CHM556/CHM557

CHAPTER 1
SPECTROSCOPY OF CARBON
COMPOUNDS
 SUBTOPICS

 Introduction to spectroscopy and structural

identification
 Infrared spectroscopy
 Proton and Carbon-13 Nuclear Magnetic
Resonance Spectroscopy
 INTRODUCTION TO
SPECTROSCOPY AND
STRUCTURAL
IDENTIFICATION
• Spectroscopy is an analytical technique which helps
determine structure.

• It destroys little or no sample.

• Spectroscopy: The study of the interaction between

ELECTROMAGNETIC (EM) RADIATION and MATTER.
- Example of interactions: Absorption, emission,
scattering, etc
- Types of EM: gamma ray, X-rays, Ultra-violet,
Visible, Infrared, Microwave and radio waves
- Matter: Sample analytes such as atom, molecules
and nuclei.
 ELECTROMAGNETIC SPECTRUM

• Electromagnetic radiation: Radiant energy that exhibits

wavelength-like behaviour and travels through space at
the speed of light in a vacuum.

• The important parameters associated with electromagnetic

radiation are:
 Energy (E): Energy is directly proportional to frequency, and
inversely proportional to wavelength, as indicated by the
equation below.
E = h
h = Planck’s constant
 Frequency ()
 Wavelength (l)
 Electromagnetic Spectrum
• Electromagnetic spectrum: The entire range and scope of
frequencies of electromagnetic radiation.

Types of EM:
gamma ray, X-rays,
Ultra-violet, Visible,
Infrared,
Microwave and
radio waves
EFFECT OF ELECTROMAGNETIC RADIATION
ON MOLECULES

Graphics source: Wade, Jr., L.G. Organic Chemistry, 5th ed. Pearson Education Inc., 2003
• Wavenumbers (ῡ) is another way to describe
frequency.
- most often used in IR
- The number of waves in 1 cm
- Unit: reciprocal of cm (cm-1)
- Scientists use wavenumber in preference to
wavelength because is directly proportional to
Energy (E).

ῡ (cm-1 ) = 1 E = hc = h = hcῡ
l (cm) l
 ORGANIC STRUCTURE DETERMINATION

How do we know:

• How atoms are connected together?

• Which bonds are single, double, or triple?
• What functional groups exist in the molecule?
• If we have a specific stereoisomer?

The field of organic structure determination attempts

to answer these questions.
 INSTRUMENTAL METHODS OF STRUCTURE
DETERMINATION
1. Nuclear Magnetic Resonance (NMR) – Excitation of the nucleus of
atoms through radiofrequency irradiation. Provides extensive
information about molecular structure and atom connectivity.

2. Infrared Spectroscopy (IR) – Triggering molecular vibrations

through irradiation with infrared light. Provides mostly information
about the presence or absence of certain functional groups.

3. Mass spectrometry – Bombardment of the sample with electrons

and detection of resulting molecular fragments. Provides information
about molecular mass and atom connectivity.

4. Ultraviolet spectroscopy (UV) – Promotion of electrons to higher

energy levels through irradiation of the molecule with ultraviolet
light. Provides mostly information about the presence of conjugated
p systems and the presence of double and triple bonds.
INFRARED SPECTROSCOPY
 IR spectral regions
Region Wavelengths Wavenumber, Frequency (), hz
(l), m cm-1
Near 0.78 to 2.5 12800 to 4000 3.8x1014 to 1.2x1014

Middle 2.5 to 50 400 to 200 1.2x1014 to 6.0x1012

Far 50 to 1000 200 to 10 6.0x1014 to 2.0x1011

Most 2.5 to 15 4000 to 670 1.3x1014 to 2.0x1013

used

Whereby:
Wavenumber = 1/wavelength
 Applications of IR
• The main goal of IR spectroscopic analysis is to determine
the chemical functional groups in the sample.

• Example:
- Analysis of organic materials
- Polyatomic inorganic molecules
- Organometallic compounds

• Near IR - carbohydrates and proteins

• Middle IR - organic molecules

• Far IR - inorganic (co-ordination bonds & quaternary

ammonium compounds)
 MOLECULAR VIBRATIONS
• Covalent bonds vibrate at only certain allowable frequencies.
• Imagine a covalent bond between two atoms acts like a spring.
- If the bond is stretched, a restoring force pulls the two atoms
together towards equilibrium bond length.
- If the bond is compressed, the restoring force pushed the two
atoms apart.
- if the bond is stretched or compressed and then released, the
atoms vibrate.
 MOLECULAR
VIBRATIONS

STRECTHING BENDING

IN-PLANE IN-PLANE
SYMMETRIC ASYMMETRIC
ROCKING SCISSORING

OUT-OF-PLANE OUT-OF-PLANE
WAGGING TWISTING
A) STRETCHING VIBRATIONS:
• A continuous change in the interatomic distance along the axis of the
bands between the two atoms.
• The most useful bands in an infrared spectrum correspond to stretching
frequencies
• Causes by vibration of the bond length.
• Two vibrational stretching modes:
i) symmetric stretching
ii) asymmetric stretching

Symmetric stretching Asymmetric stretching

 Stretching Frequencies

• Frequency decreases with increasing atomic weight.

- heavier atoms vibrate more slowly than lighter atoms.
- example: C-D bond had lower frequency than a C-H bond.
• Frequency increases with increasing bond energy.
- stronger bonds are stiffer, requiring more force to stretch
or compress.
- stronger bands usually vibrate faster than weaker bands
(assuming the atoms have similar masses)
- example: O-H bonds are stronger than C-H bonds and O-H
bonds vibrate at higher frequencies.
- strengthens of bonds: triple bonds > double bonds >
single bonds
Bond Stretching Frequencies
B) BENDING VIBRATIONS:

- causes by the vibration of the bond angles.

- four bending vibrations modes:
i) in-plane rocking
ii) in-plane scissoring
iii) out-of-plane wagging
iv) out-of-plane twisting
 Bending
Vibrations
Modes
 MOLECULAR SPECIES THAT ABSORB INFRARED RADIATION
o IR absorption only occurs when IR radiation interacts with a
molecule undergoing a change in dipole moment when the
molecule is vibrate.
o What happen when a molecule absorbs infrared radiation?
 Absorption of IR radiation corresponds to energy changes
on the order of 8 to 40 kJ/mole.
- Radiation in this energy range corresponds to stretching and
bending vibrational frequencies of the bonds in most
covalent molecules.
 In the absorption process, those frequencies of IR radiation
which match the natural vibrational frequencies of the
molecule are absorbed.
 The energy absorbed will increase the amplitude of the
vibrational motions of the bonds in the molecule.
• NOT ALL bonds in a molecule are capable of
absorbing IR energy. Only those bonds that
have change in dipole moment are capable to
absorb IR radiation.

• The larger the dipole change, the stronger

the intensity of the band in an IR spectrum.
 MOLECULAR SPECIES THAT DO NOT ABSORB INFRARED
RADIATION
• A bond is symmetrical and has zero dipole moment.
- Example: the triple bond of acetylene, has zero dipole moment,
and dipole moment remains zero if the bond is stretched or
compressed. The vibration produces no change in the dipole
moment, thus no absorption of energy is occurred.

- Examples: O2, N2, Cl2 cannot absorb IR radiation because no

net change in dipole moment occurs during the vibration or
rotation.
IR SPECTRA
 IR spectra

• Plot of %T vs. cm-1

• Linear wavenumber scale is preferred
• Direct proportionality between wavenumber and
both energy and frequency

c
E  h  h  hc
l
Example: IR absorption spectrum of a polystyrene film

%Transmittance (%T) versus wavenumber (cm-1)

Example: IR absorption spectrum of a polystyrene
film

% Transmittance
show the value of IR
radiation being
absorbed by
molecule (functional
group)
- High %T = less IR
radiation (photon)
being absorbed
- Low %T = high IR
radiation (photon)
being absorbed
Wavenumber show the very particular energy
of IR
 Comparison between transmittance (upper) vs absorbance (lower) plot

Transmittance
spectra provide
better contrast
between
intensities of
strong and weak
, cm-1
bands compared
to absorbance
spectra
Absorption
 CLASSIFICATION OF IR BANDS
 IR bands can be classified as strong (s), medium (m), or weak (w),
depending on their relative intensities in the infrared spectrum.
 A strong band covers most of the y-axis.
 A medium band falls to about half of the y-axis
 A weak band falls to about one third or less of the y-axis.
 INFRARED ACTIVE BONDS
 Not all covalent bonds display bands in the IR spectrum. Only polar
bonds do so. These are referred to as IR active.
 The intensity of the bands depends on the magnitude of the dipole
moment.
 Strongly polar bonds such as carbonyl groups (C=O) produce
strong bands.
 Medium polarity bonds and asymmetric bonds produce medium
bands.
 Weakly polar bond and symmetric bonds produce weak or non
observable bands.
 INFRARED BAND SHAPES
• Infrared band shapes come in various forms. Two of the most
common are narrow and broad. Narrow bands are thin and
pointed, like a dagger. Broad bands are wide and smoother.

• A typical example of a broad band is that displayed by O-H bonds,

such as those found in alcohols and carboxylic acids, as shown
below.
INFORMATION OBTAINED FROM IR SPECTRA
• IR is most useful in providing information about the presence
or absence of specific functional groups.

• IR can provide a molecular fingerprint that can be used

when comparing samples. If two pure samples display the
same IR spectrum it can be argued that they are the same
compound.

• IR does not provide detailed information or proof of

molecular formula or structure. It provides information on
molecular fragments, specifically functional groups.

• Therefore it is very limited in scope, and must be used in

conjunction with other techniques to provide a more complete
picture of the molecular structure.
INTERPRETATION OF
IR SPECTRA
 IR ABSORPTION RANGE
The typical IR absorption range for covalent bonds is 600 - 4000 cm-1. The graph
shows the regions of the spectrum where the following types of bonds normally
absorb. For example a sharp band around 2200-2400 cm-1 would indicate the
possible presence of a C-N or a C-C triple bond.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 5th ed. Pearson Education Inc., 2003
 The approximately regions where various common types of
bonds absorb (stretching vibrations only; bending, twisting and
other types of bond vibrations have been omitted for clarity)
 THE FINGERPRINT REGION
• Although the entire IR spectrum can be used as a fingerprint for the purposes of
comparing molecules, the 600 - 1400 cm-1 range is called the fingerprint
region. This is normally a complex area showing many bands, frequently
overlapping each other. This complexity limits its use to that of a fingerprint, and
should be ignored by beginners when analyzing the spectrum.
• Focus the analysis on the rest of the spectrum, that is the region to the left of
1400 cm-1.

Focus your analysis on this region. This is where most Fingerprint region: complex and difficult to
stretching frequencies appear. interpret reliably.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
 FINGERPRINT OF MOLECULE
 Whole-molecule vibrations and bending vibrations are also
quantized.
 No two molecules will give exactly the same IR spectrum
(except enantiomers).
 Simple stretching: 1600-3500 cm-1.
 Complex vibrations: 600-1400 cm-1, called the “fingerprint
region.”
 IR spectra is called “fingerprints” because no other chemical
species will have identical IR spectrum.
 Significant of fingerprint region:
- The complex vibrations found in this region are used to confirm
the identity of an organic compound (since different compounds
cannot show the same vibrations).
 CORRELATION CHART

Intensities: s = strong, m = medium, w = weak, b = broad

 Type of vibration Frequency (cm-1) Intensity

Intensities: s = strong, m = medium, w = weak, b = broad

 Type of vibration Frequency (cm-1) Intensity

Intensities: s = strong, m = medium, w = weak, b = broad

IR SPECTRA OF CHEMICAL CLASSES OF
ORGANIC COMPOUND

1. IR spectrum of hydrocarbons
a) IR spectrum of alkanes
b) IR spectrum of alkenes
c) IR spectrum of alkynes
2. IR spectrum of aromatic compounds
3. IR spectrum of an alcohols
4. IR spectrum of amines
5. IR spectrum of aldehydes
6. IR spectrum of ketones
7. IR spectrum of carboxylic acids
8. IR spectrum of esters
9. IR spectrum of amides
10.IR spectrum of acid chlorides
11.IR spectrum of anhydrides
12.IR spectrum of a nitrile
 1. IR SPECTRUM OF HYDROCARBONS
Carbon-Carbon Bond Stretching

 Stronger bonds absorb at higher frequencies:

C-C 1200 cm-1
C=C 1660 cm-1
CC 2200 cm-1 (weak or absent if internal)

 Conjugation lowers the frequencies:

isolated C=C 1640-1680 cm-1
conjugated C=C 1620-1640 cm-1
aromatic C=C approx. 1600 cm-1
 Carbon-Hydrogen Stretching
 Bonds with more s character absorb at a higher frequency.
 Bonds are stronger in the order sp > sp2 > sp3
 Increase % s-character make the bond more stiffer thus
increase the energy (wavenumber)

Hybridization C-H bond s character Frequency (cm-1)

sp3 ¼ x 100 = 25% 2800-3000

sp2 1/3 x 100 = 33% 3000-3100

sp ½ x 100 = 50% ~ 3300

 a) IR SPECTRUM OF ALKANES
Alkanes have no functional groups. Their IR spectrum displays only C-C and C-H
bond vibrations. Of these the most useful are the C-H bands, which appear
around 3000 cm-1. Since most organic molecules have such bonds, most organic
molecules will display those bands in their spectrum.

H H H H H H
C-C absorption is weak and
H C C C C C C H
indistinguishable
H H H H H H
 b) IR SPECTRUM OF ALKENES

• C=C absorbs at 1600-1700 cm-1 (stronger & stiffer than

C–C (μ = 0)
- sharp, medium bands
- useful for structure determination: unsymmetrical
absorption ~ 1600 – 1680 cm-1

• =C–H bond stretch at ~ 3020 – 3100 cm-1

• -C–H bond stretch at ~ 3000 – 2800 cm-1

 IR SPECTRUM OF 1-HEXENE
H H H H H H
H C C C C C C H

H H H H

• C-H stretching corresponds to =C-H bonds involving sp2 hybrid C:

3080 cm-1
• Stretching C=C: 1642 cm-1
c) IR SPECTRUM OF ALKYNES
• C≡C is stronger and stiffer than C–C and C=C
→ Absorb IR at higher ν ≈ 2100 – 2200 cm-1

~ 2100 – 2200 cm-1

sharp, weak band, Stretch very
moderate intensity weak or absent

Terminal alkyne Internal alkyne

IR SPECTRA OF 1-OCTYNE AND 4-OCTYNE

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
2. IR SPECTRUM OF AROMATIC COMPOUNDS

• =C-H stretch for sp2 hybrid: values greater than 3000 cm-1

• C=C ring stretch absorptions: occur in pairs at 1600-1585

cm-1 and 1500-1400 cm-1 (~1475 cm-1)
• =C-H bending: 900 - 690 cm-1
IR SPECTRUM OF TOLUENE
 3. IR SPECTRUM OF AN ALCOHOL

• The most prominent band in alcohols is due to the O-H bond

- Appears as a strong, broad band covering the range of about 3000 -
3700 cm-1.

• O–H stretching is broad due to the hydrogen bonding.

R O H

• Alcohol also show strong C–O stretching centered at ~1050 cm-1.

 IR SPECTRUM OF 1-BUTANOL

Broad, intense O-H stretching

absorption centered around
3300 cm-1
 4. IR SPECTRA OF AMINES
• The most characteristic band in amines is due to the N-H bond
stretch, and it appears as a weak to medium, somewhat broad band
(but not as broad as the O-H band of alcohols). This band is
positioned at the left end of the spectrum, in the range of about 3200 -
3600 cm-1.

• Primary amines (RNH2):

- have two N-H bonds
- two broad sharp spikes

• Secondary amines (R2NH2):

- have one N-H bond
- Broad, one sharp spike

• Tertiary amines (R3N):

- no N-H bonds
- No signal for NH bond
IR SPECTRUM OF 1-AMINOBUTANE (PRIMARY AMINE)

N-H
N-H bending
stretching
N-H oop
IR SPECTRUM OF DIETHYLAMINE (SECONDARY AMINE)

N-H oop
 IR SPECTRUM OF N,N-DIETHYL-1-BUTANAMINE
(TERTIARY AMINE)

CH2
bend
No signal for C-N stretch
NH bond at
3200 - 3600 CH3 bend
cm-1

CH3
C-H H3C CH2 CH2 CH2 N
stretch
CH3
 5. IR SPECTRUM OF ALDEHYDES

O C=O stretch: ~ 1725 cm-1 (s).

Conjugation moves the absorption
R C H to a lower frequency.

Two C-H stretching: ~ 2750 cm-1 and

2850 cm-1 (w)

O
C=O stretching: 1700-1660 cm-1
C H (conjugation of C=O with phenyl)

C=C aromatic: Two C-H stretching: ~ 2750 cm-1 and

1600,1450 cm-1 2850 cm-1 (w)
IR SPECTRUM OF BUTYRALDEHYDE

C-H aldehyde
C=O stretch

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
 6. IR SPECTRUM OF KETONES

O
C=O stretching: ~1715 cm-1.
R C R' Conjugation moves the absorption to
a lower frequency.

O
C=O stretching: 1700-1680 cm-1
(Conjugation of C=O with phenyl)
C R

C=C aromatic: 1600,

1450 cm-1
IR SPECTRUM OF 2-HEPTANONE

C=O stretch

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
IR SPECTRUM OF 2-BUTANONE
 7. IR SPECTRUM OF CARBOXYLIC ACIDS

O C=O stretching: broad (stake-

shaped band), occurs at 1730-1700
cm-1. Conjugation moves the
R C O H absorption to a lower frequency.

C-O stretching: O-H stretching: very broad (strongly

1320-1210 cm-1 hydrogen-bonding), occurs at 3400-
(medium intensity) 2400 cm-1 and often overlaps the C-H
absorptions
 IR SPECTRUM OF HEXANOIC ACID

C-O stretch

This O-H absorbs broadly, 2500-3500

cm-1, due to strong hydrogen bonding

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
 8. IR SPECTRUM OF ESTERS

O C=O stretch: 1750-1735 cm-1 for normal

esters. Conjugation in R moves the
absorption to a lower frequency (1740-
R C O R' 1715 cm-1 ). Conjugation with O in the
R’ part moves the absorption to a
higher frequency.

C-O stretch: two or more bands,

one stronger and broader than the
other, occurs in the range 1300-
1000 cm-1.
IR SPECTRUM OF ETHYL ACETATE
IR SPECTRUM OF ETHYL BENZOATE

C=O stretch: 1726 cm-1

(Conjugation in R moves
the absorption to a lower
frequency)
IR SPECTRUM OF VINYL ACETATE

C=O stretch: 1762 cm-1 (Conjugation

with O in the R’ part moves the
absorption to a higher frequency).
 9. IR SPECTRUM OF AMIDES
O O O R
H H
R C N R C R C N
N

H R R
1 2 3

• C=O stretching: approximately at 1680-1630 cm-1.

• N-H stretching (~ 3300 cm-1):

i) primary amides (-NH2) gives 2 spikes near 3350 and 3180
cm-1.
ii) Secondary amides have 1 spike (-NH) at about 3300 cm-1.

• N-H bending: around 1640-1550 cm-1 for primary and secondary

amides.
IR SPECTRUM OF BUTANAMIDE (PRIMARY AMIDE)

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
 IR SPECTRUM OF N-METHYL-1-
PIPERIDINECARBOXAMIDE (SECONDARY AMIDE)

CH3
O N
H
N

N-H stretch:
(~ 3300 cm-1) C=O stretch
 IR SPECTRUM OF N,N-BIS(2-
PHENOXYETHYL)PROPIONAMIDE (TERTIARY AMIDE)

** No N-H stretching

C=O stretch
10. IR SPECTRUM OF ACID CHLORIDES

C=O stretching: appear in range

O 1810-1775 cm-1 in unconjugated
chlorides. Conjugation lowers the
frequency to 1780-1760 cm-1

R C Cl

C-Cl stretching: range 730-

550 cm-1
IR SPECTRUM OF 3,3-DIMETHYLBUTYRYL
CHLORIDE

C=O stretch
C-Cl stretch
 11. IR SPECTRUM OF ANHYDRIDES

O
O
C R
R C O

• C=O stretch:
- 2 bands, 1830-1800 cm-1 and 1775-1740 cm-1 with
variable relative intensity.
- Conjugation moves the absorption to a lower frequency.

• C-O stretch (multiple bands): range 1300-900 cm-1.

IR SPECTRUM OF ACETIC ANHYDRIDE

C=O stretch

C=O stretch
C-O stretch
NORMAL BASE VALUES FOR THE C=O STRETCHING
VIBRATIONS FOR CARBONYL GROUPS

Reference point

Compounds Frequencies (cm-1)

Amides 1670-1650
Aldehydes 1740-1720
Ketones 1725-1705
Carboxylic acids 1725-1700
Esters 1750-1730
Acid halides 1810-1780
Anhydrides 1830-1800 and 1775-1740
12. IR SPECTRUM OF A NITRILE

CN triple bond stretch: around

2250 cm-1, sharp, pointed shape
IR SPECTRUM OF BUTYRONITRILE

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
Example: The following is the IR spectrum of a carboxylic acid, which has
the molecular formula C2H4O2. Select two significant peaks associated
with the carboxylic acid from the given spectrum. State the wavenumber
and the bond associated with each peak you selected.
 O-H stretch C=O stretch

Answer:
Wavenumber (cm-1) Types of Bond

3100 O-H stretching

1705 C=O stretching

Exercise: Indicate which one of the following compounds corresponds to each of the
IR spectra shown below. Indicate the important absorptions that allowed you to make
the assignment.

G
 C-O
stretch
Exercise: Indicate which one of the following compounds corresponds to each of the
IR spectra shown below. Indicate the important absorptions that allowed you to make
the assignment.

G
 G

O-H
stretch C=O C-O
stretch stretch
Exercise: Indicate which one of the following compounds corresponds to each of the
IR spectra shown below. Indicate the important absorptions that allowed you to make
the assignment.

G
Exercise: Indicate which one of the following compounds corresponds to each of the
IR spectra shown below. Indicate the important absorptions that allowed you to make
the assignment.

G
CH aldehyde C=O
(stretch) (stretch)
PROTON AND CARBON-13
NUCLEAR MAGNETIC
RESONANCE (NMR)
SPECTROSCOPY
 THEORY OF NUCLEAR
MAGNETIC RESONANCE
 Principle behind NMR

Involves the absorption of radiofrequency radiation by

atomic nuclei in an applied magnetic field. Any atomic
nucleus which show either odd mass, odd atomic
number or both has a nuclear spin that can be observed
by the NMR spectrometer.
Nuclei with…
an ODD number of protons or an ODD mass number or
an ODD number of neutrons an ODD atomic number
or both or both

.... have a quantized spin angular

momentum (l) and a magnetic moment
1. NUCLEAR SPIN
STATES
Nuclear spin

 The nuclei of the certain

atoms rotate about an
axis = SPIN

 Each spin-active nucleus

has a number of spins
defined by its spin
quantum number, I
Spin Quantum Numbers of Some Common Nuclei

The most abundance

isotope and do not
have spin

Element 1H 2H 12C 13C 14N 16O 17O 19F

Nuclear spin ½ 1 0 ½ 1 0 ½
Quantum no., I
Number of spin 2 3 0 2 3 0 6 2
states, 2I+1

The most abundance

isotope and do not have
spin
2. NUCLEAR MAGNETIC
MOMENTS ()
• In the absence of an applied magnetic field
- nuclei are free to orient their spin however they like
- all the spin states of a given nucleus are of equivalent
energy (degenerate)
- in a collection of atoms, all of the spin states are
almost equally populated, with the same number of
atoms having each of allowed spins.

No magnetic field
• In an applied magnetic field (B0), spin states are not of
equivalent energy because
- the nucleus is a charged particle (protons are positively
charged)
- any moving charge generates a magnetic field of its own
• The nucleus has a magnetic moment  generated by its
charge and spin. Behave a bit like (tiny) bar magnets.
• In an applied magnetic field (Bo), the nuclear
magnetic moments () in the two cases (+½ or -½) are
pointed in opposite directions i.e. aligned with B0 or
opposed to B0.

-½
B0


opposed
B0


B0 +½

Aligned
• The spin state +½ which aligned with B0: lower
energy
• The spin state -½ which opposed with B0: higher
energy

S N
-½
N
+½ S
B0


Aligned: Opposed:
Lower energy Higher energy
• As an external magnetic field applied (B0), the degenerate
spin states split into two states of unequal energy.

-½

Opposed:
Higher energy

B0

+½

Aligned:
Lower energy
 ABSORPTION OF ENERGY

 The nuclear magnetic resonance (NMR) phenomenon

occurs when nuclei aligned with an applied field (B0) are
induced to absorb energy (RF radiation) and change
their spin orientation with respect to the applied field.
 The NMR Absorption of Process for a Proton
Applied Opposed
Field ,B0

-½ -½

DE

E = h
Radiofrequency

+½ +½
Aligned The energy absorption is a quantized process.
- Energy absorbed must equal the energy difference between the
two states involved.
Eabsorbed = (E -½ state – E+½ state) = h
-½

+½

Eabsorbed = (E -½ state – E+½ state) = h

= DE = h
 RESONANCE
• When the nucleus is irradiated with radio-
frequency photons having energy equal to
the energy difference between the spin states
(∆E), it is said to be “in resonance”, and its
absorption of energy is detected by the NMR
spectrometer.
 The spin-state energy separation as a function of the strength of the
applied magnetic field (B0)
Energy
-½

DE = kBo = h
degenerate
at Bo = 0

+½
increasing magnetic field strength
Bo

The stronger B0, the greater the ∆E

∆E = f(B0)
 The Larmor Equation
DE = kBo = h can be transformed into

DE = h =  h B0
2p
∆E = Energy difference between two spin states
 = frequency of the incoming radiation that will cause a
transition
 = Gyromagnetic ratio, is a constant for each nucleus (26,753
s-1gauss-1 for H)
B0 = strength of the magnetic field
h = Plank’s constant

∆E is proportional to the magnetic field strength (B0),

frequency of the electromagnetic wave () and
gyromagnetic ration ()
 Resonance Frequencies of Selected Nuclei
Isotope Abundance Bo (Tesla) Frequency(MHz) (radians/Tesla)
1H 99.98% 1.00 42.6 267.53
1.41 60.0
2.35 100.0
7.05 300.0

2H 0.0156% 1.00 6.5 41.1 4:1

7.05 45.8 4:1

13C 1.108% 1.00 10.7 67.28

2.35 25.0
7.05 75.0

19F 100.0% 1.00 40.0 251.7

MAGNETIC SHIELDING OF
ELECTRONS
 Magnetic Shielding
• If all protons absorbed the same amount of energy in a
given magnetic field, not much information could be
obtained.

• Protons are surrounded by electrons that shield

them from the external field (B0).

• Circulating electrons create an induced magnetic

field that opposes the external magnetic field.
 Shielded Protons
 Magnetic field strength (B0) must be increased for a shielded
proton to flip at the same frequency.
 Protons in a Molecule

• Depending on their chemical environment,

protons in a molecule are shielded by
different amounts.
 NMR Signals
 The number of signals shows how many different
kinds of protons are present.

 The location of the signals shows how shielded or

deshielded the proton is.

 The intensity of the signal shows the number of

protons of that type.

 Signal splitting shows the number of protons on

adjacent atoms.
The NMR Spectrometer
The NMR Graph
Example of 1H NMR
SPECTRUM

Peak picking

Chemical shift
() in ppm
integration
CHEMICAL SHIFT
• Measured in parts per million.

• Ratio of shift downfield from tetramethylsilane (TMS) (Hz) to

total spectrometer frequency (Hz).

• TMS is chosen because:

- The methyl protons are more shielded than those of most other
known compounds.
- No compounds had better-shielded hydrogens than TMS.

• Organic protons absorb downfield (to the left) of the TMS

signal.

• Called the delta scale.

• Chemical shift of a proton is determined by its environment.

 PEAKS ARE MEASURED RELATIVE TO TMS

Rather than measure the exact resonance position of a

peak, we measure how far downfield it is shifted from TMS.

CH3
Reference compound:
CH3 Si CH3 Tetramethylsilane (TMS)
CH3
Highly shielded
protons appear
upfield.

TMS Chemists originally

shift in Hz thought no other
compound would
downfield
come at a higher
n 0 field than TMS.
Delta Scale

Chapter 13 122
=>
 Characteristic
values of
chemical shifts
Typical Values of Chemica
 NMR Correlation
Chart

C-H where C is CH on C
attached to an next to
acid Aldehyde Benzene alkene electronegative pi bonds aliphatic
COOH CHO CH =C-H atom C-H
C=C-C-H
X-C-H O
O-C-H C C H

12 10 9 7 6 4 3 2 0
 NMR Correlation
Chart
-OH -NH
DOWNFIELD UPFIELD
DESHIELDED SHIELDED
CHCl3 , H

TMS

12 11 10 9 8 7 6 5 4 3 2 1 0  (ppm)

H
CH3O CH2Ar C-CH-C
RCOOH RCHO C=C CH2F CH2NR2
CH2S C
CH2Cl
CH2Br C C-H C-CH2-C
CH2I C=C-CH2 C-CH3
CH2O CH3-Ar
CH2NO2 O
H
C CH3
C O O
C C H
 LOCATION OF SIGNALS

A. Electronegativity Effects

•More electronegative atoms deshield

more and give larger shift values.

•Effect decreases with distance.

•Additional electronegative atoms

cause increase in chemical shift.
 LOCATION OF SIGNALS
B. Hybridization Effects
sp3 Hydrogens

• C-CH3, C-CH2-C, C-CH-C have resonance in the range

from 0-2 ppm.

• Methyl group protons occur near 1 ppm.

• Methylene protons appear at 1.2 – 1.4 ppm.

• 3o methine hydrogens occur at higher  value (1.4-1.7

ppm).

• H attached to strained ring such as cyclopropyl H

resonate at high field (0-1 ppm).
 LOCATION OF SIGNALS

B. Hybridization Effects

 sp2 Hydrogens
Simple vinyl protons (-C=C-H) have resonance in the
range from 4.5-6.5 ppm.

 sp Hydrogens
Acetylenic hydrogens appear at 2-3 ppm
 LOCATION OF SIGNALS
C. Hydrogen bonding and exchangeable protons
- The more hydrogen bonding that takes place, the more deshielded
a proton becomes.

i. Acidic protons in carboxylic acids (-COOH)

o Strongly deshielded and resonate at 10-13 ppm.

o Both resonance and electronegativity effect of oxygen withdraw

electrons from the acid proton.

o Exchangeable protons exhibit variable absorption positions over a

wide range.

o Carboxylic acid exist as hydrogen-bonded dimers

with moderate rates of proton exchange that
broaden the absorption of the acid proton
(-COOH).
Carboxylic Acid Proton,  >10
C. Hydrogen bonding and exchangeable protons

ii. O-H and N-H

 Chemical shift depends on concentration.

 Hydrogen bonding in concentrated solutions deshield the
protons, so signal is around δ3.5 for N-H and δ4.5 for O-H.
 Proton exchanges between the molecules show variable and
broad absorption.

Exchangeable protons
 1H NMR spectrum of propanol

broad singlet: -OH

1H NMR spectrum of 2-ethylamine

broad singlet: -NH

 LOCATION OF SIGNALS
D. Anisotropy

 Larger chemical shift is due to the presence of unsaturated

system.
 Examples: Protons in benzene, aldehydes, olefines (vinyl)
and acetylene.
 Aromatic protons are deshielded and absorbs at δ7-8 ppm.
 Vinyl protons absorb at δ5-6 ppm.
 Acetylenic protons absorb around δ2.5 ppm.
 Aldehyde protons absorb at δ9-10 ppm.

H O
C C
R C H C H
Aromatic protons Vinyl protons Aldehyde protons Acetylenic protons
THE NUMBER OF SIGNALS
 EQUIVALENT

 Hydrogen nuclei that are in the same chemical and

magnetic environment are said to be equivalent.

 Equivalent nuclei will

• show the same chemical shift ()
• have the same coupling constants (J) to adjacent
nuclei.

• Equivalent hydrogens have the same chemical shift.

Protons in the same group

- usually do not split one another

- show one NMR peak

H H
C H or C
H H
1H NMR spectrum of methane

CH4
1H NMR spectrum of bromomethane
1H NMR spectrum of dichloromethane

CH2Cl2
 Examples

Molecules giving rise to one NMR absorption peak – all

protons chemically equivalent
1H NMR spectrum of acetone
 Examples
Molecules giving rise to two NMR absorption peaks –
two different sets of chemically equivalent protons
1H NMR spectrum of para-xylene

b
 Example
Molecules giving rise to three NMR absorption peaks –
three different sets of chemically equivalent protons

O
CH3CCH2CH3

1-methoxypropan-2-one
benzyl acetate
1H NMR spectrum of benzyl acetate
 Example
Use ethyl bromide to explain the meaning of equivalent
protons in NMR spectroscopy.

CH3CH2Br

• 3 equivalent proton in methyl

• 2 equivalent proton in methylene
• Therefore: 2 signal will appear
• Since the compound composed of two groups of
equivalent proton and directly connected through C-C,
this will results spin-spin coupling interaction between
them.
Exercise: Predict how many signal will appear in the 1H
NMR spectrum for the compound below:

a) O

b) 2-pentanone

c) butanoic acid
INTEGRALS AND
INTEGRATION
• The area under each peak is proportional to the number
of protons.

• Shown by integration.

1H NMR spectrum of methyl t-butyl ether

 1H NMR spectrum of benzyl acetate
The integral line rises an amount proportional to the number of H in each peak

METHOD 1
integral line
integral
line

simplest ratio
55 : 22 : 33 = 5:2:3 of the heights
 1H NMR spectrum of benzyl acetate (FT-NMR)

Actually : 5 2 3

58.117 / 11.3 21.215 / 11.3 33.929 / 11.3

= 5.14 = 1.90 = 3.00

O
CH2 O C CH3

METHOD 2
digital assume CH3
integration 33.929 / 3 = 11.3

Integrals are
good to about
10% accuracy.

Modern instruments report the integral as a number

SPIN-SPIN SPLITTING
 Spin-spin Splitting Phenomenon
(N+1) rule
o Equivalent protons do not split each other.

o Protons bonded to the same carbon will split each other only
if they are not equivalent.

o Protons on adjacent carbons normally will couple.

(N+1) rule used to predict

 Empirical rule to predict the multiplicity

 Splitting pattern of the peaks (using Pascal’s triangle)
 Presence of spin coupling for equivalent nuclei
Each type of proton can “sense” the number of equivalent protons
(N) on the neighbouring / adjacent C to which it’s bonded –
resonance peak is split into (N+1) components

Tips:
H Cl
• Identify the H(s) on each C
• Label each H(s) with a, b, c….
Cl C C H Note: in saturated chain (aliphatic) and
ring – H on same carbon is consider as
Cl H equivalent to each other.

• Determine the position:

1,1,2- trichloroethane upfield/downfield based on shielding
effect.
• Used (N+1) rule to predict it
multiplicity.
Multiplicity Nomenclature

Peak multiplicity No. of neighbouring H

Singlet 0
Doublet 1
Triplet 2
Quartet 3
Quintet 4
Sextet 5
Septet 6
Octet 7
Nonet 8
Multiplicity
 1H NMR SPECTRUM OF 1,1,2-TRICHLOROETHANE

doublet

triplet

(N+1); N = 2 (N+1); N = 1
2+1 = 3 (triplet) 1+1 = 2 (doublet)
 1H NMR SPECTRUM OF ETHYL IODIDE
H I
H I
H C C H
H H
H C C H

H I (N+1); N =2 H H
H C C H 2+1 = 3
(triplet)
H H Integral = 3

(N+1); N = 3
2+1 = 4
(quartet)

Integral = 2

quartet triplet
1H NMR SPECTRUM OF ETHYLBENZENE
 Exceptions to the (N+1) rule

Protons that are equivalent by symmetry usually do not split one

another

X CH CH Y or X CH2 CH2 Y

no splitting if X = Y no splitting if X = Y

Protons in the same group usually do not split one another

H H
C H or C
H H
SOME COMMON SPLITTING PATTERNS

X CH CH Y CH3 CH
(X=Y)

CH2 CH CH3 CH2

CH3
X CH2 CH2 Y
CH
(X=Y) CH3
1H NMR SPECTRUM OF 2-NITROPROPANE

1:6:15:20:16:6:1 in higher multiplets; the outer peaks

are often nearly lost in the baseline
Septet
 1H NMR SPECTRUM OF ACETALDEHYDE

offset = 2.0 ppm

 Intensity of multiplet peaks
- Pascal’s Triangle
Note: 1 singlet
The interior entries
are the sums of 1 1 doublet
the two numbers
immediately above. 1 2 1 triplet

1 3 3 1 quartet

1 4 6 4 1 quintet

1 5 10 10 5 1 sextet

septet/
1 6 15 20 15 6 1 heptet
1 7 21 35 35 21 7 1 octet
 COUPLING CONSTANTS

Definition:

- The distance (spacing) between the peaks of a

multiplet
- Measured in Hz
- Symbolized as ‘J’
- Is a measure of how strongly a nucleus is affected by
the spin states of its neighbour
- Not dependent on strength of the external field
 Coupling Constant, J

H H
J
C C H

J J H H

J J
J

J is a measure of the amount of interaction between the

two sets of hydrogens creating the multiplet.
 SOME REPRESENTATIVE COUPLING CONSTANTS

H H 3J
vicinal three bond
C C 6 to 8 Hz

H 3J
trans C C 11 to 18 Hz three bond
H

H H 3J
cis 6 to 15 Hz three bond
C C

H
geminal 2J
C 0 to 3 Hz two bond
H
 SOME REPRESENTATIVE COUPLING CONSTANTS

four bond 4J
C C C H 0 to 3 Hz
allylic
H

C 3J
H 3 to 11 Hz three bond
C C
H

4J
H C C C H 2 to 3 Hz four bond

Couplings that occur at distances greater than three bonds are called long-range
couplings. They are usually small (<3 Hz) and frequently nonexistent (0 Hz).
 SOME REPRESENTATIVE COUPLING CONSTANTS
H

ortho 7 to 10 Hz three bond 3J

four bond 4J
meta 2 to 3 Hz

para five bond 5J

0 to 1 Hz

Couplings that occur at distances greater than three bonds are called long-range
couplings. They are usually small (<3 Hz) and frequently nonexistent (0 Hz).
Interpretation of proton
NMR spectra
 1H NMR SPECTRUM OF METHYL ISOPROPYL KETONE

Coupling constant, J: Peak multiplicity/spin-spin splitting: number

arrangement of the of hydrogens on adjacent carbons
atoms involved

Chemical shift () in ppm:

Type of hydrogen Integral: number of
hydrogen
 1H NMR SPECTRUM OF 5,6-DEHYDROKAWAIN
Peak multiplicity/spin-spin splitting:
number of hydrogens on adjacent
Coupling constant, J: carbons
arrangement of the
atoms involved

Chemical shift () in ppm:

Integral: number of Type of hydrogen
hydrogen
 HINT TO INTERPRET 1H NMR SPECTRUM

1. Any broadened singlets might be due to –OH or –NH protons.

• Broad singlet at δ > 10 ppm  acid –OH

O
O H N H C OH
frequently broad singlets broad (or sharp) singlet, δ > 10 ppm

2. A signal ~ δ 3 – 4 ppm  Protons on a carbon bearing an

electronegative elements such as O or a halogen.
• Protons that are more distant from the electronegative atom will be less
strongly deshielded.

O C H Br C H Cl C H I C H
 HINT TO INTERPRET 1H NMR SPECTRUM

3. Signal ~ δ 7 – 8 ppm  aromatic proton

Y
H

4. Signal ~ δ 5 – 6 ppm  vinyl proton

• Splitting constant, J  differentiate cis and trans

H
C C C C
H H H

~ δ 5 – 6 ppm; J = 6-15 Hz (cis) ~ δ 5 – 6 ppm; J = 11-18 Hz (trans)

 HINT TO INTERPRET 1H NMR SPECTRUM
5. Signal ~ δ 2.1 – 2.5 ppm  proton adjacent to a carbonyl group or an
aromatic ring. Singlet at δ 2.1 often for methyl group (-CH3) bonded to
a carbonyl group.
O O
C C H C CH3 CH3

~ δ 2.1 – 2.5 ppm singlet, δ 2.1 singlet, δ 2.3

6. Signal δ 9 – 10 ppm  proton aldehyde

O
C H
δ 9 – 10 ppm

7. A sharp singlet around δ 2.5 ppm  proton for terminal alkyne

C C H

sharp singlet, δ 2.5 ppm

 Example
Compound A is an alcohol and has molecular formula C2H6O. Based on the 1H
NMR spectrum below, propose the structure of A.

1.10

3.00
1.99
 Solution:
 (ppm) No. of Multiplicity Type of proton Assignment
hydrogen
0.87 3 triplet (t) (neighbour: CH2) CH3-CH2- a
3.31 2 quartet (q) (neighbour: CH3-CH2-O b
CH3)
4.44 1 broad singlet (br s) (no -OH OH
proton-proton coupling)
H = 6

Partial structure:
a
CH3-CH2- a b
b
CH3 CH2 OH
CH3-CH2-O

-OH H 0.87 ppm (t) H 4.44 ppm (br s)

H 3.31 ppm (q)

 Example
Compound B is a ketone and has molecular formula C4H8O. Based on the 1H
NMR spectrum below, predict the structure of the compound.

1.99 3.04 2.95

 Solution:
 (ppm) No. of hydrogen Multiplicity Type of proton Assignment

1.01 3 Triplet CH3-CH2- a

(neighbour: CH2)
2.50 3 Singlet (no O c
proton-proton
C CH3
coupling)
2.42 2 Quartet CH3-CH2-C=O b
(neighbour: CH3)
H = 8

Partial structure:
a
O
a b c
CH3-CH2- H3C CH2 C CH3
O
c
C CH3

b
H 1.01 ppm (t) H 2.50 ppm (s)
CH3-CH2-C=O
H 2.42 ppm (q)
 Example
Compound C is an ester with molecular formula C4H8O2
and has the following 1H NMR data. Elucidate the
possible structure of C.

Compound C
Quartet, 3.60 ppm
Singlet, 1.50 ppm
Triplet, 0.70 ppm
 Solution:

 (ppm) Multiplicity Type of proton Assignment

0.70 Triplet CH3-CH2- a

(neighbour: CH2)
1.50 Singlet (no O c
proton-proton
C CH3
coupling)
3.60 Quartet CH3-CH2-O- b
(neighbour: CH3)

Partial structure:
a c b a
CH3-CH2-

O
c
C CH3

b
H 1.50 ppm (s) H 0.70 ppm (t)
CH3-CH2-O
H 3.60 ppm (q)
 Example:
Sketch a predicted 1H NMR spectrum of 3-pentanone. Show all proton
signals with estimated chemical shifts and multiplicities.

 No. of Multiplicity Type of Assignment

(ppm) hydrogen proton
O
a b b a 0.70 – 6 triplet CH3-CH2- a
H3C CH2 C CH2 CH3 1.30 (neighbour:
CH2)
2.10 – 4 quartet CH3-CH2-C=O b
2.50 (neighbour:
2 signals CH3)
H = 10
 Exercise
Sketch a predicted 1H NMR spectrum of ethanoic
acid. Show all proton signals with estimated
chemical shifts and multiplicities.
CARBON-13( C)
13 NMR
SPECTROSCOPY
 12C 13C 1H

Nuclear spin quantum number (I) 0 ½ ½

Number of spin states (2I+1) 0 2 2

Natural abundance 98.9% 1.108% 99.98%
Magnetogyric ratio,  (radians/Tesla) - 67.28 267.53

1: 4
 12C is NMR inactive
- Has nuclear spin quantum number equal to zero, I = 0
CORRELATION DATA AND
TABLES FOR 13C NMR
SPECTRA
CORRELATION CHART FOR 13C CHEMICAL SHIFTS (ppm)

13C chemical shift range 0-220 ppm

 Chemical Shift in 13C NMR spectrum

• Arises in the same way as in the proton NMR spectrum.

• Each carbon nucleus has its own electronic environment,
different from the environment of other.
• Non-equivalent nuclei; it feels a different magnetic field, and
absorbs at different applied fields strength.
• Electronegative atoms and pi bonds cause downfield shifts.
• Anisotropy responsible for the large chemical shifts of the
carbons in aromatic rings and alkenes.
• The carbons of C=O groups have the largest chemical shifts
due to sp2 hybridization.
• Attachment of electronegativity oxygen to the C=O,
deshielding the C of C=O further.
INTERPRETATION OF
13C NMR SPECTRA
 INTEGRATION

 The area of a peak is not proportional to the

number of carbons giving rise to the signal.

 Therefore, integrations are usually not done.

Each unique carbon in a molecule gives rise to a 13C NMR signal

The proton-decoupled 13C NMR spectrum of ethyl acetate (C4H8O2)

4 carbons

4 carbon peaks
If there are fewer signals in the spectrum than carbon atoms
in the compound, the molecule must possess symmetry

The proton-decoupled 13C NMR spectrum of 2,2-dimethylbutane (C6H14)

b b
CH3
b c d a 6 carbons
CH3 C CH2 CH3

CH3 4 carbon
b
peaks
d
Three CH3 groups are equivalent a
by symmetry c
- Appear at same chemical shift
 The proton-decoupled 13C NMR spectrum of
cyclohexanol (C6H12O)

4 carbon peaks c
c
d OH a
a
Carbon d
deshielded by
b c oxygen
a
d b
6 carbons

Carbons a and c are doubled due

to symmetry and give rise larger
peaks than carbons b and d
The proton-decoupled 13C NMR spectrum of cyclohexene
(C6H10)

3 carbon peaks b
a
c
b c
c

a b Carbon c deshielded due

to its sp2 hybridization
a and some diamagnetic
anisotropy
6 carbons
The proton-decoupled 13C NMR spectrum of toluene
(C7H10)

a
c
e
d d
5 carbon peaks
c b c
d

b
7 carbons
e a
 The proton-decoupled 13C NMR spectrum of the three isomers of
dichlorobenzene
b
a c Cl

a c
b Cl
ortho-dichlorobenzene

Cl b Cl
d d 3 carbon
peaks 4 carbon 2 carbon
peaks peaks
a a
c

meta-dichlorobenzene

Cl
b
a a

a a
b
Cl
para-dichlorobenzene
ortho-dichloro meta-dichloro para-dichloro
 Exercise
Indicate how many nonequivalent peaks can be observed
in the 13C NMR spectrum of each compound in the
following set:

A B
C
7 7 5
STRUCTURE ELUCIDATION OF
SIMPLE ORGANIC COMPOUNDS
FROM IR AND NMR SPECTRA
 Example
An aromatic compound A with molecular formula of C9H10O shows an infrared
spectrum with a strong absorption at 1710 cm-1. Based on the following 1H NMR
and IR data, elucidate the structure of the compound. Gives the analysis based
on the values given.

Compound A
2.0 ppm, singlet, 3H
3.7 ppm, singlet, 2H
7.4 – 7.6 ppm, multiplet

Solution
1. C9H10O  Maybe alcohol or ketone or aldehyde or ether.

2. IR spectrum: strong absorption at 1710 cm-1  C=O stretch

 Maybe ketone.
 Cannot be aldehyde (C=O stretch: 1720-1740 cm-1)
 Cannot be ether (ether does not show absorption band at 1710 cm-1
 Cannot be alcohol (alcohol does not show absorption band at 1710 cm-1
 Solution

3. 1H NMR:
 (ppm) No. of hydrogen Multiplicity Type of proton

2.0 3 Singlet (no O

proton-proton
coupling) C CH3

3.7 2 Singlet (no H O

proton-proton C C
coupling) H

7.4-7.6 5 Multiplet H
H C
(neighbour: many
H) H H
H

H = 10

H O
C C CH3
H
 Example
Predict the molecular structure of an unknown compound with a molecular formula
of C4H8O2. The IR, 1H NMR and 13C NMR spectra of the compound are given below.
Assign the major peaks from all spectra.

1. C4H8O2  Maybe carboxylic acid or ester

2. IR spectrum:
Functional Frequency
group (cm-1)
C=O stretch 1752
(ester)
C-O stretch 1243
sp3 CH 2984
stretch

Compound maybe is
an ester
 b

Assignment  No. of Multiplicity Type of proton

(ppm) hydrogen
a ~1.40 3 triplet (neighbour: CH2) CH3-CH2-
b ~2.20 3 singlet (no proton-proton coupling) CH3-C=O
c ~4.20 2 quartet (neighbour: CH3) CH3-CH2-O
H = 8H
 c a

b
d

carbon  (ppm) Type of carbon

a ~13 CH3-C
b ~21 CH3-C=O
c ~60 CH2-O
d ~170 C=O (ester)
Proposed structure:

C ~60 ppm C ~21 ppm

O
C ~13 ppm
CH3CH2OCCH3

H ~1.40 ppm (t)

H ~2.20 ppm (s)
H ~4.20 ppm (q)

C ~170 ppm