Alcohols, Ethers and Amines Pavia 8.

8 N
Pavia 8.8 N‐‐O,T

1-hexanol (C6H14O, M = 102) 56

M–46
E.I.

nds (SDBS)
43

pectral Database for Organic Compoun
M–59

31 69
M–71 M–33
84
102
M–18
M+

Sp
m/z = 31 Base peak M–18
m/z = even !! ??

Summary: Alcohols 
y
1. Weak M+ peak
2. α‐cleavage of an alkyl radical
3. Dehydration
4. Dehydration with loss of CH2=CH2
Mechanisms for Dehydration of Alcohols (M‐18)
Thermal dehydration of neutral molecule 
OH E.I.
C6H12
heat
(inlet system)

Fragmentation of radical cation
OH C6H12 H2O

2-hexanol (C6H14O, M = 102) 45

M–57
E.I.
nds (SDBS)
pectral Database for Organic Compoun

69
M–33
84 87 102
M–18 M–15 M+
Sp

OH O O

CH3
 56 70
Which is which?
43
(all C7H16O; M = 116)

1-heptanol
98 2,2-dimethyl-3-
83
pentanol
59 3-ethyl-3-pentanol

41
87

69
101

87
45

69
98

diisopropyl ether
(C6H14O, M = 102) 45
M–57
E.I.
Spectrral Database for Organic Compounds (SDBS)

87
M–15

102
M+
Summary: Ethers 
1. α‐cleavage of alkyl radical
2. C‐O bond cleavage

dibutyl amine (C8H19N, M = 129) 86

M–43
E.I.
nds (SDBS)

The Nitrogen Rule:

C,H,N,O,S
C H N O S molecules
l l with
ith
pectral Database for Organic Compoun

an odd molecular mass

must contain an odd
number of nitrogen atoms

129
M+
Sp
 Which amine?
44
M– 85
1-methylheptylamine (C8H19N, M = 129)

58
M–71
M+
129

E.I.
E.I.

M+
129
Spectraal Database for Organic Compounds (SDBS) Sp
pectral Database for Organic Compoun
nds (SDBS)
 43
Identify each
31
compound

59 73 There is one alcohol,

102 one ether and one
amine
57
45

69 87

102

86

30 58
101

E.I and C.I of tri‐n‐butylamine

C12H27N (MW = 185)
science.widener.edu/svb/masssspec/ci.html

E.I.

C.I. (CH4)
Aldehydes and ketones Pavia 8.8 P
Pavia 8.8 P‐‐Q

propanal (C3H6O, M = 58)

58 E.I.
29 M+
M–29

nds (SDBS)
pectral Database for Organic Compoun
57
M–1

Sp

2-butanone (C4H8O, M = 72) 43

M–29
E.I.
nds (SDBS)
pectral Database for Organic Compoun

72
M+
57
M–15
Sp

O O O

C
CH3 CH3 CH3
 hexanal (C6H12O, M = 100) 44
M–56
56 E.I.
M–44

nds (SDBS)
pectral Database for Organic Compoun
100
M+

Summary: Aldehydes and Ketones Sp

1. α‐cleavage: C–C(=O) and C(=O)‐H

2. McLafferty rearrangement for CH‐C‐C‐C(=O)
2-hexanone 43
(C6H12O, M = 100) M–57
E.I.

Spectral Database for Organic Compoundss (SDBS)
58
M–42

29
M–81 85 100
M–15 M+

O H
O

C
H2C CH3

benzaldehyde (C7H6O, M = 106) 106

77 M+
M–29 E.I.
105
nds (SDBS)

M–1
pectral Database for Organic Compoun
Sp
 acetophenone (C8H8O, M = 120) 105
M–15
E.I.
77

nds (SDBS)
M–43

pectral Database for Organic Compoun
120
M+

Which is which? Sp

O
H C(CH2)8CH3
O
CH3 C(CH2)7CH3
O
CH3CH2 C(CH2)6CH3
O
CH3(CH2)2 C(CH2)5CH3
Which ketone?
105
M–43
E.I.

Spectraal Database for Organic Compounds (SDBS)
77
M–60

148
M+

Carboxylic acids and derivatives Pavia 8.8 R=S

propanoic acid (C3H6O2, M = 74)

E.I.
29 74
nds (SDBS)

M–45 M+
pectral Database for Organic Compoun

45
M–29 73
M–1
57
M–17
Sp
butanoic acid (C4H8O2, M = 88) 60
M–28
E.I.
pectral Database for Organic Compounds (SDBS)

43
45
M–45
M–43 71 88
M–17 M+
Sp

H
O O

C
OH H2C OH
Summary: Carboxylic acids
1. M‐1
2. Cleavage of OH
3. Cleavage of R‐C(O) → [CO2H]+, M = 45
→ R+

4. McLafferty rearrangement for CH‐C‐C‐C(=O)OH

benzoic acid (C7H6O2, M = 122) 105

M–17 E.I.
122
77 M+
nds (SDBS)

M–45
pectral Database for Organic Compoun
Sp
 methyl acetate (C3H6O2, M = 74)
43 E.I.
M–31

nds (SDBS)
pectral Database for Organic Compoun
74
M+
59
M–15

Summary: Esters Sp

1. Cleavage of C(=O)–OR
2. α‐cleavage of R‐C(O)
Which ester?

E.I.
105

Spectraal Database for Organic Compounds (SDBS)
77

51 148
120 M+

43
Identify each
58 compound
All of these
compounds are
101
102 esters

74

43
57 84

58 86

43
75
101
101
Halogen Containing Compounds Pavia 8.8 V

2-chloropropane (C3H7Cl, M = 78 [35Cl])

43 E.I.
M–35

ds (SDBS)
Spectral Database for Organic Compound
63
M–15 78     80
M+ M+2

Summary: Alkyl halides (1)
C‐Cl bond cleavage
α‐cleavage

43 63 78     80
M+–35 M+–15 M+ M+2
 1-chloropropane (C3H7Cl, M = 78 [35Cl])

E.I.
42

ds (SDBS)
M–36

Spectral Database for Organic Compound
78
M+

Summary: Alkyl halides (2)
Dehydrohalogenation (‐HCl: ‐36)

42 78
M+–36
36 M+
 2-chloroheptane (C7H15Cl, M = 134 [35Cl])

56 E.I.
M+–78

Spectraal Database for Organic Compounds (SDBS)
98
M+–36
134  136
M+ M+2

Summary: Alkyl halides (3)
Dehydrohalogenation and loss of an alkene
 2-bromopropane (C3H7Br, M =122 [79Br])

E.I.
43
M–Br

Spectraal Database for Organic Compounds (SDBS)
122  124
M+ M+2

SUMMARY: SOME COMMON FRAGMENT PEAKS
see Pavia App 12
Peak Fragment  Interpretation
lost
M 1
M–1 H• aldehydes, 3
aldehydes, 3° alcohols, cyclic amines
alcohols, cyclic amines
M–2 Multiple H •  2° alcohols
M–3 Multiple H •  1° alcohols
M–15 CH3 •  methyl groups 
M–17 HO •  alcohols, phenols, carboxylic acids
M–18 H2O alcohols
M–26 HC≡CH
M–27 • HC=CH
2
M–28 CH2=CH2 cyclic alkanes, alkenes
CH3CH2CH2C(=O)X [McLafferty rearr.]
M–19,35/37,79/81 • halogen
M–15,29,43,57,71,… • alkyl
M–31,45,59,73,87…  • alkoxy esters, ethers
Peak Fragment Interpretation
observed

43 H2C=C=OH from 1° alcohol

42 H2C=C=NH2 from 1° amine (R

from 1 amine (R–CH
CH2NH2)
H2C–CH=CH2
allyl cation

36 H2C–C≡CH
propargyl cation from alkyne

77 C6H5+ from substituted phenyl

91  C7H7+ from C‐substituted phenyl 

tropylium cation

WORK AS MANY PROBLEMS AS

WORK AS MANY PROBLEMS AS 
POSSIBLE!
Pavia, chap 8 questions:
7 (a)‐‐(x), 8, 9, 10, (a)
7 (a) (x), 8, 9, 10, (a)‐‐(f), 11, (a)
(f), 11, (a)‐‐(g), 12 (a)
(g), 12 (a)‐‐(c), 13, 
14, 15 (a)‐
, ( )‐((b))
14, 15 (a)
Compound X revisited, yet again
Analysis of  fragmentation ⇒ STRUCTURAL information 

mpounds (SDBS)
E.I.

Spectral Database for Organic Com
Fragmentation:

Structure contains: 

Problem sets based on M.S. alone
http://science.widener.edu/~svanbram/chem465/htmldocs/ms_unk.html
Intensities of peaks are provided, you need to download free spectral 
visualization software to view actual spectra
Reporting MS Spectra in Papers and Progress Reports

MS (EI, 70 kV): 
m/z 91 (tropilium, 100%), 207 (M 
m/z  , 28%), 234(M+, 35%), 235 (M
91 (tropilium, 100%), 207 (M – CH2CH3, 28%), , 35%), 235 (M
B C D
Fragments that help in  molecular ion M+1 pe
base peak structure determination that indic
about
structu
A Ionization technique/method (e.g., EI, CI, FAB, MALDI). isotope

B Mass
C Assignment of the peak to a particular ion
D Height of the peak relative to the base peak (100%)

Reporting HRMS Spectra in Papers and Progress Reports

HRMS (EI, 70 kV):
m/z 101.07094. Calc. for C
m/z  O, 39%, Δ = 3 ppm. 
101.07094. Calc. for C4H9N2O, 39%, Δ 3 ppm.
B C D E

A ionization technique/method (e.g., EI, CI, FAB, MALDI).
B mass
C Assignment of the peak to a particular ion
D Height of the peak relative to the base peak (100%)
E The difference between the experimental value of molecular weight a
value calculated for the putative molecular formula, in ppm:
Δ = | Mexp – Mcalc | × 106/Mexp
 Determine the structures of the
Determine the structures of the 
compounds for which the mass spectra 
are provided on the following slides. In 
some cases you might not be able to 
id
identify a single compound.
tif i l d

Exact mass = 114.1043
⇒ Exact mass = 116.1203

Exact mass = 169.9735

Exact mass = 150.0041
 Exact mass = 100.0893

Exact mass = 74.0363

Exact mass = 73.0896
⇒Exact mass = 56.0261

Exact mass = 138.0687

Exact mass = 122.0733
 Exact mass = 102.0678

Exact mass = 113.0845

Exact mass = 208.0094
 Exact mass = 98.0740

Exact mass = 126.1041

Exact mass = 116.0842