OC 307

Chapter 13

NMR Spectry-3

H. D. Roth

Nuclear Magnetic Resonance 2

!Features of 1H NMR!

HDR
Chem 307, Fall, 2015

!!High!resolu>on!1H!NMR!has!three!useful!features!!

!Chemical!

!Intensity!

shi:!

!Spin!Spin!
Spli'ng!!

Chemical!Shi:!

Signal!Intensity!

Spli'ng!Pa@ern!

The!chemical!
environment!of!a!
group!of!
equivalent!nuclei!

The!rela>ve!number!
of!nuclei!
represented!by!the!
signal!

The!number!of!
nearby!nuclei!
interac>ng!with!the!
nucleus!

The!number!of!lines!reveals!the!number!of!dierent!types&of&groups;&
this&is&valid&only&for&molecules&with&limited&size&(as&we&are&studying)&!

Equivalence
Equivalent hydrogens: are hydrogens that have the same
chemical environment.
A molecule with one set of equivalent hydrogens gives one
NMR signal.
O
CH 3 CCH 3
Propanone
(Acetone)

CH 3

H3 C
ClCH 2 CH 2 Cl
1,2-Dichloroethane

C
H3 C
Cyclopentane

C
CH 3

2,3-Dimethyl2-butene

These cases of equivalence are due to symmetry; other principles

can cause equivalence as well.

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Chapter 13

NMR Spectry-3

H. D. Roth

Equivalence due to rotation

All three 1H nuclei of the methyl group are equivalent due to

rotation; both 1H nuclei of the methylene group are equivalent.
Equivalence due to ring inversion
F

F
19

F Nuclei are equivalent due to cyclohexane inversion

A molecule with two or more sets of equivalent hydrogens gives

Cl
CH3CHCl
a b
a

1,1-Dichloroethane
a (2 signals)

b
b

a
O

Cl
C C
Hb

Cyclopentanone
(2 signals)

a
CH3
Hb

(Z)-1-Chloropropene
(3 signals)

different NMR signal for each set.

c
c

a
b
Cyclohexene
(3 signals)

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Chapter 13

NMR Spectry-3

H. D. Roth

chloromethyl methyl ether: two different groups - two signals

O
C

CH3

H3C

C
H2

2.2

2.4

1.0 ppm

Three different 1H groups - three signals

Three different groups three signals

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Chapter 13

NMR Spectry-3

H. D. Roth

Seven 1H types five signals

Conclusion/Summary
In some (many) cases: one distinct NMR signal for each distinct
group BUT similar groups are not always (!) resolved.
Chemical Shift
Terms used to describe peak position
!

!Three!Useful!Features!

HDR
Chem 307, Fall, 2015

Terms used to describe peak position

upfield

Field

downfield

!!

!!

!!

high frequency

Frequency

low frequency

deshielded

Shielding

shielded

high shift

Chemical shift

low shift

10

TMS

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Chapter 13

NMR Spectry-3

Chemical shift depends on the

(1) electronegativity of nearby atoms,

(2) hybridization of adjacent atoms, and

(3) effects from adjacent pi bonds.

CH3-X
CH3F
CH3OH
CH3Cl
CH3Br
CH3I

(CH3) 4C
(CH3) 4Si

Electronegativity of X

Chemical
Shift ()

4.0
3.5

4.26
3.47

3.1
2.8
2.5

3.05
2.68

2.1

0.86

1.8

0.00

2.16

Electronegative atoms deshield neighbors

shielding region

H. D. Roth

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Chapter 13

NMR Spectry-3

H. D. Roth

CH3 groups shielded CH2 group deshielded by OH

O
C

CH3

H3C

C
H2

2.2

2.4

1.0 ppm

CH3 and CH2 group deshielded by C=O, CH3 of ethyl

deshielded.

Br deshields tertiary 1H; gradual decrease of deshielding by Br

with distance

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Chapter 13

NMR Spectry-3

H. D. Roth

Electronegative atoms/groups have an inductive effect

NOCHCHCH
4.37 2.09 1.04 ppm
BrCHCHCH
3.39 1.88 1.03 ppm
The effect falls off with distance.

(2) hybridization of adjacent atoms, and

(3) effects from adjacent pi bonds.
The hybridization of the adjacent carbon atom affects the
chemical shift of the adjacent 1H nuclei. For example, alkene
hydrogens (@ sp2 C), are more deshielded (4.55.7 ppm) than
alkane protons (@ sp3 C; 0.81.7 ppm) because the sp2 C has
more s character (greater electron density near the atom) than the
sp3 hybridized alkane C.
These effects are enhanced or diminished by effects from
adjacent pi bonds. Alkyne hydrogens(sp C) are less deshielded

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Chapter 13

NMR Spectry-3

H. D. Roth

than alkene ones. The alkene shifts are affected more strongly by
the adjacent electrons.
Shielding and deshielding effects from adjacent pi bonds

Alkenes: 4.5 6.0 ppm; alkynes: 2.0 3.0 ppm; aromatics: 7.0
8.0 ppm.
Chemical Shift Benchmarks
high field

0.5 1.5

alkane, cycloalkane shielded

2.0 2.5

allylic, benzylic

2.5 4.0

alkyl at electronegative atoms

4.5 6.0

alkenes

7.0 8.0

benzene and aromatics

10.0
low field 11.5

aldehydes
carboxylic acids

deshielded

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Chapter 13

NMR Spectry-3

Chemical
Type of
Hydrogen
Shift ()
(CH 3 ) 4 S i
0 (by definition)
RCH 3
0.8-1.0
RCH 2 R
1.2-1.4
R 3 CH
1.4-1.7
R 2 C=CRCH R 2 1.6-2.6
RC CH
2.0-3.0
A rCH 3
2.2-2.5
A rCH 2 R
2.3-2.8
ROH
0.5-6.0
RCH 2 OH
3.4-4.0
RCH 2 OR
3.3-4.0
R 2 NH
0.5-5.0
O
RCCH 3
2.1-2.3
O
RCCH 2 R
2.2-2.6

Type of
Hydrogen
O
RCOCH 3
O
RCOCH 2 R
RCH 2 I
RCH 2 Br
RCH 2 Cl
RCH 2 F
A rOH
R 2 C=CH 2
R 2 C=CHR
A rH
O
RCH
O
RCOH

H. D. Roth

Chemical
Shift ()
3.7-3.9
4.1-4.7
3.1-3.3
3.4-3.6
3.6-3.8
4.4-4.5
4.5-4.7
4.6-5.0
5.0-5.7
6.5-8.5
9.5-10.1
10-13

Signal Intensity
Relative areas of signals are proportional to the number of H giving rise to each signal.
NMR spectrometers electronically integrate the relative area of each signal.

OC 307

Chapter 13

Integration:

NMR Spectry-3

H. D. Roth

O
C

CH3

H3C

C
H2

2.2

2.4

1.0 ppm

1.0 ppm

3H; 2.2 ppm

3H; 2.4 ppm

2H.

Spin Spin Splitting

1

H nuclei with adjacent 1H nuclei show Multiplets, i.e., they

contain more than one signal (evenly spaced Peaks).

Multiplets are due to Spin Spin Coupling, an interaction by
which the nuclear spins of adjacent atoms influence each other,
leading to Signal Splitting in the NMR.
The signal of a 1H nucleus with n 1H nuclei on adjacent Cs
has n + 1 peaks, (n + 1) rule.
The separation between adjacent peaks in a multiplet (in Hz)
is called the Coupling Constant (J).

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Chapter 13

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H. D. Roth

How do Multiplets Arise?

Multiplets are due to spin-spin interactions. The nuclear magnets,
aligned parallel (a) and anti-parallel (b) to the magnetic field vector
create different magnetic environments, deshielding or shielding
neighboring nuclei
Different magnetic environments cause slightly different
chemical shifts for adjacent nuclei
The multiplet intensities and the number of peaks are determined
by statistics (how many , ).

Shifted slightly upfield and downfield from the intrinsic

chemical shift.

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Chapter 13

NMR Spectry-3

H. D. Roth

Number of lines and their intensities Pascals Triangle

1
1
1
1
1
1
1

2
3

4
5

1
3
6

10
15

1
1
4
10

20

1
5

15

1
6

multiplet

singlet

doublet

triplet

quartet

quintet

sextet

septet

Each entry is the sum of the values immediately above it left and
right

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Chapter 13

NMR Spectry-3

H. D. Roth

O
C

CH3

H3C

C
H2

2.2

2.4

1.0 ppm

1.0 ppm 3H
CH interacting with CH
(n + 1) triplet
2.2 ppm 3H
CH not coupled
(n + 1) singlet
2.4 ppm 2H
CH interacting with CH
(n + 1) quartet
Nota Bene: equivalent nuclei do not couple (split) each other;
splitting observed only for nuclei with different chemical shifts.
Nota Bene: Coupling is reciprocal; The coupling constant
observed for for two interacting nuclei, A and B, are identical.
This helps us to recognize which groups are adjacent to each
other and interacting with each other.

= J
H -CC-H
a
b

H -CC-H
b
a

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Chapter 13

NMR Spectry-3

H. D. Roth

The angle, , between two C-H sigma bonds is an important factor in

vicinal coupling (through 3 bonds); it also matters whether the angle is fixed (as
in a bicyclic compound). Coupling has maximum values when Q is 0 and
180; it has a minimum values when Q is 90.

Table 13.4 Approximate Values of J for Compounds Containing

Alkyl and Alkenyl Groups
Ha

Ha Hb
C C

H
Hb a

Hb
Hb
8-14 Hz

6-8 Hz
Ha

Ha

Ha

0-5 Hz

Hb

Hb

Ha

Ha

Hb

Hb

0-5 Hz

5-10 Hz

11-18 Hz

0-5 Hz

8-11 Hz

Vinyl groups have small (or negligible) 2Jgem couplings; The cis
and trans couplings can have values in a wide (overlapping)
range; the relative magnitude is always
3

Jtrans >

3J

Jcis > |2Jgem|

cis
Hcis

Hint

2J
R

3J

Htrans

trans

gem

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Chapter 13

NMR Spectry-3

Bromoethane

2-Iodoethane

1,1-Dichloro-2,2-diethoxyethane

H. D. Roth

OC 307

Chapter 13

NMR Spectry-3

H. D. Roth

Multiplets can be represented as splitting trees, showing the

splitting of signals due to neighboring nuclei and their intensities

Methylene protons:

1 : 3 : 3 : 1 quartet

Methyl protons: 1 : 2 : 1

triplet

1-Bromopropane

CH3CH2CH2Cl : Splitting tree for methylene protons @ C-2

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Chapter 13

NMR Spectry-3

H. D. Roth

The CH2 group splits the signal into a

1 : 2 : 1 triplet; then the CH3 group splits each of those lines into
a 1 : 3 : 3 : 1 quartet.
Because the splittings by methyl and methylene have the same
coupling constant, J, the signal appears as a
1 : 5 : 10 : 10 : 5 : 1 sextet (5 n), not as a triplet of quartets.
Nota Bene: Coupling in molecules with unrestricted bond
rotation often gives only (m + n) + 1 peaks.

CHCl2CHClCH3

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Chapter 13

NMR Spectry-3

H. D. Roth

The coupling to non-equivalent nuclei is not always the same.

You cant count on them being the same. Coupling to non-equivalent
nuclei with different coupling constants
CHCl2CHClCH3
Non-Equivalent Neighboring Nuclei
The methyl group has one neighbor and is a doublet (as expected) J =
6.8 Hz
The CHCl2 group has one neighbor and is a doublet (as expected) J =
3.6 Hz
The central CHCl group is more complicated:
It is a quartet (J = 6.8 Hz) of doublets (J = 3.6 Hz)

CH2ClCHClCH3
1,2-dichloropropane
1.6 ppm 3H

3.6 ppm 1H

d(d)

3.8 ppm 1H

d(d)

4.2 ppm

q(d,d)

complex m

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Chapter 13

NMR Spectry-3

H. D. Roth

Stereochemistry & Topicity

The simplest way to visualize topicity is to substitute an atom or group by an isotope

or a different nucleus.

When this is done,

if the resulting compound has no chiral center, the protons are

homotopic

if the resulting compounds are mirror images, the protons are

enantiotopic

if the resulting compounds are diastereomers, the protons are

diastereotopic

Homotopic groups
Homotopic atoms or groups have identical chemical shifts under all conditions.

OC 307

Chapter 13
Cl

Substitute
one H by D

Cl

Dichloromethane
(achiral)

NMR Spectry-3
H

H. D. Roth

Substitution does not

C
produce a stereocenter;
Cl therefore hydrogens
D
are homotopic.
Achiral
Cl

Homotopic atoms or groups are equivalent and have identical chemical shifts.

Enantiotopic groups

Enantiotopic atoms or groups have identical chemical shifts in achiral environments.

They have different chemical shifts in chiral environments.
OH

H
HA H

HBOH

COOH

Ha

Hb

H
COOH

OH

OH

Ha

Cl

Cl

Hb

H
COOH

H
COOH

Geminal 1H Nuclei whose replacement gives enantiomers (enantiotopic) are equivalent

Diastereotopic groups

H atoms on C-3 of 2-butanol are diastereotopic.

Substitution by deuterium creates a chiral center.
Because there is already a chiral center in the molecule, the resulting substitution products are
diastereomers.
Diastereotopic hydrogens are non-equivalent and have different chemical shifts.

OC 307

Chapter 13

NMR Spectry-3

HA

Hb

Ha
HB CH3
H

COOH

Cl

CH3
COOH
OH

OH

H. D. Roth

OH

OH
H

Hb
CH3
COOH

Ha
H

Cl
CH3
COOH

Geminal 1H Nuclei whose replacement gives diastereomers (diastereotopic) are

nonequivalent

The methyl groups on carbon 3 of 3-methyl-2-butanol are diastereotopic.

If a methyl hydrogen of carbon 4 is substituted by deuterium, a new chiral center, carbon 3, is

created.
Because there is already one chiral center, the resulting substitution products are
diastereomers.
The protons of the methyl groups on carbon 3 are non-equivalent and have different chemical
shifts.
3-Methyl-2-butanol
500MHz 1H-NMR spectrum
The methyl groups on carbon 3 are diastereotopic and appear as two doublets (a).

OC 307

13

Chapter 13

NMR Spectry-3

H. D. Roth

Carbon NMR

Three significant disadvantages

Low natural abundance (1.1% 13C)
Lower sensitivity (resonance frequency
is only that of 1H)
Signals are split by many 1H Nuclei

A triplet of quartets and a quartet of triplets make it difficult to observe.

Broad-Band 1H Decoupling simplifies

13

C spectra by eliminating all coupling due to 1H ,

giving single lines

1

Methylcyclohexane 5 types of carbon atoms 5 signals

OC 307

Chapter 13

NMR Spectry-3

H. D. Roth

Dichloropropanes have two or three 13C signals

l
H

H H

CH3
lC

t
r h e C1
3

Because of the wide range of 13C chemical shifts, nonequivalent carbons are more likely to be
resolved than nonequivalent 1H nuclei; the number of signals is more likely to equal the
number of nonequivalent carbons.

Each nonequivalent 13C may give a different signal

Because 13C signals are split by an 1H bonded to it according to the (n + 1) rule. Coupling
constants of 100-250 Hz are common, which means that there is often significant overlap
between signals, and splitting patterns can be very difficult to determine. Therefore 13C-NMR
spectra most commonly are recorded in a proton-decoupled mode.
Proton-decoupled 13C-NMR spectrum of 1-bromobutane.

4 types of carbon atoms 4 signals

Carbon-13 Chemical Shifts

OC 307

Chapter 13

Type of
Carbon

Chemical
Shift ()

RCH3
RCH2R
R3CH

10-40
15-55
20-60

RCH2I
RCH2Br

0-40
25-65
35-80

RCH2Cl
R3COH
R3COR
RC CR
R2C=CR2

40-80
40-80
65-85
100-150

Magnetic Resonance Imaging

NMR Spectry-3

Type of
Carbon
C R
O
RCOR
O
RCNR2
O
RCCOH
O
O
RCH, RCR

H. D. Roth

Chemical
Shift ()
110-160

160 - 180
165 - 180
165 - 185
180 - 215

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Chapter 13

NMR Spectry-3

H. D. Roth

1-Bromopropane

The methyl group (1.0 ppm) has two 1H neighbors and is a triplet;
the CH2Br group (3.4 ppm, deshielded) has two 1H neighbors and is a triplet;
the central CH2 group (1.9 ppm, somewhat deshielded) has 3 and 2 1H neighbors; here the
coupling constants are identical, so that the group shows a sextet [(3+2) + 1].

OC 307

Chapter 13

NMR Spectry-3

H. D. Roth

1-Chloro-3-iodopropane

The central CH2 (Hc)has the possibility for 3 x 3 = 9 peaks (a triplet of triplets). but Jab and Jbc
are similar. Therefore only 4 + 1 = 5 peaks are distinguishable [(n + m) + 1].
1,1,2-Trichloropropane
Coupling to Non-Equivalent Nuclei

Explanation:
The methyl group has one neighbor and is a doublet (as you expected) J = 6.8 Hz;
the CHCl2 group has one neighbor and is a doublet (as you expected) J = 3.6 Hz;
Because the coupling constants are different, the central CHCl group is more complicated:
it is a quartet (coupling to 3H, CH3) of doublets (coupling to 1H). [(n + 1)(m + 1)]

OC 307

Chapter 13

NMR Spectry-3

H. D. Roth

2-Methyl-2-vinyloxirane

Tree diagram for the complex coupling seen in 1H NMR signals for the vinyl group and the
oxirane ring H atoms of 2-methyl-2-vinyloxirane.
3-Methyl-2-butanol

The methyl groups on carbon 3 are diastereotopic; they appear as two separate doublets
(signal a).
NOTE: If a methyl hydrogen of carbon 4 is substituted by deuterium, a new chiral center,
carbon 3, is created.
Because there is already one chiral center, the substitution would generate diastereomers.
The protons of the methyl groups on carbon 3 have different chemical shifts.

OH
1

2
3

3-Methyl-2-butanol

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Chapter 13

NMR Spectry-3

Vinyl Acetate Note the spectrum of the vinyl group

1-Propanol

Unknown Spectrum
Molecular formula C5H10O.

A 3 H triplet plus a 2 H quartet can only be a C2H5 group

H. D. Roth

OC 307

Chapter 13

NMR Spectry-3

H. D. Roth

Unknown Spectrum
Molecular formula C7H14O.

2,32 (s)

1.01 (s)

CH 3 O
CH 3 -C-CH2 -C-CH3

2.11 (s)

CH 3
4,4-Dimethyl-2-pentanone

A 9 H singlet can only be a t-butyl group

Unknown Spectrum
Molecular formula C7H12.
The compound reacts with bromine in carbon tetrachloride to give a compound with the
molecular formula C7H12Br2. The 13C-NMR spectrum shows signals at 150.1,106.4, 35.4,
28.4, and 26.6.

The molecular formula, C7H12, indicates a hydrogen deficiency of 2: there will be a

combination of two (rings and/or pi bonds).
The compound reacts with only one mole of bromine: there is one double bond plus one ring.

OC 307

Chapter 13

NMR Spectry-3

H. D. Roth

The 13C-NMR shows only two sp2 resonances: again there is only one double bond.
The compound is cycloheptene.
NOTE: there are only three 1H signals but cycloheptene has four groups of protons. Alkene
(4.6 ppm) and allylic (2.1 ppm) protons are clearly separated; the remaining two types,
protons at C-4,6 and C-5 are not resolved.
Unknown Spectrum

0.9 ppm 9H t (=2n) shielded

1.5 ppm 6H q (=3n)

The combination of t (=2n) and q (=3n) is

1.3 ppm 1H s (=0n)

slightly deshielded
always -CH-CH

Because the signal @ 1.3 cannot be less than 1H, there must be three -CH-CH
groups.
The signal @ 1.3 is not coupled: OH
The compound is (CHCH)C-OH
13

C spectrum confirms

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Chapter 13

NMR Spectry-3

H. D. Roth

Unknown Spectrum

4.3 ppm 1H t (=2n) strongly shielded

2.4 ppm 1H t (=2n)

deshielded

2.2 ppm 1H qui (=4n)

deshielded

3 nuclei (1+1+1) cannot explain the observed multiplets: we try 2+2+2

This works if the nuclei @ 4.3 AND 2.4 ppm interact with those @ 2.2 ppm:
Y-CH-CH-CH-X
2.4

2.2 4.2
H

H H

O
H
13

C spectrum confirms

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Chapter 13

NMR Spectry-3

H. D. Roth

Unknown Spectrum

1.1 ppm d(?), 6: two possibilities: 2 equiv. CH with 1 neighbor

or

two nonequiv. CH w/o neighbor

2.8 ppm sep., 1 (= 6n) requires that the 6H have 1n. This gives us isopropyl.

2.8 ppm is deshielded, but not enough for a halogen: how and to what is isopropyl attached?
The answer comes from the 13C spectrum. The tiny signal @ 220 ppm signifies a carbonyl.
Our compound is diisopropyl ketone.

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Chapter 13

NMR Spectry-3

H. D. Roth

Unknown Spectrum

Unknown Spectrum

1.2 ppm 3H t (=2n)

shielded

3.5 ppm 2H q (=3n)

strongly deshielded

The combination of t (=2n) and q (=3n) is

4.0 ppm 2H d (=1n)

again -CH-CH

The signals @ 3.5 and 4.4 ppm could be adjacent to O, giving us a CH-O-CH-CH unit.
The remaining signals belong to a vinyl group, a mono-substituted alkene group.
Unknown Spectrum

1.0
1.5 sex

3H
2H

CH

CH
5n

2n
(CH, CH)

(CH)

OC 307
1.8 qui
4.3

Chapter 13

2H
t

CH
2H

NMR Spectry-3

4n

H. D. Roth

(CH, CH)

CH 2n

(CH)

deshielded by Eneg group

Eneg cannot be a Hal because a Hal would terminate the molecule; we need O (or S or N,
etc) to attach the rest of the molecule.
This adds up to a OCHCHCHCH group.
The rest of the molecule is a phenyl group; you learn about that in 308.
Unknown Spectrum

1.0

3H

CH

2n

(CHCH)

1.4 sex

2H

CH

5n

(CHCHCH)

1.6 qui

2H

CH

4n

(CHCHCHCH)

(this requires one more CH; there are three, @

3.5, 3.6, 3.8, all (t 2H)

requiring CH

2n

all deshielded by Eneg group: 2 O?

This adds up to a OCHCHCHCH group and a OCHCHO
One O is an OH (2.4, s, 1H)
Molecule:
HOCHCHO OCHCHCHCH

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Chapter 13

NMR Spectry-3

H. D. Roth

Unknown Spectrum

1.0

3H

1.5 sex

2H

CH

5n

(CH, CH)

1.8 qui

2H

CH

4n

(CH, CH)

4.3

2H

CH 2n

CH 2n

(CH)

(CH)

deshielded by an electronegative group

The electronegative group cannot be a halogen because a halogen would terminate the
molecule; we need O (or S or N, etc) to attach the rest of the molecule.
This adds up to a OCHCHCHCH group.
The rest of the molecule is a phenyl group; you learn about that in 308.
Unknown Spectrum

C6H12O2; Hsat = 2 x 6 + 2 = 14; Hact = 12; Hsat Hact = 2; D(U) = 1). 2 CH3 groups, 0.9, t, 1.2
ppm, t, (n + 1 = 3), @CH2. 3 CH2 to choose from. @ 2.3 ppm: q (n + 1 = 4) CH3; CH3CH2;

OC 307

Chapter 13

NMR Spectry-3

H. D. Roth

Sextet @ 1.7 requires 5 neighbours; 3 @ CH3; remaining two must be CH2 @ 3.7: CH3CH2
CH2; how to connect? C6H12O2 C2H5 C3H7 = OC=O: one group at O, one at C=O. q @ 3.7
must be near O: CH3CH2O, t @ 2.3 attached @ C=O: CH3CH2CH2C=O.

O
O
Unknown Spectrum

1.0

3H

CH

2n

(CHCH)

1.4 sex

2H

CH

5n

(CHCHCH)

1.6 qui

2H

CH

4n

(CHCHCHCH)

(this requires one more CH; there are three, @ 3.5, 3.6, 3.8, all (t 2 H) requiring CH
all deshielded by an electronegative group: 2 O?
This adds up to a OCHCHCHCH group and a
OCHCHO
One O is an OH (2.4, s, 1 H)
Molecule:
HOCHCHO OCHCHCHCH

(2n)

OC 307

Chapter 13

Splitting trees for a vinyl group

NMR Spectry-3

H. D. Roth