CHEM 2OA3- FALL 2013

ASSIGNMENT 3; DR. HARRISON

DUE: Weds. Nov. 20th, 2013 AT 2:30 PM.

NAME:_______________________

ID#:_____________

Lab Bench (2 to 72, NOT L01, L02 etc):_____ (On Avenue in grade book)
Please circle your lab section and tutorial room.

Lab
Group

Tut. Room Tuesday Wednesday

A (Labs in
week 1)

ABB 162

B (Labs in
week 2)

ABB 162

Exempt

ABB 162

Exempt

ABB 270

Thurs.
am

Thurs.
pm

Friday

L01

L02

L03

L04

L05

L06

L07

L08

L09

L10

ABB 270
ABB 270

[-2] Marks for not completing ALL of the above information correctly
Total marks: 100
Students Responsibility:
1.
Answers must be filled in, in the space provided.
2.
Completed work MUST be placed in the drop-off slots, which are in the corridor
opposite to the chemistry office, close to ABB-119. You MUST place your work in
the slots designated CHEM 2OA3/2OB3, in the CORRECT slot, FOR THE
CORRECT LAB DAY.
3.
Any assignment not submitted in the correct place and/or after the due date and
time will be graded zero.
4.
Students who cannot complete the assignment for medical or other reasons
MUST seek exemption through an MSAF, a note from the appropriate Deans
office or other accepted routes.
5.
You are responsible for ensuring that your print-out is complete and that all
questions are answered. There are 14 pages and 6 questions in this assignment.
______________________________________________________________________________________

TOTAL

CHEM 2OA3 Fall 2013 Assignment 3

1.
[22] This question concerns the nucleophilic substitution reaction of 1-chloro-2ethyl-cyclohexane with nucleophiles.
Note: in this question, it is important to ensure that you have the correct answer(s) before
moving on to the next part, in order to avoid propagating errors! NOTE that we will NOT
be able to compensate for such errors during marking.
(a) Using the template shown below, draw the structure of (1S, 2R)-1-chloro-2-ethylcyclohexane. Make sure you show the correct location and orientation of chlorine and
ethyl groups, using the wedged and dashed bonds provided in the template, and add
hydrogen atoms in the correct position at these sites. (Note that the templates do not
show a tetramethylcyclohexane, but just four bonds in the correct conformation ready
for you to draw).

1
2

(b) Redraw the structure, using the chair template shown below. Make sure you show the
correct orientation of chlorine and ethyl groups in this template, using the equatorial
and axial bonds and the carbon numbers provided. Include hydrogens at these two
sites. Do not perform any ring flips yet.

1
2

(c) Give the term, axial or equatorial, that describes the orientation of the groups in the
structure you have drawn in (b) above:
(i)

The chlorine atom is __________________________

(ii)

The ethyl group is

__________________________
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CHEM 2OA3 Fall 2013 Assignment 3

(d) Is this compound the cis or the trans isomer?

(e) In its most stable conformer, is this compound most likely to have the di-equatorial,
the di-axial or the equatorial-axial conformation?

(f) Draw the most stable conformation of this compound, (1S, 2R)-1-chloro-2-ethylcyclohexane, on the template provided. Use the axial and equatorial bonds provided,
then add other equatorial/axial bonds to C-1 and C-2

(g) Draw the most stable conformation of the product of an S N2 substitution reaction of
this compound with sodium hydroxide, showing the stereochemistry on the template
below

(h) Give the IUPAC name for the product in (g), showing the correct absolute
configurations in brackets as per the IUPAC rule

CHEM 2OA3 Fall 2013 Assignment 3

(i) Draw the most stable conformations of the products formed when this starting
material, (1S, 2R)-1-chloro-2-ethyl-cyclohexane, reacts with water in an SN1 reaction.
Use the templates provided below, where A is formed by inversion and B by retention
of configuration.

(j) What is the relationship between the two products formed in part (i) above:
enantiomers, diastereomers, constitutional isomers, conformers, or non-isomeric?

(k) Which compound (A or B) from answer (i) above is the most stable, or are both
equally stable? Explain your answer in ONE sentence.

(l) Do you expect an equal amount of the two compounds A and B in this reaction? If
so, why? If not, why not?

CHEM 2OA3 Fall 2013 Assignment 3

2.
[18] The compound (S,S)-1,3,5-trichloro-3-methylhexane can undergo a range of
possible reactions with reagents that can act as nucleophiles (Nuc).
(a)

[2]
Draw the structure of (S,S)-1,3,5-trichloro-3-methylhexane in the box
provided in the CENTRE of the scheme below. You MUST complete the
template structure provided, making sure to show the chain of carbon atoms in the
plane of the paper, and keeping carbon-1 on the left hand side. Show the chirality
centres correctly and clearly, using wedges and dashed bonds.

(b)

[6] Complete the remaining boxes provided, to show the MAJOR product(s) of
each of the reaction types indicated. Use the generalized atom Nuc as
appropriate in your structures. Keep the products oriented the same way as the
starting material in the box.

S N2

S N1

(1 mole
equivalent)

(1 mole
equivalent)
1

SN2 (Excess reagent)

CHEM 2OA3 Fall 2013 Assignment 3

(c)

(d)

[6] Indicate the predominant organic reaction product that will be obtained when
this substrate (i.e. S,S)-1,3,5-trichloro-3-methylhexane) reacts under each of the
following sets of conditions:
(i)

The reagent is a 10-fold excess of potassium cyanide in dimethyl sulfoxide

(dmso), and the mixture is stirred at room temperature.

(ii)

The reagent is methanol, which is also the solvent, and the mixture is stirred
at room temperature.

(iii)

The reagent is 1.2 equivalents of KSMe in methanol, and the mixture is

stirred at room temperature.

[4] Which, if any, of the three reactions in part (c):

(give your answer as (i), (ii) or (iii), or a combination, or ALL or NONE)
(i)

Give(s) a single chiral product with inversion of configuration

(ii)

Give(s) a racemic mixture

(iii)

Give(s) a mixture of diastereomers

(iv)

Proceed(s) through a single transition state

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CHEM 2OA3 Fall 2013 Assignment 3

3.
[15] This question relates to the mechanisms and intermediates in the sequence of
reactions shown below, which give the expected product C and unexpected product D. For
each mechanism, show all curly arrows to illustrate the movement of electrons and make
sure your arrows are clear. Where necessary, show the formal charges on atoms. Show
ONLY the lone pairs of electrons that are involved in the reaction.
H2O

H2SO4
Cl

KOH

B
(reactive
intermediate,
C5H9)

C
(expected)

+
OH

(D)

(a) Draw a mechanism for the first step, and suggest a structure for compound A.

(b) Draw a mechanism for the second step, and suggest a structure for reactive
intermediate B.

(c) What factor(s) affect the stability of intermediate B? Illustrate your answer.

CHEM 2OA3 Fall 2013 Assignment 3

(d) Draw mechanisms for the third step, that account for formation of BOTH the products
C and D, and provide a structure for C.

(e) What sort of isomers are C and D (e.g. enantiomers)?

CHEM 2OA3 Fall 2013 Assignment 3

4.
[20] In the following reaction, there are several rearrangements.
(a) Propose a reasonable, detailed mechanism for this process, showing every single
step, all curly arrows, charges, intermediates, etc.. You can start with the structure
provided.

H3O+

(b) Carefully consider the stereochemistry of each step. Can you make a generalized
statement about the stereochemical consequence of rearrangement reactions, and if so
what? Does this make sense based on what you have learned about carbocation
stability?

CHEM 2OA3 Fall 2013 Assignment 3

(c) Draw a reaction co-ordinate diagram to illustrate this reaction sequence. Make sure
have the correct number of transition states, intermediates, etc., and that endo- and exergonic reactions are shown correctly. Assume that the overall reaction is
spontaneous.

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CHEM 2OA3 Fall 2013 Assignment 3

5.
[10] Indicate whether the statements below are Correct or Incorrect; ONLY pick
correct for statements that are COMPLETELY correct; for statements that are partially
correct or sometimes correct but not always, explain your answer in one sentence (10):

a. In a DEPT nmr spectrum, a carbon in a methylene (CH2) group always has the same
phase as one in a methyl group.

b. In the proton nmr spectrum, two enantiomers will give different spectra.

c. In the proton nmr spectrum of 2-bromopentane, there will be one signal for the methine
proton that will appear a sextet.

d. In the proton nmr spectrum of 1-butene, the two protons on the terminus of the alkene
(the =CH2) group will have identical chemical shifts and each will appear as a doublet of
doublets.

e. When a tertiary alcohol is dissolved in CDCl3 and the proton nmr spectrum is recorded,
the OH proton appears as a broad singlet, but the signal disappears when the nmr spectrum
is run in deuterated methanol as solvent (CD3OD).

11

CHEM 2OA3 Fall 2013 Assignment 3

6. [15] This question requires you to answer a series of questions aimed at identifying
an unknown compound (1).
Compound 1 shows a molecular ion at m/z 116 in the mass spectrum.
The proton and 13C NMR spectra as well as the IR spectrum, are provided, with
blow-ups showing coupling patterns and integration lines (RELATIVE integrals
are given) in the proton NMR spectrum. Note that the 13C NMR spectrum contains
a signal from the solvent (CDCl3) at 77ppm.
Integral: 1

1.5

1.5

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CHEM 2OA3 Fall 2013 Assignment 3

(i)

Do the NMR spectra show evidence that any alkyl groups are attached to (an)
electron-withdrawing element(s), and if so which signals show is this evidence?
Answer by completing the boxes and spaces below.
Yes No
Evidence (chemical shift)
13

__________________________

Proton nmr?

__________________________

C-nmr?

(ii) Is an aromatic ring likely present, and how could you tell from the NMR spectra?
Yes
Aromatic?

No

Evidence (chemical shift)

__________________________

(iii) List ALL the evidence for the presence or absence of (a) carbonyl group(s).
Present?
Yes No

Evidence (chemical shift or frequency)

__________________________

Proton nmr?

__________________________

13

__________________________

IR?

C-nmr?

(iv) How many carbon atoms are likely present? How many protons?
Carbons?

(v)

______________ Protons?

_______________________

Determine the molecular formula for compound 1. How many degrees of

unsaturation are present in compound 1?

Formula:

______________ Degrees of unsaturation: ______________

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CHEM 2OA3 Fall 2013 Assignment 3

(vi) What alkyl group gives rise to the proton nmr signal at 1.85 ppm in compound 1?

(vii) Draw the most likely structure of the unknown molecule, given the above
spectroscopic information.

THE END
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