1.

This question concerns the three isomers A, B and C, each of which has a relative molecular mass of 134. O C A C H
2

O C H
3

C H

CH B

C H

C H C

C H

C H 2O H

(a)

The mass spectrum of substance A is shown below. Identify the species responsible for the peaks labelled 1, 2 and 3. Peak 1 ......................................................................................................................... Peak 2 ......................................................................................................................... Peak 3 .........................................................................................................................
(3)

(b)

The infra-red spectra of two of these substances were also measured. (i) Use the table and the spectra below to identify which spectrum is that of substance C. Wavenumber 1 / cm 3000-3100 2850-3000 1680-1750 Wavenumber 1 / cm 3200-3570 3580-3650 1450-1600

Bond CH (arenes) CH (alkanes) C==O

Bond OH (hydrogen bonded) OH (not hydrogen bonded) C==C (arenes)

The spectrum of substance C is spectrum number ..........................................

(1)

(ii)

Give one reason for your choice. ......................................................................................................................

(1)

(iii)

Give one other reason why the other spectrum could not be that of substance C. ...................................................................................................................... ......................................................................................................................
(1)

100 80 R e la t iv e in t e n s ity 60 40 20 0 25 50 m /e 75 100 1

125

100

T ra n s m itta n c e

50

4000

3000

2000 1500 W a v e n u m b e r /c m 1

1000

100

T ra n s m itta n c e

50

4000

3000

2000 1500 W a v e n u m b e r /c m 1

1000

(c)

State which of the substances A, B and C will react with the following reagents and state what would be observed. (i) Bromine dissolved in hexane. Substance(s) ..................................................................................................... Observation ......................................................................................................
(2)

(ii)

A warm ammoniacal solution of silver nitrate. Substance(s) ..................................................................................................... Observation ......................................................................................................

(2)

(iii)

2,4-dinitrophenylhydrazine solution. Substance(s) ..................................................................................................... Observation ......................................................................................................

(3)

(iv)

Give the structural formula of the organic product(s) obtained in (c)(i).

(1)

(v)

Give the structural formula of the organic product(s) obtained in (c)(ii).

(1) (Total 18 marks)

2.

The drug ibuprofen can be synthesised from benzene by the route shown below.

C H C
S t A p e

3H

C C3 H C H C
S t B p e

3H

C C3 H C H C
S t C p e

3H

C C3 H C H C
C O / P d c a t a l y s t

3H

C3
2H

2H

2H

2H

C C
3H

C
3H

H O H C I b u
3H

C2

r o f e n

(a)

Name the type and mechanism of the reaction in Step A, and suggest a suitable reagent and catalyst. Type and mechanism .................................................................................................. Name of the reagent for Step A .................................................................................. Catalyst .......................................................................................................................
(3)

(b)

Step C is a reduction. Give ONE reason why lithium tetrahydridoaluminate, LiAlH4, is preferred to hydrogen as a reducing agent in this reaction. ..................................................................................................................................... ..................................................................................................................................... .....................................................................................................................................
(2)

(c)

A sample of the final product was analysed by combustion. 1.00 g was burnt in oxygen. It produced 2.78 g carbon dioxide and 0.786 g water. State the molecular formula of ibuprofen and show that these results are consistent with it.

(4)

(d)

Ibuprofen can be analysed by instrumental methods. The infrared spectra of ibuprofen and two other drugs, aspirin and paracetamol, not necessarily in that order, are shown opposite.
C H C I b u p r o f e n h
2H 3H

C3

a s

t h

f o

r m

l a

C C
3H

C2

2O

H t h O e

O C fCo H m r 3 u l a

s p

i r i n

a s

a r a c e t a m H

l N

h C O

a s
3H

t h C

f o

r m

l a

(i)

Explain, referring to the structure of each molecule, why infrared spectroscopy is not a good technique to distinguish aspirin from ibuprofen. ........................................................................................................................... ........................................................................................................................... ...........................................................................................................................
(1)

(ii)
S p

Deduce which of X, Y or Z is the infrared spectrum of paracetamol, giving a piece of evidence from the spectrum you select.
m 1 0 X 0

e c t r u

T ra n s m itta n c e (% )

0 4 0 S p e c t r u m 1 0 Y 0

0 W

2 a v

0 30 0 0 0 e n u 1 m b e r / c m

T ra n s m itta n c e (% )

0 4 0 S p e c t r u m 1 0 Z 0

0 W

2 a v

0 30 0 0 0 e n u 1 m b e r / c m

T ra n s m itta n c e (% )

0 4 0

0 W

2 a v

0 30 0 0 0 1 1 e n u m b e r / c m

........................................................................................................................... ........................................................................................................................... ........................................................................................................................... ...........................................................................................................................

(1)

(iii)

Ibuprofen and aspirin can be distinguished using their mass spectra. A line at mass/charge ratio 57 occurs only in the mass spectrum of ibuprofen. Give the formula of the ion which produces this line. ........................................................................................................................... Suggest the mass/charge ratio of one line which occurs in the mass spectrum of aspirin but not ibuprofen, and the formula of the species which produces it. ........................................................................................................................... ...........................................................................................................................
(3) (Total 14 marks)

3.

This question concerns the following compounds containing four carbon atoms. A B C D Butanoic acid, CH3CH2CH2COOH Butanone, CH3COCH2CH3 Propyl methanoate, HCOOCH2CH2CH3 Butanoyl chloride, CH3CH2CH2COCl

Select, from A to D, the compound that

(a)

can be made by the oxidation of a primary alcohol. A B C D

(1)

(b)

would be expected to react most rapidly with ethanol. A B C D

(1)

(c)

would have 4 different chemical shifts in its nmr spectrum and a broad absorption 1 between 25003300 cm in its infrared spectrum. A B C D
(1) (Total 3 marks)

4.

In moths a pheromone, P, acts as an attractant for the opposite sex. P has the molecular formula C7H12O. What can be deduced about the structure of P from the following information? (a) (i) 1 mole of P reacts with 1 mole of Br2 molecules to form a compound with the formula C7H12OBr2. ........................................................................................................................... ...........................................................................................................................
(1)

(ii)

When lithium tetrahydridoaluminate is reacted with P a compound with the formula C7H14O is formed. ........................................................................................................................... ...........................................................................................................................
(1)

(iii)

P forms an orange precipitate with 2,4-dinitrophenylhydrazine. ...........................................................................................................................

(1)

(iv)

When P is heated with Fehlings or Benedicts solution, the solution remains blue. ........................................................................................................................... ...........................................................................................................................
(1)

(v)

P is a Z-isomer. ........................................................................................................................... ........................................................................................................................... ........................................................................................................................... ...........................................................................................................................

(1)

(b)

What does the following physical data tell you about the structure of P? Use your Data booklet where necessary. (i) The infrared spectrum of P has the following absorptions at wavenumbers above 1 1600 cm . 3060 cm 2920 cm 1690 cm 1660 cm
1 1 1 1

........................................................................................................................... ........................................................................................................................... ........................................................................................................................... ........................................................................................................................... ...........................................................................................................................

(3)

11

(ii)

The nmr spectrum does not have a peak corresponding to a chemical shift, , of between 9 and 10. ........................................................................................................................... ........................................................................................................................... ...........................................................................................................................
(1)

(iii)

The mass spectrum showed the presence of peaks at mass/charge ratios of 15 and 29, but no peak at 43. ........................................................................................................................... ........................................................................................................................... ........................................................................................................................... ........................................................................................................................... ........................................................................................................................... ...........................................................................................................................
(3)

(c)

Given that P has a straight chain of carbon atoms in its formula, use the information you have deduced above to suggest a displayed formula for the pheromone P.

(2)

(d)

How could you use a purified sample of the orange precipitate in (a)(iii) to confirm the formula of P? ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... .....................................................................................................................................
(2) (Total 16 marks)

13