Chapter 13: Proton and Carbon-13 NMR Spectroscopy

1. Molecular spectroscopy
2. Degree (sites) of unsaturation / Index of hydrogen deficiency
3. Proton NMR
4. 13C NMR
Spectroscopy and Electromagnetic Radiation:
diff molecular structures absorb/emit
1. Molecular Spectroscopy:
diff types o f radiation
Molecular spectroscopy is the study of the interaction between the substances and electromagnetic radiations.
There are number of spectroscopic techniques which measure energy of radiations absorbed or emitted by a particular
substance and then the pattern of energy absorption or emission is corelated with the molecular structure.
a. Characteristics

All electromagnetic radations have a dual character to behave as wave and particle. The energy associated with these
radiations (photons) can be related to their frequency/wavelength/wave no.

E = hv = hK = h c
I = hot
C= v X %, = T
wave because wavelength
number u s e f u l c a n
g e t s o l a r that i t s hard t o r e a d

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 1

Molecules undergo vibrational, electronic or nuclear transitions and the energy associated in the transition corresponds to
different electromagnetic spectrum regions.
In this course we will learn three common spectroscopic techniques to determine structures of organic compounds.
1. Nuclear Magnetic Resonance Spectroscopy (NMR) Low energy radio waves are absorbed in the transition between nuclear
spin states and gives information about the connectivity of carbon and hydrogen atoms in the molecule.
bends
2. Infrared Spectroscopy (IR) It is useful technique to identify the functional group in organic compounds. The energy
associated with molecular vibrations fall in IR region."fingerprinting" a molecule
3. Ultraviolet Spectroscopy (UV-vis)- This UV and visible regions are involved in electronic transitions in the molecule. This
technique gives useful information about molecules that contain conjugated pi bonds. conjugatedsystems
In addition to above spectroscopic techniques, we also use Mass Spectrometry (MS or Mass Spec) -This technique gives
information about molar mass, and composition by analyzing the fragments of radical ions. breaking molecules into
stable components
(C,H , functionalgroups)

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 2

Spectre characters b e s determine tools

nuclear spin = N MR

molecular dipole = I R spec

electronic transitions = UVN B

NMR= bend connechwty

I R specific bond presence
=

U V- v i s = conjugation
mass spec= structure
Degree warsaturation = cumulatie total o f r i n g s / t bends

Degree or sites of unsaturation /Index of hydrogen deficiency (Sec 14.1c)

The total no of cyclic rings and bonds in a compound is called its degree of unsaturation. One bond or one cyclic ring is one
degree of unsaturation.

y t x t z -Y. a t = I t t I
In case the compound contains halogens(X), oxygen(O) and nitrogen(N) in the molecular formula CnHmXpNqOr

Degree of unsaturation = oxygen n o effect

y Degree of unsaturation can have 2 bonds or one ring and one

( = 213)t 2 =
8-lH.at#=
bond or two rings.

1
The possible structure formulas:

o r

aTry: Determine site of unsaturation in the given MFe a

:C3H9N, C6H4Cl4N2, C5H6O2, C3H3Cl3O

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 3

64%1.1×2+157=4,#
I t

0546025×2%-12--26=3

i:i÷i÷÷÷÷
 NMR spectroscopic technique is used to determine the molecular structure by detecting the local magnetic field around the
atomic nuclei.
Like electrons, the nucleus of atom can be described as nuclear spin quantum states (due to charged protons in the nucleus).
Nuclei with an odd mass number have spin states that can be studied with this technique - 1H, 13C, 31P. (All nuclei with an odd
mass number (1H, 13C) have spin angular momentum because they have an unpaired proton.) (charged)
Two common types of NMR spectroscopy are used to characterize organic structure.
1H NMR is used to determine the type and number of H atoms in a molecule.
13C NMR is used to determine the types of carbon atoms in a molecule.

Proton NMR (1H NMR)

normallThe atomic nucleus has spinning charged particles (protons) which generates a magnetic field. The nuclear magnetic spins are
y randomly oriented. When placed in external magnetic field, the nuclear magnetic field can align themselves with the external
magnetic field or against the external magnetic field.
spin state => protons spin that align themselves with external
magnetic field => lower in energy
spin state => protons spin aligned against external magnetic
field => higher in energy

The energy difference between and spin states depends on

applied magnetic field. Stronger the strength of applied magnetic
field, larger is energy difference between these spin states. The E
between the and spin state lies in the radio frequency region.
Radio waves frequency causes the spin to flip and nuclei are said to
be in resonance with applied field and produces an NMR signal.

strong magnets pull harder and thus

fewer protons g o against
Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 4
Characteristic features of 1H NMR for structural information.
1. Number of signals
2. Position of signals
3. Integration or intensity of signals
4. Splitting of signals

1. Number of Signals: Nuclei of a given type will resonate at different frequency depending on their chemical and electronic
environment. Each chemically equivalent proton (proton in the same molecular environment) resonates at the same
frequency and gives a single signal.

x " × Y,
Protons within a molecule can be magnetically equivalent if they experience identical influence when placed in an external
magnetic field. The absorption frequency for magnetically equivalent protons is same.

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 5

 To decide whether the protons are magnetically equivalent or nonequivalent, replace any of the protons with other atoms like
Br, Cl, or D. Protons that are replaced to form same compound (Homotopic), or its enantiomer (Enantiotopic) are
magnetically equivalent and if the replacement results in diastereomers then protons are nonequivalent (Diastereotopic)

Protons attached to symmetry relatedMahatma

atoms are also magnetically equivalent. This equivalency is due to presence of
plane, axis or center of symmetry.
'molecules

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 6

 To determine equivalent protons in cycloalkanes and alkenes, draw all bonds to hydrogen atoms on a ring or double bond, two
protons are equivalent only if they are cis (or trans) to the same group.

For example:

tommenay
also

Proton equivalency in cycloalkanes can also be determined similarly.

For example, 1-chlorocyclobutane has 5 signals. Ha and Hb are not equivalent as Ha is trans to Cl
whereas Hb is cis to Cl. Hc and Hd are not equivalent because Hc is trans to Cl and Hd is cis to Cl.

Try: How many 1H NMR signals are expected in the following compounds?

*¥¥¥¥
O O

" " e "o

'jacamar.
¥. CH,
Z 4 -

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 7

N M R instruments are d i f fe re n t - d i f f magnets,d i f f freqs
Position of Signals:
The position of signals in NMR spectrum gives information about the kind of proton responsible for the signal.
An NMR spectrum is a plot of intensity of a peak against its chemical shift, measured in parts per million (ppm).

Chemical shift scale: Chemical shift, reported in ppm, is a measure of position of signal that is produced for the protons
relative to the reference signal. Tetramethyl silane (TMS) is used as reference standard and assigned chemical shift 0 ppm.

The electrons surrounding a nucleus affect the effective magnetic field sensed by the nucleus.
Different types of protons (i.e., protons in different molecular environment) are shielded to different extent
(greater the e density around the nuclei larger the magnetic field of surrounding e around the nuclei, more the proton is
shielded from applied magnetic field). electrons shield protons from appliedmagnetic fields
Protons in electron rich environment are more shielded and are therefore more upfield, i.e., farther on the right.
Protons in electron poor environment sense more effective magnetic field due to less shielding and are more downfield (at
higher ppm).

1H NMR for CH3OC(CH3)3

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 8

 fe w e r H
a) The chemical shift of a C-H bond increases with increasing alkyl substitution. lessshielding

RCH2-H R2CH-H R3-C-H

0.9 ppm - 1.3 ppm - 1.7 ppm

b) Presence of electronegative atom, electron withdrawing groups (inductive effect) deshielding of protons higher the value
and its influence diminishes with distance.

More the number of electrons withdrawing attached to the carbon the proton signal shift farther downfield.

c) Ring current effect (magnetic anisotropy): is the magnetic field created by electrons or rings. electrons are held
less strongly so they are able to move in response to magnetic field. The induced local magnetic field of bonds either
add to or subtract from the applied field depending on geometry of the induced electron density circulation relation to the
atom.

electrons in alkenes, aromatic systems and other compounds tend to deshield the nuclei of adjacent protons through
ring currents, i.e., protons feel larger effective magnetic field. For example, the aryl hydrogen of benzene is de-shielded by
ring currents = 6.5 8 ppm.

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 9

a l la r e duethe bends d eshield nuclei,increasing effect a t appliedfield
8 ¥ → 0=0
decrease applied field due to t h e i r
triple bonds the effect o f the
geometry
¥¥
 The large chemical shift of aldehydes is combined effect of electrons and electronegative O.

C-C< C E C L C E C
0
¥
In a magnetic field, the but, in this case, the
induced magnetic field opposes the applied magnetic field. Thus, protons feel a weaker
magnetic field. Thus, a lower frequency is needed for resonance. The nucleus is
shielded, and absorption is up-field, approximately at 2.5 ppm.
lower shift
Characteristic chemical shift

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 10

0
Try: Assign chemical shift to the indicated protons in each of the given compounds.

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 11

A@IIyItgZl8PPM2. ppm

88ppm2.qz
§ t m ¥ p m
t.A-
T#=.m.36PPmo.6oppm
Integration/Intensity of signals
Integration is the total area under the signal (signal intensity). The area under each signal is proportional to the number of
equivalent protons that give rise to that signal. The spectrometer calculates integrated relative area of each signal.
The numbers do not correspond to the exact or absolute number of protons.

Splitting of Signals:
Proton resonance are influenced through interaction of bonds by local fields generated by the protons attached to adjacent
carbons. The spin of one nucleus polarizes the spins of intervening electrons thus the energy levels of neighboring magnetic
nuclei are polarized by these electrons. This effect is called spin-spin splitting.
Splitting of signals also called J coupling provide information on connectivity of chemical bonds.it is responsible for complex
splitting of resonance lines in the NMR spectrum.
Peaks are often split into multiple peaks due to magnetic interactions between nonequivalent protons on carbons that is
separated by three bonds (also called vicinal coupling) or two bonds (also called geminal coupling) sometimes four
bonds coupling.
The J coupling is represented as nJAB where n refers to the number of intervening bonds, and A and B identify the two
coupled spins.
4T coupling → alkynes,aromatic
Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 12
 ¥410 adjacent non-equiv H t magnetically affect eachother
equivalent At split the signal dependingo n whether
add o r subtract from the applied field
neighboring Itt t o

3T Hb H Ha
J
I-I-I-Ha
Z

c-C-Ha
, Ha
H,
Example
In the given compound 1,1,2-tricholoro ethane, Hb peak splits into two peaks. The neighboring proton (Ha) spin adds to the
field felt by Hb and neighboring proton (Ha) spin weakens the field felt by Hb. When they are parallel, Ha feels a stronger field
(applied field + Hb) and when they are anti-parallel, Ha feels a weaker field. This results in two close signals. Thus, Hb appears
as ardoublet.
unnin
triplet

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 13

Ha and Hb

Multiplicity: A resonance line that is split due to J-coupling is generally

referred to as a multiplet (The number of peaks in a signal).
The set of peaks is a multiplet (2 = doublet, 3 = triplet, 4 = quartet,
5=quintet
The number of equivalent protons bonded the adjacent carbon
determines multiplicity.

peaks = adjacent t self

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 14

i) number of peaks given by (n + 1) rule the adjacent carbons.

The relative intensities are in

proportion of a binomial distribution
.

- i t
Coupling constant (J): The distance between two adjacent peaks of a split signal is called coupling constant J.
The magnitude of J is a measure of how strongly the nucleus spins of the coupled protons influence each other. Therefore, it is
dependent on number and types of bonds that connect the coupled protons and their geometric relationship.
43-H
The coupling constants (expressed in Hz) give useful information about the structure of compound. In molecules where there is
restricted rotation about the bond (double bonds or rings), It provide information about stereochemistry for instance cis or trans
in alkenes.
%
I
standard closer farther close
together

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 15

 i) Jab ~ Jbc In acyc 7 H Z.
(n+1) rule and Pascal triangle apply.
HasHe
Hasshows

Jab= Jsc triplet

(A) a
of
(B) for each is ~ 7Hz. It is coupled to two different CH2

NOTE: 1) Equivalent protons do not couple

-
only 1 signal/peak
Cl-CH2-CH2-Cl
at 4H (singlet)

q~4
In aromatic compounds, spin coupling occurs between protons attached to benzene ring (3 bond coupling) but not with protons
on groups attached to ring. becauseo f delocalizede - density

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 16

Br-citrate-citz-4
Zita 2h, 2h,

Ha
Br-ftp.#I,tqt-c1P-
triplets
HisHb,son=2Inti=3
13r-tIV.ie/P-
H, HisHaandHc,soginenJab=5bcn=4
Intlesquintetf

HE>
#H
Br-E,-'II-414 P-His Hb,s o n a r I n t l =3

It
e triplet
 " t
Hi¥o#*J
'GH
doubletotdenbletM
Hb
When coupling constants are not same

larger distance f i r s t ¥577,71

K¥4,4
splitting pattern is represented as

Ha appears as a doublet of doublets (d,d)

No of lines for Ha = (nb + 1)(nc + 1) = (1+1)(1+1) = 4 lines,

&
Multiplicities are generally reported starting with the largest coupling constant.
Hb
i ÷ ¥ ÷ ,
Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 17
 yqtusekuscrde
Rapid exchange Protons:
r-qqhertnt-q.cl
Protons on O and N can exchange due to intermolecular H bonding. Rapid intermolecular exchange of the OH protons of
alcohols often prevent their coupling with hydrogen on adjacent carbon, these protons are often decoupled.
1H NMR of O-H or N-H generally appears as broad singlet.
noHandrivitzappearsame
Long range coupling:
This occurs when the protons are separated by more than 3 bonds and one of the bonds is double or triple bond. Four bond
coupling is observed in pi systems like terminal alkynes, allylic systems and in aromatic compounds. A small splitting is
sometimes observed due to 4 bond coupling.

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 18

In aromatic system:
pa%
Ortho meta (no coupling)
-

If we consider only 3-bond coupling for disubstituted benzene,

Itf 'to
we expect the splitting of signals as shown.
It' - p l a n e '
Hdiscaepk
ittas-tbclhenltb-tn.net
i t Tatted then Hectriplet
2+190%+901+1 symmetry

dufttc.edu#
Haiscouptedulitbidenblety,
In case of 4-bond coupling is observed then the signal further get split by hydrogens at meta position.
NMR of 4-methyl-2-nitrophenol shows Ha (d), Hb(d,d), Hc (d)

4J
3¥ 3J

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 19

 4 5 W meter coupling
If)¥¥
Ha,
Hahasenly 3Toupling
Hbhas both 3 5 2 4 5 coupling
¥THc H e n l y has 4 J coupling
Try: Write multiplicity of different protons in each compound.

O o a
13C NMR
The number of signals in a 13C NMR spectrum tells different kinds of carbons in the compound.
Frequency to cause spin flip is about 1/4th what it is to spin-flip proton.
13C coupling has much larger J values (~ 100Hz) in comparison

to 1H J values
13C NMR absorption range from 0.0 to 250 ppm (0.0 is
defined as signal of TMS)
Wide range i.e., each carbon gives a signal well separated from
other
Broad band decoupled proton 13C NMR is recorded under
conditions of proton decoupling. A
frequency radiation, therefore 13C-H coupling not observed.
Thus, a single line signal is observed for each of the chemically
different carbons.
This gives idea about the different types of carbons in the compound.
The chemical shift gives some idea about the functional groups.
* 13C chemical shifts:

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 20

 Hasplitbytts → doubhetlnogeminal
af,-gotta
'O-Cbd
Hd has n o 13-H → singlet
Hb' Hysplitbyttbandbytto → dif
trans distance
higherthanttb-
sttc.ii.iiiii.it?.i:.In..... quartetatdoublets
CHI-¢-CEC-Ha HysplitbyttaandHc →

Jab=2HzHJbe=7Hz befirst
Hb b i . n = 3 H = 4 → quartet
Hcstiiifibtitf-sinipdiifht-FEF.it,
Example: 13C and 1H NMR

c a c
b b

a b c

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 21

 baab

a b

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 22

 HO
ftp.i-
1-butene n o
13C NMR:

iitfo:
a
b

1H NMR:

- -

c e d a
b
Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 23
4-methoxybutan-2-one
13C NMR

1H NMR

I
234 5

4 53 I

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 24

Try:
1. How many 1H NMR signals and 13CNMR signals are expected in the compounds shown?

'I:L It: z
tiff} c. 3×4

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 25

 none in 308
2. Draw the expected structure of the compound from the 1H NMR and 13C NMR shown:
a) C6H12O2
13C NMR
6×2t 2 = 14-to = % = I d e g unseet/t bond o n nth

p l o tH,
1H NMR

R-E-O-C
Hs

Chapter 13: Proton and Carbon NMR Spectroscopy (KSethi) Page 26

atoms w/odd atomic#'s a r e magnetica n d spin btwn 2 spin slates
external magnetic fields c a n hold atoms in o n e spin state
flipping nuclear spin states takes energy; the energy gap i s 0 E
o v e r c o m e O E b y hitting nuclei w / E M F radiation

higher freq= higher e n e r g y, therefore higher 0 E requires higher

freq to spin
H t w/same bond anaeclivilies a r e magnetically identical s a m eo E
replacea n H t and i t makes s a m e molew e (homotop,2)o r e v e nh e m e r

(enantiotop,c ) then magnetically identical

w w w. E t E E E E r r
N M R shifts:
u pfield = lower DE-lower ppm = lowershift = right
downfield= higherO E = higher
ppm= highershift = l e f t
shielding
At w i t h m a n y elections shielding i t are affected less by applied
magnetic fields
shielded Ht
have lounge 0 E and therefore only need
therefore, a

a lower t r y to enter magnetic resonance

therefore, shielded H
t
freq = l o w e r shift a n d
= lower vice ve r s a

decrease shielding around protons, increasing s h i f t

mere R groups
atoms electrons from Itt, decreasing shielding
electronegative pull a w a y
m o r e heteroatoms = less shieldinga increased s h i f t
effect diminishesquickly w/distance
T o electrons a r e delocalized compared t o T electrons,s o they shield less
AND affectt h e applied magnebe field
double bonds increase the effect a t the magnetic field, increasingshift
triple bonds decrease the effecto f the magneticfield b y geometry,
decreasing shift
splitting/Coupling
t
heightofa n N M R peak i s proportional to n u m o f equiv. H
t

local magneticfields o f adjacent (vicinal/seminal) H taffect each other

i n

symbol f o r this B n JAB, w h e r e n number of bends btwn Ita& Hp

=

2 5 = Gemmell, 3 J = vicinal, 4 5 only A r a n d alkynes

=

J represents t h e distance btwn adjacent peaks o f a splitsignal a n d

depends o n
length/type o f bends-closer smaller T I v i c e v e r s a
=

* it a " Fe t s ' ¥ ' t s ' # a

number o f peaks i n a split signal 13 n t 1 where n n u m o f adjacent
=

(coupled) H t given J i s t h e s a m e f o r a l l
equiv.
i t t not the s a m e , do n t 1 f o r the larger J then in decreasing
order (Pgh)
 ppm'HNMRsh
R-CHs 0. 9 - 1 . 2 PPM R- c - 1 + 2 . 2 - 2 .a

fictitztz-1.5 R-O-CH, 3.3-3.4

k R - C h - x 3-1-3.8
Right 1.4-1.9 Ail,Br)(3.0-4.5)
R-O-H r t - 5
%=µµµl5-2.5
R'
R-MHz - 1 - 5

RICH, 2.0-2-6 RYE#4.8-6.0

It
Ar-Ut, 2 . 2 - 2 5 Ar-H 6.0-8.5

RIA 9 - 10

RIO-H 10-13
F i g u r e 13.3
 BCNMRshift
> zoo →
R-I-H, p-E-R
R-E-O, R-E-O-H,R-E-OR, R-E-CI,R-i-NH,
170490 →
110-130→ Nitrite
l o o t be → H r , alkenes
6 5 - 9 5 → alkynes
70-85-730alcohol R,
Colt

bo-80 → 20alcohol
R,-CHOH
to alcohol R-UtzOH
40-70 →

5 5 - 8 0→ C H - X ( B r, Cl)

30-Go → 30 a l k y l R,C H
25-45→ 20 a l k y l R-CHER
15-30-710 alkyl R-CH,

Figure 13.23