Dr.

Bapu R Thorat

Spectroscopy
its application in Organic Chemistry
Bapu R Thorat
Assit. Professor of Chemistry
Govt. of Maharashtra, I. Y. College, Jogeshwari (E),
Maharashtra 400060

Dr. Bapu R Thorat

How it can be analyze?

ORGANIC CHEMIST LABORATORY

Analyze it

Dr. Bapu R Thorat

What is to be
present and how
much it can be
present?
What

Analysis by using
instruments

How

Identification

Total
information

Estimation

Characterization

It is branch of science used

for the Dr. Bapu R Thorat

According to the nature of information required,

Analysis method, its procedure and data are selected

Dr. Bapu R Thorat

Dr. Bapu R Thorat

The known methods of Analysis

Physical and chemical properties of organic molecules

Titrimetric and chemical analysis

Spectroscopy
1. Atomic spectrophotometry (Absorption)
2. Molecular emission spectroscopy
3. Ultaviolet and visible spectroscopy
4. Infrared spectroscopy
5. Nuclear magnetic resonance spectroscopy
6. Mass spectrometry
Chromatography
1. Gas chromatography
2. High-pressure liquid chromatography
3. Thin layer chromatography
High-performance capillary electrophoresis
Separation methods
Dr. Bapu R Thorat

Interaction of light with matter such as atoms,

ions or molecules.
Dr. Bapu R Thorat

Electromagnetic Spectrum

Dr. Bapu R Thorat

Matter (Molecules)
Total energy of the molecule = E electronic + E Vibrational + E rotational
The magnitude of these energies are in the following order
Eelect > Evibr > Erot

OH

NH2

H3C

CN

COOH
Cl
O

Above molecule contains s electrons (Single bond), p electrons (Multiple bonds) and nelectrons (Un shared pair of electrons on elements like N, O, S, halogens).
1. The energy required for the excitation of these electrons is in the range of 35-143 K cal.

2. The energy required for vibrations is in the range of 2-12 K cal.

3. There are several hydrogen atoms which can be oriented in two spin states in an external
magnetic field. They can be flipped. Energy required is of low.
Dr. Bapu R Thorat

Summary
Organic Molecule

UV/ Visible
radiation
200-800 nm
35-143 K cal

Electronic excitations

p*

p*

etc

UV / visible spectroscopy

IR radiation
2.5-15 m
2-12 K cal

Vibrational and rotational

excitation
C-H, C-OH, etc

IR Spectroscopy
Dr. Bapu R Thorat

NMR radiation
Radiofrequency
radiations

Flipping of protons
from a to b spin states.
NMR spectroscopy

U.V. Spectroscopy
Electronic Transitions:
Both inorganic and organic compounds show electronic transitions.
The absorption of radiation by the organic molecule in UV and visible region involves
the transition of the electrons from bonding and or and non-bonding n orbitals into
higher energy anti-bonding orbital * and or *.

s*

Unoccupied levels
p*

Energy

Atomic orbital

Atomic orbital

Occupied levels
p

Molecular orbitals

Dr. Bapu R Thorat

The anti-bonding molecular orbital is denoted by an asterisk. The various types of

electronic transitions *, n *, n * and * depending on the electronic
arrangement or configuration in given organic compounds.
*

anti-bonding
orbitals

non-bonding
orbital

bonding
orbitals
E

s*
p*

Energy

n
p
s

s*

alkanes

p*

carbonyls

p*

unsaturated
cmpds.

s*

O, N, S, halogens

p*

carbonyls

The energetic order of the transitions is * > n *Dr. >Bapu

R
* > n *.
Thorat

Woodward-Feiser Rules (Calculation of max of diene and triene)

-----------------------------------------------------------

* (K-band) max in nm.

Acyclic and heteroannular dienes

214

Homoannular dienes

253 (214 + 39)

Addition for each substituent.

-R alkyl (including part of ring)

05

-OR

06

-Cl, -Br

05

-OCOR

00

-CH=CH- additional conjugation

30

Exocyclic double bond

05

Exocyclic double bond on two rings simultaneously

10

Basic value
= 214 nm
homoannular = 39 nm
component
= 15 nm

3 x -R
obs

max

= 275 nm

one exocyclic bond

Total

cal

max

= 05 nm

obs

max

= 273 nm

Dr. Bapu R Thorat

= 235 nm

Basic value

= 214 nm

3 x -R

= 15 nm

one exocyclic bond

= 05 nm

Total

cal

max

= 235 nm

Woodward rule for calculation of max of enone compounds

Values assigned to-

* in nm (ethanol)

Ketone C=C-CO- (acyclic or six membered cyclic)

215 nm

Ketone C=C-CO- (five ring cyclic)

202 nm

Aldehydes C=C-CHO

210 nm

Acids and esters C=C-COOH/R

197 nm

Extended conjugation (-C=C-)

30 nm

Homoannular components

39 nm

Ring residues

nm

nm

nm

nm

-R alkyl including part of carbocyclic ring

10

12

18

18

-OR

35

30

17

31

-OH

35

30

30

50

-SR (thioether)

--

80

--

--

-Cl

15

12

12

12

-Br

25

30

25

25

-OCOR

06

06

06

06

-NH2, -NHR, -NR2 (amino)

--

95

--

--

Exocyclic double bond to one ring

05 nm

Exocyclic double bond to two rings simultaneously.

10 nm

Dr. Bapu R Thorat

Infrared Spectroscopy (4000 650 cm-1)

The infrared region (100 104 cm-1) important for the infrared spectroscopy
is 4000 650 cm-1
Vibrate without change
in dipole moment

Molecule

IR inactive

Vibrate with change in

dipole moment
IR active

Higher change in
dipole moment
Polar
functional
groups

Small change in
dipole moment
Less polar
functional
groups/
symetric groups

Intense band
Low Intense
band
Dr. Bapu R Thorat

Three translational &

two/three rotations motions
are double degenerate

Vibrations
Fundamental vibrations

bending vibrations

stretching vibrations

Scissoring
symmetrical stretching

antisymmetrical stretching

Wagging

Rocking

(2N-5)/(2N-4) are bending vibration

stretching

compression
(N-1) are stretching vibration
O-H stretches

Bend

C=O stretches

Bend

Dr. Bapu R Thorat

Twisting

Dr. Bapu R Thorat

Nuclear Magnetic Resonance spectroscopy (NMR) The

principle
1.

In an applied external magnetic field, radio waves interact with atomic nuclei
whose I > 0, 1H, 13C, 19F, 31P, etc.
(I = spin quantum number / angular momentum).
Nuclei (isotopes)

% natural abundance

Nuclear spin

1H

99.98
0.02
0.00
19.6
80.4
98.89
1.11
99.63
0.37
99.76
0.04
0.20
100.00
100.00

3
3/2
0

0
5/2
0

2H
3H
10B
11B
12C
13C
14N
15N

16O
17O
18O
19F
31P

Dr. Bapu R Thorat

Magnetic & Non-magnetic nuclei

Nuclei

1H,13C,17O,19F

2D,10B,14N

12C, 18O

I = , 3/2, 5/2

I = 1, 2, 3

I=0

MAGNETIC

MAGNETIC

NON-MAGNETIC

Dr. Bapu R Thorat

Proton Chemical Shift Ranges

Dr. Bapu R Thorat

Multiplicity or Spin-spin coupling

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

1. NMR (all nuclei) is usually used:

To analyze the product of a chemical reaction

To elucidate the structures of natural products, in conjunction with mass

spectrometry (which gives molecular weights and formulas), IR and UV
2. In this course, you will be given one of three pieces of data with an 1H NMR for
consideration:

A molecular formula

An IR spectrum

The first part of a chemical reaction

O
for example:
NaBH4
EtOH

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

NMR Spectral Analysis Introductory
Step 1: Do a quick assessment of the information you are given
Molecular formula one of the most important pieces of information.
Use the index of hydrogen deficiency (HDI)
to determine the possible number of rings, double and triple bonds in the
molecule:
For a chemical formula: CxHyNzO (halogens count as Hs)
HDI = x Y + Z + 1
Example: C4H8O -

or

HDI = 4 (8) + (0) + 1

HDI = 1 This compound contains either one
double bond or one ring

Dr. Bapu R Thorat

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Step 2: Do a quick assessment of the 1H NMR you are given

Is the molecule simple or complex?

Is the molecule aromatic, aliphatic or both? (IHD)
What are the total number of resonances that you observe

Be careful with overly simple spectra remember a large molecule may

appear to be small and simple if it is highly symmetrical
Consider: Durene, C10H14
1H

NMR spectrum consists of two singlets!

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example: 1H NMR for C4H8 (which has an HDI of 1)

Area under the peak, area of

integration

Gives information of number of

protons responsible for signal

singlet

1
triplet

Splitting of signal - number of protons

affecting the signal of reference proton
(By coupling)

2
quartet

3
Three types of protons present having different
Dr. Bapuenvironment
R Thorat
magnetic
3

Spectral Analysis 1H NMR

Step 3: Use the integration along with the molecular formula to make sure you can
find all of the 1Hs.
If you do not have a molecular formula, use the integration to attempt to tabulate the
number of 1Hs in the formula (does it make sense?)

E
X
A
M
P
L
E

If one hydrogen appears to be missing, you may suspect it is acidic or exchangeable

with the dueterated NMR solvent
Keep in mind organic molecules contain C-Hs, -CH2- s, -CH3 s and multiples of
chemically equivalent ones!
Dr. Bapu R Thorat

Spectral Analysis 1H NMR

For C4H8O we need to find 8 protons
The integral for the
quartet at d 2.5 measures 30 mm,
singlet at d 2.2 measures 44 mm,
triplet at d 1.1 measures 43 mm

43

Total area under peak =

(30+44+43) = 117
Area under peak per proton =
117/8 = 14.625 15
The ratio:
30:43:42 is roughly 2:3:3
2+3+3=8
We found all 8 protons

44

30

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Step 4: Classify each of the proton resonances by using the general correlation table

Reconsider the number of rings, double or triple bonds that are possible given
the HDI, and reconcile this data with what the 1H chemical shifts

Some hints:
If you calculate an HDI > 4, you probably have an aromatic ring, and this should
show on the spectrum
If you calculate an HDI of 1 or 2 and see no protons that are part of an alkene
and alkyne suspect rings if no oxygen's are present, carbonyls if (C=O) they are

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

NMR Spectral Analysis:

EWG CH3

For C4H8O : 3 families of

chemically equivalent protons or
CH2-, -CH3, -CH3
Both the 2.2 and 2.5 resonance
correspond to protons on carbons
next to electron withdrawing groups

EWG
R CH2

The 1.1 resonance corresponds to

protons on carbons bound to other
aliphatic carbons

Dr. Bapu R Thorat

R CH3

Spectral Analysis 1H NMR

NMR Spectral Analysis

We found CH2-, -CH3 and
CH3, subtract these from our
original formula:
C4H8O - CH2 = C3H6O
C3H6O CH3 = C2H3O
C2H3O CH3 = CO

EWG CH3

EWG
R CH2

We needed an HDI of 1 and there is

no evidence for 1H-C=C on the 1H
NMR, our missing HDI, and EWG
is a C=O!

Dr. Bapu R Thorat

R CH3

Spectral Analysis 1H NMR

Step 5: Analyze the spin-spin coupling multiplets to elucidate the carbon chains of the
molecule
Hints:

Singlets indicate you have protons on carbons that have no chemically nonequivalent protons on any adjoining atom

Multiplets mean you have chemically non-equivalent protons on adjoining carbons

(or atoms), use the n+1 rule in reverse to find out how many

Spin-spin coupling or splitting is MUTUAL, if you observe a multiplet there must

be another multiplet it is related to (split by)

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

NMR Spectral Analysis

the C=O is the electron withdrawing
group
The CH3 singlet at 2.2 - no 1Hs on
adjoining carbons, as it is next to the
carbonyl.

EWG CH3

EWG
R CH2

The 2.5 CH2- quartet - next to a

CH3 (n+1 = 4, so n = 3, it is next to a
CH3)

The 1.2 CH3 is a triplet - next to a

CH2

Dr. Bapu R Thorat

R CH3

Spectral Analysis 1H NMR

Step 6: Construct the molecule and double-check consistency

Does the HDI match? Have you accounted for all atoms in the formula?

From your constructed molecule, pretend you are trying to verify if that
spectrum matches, and quickly re-do the problem

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

We concluded we have:

O H
2
H3C C C CH3
2-butanone
C4H8O, HDI = 1
3 proton resonances
2 mutually coupled (split)

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 2: C9H9BrO
HDI =

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 2: C9H9BrO
HDI = 9 (10) + 0 + 1 = 5
C=C, CC, C=O, ring, and substituted aromatic ring may be present

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 2: C9H9BrO
HDI = 9 (10) + 0 + 1 = 5

2H, m
1H, m

3H, d

1H, q
2

3
2H, m
5

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 2: C9H9BrO

HDI = 9 (10) + 0 + 1 = 5

Br

Aromatic
protons

Coupling partners

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 3: C4H10O
HDI =

No protons in olefinic
and aromatic region

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 3: C4H10O
HDI = 4 (10) + 0 + 1 = 0

No unsaturation or ring.
double, triple bond, ring, etc
are absent

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 3: C4H10O

HO

HDI = 0

3H, t

2H, m

2H, m
1H, bs
2H, t

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 4: C5H10O2
HDI =

No protons in olefinic
and aromatic region
bs, 1H

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 4: C5H10O2
HDI = 5 (10) + 0 + 1 = 1

6H

1H
2H
1H
Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 4: C5H10O2
HDI = 1

2H, d

1H, m
6H, d

1H, bs

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 4: C5H10O2

HDI = 1

HO

Dr. Bapu R Thorat

Chemically
equivalent H

Spectral Analysis 1H NMR

Example 5: C10H12O2
HDI =

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 5: C10H12O2
HDI = 10 (12) + 0 + 1 = 5

3H

1H
Carboxylic
acid H

1H

Aromatic
protons

5H

Dr. Bapu R Thorat

1H
1H

Spectral Analysis 1H NMR

Example 5: C10H12O2
HDI = 5

1H, m
1H, bs

1H, m
1H, t(dd)

5H, m

Dr. Bapu R Thorat

3H, t(dd)

Spectral Analysis 1H NMR

Example 5: C10H12O2

Chiral centre

HDI = 5

OH

Methylene H shows
geminal coupling

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 6: C6H4ClNO2
HDI =

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 6: C6H4ClNO2
HDI = 6 (5) + (1) + 1 = 5

1H

1H

No H attached to saturated
carbon / alphatic alkyl groups
are absent

1H
1H

Dr. Bapu R Thorat

Spectral Analysis 1H NMR

Example 6: C6H4ClNO2

1H, t, ortho-coupling

HDI = 5

1H, dd, meta-coupling

1H, dd, o& mcoupling

Dr. Bapu R Thorat

1H, dd, o& mcoupling

Spectral Analysis 1H NMR

O
N

Example 6: C6H4ClNO2
HDI = 5

B
A
C

Dr. Bapu R Thorat

Cl

Deduce the structure of the compound based on following data:Molecular formula:C10H12O2.

U.V.

:- 211 ( 1200).

I.R.

:- 3250-2700 (broad), 1710, 1603, 758, 688 cm-1.

M.S. (m/z)

:- 164 (M+), 105, 77, 60, 45.

P.M.R. ()

:- 1.3 (d, J=7Hz, 3H), 2.6 (d, J=7Hz, 2H), 3.24 (sextet, J=7Hz, 1H),
7.20 (m, 5H), 10.8 (bs, exchange with D2O, 1H).

10.8 (bs,
exchange with
D2O, 1H)

2.6 (d, J=7Hz, 2H)

COOH

H
H

7.20 (m, 5H)

H
H

Dr. Bapu R Thorat

CH3
1.3 (d, J=7Hz, 3H)
3.24 (sextet, J=7Hz,
1H)

Deduce the structure of the compound based on following data:Molecular formula:C15H20O2.

U.V.

:- 275 nm ( 21000).

I.R.

:- 1720, 1626, 1605, 1150, 850, 820 cm-1.

M.S. (m/z)

:- 232 (M+), 176 (Mc-Lafferty rearrangement)

P.M.R. ()

:- 1.0 (d, J=7Hz, 6H), 2.0 (m, 1H), 2.38 (s, 3H), 3.95 (d, J=7Hz, 2H),
6.16 (d, J=16Hz, 1H), 7.20 (d, J=8Hz, 2H), 7.41 (d, J=8Hz, 2H),
7.75 (d, J=16Hz, 1H).

Dr. Bapu R Thorat

Deduce the structure of the compound based on following data:Molecular formula:C15H20O2.

U.V.
:- 275 nm ( 21000).
I.R.
:- 1720, 1626, 1605, 1150, 850, 820 cm-1.
M.S. (m/z)
:- 232 (M+), 176.
P.M.R. ()
:- 1.0 (d, J=7Hz, 6H), 2.0 (m, 1H), 2.38 (s, 3H), 3.95 (d, J=7Hz, 2H),
6.16 (d, J=16Hz, 1H), 7.20 (d, J=8Hz, 2H), 7.41 (d, J=8Hz, 2H),
7.75 (d, J=16Hz, 1H).

J = 16 Hz

J = 7 Hz H

CH3

H
O
H

H
H

J = 8 Hz

Dr. Bapu R Thorat

CH3

Deduce the structure based on the following carbon-13 N.M.R. data.

Molecular formula:- C8H10O.
C-13 NMR () :- 38(q), 63(t), 126(d), 128(d), 129(d), 139(s).
Saturated carbons attached to
electronegative atom

63(t), and then 38(q)

Olrfinic or aromatic carbons

126(d), 128(d), 129(d), 139(s).

If aromatic carbons,
monosubstituted benzene ring

Dr. Bapu R Thorat

Deduce the structure based on the following carbon-13 N.M.R. data.

Molecular formula:- C8H10O.
C-13 NMR () :- 38(q), 63(t), 126(d), 128(d), 129(d), 139(s).

Olrfinic or aromatic carbons

Saturated carbons attached to
electronegative atom
126(d), 128(d), 129(d), 139(s).
63(t), and then 38(q)
If aromatic carbons,
monosubstituted benzene ring
H
H

H
H

H
H

H
Dr. Bapu R Thorat

Deduce the structure of the organic compound having the following analytical and spectral
data.
Analysis: : C, 74.98; H, 6.86.
Gives empirical formula
Mass:

: 176 (M+), 131, 103, 77.

IR:

: 1714, 1639 cm-1.

P.M.R. (): 1.31 (t, J=7.1Hz, 3H), 4.2 (q, J=7.1Hz, 2H),
6.43 (d, J=15.8Hz, 1H), 7.67 (d, J=15.8Hz, 1H),
7.24-7.57 (m, 5H).
C.M.R. (): 14.3, 60.4, 118.4, 128.1, 128.9, 130.2, 134.5, 144.5, 166.8.

Dr. Bapu R Thorat

Structure
Mass:

: 176 (M+), 131, 103, 77.

H
77

O
103

H
H

131

O
H
H

H
H
Dr. Bapu R Thorat

H
H

The absorption at max 279 nm ( 15) in the UV spectrum of acetone is due to1. *

2. n *

3. *

Dr. Bapu R Thorat

4. n *

Electronic transition in Carbonyl compounds

C=O compounds, have , , n, *
and * Orbitals
Energy of orbitals < < n < * < *
*

n *

n *

Lower energy transitions

These non-bonding electrons are not tightly held as are pi-electrons; therefore, the
non-bonding electrons excited to anti-bonding orbitals by lower energy.

When the carbonyl group is substituted by an auxochrome as OH, -OR, -X, -NR2,
etc the * orbital energy is raised. Therefore, the n * transition of these
compounds shifted towards shorter wavelength.

Dr. Bapu R Thorat

Which of the following spectroscopic techniques will be useful to distinguish between MSCN and M-NCS binding modes?
1.
2.
3.
4.

Dr. Bapu R Thorat

NMR
IR
EPR
Mass

Electromagnetic Spectrum

Dr. Bapu R Thorat

The order of carbonyl stretching frequency in the IR spectra of ketone, amide and
anhydride is-

1. Anhydride > amide > ketone

2. Ketone > amide > anhydride

3. Amide > anhydride > ketone

4. Anhydride > ketone > amide

Dr. Bapu R Thorat

Factor affecting the vibrational frequencies

Inductive and Resonance effect

Electron donating
inductive
and
resonance effect

Absorption
frequency shifted
towards
lower
frequency value by
large magnitude

Opposite inductive
and
resonance
effect
Change
in
frequency
are
depends on the
nature
and
strength
of
electronic effect

Electron
withdrawing
inductive
and resonance effect

Absorption frequency
was shifted towards
higher frequency side

The double bond character increases by electron withdrawing group and vice-versa
O
X

X=
C=O stret.(cm)
in hexane

Br
-1

1760
-I

OPh

OMe

1750

1735

1714

1697

--

+I

-I & +R

& +M
Dr.-IBapu
R Thorat

Me

NMe 2
1660
-I & +R (strong)

An organic compound (C7H12O2) exhibited the following data in the 1H NMR spectrum 7.10 (1H, dt, J = 16 and 7.2 Hz); 5.90 (1H, dt, J = 16 and 2 Hz);
4.1 (2H, q, J = 7.2 Hz); 2.10 (2H, m); 1.25 (3H, t, J = 7.2 Hz); 0.90 (3H, t, J = 7.2 Hz) ppm
The compound, among the choices given below, isO
O

1.

2.

O
O
3.

4.

Coupling partners [ J = 16 Hz]

(trans- vicinal coupling)
Chemical shift : highly deshielded [olefinic]

Coupled with CH2Deshielded (O-CH2-CH3)

7.10 (1H, dt, J = 16 and 7.2 Hz);

5.90 (1H, dt, J = 16 and 2 Hz);
4.1 (2H, q, J = 7.2 Hz);
2.10 (2H, m);
1.25 (3H, t, J = 7.2 Hz);
0.90 (3H, t, J = 7.2 Hz) ppm

Dr. Bapu R Thorat

Compound

(CH3)4C

(CH3)3N

(CH3)2O

CH3F

0.9

2.1

3.2

4.1

Compound

(CH3)4Si

(CH3)3P

(CH3)2S

CH3Cl

0.0

0.9

2.1

3.0

Dr. Bapu R Thorat

The NMR spectrum of a compound exhibits a doublet at 1.00 with coupling constant
of 8 Hz recorded on a 100 MHz instrument. The two line positions of the doublet in Hz
will beA) 100 & 108 B) 92 & 100 C) 96 & 104 D) 104 & 112.

Dr. Bapu R Thorat

It is generally frequency difference () (in term of Hz) between the

absorption frequencies of sample and the reference compound.

Chemical shift in ppm = (chemical shift in Hz).106/(strength of applied magnetic field in Hz).
(delta) scale - (delta) = in Hz.106/radio frequency in Hz.
(tau) scale - (tau) = 10 - .

Dr. Bapu R Thorat

An organic compound A (C8H16O2) on treatment with an excess of methylmagnesium

chloride generates two alcohols B and C whereas reaction of A with LAH generates only a
single alcohol C. Compound B on treatment with an acid yielded an olefin (C6H12) which
exhibited only a singlet at 1.6 ppm in the NMR spectrum. The compound A isO

1.

2.
O

O
O

3.

4.

A
ester

methylmagnesium chloride
Grignard reaction

Alcohol

LAH
Red.

C
Alcohol

A should be carbonyl compound, ester

B
Alcohol

Acid, ellimination
Dr. Bapu R Thorat

C6H12

Gives one
signal in
PMR.
One set of
protons

Deduce the structure for the following spectral data:

Molecular formula: C9H12O2
IR cm-1 3100-2900.
NMR: ppm 3.4 (6H, s); 5.5 (1H, s); 7.5 (5H, m).
Mass spectra (m/z): 152 (molecular ion peak), 121
[University of Mumbai M.Sc. ]
Molecular formula: C9H12O2

Site of unsaturation: Number of multiple bonds/ring present in the molecule

C9H12O2

Conclusion

The molecular formula

of saturated
hydrocarbon is C9H12.

(18+2-12)/2 = 8/2 = 4

Presence of C=C, C=O, epoxide ring, ring, CC, phenyl ring, etc
Dr. Bapu R Thorat

IR cm-1 3100-2900

Stretching
of
=C-H
group of olefinic or
aromatic protons

Dr. Bapu R Thorat

NMR: ppm 3.4 (6H, s); 5.5 (1H, s); 7.5 (5H, m)

Signal of
monosubstituted
benzene ring

Singlet, highly
deshielded
proton attached
to olefinic carbon
or carbon
attached to
oxygen

Dr. Bapu R Thorat

singlet , Highly
deshielded
magnetically
equivalent 6H,
2 OCH3

Deduce the structure for the following spectral data:

Molecular formula: C9H12O2
IR cm-1 3100-2900.
NMR: ppm 3.4 (6H, s); 5.5 (1H, s); 7.5 (5H, m).
Mass spectra (m/z): 152 (molecular ion peak), 121

Structure:
3.4 (6H, s)
b H3C

CH3 b
O

Ha

5.5 (1H, s)
Ha
3100-2900 cm -1

Ha

Ha
Ha
7.5 (5H, m)

Mass Spectra: The molecular ion peak is at 152. It gives another peak at 121 is
[M 31] or [M OCH3] indicate presence of OCH3 group.
OMe
OMe

OMe
-e

+
+
O CH3

OMe
m/z = 152
Dr. Bapu
Molecular
ion R Thorat

m/z = 121

A compound with molecular formula C4H5SO2N gave following spectral data:

IR (cm-1) : 2250 (M), 1740 (S).
PMR (PPM) : 3.8 (s, 3H); 3.5 (s, 2H).
Mass spectra (m/z) : 99, 73, 59.
Deduce the structure of the compound
Molecular formula: C4H5SO2N

Site of unsaturation: Number of multiple bonds/ring present in the molecule

C4H5SO2N

Conclusion

The molecular formula of

saturated hydrocarbon is C5H6.
(neglect S and O, replace N by CH)

(10+2-6)/2 = 6/2
=3

Presence of C=C, C=N, N=O, C=O, epoxide ring, ring, CN, NO2, etc
Dr. Bapu R Thorat

IR cm-1 2250 (M), 1740 (S)

Stretching of
CN
group
(2250 cm-1)

Stretching vibration of
CO- group of acid or
ester or thio-ester

Dr. Bapu R Thorat

NMR: ppm 3.8 (s, 3H); 3.5 (s, 2H).

Singlet, highly de-shielded

proton attached to olefinic
carbon or carbon attached
to oxygen, S, N

Dr. Bapu R Thorat

singlet , Highly
deshielded
magnetically
equivalent 3H,
OCH3

A compound with molecular formula C4H5SO2N gave following spectral data:

IR (cm-1) : 2250 (M), 1740 (S).
PMR (PPM) : 3.8 (s, 3H); 3.5 (s, 2H).
Mass spectra (m/z) : 99, 73, 59.
Deduce the structure of the compound
Structure:
1740 cm
3.8 (s)

-1

H3C

O
O

3.5 (s)

H H

2250 cm

-1

Mass spectra (m/z)

O
CH3O

-e
S

CN

.+

O
S
CH3O
m/z = 99

CN

+
S
CH3O
m/z = 59
Dr. Bapu R Thorat

+
CH2

S
CH3O
m/z = 73

A colourless liquid A (molecular formula C9H10O2) gives following spectral

data:IR:- (frequency in cm-1)- 1720(s), 1602(m), 1581(m), 1270(s), 1105(s) cm-1.
1HNMR (neat): 1.29[3H, t(J= 8Hz)]; 4.35[2H, q(J= 8Hz)]; 7.40[3H, m];
8.81[2H, m].
Determine the structure of A.

Molecular formula: C9H10O2

Site of unsaturation: Number of multiple bonds/ring present in the molecule

C9H10O2

Conclusion

The molecular formula of

saturated hydrocarbon is C9H10.
(neglect S and O, replace N by CH)

(18+2-10)/2 =
10/2 = 5

Presence of C=C, C=O, epoxide ring, ring, phenyl ring, etc

Dr. Bapu R Thorat

IR cm-1 1720(s), 1602(m), 1581(m), 1270(s), 1105(s)

Stretching vibration of
CO- group (1720 cm-1)
of ester or deshielded
ketone

Stretching of
Aromatic C=C bonds
(1602, 1581 cm-1)

Dr. Bapu R Thorat

Skeleton vibration of
C-O-C (1270 cm-1)

NMR: ppm 1.29[3H, t, (J= 8Hz)]; 4.35[2H, q, (J= 8Hz)];

7.40[3H, m]; 8.81[2H, m]

7.40[3H, m]; 8.81[2H, m]

signal of monosubstituted Phring attached to group shows
strong electronic effect

4.35, quartet, de-shielded

proton attached to olefinic
carbon or carbon attached
to oxygen

It should be coupled with CH3

group with coupling constant J =
8Hz (vicinal coupling)

1.29, t, shielded proton attached

to carbon shows weak I effect

It should be coupled with CH2

group with coupling constant J =
8Hz (vicinal coupling)

Dr. Bapu R Thorat

A colourless liquid A (molecular formula C9H10O2) gives following spectral

data:IR:- (frequency in cm-1)- 1720(s), 1602(m), 1581(m), 1270(s), 1105(s) cm-1.
1HNMR (neat): 1.29[3H, t(J= 8Hz)]; 4.35[2H, q(J= 8Hz)]; 7.40[3H, m];
8.81[2H, m].
Determine the structure of A.

O
O

Dr. Bapu R Thorat

CH3

An organic compound A having molecular formula C10H12O2 gives following

spectral data:
IR:- (frequency in cm-1)- 1730(s), 1602(m), 1581(m), cm-1.
1HNMR (neat): 2.0[3H, s]; 3.93[2H, t(J= 7Hz)]; 4.30[2H, t(J= 7Hz)];
7.30[5H, bs].
Determine the structure of A

CH3

O
O

Dr. Bapu R Thorat

An organic compound A exhibits only a singlet at 2.17 in the PMR spectrum

and prominent peaks at
m/z 58(M+.), 43(base peak), 39, 27, and 15 in the mass spectrum.
When compound A is treated with benzaldehyde and dilute ethanolic sodium
hydroxide, it yields B. the IR spectra of B exhibits the band at 3025, 1665, 1630,
1600, 1495, 763 and 705 cm-1.
The PMR peaks of B gives following signals:- 7.82[1H, d(J= 18Hz)]; 7.60[5H, m(J= 7Hz)]; 7.05[1H, d(J= 18Hz)].
Deduce the structure of A and B.

Dr. Bapu R Thorat

Calculation of molecular formula of A

The mass of molecule A is 58 (from mass spectra)
The molecular formula can be determined by C-13 rule

Total number of carbon atom present in the molecule (A) = 58/13 = 4 and hydrogens are
(4 + 6) = 10

Molecular formula of given organic compound is C4H10.

Replace CH4 by O; molecular formula of A containing oxygen is C3H6O (because A
undergoes aldol condensation)
Molecular formula of A is C3H6O

Dr. Bapu R Thorat

O
H3C

CH3

CH3

NaOH
EtOH

O
H3C

O
CH3

CH3
A

Dr. Bapu R Thorat

2. N2

1. H2

Which one of the following exhibits rotational spectra?

3. CO

Dr. Bapu R Thorat

4. CO2

In the broad band decoupled CMR spectrum, the number of signals appearing for the
bicyclooctane A-C, respectively are1. 5, 4 and 8

2. 3, 2 and 5

4. 3, 2 and 8

3. 2, 4 and 5

Dr. Bapu R Thorat

1. 1 : 1 : 1,
3. 1 : 2 : 1,

2.
4.

Dr. Bapu R Thorat

3:3:1
3:2:8

In the mass spectrum of the compound given below, during the -cleavage,
the order of preferential loss of groups isMe
Et

OH
C3H7

Dr. Bapu R Thorat

1.
2.
3.
4.

Me > C3H7 > Et

C3H7 > Et > Me
Et > Me > C3H7
Et > C3H7 > Me