SPECTRA Tables
SPECTRA Tables
SPECTRA Tables
C N C O C O
C C C C C N
C O
C C C N
C C C N
1640-1810
expanded table
1600-1680 1640-1690 on next page 2100-2250 2240-2260
Stronger dipoles produce more intense IR bands and weaker dipoles produce less intense IR bands (sometimes none).
C H
O
C C H
C H C H
3000-3100
sp3 C-H 3300 2700-2760
sp3 C-H 2800-2860
2850-3000 (see sp2 C-H bend aldehyde C-H
sp3 C-H patterns below) (sp C-H bend ≈ 620) (two bands)
H
O
C N C N R S H
R O H C O H
H H
3100-3500 3100-3500 2550 -2620
primary NH2 secondary N-H 3200-3400 2500-3400 (very weak)
(two bands) (one band)
alcohol O-H acid O-H thiol S-H
amides = strong, amines = weak
C C C R' C H
R H R R R O R O
saturated = 1725 saturated = 1715 saturated = 1735 saturated = 1715
conjugated = 1690 conjugated = 1680 conjugated = 1720 conjugated = 1690
aromatic = 1700 aromatic = 1690 aromatic = 1720 aromatic = 1690
6 atom ring = 1715 6 atom ring = 1735
5 atom ring = 1745 5 atom ring = 1775
4 atom ring = 1780 4 atom ring = 1840
3 atom ring = 1850
sp2 C-H bend patterns for alkenes sp2 C-H bend patterns for aromatics
absorption absorption
alkene substitution descriptive frequencies (cm-1) aromatic substitution descriptive frequencies (cm-1)
pattern alkene term pattern aromatic term due to sp2 CH bend
due to sp2 CH bend
R H
monosubstituted 985-1000 monosubstituted 690-710
C C X
alkene 900-920 aromatic 730-770
H H
R R X
H R
R H
meta disubstituted 680-725
X
geminal disubstituted 880-900 aromatic 750-810
C C
alkene 880-900 (sometimes)
R H
R R
1o N-H2 mono
N-H bend
stretch
ortho
4000 3500 3000 2500 2000 1700 1500 1400 1300 1200 1100 1000 900 800 700 600 500
expansion of alkene & aromatic sp2 C-H bend region (units = cm-1)
1000 900 800 700 600 500
mono mono
cis
alkene sp2 C-H
trans
geminal bend
tri
mono mono
para
Saturated C=O lies at carboxylic acid C=O (also acid "OH") Conjugated C=O
higher cm-1 lies at lower cm-1
C=O in samll rings ester C=O (also acyl C-O and alkoxy C-O)
lies at higher cm-1
aldehyde C=O (also aldehyde C-H)
IR Spectrum
has C=O band
(1650-1800 cm-1) does not have
C=O band
very strong C C
C N
aldehydes
O alkanes
1725-1740 (saturated) ≈ 2250 sp3 C-H stretch 2850-3000
1660-1700 (unsaturated) nitriles
C sharp, stronger 1460 & 1380
sometimes lost than alkynes, sp3 C-H bend
2860-2800 in sp3 CH peaks C N
C C not useful
aldehyde C-H 2760-2700 a little lower
(both weak) when conjugated alkenes
sp2 C-H stretch 3000-3100
ketones alkynes 650-1000
O 2150 sp2 C-H bend (see table for
1710-1720 (saturated) C C spectral patterns)
1680-1700 (unsaturated) (variable intensity)
C 1715-1810 (rings: higher not present or weak when symmetrically 1600-1660
in small rings) substituted, a little lower when conjugated C C
weak or not present
esters - rule of 3
O sp C-H stretch 3300 aromatics
1735-1750 (saturated) sharp, strong
1715-1740 (unsaturated) sp2 C-H stretch 3050-3150
C 1735-1820 (higher in small rings) sp C-H bend 620 690-900 (see table),
acyl sp2 C-H bend overtone patterns
1150-1350 (acyl, strong) All IR values are approximate and have a range between 1660-2000
C O
alkoxy of possibilities depending on the molecular 1600 & 1480
C O
(1000-1150, alkoxy, medium) environment in which the functional group resides. C C can be weak
Resonance often modifies a peak's position
acids because of electron delocalization (C=O lower,
O alcohols
1700-1730 (saturated) acyl C-O higher, etc.). IR peaks are not 100%
reliable. Peaks tend to be stronger (more intense) alcohol
1715-1740 (unsaturated) 3600-3500
C when there is a large dipole associated with a O H
1680-1700 (higher in small rings)
vibration in the functional group and weaker in alkoxy 1000-1260
acyl less polar bonds (to the point of disappearing in C O (3o > 2o > 1o)
C O 1210-1320 (acyl, strong) some completely symmetrical bonds).
thiols
acid ≈ 2550 (weak)
2400-3400, very broad thiol
O H (overlaps C-H stretch) 2 S H (easy to overlook)
Alkene sp C-H bending patterns
amides amines
O monosubstituted alkene (985-1000, 900-920) H
3300 - 3500, two bands
1630-1680 (saturated) geminal disubstituted (960-990)
1745 (in 4 atom ring) N for 1o amines, one band
C cis disubstituted (675-730) o
N H for 2 amines, weaker
trans disubstituted (880-900) 1o
H 3350 & 3180, two bands H
2o than in amides,
trisubstituted (790-840)
for 1o amides,
tetrasubstituted (none, no sp2 C-H) N-H bend, 1550-1640,
N one band for 2o amides, N H
stronger in amides than amines
o
1 N H stronger than in amines, extra
H
2o overtone sometimes at 3100 N C 1000-1350
Aromatic sp2 C-H bending patterns (uncertain)
ethers
N H N-H bend, 1550-1640, monosubstituted (730-770, 690-710) 1120 (alphatic)
stronger in amides than amines alkoxy
ortho disubstituted (735-770) C O 1040 & 1250 (aromatic)
acid chlorides meta disubstituted (880-900,sometimes,
nitro compounds
O 1800 (saturated) 750-810, 680-725)
O
1770 (unsaturated) para disubstituted (790-840) 1500-1600, asymmetric (strong)
C Inductive pull of Cl increases the N 1300-1390, symmetric (medium)
electron density between C and O. O
There are also weak overtone bands between
anhydrides 1660 and 2000, but are not shown here. You
O can consult pictures of typical patterns in other carbon-halogen bonds
1760 & 1820 (saturated) reference books. If there is a strong C=O band,
1725-1785 (unsaturated) they may be partially covered up.
C two strong bands
C X usually not
acyl very useful
C O 1150-1350 (acyl, strong)
X = F, Cl, Br, I
5 1
amide N-H
6 1
S C H
thiols, sulfides
2.5 2.0
N C H
amines
X C H
3.0 2.3
X = F,Cl,Br,I allylic C-H
5 3 2.5 1.5
benzylic C-H thiol
alkene C-H carbonyl alpha C-H SH
12 11 10 9 8 7 PPM 6 5 4 3 2 1 0
220+ 180 50 30
O
O
C
R X epoxides
C C with & without H
carboxylic acids
anhydrides with & without H
N C 60 40
esters
amides no H 90 +
70 -
S C
acid chlorides
125 110 thiols, sulfides
no H
with & without H
180 160 O C alcohols, 40 20
ethers, esters
O
with & without H
C +
R H C 80 50
C C simple sp3 carbon
aldehydes C > CH > CH2 > CH3
with H with & without H with & without H
Estimation of sp3 C-H chemical shifts with multiple substituent parameters for protons within 3 C's of consideration.
H
C α Cβ C γ α = directly attached substituent, use these values when the hydrogen and substituent are attached to the same carbon
β = once removed substituent, use these values when the hydrogen and substituent are on adjacent (vicinal) carbons
γ = twice removed substituent, use these values when the hydrogen and substituent have a 1,3 substitution pattern
a. methine = 1.5 + (1.4)α + (2.3)α + (0.2)β = 5.4 ppm d. methyl = 0.9 + (0.1)α = 1.0 ppm
actual = 5.2 actual = 1.0
b. methylene = 1.2 + (1.5)α + (0.4)β + (0.3) β = 3.4 ppm e. methylene = 1.2 + (0.3)α = 1.5 ppm
actual = 3.0 and 3.2 actual = 1.7
c. methyl = 0.9 + (1.5)α = 2.4 ppm f. methylene = 1.2. + (1.7)α = 2.9 ppm
actual = 2.6 actual = 2.9
3.6 1.5 1.3 1.3 0.9 3.0 1.3 1.0 0.9 0.9
multiple substituents
CH4 CH 3Cl CH2Cl2 CHCl3 CCl4
δ (ppm)
2. Two nearest neighbor protons (both on same carbon or one each on separate carbons)
the ratio of these
two neighbor four populations
H1
Ha protons is about 1:2:1
C C Hb H1
observed
proton ∆Eto flip proton ∆E1
∆E2 J1a
∆E3
Bo J1b J1b
two equal energy 1 2 1
H1 two neighbor protons are like
populations here
two small magnets that can be
C C arranged four possible ways
N + 1 rule (N = # neighbors)
(similar to flipping a coin twice)
J (Hz) J (Hz) # peaks = N + 1 = 2 + 1 = 3 peaks
δ (ppm)
3. Three nearest neighbor protons (on same carbon, or two on one and one on another, or one each on separate carbons)
three neighbor the ratio of these
H1
Ha protons eight populations
is about 1:3:3:1
C C Hb
observed H1
proton Hc
∆E1
∆Eto flip proton ∆E2 J1a
∆E3
∆E4
Bo
J1b J1b
N + 1 rule (N = # neighbors)
J (Hz) J (Hz) J (Hz)
# peaks = N + 1 = 3 + 1 = 4 peaks
δ (ppm)
N=4 N=5
H H
H H H H
CH C CH3 CH C CH2
C CH3 C CH2 CH C CH2 C CH3
CH CH2
CH CH2 CH CH2
qnt, J=7 sex, J=7
I=1H I=1H
N=4 N=5
CH3 H2 C CH2
CH3 CH2
oct, J=7
sep, J=7 I=1H
I=1H N=7
N=6
Ha Ha C Hb 0-3 Hz 1 Hz
C 0-30 Hz 14 Hz
C C
Hb
geminal protons - can have different chemical shifts cis / allylic coupling,
and split one another if they are diastereotopic notice through 4 bonds
Range Typical Range Typical
Ha Hb Ha
6-8 Hz 7 Hz C C 0-3 Hz 1 Hz
C C
C Hb
vicinal protons are on adjacent atoms, when freely trans / allylic coupling,
rotating coupling averages out to about 7 Hz notice through 4 bonds
Ha 0-3 Hz 2 Hz Ha Hb
5-8 Hz 6 Hz
C C C C
Hb C O
2
sp2 geminal coupling sp vicinal aldehyde coupling
CH2 CH C
Simple alkane CH3
carbons
d 0 - 30 ppm d 20 - 40 ppm d 30 - 50 ppm d 30 - 60 ppm
(q) (t) (d) (s)
CH3 O CH2 O CH O
sp3 carbon C O
next to oxygen
d 50 - 60 ppm d 55 - 80 ppm d 60 - 80 ppm d 70 - 90 ppm
(q) (t) (d) (s)
CH2 N CH N
sp3 carbon CH3 N C N
next to nitrogen d 35 - 55 ppm
d 10 - 50 ppm
d 50 - 70 ppm d 50 - 70 ppm
(q) (t) (d) (s)
CH2 X CH X
sp3 carbon next to C X
bromine or chlorine
(X = Cl, Br) d 25 - 50 ppm d d 60 - 80 ppm
60 - 80 ppm
(t) (d) (s)
O O O
C C C
X H R
δ 160 - 180 ppm δ 180 - 210 ppm δ 180 - 220 ppm
carboxyl carbons aldehyde carbons, lower ketone carbons, lower
(acids, esters, amides) values when conjugated values when conjugated
(s) (d) (s)
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.
Steric Corrections for sp3 carbon chemical shift calculations Approximate 13C shift calculation from scratch.
The attached Cα carbons are:
13
C shifts for various carbon alkane skeletons - useful starting points for calculating sp3 carbon chemical shifts
22.3
C2 C3 C4 C5
16.3 25.4 22.6 32.0
25.0 30.2 11.8 29.7
CH4
25.0
-2.3 5.9 15.8 14.1 34.4 31.9 32.0
13.8
C6 29.0
22.7 11.5
22.9
19.5
27.9 20.6 8.9
30.4
14.1 32.9 18.8 33.9
36.3
41.5 14.4 29.3 36.5
C8
14.5 39.6
22.9 29.5 22.7 29.6 36.5 19.3
27.2 22.8 34.6 10.9 40.3 20.1
20.3 32.4
14.1 32.1 28.1 11.5 29.7 14.1
39.2 32.3 14.1 25.6 35.4 14.6
19.7
C9 C10
22.8 29.6 22.9 29.6
CH3 9 9 -2 6 8 -2
CH2CH3 18 7 -2 9 6 -2
CH(CH3)2 26 4 -2 14 3 -2
C(CH3)3 32 2 -2 20 1 -2
C
H
CH2 20 6 -1 15 5 -1
C CH 5 5 -4 2 6 -4
23 9 -2 17 7 -2
X is attached to a terminal carbon atom (ppm) X is attached to an internal carbon atom (ppm)
Substituent = X Cα correction Cβ correction Cγ correction Cα correction Cβ correction Cγ correction
OH 48 10 -6 44 7 -4
OR 60 7 -6 57 5 -6
O
51 6 -6 5 -6
O C 49
NH2 28 10 -5 24 8 -5
NH(CH3) 38 8 -5 32 5 -4
N(CH3)2
45 5 -5 37 3 -4
O
H
N C 26 7 -5 5 -5
21
R
NO2 62 5 -5 58 2 -5
X is attached to a terminal carbon atom (ppm) X is attached to an internal carbon atom (ppm)
Substituent = X Cα correction Cβ correction Cγ correction Cα correction Cβ correction Cγ correction
F 70 8 -7 67 5 -7
Cl 31 10 -5 36 8 -5
Br 20 10 -4 28 10 -4
I -7 11 -2 7 11 -2
O
C 30 0 -3 24 -1 -3
H
O
C 31 1 -3 26 0 -3
CH3
O
C 22 2 -3 18 1 -3
OH
X is attached to a terminal carbon atom (ppm) X is attached to an internal carbon atom (ppm)
Substituent = X Cα correction Cβ correction Cγ correction Cα correction Cβ correction Cγ correction
O
C 20 2 -3 16 2 -3
OCH3
O
C 25 3 -3 19 2 -3
NH2
C N 3 3 -3 3 3 -3
O
C 33 2 -3 30 2 -3
Cl
SH 11 10 -3 12 8 -3
SR 22 8 -3 20 6 -3
Additional starting point for calculating 13C chemical shifts (ppm) of substituted benzene rings (just a few possibilities)
Additional starting point for calculating 13C chemical shifts (ppm) of substituted alkenes (just a few possibilities)
γ β α C C
α' β' γ' 2 1 Effect of substituents on alkene 13C shifts (ppm)
C C C C C C C C
Substituent Z1 Z2 Substituent Z1 Z2
-H 0 0 -F 24 -34
δC = 123 ppm + Zi -CH3 13 -7 -Cl 3 -6
123 + correction factors -CH2CH3 17 -10 -Br -9 -1
-CH2CH2CH3 16 -9 -I -38 7
increments for directly attached carbon atoms -OCH3 29 -39
-CH(CH3)2 23 -12
α = 11 α ' = -8 -C(CH3)3 26 -15 -O2CCH3 18 -27
β=5 β ' = -2 -CH2Cl 10 -6 -N(CH3 )2 28 -32
γ = -2 γ'= 2 -NO2 22 -1
-CH2Br 11 -5
-CH2I 14 -4 -CN -15 14
steric corrections -SCH2CH3 9 -13
for each pair of cis-α,α ' substituents -1 -CH2OH 14 -8
for each pair of geminal-α,α substituents -5 -CH=CH2 14 -7 -CHO 15 14
for each pair of geminal-α,α 'substituents 3 -CCH -6 6 -COCH3 14 5
if one or more β sutstituents are present 2 -C6H5 12 -11 -CO2H 5 10
-COCl 8 14
R
C C C C C C C C C
radical cation Pi electrons partially fill in loss of electrons at Characteristic carboncation stability also applies.
carbocation site via resonance. This is common
π bond of an alkene fragmentation for alkenes and aromatics 3o R > 2o R > 1o R > CH3
or an aromatic
R
X C 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) bond…and possible subsequent loss of carbon monoxide, CO
R1 C O R1 C O R1
O
loss of
C
R1 R2
C O R2
radical cation R2 C O R2 C O
R1 or R2 can be lost from An oxygen lone pair partially fill in the loss of electrons at the subsequent loss of CO is possible
aldehydes, ketones, acids, carbocation site via resonance. This is a common fragmentation after α fragmentation so not only can
esters, amides...etc. pattern for any carbonyl compound and can occur from either you see loss of an α branch you can
side, though some are more common than others. see the mass of an α branch.
4. McLafferty Rearrangement
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.
R R
CH3 = 15 R R
CH3CH2 = 29 C
C3H7 = 43 mass = 39 (R = H) H
C4H9 = 57 53 (R = CH3)
67 (R= CH2CH3) mass = 41 (R = H) mass = 65 (R = H) mass = 91 (R = H)
C5H11 = 71
also works for 55 (R = CH3) 79 (R = CH3) 105 (R = CH3)
C6H13 = 85
69 (R= CH2CH3) 93 (R= CH2CH3) 119 (R= CH2CH3)
R CH2
H
H2N C O R O C R
H
C
H2 mass = 29 (R = H)
mass = 44
43 (R = CH3)
mass = 42 (R = H)
H 57 (R= CH2CH3)
mass = 27 56 (R = CH3) 71 (R = C3H7)
mass = 77 RO C O
70 (R= CH2CH3) 105 (R = C6H5)
mass = 45 (R = H)
59 (R = CH3)
73 (R= CH2CH3)
Loss of small molecules via elimination reactions.
H2 O H2 S CH3OH C2H5OH NH3 CH3CO2H HF HCl HBr
80
mass = 18 34 32 46 17 62 20 36 82
38
McLafferty Possibilities
H
H
O R
O R2 McLafferty R2
Notice! HC
even masses C =
R1 R1
R CH2 CH2
R C variable mass,
H2 mass = 44 (R = H) mass = 28 (R = H)
58 (R = CH3) (can sometimes see 42 (R = CH3)
72 (R= CH2CH3) cation on this side too) 56 (R= CH2CH3)
86 (R = C3H7) 70 (R = C3H7)
Similar Patterns
H H
H
CH2 R2 H H
R2
C R2 N R2
R1
R1
R C R1 R1
H2 C
H2 C C
H2 H2
H H
H2C H H H
R2
H C R2 N
R2 R2
C R1 R
R CH2 C R1 C R1
R1
CH2 CH2