Beauchamp Spectroscopy Tables 1

Infrared Tables (short summary of common absorption frequencies)

The values given in the tables that follow are typical values. Specific bands may fall over a range of
wavenumbers, cm-1. Specific substituents may cause variations in absorption frequencies. Absorption
intensities may be stronger or weaker than expected, often depending on dipole moments. Additional
bands may confuse the interpretation. In very symmetrical compounds there may be fewer than the
expected number of absorption bands (it is even possible that all bands of a functional group may
disappear, i.e. a symmetrically substituted alkyne!). Infrared spectra are generally informative about
what functional groups are present, but not always. The 1H and 13C NMRs are often just as
informative about functional groups, and sometimes even more so in this regard. Information obtained
from one spectroscopic technique should be verified or expanded by consulting the other spectroscopic
techniques.
IR Summary - All numerical values in the tables below are given in wavenumbers, cm-1
Bonds to Carbon (stretching wave numbers)
sp3 C-X single bonds sp2 C-X single bonds

C N C O C O
C C C C C N

1000-1350 1050-1150 1100-1350

not used not very useful alkoxy C-O not very useful 1250 acyl and phenyl C-O
sp2 C-X double bonds sp C-X triple bonds

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).

Bonds to Hydrogen (stretching wave numbers)

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

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 Beauchamp Spectroscopy Tables 2

Carbonyl Highlights (stretching wave numbers)

Aldehydes Ketones Esters Acids

O O O O

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

Amides Anhydrides Acid Chlorides nitro

O O O
O
O
C C
C R N
R O R R Cl
R NR2
saturated = 1650 saturated = 1760, 1820 saturated = 1800 O
conjugated = 1660 conjugated = 1725, 1785 conjugated = 1770
aromatic = 1725, 1785 aromatic = 1770 asymmetric = 1500-1600
aromatic = 1660 symmetric = 1300-1390
6 atom ring = 1670 6 atom ring = 1750, 1800
5 atom ring = 1700 5 atom ring = 1785, 1865
4 atom ring = 1745 Very often there is a very weak C=O overtone at approximately 2 x (3400 cm-1).
3 atom ring = 1850 Sometimes this is mistaken for an OH or NH peak.,

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

C C cis disubstituted 675-730

alkene (broad) 735-770
ortho disubstituted
H H X aromatic
R H

C C trans disubstituted 960-990

alkene 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

C C trisubstituted para disubstituted 790-840

alkene 790-840 X X aromatic
R H
R R Aromatic compounds have characteristic weak overtone bands
that show up between 1650-2000 cm-1). Some books provide
C C tetrasubstituted
alkene none pictures for comparison (not here). A strong C=O peak will
R R cover up most of this region.

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Beauchamp Spectroscopy Tables 3

units = cm-1
4000 3500 3000 2500 2000 1700 1500 1400 1300 1200 1100 1000 900 800 700 600 500

sp3 C-H C C C=O alkene sp2 C-H

sp C-H bend
stretch stretch stretch 3
sp C-H
thiol S-H bend mono
sp2 C-H stretch
C=N cis
stretch C N stretch trans

aldehyde C-H acyl C-O geminal

stretch phenol C-O
C=C stretch tri
alcohol O-H alkene
stretch
alkoxy C-O

carboxylic acid O-H C=C stretch

aromatic aromatic sp2 C-H
stretch
bend

1o N-H2 mono
N-H bend
stretch
ortho

2o N-H nitro nitro meta

stretch para

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

ortho aromatic sp2 C-H

bend
meta meta meta

para

expansion of carbonyl (C=O) stretch region (units = cm-1)

1800 1750 1700 1650 1600

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)

ketone C=O (nothing special)

amide C=O (low C=O, amide N-H)

acid chloride C=O (high C=O, 1 peak)

anhydride C=O anhydride C=O (high C=O, 2 peaks)

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Beauchamp Spectroscopy Tables 4

IR Flowchart to determine functional groups in a compound (all values in cm-1).

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)
nitriles 2250 sp3 C-H stretch 2850-3000
C 1660-1700 (unsaturated) sharp, stronger
sometimes lost sp3 C-H bend 1460 & 1380
than alkynes,
2860-2800 in sp3 CH peaks C N not useful
C C
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
C C 1600-1660
in small rings) substituted, a little lower when conjugated 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) (easy to overlook)
Alkene sp2 C-H bending patterns S H
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
H 3350 & 3180, two bands 2o than in amides,
trisubstituted (790-840)
for 1o amides,
tetrasubstituted (none, no sp2 C-H) N H N-H bend, 1550-1640,
N one band for 2o amides, stronger in amides than amines
o N H stronger than in amines, extra
1
H 1000-1350
2o overtone sometimes at 3100 N C
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

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Beauchamp Spectroscopy Tables 5

deshielding side = less electron rich Typical 1H and 13C NMR chemical shift values. shielding side = more electron rich
(inductive & resonance) (inductive & resonance)
typical proton chemical shifts
amine N-H
Carbon and/or heteroatoms without hydrogen do
not appear here, but influence on any nearby protons 2 1
may be seen in the chemical shifts of the protons. alcohol O H

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

carboxylic acid O-H 7+ 4 3+ 2 1.5 1.3

epoxide C-H
12 10
3.5 2.5
H
alcohols simple sp3 C-H
O C ethers
aldehyde C-H aromatic C-H CH > CH2 > CH3
esters C H
10 9 8+ 6 5+ 3.3 3 2 2 0.5

12 11 10 9 8 7 PPM 6 5 4 3 2 1 0

typical carbon-13 chemical shifts F 80-95

halogen C
Cl 45-70
Br 35-65
with & without H I 15-45
O
95 15
C N C
R R
ketones
amines, amides
no H with & without H

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

210 180 160+ 100- 60+ 0

240 220 200 180 160 140 PPM 120 100 80 60 40 20 0

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Beauchamp Spectroscopy Tables 6

Calculation of chemical shifts for protons at sp3 carbons

Estimation of sp3 C-H chemical shifts with multiple substituent parameters for protons within 3 C's of consideration.
H
C C C = 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

X = substituent Starting value and equations for CH3's

R- (alkyl) 0.0 0.0 0.0
R2C=CR- (alkenyl) 0.8 0.2 0.1 CH3 = 0.9 + H3C
RCC- (alkynyl) 0.9 0.3 0.1
Ar- (aromatic) 1.4 0.4 0.1
F- (fluoro) 3.2 0.5 0.2 CH3 = 0.9 + ( + ) H 3C C C
Cl- (chloro) 2.2 0.5 0.2
Br- (bromo) 2.1 0.7 0.2
I- (iodo) 2.0 0.9 0.1 is the summation symbol for all substituents considered
HO- (alcohol) 2.3 0.3 0.1
RO- (ether) 2.1 0.3 0.1
epoxide 1.5 0.4 0.1 Starting value and equation for CH2's
R2C=CRO- (alkenyl ether) 2.5 0.4 0.2
ArO- (aromatic ether) 2.8 0.5 0.3 In a similar manner we can calculate chemical shifts
RCO2- (ester, oxygen side) 2.8 0.5 0.1 for methylenes (CH2) using the following formula
ArCO2- (aromatic ester, oxygen side) 3.1 0.5 0.2
ArSO3- (aromatic sulfonate, oxygen) 2.8 0.4 0.0 CH2 = 1.2 + ( + + ) H
H2N- (amine nitrogen) 1.5 0.2 0.1 H C C C
RCONH- (amide nitrogen) 2.1 0.3 0.1
O2N- (nitro) 3.2 0.8 0.1
is the summation symbol for all substituents considered
HS- (thiol, sulfur) 1.3 0.4 0.1
RS- (sulfide, sulfur) 1.3 0.4 0.1 Starting value and equation for CH's
OHC- (aldehyde) 1.1 0.4 0.1
RCO- (ketone) 1.2 0.3 0.0
ArCO- (aromatic ketone) 1.7 0.3 0.1 In a similar manner we can calculate chemical shifts
HO2C- (carboxylic acid) 1.1 0.3 0.1 for methines (CH) using the following formula
RO2C- (ester, carbon side) 1.1 0.3 0.1 H
H2NOC- (amide, carbon side) 1.0 0.3 0.1 CH = 1.5 + ( + + )
C C C
ClOC- (acid chloride) 1.8 0.4 0.1
NC- (nitrile) 1.1 0.4 0.2
RSO- (sulfoxide) 1.6 0.5 0.3 is the summation symbol for all substituents considered
RSO2- (sulfone) 1.8 0.5 0.3
a. methine b. methylene

d. methyl HO CH2 CH3

O CH N
H 2C H
H 3C H2C c. methyl

e. methylene
f. methylene

a. methyl = 0.9 + (1.5) + (0.1) = 2.5 ppm d. methyl = 0.9 + (0.1) = 1.0 ppm
actual = 2.6 actual = 1.0

b. methylene = 1.2 + (1.5) + (0.4) + (0.3) = 3.4 ppm e. methylene = 1.2 + (0.3) = 1.5 ppm
actual = 3.0 and 3.2 actual = 1.7

c. methine = 1.5 + (1.4) + (2.3) + (0.2) = 5.4 ppm f. methylene = 1.2. + (1.7) = 2.9 ppm
actual = 5.2 actual = 2.9

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Beauchamp Spectroscopy Tables 7

Estimated chemical shifts for protons at alkene sp2 carbons

Substituent geminal cis trans Substitution relative to calculated "H"

cis
H- 0.0 0.0 0.0 H
Hydrogen C C
R- 0.5 -0.2 -0.3 trans gem
Alkyl
C6H5CH2- 0.7 -0.2 -0.2 (ppm) = 5.2 + gem + cis + trans
Benzyl
X-CH2- 0.7 0.1 0.0
Halomethyl Example Calculation
(H)/ROCH2- 0.6 0.0 0.0
alkoxymethyl gem
(H)2/R2NCH2- 0.6 -0.1 -0.1 H
aminomethyl trans
C H
RCOCH2- 0.7 -0.1 -0.1 C
-keto H
NCCH 2- 0.7 -0.1 -0.1 CH3O cis
-cyano
R2C=CR- 1.2 0.0 0.0
Alkenyl gem = 5.2 + 1.4 = 6.6
C6H5- 1.4 0.4 -0.1 actual = 6.6
Phenyl
F- 1.5 -0.4 -1.0 trans = 5.2 - 0.1 = 5.1
Fluoro actual = 5.1
Cl- 1.1 0.2 0.1
cis = 5.2 + 0.4 = 5.7
Chloro
actual = 5.6
Br- 1.1 0.4 0.6
Bromo
I- 1.1 0.8 0.9 c d e
Iodo bH H H H
RO- 1.2 -1.1 -1.2 C C C C
akoxy (ether) aH O C Hf
RCO2- 2.1 -0.4 -0.6
O-ester O
(H)2/R2N- 0.8 -1.3 -1.2 a = 5.2 + (-0.4) = 4.8
N-amino actual = 4.9 (J = 14, 1.6 Hz)
RCONH- 2.1 -0.6 -0.7
N-amide b = 5.2 + (-0.6) = 4.6
O2N- 1.9 1.3 0.6 actual = 4.6 (J = 6, 1.6 Hz)
Nitro c = 5.2 + 2.1 = 7.3
RS- 1.1 -0.3 -0.1 actual = 7.4 (J = 14, 6 Hz)
Thiol
OHC- 1.0 1.0 1.2 d = 5.2 + 0.8 = 6.0
Aldehyde actual = 6.2 (J = 18, 11 Hz)
ROC- 1.1 0.9 0.7 e = 5.2 + 0.5 = 5.7
Ketone actual = 5.8 (J = 11, 1.4 Hz)
HO2C- 0.8 1.0. 03
C-acid f = 5.2 + 1.0 = 6.2
RO2C- 0.8 1.0 0.5 actual = 6.4 (J = 18, 1.4 Hz)
C-ester
H2NOC- 0.4 1.0 0.5
C-amide
NC- 0.3 0.8 0.6
Nitrile

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Beauchamp Spectroscopy Tables 8

Estimated chemical shifts for protons at aromatic sp2 carbons

Substitution relative to calculated "H"
Substituent ortho meta para
meta ortho
H- 0.0 0.0 0.0
Hydrogen
CH3- -0.2 -0.1 -0.2 para H
Methyl
ClCH2- 0.0 0.0 0.0 meta ortho
Cholromethyl
Cl3C- 0.6 0.1 0.1 (ppm) = 7.3 + ortho + meta + para
Halomethyl
HOCH 2- -0.1 -0.1 -0.1
Hydroxymethyl
R2C=CR- 0.1 0.0 -0.1 Example Calculation
Alkenyl 2
C6H5- 1.4 0.4 -0.1 H
1
Phenyl 3 5
CH3O H
F- -0.3 0.0 -0.2 H
Fluoro
Cl- 0.0 0.0 -0.1 H 6
Chloro 2H CH2
H 4 H
Br- 0.2 -0.1 0.0
Bromo 3 7
I- 0.4 -0.2 0.9
Iodo 1. (CH3) = 0.9 + 2.8 = 3.7
HO- -0.6 -0.1 -0.5 actual = 3.8
Hydroxy
RO- -0.5 -0.1 -0.4 2. (2) = 7.3 + (-0.5) ortho + (-0.1) para = 6.7
Alkoxy actual = 6.8
RCO 2- -0.3 0.0 -0.1
O-ester 3. (3) = 7.3 + (-0.2) ortho + (-0.4) para = 6.7
(H)2/R2N- -0.8 -0.2 -0.7 actual = 7.1
N-amino
RCONH- 0.1 -0.1 -0.3 4. (CH 2) = 1.2 + (0.8) + (1.4) = 3.4
N-amide actual = 3.3
O 2N- 1.0 0.3 0.4
Nitro 5. (5) = 5.2 + (0.7) gem = 5.9
RS- -0.1 -0.1 -0.2 actual = 5.9
thiol/sulfide
OHC- 0.6 0.2 0.3 6. (6) = 5.2 + (-0.2) trans = 5.0
Aldehyde
ROC- 0.6 0.1 0.2 actual = 5.1
Ketone
HO2C- 0.9 0.2 0.3 7. (7) = 5.2 + (-0.2) cis = 5.0
C-acid actual = 5.1
RO2C- 0.7 0.1 0.2
C-ester
H 2NOC- 0.6 0.1 0.2
C-amide
NC- 0.4 0.2 0.3
Nitrile

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Beauchamp Spectroscopy Tables 9

Real Examples of Combination Effects on Chemical Shifts

bond anisotropy 0.8 shielded bond example too
(CH 2)
0.8, shielded
H shielding cone
from bond
CH2
2.6
H deshielded H
7.2 1.5
electronegativity and bond 10-12 15, hydrogen
H bonded enol
O O H O O O
C H 9.5 C C C C
H 3C C CH3
O H O hydrogen
bonding H
electronegative substituent and distance from protons
O CH2CH 2CH2CH2CH 3 CH3 Cl CH3CH 2 Cl CH3CH2CH 2 Cl CH3CH 2CH 2CH2 Cl CH3CH 2 R

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 CH 2Cl2 CHCl3 CCl4

0.2 = 2.8 3.0 = 2.3 5.3 = 1.9 7.2 =? ? (oops)

substituents at methyl (CH3), methylene (CH2) and methine (CH) O O O
CH3Cl CH3CH 2Cl (CH 3)2CHCl H 3C C Ph H 3CH2C C Ph (H3C)2CH C Ph

3.0 3.5 4.1 2.6 3.0 3.5

alkene substituent resonance and inductive effects O
0.9 1.4 2.0 O 3.7 4.2 4.9
H H CH CH CH 3.8 6.4
3 2 2 H 5.0 CH O C H H 2 C O H C O H
C C 3
C C H 3C C C H 3C C C
C C 2.1
H H H H 1.3 H H H H
H H
5.3 5.8 4.9 6.1 5.8 6.5 4.0 7.3 4.6
aromatic resonance and inductive effects
H H 7.3 6.6 7.1 8.2 7.5
H H H H H H H H
6.7 O 7.7 O
H H
H 2N H H 2N H N H N H
O O
H H
bond anisotropy H H H H H H H H
produces deshielding Extra electron density via resonance produces Withdrawal of electron density via resonance
effect on aromatic shielding effect on aromatic protons, especially produces deshielding effect on aromatic protons,
protons. at ortho/para positions. especially at ortho/para positions.

sp C-H RO H alcohol H = 1-5 R2N H amine H = 1-5 enol H = 10-17 H O

H C C H2.4 ArO H C C
phenol H = 4-10 O O
R C C H 1.9 RS H thiol H = 1-2.5 R C amide H = 5-8
R C
Ar C C H 3.0 ArO H aromatic thiol H = 3-4 NH2 O H acid H = 10-13

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Beauchamp Spectroscopy Tables 10

Proton chemical shifts of hydrogen on sp3 carbons depend on two main factors (electronegativity and pi
bond anisotropy). All values listed below are only approximate and have a small plus or minus range
about the listed value.
All things being equal, methine protons (CH) have greater chemical shifts than methylene
protons (CH2) which have greater chemical shifts than methyl protons (CH3).

H H
C H C H C H
H
1.5 ppm 1.2 ppm 0.9 ppm
methine protons methylene protons methyl protons
Chemical shifts in an only "alkane" environment.
3
1. sp C-H Electronegative atoms in the vicinity of hydrogen deshield protons and produce a larger
chemical shift. If the electronegative atom is in resonance with an adjacent pi system that further
withdraws electron density, the chemical shift is increased.
a. next to a halogen
H H H H
C F C Cl C Br C I

4.1 - 4.7 ppm 3.1 - 3.7 ppm 3.0 - 3.6 ppm 2.9 - 3.5 ppm
fluoro alkanes chloro alkanes bromo alkanes iodo alkanes
b. next to a oxygen
O O
H H H O H H
C R C
C OH C OR C O C C O C O
H
3.1 - 3.7 ppm 3.0 - 3.6 ppm 3.7 - 4.3 ppm 2.5 - 3.2 ppm 3.7 - 4.3 ppm 4.0 - 4.6 ppm
alcohol alkyl ether aromatic ether alkyl ester aromatic ester
epoxide ether (oxygen side)
(resonance withdrawal) (oxygen side)
(resonance withdrawal) (resonance withdrawal)
c. next to a sulfur or nitrogen
O
H H H H
C
C SH C SR C N C N

2.2 - 2.8 ppm 2.2 - 2.8 ppm 2.3 - 3.1 ppm 3.0 - 3.6 ppm
thiol alkyl ether amines (r esonance withdrawal)
amides

2. sp3 C-H Pi bonds in the vicinity of hydrogen also deshield protons via pi bond anisotropy and
produce a larger chemical shift. The closer the sp3 C-H is to the pi bond the greater chemical shift
observed. When an electronegative atom is part of the pi bond, the chemical shift also increases.
H O
H O H O H O
C C
C C C C C N
Cl O
1.9 - 2.7 ppm
aldehydes, ketones, 2.6 - 3.3 ppm 2.7 - 3.4 ppm 2.7 - 3.4 ppm
carboxylic acids, amides, aromatic ketones acid chlorides nitro compounds
alkyl ester (oxygen side) (resonance withdrawal) (resonance withdrawal) (resonance withdrawal)

H H
H C
C C C C
C C
1.8 - 2.4 ppm 2.3 - 2.9 ppm
propargylic protons 1.7 - 2.3 ppm
allylic protons benzylic protons

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Beauchamp Spectroscopy Tables 11

3. sp2 C-H Hydrogens at the side of a pi bond are deshielded even more than above via pi bond
anisotropy. An aldehyde produces the largest effect due to the electronegative oxygen, followed by an
aromatic ring, followed by alkenes and finally terminal alkynes. (One sp C-H)
4.0 - 4.6 ppm
alkene C-H H H 5.5 - 6.5 ppm H H
H 5.0 ppm
O C H O C H C H C H
C H C C RO C RO C
C C
R C H H H
H
H 6.0 - 6.3 ppm 6.4 - 7.4 ppm
5.7 ppm vinylic protons (resonance vinylic protons (resonance donation
simple vinylic protons and inductive withdrawal) and inductive withdrawal)
aromatic C-H 7.9 - 8.3 ppm
6.7 - 7.0 ppm 6.5 - 7.0 ppm
7.1 - 7.3 ppm H H H
H
O
C O N
R
simple aromatic protons aromatic protons (resonance aromatic protons (resonance donation
and inductive withdrawal) and inductive withdrawal)
aldehyde C-H alkyne C-H
O
C C C H
H
9 - 10 ppm 1.9 - 3.2 ppm
aldehydes terminal alkyne protons

4. There are several kinds of hydrogen attached to heteroatoms. Some of these are listed below. Often
these hydrogens do not follow the N+1 rule because they exchange via acid/base proton exchanges and
are not next to neighbor protons long enough to allow coupling to be observed. They are often
observed as broad singlets (sometimes so broad they are not easily seen in the spectra). If the
exchange rate is very fast among the exchangeable protons on the NMR time scale, all of the
exchangeable protons may appear together at a single, averaged chemical shift.

O O O O
O H
H N C C
H
H O H N H
1 - 5 ppm
1 - 2 ppm 10 - 12 ppm
alcohols 7 - 15 ppm 1 - 6 ppm
amines carboxylic acids
phenol and amides
enol protons

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Beauchamp Spectroscopy Tables 12

When carbons are decoupled from their attached hydrogens they all appear as singlets (as if there were
no hydrogen neighbors). When carbons are coupled to their hydrogens, carbons follow the N+1 rule.
Methyls appear as quartets = q, methylenes appear as triplets = t, methines appear as doublets = d, and
carbons without hydrogen appear as singlets = s. Carbon chemical shifts are spread out over a larger
range than proton chemical shifts (they are more dispersed). It is less likely that two different carbon
shifts will fall on top of one another. However, 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 CH C
Simple alkane CH3
carbons
0 - 30 ppm 20 - 40 ppm 30 - 50 ppm 30 - 60 ppm
(q) (t) (d) (s)

CH3 CH2
sp3 carbon CH C
next to oxygen
50 - 60 ppm 55 - 80 ppm
60 - 80 ppm 70 - 90 ppm
(q) (t) (d) (s)

CH2
sp3 carbon CH3 CH C
next to nitrogen
10 - 50 ppm 35 - 55 ppm
50 - 70 ppm 50 - 70 ppm
(q) (t) (d) (s)

CH2
sp3 carbon next to CH C
bromine or chlorine
25 - 50 ppm
60 - 80 ppm 60 - 80 ppm
(t) (d) (s)

sp carbon (alkynes) C C sp carbon (nitriles) C N

70 - 90 ppm 110 - 125 ppm

sp2 carbon (alkenes

and aromatics) C H C X C X
C H

100 - 140 ppm 140 - 160+ ppm

simple sp2 carbon
resonance donation moves lower,
resonance withdrawal moves higher
2
sp carbon attached to an electronegative atom
(X = oxygen, nitrogen, halogen) or C carbon
conjugated with a carbonyl group

O O O
C C C
X H R
160 - 180 ppm 190 - 210 ppm 190 - 220 ppm
carboxyl carbons aldehyde carbons, lower ketone carbons, lower
(acids, esters, amides) values when conjugated values when conjugated
(s) (d) (s)

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Beauchamp Spectroscopy Tables 13

1. One nearest neighbor proton

increasing
one neighbor
H1 proton = Ha increasing E (, Bo)
Ha
C C the ratio of these
observed
perturbation(s) by two populations
proton neighbor proton(s) is about 50/50 (or 1:1)
Eto flip proton H1
E2 (observed)
Bo E1 (observed)
J1a
1 1
Protons in this environment have a small cancellation H1 H1 Protons in this environment have a small
of the external magnetic field, Bo, and produce a additional increment added to the external
smaller energy transition by that tiny amount. C C C C magnetic field, Bo, and produce a higher
energy transition by that tiny amount.

J = coupling constant N + 1 rule (N = # neighbors)

small difference in
energy due to differing J (Hz)
# peaks = N + 1 = 1 + 1 = 2 peaks
neighbor's spin (in Hz)

(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

(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

H1 three neighbor protons are like J1c J1c J1c

three small magnets that can be three equal energy 1 3 3 1
C C arranged eight possible ways populations at each
(similar to flipping a coin thrice) of middle transitions

N + 1 rule (N = # neighbors)
J (Hz) J (Hz) J (Hz)
# peaks = N + 1 = 3 + 1 = 4 peaks

(ppm)

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Beauchamp Spectroscopy Tables 14

Multiplets when the N + 1 rule works (all J values are equal).

1 peak = 100%
s = singlet 1 1 peak = 50%
d = doublet 1 1 1 peak = 25%
t = triplet 1 2 1
1 peak = 12% relative sizes of
q = quartet 1 3 3 1 peaks in multiplets
1 peak = 6%
qnt = quintet 1 4 6 4 1 1 peak = 3%
sex = sextet 1 5 10 10 5 1 1 peak = 1.5%
sep = septet 1 6 15 20 15 6 1
o = octet 1 peak = 0.8%
1 7 21 35 35 21 7 1

Combinations or these are possible.

dd = doublet of doublets
ddd = doublet of doublet of doublets
dddd = doublet of doublet of doublet of doublets
dt = doublet of triplets
td = triplet of doublets

etc.

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Beauchamp Spectroscopy Tables 15

Typical Coupling Constants

Range Typical Range Typical

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

Range Typical Range Typical

= dihedral C C
Ha Hb
angle
H 0-12 Hz 7 Hz C C 9-13 Hz 10 Hz
C C
Ha Hb
depends on dihedral
H angle, see plot of sp2 vicinal coupling
Karplus equation (different bonds)

Range Typical Range Typical

Ha Hb Ha Hb
0-1 Hz 0 Hz 1-3 Hz 2 Hz
C C C C C
O
protons rarely couple through 4 chemical bonds 3
sp vicinal aldehyde coupling
unless in a special, rigid shapes (i.e. W coupling)
Range Typical Range Typical

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

Range Typical Range Typical

Ha Hb
5-11 Hz 10 Hz Ha
C C 2-3 Hz 2 Hz
C C C Hb

sp2 cis (acylic) coupling (always sp / propargylic coupling

smaller than the trans isomer) notice through 4 bonds

Range Typical Range Typical

Ha
C C Ha Hb
11-19 Hz 17 Hz 2-3 Hz 3 Hz
Hb C C C C

sp2 trans coupling (always bis-propargylic coupling

larger than the cis isomer) notice through 5 bonds

Range Typical ortho, meta and H Range Typical

Ha para coupling to
H ortho
C C 4-10 Hz 7 Hz this proton ortho 6-10 Hz 9 Hz
C Hb meta 2-3 Hz 2 Hz
H meta para 0-1 Hz 0 Hz
sp2 / sp3 vicinal coupling 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.

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