CHEM1102 2014-J-8 June 2014

Marks
• Complete the following table. Make sure you give the name of the starting material 4
where indicated.
STRUCTURAL
REAGENTS/
STARTING MATERIAL FORMULA(S) OF MAJOR
CONDITIONS
ORGANIC PRODUCT(S)

O
(CH3)2NH
Cl

hot 3 M NaOH
CHEM1102 2014-J-9 June 2014
Marks
• Methylphenidate, also known as Ritalin, is a psychostimulant drug approved for the 7
treatment of attention-deficit disorder. Identify all stereogenic (chiral) centres in
methylphenidate by clearly marking each with an asterisk (*) on the structure below.

methylphenidate

Using one stereogenic centre you have identified, draw the (R)-configuration of that
centre.

How many stereoisomers are there of methylphenidate? Describe the relationships

between these isomers.

4 isomers: there are 2 pairs of enantiomers:

Each isomer has 1 enantiomer and 2 diastereoisomers

Give the products formed when methylphenidate is hydrolysed with 4 M HCl.

CHEM1102 2014-J-12 June 2014
Marks
• Show clearly the reagents you would use to carry out the following chemical 3
conversions. More than one step is required in each case. Give the structure of any
intermediate compounds formed.
CHEM1102 2014-N-8 November 2014
Marks
• Complete the following table. 1
THE MAJOR
STARTING MATERIAL REAGENTS/CONDITIONS
ORGANIC PRODUCT(S)
O

SOCl2
Cl
CHEM1102 2014-N-9 November 2014

• Draw the structure of the organic product(s) formed when each of the following
3
compounds is treated with 4 M sodium hydroxide. The first reaction requires heating.

Compound Organic products

O H 2N

OH O
CHEM1102 2013-J-9 June 2013
Marks
• Complete the following table. 3
CONSTITUTIONAL
REAGENTS/
STARTING MATERIAL FORMULA(S) OF MAJOR
CONDITIONS
ORGANIC PRODUCT(S)

SOCl2

CH3NH2
CHEM1102 2013-J-14 June 2013
Marks
• Below is the reaction between an acid chloride and water to give a carboxylic acid. 6
Provide curly arrows for this mechanism and draw the structures of the two
intermediates on the pathway.

Indicate the hybridisation of the two oxygen atoms in the starting materials.

acid chloride: sp2 water: sp3

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.
CHEM1102 2013-N-8 November 2013
Marks
• Complete the following table. 1
CONSTITUTIONAL
REAGENTS/
STARTING MATERIAL FORMULA(S) OF MAJOR
CONDITIONS
ORGANIC PRODUCT(S)

SOCl2
CHEM1102 2013-N-12 November 2013
Marks
• The polymer Nylon 66 can be made by mixing the following two reagents. 2

Draw the structure of Nylon 66.

CHEM1102 2013-N-12 November 2013
Marks
• Consider the three compounds shown below.
3

Arrange these compounds in order of increasing acidity. Explain your reasoning.

Ethanol is the weakest acid as its conjugate base is not resonance stabilised.
Phenol is a stronger acid as its conjugate base is resonance stabilised – the
negative charge can be delocalised into the aromatic ring as shown below.

There is even greater resonance stabilisation for the acetate ion (the conjugate
base of acetic acid), as the negative charge is delocalised onto the electronegative
oxygen atoms (as opposed to the carbon atoms in the case of phenol).
CHEM1102 2013-N-13 November 2013
Marks
• The incomplete mechanism for the reaction of acetyl chloride with hydroxide ions is 3
shown below. The reaction occurs in three steps. In each step complete the
mechanism by adding curly arrows to indicate the bond changes taking place.
CHEM1102 2012-J-9 June 2012
Marks
• Indicate the hybridisation of the carbon and nitrogen atoms in the diamine P. 4

Draw the product of the reaction when diacyl chloride Q reacts with water.

Kevlar (used in bullet-proof vests) is a polyamide polymer which is made from diacyl
chloride building block Q and diamine building block P. Draw the repeating polymer
unit formed in the reaction of P with Q.

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

CHEM1102 2012-J-10 June 2012
Marks
• Complete the following table. If there is no reaction, write “NR”. Show any relevant 7
stereochemistry.
CONSTITUTIONAL
REAGENTS/
STARTING MATERIAL FORMULA(S) OF MAJOR
CONDITIONS
ORGANIC PRODUCT(S)

Cr2O72– / H+

H+ catalyst / heat

(CH3)2NH / heat
CHEM1102 2012-J-12 June 2012
Marks
• Consider the following molecule (M) isolated from a natural source. 6
H
N COOH
H2N
O (M)

NH2

Give the products when molecule (M) is hydrolysed by heating it with 6 M HCl.
Make sure you show the products in their correct ionisation states.
CHEM1102 2012-J-13 June 2012
Marks
• Compound T is a precursor in the synthesis of the asthma drug salbutamol. 3

Give the molecular formula of compound T. C11H12O4

Give the structure(s) of all organic products formed when compound T is heated with
4 M NaOH.

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

CHEM1102 2012-N-10 November 2012
Marks
• Complete the following table. 1
CONSTITUTIONAL
REAGENTS/
STARTING MATERIAL FORMULA(S) OF MAJOR
CONDITIONS
ORGANIC PRODUCT(S)

SOCl2
CHEM1102 2012-N-11 November 2012
Marks
• Draw the structure of the organic product(s) formed when each of the following 4
compounds is treated with 4 M sodium hydroxide. The first two reactions proceed at
room temperature; the last one requires heating.

Compound Organic Product(s)

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

CHEM1102 2010-J-11 June 2010
Marks
• Give the constitutional formula(s) of the major organic product(s) formed in each 7
of the following reactions.

Br COOCH3
1. LiAlH4

2. H / H2O

10 M HCl
OH

O 4 M NaOH
heat

O
Me 6 M HCl
N heat
H

O excess CH 3NH 2
CHEM1102 2010-N-9 November 2010
Marks
• Complete the following table. 2
CONSTITUTIONAL
REAGENTS/
STARTING MATERIAL FORMULA(S) OF MAJOR
CONDITIONS
ORGANIC PRODUCT(S)

O O
SOCl2
OH Cl

H / H2O / heat
O
CHEM1102 2010-N-10 November 2010
Marks
• The following is a nucleophilic addition-elimination reaction between ammonia and 5
an acid anhydride. Provide curly arrows needed for the mechanism, and draw the
structures of the two intermediates on this pathway.
CHEM1102 2009-J-8 June 2009
Marks
• Complete the following table. Make sure you indicate any relevant stereochemistry. 4
CONSTITUTIONAL
REAGENTS/
STARTING MATERIAL FORMULA(S) OF MAJOR
CONDITIONS
ORGANIC PRODUCT(S)
OH O
1. dilute NaOH
2. CH3Br

O
OH
Cr2O72 / H OH

Br
1. Mg / dry ether
2. H2O

OH
O
1. NaBH4
2. H+ / H2O COOH
COOH

The final product may react further:

which might undergo

OH intramolecular esterif ication O
to give the cyclic es ter O
COO H
CHEM1102 2009-J-9 June 2009
Marks
• Give the constitutional formula(s) of the organic product(s) formed when each of 7
the following compounds is treated with 4 M sodium hydroxide. The first three
reactions proceed at room temperature; the last two require heating.
COMPOUND ORGANIC PRODUCT(S)

CH3CH2COOH CH3CH2CO2

CH3
H 3C CH3
H CH3 N
N
Br CH 3
CH3

H3C O H3C O
CH C CH C
H3C Cl H3C O Na

O O
C C Na O
H 3C O H3C O Na +

O O

N O Na
+ H N
CHEM1102 2009-J-9 June 2009
CHEM1102 2009-N-9 November 2009
Marks
• Consider the following reaction sequence. 6
O

OH
K

Reagent A Reagent B

L + M

O + HCl
N

Compound K below can be converted into two different intermediates, L and M,

which can react together to give compound N and the inorganic byproduct HCl.
Give the reagents A and B and draw the structure of the intermediates L and M.
A B

SOCl2 1. LiAlH4 / dry ether 2. H+ / H2O

L M
O
HO
Cl
CHEM1102 2009-N-10 November 2009
Marks
• Give the constitutional formula(s) of the organic products formed in each of the 3
following reactions

NH2 H
N
+ CH 3OH
OCH3
O

Br CN
NaCN

O O
4 M NaOH
+ OH
O heat O
CHEM1102 2008-J-8 June 2008
Marks
• Complete the following table. Make sure you indicate any relevant stereochemistry. 4
CONSTITUTIONAL
REAGENTS/
STARTING MATERIAL FORMULA(S) OF MAJOR
CONDITIONS
ORGANIC PRODUCT(S)

CH3CH2COOCH2CH3
1. SOCl2
CH3CH2COOH O
2. CH3CH2OH
O

O
C
O O CH3 OCH2CH2CH2CH2CH3
CH3CH2CH2CH2CH2OH C C O
CH3 O CH3 +
C
CH3 OH

O
O
H2O CH3 C OH
CH3 C Cl

O OH
1. LiAlH4 / dry ether
C CH2
H 2. H / H2O
CHEM1102 2008-J-10 June 2008
Marks
• The structure of methyl 4-aminobenzoate, (E), is given below. 5

O
(E)
O
b
H2N
a

Give the molecular formula of compound

C8H9NO2
(E).

Name the functional groups in molecule (E) indicated by the boxes “a” and “b”.

a: amine b: ester

Give the structure(s) of all organic products formed when compound (E) is treated
with the following reagents. If no reaction occurs, write “NO REACTION”.

No hydrolysis of the ester under these conditions. The

amine group will be protonated by the strong acid.
cold HCl (1 M) O

H3N

Treatment with base will lead to hydrolysis of the ester.

In the basic solution, the carboxylic acid will be
hot NaOH (4 M) deprotonated and the amine will not be protonated.
O

O + CH3OH

H2N

Hydrolysis of ester. In acidic conditions, the carboxylic

acid will not be deprotonated and the amine group will
hot HCl (4 M) be protonated.
O

OH + CH3OH

H3N
CHEM1102 2008-N-10 November 2008
Marks
• The structure of the antihistamine, ZyrtecTM, is given below. 5

What is the name of the functional group in Box A? Amine (tertiary)

What is the name of the functional group in Box B? Ether

What is the name of the functional group in Box C? Carboxylic acid

By drawing an arrow on the structure above, clearly indicate the stereocentre in the
structure of Zyrtec.
Draw the product of the reaction when Zyrtec is treated with LiAlH4 followed by
dilute acid.

LiAlH4 will reduce the carboxylic acid all the way to an alcohol.
CHEM1102 2007-J-7 June 2007
Marks
• Draw the structure of the major organic product formed in the following reactions. 5

O HO CH3
1. CH3MgBr

2. H / H2O

O O

OH CH3CH2OH / H
O

O OH
1. NaBH4

2. H / H2O
CHEM1102 2007-J-8 June 2007
Marks
• Suggest reagents you could use to achieve the following transformations. 4
O O
A
OCH3 O Na

O
Br C intermediate D
compound OH

A: NaOH / H2O / heat B: H2 / Pd catalyst

C: Mg / dry ether D: 1.CO2 2. H / H2O

CHEM1102 2007-J-10 June 2007
Marks
• The amino acids serine and valine are shown below. 7
OH
4 3
H H
H2N CO2H H 2N CO2H
1 2
serine valine

List the substituents attached to the stereogenic centre of valine in order of decreasing
priority.
highest priority lowest priority

-NH2 -COOH -CH(CH3)2 -H

(S)
Assign the absolute configuration of the stereoisomer of valine
shown above. (anticlockwise)

Draw a dipeptide formed by the condensation of serine with valine.

H2N CH CO NH CH COOH
CH2OH

What are the two key elements of protein secondary structure?

The secondary structure describes the orientation of segments of the peptide

chain and is defined by the H-bonding between amino acid residues. The
most common secondary structures are:
- α-helices, right handed coils stabilized by H-bonds between amide N-
H and C=O groups four residues apart and
- β-pleated sheets, extended structures stabilized by H-bonds between
amide N-H and C=O groups on different chains
CHEM1102 2007-N-9 November 2007
Marks
• The structure of salbutamol, a drug used to treat bronchospasms, is given below. 5
OH H
N
HO

HO

Give the molecular formula of salbutamol. C13H21O3N

Calculate the m/z value for the major peak you would expect to see for the molecular
ion in the high resolution mass spectrum.
[Atomic masses: 1H = 1.0078; 12C = 12.0000; 16O = 15.9949; 14N = 14.0031]

The molar mass of C13H21O3N is

13 × 12.0000 (C) + 21 × 1.0078 (H) + 3 × 15.9949 (O) + 1 × 14.0031 (N)

Answer: 239.1516

Give the structure(s) of the major organic products formed when salbutamol is
treated with the following reagents.

OH H
N
cold HCl (1 M) HO
H
HO

OH H
N
HO
NaOH (1 M)

O O H
N
Cr2O72 / H HO

HO
CHEM1102 2007-N-10 November 2007
Marks
• Complete the following table. 2
Starting material Reagents / Conditions Major organic product(s)

O O
C C
OH SOCl2 Cl

H 1. NaBH4
OH
O 2. H / H2O

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

CHEM1102 2007-N-11 November 2007

• Consider the reaction sequence below. 2

O O
OH
O
A + B
Cl
H
Draw the structures of products A and B.
A B

O O

O OH
Cl

• Draw the structure of the product, C, from the following reaction. 3

C
O
O
excess H2 O
O
Pd/C catalyst OCH3
OCH3

Product C undergoes hydrolysis when heated with 4 M NaOH. Give the structures of
the products (in their correct ionic states) formed in this reaction.

O
HO
O OCH3
CHEM1102 2007-N-12 November 2007
Marks
• The incomplete proposed mechanism for the reaction of acetyl chloride with 5
ammonia is shown below. Complete the mechanism by adding curly arrows to
illustrate the bonding changes that take place.

O
O Cl
Cl H
N
H
NH3
H

O Cl
O + H
Cl + N
NH2
H
H

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

CHEM1102 2006-J-7 June 2006
Marks
• Draw the structure of the major organic product formed in the following reactions. 5

O O
SOCl2
OH
Cl

OH O OH
1. LiAlH 4

H 2. H / H 2O
OH
CHEM1102 2006-J-10 June 2006
Marks
• The amino acid serine is shown below: 6
HO (c)

H
H2N COOH
(a) (b)

List the substituents attached to the stereogenic centre in order of decreasing priority.
highest priority lowest priority

NH2 COOH CH2OH H

Assign the absolute configuration of the stereoisomer shown above. S

Draw the dipeptide formed by the condensation of two serine residues.

NH2 CH CO NH CH COOH

CH2OH CH2OH
Explain briefly what is meant by the primary structure of a protein.

The primary sequence is the sequence in which the amino acids occur. For
example, ala-ser-tyr:

2
• Draw the repeating unit of the polymer formed in the following reaction.

O Cl

Cl O
+
NH2
H2N

N
N

O H
n
CHEM1102 2006-N-7 November 2006
Marks
• The structure of lignocaine, a local anaesthetic, is given below. 7

H
N
N
O
a b

Give the molecular formula of lignocaine. C14H22ON2

Name the functional groups in lignocaine indicated by boxes “a” and “b”.

a: amide b: tertiary amine

Give the structure(s) of all organic products formed when lignocaine is treated
with the following reagents. If no reaction occurs, write “NO REACTION”.

cold HCl (1 M) N
N H

O
hot NaOH (4 M) NH2 N

hot HCl (4 M) HO
NH3 N H

O
CHEM1102 2006-N-8 November 2006
Marks
• Draw the constitutional formula of the major organic product formed in each of the 6
following reactions.

O
O

OH SOCl2 Cl

O
CH3COOH
OH
H / heat
O

O
OH 2
Cr2O7 /H

1. LiAlH 4
COOH
2. H / H 2O OH