CHEM 344 ChemDraw Exercise : Anisah A-D

INSTRUCTIONS FOR ACCESSING AND USING CHEMDRAW TUTORIALS

Open ChemDraw
•click on "Help Menu"
•"Getting Started"
• Expand the "tutorials" list to get a list of the available tutorials

Important ChemDraw Info to Remember:

-Always start a new ChemDraw document in ACS format (File > Open Special > ACS Document 1996)
-Make all bond angles consistent and keep all structure sizes equivalent
-Line up your equations/structures on grid lines (View > Show Gridlines)
-Do not forget the “Clean Up Structure” option in the structure menu

ChemDraw Tools:
-Product Analysis: (scientific name, chemical formula, mass)
Draw a structure, highlight with Marquee Tool then right click on molecule and select Analysis > All

-NMR Prediction:
Draw a structure, highlight with Marquee Tool then select Structure > Predict 1H-NMR Shifts or Predict 13C-
NMR Shifts

-Molecule Weight Fragmentation Tool: (identify fragments seen in Mass Spectra)

Draw product structure then select the MW Fragmentation tool in the left side toolbar and click and drag
across a bond in your structure to break into fragments and see molecular weight of the fragments

-Templates: (use ChemDraw pre-drawn items)

Select the template button in the left side tool bar to see available drawings
Follow the directions below, completing any drawing exercises in ChemDraw and any data searches in
SciFinder. In the mechanism, all bond angles, molecule spacing, etc. must be consistent and look professional,
or points will be lost. (10 pts total)

1. Redraw the structures below and then complete the mechanism of nitration (including formation of the
electrophile, the nitronium ion NO2+, in the box below). You should delete the original structures in
the Word document and replace them with your answer.

O O
HNO3, H2SO4 O 2N
OH OH
0°C
O OH OH
N O
HO O
H O S O H
O
O O
-H2O H H
H N N O
O O O
O H
H O2N OH

OH

2. Below is the structure of the semi-synthetic opioid known as heroin, which is a derivative of morphine.
To prepare heroin from morphine, two hydroxyl groups are acetylated (possible in a similar method to
the synthesis of isopentyl acetate in C343). Describe predicted shifts for 13C-NMR and 1H-NMR peaks
that could differentiate the presence of morphine vs. heroin.

O N

O H
H

distinctive 13C-NMR shifts for heroin: 169 170.2 90.6 150.1

distinctive 13C-NMR shifts for morphine: 144.4 138.9

distinctive 1H-NMR shifts for heroin: 6.74 2.19

distinctive 1H-NMR shifts for morphine: 2.26 6.4

 3. Use the mass fragmentation tool to see if you can identify any of the fragment peaks in the mass
spectrum below. Create a table that shows what fragment represents the observed peak.
Use the mass fragmentation tool to see if you can identify any of the fragment peaks in the mass spectrum below.
Create a table that shows what fragment represents the observed peak.
93

121
M+ 213
65
39

17 77

m/z actual molecular fragment

With the skills you learned in the library assignment, you have your choice of three final tasks using
SciFinder/Beilstein searches: (Choose one of the three, do not hand in the same assignment as the person sitting
next to you)

1) Attach a printout of any information you can find listing experimentally derived NMR values for morphine or
one of its close derivatives, so you could hypothetically compare experimental and predicted results. Only attach
1 sheet, actually containing NMR values.

2) Find the earliest available synthesis of heroin reported in scientific literature that we have access to. Attach
only the first journal page.

3) Attach a medical report on the effects of morphine on humans. Attach only the first journal page. (-0.5 points if
you choose this easier option)

m/z molecular fragment

77 aromatic

121 Aromatic with OH group on it

17 ketone oxygen

93 aromatic with amine group

With the skills that you learned in the library assignment, you have your choice of three final tasks using
SciFinder searches: (Choose one of the three, do not hand in the same assignment as the person sitting next to
you).

1) Attach a printout of any information you can find listing experimentally derived NMR data for
morphine or one of its close derivatives, so you could hypothetically compare experimental and
predicted results. Only attach one sheet that actually contains the NMR values.

2) Find the earliest available synthesis of heroin reported in scientific literature that we have access to.
Attach only the first journal page.

3) Attach a medical report on the effects of morphine in humans. Attach only the first journal page. (-0.5
points if you choose this easier option)