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Experiment 4: ISOLATION AND IDENTIFICATION OF THE PRINCIPAL

CONSTITUENT OF CLOVE OIL


CHM 303 Section B07 (Wed. 7:30-10:20 PM)
Mideum Abraham Park
Xin Teng
Completed: 11/12/15
Reported: 11/28/15
Re-reported: 12/9/15

Purpose:
To isolate clove oil from freshly ground cloves by steam distillation and to come up with
the structure using IR and 1H NMR.
Procedure:
(Refer to OPB(14)-pp 34-37 for the full procedure.)
Data:
Weight of the clove buds used: 5.138 g
Weight of clove oil collected: 260 mg*
Plateau temperature (during steam distil.): 97.4 C
IR of alcohol attached
*the low amount of collection is due to the spillage that occurred after the steam distillation. I lost about
25 mL of the 35 mL collected.
http://sdbs.db.aist.go.jp/sdbs/cgi-bin/direct_frame_top.cgi

IR Table of Peaks in 4000-500 cm-1:


Obtained IR
Wavenumber
(cm-1)
3519.75

Intensit
y

Character
(w, m, s,
br)
m, br

Authentic IR
Wavenumber
(cm-1)
3669

3076.48
3003.66

w
w

3081
3006

2975.37
2938.13
2842.39
1637.78,
1612.32
1514.01,
1490.22

w
w
w
m, double
peak
s

2979
2940

Intensit
y

Character
(w, m, s,
br)

Representation

O-H stretch w/
H-bonds
=C-H stretches
aromatic =C-H
stretches
C-H stretches
C-H stretches
C-H stretches
C==C stretches
aromatic C==C
stretches

1462
1433
1369
1206

H NMR Peaks in CDCl3, 500 MHz:

a
b

Chemical shift
(ppm)
6.85
6.69

Area
1.00
2.00

d
e
f
g

5.95

1.00

5.48
5.06
3.88

1.00
2.00
3.00

3.33

2.00

Splitting pattern
(s ,d ,t)
d (J = 8.5 Hz)
mult.
10 peaks (J = 7
Hz, 10 Hz, 17
Hz)
s
mult.
s
d (J = 7 Hz)

Notes
aromatic H
two different
aromatic H
12 peaks (ddt)
vinylic H
O-H
vinylic 2H
segregated CH3
-CH2- with only
one side

d
f

H NMR Peaks in C6D6, 500 MHz:

a
b1
b2
c

d
e
g
f

Area
1.00

6.60

1.00

6.44

1.00

5.90

1.02

5.37
5.01
3.88
3.33

1.01
2.01
1.95
2.92

Splitting pattern
(s ,d ,t)
d (J = 8.5 Hz)
dd ( J = 1.7 Hz,
8 Hz)
d ( J = 1.9 Hz)
10 peaks (J = 7
Hz, 10 Hz, 17
Hz)
s
mult.
d (J = 7 Hz)
s

Notes
different from
in CDCl3

c
b e

Chemical shift
(ppm)
7.00

b2

12 peaks (ddt)
b
1

O-H
order changed
between these

Report Questions:
1. Characterize your IR spectrum and the authentic IR spectrum of the
principal constituent, A, of clove oil in tabular form in the usual manner.
Identify as many peaks in the spectra as possible. (Hint: The authentic IR
spectrum of A is contained in the Aldrich IR spectral compilations and the
SDBS. This means that you can do a molecular formula search if you need
structural help, or you could consult your dentist.)
Please see the data section (under IR Table of Peaks in 4000-1500 cm -1) for
more details.

The only difference I noted between the authentic and my IR spectrum is


the broadness of the 3500 cm-1 peak. Authentic on SDBS shows up as
more sharp.
2. Summarize the 1 H NMR spectrum of A, taken in CDCl3. Assign the peaks
to specific protons in the molecule. (Hints: The 2H multiplet at ~ 5.025.10 ppm is not first order; i.e., the two protons have very similar
chemical shifts. Also, two protons overlap to give the signal at ~ 6.676.71 ppm.)
See data section (under 1H NMR Peaks in CDCl3, 500 MHz) for details.
3. Carefully analyze the complex multiplet centered at 5.96 ppm in the 1 H
NMR spectrum of A, taken in CDCl3. (Your lab TA will also provide you with
an expansion of this multiplet along with a printout of peak positions.) A
splitting diagram should be helpful here. You should be able to extract
three different 37 coupling constants from an analysis of this multiplet.
(Hint: There should actually be 12 lines in this multiplet; however, several
of the lines overlap. Start by looking for four sets of triplets with coupling
constants that match the coupling constant observed for the 2H doublet
centered at ~ 3.33 ppm.)
The 3 different coupling constants are 7 Hz, 10 Hz, and 17 Hz. The pattern

shown on 1H NMR:
4. As noted in Lab Report Question 2, the 1 H NMR spectrum of Compound A,
taken in CDCl3, suffers from two shortcomings: (1) the non-first order 2H
multiplet at ~ 5.02-5.10 ppm and (2) the overlap of two protons at
6.67-6.71 ppm. Coupling constants are largely independent of the NMR
solvent, but this is not so with regard to chemical shifts. So, the potential
solution to our overlap problems is to try a different NMR solvent. And,
this is where the second NMR spectrum of Compound A, taken in C6D6,
comes into play. Unfortunately, the 2H multiplet at 4.98-5.05 ppm is still
not first order. However, the three protons between 6.4 and 7.05 ppm
are now nicely resolved. Please assign these peaks to the specific protons
in A. And, explain the observed splitting patterns and make coupling
constant assignments.

a
b

Chemical shift (ppm)


6.60
6.44

Area
1.00
1.00

Splitting pattern (s ,d ,t)


dd ( J = 1.7 Hz, 8 Hz)
d ( J = 1.9 Hz)

Notes
different from in
CDCl3

Hc

Ha

Hb

Ha has both the coupling with adjacent aromatic H c (8 Hz) and long range
coupling of aromatic ring ( 1.7 Hz), while H c has only the long range
coupling of aromatic ring ( 1.9 Hz).
5. What structure do you propose for the principal constituent, A, of clove
oil? Do your IR and 1 H NMR spectral data corroborate each other? If not,
explain why.
I propose that the principle constituent of clove oil is
eugenol, which has the structure as show above. The IR
spectra corroborate with this structure in that it has the OH peak, aromatic hydrogen peaks, and C=C peak. The 1H
NMR spectral data corroborate with the notes on table of
1
H NMR Peaks in CDCl3, 500 MHz (see data section).

6. Calculate the percentage of A obtained, based on the mass of ground


cloves used.

yield of clove oil=

260 mg
=5.06 yield
5139 mg

Discussion:
1. The methylene chloride layer remaining after the aqueous alkaline
extractions, which was discarded, still contained some residual unextracted A. However, the major component of this methylene chloride
layer was the secondary constituent, B, of clove oil. Compound B has a
molecular formula of C12H14O3. The IR spectrum of B is quite similar to
the IR spectrum of A, except that the broad band centered at about 3500
cm-1 is absent, while an intense band at 1765 cm-1 is now present. (Hint:
Pay particular attention to the frequency of this new absorption.)
Additionally, the 1 H NMR spectrum of B, taken in CDCl3, is similar to the
NMR spectrum of A. The 1H singlet at ~ 5.5 ppm in the NMR spectrum
of A is absent in the spectrum of B, while the spectrum of B displays a
new 3H singlet at 2.31 ppm, which is absent in the spectrum of A.
Propose a structure for the secondary constituent, B, of clove oil. Explain
how you arrived at this proposed structure.
Proposed structure is 4-allyl-2-methoxyphenyl acetate:

IR spectrum indicates the disappearance of O-H group (3500 cm-1, br) and
appearance of C=O group (1765 cm-1, s), and the most obvious chemical
reaction that can be done to achieve such thing is esterification. Only
acetate is attached because only 3H singlet at 2.31ppm appears with the
disappearance of 1H singlet at ~ 5.5 ppm. Molecular formula backs up
the proposed structure as well.
2. Carefully explain the basis of the chemically active extraction of the
principal constituent, A, of clove oil. Explain why A is soluble in aqueous
alkali, while B is not.
The extraction could be done by adding NaOH to the mixture in DCM
solution. Since phenol group on A is slightly acidic, it will be deprotonated
to form an anion, entering the aqueous layer. B cannot be deprotonated
because it does not have a phenol group, and since it is not ionized it is
not soluble in aqueous alkali.
B

NaO
Aconj.
base

NaO