Tutorial questions
1 (a) Define the following terms as used in organic chemistry
(i) M+ peak
(ii) Deshielded protons
(ii) Enolate ion
(b) Predict the products of the following reactions;
O
1. NaOCH2CH3
(i) 2 H3C O CH3
2. H3O+
O 1. Et2O
(ii) + O 2. H3O+
(c) Suggest a synthetic route of the following compound
O O
OEt
(d) Predict the absorption bands in the IR spectra of;
O
2 (a) Discuss the following reactions;
(i) Crossed Aldol
(ii) Intramolecular cyclization
(iii) Gatterman Koch reaction
(b) Describe the practical considerations that need to be taken into account
when synthesizing a Grignard reagent.
H3C O
3 (a) Mechanistically show the synthesis of estrone, HO
from reagents below,
CH2
O
H3C
O
and
H3C O
O
(b) (i) Retrosythetically synthesize the following compound;
(ii) Suggest reagents that are necessary to accomplish transformation
(i), (ii) and (iii)
O O
OEt
(i)
O
O (ii)
(iii)
4 (a) Differentiate malonic ester synthesis from acetoacetic
ester synthesis
(b) (i) Predict with reaction mechanism the products of the reactions
below.
H3C
CuCl/AlCl3
+ CO + HCl
CHO
+ Ac2O + AcO K
- +
(ii) Propose a mechanism for both steps of the Wolff-Kishner reduction of
cyclohexanone.
5 (a) Sketch the 1H-NMR and 13C-NMR spectrum of the molecule below;
(b) (i) Why is tetramethylsilane used as a reference compound in NMR
spectroscopy?
(ii) Why are deuterated solvents used in NMR experiments?
6 (a) Explain how IR spectroscopy could be used to distinguish the following
Compounds;
NH2 OH
CH3 CH3
H3C and H3C
(b) Propose a structure for the compound of molecular formula C8H18O using
the 1H-NMR spectra labeled B if its IR spectrum shows the presence of an
OH group.
7 Using the IR, MS, NMR and UV data identify unknown C. Clearly show steps
leading to the structure.
1H-NMR SPECTRA B
Unknown C
8 (a) Define the following terms as used in organic chemistry
(i) Chromophore
(ii) Grignard reagent
(ii) Base line
(b) Predict the products of the following reactions;
H2C
CH2
(1) +
CH2
CH2
O
Mg, H+
(ii)
CH3 + CH 3CH 2Br
-H2O
CH3
(c) Suggest a reaction mechanism of the following synthesis;
OH H O
O -OH, H2O
2H3C H3C
H H
H H
(d) Sketch the predicted FT-IR spectrum of the compound below
O OH
H3C CH2
2 (a) Discuss the following reaction types;
(i) Gilman reactions
(ii) Robinson annulation
(iii) Aldol reaction
(b) Describe the practical considerations that need to be taken into account
when selecting reactants for a synthetic route.
3 (a) Predict the starting materials required to prepare each of the compounds
below by an aldol reaction
O
(i)
O
H
HO
H H
H
(ii) H
(b) (i) Retrosythetically synthesize the following compound by a Wittig
reaction;
H3C
CH2
CH3
(c) Give the diene and dienophile used to synthesize the compounds below
O
(i) O
(ii) CH3
4 (a) Mechanistically differentiate self Aldol synthesis from internal Aldol
synthesis
(b) Label all of the acidic hydrogen atoms on the molecules below,
O O O
H3C CH3
O O
(i) (ii)
(c) Apply a detailed retro- synthetic analysis to synthesize 4-ethyl-4-
nonanol. Show all disconnections involved.
5 (a) Predict the relative intensities of M+, M + 2 and M + 4 peaks for CH2Br2
Assume that 79Br/81Br = 1/1.
(b) How would you distinguish an alcohol from a carboxylic acid using NMR,
MS and IR techniques?
6 (a) What is the requirement for a nucleus to exhibit the nmr phenomenon
(d) When recording nmr spectra using Pulsed Fourier Transform (PFT)
techniques, why is it necessary to dissolve the sample in a deuterated
solvent?
(e) (i) Explain the use of the rule of 13 in mass spectrometry.
(ii) What are the 3 basic parameters in 1H nmr spectrum
(iii) Define the terms chemical shift and spin-spin coupling.
(f) How is infrared spectroscopy used in simple structural analysis
7 Using the IR, MS, NMR and UV data identify unknown A (figures attached).
Clearly show steps leading to the structure.
Unknown A
2 (a) With the aid of examples discuss the following synthesis;
(i) Claisen condensation [5 marks]
(ii) Wittig reaction [5 marks]
(iii) Self Aldol Reaction [5 marks]
(b) Describe the desirable characteristics of a synthetic product.
[5 marks]
3 (a) Predict the starting materials required to prepare each of the compounds
below by Diels Alder reactions
O
(i) O
(ii) CH3
[8 marks]
(b) Suggest a synthetic route of the following compound;
[10 marks]
(c) Predict the products of the synthesis below
N
1. CH3CH2MgBr, ether
(i)
2. H3O+
CO 2CH 2CH 3 1. NaOC2H5
(ii)
CO 2CH 2CH 3
2. CH3CH2OH
[2 marks]
4 (a) Using reaction outlines differentiate crossed Aldol condensation from
Robinson annulation.
[12 marks]
(b) Draw and label all of the acidic hydrogen atoms on the molecules below,
O O
O
CH3
H3C H3C O O CH3
OH
H3C
(i) (ii)
[2 marks]
(c) Apply a detailed retro-synthetic analysis to synthesize the compound
below
[6 marks]
5 (a) Propose possible molecular formulas for a compound with a molecular ion
at m/z = 86. [10 marks]
(b) How can two isomers having molecular formula C2H6O be distinguished
by IR spectroscopy? [10 marks]
6 (a) Interpret the mass and IR spectrum of X shown below; [10 marks]
(b) Calculate the HDI for a compound with molecular formula C4H8ClNO2, and
identify the structural information provided by the HDI. [10 marks]
7 Using the IR, MS, NMR and UV data identify unknown B (figures attached).
Clearly show steps leading to the structure. [20 marks]
Unknown B