Department of Chemistry

CMY 284: Organic Chemistry

FINAL EXAMINATION

Time: 120 min 14 June 2018

Marks: 80 (+3)

Internal Examiners: Ms BMP Beebeejaun & Dr LA Pilcher

External Examiner: Dr N October
___________________________________________________________________________________

Initials & Surname: ______________________________________________

Student Number: _______________________________

Signature: ______________________________________________
___________________________________________________________________________________

Q1 Q2 Q3 Q4
Marks: Total
25 18 23 17
(%)

Instructions:
1. Answer the questions directly on the question paper. Final answers should be given in blue or
black pen. If an answer is not given in the space provided, clearly indicate location. Cancel
answers that should not be marked with pen. No Tippex.
2. Cell phones must be switched off.
3. Use line structures where structures are required, unless specified otherwise.
4. Use curved arrows to obtain related resonance structures and where mechanisms are requested.
5. Abbreviations: s.m. = starting material T.M. = target molecule (final product)

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Question 1 25 marks

1.1 Aromaticity: For each molecule below, predict whether the molecule would be expected to show
aromatic character or not. Explain your answer, include showing how electrons are counted. (6)

H
H N N
N

N N N
H

1.2 Which is the most acidic proton in the following molecule? To justify your answer, use curved
arrows to draw appropriate resonance structures. Explain why the acidity is determined by the
stability of the conjugate base. (11)

O
N
C

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1.3 Which dibromobenzene is represented by the given 13C NMR spectrum? Show your reasoning. (4)

Br Br Br
Br

Br
Br

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

1.4 Draw the expected 13C NMR spectrum of methoxyacetone taking care to show the approximate
chemical shifts. Indicate using (+) or (-), what you expect the orientation of the peaks to be in
the DEPT-135 NMR spectrum. Use a (0) to indicate a 13C peak that will be absent from the DEPT-
135 NMR spectrum (4).

O
OMe

200 150 100 50 0 ppm

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Question 2 18 marks

2.1 Consider the following reaction.

Br NaSH HS
DMSO

(a) Use reaction mechanisms to explain the formation of the substitution product. You must
include the transition state in your mechanism (4)

(b) What is the rate of the reaction equation for this reaction? (1)

(c) What would happen to the rate if the solvent is changed from DMSO to ethanol? (1)

2.2 The following compound can react rapidly via an SN1 process. Explain why this primary substrate
will undergo an SN1 reaction so rapidly based on the leaving group and the reaction intermediate. (3)

O OTs

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2.3 (3R,4S)-2,3-Dimethyl-4-bromohexane reacts with a strong base to produce the cis-alkene, while its
diastereomer gives only the trans-alkene upon treatment with the same base.

Br
NaOEt

(3R,4S)-2,3-dimethyl-4-bromohexane
Cis-alkene

(i) This reaction is stereoselective, and produces only the cis-alkene. Use reaction
mechanism to explain the formation of the cis-alkene. (5)
(Hint: Use your molecular model set to draw the Newman projection that leads to the
formation of the product.)

Newman Projection Explanation

Br

(ii) On the template below, draw the structure of the diastereomer and explain the
change in the stereochemical outcome when the diastereomer is treated with NaOEt
using the Newman projection . (4)
(Hint: Use your molecular model set to build the diastereomer.)

Line structure of diastereomer Explanation

Newman Projection

Br

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Question 3 23 marks

Provide the missing reagents and structures of substrates and products (A - K) in the reactions below.
One alphabetical letter may represent more than one reagent/product/step. Show stereochemistry
where appropriate.
(a)
O O
i. O3 Cl2, H2O
A B
H
ii. Zn, H2O

(only product)
(5)

A= B=

(b)
OH OH
C CrO3
OH D
H2SO4 (aq)
OH

+ enantiomer
(4)

C= D=

(c)
O
i. HC C Na HCl
E F
ii. H2O

(4)

E= F=

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(d)
O
i.LiAlH4 H2 (1 eq)
G H
ii. H2O Pd/C
Br
(4)

G= H=

(e)
OH
i. NaH
I
ii CH3I
(2)

I=

(f)
O
HO
-
H3 O +
J K
O
H2O

(4)

J= K=

Question 4 17 marks

4.1 Explain why the following alcohol cannot be prepared via the hydroboration-oxidation
reaction. (3)
OH

Explanation:

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4.2 Provide only a retrosynthesis for the following target molecule (T.M.) from the given starting
material (S.M.) and any other starting material. The synthetic sequence (synthesis) and
mechanism are not required. (5)
NOTE: The pathway should go via AN ALKENE

Cl
CHO from

T.M. S.M.

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4.3 Use line structures in a synthesis to demonstrate the merit and use of protecting groups for the
following conversion. Show each step complete with reagents and line structures of the
products. Retrosynthetic analyses, stereochemistry and mechanisms are not required. (9)

OH OH O
?
Cl N
H

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Some Physical Data

H C N O F Cl Br I
Electronegativity 2.2 2.6 3.0 3.4 4.0 3.2 3.0 2.5

pKa Acid Conjugate base Example base

–10 HI I–
–7 HCl Cl–
+
–7 RSH2 RSH
+
–2 H3O H2O
–1.4 HNO3 NO3–
4-5 RCO2H RCO2–
+
5 C5H5NH C5H5N pyridine
6 H2CO3 HCO3– NaHCO3
7 PhSH PhS–
9.2 HCN CN– NaCN or KCN
+
9.2 NH4 NH3 NH3
9.9 PhOH PhO–
10.3 HCO3– CO32– Na2CO3 or K2CO3
11 RSH RS–
15.7 H2O HO– NaOH or KOH
16 ROH RO– NaOEt or NaOMe
t t
18 BuOH BuO– t
BuOK
–
25 HC≡CH HC≡C
35 H2 H– NaH or KH
38 NH3 NH2– NaNH2 or LDA
40 PhCH3 PhCH2–
43 Ph-H Ph–
45 CH2=CH2 CH2=CH–
50 CH4 CH3– MeLi or MeMgBr

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 Data Sheet of Some Reagents used in Organic Synthesis (Smith Organic Chemistry)

Alkylating agents (R = alkyl, phenyl, etc) Halogenating agents

• Grignard: • X2, CCl4 (X = Cl, Br)
i. RX (X = Cl, Br, I), Mg, dry ether, • X2, H2O (X = Cl, Br) or NBS, DMSO (aq)
ii. Carbonyl cmpd, • X2, hν
iii. H2O or H3O+ • HX (X = Cl, Br, I)
• Grignard in carboxylation: • HX (X = Cl), ZnCl2
i. RX (X = Cl, Br, I), Mg, ether, • PBr3, ether
ii. CO2, • SOCl2, pyridine
iii. H3O+

Hydrating agents Dehydrating agents

• H2O, H+ or H3O+ • Conc. acid, e.g. H3PO4 or H2SO4 or
• i. BH3, THF, ii. H2O2, HOˉ TsOH (p-CH3C6H4SO3H)
• H2O, HgSO4, H2SO4 • POCl3, pyridine

Hydrohalogenating agents Dehydrohalogenating agents

• HX (X = Cl, Br, I) • ROˉ or HOˉ

Oxidising agents Reducing agents

• i. OsO4, ii. NaHSO3 • H2, Pd-C or PtO2 or Lindlar catalyst
• KMnO4, HO¯ • i. NaBH 4, CH3OH [Optional: ii. H3O+]
• i. RCO3H (e.g. mCPBA), ii. H3O+ or H2O, HOˉ • i. LiAlH4, dry ether, ii. H2O
• i. O3 ii. Zn, H2O or Zn, HOAc or Me2S • i. DIBAL-H, -78○C, ii. H2O
• CrO3, H2SO4 (aq) (Jones’ reagent) • Na, NH3(l)
• Na2Cr2O7 or K2Cr2O7 , H2SO4 (aq) = (H2CrO4)
• PCC (C5H6N+ClCrO3ˉ), CH2Cl2
• Tollens: i. Ag2O, NH4OH, ii. H3O+

Carboxylic acid derivatization reagents Hydrolysis reagents

• PBr3, ether • H3O+, ∆ or H2O, H+, ∆
• SOCl2, pyridine • H2O, HOˉ, ∆
• ROH, H2SO4 (c)
• ROH, pyridine
• i. NH3 or NH2R or NHR2 ii. ∆ > 100 oC
• NaOH, H2O
• i. NaOH ii. RX

Protecting reagents Deprotecting reagents

• ROH, TsOH or H+ • H2O, H+ or H3O+
• TBDMSCl, imidazole • TBAF or Fˉ
(show structure in syntheses) (show structure in syntheses)

Other reagents
• Na (s) or K (s) or NaH or NaNH2 • HOˉ • NC¯ • N3¯
• ROˉ, ROH • ROH • RCO2¯ • HCC:¯
• HS¯ or RS¯ • H2O • TsCl, pyridine
Note: Specify symbols such as R, X, etc.!

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