Summer 2000 CH4

1.

Adrenalin is a hormone which raises blood pressure, increases the depth of breathing and delays
fatigue in muscles, thus allowing people to show great strength under stress.
Benzedrine is a pharmaceutical which stimulates the central nervous system in a similar manner
to adrenalin.
HO
CH 2

CH(CH 3 )

NH 2

HO

CH(OH)

Benzedrine

(a)

(i)

H
CH 2

CH 3

Adrenalin

On the structure for benzedrine mark with a (*) any asymmetric carbon atom that
causes chirality.
(1)

(ii)

Suggest why adrenalin is more soluble in water than is benzedrine.

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(2)

(b)

Give the structural formulae of the organic products obtained when benzedrine reacts
with:
(i)

an aqueous acid such as dilute hydrochloric acid;

(1)

(ii)

ethanoyl chloride in the absence of a catalyst;

(1)

(iii)

excess ethanoyl chloride in the presence of the catalyst anhydrous aluminium

chloride.
(2)

(c)

State the two reagents needed to convert

CH 2

CH(CH3 )

CONH2

into benzedrine.
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(2)

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Summer 2000 CH4

(d)

It is possible to eliminate a molecule of water from adrenalin which for the purpose of this
question may be represented as RCH(OH)CH2NHCH3. Draw the structural formulae
of the two stereoisomers produced.

(2)

(e)

The mass spectra of both benzedrine and adrenalin have a peak at a mass/charge ratio of
44. Draw the structure of the species which give these peaks.
(i)

in benzedrine;
(1)

(ii)

in adrenalin.
(1)
(Total 13 marks)

2.

(a)

State the reagent(s) used for the conversion of ethanol to

(i)

iodoethane
..........................................................................................................................
(1)

(ii)

ethene
..........................................................................................................................
(1)

(b)

Suggest a series of reactions by which ethanol can be converted to 2-hydroxypropanoic

acid, CH3CH(OH)COOH. For each reaction specify the reagents and conditions
necessary.

(6)

(c)

Explain whether a solution of 2-hydroxypropanoic acid, made in this way, would have
any effect on a beam of plane polarised monochromatic light.
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(2)

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Summer 2000 CH4

(d)

2-hydroxypropanoic acid reacts with lithium tetrahydridoaluminate (III)(lithium

aluminium hydride).
State the conditions necessary for this reaction and give the structural formula of the
organic product.
Conditions ................................................................................................................
...................................................................................................................................
Structural formula

(2)
(Total 12 marks)

3.

This question concerns the compounds linked by the reaction scheme

C4H8O C4H10O C4H9Br C4H8

A

A reacts with 2,4-dinitrophenylhydrazine to give a solid E which, when recrystallised, has a

melting temperature of 126C. The melting temperatures of some 2,4-dinitrophenylhydrazine
derivatives are listed below:
Compound

Melting temperature of
2,4-dinitrophenylhydrazine derivatives/C

propanone

126

butanone

116

propanal

155

methyl propanal

187

butanal

126

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Summer 2000 CH4

The infra red spectrum of A has a peak at 1720 cm1, but none at about 3500cm1 or 1650cm-1.
The spectrum of B has a very broad peak at 3500cm1, but none at about
1720cm1 or 1650cm1.
Some typical infra red absorption wavenumbers are shown in the table below:

(a)

(i)

Bond

Wavenumber/cm1

OH

3600 to 3300

CO

1200 to 1150

CC

1680 to 1620

CO

1750 to 1680

Why must solid E be recrystallised before its melting temperature is measured?

...........................................................................................................................
(1)

(ii)

What bond in A is responsible for the peak at 1720cm1?

...........................................................................................................................
(1)

(iii)

Why is the peak at 3500cm1 in the spectrum of B very broad?

...........................................................................................................................
...........................................................................................................................
(2)

(iv)

Draw the structural formula of A and B.

A

B
(2)

(b)

(i)

Name the reagent and the solvent used for the conversion of C to D.
...........................................................................................................................
...........................................................................................................................
(2)

(ii)

Draw the structural formula of D.

(1)

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Summer 2000 CH4

(iii)

Draw the structural formula of the major product of the addition of HBr to D.

(1)

(iv)

Suggest why the reaction in (iii) does not produce C as the major product.
...........................................................................................................................
...........................................................................................................................
(1)
(Total 11 marks)

4.

Grignard reagents are useful in organic syntheses where it is necessary to form a new carboncarbon s bond.
(a)

Draw a diagram of suitable apparatus, state the conditions and ONE specific safety
precaution for the preparation of the Grignard reagent 1-propylmagnesium bromide,
CH3CH2CH2MgBr, from 1-bromopropane. The following data will be useful.
Substance

Boiling temperature

Flammability

/C
1-bromopropane

70.8

low

ethoxyethane (ether)

34.5

very high

(7)

(b)

Give the names and structural formulae of the organic products obtained when 1propylmagnesium bromide reacts with:
(i)

ethanal, followed by dilute hydrochloric acid

(2)

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Summer 2000 CH4

(ii)

carbon dioxide followed by dilute hydrochloric acid

(2)
(Total 11 marks)

5.

Ethyl benzene is prepared by the reaction between bromoethane and benzene, using anhydrous
aluminium bromide as a catalyst in a solution of ethoxyethane (ether). After the reaction is
complete the ether and any unreacted bromoethane are distilled off. Finally the ethyl benzene
and unreacted benzene are separated by fractional distillation.
(a)

Suggest the mechanism for the reaction between benzene and bromoethane.

(4)

(b)

Benzene (boiling temperature 80C) and ethyl benzene (boiling temperature 136C)
dissolve in each other and form solutions which obey Raoults Law.
Draw a boiling temperature/composition diagram, labelling the liquid and vapour lines.
Use your diagram to explain what happens when a mixture containing 40% benzene and
60% ethylbenzene is fractionally distilled.

Boiling temperature /C

% composition

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Summer 2000 CH4

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(6)

(c)

Give the reagents and conditions necessary for the conversion of ethyl benzene,
C6H5CH2CH3, into potassium benzoate C6H5COOK.
Reagents ....................................................................................................................
....................................................................................................................................
Conditions .................................................................................................................
....................................................................................................................................
(3)
(Total 13 marks)

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