SEMESTER 20204 ASSIGNMENT 1 CHM557

ORGANIC CHEMISTRY

ASSIGNMENT 1

SPECTROSCOPY
Semester October 2020-February 2021
Online Assessment COVID19

NAME STUDENT ID GROUP

1) MUHAMMAD NURHAZIQ BIN NORDIN 2019630872 RAS2452B

2) MUHAMMAD KAMARUL ZAMAN BIN ZAINAL 2019294294 RAS2452B

3) MOHD NAJIBULLAH BIN ABDUL RASHID 2020970377 RAS2453C

SEMESTER 20204 ASSIGNMENT 1 CHM557
ORGANIC CHEMISTRY

QUESTION 1

An unknown compound with a molecular formula of C6H1 02 gives the IR and NMR spectra
shown below.

a) Identify the functional groups in the IR spectrum, and explain your answer.

b) Avery deshielded signal is observed at 172 ppm inthe carbon NMR spectrum.
How does this signal correlate with absorption in the IR spectrum.

c) Determine the degree of unsaturation for the compound.

d) Suggest astructure for this compound (students arenot required toexplain thesplitting pattern
from the proton NMR spectrum).

2()) 12() IO(T H(l 60 40 20

1(I O S 7 6 .5
Question 1
a) From the IR spectrum, the functional group can be identified based on molecular formula
C6H10O2 is ester. From the range of 1735 – 1780 cm-1, there is C=O stretching peak in IR
spectrum. From the range of 1000 – 1250 cm-1, there is C-O stretching peak in IR spectrum.
For the alkene functional group, there is C=C stretching peak from the range 1600 – 1680
cm-1 and CH2 bending peak from the range 1450 – 1475 cm-1 in IR spectrum. From the
range 2720 – 2820 cm-1, there is sp2 C-H peak in the IR spectrum.

b) The signal in carbon NMR spectrum correlate with absorption in the IR spectrum because
the ester group for carbon in carbon NMR spectrum was determined by a very deshielded
signal and it is observed at 172 ppm from the compound. From the IR spectrum, there are
the peaks that shows the presence of ester group in the compound.

c) Degree of unsaturation for the compound:

2𝐶 + 2 + 𝑁 −𝑋− 𝐻
Degree of unsaturation =
2
2(6) + 2 + 0 − 0 − 10
=
2
=2

d) A structure for this compound is ethyl-2-butenoate because it has 5 peaks of H NMR

spectrum as same as in the proton NMR spectrum that have 5 peaks were obtained from
the spectrum.

H3 = 1.86 – 1.92δ H = 5.8-5.9δ H3 = 1.86 – 1.92δ

H = 6.9 – 7.4δ H2 = 4.12 – 4.24δ

SEMESTER 20204 ASSIGNMENT 1 CHM557
ORGANIC CHEMISTRY

QUESTION 2

The following spectra for A and B correspond to two structural isomers with a molecular formula of
C4H11N. The NMR singlet at δ1.16 in spectrum A disappears when the sample is shaken with D2O. The
singlet at δ0.60 ppm in the spectrum of B disappears on shaking with D2O. Propose structures for these
isomers, and explain how it is consistent with the observed absorptions.
SEMESTER 20204 ASSIGNMENT 1 CHM557
ORGANIC CHEMISTRY
Question 2
The structure of A is 2-Aminobutane because it have primary amide (2 peak or W-shape at 3300-
3500cm-1), sp3 C-H stretching (2800-3000cm-1), CH2 bending (1450-1475cm-) and CH3 bending
(1360-1390cm-1). It also produces 5 peaks for H-NMR which same signal multiplicities as H-NMR
spectra provided.
Doublet
Multiplet

Multiplet
N
Triplet H H

Singlet

The structure of B is Diethylamine because it have secondary amide (1 peak or V-shape at 3300-
3500cm-1), sp3 C-H stretching (2800-3000cm-1), CH2 bending (1450-1475cm-1) and CH3 bending
(1360-1390cm-1). The spectra of diehylamine shows by 3 peaks which same signal multiplicities
as H-NMR spectra provided.

N
H Triplet

Singlet

Quartet
The compound A and B, the NMR singlet at δ 1.16 and singlet at δ 0.60 disappeared by these
compound was shaken with (D2O) but other peaks did not. This because these peak are peak of N-
H. In addition of D2O into the compound A and B that containing acidic protons was replaced by
deuterium and other stay remain. That causes the peaks disappear because the new N-H group
would not appear in H NMR spectra. The mechanism of this substituent is:

N N

H H+ 2D2O D D + 2DOH

N N
H + D2O D + 2DOH
SEMESTER 20204 ASSIGNMENT 1 CHM557
ORGANIC CHEMISTRY

QUESTION 3

Compounds Y and Z are isomers with the molecular formula C10H12O. The IR spectrum of each
compound shows a strong absorption band near 1710 cm−1. The 1H NMR spectra of Y and Z are
given below. Propose structures for Y and Z.
Question 3

COMPOUND Y

CH3
O

COMPOUND Z

CH3
SEMESTER 20204 ASSIGNMENT 1 CHM557
ORGANIC CHEMISTRY

QUESTION 4

Compound A (C9H18O) forms a phenylhydrazone, but it gives a negative Tollens’ test. The IR
spectrum of A has a strong band near 1710 cm−1. The broadband carbon NMR spectrum of A is given
below.

a) Propose a structure for A and explain how your structure fits the spectral data.

b) Propose a mechanism for this reaction.

QUESTION 5

Compounds W and X are isomers. They have the molecular formula C9H8O. The IR spectrum of
each compound shows a strong absorption band near 1715 cm−1. Oxidation of either compound with
hot, basic potassium permanganate followed by acidification yields phthalic acid. The proton NMR
spectrum of W shows a multiplet at δ 7.3 and a singlet at δ 3.4. The proton NMR spectrum of X
shows a multiplet at δ 7.5, a triplet at δ 3.1, and a triplet at δ 2.5. Propose structures for W and X.
Question 4
a) Structure for A is 2,6-dimethyl-4-heptanone or Diisobutyl Ketone because in this structure
has 4 peaks in the carbon NMR spectrum. The functional group for structure A is ketone
because it has C=O in the structure based on the IR spectrum that has a strong band near
1710 cm-1 and ketone gives a negative Tollens’ test. This structure fits the spectral data
because in this structure, it has 4 peaks same as in spectral data.

Cb = CH Cc = CH2 Cd = C
Ca = CH3

Ca = CH3
Cc = CH2
Cb = CH
b) A mechanism for this reaction as shown below:
Question 5
The compound W and X are ketone because they showed a strong absorption near 1715cm-1 (C=O
stretch) and they are oxidize with hot, potassium permanganate followed by acidification yield
phthalic acid. The compound of W is 2- Indanone because it produced 2 peaks as 1 multiplet and
1 singlet.

Multiplet at δ7.3

Singlet at δ3.4

The compound of X is 1- Indanone because its H NMR spectra showed 3 peaks as 2 triplet and 1
multiplet.
O

Triplet at δ3.1

Multiplet at δ
7.5 Triplet at δ2.5
SEMESTER 20204 ASSIGNMENT 1 CHM557
ORGANIC CHEMISTRY

QUESTION 6

The manager of an organic chemistry stockroom prepared unknowns for a ‘Ketone and Aldehyde’
experiment by placing two drops of the liquid unknowns in test tubes labelled A and B. He then
stored the test tubes for several days until they were needed. On the day of the experiment, the
students complained the IR spectrum measured for test tube A is different from the spectrum shown
by the stockroom manager at the end of the class (refer the picture below). Obviously something has
happen to the solution while being left for a few days.
Test tube A - manager Test tube A - students

1725 cm-1 1710 cm-1

a) Identify the functional group revealed by the IR spectrum of

i. The stockroom manager
ii. The students

b) Explain the reason of discrepancy between the stockroom manager’s spectrum and the
student’s results.

c) Suggest how this misunderstanding might be prevented.

Question 6

Identify the functional group revealed by the IR spectrum of

i. The stockroom manager

- Aldehyde
ii. The students
- Carboxylic Acid

b) Explain the reason of discrepancy between the stockroom manager’s spectrum and the
student’s results.

- Oxidation occurs when the aldehyde is exposed to the Oxygen atoms. So, the aldehyde is easily
oxidized into carboxylic acid. Peak at the stockroom manager IR spectrum show that the functional
group is Aldehyde because at 2710 and 2810 cm-1 are fermi doublet peak (CH) and the sharp peak at
1725cm-1 was the C=O bond. The student’s IR spectrum shows that their sample changed into
carboxylic acid due to the exposure. The peak below 3000 is broad peak which may be O-H bond and
peak at 1710 is not sharp as the aldehyde and look like a U-peak.

c) Suggest how this misunderstanding might be prevented.

- This misunderstanding might be prevented by avoiding the unknown sample to be exposed to the
surrounding or prepared the sample on the day of the experiment is carried out.