Chemistry 14C Lecture 1

Spring 2013

Exam 2

Page 1

Please use the back of the data table and information pages for scratch space. Please do
not use the exam margins for this purpose.
Questions 18 concern these molecules (which can also be found on exam page 9):
OH

OH
CH3

OH

HO

HO

NH2

CH3
N
H

CH3

HO

HO

Pseudoephedrine (C10H15NO)

Adrenaline (C9H13NO3)

H
O

Norepinephrine (C8H11NO3)

CH3
CH3

MDMA (ecstasy; C11H15NO2)

O
O

Piperonal (C8H6O3)

Safrole (C10H10O2)

1.

(2) Write a number in the blank. The molecule that has the most DBE has _______________ DBE.

2.

(8) Circle one molecule in each set or more than one if there is a tie.
(a) The molecule whose mass spectrum has M with the highest m/z is:
Pseudoephedrine
Piperonal

Adrenaline
Safrole

Norepinephrine

None of these

MDMA

Cannot determine

(b) The molecule in whose mass spectrum M is not the base peak is:
Pseudoephedrine
Piperonal

Adrenaline
Safrole

Norepinephrine

None of these

MDMA

Cannot determine

(c) The molecule whose mass spectrum contains an M+2 peak of at least 4% intensity when the intensity of M
is 100%:
Pseudoephedrine
Piperonal

Adrenaline
Safrole

Norepinephrine

None of these

MDMA

Cannot determine

(d) The molecule that gives the following mass spectrum: m/z = 193 (M; 100%), m/z = 194 (12.84%), and m/z =
195 (0.54%):
Pseudoephedrine
Piperonal

Adrenaline
Safrole

Norepinephrine

None of these

MDMA

Cannot determine

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Chemistry 14C Lecture 1

3.

Spring 2013

Exam 2

Page 2

(9) The following IR spectrum of a pure substance might have been produced by one or more of the molecules
listed on page one:

4000

3000

2000

1500

1000

500

Complete each statement by circling "might be" or "cannot be", as appropriate. If you circled "might be" you
are done with this part. If you circled "cannot be" complete the statement by adding no more than ten words of
explanation. For maximum credit, make your explanations very different.
(a) The molecule that produced this IR spectrum might be / cannot be pseudoephedrine because...

(b) The molecule that produced this IR spectrum might be / cannot be adrenaline because...

(c) The molecule that produced this IR spectrum might be / cannot be norepinephrine because...

(d) The molecule that produced this IR spectrum might be / cannot be MDMA because...

(e) The molecule that produced this IR spectrum might be / cannot be piperonal because...

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Chemistry 14C Lecture 1

4.

Spring 2013

Exam 2

Page 3

(2) Let's assume that you've decided to make your own MDMA (also know as ecstasy) because MDMA
purchased from a street vendor is slightly to very impure. Perhaps your MDMA synthesis will begin with the
conversion of safrole into molecule A by Wacker oxidation: purity will be analyzed by IR spectroscopy.
O

O
O2, PdCl2, CuCl2

Safrole

Molecule A

The purity of molecule A is then determined by IR spectroscopy. Here is the IR spectrum of one batch of
molecule A:

4000

3000

2000

1500

1000

500

Circle the correct statement:

(a) The batch of molecule A is pure. It contains no safrole.
(b) This batch of molecule A is impure. It is a mixture of safrole and molecule A.
(c) The batch of molecule A is a complete waste. It is nothing but safrole.
(d) This IR spectrum is inconclusive. Other tests are needed.

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Chemistry 14C Lecture 1

5.

Spring 2013

Exam 2

Page 4

(17) At the end of the MDMA synthesis you have a pile of white powder, but how can you be sure you actually
have MDMA? NMR spectroscopy can be very useful in this regard. Let's make some predictions about the 1HNMR spectrum of MDMA by completing the following table.
(a) In the chemical shift table, write one of the following numbers: 9.5 ppm, 7.0 ppm, 6.1 ppm, 3.3 ppm, 3.2
ppm, 2.8 ppm, 2.0 ppm, 1.1 ppm, or 0.0 ppm. (Each chemical shift will be used only once, but not all will
necessarily be used.)
(b) In the integral column, write the corresponding integral. Notice that one number has already been given.
(c) In the splitting column circle "s" if the signal is a singlet, "d" for doublet, "t" for triplet, and "m" more
complex than triplet.
Hint: Practice this problem on scratch paper before writing your final answer here.
Chemical Shift
B
C

ppm

HB

CH3

ppm

HC

ppm

CH3

HD

ppm

HE

ppm

HF

ppm

2.0

Splitting Pattern
s

HA
D

Integral

6.

(2) By adding, subtracting, or changing into another element exactly one atom, redraw MDMA so that the
highest chemical shift signal of hydrogens HAHF in the previous question has an even higher chemical shift,
but still has the same splitting pattern.

7.

(10) Circle the requested molecule in each set.

(a) Which molecule has the least signals with chemical shift less than 6.5 ppm?
Pseudoephedrine

Adrenaline

Norepinephrine

MDMA

Piperonal

Safrole

Molecule A

MDMA

Piperonal

Safrole

Molecule A

MDMA

Piperonal

Safrole

Molecule A

(b) Which molecule has the most deshielded hydrogen atom?

Pseudoephedrine

Adrenaline

Norepinephrine

(c) Which molecule has the signal at the highest ppm?

Pseudoephedrine

Adrenaline

Norepinephrine

(d) The following 1H-NMR data corresponds to which molecule: 7.066.88 ppm (multiplet; integral = 3.0), 5.35
ppm (singlet; integral = 1.0), 2.60 ppm (quartet, integral = 2.0), 2.15 ppm (singlet; integral = 3.0), and 1.25
ppm (triplet; integral = 3.0)?
Pseudoephedrine

Adrenaline

Norepinephrine

MDMA

Safrole

Molecule A

None of these

(e) The following 1H-NMR data corresponds to which molecule: 6.756.63 ppm (multiplet; integral = 1.5), 5.91
ppm (singlet; integral = 1.0), 3.59 ppm (singlet; integral = 1.0), and 2.13 ppm (singlet; integral = 1.5)
Pseudoephedrine

Adrenaline

Norepinephrine

MDMA

Piperonal

Safrole

Molecule A

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Chemistry 14C Lecture 1

8.

Spring 2013

Exam 2

Page 5

(6) Circle the requested molecule in each set.

(a) Circle the molecule whose 13C-NMR spectrum contains the most signals. If there is a tie circle more than
one.
Pseudoephedrine

Adrenaline

Norepinephrine

MDMA

Piperonal

Safrole

(b) Circle the molecule whose 13C-NMR spectrum contains the most doublets. If there is a tie circle more than
one.
Pseudoephedrine

Adrenaline

Norepinephrine

MDMA

Piperonal

Safrole

Piperonal

Safrole

(c) Circle the molecule whose 13C-NMR contains the highest chemical shift.
Pseudoephedrine
9.

Adrenaline

Norepinephrine

MDMA

(2) Complete this sentence by adding no more than ten words: X-ray crystallography can be used to study the
molecular structure of ice but not the molecular structure of water because...

10. (2) Which of the following aspects of the structure of ice can be studied by x-ray crystallography? Circle all that
apply:
Number of lone pairs

OH bond length

HOH bond angle

Lone pairOH angle

OH bond polarity

11. (6) Quickies! In each box write a reasonable structure for each set of spectra. These problems **do not**
require the same thorough analysis as does a normal combined spectroscopy problem like problem ## below.
Such an analysis is a waste of your time! Answers outside the boxes will be ignored.
(a)

Formula: C4H8O
IR: No peaks in zone 1 or zone 4. Other peaks present.
1

H-NMR: 3.7 ppm (triplet; integral = 1) and 1.8 ppm (triplet;

integral = 1).
13

(b)

C-NMR: 68 ppm (triplet) and 26 ppm (triplet).

Formula: C4H8O
IR: Strong peak at 1722 cm-1. Other peaks present.
1

H-NMR: 2.4 ppm (quartet, integral = 1.0), 2.1 ppm (singlet;

integral = 1.5), and 1.1 ppm (triplet; integral = 1.5).
13

C-NMR: 209 ppm (singlet), 37 ppm (triplet), 29 ppm (quartet),

and 8 ppm (quartet).

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Chemistry 14C Lecture 1

Spring 2013

Exam 2

Page 6

Final Structure Box

12. (34) Deduce the structure that corresponds to the spectral
data on pages 68. Write your final answer in the box. A
correct answer is worth full credit. If the answer is
incorrect, your analysis of the spectra can be worth
significant partial credit, so show your work clearly in the
space below each set of data only. Answers outside of
these places will be ignored.

(4) Mass spectrum: m/z = 268 (M; 100%), m/z = 269 (14.7%), and m/z = 270 (98.6%). No fluorine or iodine.

Write in the box the one formula that is consistent with the mass spectrum, and is not
rejected due to other reasons.

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Chemistry 14C Lecture 1

Spring 2013

Exam 2

Page 7

(13) IR:

1711 cm-1
4000

3000

2000

1500

1000

500

IR workspace:

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Chemistry 14C Lecture 1

Spring 2013

Exam 2

Page 8

Anything written outside the boxes on this page will be ignored. Write only H-NMR implications in the 1H-NMR
boxes.
(12) 1H-NMR:
Chemical shift

Splitting

Integral

7.307.27 ppm

multiplet

3.20 ppm

singlet

2.45 ppm

triplet

2.17 ppm

singlet

1.68 ppm

sextet

0.90 ppm

triplet

#H

Implications

(2) 13C-NMR: 210.8 ppm (singlet), 146.6 ppm (singlet), 128.4 ppm (doublet), 125.9 ppm (doublet), 124.1 ppm
(doublet), 57.6 ppm (triplet), 44.4 ppm (triplet), 40.4 ppm (singlet), 32.5 ppm (quartet), 16.9 ppm (triplet), and 13.6
ppm (quartet).

Page 8 score =

Chemistry 14C Lecture 1

Spring 2013

Exam 2

Page 9

Information Sheet
Nothing on this page will be graded. The graders will discard it. It can be
removed from the exam if you wish.
Questions 18 concern these molecules:
OH

OH
CH3

OH

HO

HO

NH2

CH3
N
H

CH3

HO

HO

Pseudoephedrine (C10H15NO)

Adrenaline (C9H13NO3)

H
O

CH3

O
O

CH3

Norepinephrine (C8H11NO3)

MDMA (ecstasy; C11H15NO2)

Piperonal (C8H6O3)

Safrole (C10H10O2)

Questions 18 concern these molecules:

OH

OH
CH3

OH

HO

HO

NH2

CH3
N
H

CH3

HO

HO

Pseudoephedrine (C10H15NO)

Adrenaline (C9H13NO3)

H
O

Norepinephrine (C8H11NO3)

CH3
CH3

MDMA (ecstasy; C11H15NO2)

O
O

Piperonal (C8H6O3)

Safrole (C10H10O2)

Page 9 score =