–CH= CH–CH=O,
–CF2CH2OH, , , CH3CFCl–,
O CH2
C6H9, (HO)2P + O present in phosphate spectra

548 Appendix Q

Loss of C3H4N3,
CH2
N
N CH
HC N
Aliphatic nitriles (–CH2CH2CH2CH2CN) (m/z 82, 96, 110, 124,
138, 152, etc. suggest straight-chain nitriles)
Benzoquinones
Piperidine alkaloids
Some fluoroalcohols
m/z 82 and 67 suggest cyclohexyl compounds (see m/z 83)
m/z 82 and 182 suggest cocaine (MW = 303 Da)
CCl2, C6H10, C2F3H, CHF=CF2, (CD3)3Si–, C5H8N,
H2C CH OCH3
C C

Dicyclohexylbenzene
Aliphatic nitriles
Cyclohexanes (C6H11) (m/z 83, 82, 55, and 41 suggest a
cyclohexyl ring)
Thiophene derivatives
Trialkyl phosphites
SO2F, CHCl2, C2H3F3,* CHF2CHF–, –CF2CH2F, CF3CH2–, C5H7O,
**
C5H9N–, (CH3)2C=CH–C(O) (e.g., mesityl oxide)
CH3CH=CHCH2C(O)
CH3CH2CH=CHC(O)
CH2=CHCH2CH2C(O)
HP(OH)3, phosphonic acid derivatives
H3C
HC C Si
H3C
*
m/z 83 and 33 suggest CF3CH2–
**
m/z 55 and 83 suggest this structure.
Loss of N (C5H10N) observe m/z 84 and 56
Aliphatic isocynate –CH2CH2CH2NCO
Esters of aliphatic dibasic carboxylic acids (>dimethyl suberate)
Piperidines (m/z 84, 56, etc.) , C5H10N,

N
Pyrrolidines , CH2Cl2, C5H10N, , CDCl2,

N
NH CH3
C3H7–CN–CH3, C4H8Si, C , C4H4O2

O NH

Glycol diacrylates (M–CH2=CHC(O)OCH2–)
Loss of (C4H9 + CO) from TBDMS derivatives of amino acids
Caffeine [–C(O)N(CH3)C(O)–]
Butyl ketones (C4H9C(O))
N-TFA, n-butyl glutamic acid
Piperazines (C4H9N2)
Tetrahydropyranyl ethers
Lactones
Methyl-8� derivatives of primary amines
SiF3, CF2Cl, CF3O, POF2, C4H5O2, C5H9O, C5H11N, C6H13,
(CH3)2NCH=NCH2–
CH3C(O)C(CH3)2–, , –CH=CH–C(O)OCH3,
O CH2
O O R
C ,
R O O
(See if a peak at m/z 101 is also present.)
550 Appendix Q

Loss of CH2=C(CH3)C(O)OH from methacrylate esters
Propyl ketones (C3H7C(O)CH2 + H)
α-Methylisothiocyanates
SOF2, C4F2, (C2H5)2NCH2–, C4H9–NHCH2, C5H12N
C4H9CHNH2, HC(O)NH–C(CH3)2, –CHCH3–N=C=S, –CH2NHC4H9
C2H5NHCH2CH2CH2– (will observe peaks at m/z 44, 58, 72
and 86)
n-Amyl esters
Loss of –CHCH3C(O)OCH3
Loss of C(O)OC3H7 from N-TFA, isopropyl esters of amino
acids
Methyl esters of aliphatic acids (m/z 74 and 87 indicate a
methyl ester)
Glycol diacetates (m/z 87 and 43 are characteristic ions)
Methyl dioxolanes
Long-chain methyl esters
Esters of n-chain dibasic carboxylic acids
CH2CH2C(O)OCH3
C4H7O2:
H3C O CH3 H O
H
, , ,
H C C C C C C
H3C O CH3 H3C O H H3C CH2 OH
CH3C(O)OCH2CH2, C2H5C(O)OCH2–C5H11O:
CH3CH2CH(CH3)OCH2–, –CH(OH)CH2CH(CH3)2,
–CH2OCH2CH(CH3)2
O
C
C4H4Cl, C4H7S, [(C2H5)2NCH2 H], C(O)OC3H7,
Long-chain ethyl esters (look for m/z 101)
(C2H5OC(O)CH2 + H)
C3H6NO2, CF4, C4F2H2, –C(CH3)2NCO
H + CH(CH3)C(O)OCH3, C4H10NO, C4H8S,
– CHNH2C(O)OCH3
Long-chain methyl esters with an α-methyl group
H
H +
HO OCH3
C O
R C
Loss of
H2C C
CH3 RCH CH2 C
C O CH3
H
H
CH3

Loss of OSi(CH3)3 from TMS derivatives (m/z 90 should be
more prevalent)
Triethylene glycol (also look for m/z 45)
O- and N-containing heterocyclic compounds
Characteristic rearrangement ion of butyrates except methyl
Dinitrotoluenes
TMS derivative of primary aliphatic alcohols
[H2C=O+SiH(CH3)2]*
Sulfur-containing compounds (also expect m/z 61)
C7H5, C4H6Cl, C3H7SCH2–, , C4F2H3,
H3CO CH3
H3CO C
C4H9S–, C3H7SCH2–, CH2=CHCF=CF–, –CH2OSiH(CH3)2

–CH(OH)CH2CH(OH)CH3, (CH3)3SiO–, [C3H7OC(O) + 2H],
(CH3O)2CCH3, CH3OSi(CH3)2
–CF=CHCH2OCH3 (should observe m/z 45 and 59 as well)
Loss of (CH3)3SiOH from TMS derivatives (may see the loss of
180 Da and/or 270 Da from the molecular ion,
depending on the number of OH groups present)
O- and N-containing heterocyclics
Aliphatic nitrates with an α-methyl group
(CH3CHONO2)
*
Look for homologs in the spectra of 2° and 3°, for example, m/z 103 (without a peak at m/z
89), m/z 117, etc.
552 Appendix Q
Methyl esters of α-hydroxy carboxylic acids
C6H4N, C3FCl, C6H5CH, C7H6, (C2H5)2PH,
R O
P CH3
H2C N
H2C CH2
Alkyl benzenes (C7H7) (m/z 104 and/or 117 are also
characteristic ions)
Phenols
Aromatic alcohols
Benzyl esters
Alkyl chlorides (C6–C18); C4H8Cl from terminal chloroalkanes
N-TFA, n-butyl phenylalanine
CH2 CH3
CH2ClCH2C(O), ,
ClCH2CHCH3CH2–, C4H5F2, Cl(CH3)2CCH2–

CF2=C(CH3)CH2–, –CF2–C(CH3)CH2, m/z 43 and 91 suggest 1-chlorodecane
H
H
H3C C CF2, C2H4O2P
C

Certain esters of dibasic carboxylic acids
Loss of (C3H9SiF) for fluorinated sugars
β- and γ-monoalkyl pyridines
CH2
Phosphorus compounds
Salicylates (see m/z 138)
Benzyl compounds with a γ-hydrogen
NH NH2
, , ,
C C O
(CH3)3SiF, N3CF2–
C7H8 double rearrangement ion common to alkylbenzenes
CFClCN
C3H8PO
Phenoxy derivatives
OH
Nitrophenols
Fluorocarbons
Salicylates (see m/z 138)
Alkyl pyridines
O
, ,
+H
N CH2 +H
OH
, C3H3FCl: –CFClCH=CH2, CH3OCF=CF–
C3F3: CF3–C C–
(CH3O)2P, –C(O)OCH2Cl, C3H6OCl: C2H5OCHCl–,
OH H3C Cl
C H5C2 Cl
C2H6SiCl: , Si
ClH2C CH3 Si H3C
Alkyl phenyl ethers (except anisole)
Dimethyl pyrroles
554 Appendix Q
C6H5OH from Benzopyrans

O
Alkylpyrazines
O
C H
NH C CH2
, C2Cl2, C3F3H, CH3OP(OH)CH3, C
H
O
Cl F
C C
O O
CH3Br, ClCC(O)F from
C
CF3
F

Methyl esters of aromatic sulfonic acids (SO2OCH3)
Derivatives of furan carboxylic acids
O
Hydroxymethylcyclohexanes
Methylfurans
Methyl esters of sulfonic acids
Segmented fluoroalcohols: CnF2n+2CH2CH2OH (m/z 31, 95, 69,
and 65)
O
OCH3
S
F3C
, C7H11, C CH2 , C6H9N, CF3CN,
–CF2CH2CH2OH, CHF2CF CH–, C6H4F, C6H7O,

H
C
C3H5ClF, C5H7N2, H3C C , C2F2O2H,
C
O H
CF3CH CH–, C7H11, C3F3H2, F

Aliphatic nitriles (–(CH2)5CN) (m/z 96, 82, and 110 suggest
nitriles)
Piperidines
Esters of dibasic carboxylic acids
Dicycloalkanes
(CH3)2SiF2, C6H5F, CH3CH2CFCl–
C6H8O:

Loss of (CF2=CFO) from fluoroesters, fluoroamides, and
fluoronitriles
(e.g., CF2=CFOCF2CF(CF3)OCF2CF2C(O)OCH3,
CF2=CFOCF2CF(CF3)OCF2CF2C(O)NH2,
CF2=CFOCF2CF(CF3)OCF2CF2CN)
Alkyl thiophenes
H
C
C
S H
O- and F-containing compounds:
C CF2
CF3C(O)–, –CF2C(O)F, F , CF2 CF–O–
O
Aliphatic nitriles (C6H11N) C NH
CF3–N N–, , , CFCl CF–,

C C
O OH
CH2=CHCH2CH(CH3)C–, C7H13, C2F2Cl

CH3CCl2–, CH3CH2CH2CH=CHC(O)–
CH3P(O)Cl, C7H13, CH3P(OH)3, CH2ClCHCl–
556 Appendix Q

Loss of –(C7H14)
(CH2)8
HC (CH2)8 CH
(CH2)8
Piperidine alkaloids (N-alkyl)
N
H
C
H
Dicarboxylic esters
Alkyl thiophenes
Dicarboxylic acids (e.g., palmitic and fumaric acids)
Bis(hexamethylene)triamine
NCH2
C
, N O , H3C N ,
H2C H
H
, , ,
O C +H N
N
R HO H3C
H
, C6H12N,
O CO + H N O
H C

Loss of (CD3)3SiOH from deuterated TMS derivatives
Maleates (>methyl)*
*
Look for a fragment ion with m/z 29 and an ion with m/z 99 + 28 = 127 for diethyl-; a
fragment ion with m/z 41 and 99 + 40 = 139 for dipropyl-; and so forth.
+
OH
N-TFA, n-butyl aspartic acid
Acrylates (m/z 99 and 55 suggest glycol acrylates)
Isocyanates (C5H9NO) (also look for m/z 56)
Ethylene ketals of cyclic compounds (e.g., steroids)
Amyl ketones (CH3(CH2)4C(O))
Pentafluorobenzene
γ-Lactones, CH2=CH–C(O)OCH2CH2
CF3OCH2–
CF3CHOH, C5F2H, CH3C(O)C2H4C(O), C5H9NO,
H
H2C C
, H3CN N
O O , C6H11O–,
H CH CH2
C6H13N, , R OH ,
C
R O
O
OH
HO
CH2 CHC(O)NHCH2NH–, P OH
HO
(Methyl-8® derivatives of amides) → –C(O)N=CH–N(CH3)

[M – 100] +
Possible Precursor Compounds
Loss of C2F4 from fluorine compounds
Perfluoroalkenes and perfluorocycloalkanes (C2F4)
(C2H5)2NC(O), –C5H11CHNH2, C4H9C(O)CH2 + H,
+ H, C5H5Cl, (CH3)2SiN3, (CH3)2CHN(CH3)C(O)
m/z 86, 100, 114, 128, 142, 156, etc. suggest diamines. Look
for a large m/z 30 peak.
558 Appendix Q

Loss of –C(CH3)2C(O)OCH3
N-TFA, n-butyl amino acids
Loss of (–C(O)OC4H9)
Ethyl esters (–CH2CH2C(O)OC2H5)
Butyl esters (–C(O)OC4H9)
Succinates (e.g., dicyclohexyl succinate)
Hexafluoropropylene oxide (HFPO) dimers and trimers
Fluorochloro compounds having CFCl2
Malonic acids C(O)CH2C(O)OCH3
Cyclic sulfides
C4H5O3, CF3CFH–, CFCl2, CHF2CF2–, C6H13O, C5H9O2,
CH3(CH2)4CHOH–, CH3SC(O)CH=CH–,
–CH2CH2OC(O)C2H5,
H3C
CH3C(O)OCHC2H5, H7C3 C , PSF2, CF3S, PCI2,
HOH2C
H3C
O O
H3C
C
,
H3COC

Loss of acetic anhydride from sugar acetates
Quinolines
Long-chain propyl esters (C3H7OC(O)CH2 + H)
CN
, C6H5C≡CH (e.g., phenylmaleic anhydride)
CH3OC(O)C(CH3)2 + H
(e.g., CH3OC(O)C(CH3)2C(O)OCH3)
(CH3)3SiNHCH2–, –CHNH2–C(O)OC2H5
Loss of [CH2OSi(CH3)3] from the molecular ion of TMS
Ketohexoses and 1,2,6-hexanetriol
Alkyl indoles (characteristic rearrangement ion)
Cinnamates (C6H5CH=CH–)
Valerates (>methyl)
Double rearrangement of protonated carboxylic acids
Trimethylsilyl derivatives [CH2=O+Si(CH3)3] of primary

aliphatic alcohols*
[1,1-Diethoxyalkanes (C2H5O)2CH–]
(CH3)2CHSCH2CH2–, C8H7, C4H9OC(O) + 2H,
O H3C H
H ** ,
H C O C ,
C
H3CO
OH OH H
H2 C C
Cl
CH3CH2C(OCH3)2–
H3 C CH

3

Tetralins (tetrahydronaphthalene)
m/z 104 and 158 (see phenylcyclohexene)
CF3Cl, N2F4, SiF4, C8H8, C2H5CHONO2,
H H
C C , CH3SCH2CH2CHNH2–,
H
H
C O
, or C O
m/z 104 and 91 or 117 are characteristic of some

alkybenzenes
Benzoin ethers (e.g., benzoin isopropyl, benzoin isobutyl)
H
HC C
CH3
Loss of C C from
H H
H H
H3C C N N C CH3
H H
*
Look for homologs in the spectra of 2° and 3°, for example, m/z 117 (without a peak at
m/z 103), m/z 131, etc.
**
From dimethyl malate.
560 Appendix Q
Loss of [CH3 + (CH3)3SiOH] from TMS derivatives of

aldohexoses, etc.
Benzoates
Aromatic alcohols
Azobenzenes
(C2H5)2SiF, C6H5C=O, C6H5N=N, C4F3, (CH3O)2SiCH3
C6H5CHCH3, C6H5CH2CH2, C7H7N,
O
H
Cl C OH
H3C C
C C
H , H

Esters of long-chain dibasic carboxylic acids
Substituted N-alkylanilines (C6H5NHCH2–)
Alkyl pyridines:
, C H N, C F H,
C 7 8 4 3
N CH2 H
H3C CH2
, H N CH2 ,
2
N
NH2 CH2
, ,
C N
H H
(CH3)2NP(O)CH3, O
N C

Loss of (CH3C6H4O–) as in (CH3C6H4O)3P
(CH3 + C3H9SiF) from TMS derivative of fluorinated sugars,
for example,
H
F3C
C OH
F3C C OH
F3C C OH
C OH
F3C H

Alkyl phenols (HOC6H4CH2–), pyrethrin II (MW = 372 Da)
See benzoin isopropyl ether (MW = 254 Da)
OH
C6H4CH2O–,
H , –CF2C4H9,
–CH2CH2OCH2CH2Cl, C6H5SiH2
CH3(CH2)3CH=CH–C≡C– or CH3(CH2)3–C≡C–CH=CH–
C6H5OCH2–, CH3C6H4O–, –C6H4OCH3
Ph
H Ph H H
Si
Loss of H Si from Ph Si Si Ph
H H
H H
H
N OH

Tolyl ethers (CH3C6H4O + H)
Alkyl pyrroles
Benzothiazoles (C6H4S)
H2NC6H4O–, C6H5SH, C6H5CH2O– + H,
562 Appendix Q
∗
P
H
C6H5CH2OH, HO C
, P OCH3
N C
N
CH3 O H CH3

Purines (C5H7N3)
Certain perfluoroketones (C3F3O)
C3F2Cl, HOC6H4O–, CH3OCF=CFO–,

S
O , CF2=CFC(O), C4H4F3, C8H13, C3F2Cl,
F 3C
C C , , CH3CCl=CCl–,
F 3C H
C , HO NH + H,
H
OCH3
–CCl2CH=CH2, P HOP(O)OC2H5
O OCH3

Aliphatic cyanides** (CH2)6CN, C7H12N,
C6F2, C2Cl2O, C7H10O, CH3OPOH(O)CH3, C4H5F3,
*
See triphenylphosphine, MW = 262 Da.
**
m/z 110, 96, and 82 suggest nitriles.
N H
CH2=CCF3–CH3,
C
H3C O CH2 H

Suggests an octyl group (C8H16)
Methyl alkyl thiophenes
Adipates, C6H7O2
Long-chain methyl esters of carboxylic acids
O
CH3CH2CCl2–, –C6H5Cl, C8H15,
S C
C7H11O, CFBrH, CF3CH(CH3)CH2–, C3H5Cl2

C2H5OP(O)C2H5, CHCl2C(O), –CF2CH2C(O)F
CH3
N N
CH3
CF3C(O)CH2–, CF3C=N–NH2, C CH3 ,
C C
H H
CH2 H
H
C
N C
H, ,
H
H
C
CH3
, –CF2C(Cl)=CH2, C2H5P(OH)3

Loss of
O
N C
R′–H (suggests an octyl group)

Loss of (CH2)5NCO from isocyanates
N-Alkylcyclohexylamines
564 Appendix Q
Dibutylhexamethylenediamine
2,7-Dioxo-1,8-diazacyclotetradecane
C7H14N, C3F4, C6H12Si, C6H5Cl, C6H8O2, (CH3)2P(O)Cl
NH
C C
O N O, H3C
,
H2C CH2
H
N
CH2 , CH2
C SiH
H

Methyl esters of Δ2-fatty acids
–CH2CH2CH=CHC(O)OCH3
Methacrylates (CH2=C(CH3)–C(O)OCH2CH2–)
Certain diketones
N-Methylsuccinimide
Cyclic ethers (C7H13O)
C4H9C(O)CH2CH2–, (CH3)2CHC(O)CH2C–,
CH3CH2C(O)CH2CH2C(O),
H3C O
C OCH3
HN NH ,
C
CH3C(O)CHCH2C(O)CH3,
–CH2C(CH3)=CH–C(O)OCH3, CF3CH=CF–,
–CF2CH=CF2, C2FCl2, CH2ClCHClCH2–,
C2F2ClO, C3F4H, C6H3F2, C6H13C(O),
C8H17, C7H15N, C6H13N2, C6H11NO, C6H9O2,
CF3C(O)NH2,
RCH2 OH, C7H13O, CH3SiCl2

CF2=CFS–, CH2=CCH3C(O)NHCH2NH–
Steroid alkaloids:
H3C OH
H7C3 C
H N
N C O
H7C3 H O
,
C7H16N, C6H4F2, CHCl–CClF, CF3C(O)–OH,

–CF2N=CF2, –CH2CH2C(=NOH)C3H7,
–CF2–CF=NF, C2F4N
Sugar acetates
Glutarates
Alkyl indoles (other than methyl)
C9H7 ion from naphthalenes (may produce a double-charge
ion at m/z 57.5)
Creatinine-TRITMS (MW = 329 Da)
Quinolines (C9H11)
–C(O)CH2-C(O)OC2H5, C2H2FCl2, CHCl2CHF–, C7H15O,
CFCl2CH2–, (C2H5)3Si–, (CH3)2CH–C(O)OCH2CH2–,
C
H2C OCH3
(CH3)3CSi(CH3)2–, CH3CHCH=C(OH)OC2H5,
H2C
C
C CH
H
H
C
O O
C
H H

Loss of CH2=CHC(O)O(CH2)2OH from some acrylates
566 Appendix Q

Amino alcohols and ethers (C6H14NO)
N-TFA, n-butyl glutamic acid
–CH2C6H4CN, C2F3Cl, –CF2CFCl, ,

S SH
F
F2C C Cl
C3H7C(O)–OC2H5, C5H5OCl, ,
F2C C Cl
F
H5C6 C
CN

Loss of CCl3 (e.g., DDT)
Loss of –COOTMS
Loss of CF3CHFO from CF3CHFOCF2CF(CF3)OCF2CF2CN
Alkyl indans
Styrenes (C9H9), caproates (>methyl)
CCl3, C2F4OH, C5F3, C6H5CH2CH=CH–,
CH3C6H4CH=CH–, –CF2OCHF2, –CF2CHClF,

POCl2, C6H5CH=CH–CH2–, C2HF3Cl,
CF2ClCHF–, CH3OCHCH2C(O)OCH3, C2HF4O,
–C(O)OSi(CH3)3, –CH2CH2OSi(CH3)3
Intense peaks at m/z 117 and 104 (characteristic of alkyl
benzenes)
If a peak is at m/z 117 in the spectrum of a TMS derivative, it
probably indicates that a carboxyl group is present.
H3C O
O O
CH3

C4H9OCH2CH2OH, (CH3)2NSi(CH3)2O–
N C
, CH3 ,
H3C
H 3C H C CH2 118
C C
H from C S O
F3C CF3 O

Fluorocarbons (CF3CF2–)
Toluates (CH3C6H4C≡O)
Alkyl benzenes: for example,
CH3
C
CH3
Pyrrolizidine alkaloids
N
N
N NH
C
H H3C C
O H
, ,
O
CH2
C
CH3
O

Salicylates
Pyrrolizidine alkaloids
Flavones
568 Appendix Q
Isoflavones
N N O
C
, ,
O
H2N
CH2 H N CH3
C
, C5H13PO∗, CH3
H2N
C O
H2N
C6H5CH2CHNH2
Salicylates (also see m/z 138)
OH
Alkyl phenols
Terpenes
CH3OC6H4CH2–, C8H9O, (CH3O)3Si–, (C2H5)2SiCl, (CH3)2CBr
O
CH3
C3H7S–CHSH, C6H5CHOCH3
H2C
H3C
N O
(CH3O)2Si(CH3)O–, H P
(CH3)2N
HOC6H4CHCH3
*
From tributylphosphine oxide.

Δ3-ketosteroids
C6H5CO2 + H,
HO
CH2
,
O2N CN

Pyrethrin I
Benzoates (by double hydrogen rearrangement. The ester
must be ethyl or higher.)
Trichlorobutenes
CF3CH=CHC(O)–, (HO)2C6H3CH2–, C6H5CH2S–
CH3
C
HC CH
CH3C6H4S–, FC6H4C(O)–, C8H11O,
C C
H3C O
CH3
H3C CH3
C2H3SO4, –(CH2)2SO3CH3,
CH3
C6H5SCH2–, CH2FC6H4CH2, –OS(O)2OCH2CH–

Suggests an alkaloid in certain cases
Aliphatic cyanides (also may see m/z 96, 110, 138, 152, etc.)
Testosterone (also may see m/z 124, 288, 246)
570 Appendix Q
C4F4, (CH3O)2P(O)CH3, C8H12O,

H3C CH2
C C ,
O N O
O
N O C CH2
, N
H3C O CH2 H

C6H5SO (e.g., the base peak in diphenylsulfone) (should also
observe m/z 141)
C4F4H, ClC6H4CH2–, C6H5CHCl–, (CH3O)2P=S, C7H9O2,
CH3
CH3
S C

O
C CH3
CF3C(O)NHCH2–,
N
F
C
C , C CF2 , –CF CF CN,
F 2 2
F3C
CN
F N
C C
C4F4H2, C , O N O,
N O H
H2C H
H2C CH2 C
–(CH2)6NCO,
N C C
CH2
H

Iodides

Iodo compounds
Naphthyl compounds:
I, CF3SCN, C4F4H3, CH2=CHCF2CF2–,
CN
C C8H15O, C9H19, C6H5CF2–
H
H H
C(O)OCH2CF3, C7H15N2, R C C C OH ,
H
H3CO OH
P
H3CO OH

Loss of HI from iodides
Quinolines
Naphthalene
FC CF2
FC O
–CH2CH2C(O)N(C2H5)2, C3F4O, –CF2CF2C(O)–

C3F3Cl, HI, C2N2F4, C3H3Cl2F, ClC6H4O + H,
–CH2CH(CH3)CH2N(CH3)C3H7,
–CH2CH(CH3)CH2N(CH3)C(O)CH3
H
C CH2
+
(CH3)3SiO C
H
(from the A ring in TMS derivatives of steroids)

572 Appendix Q

Adipates:
O
C +
OH
C
O
(CH3)3Si–O–CH–CH=CH2
C2FCl2O, C6F3, C2Cl3, C3H4FCl2, C6H5CH=CHCN,
–CF2Br, C10H9, CF3CH=CCl–, H2N(CH2)6NHCH2–
CH3OC(O)C(CH3)2C(O),
–CH2C(O)–CH2CH2C(O)–OCH3

Indoles
C6H4FCl, (CH3)2CH–CH=C(OH)OC2H5,
C
S
C6H10O3, C9H8N, CH2 N
CH2
C
O
CH2
CN
–CF2–CF=NCl, , O
NH C
(CH3)2NCH=COC2H5
Cinnamates (C6H5CH=CHC≡O)
Fluorocarbons (C3F5)
–CF2–CF=CF2, CF3CF=CF–, CF3C=CF2, CHF2CF2OCH2–,
C6H2F3, CH3OCF2CF2–
CH2R
C9H7O m/z 131
O

Benzimidazoles
C6H3F3, F2C=CCl2
A Cl B Cl
116 F2C CF F2C

CF
116 > 132 A
116 F2C CF F2C CF
132 Cl
Cl
(CH3)3SiOCH2NCH3, C9H10N,
H NH2
C
C
H CH2
C6H4
CH3P(O)Cl2

H O
C C OC2H5
H3CS

Acetanilides
CH3SCH–C(O)OC2H5, CH3C6H4–C(CH3)2
O
H3C
O CH3 C
Si
Si , , CF3CH2CF2–,
H
H3C CH3 O
CF3CF2CH2–, CHF2CHFCF2–, HC C ,
H3C 59 103 H 133

H C O CH2 C
HO CH2 CH2 O
H
–SiCl3
CH3C5H4Mn–
CH3C(CF2)CH2NHC(O), –CF2NHCF3
C6H5C(O)NHCH2
574 Appendix Q
CH3 N C2H5
N ,
CH2
CH3

Adamantanes (C10H15), C6–C18 n-alkylbromides (CH2)4Br (with
an isotope peak at m/z 137)
C6H5C(OH)C2H5, C6H5C(O)OCH2–
PTH-amino acids,
O
H3CO
–CF2CF2Cl, CF3CFCl–, CF3CF2O–,
CF3OCF2–, C8H7S, C6H5Si(CH3)2, C6H5Si(H)2CH2CH2–,
O
N C S , H 2C
O CH2
[(CH3)2N]2P(O)
O2N(C4H6)CH2–, C5F4, CH2N(CH2CH2CN)2 (also should observe
peak at m/z 54)
C9H13O
Decalins
C5F4H, S –(CH2)3SO3CH3, (C2H5O)2P(O)
C O
Salicylate OH and [M + H]+ m/z 139
OH
Nitriles [(CH2)8CN] (also may see ions at m/z 96, 110, 124, etc.)
Base peak in dicyclohexylamine and nitroanilines
C5H5FeOH, C2F6, (CH2=CHCH2)2Fe (m/z 110, 124, 138, and 152

suggest nitriles; may observe [M – 1]+ instead of M+•)
Salicylates (protonated salicylic acid) also may have an
intense peak at m/z 138, N-TFA, n-butyl serine
O
N N C
,
Cl Cl
C5F4H3, CF3CH(CH3)CH2C(O), CF2CF2C(CH3)=C–

Methyl esters of dibasic carboxylic acids > dimethyl suberate
(usually have a series of peaks at m/z 84, 98, 112, 126, 140, etc.)
N-TFA butyl ester of alanine
O
N C
CH3
C4F4Cl, C3Cl3,

Naphthalenes [C11H9 (alkyl naphthalenes should also have m/z
91)]
O
O CH2 HN C
, C6H5SS–, O H
C C C CH2
F3C O CH2 HN C
O
O O
C C4H9 , C7F3, C4H7Cl2O,

C C
H 3C H
C H
OH , C8H17N2,
Cl
C6H5SO2 (also should observe m/z 125)
CH2
– CF2CF = CHC(O)F, – CF2CF = CHCH2SH
576 Appendix Q

(C4H9)2NCH2–
C10H8N (from quinolines)
–CF2CF2N3

Indole and indoline alkaloids
–C(O)(CH2)4CO2CH3 from dimethyl adipate
(CH3OC(O)C=CHC(O)CH3)
C4F5, C8H15O2, –C(Cl)=C(Cl)CH2Cl, –CH=C(Cl)CHCl2,
O
O C C2H5
–C(Cl)=CHCHCl2, (C4H9)2SiH,
H2C C O
CH2

Indoles
H3C
C OC3H7
C
H3C
NH
H3 C
CH
NH

The loss of CF3CF2CN has been seen from a compound whose
probable structure is (CF3)2C=CFC(CF3)=CFN(CH3)2
Tetralins
CF3OCH2CF2
Cl
CF2
, H2C C , CFClBr, CF3C6H4–,
CF3
Cl
CF3CH = CHCF2–, C4F5H2, CCl3CH2CH2–,
O O
C OCH3 C OCH3
H3C H3C
H C OH C H
–CCl2CH2CH2Cl, H
C C C C
H3C H H3C
H OH H
,

CF3CF2C=NH
CFClBrH, C6H5CF3, isomers of
Cl
Cl

CF3C(O)CF2–, C3F5O, CF3CCl=CF–, C3F4Cl
CH3
H
C
CH3 H3C
, O , C5H11OSiO2
H Si Si(CH3)3
CH3 H3C
C
CH2
C10H11O
578 Appendix Q

Aminopurines
CH2
HN
N
N , C6F4, C2FCl3, C6H3F2Cl,
NH
N
C
O
C6H5CH2CHN(CH3)2,
(CH3)2N

Esters of phthalic acid*:
O
C
+
OH
C
CO2C2H5
CF3CH2OCF2–, C2H5C6H4C(O)–, C6HF4, –CF2SO3F,
C C3H7
O
FCl2CHCl–, , –CF2CH2CF2Cl,
H
N
C3H7
CH2
Si H
C3H7 H5C2
Cl
N
, H
C9H13N2
Steroid alkaloids
C3F6H2F4, CF3CF=CF2, C3F6
Loss of CF3CFClO–
*
m/z 149, 167, and 279 suggest dioctyl phthalate or di(2-ethylhexyl) phthalate.

C9H15C(O), C5H11CH=CH–CH=CH–C(O)
OCH3 H3CO CH2

C
OCH3,
H3CO
(CF3)2CH–, CF3CCl2–, CFCl2CF2–, CF2ClCFCl–, C2F3Cl2, C6H3F4

(CF3)2N–, C2F5NF
N-TFA, n-butylthreonine
H
N
C (formation of isocyanate gives m/z 153)
Cl O
O
H O
C C
F3C
N CH3
CH3
O2N

Loss of C8H17 + C3H6 from steroids (alkyl chain at C17)
Loss of
Br

CF3C(O)OC(CH3)2–, C5F5, CH3C6H4–SO2–,
CH2CH2I, C4H9SiCl2–
580 Appendix Q

(C4H9)2NC(O),
CH3
N C C
, H3C N CH3
H17C8 CH2 H3C CH3
O
C5F5H, C9H18NO
O
S CH2 S
, O
Cl OH
(CH3C(O)O)2CHCH=CH–, C5F5H2, ClC6H4NO2

C12H14
CH2–C(O)CH2CH2CH2CH2C(O)OCH3
Trichlorobutenes, C4H5Cl3
The loss of –C(O)OSi(CH3)2C(CH3)3 is characteristic of TBDMS
derivatives of amino acids
Cl
C6H5CCl2–, CH2
Cl
F3C N
C6H5SCF2–, (C4H9O)2CH–, C , –CF2CF2C(O)OCH3,
F2C N
O
O
S F 3C
C
O , C OCH3
F
F
NH
, [(CH3)2N]3Si–,
F3C
NCH2
,
F3C N
NH2
N
Cl H
+
NH
Cl
CCl2Br–, CHF2CF2OCH2OCH2–
CH3
H5C2 C4H9
N , C4F6, N
H5C2 CH2
H3C CH3
H7C3 C
CH2Br, N N ,
H3C H3C CH2
CH2CO2CH3
H3C C
, CO2CH3
H5C6
CH2
CF3CF2CH2OCH2–, CHF2CHFCF2OCH2–
CF3CH2CF2OCH2–, C3F3Cl2, C4F6H, C3F4ClO,
582 Appendix Q
O
O
C OCH3
OCH3 , ,
C
H 5C 2 C
OC2H5
H5C6

CCl3CCl–, –CF2N=CFCF3, C4F6H2, C6H3FCl2, C7H10Cl2
Dinitrotoluenes
C13H9,
, CCl3CHCl, –Sn(CH3)3
(Sn isotope peaks at m/z 161, 163, and 165)

O
P
, C6H2F3Cl,
H3CO NHSi(CH3)3 S
S

O , CF3CFHOCF2–, CCl3CF2–, C6F5–,
P
H3CO Si(CH3)3
CFCl2CFCl–, CF2ClCCl2–, (C6H5)2CH, C2F2Cl3

Certain phthalates:
Cl
(H3C)C

Dichlorophenyl phenyl ethers
CF3C(O)NH(CH2)4–, C6H9F3ON, C6F5H

Loss of C3F7 from perfluoro compounds
H3C CH2 O CH OH
C
, CF3CF2CF2–, C6F5H2
O
C10H21C(O)
(CH3)2N
, C2F4Cl2,
Cl CH2
, (C5H11)2NCH2–
O2N

Loss of
O
F S +F

O
HO
OH
N P + H
OH
584 Appendix Q

Cl
OH
Si , , CF3C6H4C(O),
H17C8 CH3
Cl N N
C
HC OC2H5
C8H5F3O, , CF3C6H4N=N–
H2C OC2H5
C

*
–CH2N(SiC3H9)2loss is observed when
HO
CH2
C N(TMS)2
H
or –(CH2)3N(TMS)2 is present
C
CSi(CH3)3
C5F6H, ,
H
C CH3
C Si ,
CH3 CH3
H
SO2 O H2C
OH
C C OCH3
, H CO CH2 C
3
Cl
O

CN
C
F
F3C C , C5F6H2
F
F
*
Apparently two TMS groups can add to the amino group, especially for –(CH2)nN when n >2.

SnC4H9(m/z 173, 175, 177)
F3C O CHF
C
C6H5NHC(O)CH2C(O)CH3, C5H2F6, O CHF ,
C
OC2H5
(C4H2F5O2), O , (C4H9)2SiCl

C4F5Cl, CF2=CFCF=CFCl
C6H5CHOSi(CH3)3, C3F3Cl2O, (CF3)2CHC(O)–, C4HF6O
(CF3)2C=C•–OH
C10H11O3

C6H3Cl3
C6H5CH2OC(O)CO2H

C4F7
(see tetraphenylsilane)
(C6H5)2Si–
F5 O

C2FCl4, –CF2CF2SO2F, –CFCl2CCl2–, (C6H5)2COH, (C6H5)2SiH
C C8H17
H 3C N
CH2

C8H11NO2S
586 Appendix Q
Tributyl citrate (MW = 360 Da)
+H
CH2 , (C2H5O)2PS2,
N O
(CH3)2SnCl, (m/z 181, 183, and 185; isotopes for Sn)

O
CH2 C
H2C N N CH2 O CH3 (C6H5)2CF–,
C9H19N3O, C11H21O2, C10H17O3, C4H9OC(O)(CH2)4C(O)–

(m/z 185 and 129 suggest dibutyl adipate)
C6F6
C13H15O, C6F6H
NH
F 3C C NH2
CF2 N C
O Cl
CH2 O
C CH2
F3CO
C Cl , C C
F3C N NH
CH3 H
H

m/z 191, 204, and 217 suggest a TMS hexose (CH[OSi(CH3)3]2)
CH3 OH
H3C
C CH2
H 3C
C2H5

(m/z 193, 191, 189)
–SnSi(CH3)3
C5F7, (C2H5O)3SiOCH2–
C O
(CH3)3SiO

C3F2Cl3O, C5F7H2,
CF2
F3C
NH
H2C
CH2

C5H3F7,
C CN
H3CO

O
C4F7O, O , C13H9O2

Loss of two CD3SiOH groups from deuterated TMS derivative
(e.g., cholic acid)
CH2
H13C6 C6H13
588 Appendix Q

(C4H9)3Si–
CF3CF2CF2OCH2–
C4F8

Appendix Q - Ions For Determining Unknown Structures

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Appendix Q - Ions For Determining Unknown Structures

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A P P E N D I X Q

IONS FOR DETERMINING UNKNOWN

[M + 1]+ Possible Precursor Compounds

Some fluorinated compounds (e.g., C6F5–CH2OCH2C≡CH)

Segmented fluoroalcohols (some even lose •H and HF)

[M – 15]+ Possible Precursor Compounds

CH3OCH = CH2, CH3OCF = CF2, H3C S CH3

Simple aromatic acids

[M – 21]+ Possible Precursor Compounds

[M – 27]+ Possible Precursor Compounds

Loss of CH2O from

(see dioxane, dioxolanes, and epichlorohydrin)

Primary straight-chain alcohols

[M – 33]+ Possible Precursor Compounds

[M – (H2O + OH)]+ from certain dihydroxy and polyhydroxy

Cyclic carbonate compounds

Segmented fluoroalcohols such as (loss of H2F2)

Dinitriles (may have m/z 41, 54, and 68)

C3H4, CN2, C2O, CH3C≡CH, CH2=C=CH2, C2H2N, – CH2C≡N

m/z 69, 41, and 86 suggest segmented fluoromethacrylates**

N-Acetylated compounds (acetamides)

Simple purines (loss of cyanamide)

Loss of ketene from bicyclic structures (e.g., for camphor)

Ions for Determining Unknown Structures 531

C3H6, C2H2O, CNO, CH2N2, C2H4N, CH3N=CH–

(CH3)2N– also should observe m/z 44

C3H7OC(O)R, C3H7X, C3H7NO2

[M – 44]+ Possible Precursor Compounds

Vinyl alkyl ethers

(CHO + F) from fluoroaldehydes

(from branched dinitriles)

Indicates a cyclohexyl ring (m/z 55, 83, and 41)

Base Next Most Compound Highest m/z

55 82 54 67 27 1,6-Hexanediol diacrylate 113

[M – 56]+ Possible Precursor Compounds

[M – 57]+ Possible Precursor Compounds

Thiocyanates and isothiocyanates

Rearrangement ion of 2-methylaldehydes

(CH3)2CNH2, (CH3)3CH, C3H8N

(CH3)2NCH2– (sometimes an m/z 42 peak also is present),

(look for m/z 59, 44, and 72)

(CH3)2COH (tertiary alcohols)

Largest peak in the mass spectrum of propylene glycol ethers

CH3OCH2CH2– (diethylene glycol dimethyl ether)

CH3CHOHCH2–, C2H5OCH2–, (CH3)2COH

CH3OC(O)–, CH3CHCH2OH, C3FH4

Peaks at m/z 31, 45, and 59 reveal oxygen in alcohols, ethers,

m/z 60 with an m/z 58 peak suggests CH3C(O)NH + 2H C3H5F

Base peak in 1,2-difluorobutanes

Primary thiols (CH2CH2SH)

m/z 61 and 89 suggest sulfur-containing compounds (RSR′)

TMS derivatives; for example,

CH3CH2CHF–, CH3C(O)C + 2H, CH3CFCH3

[M – 65]+ Possible Precursor Compounds

Certain sulfones (HSO2)

m/z 67, 81, 95, 109, etc. suggest 1-acetylenes

C5H8 (cyclopentane derivatives), –CH2CH2CH2CN, NCCH2C(O)

Abundant Ions Compound MW

69 41 87 39 Ethylene glycol monomethacrylate 30

[M – 70]+ Possible Precursor Compounds

If the mass spectrum has a large peak at m/z 42, check

[M – 72]+ Possible Precursor Compounds

[M – 73]+ Possible Precursor Compounds