NMR

Nuclear Magnetic Resonance

Proton NMR:
Symmetry

Index

NMR-basics

H-NMR

Homotopic protons: A2 spin System

Chemical shift equivalence : Isochronous nuclei

These nuclei are interchangeable by symmetry or rapid exchange

Cl

Cl

Protons are equivalent in chiral and achiral

environment

Homotopic protons examples

CH2Cl2

CH2CF2

A2X2

A2
H

Cl

Cl

Cl

Cl

A4

Enantiotopic Protons
Plane of symmetry
H

Cl

Me

COOH

A2X3

A2X
d =6.15
J = 53.6 Hz
6.0

2.5

2.0

1.5

1.0

Enantiotopic protons are

Equivalent in Achiral environment (like CDCl3)
Non-equivalent in Chiral environment (optically active solvent)

A2X2 spin system??

F

AAXX
F

H1 & H2 => same shift : chemically equivalent (homotopic)

3J

H1-F4

=> cis

3J

H2-F4

=> trans

The two protons are coupled to the same nuclei with different coupling!
Magnetic Non-Equivalence

Magnetic Equivalence
2-H

H-1 Cl
Cl
3-H
F

The 2 H geminal to Fluorine are enantiotopic

The 2 H geminal to Chlorine are enantiotopic

H-4 The 2 H(1,3) and 2 H(2,4) are chemically equivalent

Is this an A2M2X2

spin system?

These protons are chemically equivalent but are magnetically nonequivalent because they have different couplings with neighbors
JH1-H2

JH1-H4

AAMMXX spin system

No symmetry: Asymmetric center

OH

HC

OH
Me

OH

COOH

ABX

HB

HA
H

CH3

HO

Me

H
Me

COOH

H
OH

COOH

Protons A and B have different shifts: they are Diastereotopic

Accidental overlap can occur producing deceptively simple spin system

H1-NMR
OH

OH

HC

7.0

CH3

CH2

HO
6.5

CH3

CH

2.70

2.60

4.20
1.20

4.0

3.5

3.0

2.5

2.0

1.5

Dissymmetric center
H

OH
COOH

HOOC

H H

H H
B1

B2

A1

A2

Plane of symmetry
Enantiotopic groups
Ha1 = Ha2

Hb1 = Hb2

Diastereotopic protons
A2B2X

AB

AB
X

AB

Me
HOOC
H
H

2 dissymmetric centers in
symmetrical molecule

Me
H

H
H
COOH

COOH Me
H
COOH

H
H

Me

Me
Symmetrical : s plane
Diastereotopic protons

Symmetrical : C2 axis
Enantiotopic protons
CH

CH2
HA

Mixture of 2 isomers

HB

Equivalence, non-equivalence and symmetry

H2

HO

H2

HO
H1

Me2

H1

*
Me2

Cl

Me1

HO

Me1
Me2

H3 C

Cl

Cl

Cl

Cl

d H1 = d H2
d H1 d H2

d Me1 = d Me2
H1
H5

d Me1 d Me2

H2

CH3

d H1 d H2 AB

d H3 d H4 AB

Br
H6

CH3

H3

H4

d H3 = d H4 A2

Example of dissymmetric spin system

H
O

2J

CH3

ABX3

H3C

3J

A-Me

AB

= 9.4 Hz

= 3JB-Me = 7.0 Hz

CH3

dq

3.60

4.5

d B = 3.55

d A = 3.40

3.50

4.0

3.5

3.40

3.0

2.5

2.0

1.5

Chemical Shift Non-Equivalence over a distance

Diastereotopic protons
H2 N

COOH

AB

AB

H3 C

CH3

2 doublets

Magnetic Equivalence
H

A1

A2

B1

Enantiotopic protons:

B2

Ph

HA1 = HA2
HB1 = HB2

Diastereototopic protons:

HA1 HB1
HA2 HB2

Magnetic equivalence
JA1-B1 JA2-B1

A1 and A2 are
Magnetically different
AABB

AABB

AABB
Cl
N

A'

H
B

B'

2 sets of homotopic protons : magnetically non-equivalent

AABB: para

AABB: Ortho

Spin System: Pople Notation

Each Chemical Shift is designated by a letter
Dn -> Difference in Shift in Hz
J -> Coupling in Hz
If the ratio Dn/J is Small (<8), Letters used to designate the shift are close
AB, ABC
This represent case of second order spectra: These spectra must be
simulated with the help of quantum mechanic equations. Such programs
are available on Nuts or Mestrec or Spectrometer software. This case is
also called strongly coupled
If the ratio Dn/J is large (>8), Letters used to designate the shift are far
AM, AX
This case give rise to first order type spectra Is is also refer to as weakly
coupled case

Pople Notation
A2X (if the shift difference of CH2 and CH is large
Y

CH2 HC

OR

compare to coupling).

OR

A2B (if the shift difference of CH2 and CH is small

compare to coupling).

3 Spins

AMX -> if the 3 spins have large chemical shift difference

ABX -> if 2 spins are close and 1 is far away
ABC -> if 3 spins are close

When nuclei have identical shift but different magnetic coupling,

prime symbol is used. For example:
AABB or AAXX

AABBC
JAX = Jcis = 10 Hz
JAM = Jtrans = 17 Hz
JMX = Jgem = 2 Hz

A : dd

Jtrans

Jcis

Virtual Coupling
Virtual coupling

First order
O2N

CH3

HO

CH3

Same shift

CH2-OH

CH3 broad

CH2b

Virtual
Coupling

Me broad doublet

COOH
H

Me

COOH

A2B2CX3

Because of the close shifts of ABC protons we observe virtual coupling

Virtual Coupling : Symmetrical chains

1

1)

2)

3)

CO2Me CH2 CH2 CO2Me

A2
A2
A4
1

Singlet

CO2Me CH2 CH2 CH2 CO2Me

A2
X2
A2
A4X2 Triplet, Quintet

CO2Me CH2 CH2 CH2 CH2 CO2Me

A2
X2
X2
A2
A2 A2 X2 X2
Complex spectra
Same shift, different J with A/A
Virtual coupling

Virtual Coupling
3)

CO2Me CH2 CH2 CH2 CH2 CO2Me

Symmetrical Molecules with 2 chiral centers

Ph

Ph
Br

H1
H

H2
Br
Ph

1r, 3r; erythro

H1 = H 2
Enantiotopic protons
Magnetically non-equivalent
AAXX
Due to fast rotation, J is average
A2X2

H
H1

Br

Br

H2

Ph
1r, 3s; Meso
H1 = H2
diastereotopic protons
ABX2

Chiral Centers in Symmetrical Molecules

COOH

COOH
H1

H1

H1

H1

OH

OH

H2

H2

H2

H2

OH

H
H3

H
H3

OH

H3

COOH

Meso: plane of symmetry

H3
COOH

Erythro: axis of symmetry

H1 H1 diastereotopic

H1 H1 diastereotopic

H3 H3 diastereotopic

H3 H3 diastereotopic

Group1 = Group3

Group1 = Group3

H2 H2 diastereotopic

H2 = H2 enantiotopic

Chiral Centers in polymers

X

H A X HA X HA X HA

R HB R HB R HB R HB

Isotactic polymer
AB

H A R HA X HA R HA

Syndiotactic polymer
A = B A2
R HB X HB R HB X HB

Calculating Shifts for simple aliphatic compounds

d = 0.23 + SSi(d)

CH3Cl d(calc)=2.76
d(exp.)=3.1
CH2Cl2 d(calc)=5.29
d(exp.)=5.3
CHCl3 d(calc)=7.82
d(exp.)=7.27

Calculating Shifts for aliphatic compounds

d = 0.933 + SSi(d)
1

e.g. CH3-CO-CO-CH3
Subst. Effect
- C2-C3
=O (at C2)
=O (at C3)
-CR3 (at C3)

value
+0.244
+1.021
+0.004
-0.038

SSi(d)

+1.231

d = 0.933 + 1.231 = 2.164

Experimental = 2.23

Calculating
Shifts for
olefinic
compounds

Calculating Shifts for olefinic compounds

Ph

H1

OEt

+ 1.35 + (-1.28)

H1

d = 5.23 + Phgem + OEttrans

d = 5.32

H2

H2

d = 5.23 + Phtrans + OEtgem

+ (-0.10) + 1.18
d = 6.33

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

Calculating Shifts for olefinic compounds (deciding which isomer)

Experimental: 8.22 ppm
H

CN

COOEt

Which one ??
COOEt

CN

Z isomer
Base
Ph (gem)
CN (cis)
COORconj *(trans)

effect
5.23
1.43
0.78
0.33

E isomer
Base
Ph (gem)
CN (trans)
COORconj * (cis)

effect
5.23
1.43
0.58
1.02

Total

7.77

Total

8.26

* Double bond is further conjugated

Calculating Shifts
for aromatic
compounds

Aromatic substitution pattern: ortho

AA XX
Typical spectra for ortho (symmetrical)
O
CH3
O

CH3

8.00

7.90

7.80

7.70

7.60

7.50

7.40

Aromatic substituent pattern: para

Aromatic substituent pattern

O

CH3

CH3

NO 2

NO 2

t
J=1.8

dt
J=7.7, 1.5
ddd
J=8.1, 2.2, 1.1

8.5

8.0

t
J=8.1

Aromatic substituent pattern

O

CH3

CH3

NO 2
NO 2

td
J=7.4, 1.1

dd
J=8.1, 0.7

8.1

8.0

7.9

7.8

7.7

~td
J=8.1, 1.5

7.6

dd
J=7.7, 1.5

7.5

7.4

NO2

C5H9NO4
3H

CH3

CH3

CH

t
3H

CH2

O
q
2H
q
1H

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

C5H8O
CH3

CH2

CH
CHO
CHO, d
J=8.1 Hz

CH

t,
J=7.4

Trans J

ddt,
J=15.8, 8.1, 1.5

CH2

dt,
J=15.8, 6.9

1.20

9.55 9.50 9.45

6.15
7.0

2.45 2.40

1.10

2.35

6.9

1.00

1.16

6.10 6.05

1.15

0.93

2.45

3.73

C4H6O2
H

CH3

O
C

I = C H/2 + 1 = 2
s

H
O

Jcis = 6.6

2J
gem

dd
14.0, 6.6

7.3

dd
6.6, 1.5

dd
14.0, 1.5

Jtrans = 14.0

4.9

4.8

= 1.5
4.7

4.6

7.2

CH=
1.00

2.14

3.09

400 MHz
O

3, ddd
5.0, 1.5, 0.9

5, dd
9.2, 2.4

8.5

3, d(2.4)

5, ddd
7.9, 7.4, 1.6

5
4

3
6, dt
7.9, 1.0

8.0

8.5

8.0

4, ddd
7.4, 5.0 , 1.0

7.5

80 MHz

9.0

6, d
(9.2)

7.5

NEXT

Proton and Heteronuclear NMR

Index

NMR-basics

H-NMR NMR-Symmetry Heteronuclear-NMR