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IR Frequencies
IR Frequencies
C
C
1050-1150
alkoxy C-O
1000-1350
not very useful
not used
sp2 C-X double bonds
1600-1680
1640-1810
expanded table
on next page
1640-1690
1100-1350
acyl and phenyl C-O
1250
2100-2250
2240-2260
Stronger dipoles produce more intense IR bands and weaker dipoles produce less intense IR bands (sometimes none).
H
C
3000-3100
sp3 C-H
(see sp2 C-H bend
patterns below)
2850-3000
sp3 C-H
2700-2760
2800-2860
aldehyde C-H
(two bands)
3300
sp3 C-H
(sp C-H bend 620)
H
C
O
C
3100-3500
primary NH2
(two bands)
3100-3500
secondary N-H
(one band)
3200-3400
2500-3400
alcohol O-H
acid O-H
2550 -2620
(very weak)
thiol S-H
Ketones
Esters
Acids
O
C
H
saturated = 1725
conjugated = 1690
aromatic = 1700
Anhydrides
Amides
saturated = 1715
conjugated = 1690
aromatic = 1690
nitro
Acid Chlorides
O
NR2
saturated = 1650
conjugated = 1660
aromatic = 1660
6 atom ring = 1670
5 atom ring = 1700
4 atom ring = 1745
3 atom ring = 1850
alkene substitution
pattern
Cl
saturated = 1800
conjugated = 1770
aromatic = 1770
N
O
asymmetric = 1500-1600
symmetric = 1300-1390
Very often there is a very weak C=O overtone at approximately 2 x (3400 cm-1).
Sometimes this is mistaken for an OH or NH peak.,
absorption
frequencies (cm-1)
due to sp2 CH bend
descriptive
aromatic term
aromatic substitution
pattern
absorption
frequencies (cm-1)
due to sp2 CH bend
H
C
monosubstituted
alkene
R
C
H
C
H
C
R
C
R
C
monosubstituted
aromatic
675-730
(broad)
ortho disubstituted
aromatic
trans disubstituted
alkene
960-990
geminal disubstituted
alkene
880-900
trisubstituted
alkene
790-840
tetrasubstituted
alkene
985-1000
900-920
690-710
730-770
cis disubstituted
alkene
saturated = 1735
conjugated = 1720
aromatic = 1720
6 atom ring = 1735
5 atom ring = 1775
4 atom ring = 1840
saturated = 1715
conjugated = 1680
aromatic = 1690
6 atom ring = 1715
5 atom ring = 1745
4 atom ring = 1780
3 atom ring = 1850
R'
none
735-770
meta disubstituted
aromatic
para disubstituted
aromatic
680-725
750-810
880-900 (sometimes)
790-840
3
units = cm-1
4000
2500
3000
3500
sp C-H
stretch
1700
2000
sp3 C-H
stretch
C C
thiol S-H
stretch
sp2 C-H
stretch
C=O
stretch
aldehyde C-H
stretch
geminal
acyl C-O
phenol C-O
tri
N-H bend
ortho
2o N-H
stretch
nitro
meta
nitro
para
3000
2500
1700
2000
expansion of alkene & aromatic sp2 C-H bend region (units = cm-1)
700
600
800
900
mono
cis
trans
C=C stretch
aromatic
1o N-H2
stretch
1000
mono
alkoxy C-O
3500
sp C-H
bend
C=C stretch
alkene
alcohol O-H
stretch
4000
C=N
stretch
C N
600 500
800 700
600 500
500
mono
cis
trans
geminal
tri
mono
mono
ortho
meta
meta
meta
para
1750
1800
1650
1600
Conjugated C=O
lies at lower cm-1
aldehydes
O
1725-1740 (saturated)
1660-1700 (unsaturated)
C
sometimes lost
2860-2800
in sp3 CH peaks
2760-2700
aldehyde C-H
(both weak)
ketones
1710-1720 (saturated)
1680-1700 (unsaturated)
1715-1810 (rings: higher
in small rings)
esters - rule of 3
O
1735-1750 (saturated)
1715-1740 (unsaturated)
1735-1820 (higher in small rings)
acyl
O
alkoxy
acids
O
1700-1730 (saturated)
1715-1740 (unsaturated)
1680-1700 (higher in small rings)
acyl
C
acid
O
nitriles
C
a little lower
when conjugated
2150
(variable intensity)
not present or weak when symmetrically
substituted, a little lower when conjugated
C
sp C-H stretch
sp C-H bend
3300
sharp, strong
620
not useful
alkenes
sp2 C-H stretch
3000-3100
650-1000
(see table for
spectral patterns)
1600-1660
weak or not present
aromatics
sp2 C-H stretch
3050-3150
690-900 (see table),
overtone patterns
between 1660-2000
alcohols
alcohol
O
3600-3500
1000-1260
(3o > 2o > 1o)
2550 (weak)
(easy to overlook)
alkoxy
C
amines
1630-1680 (saturated)
1745 (in 4 atom ring)
C
H
N
o
N
H
2o
acid chlorides
1800 (saturated)
1770 (unsaturated)
anhydrides
O
acyl
C
2850-3000
thiols
thiol
amides
alkanes
sp3 C-H stretch
alkynes
2250
sharp, stronger
than alkynes,
H
N
N
1o
2o
1000-1350
(uncertain)
ethers
alkoxy
C
1120 (alphatic)
1040 & 1250 (aromatic)
nitro compounds
O
carbon-halogen bonds
usually not
very useful
5
Typical 1H and 13C NMR chemical shift values.
amine N-H
alcohol
1
amide N-H
S C H
thiols, sulfides
2.5
N
3.0
X C H
X = F,Cl,Br,I
10
8+
6
7
PPM
alcohols
ethers
esters
5+
5
ketones
no H
15
N C
amines, amides
with & without H
180
50
O
O
C
180
C C
with & without H
N C
no H
90
70
40
S
thiols, sulfides
with & without H
160
O
C
60
-
110
125
30
epoxides
with & without H
carboxylic acids
anhydrides
esters
amides
acid chlorides
no H
alcohols,
ethers, esters
40
20
aldehydes
with H
200
F 80-95
Cl 45-70
Br 35-65
I 15-45
220+
220
95
210
0.5
halogen
3.3 3
240
1.5 1.3
2.5
3.5
H
O C
aromatic C-H
10
thiol
SH
epoxide C-H
10
11
1.5
3+
7+
aldehyde C-H
12
2.5
benzylic C-H
carbonyl alpha C-H
alkene C-H
12
2.3
allylic C-H
2.0
C H
amines
80
50
180
160+
160
100-
100
60+
80
60
40
20
6
Calculation of chemical shifts for protons at sp3 carbons
H
C C C
Estimation of sp3 C-H chemical shifts with multiple substituent parameters for protons within 3 C's of consideration.
= directly attached substituent, use these values when the hydrogen and substituent are attached to the same carbon
= once removed substituent, use these values when the hydrogen and substituent are on adjacent (vicinal) carbons
= twice removed substituent, use these values when the hydrogen and substituent have a 1,3 substitution pattern
0.0
0.8
0.9
1.4
3.2
2.2
2.1
2.0
2.3
2.1
1.5
2.5
2.8
2.8
3.1
2.8
1.5
2.1
3.2
1.3
1.3
1.1
1.2
1.7
1.1
1.1
1.0
1.8
1.1
1.6
1.8
X = substituent
R- (alkyl)
R2C=CR- (alkenyl)
RCC- (alkynyl)
Ar- (aromatic)
F- (fluoro)
Cl- (chloro)
Br- (bromo)
I- (iodo)
HO- (alcohol)
RO- (ether)
epoxide
R2C=CRO- (alkenyl ether)
ArO- (aromatic ether)
RCO2- (ester, oxygen side)
ArCO2- (aromatic ester, oxygen side)
ArSO3- (aromatic sulfonate, oxygen)
H2N- (amine nitrogen)
RCONH- (amide nitrogen)
O2N- (nitro)
HS- (thiol, sulfur)
RS- (sulfide, sulfur)
OHC- (aldehyde)
RCO- (ketone)
ArCO- (aromatic ketone)
HO2C- (carboxylic acid)
RO2C- (ester, carbon side)
H2NOC- (amide, carbon side)
ClOC- (acid chloride)
NC- (nitrile)
RSO- (sulfoxide)
RSO2- (sulfone)
0.0
0.2
0.3
0.4
0.5
0.5
0.7
0.9
0.3
0.3
0.4
0.4
0.5
0.5
0.5
0.4
0.2
0.3
0.8
0.4
0.4
0.4
0.3
0.3
0.3
0.3
0.3
0.4
0.4
0.5
0.5
0.0
0.1
0.1
0.1
0.2
0.2
0.2
0.1
0.1
0.1
0.1
0.2
0.3
0.1
0.2
0.0
0.1
0.1
0.1
0.1
0.1
0.1
0.0
0.1
0.1
0.1
0.1
0.1
0.2
0.3
0.3
CH3 = 0.9 +
H3C
CH3 = 0.9 + ( + )
H3C C C
H
H C C C
H
C C C
a. methine b. methylene
d. methyl
H3C
CH2
CH3
HO
N
CH
O
H2C
H2C
e. methylene
f. methylene
c. methyl
Substituent
HHydrogen
RAlkyl
C6H5CH 2Benzyl
X-CH2Halomethyl
(H)/ROCH2alkoxymethyl
(H)2/R2NCH2aminomethyl
RCOCH2-keto
NCCH2-cyano
R2C=CRAlkenyl
C6H5Phenyl
FFluoro
ClChloro
BrBromo
IIodo
ROakoxy (ether)
RCO2O-ester
(H)2/R2NN-amino
RCONHN-amide
O2NNitro
RSThiol
OHCAldehyde
ROCKetone
HO2CC-acid
RO2CC-ester
H2NOCC-amide
NCNitrile
geminal
cis
trans
0.0
0.0
0.0
0.5
-0.2
-0.3
0.7
-0.2
-0.2
0.7
0.1
0.0
0.6
0.0
0.0
0.6
-0.1
-0.1
gem
0.7
-0.1
-0.1
0.7
-0.1
-0.1
1.2
0.0
0.0
1.4
0.4
-0.1
1.5
-0.4
-1.0
1.1
0.2
0.1
1.1
0.4
0.6
1.1
0.8
0.9
1.2
-1.1
-1.2
2.1
-0.4
-0.6
0.8
-1.3
-1.2
2.1
-0.6
-0.7
1.9
1.3
0.6
1.1
-0.3
-0.1
1.0
1.0
1.2
1.1
0.9
0.7
0.8
1.0.
03
0.8
1.0
0.5
0.4
1.0
0.5
0.3
0.8
0.6
trans
H
cis
CH3O
bH
C
aH
c
d
H H
C
C
O C
O
e
H
C
Hf
Substituent
HHydrogen
CH3Methyl
ClCH2Cholromethyl
Cl3CHalomethyl
HOCH 2Hydroxymethyl
R2C=CRAlkenyl
C6H5Phenyl
FFluoro
ClChloro
BrBromo
IIodo
HOHydroxy
ROAlkoxy
RCO 2O-ester
(H)2/R2NN-amino
RCONHN-amide
O 2NNitro
RSthiol/sulfide
OHCAldehyde
ROCKetone
HO2CC-acid
RO2CC-ester
H 2NOCC-amide
NCNitrile
ortho
meta
para
0.0
0.0
0.0
-0.2
-0.1
-0.2
0.0
0.0
0.0
0.6
0.1
0.1
-0.1
-0.1
-0.1
0.1
0.0
-0.1
1.4
0.4
-0.1
-0.3
0.0
-0.2
0.0
0.0
-0.1
0.2
-0.1
0.0
0.4
-0.2
0.9
-0.6
-0.1
-0.5
-0.5
-0.1
-0.4
-0.3
0.0
-0.1
-0.8
-0.2
-0.7
0.1
-0.1
-0.3
1.0
0.3
0.4
-0.1
-0.1
-0.2
0.6
0.2
0.3
0.6
0.1
0.2
0.9
0.2
0.3
0.7
0.1
0.2
0.6
0.1
0.2
0.4
0.2
0.3
ortho
para
H
meta
ortho
Example Calculation
2
H
1
CH3O
2H
H
3
CH2
4
5
H 6
H
7
0.8, shielded
H
shielding cone
from bond
CH2
2.6
H
7.2
O
C
10-12
H O
O
C
9.5
H
1.5
deshielded
H 3C
hydrogen
bonding
O H
H
C
O
C
15, hydrogen
bonded enol
CH3
CH3 Cl
3.0
CH3CH 2 Cl
CH3CH2CH 2 Cl
1.3
1.0
CH 3Cl
CH2Cl2
3.0
= 2.8
H 3C C
3.0
3.5
4.1
2.4
C H 1.9
C C H 3.0
R C
Ar
RO
ArO
RS
ArO
H
H
H
H
CCl4
6.4
C
H
5.8
Ph
3.7
H 2C
H 3C
1.3
? (oops)
H 3CH2C C
Ph (H3C)2CH C
H
C
4.2
C
H
4.0
8.2
H
7.5
H
Ph
3.5
H
6.5
O
H 2N
=?
3.0
H
H
H
H
H
H
bond anisotropy
produces deshielding Extra electron density via resonance produces
shielding effect on aromatic protons, especially
effect on aromatic
at ortho/para positions.
protons.
sp C-H
H C C H
CHCl3
2.6
0.9
0.9
7.2
= 1.9
5.3
= 2.3
7.7
H
C O
H 3C
2.1
H
C
H
7.3
4.9
C
H
4.6
O
N
O
H
H
H
H
Withdrawal of electron density via resonance
produces deshielding effect on aromatic protons,
especially at ortho/para positions.
O
10
Ha
increasing
one neighbor
proton = Ha
increasing E (, Bo)
perturbation(s) by
neighbor proton(s)
Eto flip proton
E2 (observed)
E1 (observed)
Bo
J1a
1
H1
C
H1
C
J = coupling constant
small difference in
energy due to differing
neighbor's spin (in Hz)
N + 1 rule (N = # neighbors)
J (Hz)
# peaks = N + 1 = 1 + 1 = 2 peaks
(ppm)
2. Two nearest neighbor protons (both on same carbon or one each on separate carbons)
observed
proton
H1
two neighbor
Ha protons
Hb
H1
E1
E2
J1a
E3
Bo
H1
C
J1b
J1b
N + 1 rule (N = # neighbors)
J (Hz)
J (Hz)
# peaks = N + 1 = 2 + 1 = 3 peaks
(ppm)
3. Three nearest neighbor protons (on same carbon, or two on one and one on another, or one each on separate carbons)
H1
observed
proton
three neighbor
Ha protons
C C
Hb
H1
Hc
Eto flip proton
E1
E2
Bo
H1
C C
E3
J1a
E4
J1b
J1c
J1b
J1c
J1c
N + 1 rule (N = # neighbors)
J (Hz)
J (Hz)
(ppm)
J (Hz)
# peaks = N + 1 = 3 + 1 = 4 peaks
11
Splitting patterns when the N+1 rule works (common, but not always true)
= group without any coupled proton(s)
N=1
N=0
N=2
H
H
C
N=3
H
H
C
H2
C
CH
CH2
CH3
CH
CH
CH
= calc or exp
CH
d, J=7
I=1H
N=1
t, J=7
I=1H
N=2
= calc or exp
= calc or exp
s, J=none
I=1H
N=0
CH
q, J=7
I=1H
N=3
= calc or exp
N=4
N=5
H
C
H
CH
CH3
CH2
CH
CH2
CH3
CH3
CH
CH
CH
CH2
CH2
CH2
CH2
CH
sex, J=7
I=1H
N=5
qnt, J=7
I=1H
N=4
= calc or exp
= calc or exp
N=6
N=7
H
H
C
CH
CH3
CH3
H2C
CH2
CH
CH2
H2 C
CH3
H
CH3
CH3
sep, J=7
I=1H
N=6
oct, J=7
I=1H
N=7
CH3
CH2
= calc or exp
= calc or exp
N=8
H2 C
CH3
CH3
non, J=7
I=1H
N=8
1 peak = 100%
s = singlet
d = doublet
t = triplet
1
1
1
q = quartet
qnt = quintet
sex = sextet
= calc or exp
sep = septet
o = octet
1
1
1
1
6
7
2
3
4
5
1 peak = 50%
1 peak = 25%
1
1
3
6
1 peak = 12%
1
10 10 5
1 peak = 6%
1
1 peak = 3%
1
15 20 15 6
1
21 35 35 21 7 1
relative sizes of
peaks in multiplets
(% edge peak shown)
1 peak = 1.5%
1 peak = 0.8%
12
Range
Typical
0-30 Hz
14 Hz
Hb
geminal protons - can have different chemical shifts
and split one another if they are diastereotopic
Range
Typical
6-8 Hz
= dihedral
angle
Range
0-3 Hz
1 Hz
Range
Typical
0-3 Hz
1 Hz
Hb
C C
Hb
7 Hz
Ha
Hb
C
C
Typical
Ha
Ha Hb
C
Ha
Range
0-12 Hz
7 Hz
depends on dihedral
angle, see plot of
Karplus equation
Range
Typical
0-1 Hz
0 Hz
Range
Typical
9-13 Hz
10 Hz
Range
Typical
1-3 Hz
2 Hz
Range
Typical
5-8 Hz
6 Hz
Range
Typical
2-3 Hz
2 Hz
Range
Typical
2-3 Hz
3 Hz
C
C
Hb
Ha
Ha
C
Hb
C
O
Ha
C
Range
Typical
0-3 Hz
2 Hz
Hb
Hb
C
Range
Typical
5-11 Hz
10 Hz
C
Hb
Range
Typical
11-19 Hz
17 Hz
C
C
Hb
C C
Hb
Hb
Ha
C
C C
bis-propargylic coupling
notice through 5 bonds
Range
Ha
C
Ha
sp / propargylic coupling
notice through 4 bonds
Ha
Ha
Hb
Ha
4-10 Hz
Range
H ortho
H meta
ortho 6-10 Hz
meta 2-3 Hz
para 0-1 Hz
Hpara
When J values are less than 1 Hz, it is often difficult to resolve them and a peak may merely appear wider and shorter.
Typical
9 Hz
2 Hz
0 Hz
13
Similar chemical shift information presented in a different format. Remember, proton decoupled
carbons appear as singlets. When carbons are coupled to their hydrogens, carbons follow the N+1 rule.
Methyls = q, methylenes = t, methines = d, and carbons without hydrogen appear as singlets = s.
DEPT provides the same information. Carbon chemical shifts are spread out over a larger
range than proton chemical shifts (they are more dispersed), so it is less likely that two different carbon
shifts will fall on top of one another. The relative positions of various types of proton and
carbon shifts have many parallel trends (shielded protons tend to be on shielded carbons, etc.)
CH2
CH3
Simple alkane
carbons
0 - 30 ppm
(q)
20 - 40 ppm
(t)
50 - 60 ppm
CH2 N
d
10 - 50 ppm
(t)
CH2 X
sp carbon (alkynes)
25 - 50 ppm
(t)
60 - 80 ppm d
(d)
50 - 70 ppm d
(d)
60 - 80 ppm
(d)
50 - 70 ppm
(s)
C
70 - 90 ppm
70 - 90 ppm
(s)
C N
sp carbon (nitriles)
60 - 80 ppm
(s)
C N
110 - 125 ppm
C
O
C
C O
CH X
30 - 60 ppm
(s)
CH N
35 - 55 ppm
(q)
(t)
CH3 N
30 - 50 ppm
(d)
CH O
55 - 80 ppm
(q)
sp3 carbon
next to nitrogen
CH2 O
CH3 O
sp3 carbon
next to oxygen
CH
R
180 - 220 ppm
14
Calculations for sp3 carbon 13C chemical shifts of functionalized carbon skeletons can be performed starting
from the actual shifts found in the corresponding alkane skeleton, and introducing corrections factors based on the
functionality present in the molecule. This assumes that the alkane 13C shifts are available, which is why several
examples are provided below.
Examples of Cn alkanes as possible starting points for calculation 13C shifts in ppm.
Approximate 13C shift calculation from scratch.
The calculated
carbon atom is:
primary
quaternary
tertiary
primary
-1.1
-3.4
secondary
-2.5
-7.5
-15.0
tertiary
quaternary
13
secondary
-3.7
-9.5
-1.5
-8.4
-15.0
(actual = 28.3)
-25.0
(actual = 34.0)
(actual = 47.9)
(actual = 27.2)
(actual = 19.5)
(actual = 8.5)
C shifts for various carbon alkane skeletons - useful starting points for calculating sp3 carbon chemical shifts
C3
C2
CH4
-2.3
15.8
5.9
C6
22.9
14.1
28.1
48.9
29.3
18.8
39.0
33.9
29.8
29.7
34.4
39.2
35.3
14.5
25.2
C9
14.1
39.2
C10
22.8
29.6
32.1
29.8
26.9
42.3
14.2
29.6
22.8
27.2
28.1
40.6
38.0
22.7
32.1
12.0
31.8
17.9
37.2
C8
14.1
18.1
17.5
27.0
36.4
29.5
15.0
14.7
48.3
33.4
11.0
9.1
22.9
32.0
31.9
20.3
27.0
25.6
29.7
19.5
14.1
23.1
32.0
11.8
36.5
11.4
29.9
32.1
34.4
8.9
30.4
19.2
22.7
29.3
22.9
36.3
14.4
30.2
29.0
11.5
41.5
22.6
14.1
20.6
32.9
C7
25.0
13.8
27.9
22.3
C5
25.4
25.0
22.7
22.9
14.1
C4
16.3
32.3
14.1
22.9
29.6
32.2
11.5
34.6
14.5
36.5
19.3
29.7
14.1
20.3
39.6
32.4
19.7
29.9
10.9
40.3
25.6
35.4
20.1
14.6
C correction C correction
C correction
15
C correction
CH3
-2
-2
CH2CH3
18
-2
-2
CH(CH3)2
26
-2
14
-2
C(CH3)3
32
-2
20
-2
C
H
CH2
20
-1
15
-1
CH
-4
-4
23
-2
17
-2
C correction C correction
C correction
C correction
OH
48
10
-6
44
-4
OR
60
-6
57
-6
51
-6
49
-6
NH2
28
10
-5
24
-5
NH(CH3)
38
-5
32
-4
N(CH3)2
45
-5
37
-4
-5
21
-5
-5
-5
O
O
C
R
O
H
N
26
C
R
NO2
62
58
16
C correction C correction
C correction
C correction
70
-7
67
-7
Cl
31
10
-5
36
-5
Br
20
10
-4
28
10
-4
-7
11
-2
11
-2
30
-3
24
-1
-3
31
-3
26
-3
22
-3
18
-3
O
C
H
O
C
CH3
O
C
OH
C correction C correction
C correction
C correction
20
-3
16
-3
25
-3
19
-3
-3
-3
33
-3
30
-3
SH
11
10
-3
12
-3
SR
22
-3
20
-3
C
OCH3
O
C
NH2
C
N
O
C
Cl
17
Additional starting point for calculating 13C chemical shifts (ppm) of substituted benzene rings (just a few possibilities)
Substituent
128 ppm starting point for
benzene carbon
3
Z1
0
9
12
10
11
20
19
8
9
9
11
12
15
2
2
12
7
6
6
13
-6
8
34
5
-5
-31
Substituent
-H
-CH3
-CH2CH3
-CH2CH2CH3
-CH2CH2CH2CH3
-CH(CH3)2
-C(CH3)3
-CH2F
-CH2Cl
-CH2Br
-CH2I
-CH2OH
-CH2NH2
-CH2NO2
-CH2CN
-CH2SH
-CH2CHO
-CH2COCH3
-CH2CO2H
-CH2=CH2
-CCH
-C6H5
-F
-Cl
-Br
-I
Z2
0
1
-1
0
0
-2
-3
-1
0
1
-1
-1
-1
2
0
-1
1
1
1
-3
4
-1
-13
0
3
9
Z3
0
0
0
0
0
0
0
0
0
0
0
0
0
1
-1
0
0
0
0
0
0
0
2
1
2
2
Z4
0
-3
-3
-3
-3
-3
-3
0
0
0
-1
-1
-2
1
-1
-2
-1
-2
-1
-1
0
-1
-4
2
-1
-1
Z1
29
34
28
18
10
22
23
22
37
20
4
10
18
12
16
-16
8
9
2
2
5
11
-43
-36
Substituent
-OH
-OCH3
-OC6H5
-NH2
-NHCOCH3
-NHOH
-NHNH2
-N=N-R
-NO
-NO2
-SH
-SCH3
-S(O)CH3
-SO2CH3
-SO2Cl
-CN
-CHO
-COCH3
-CO2H
-CO2CH3
-CONH2
-COCl
-Li
-MgBr
Z2
-13
-14
-11
-13
-8
-13
-16
-6
-8
-5
1
-2
-5
-1
-2
3
1
0
2
1
-1
0
-13
-11
Z3
1
1
0
1
0
-2
1
0
1
1
0
0
1
1
1
1
0
0
0
0
0
0
2
3
126
128
Z4
-7
-8
-7
-10
-4
-5
-10
-3
7
6
-3
-4
2
5
7
4
6
4
5
4
3
-3
3
4
134
naphathalene
136
124
pyridine
150
108
pyrrole
N
H
118
110
furan
143
126
thiophene
125
Additional starting point for calculating 13C chemical shifts (ppm) of substituted alkenes (just a few possibilities)
123 ppm starting point for alkene carbon
'
C
'
C
Z
C
2
'
C
C = 123 ppm + Zi
C
1
-1
-5
3
2
Z1
0
13
17
16
23
26
10
11
14
14
14
-6
12
Z2
0
-7
-10
-9
-12
-15
-6
-5
-4
-8
-7
6
-11
Substituent
-F
-Cl
-Br
-I
-OCH3
-O2CCH3
-N(CH3 )2
-NO2
-CN
-SCH2CH3
-CHO
-COCH3
-CO2H
-COCl
Z1
24
3
-9
-38
29
18
28
22
-15
9
15
14
5
8
Z2
-34
-6
-1
7
-39
-27
-32
-1
14
-13
14
5
10
14
18
radical cation
bond of an alkene
or an aromatic
>
2o R
> 1o R
>
CH3
X C
X C
radical cation
X lone pair electrons partially fill in loss of electrons at carbocation site via resonance. This
is a common fragmentation for any atom that has a lone pair of electrons (oxygen = alcohol,
ether, ester; nitrogen = amine, amide, sulfur = thiol or sulfide, etc.). Alcohols often lose water
(M-18) and primary amines can lose ammonia (M-17).
3. Branch next to a carbonyl (C=O) bondand possible subsequent loss of carbon monoxide, CO
R1
O
R1
C O
R1
R1
C O
loss of
R2
R2
radical cation
R1 or R2 can be lost from
aldehydes, ketones, acids,
esters, amides...etc.
R2
C O
C O
R2
subsequent loss of CO is possible
after fragmentation so not only can
you see loss of an branch you can
see the mass of an branch.
4. McLafferty Rearrangement
O
R1
H
C
C
C
O
R1
H
C
C
C
lost neutral
still a radical
fragment
cation
This is another common fragmentation pattern for carbonyl compounds (and other pi systems as well: alkenes, aromatics,
alkynes, nitriles, etc.). If the pi bond has at least 3 additional nonhydrogen atoms attached and a hydrogen on the "gama"
atom, the branch can curve around to a comfortable 6 atom arrangement and the pi bond can pick up a hydrogen atom and
cut off a fragment between the C and C positions. The positive charge can be seen on either fragment and usually the
fragments have an even mass (unless there is an odd number of nitrogen atoms).
radical cation
Knowing these few fragmentation patterns will allow you to make many useful predictions and
interpretations. Loss of small molecules, via elimination is common: H2O = 18, H2S = 34, CH3OH = 32,
C2H5OH = 46, NH3 = 17, CH3CO2H = 62, HF = 20, HCl = 36/38, HBr = 80/82, etc.
Z:\files\classes\spectroscopy\typical spectra charts.DOC
19
A sampling of unusual and/or miscellaneous peaks that are commonly seen, (even when they don't make sense).
R
CH3 = 15
CH3CH2 = 29
C3H7 = 43
C4H9 = 57
C5H11 = 71
C6H13 = 85
mass = 39 (R = H)
53 (R = CH3)
67 (R= CH2CH3)
also works for
R
CH2
C
H
mass = 41 (R = H)
55 (R = CH3)
69 (R= CH2CH3)
H2N
mass = 65 (R = H)
79 (R = CH3)
93 (R= CH2CH3)
mass = 27
mass = 77
RO
mass = 91 (R = H)
105 (R = CH3)
119 (R= CH2CH3)
C
H2
mass = 29 (R = H)
43 (R = CH3)
mass = 42 (R = H)
57 (R= CH2CH3)
56 (R = CH3)
71 (R = C3H7)
70 (R= CH2CH3)
105 (R = C6H5)
mass = 44
H
mass = 45 (R = H)
59 (R = CH3)
73 (R= CH2CH3)
Loss of small molecules via elimination reactions.
H2 O
mass = 18
CH3OH
32
H2 S
34
C2H5OH
46
HF HCl HBr
80
20 36 82
38
NH3 CH3CO2H
62
17
McLafferty Possibilities
H
H
O
O
R2
HC
R1
CH2
C
H2
R2
R1
R
McLafferty
Notice!
even masses
mass = 44 (R = H)
58 (R = CH3)
72 (R= CH2CH3)
86 (R = C3H7)
CH2
variable mass,
(can sometimes see
cation on this side too)
mass = 28 (R = H)
42 (R = CH3)
56 (R= CH2CH3)
70 (R = C3H7)
Similar Patterns
H
CH2
R2
R1
H
R2
H
H
R1
mass = 42 (R = H)
56 (R = CH3)
70 (R= CH2CH3)
84 (R = C3H7)
R1
mass = 92 (R = H)
106 (R = CH3)
120 (R= CH2CH3)
134 (R = C3H7)
R2
R1
C
H2
H
C
R2
R1
CH2
C
H2
R2
R
R2
R1
C
H2
H
H2C
R1
C
H2
R2
C
CH2
mass = 40 (R = H)
54 (R = CH3)
68 (R= CH2CH3)
82 (R = C3H7)
R2
R1
CH2
mass = 41 (R = H)
55 (R = CH3)
69 (R= CH2CH3)
83 (R = C3H7)