AS/AL-CHEM (1997-2002)

Part XI

Chemistry of carbon compounds

NOTE: Questions with an * are NOT required by the HKDSE syllabus. They are included so as to enrich your knowledge and broaden your understanding in chemistry.

1997-AL-CHEM 1
5. (b) Consider the following reactions:

conc.H2SO 4 heat

HBr

CH3CH2CH2OH

CH3CH2COCl

NHNH2 NO2

Na2Cr2O 7 + H3O
Give structures for J, K, L, M and N.

NO2

N (a red precipitate)
(5 marks)

Mark Scheme ..............................................................................................................................................

5. (b) J K : : CH3CH=CH2 1 1

CH3CHCH3 Br

L M N

: : :

CH3CH2COOCH2CH2CH3 CH3CH2CHO
O2N H C CH3CH2 N NH NO2

1 Served as a chemical test for carbonyl group 1 1

(a condensation reaction by elimination of H2O: equation

DSE)

Please identify the types of reactions involved in forming J, K, L and M.

[5]

1997-AL-CHEM 2 5. (b) The following equation represents the acid hydrolysis of a dipeptide D to produce compounds E and F, one of which is a chiral compound.

H3C O H2NCHC NHCH2CO 2H

D (i) (ii) (iii) Name all functional groups in D. Give one structure for E and one for F.

H3O +

Draw a suitable representation for the chiral product.

Suggest a method to separate E and F from the reaction mixture. (5 marks)

5.

(d)

Give a systematic name to each of the following compounds:

O (ii) CH3CH2 C CH(CH3)CH2CH3

(iii) HO 2C

C C

CH3 H
(2 marks)

Exam Practice Marking Scheme 5. (b) (i) amino group / amine

Functional groups

Do Brilliantly Mark 1

amide group / peptide linkage carboxyl group / carboxylic acid (ii) E:

CH3 O H2N CH C OH

(deduct marks for each extra functional group) F: H2NCH2CO2H

CH3 NH2 H C

and

(Also accept protonated forms of the amino acids)

1 (L or D isomer) 1 [5]

Stereo-structure of E: (iii)

CO2H

paper chromatography / thin layer chromatography / column chromatography / electrophoresis

5.

(d)

(ii) (iii)

4-methylhexan-3-one trans-but-2-enoic acid / E-but-2-enoic acid

1 1 [2]

-------------------------------------------------- Take a break ----------------------------------------------------6. (a) The following conversion can be completed in not more than three steps. Use equations to show how you would carry out each conversion in the laboratory and for each step, give the reagent(s), conditions, and structure of the product.
(ii) NH2 NHCH2

(3 marks) 6. (c) Compound H, C3H6O2, does not react with NaBH4 and displays the following infra-red spectrum. Deduce all possible structures of H.

(4 marks)

Mark Scheme ..............................................................................................................................................

6. (a) (ii)

NOTE: Step 1 amide formation (in basic medium); Step 2 Reduction of amide to give amine (in dry ether)

AS/AL-CHEM (1997-2002)

Part XI
-1

Chemistry of carbon compounds

6.

(c)

IR peak at ~ 1750 cm indicates the presence of a carbonyl group (C=O) No broad OH absorption band implies that H is not a carboxylic acid No reaction with NaBH4 implies H is not ketone or aldehyde / may be an ester Possible structures of H:

O CH3 C OCH3 ;

O H C OCH2CH3

1+1

(Deduct 1 mark for each extra structure.) NOTE: NaBH4 is a milder reducing agent compared with LiAlH4. It is more selective in use and can only reducing carbonyl compounds to alcohols but not carboxylic acids (and their derivatives, e.g. esters).

[4]

-------------------------------------------------- Take a break ----------------------------------------------------7. (a) Suggest a chemical test to distinguish one compound from the other in each of the following pairs. Each test should include the reagent(s), the expected observation with each compound and the chemical equation(s).

(i)

and

O (iii) C2H5 C O(CH2)2CH3 and C2H5

O C CH2OC 2H5

O (iv) C2H5 C C2H5 and CH3(CH2)3

O C H
(9 marks)

Mark Scheme ..............................................................................................................................................

7. (a) (i) Treat compound with Br2 (in CCl4 or in CH3CCl3) 1

rapidly decolorizes the red-orange Br2 solution while

CCl4 Br Br

does not

Br2

(Also accept Baeyers test or using acidified potassium permanganate solution) (iii) Treat compound with a solution of 2,4-dinitrophenylhydrazine in methanol/Bradys reagent
O

Red/orange/yellow ppt. is observed with CH3CH2CCH2OCH2CH3

O

No ppt. with CH3CH2C OCH2CH2CH3

O2N O2N O O H2NNH NO2 N NH O NO2

( + H 2O )

1 1

(iv)

Treat compound with Tollens reagent/ammoniacal silver nitrate A silver mirror / silver deposit is observed with CH3(CH2)3CHO; No silver mirror / silver deposit with CH3CH2COCH2CH3

CH3(CH2)3CHO

[Ag(NH3)2]+ / OH-

CH3(CH2)3COO- + Ag(s) silver mirror

1 9 marks

Exam Practice

Functional groups

Do Brilliantly

1998-AL-CHEM 1
4. Alcohol E has the structure CH3CH(OH)C2H5. (a) (i) (ii) (b) (i) *(ii) Draw a three-dimensional representation of E. What type of isomerism can be exhibited by E? (2 marks) Draw the structures of three structural isomers of E, all of which are alcohols.

(c)

Describe how the reagent Zn/concentrated HCl can be used to distinguish E from the three structural isomers. (3 marks) When heating with concentrated H2SO4(l), E gives mainly two isomeric compounds, F and G, both of which have the formula C4H8. On treatment with bromine, both F and G give a product H with formula C4H8Br2. (i) Draw structures for F, G and H. What is the isomeric relationship between F and G? Outline the mechanism for the formation of H from either F or G. (5 marks) Mark
(Accept any correct representation of butan-2-ol showing the arrangement of groups at the chiral carbon)

(ii) *(iii)

4.

Marking Scheme (a) (i)

H C CH3
(ii) (b) (i)
CH3 CH3CH2CH2CH2OH CH3CHCH2OH CH3 CH3 C OH CH3

C2H5 OH

1 1
2 marks

optical isomerism / enantiomerism

++

(ii)
NOTE:

Upon reaction with Zn/conc.HCl, E gives turbidity (or cloudiness) at a slower rate than (CH3)3COH, but at a faster rate than CH3(CH2)3OH and (CH3)2CHCH2OH. ,
This test is a modified version of Lucas test (conc.HCl/ZnCl2) used to distinguish 1, 2 and 3 ROH. Please refer to 1999-AL-CHEM 2 Q.7(a) for further information. conc.HCl/ZnCl2 ROH RCl (RCl formed is insoluble in water) 3 marks

(c)

(i)

F and G:
H H C CH3
Br CH3 Br C H H C Br CH3

1+1
H and CH3 CH3 C C H CH3

and

H: (ii) (iii)

Br

1 1

Geometrical isomerism / cis-trans isomerism () ()

Br Br Br or,
Electrophilic addition mechanism DSE
+

Br Br Br

Br

5 marks

AS/AL-CHEM (1997-2002)

Part XI

Chemistry of carbon compounds

1998-AL-CHEM 2 6. (a) Consider the structures of the two synthetic polymers shown below:

CH2CH2 n poly(ethene)
(i) (ii)

HN(CH2)6NHCO(CH2)4CO n nylon-6,6

Suggest an explanation for the fact that nylon-6,6 has a higher tensile strength than poly(ethene). Briefly explain why aqueous acids can more readily attack nylon-6,6 than poly(ethene) inducing degradation. Apart from acidic conditions, state one other condition under which nylon-6,6 degrades more readily than poly(ethene). (5 marks)

(iii)

(c)

2-Ethanoyloxybenzoic acid (aspirin) is one of the most common substances used to relieve pain.

COOH OCOCH3

2-ethanoyloxybenzoic acid
*(i) (ii) Outline a synthetic route for preparing 2-ethanoyloxybenzoic acid from 2-methylphenol. Suggest how you could show the presence of the two functional groups in 2-ethanoyloxybenzoic acid. (4 marks) (d) Identify J, K, L and M in the following reactions.

CONH2 (ii)

CN K

(iii)

H2C=CH Cl

CH2

CH Cl

n
(4 marks)

Mark Scheme ..............................................................................................................................................

6. (a) (i) The interaction between polymer chain of PE is van der Waals forces while that between Nylon 6.6 is hydrogen bond. 1

The higher tensile strength of nylon is due to its stronger intermolecular attraction. (ii) CC linkage in PE is non-polar. not readily attacked by acids/has no reaction with acids. The amide linkage in nylon hydrolyse in acids to give NH3+ and COOH groups causing shortening of the chain. (iii) alkaline conditions / enzyme 1

, 1 5 marks

Exam Practice 6. (c) (i)

Functional groups

Do Brilliantly 2

OH CH3 (1/2) KMnO4/H+ heat (1/2)

OH CO2H

(1/2) CH3COCl or, (CH3CO)2O

OCOCH3 CO2H

Note:

(1/2) In carrying out the ethanoylation of phenol, we usually convert the phenol to phenoxide ion (by adding NaOH) before adding ethanoyl chloride (or ethanoic anhydride) for the ethanoylation.
Use IR spectroscopy: Absorption at 2500 to 3300 cm-1 indicates the presence of OH of the carboxylic acid

(ii)

[Note that extensive H-bonding in the acid gives rise to the very broad characteristic absorption band.] Absorption at 1680 to 1750 cm-1 indicates the presence of C=O of the acid and the ester. or, Chemical test: treat compound with Na2CO3(aq) / NaHCO3(aq) evolution of (colourless) gas bubbles, CO2(g), indicates the presence of CO2H or, ,

() ()

warm compound with dilute acid. Smell of vinegar indicates the presence of an ethanoyl ester. (,) 4 marks P2O5 (a dehydrating agent), heat
NOTE: P2O5 is the empirical formula of P4O10. 1 Although this dehydration reaction is NOT mentioned in DSE, the reagent is worth learning.

(d)

(ii) (iii)

H2O2, or other initiators (e.g. ROOR, i.e. organic peroxide)

1 4 marks

-------------------------------------------------- Take a break ----------------------------------------------------7. (a) Briefly explain why each of the following proposed reactions cannot lead to the target molecule. In each case, using the same starting molecule, outline a feasible synthetic route to obtain the target molecule, with no more than three steps. In each step, give the reagent(s) used, the conditions required and structure of the product. Starting molecule Target molecule

O (i) C NHCH3 CH3OH

O C OCH3

O (iii) CH3CH2 C OH LiAlH4, H3O

O CH3CH2 C H

Br (iv) CH3CH2CH CH3 NaOH H3CC CCH3

(9 marks) (c) Give a systematic name to each of the following compounds. (ii) CH3CH=CHCH2CHO (1 mark)

AS/AL-CHEM (1997-2002)

Part XI

Chemistry of carbon compounds

Mark Scheme ..............................................................................................................................................

7. (a) (i) No reaction between the reactants A feasible synthetic route is shown below: 5

NOTE: The functional group transformation required is from amide to ester.

or,

O C NHCH 3 H3O+

O C OH SOCl2

O C Cl CH3OH

O C OCH 3

NOTE:

Step 1 acid hydrolysis of amide; Step 2 conversion to acyl chloride from acid; Step 3 ester formation

(iii)

LiAlH4 will react with H3O+; or, LiAlH4 reduces carboxylic acids to alcohols, not aldehydes
NOTE: LiAlH4 + 4H2O LiOH + Al(OH)3 + 4H2 The bases formed will be neutralised by the acid H3O+

A feasible synthetic route is shown below:

in dry ether

Step 1: Reduction of COOH to CH2OH Step 2: Mild oxidation of 1 ROH to aldehyde

or, using Cr2O72-/H+ to oxidize the alcohol and distilling the aldehyde out from the reaction mixture as the aldehyde is being produced. or, SOCl2 H2, Pd/BaSO4 CH3CH2COOH CH3CH2COCl CH3CH2CHO (for reference only) (iv) Only alkene / but-2-ene will be formed. or, butan-2-ol will be formed. A feasible synthetic route is shown below:
Br
2) alcoholic NaOH heat

NOTE: Elimination reaction NOTE: Substitution reaction

() 4
(1/

(1/

( /2)

( /2) Br2 / CCl4 Br

Br

2) alcoholic NaOH CH3 C C CH3 heat or, using a stronger base, e.g. NaOC2H5 or NaNH2 instead of NaOH

7.

(c)

(ii)

pent-3-enal / 3-pentenal

9 marks 1 1 mark

1999-AL-CHEM 1
5. (a) Under certain conditions, methane reacts with chlorine to give chloromethane as the major product. (i) (ii) (iii) State the conditions for the reaction. Outline the mechanism and name the mechanistic steps of the reaction. Is the reaction of methane with chlorine an appropriate method for the preparation of dichloromethane? Explain. (5 marks)
7

Exam Practice

Functional groups

Do Brilliantly Mark , 3

Marking Scheme 1999-AL-CHEM 1 5. (a) (i) diffused light; excess methane (ii) mechanism:

(iii)

No. The reaction of CH4 with Cl2 gives a mixture of CH3Cl, CH2Cl2, CHCl3 and CCl4.

1
5 marks

1999-AL-CHEM 2
5. (a) Identify D, E, F, G and J in the following reactions.

(i)

NNH

CH2CH3 (ii) O2N

E O 2N

CO2H

CH2CH2OH (iii) HO
O NH (v) H3O heat
+

Na2Cr2O7/H3O heat CH3

(Hint: J is a polymer.)
(c)

(4 marks)

Dacron is the most common of the group of polymers known as polymers. A segment of the polymer chain is shown below.

O C
(i) (ii)

O C OCH2CH2O

C OCH2CH2O C

Suggest two types of material which can be made from polyesters. Draw the structures of the two monomers used in manufacturing Dacron. Name the type of polymerization involved. How can Dacron be degraded in the environment? (5 marks)
8

(iii)

AS/AL-CHEM (1997-2002)

Part XI

Chemistry of carbon compounds

Marking Scheme 5. (a) (i) D:

1999-AL-CHEM 2

Mark 1

NHNH2
(ii) (iii) E: F: MnO4-/H3O+; heat
CO2H OR HO CH3 HO CH3 CHO

1 1

(v)

J:
HN

O (CH2)5 C n

[4] (c) (i) Any TWO of the following: fibres, plastics, coatings, clothing, etc. (ii)
O HO C O C OH or

(Accept other correct uses of Dacron)

O CH3O C O C OCH3

, 1 1 1 1 [5]

and HOCH2CH2OH condensation polymerization (iii) Hydrolysis of the ester group by enzymes /bacteria

-------------------------------------------------- Take a break ----------------------------------------------------6. (a) (i) Suggest a reagent for the following conversion:

O Cl NH2 Cl NH CCH3

4-chlorophenylamine
(ii)

N-(4-chlorophenyl)ethanamide

Based on the fact that the amino group of 4-chlorophenylamine is more basic than the amide group of N-(4-chlorophenyl)ethanamide, outline a procedure to separate a mixture of the two compounds. Suggest how to show the presence of the amide group in N-(4-chlorophenyl)ethanamide by (I) (II) a chemical test, and a spectroscopic method. (6 marks)

(iii)

6.

(c)

State the relationship between each pair of structures shown below: CH2CH3 CH2CH3
(i) Cl Cl Cl and Cl

CH3 (ii) H C C

H and CH2CH3
Br

CH3CH2 C H
H and CH2
9

CH3 C H

(iii)

CH2

CH

C CH 3 H

CH

C CH 3 Br

(3 marks)

Exam Practice Marking Scheme 6. (a) (i) (ii) (CH3CO)2O / CH3COCl

Functional groups

Do Brilliantly Mark 1,

1999-AL-CHEM 2

Shake the mixture with dilute HCl and ether in a separating funnel. The amine will form the aminium salt and dissolve in the aqueous solution. The amide is not basic enough to be protonated by HCl and dissolves in the ether. Separate the aqueous layer from the ethereal layer. Treated the aqueous layer with NaOH(aq) to liberate the free amine. Use ether (or an appropriate solvent, e.g. THF, hexane, etc.) to extract amine from aqueous layer. (Distil off the organic solvent to obtain amine.) Distil off ether from the ethereal layer to obtain the amide. (I) Chemical test: Heat the amide with acid, smell of vinegar can be detected.

(iii)

(II)

Spectroscopic method: IR: strong absorption at 1680 1750 cm-1 indicates the presence of C=O functional group / at 3350 3500 cm-1 indicates the presence of NH group. ,
6 marks

(c)

(i) (ii) (iii)

identical compound geometrical isomers /cis-trans isomers / Z-E isomers enantiomers /optical isomers

1 1 1
3 marks

-------------------------------------------------- Take a break ----------------------------------------------------7. *(a) Lucas reagent, a mixture of ZnCl2 and concentrated HCl, can be used to distinguish the following alcohols from one another:

(CH3)2CHCH2OH,
(i) (ii)

CH3CH2CH(OH)CH3

and

(CH3)3COH

State the expected observation when these alcohols are separately treated with Lucas reagent. Suggest why these alcohols behave differently towards Lucas reagent.

(Hint: The zinc ion binds strongly with the oxygen atom of an alcohol, weakening the CO bond and creating a better leaving group.)

(4 marks) 7. (c) Compound M is a hydrocarbon isolated from oranges and lemons. (i) M contains 88.2% by mass of carbon and has a relative molecular mass of 136.2. Deduce the molecular formula of M. Based on the reactions given below, deduce the structure of M.

*(ii)

M + 2H2
(1) O 3 (2) Zinc dust

Pt
O

CH3
O H

CH(CH3)2

CH3 C(CH2)2CHCH2C O C CH3

HCHO

Marking Scheme 7. (a) (i)

1999-AL-CHEM 2 (CH3)2CHCH2OH : 1 ROH clear solution CH3CH2CH(OH)CH3 : 2 ROH cloudiness/turbidity appears after about five minutes (CH3)3COH : 3 ROH cloudiness/turbidity appears immediately ( marks for the appearance of cloudiness; 1 mark for the difference in rate.)

(5 marks) Mark

(ii)

The appearance of cloudiness is due to the formation of haloalkanes which are immiscible with water. Due to the formation of the relatively stable 3 carbocations, 3 alcohols reacts rapidly with Lucas reagent. The reaction mechanism is SN1. 1 carbocation is relatively unstable. The reaction of 1 alcohol with Lucas reagent proceeds through a mechanism which is not favoured in acidic conditions. (The reaction rate of 2 alcohols with Lucas reagent is moderate.)
4 marks

10

AS/AL-CHEM (1997-2002)

Part XI

Chemistry of carbon compounds

7.

(c)

(i) C Mass (g) no. of moles 88.2 H 11.8

88.2 = 7.34 12.01 7.34 =1 7.34

5

11.8 = 11.71 1.008 11.71 = 1.60 7.34

8

Mole ratio

Simple whole no. ratio Empirical formula of M is C5H8.

Relative molecular mass of M = 136.2. Molecular formula of M is C10H16. (For the empirical/molecular formula, award 1 mark for the answer + deduction) (ii) M reacts with H2 in mole ratio of 1 : 2. M possesses two C=C bond /one CC bond. Upon ozonolysis, M gives HCHO and a compound with 3 carbonyl groups. M possesses a terminal C=C bond and a cycloalkene/cyclohexene structure. Structure of M: NOTE: , 1 1

limonene

Note that limonene is optically active; the (+) form being present in citrus oils whilst the (-) form is found in pine needle oil. The racemic mixture, called dipentene, is a constituent of turpentine.

limonene isoprene

7 marks

2000-AL-CHEM 1
5. (a) Consider the reaction:
Br HBr

(i) *(ii) (iii) (iv)

Name the type of the reaction. Outline a mechanism of the reaction. Draw the structures of all possible stereoisomers of the product. Would the product rotate the plane of a beam of plane polarized light? Explain your answer. (5 marks)
11

Exam Practice 5. (b) (i)

Functional groups

Do Brilliantly

Give the reagents and conditions for the two steps of the conversion:
O CH3CH2 C N(CH3)2 OH Step 1 CH3CH2 CH N(CH3)2

Step 2

CH3CH CH

N(CH3)2

Step 1: Step 2: (ii) (iii) Suggest a chemical test for the carbonyl group in compound A. State the expected observation when HCl(aq) is added to compound A. 2000-AL-CHEM 1 (4 marks) Mark 1 2

5.

Marking Scheme (a) (i) electrophilic addition (ii)

(iii)

(iv)

No. The product is a mixture of the enantiomers in mole ratio of 1 : 1 / a racemic mixture Step 1: LiAlH4/ether, followed by acid hydrolysis or, NaBH4 / H2, Pd; high pressure Step 2: Heat with concentrated H2SO4 / Al2O3 / H3PO4 / P4O10

1 [5] 1 (,) , () () 1
4 marks

(b)

(i)

(ii)

Reagent: 2,4-dinitrophenylhydrazine / Bradys reagent Observation: yellow / orange / red precipitate or Reagent: hydroxylamine / phenylhydrazine / semicarbazide Observation: white (colourless) crystals A colourless solution is formed / only one layer is observed.

(iii)

2000-AL-CHEM 2
5. (d) A mixture of two organic products, G and H, was obtained in the reaction :

The mixture was separated by paper chromatography using a mixture of hexane and ether as solvent. The Rf values of G and H were found to be 0.84 and 0.55 respectively. (i) (ii) (iii) Deduce the structures of G and H. Suggest a chemical test to distinguish between G and H. State how the use of infra-red spectroscopy can provide further proof for the structures of G and H. (8 marks)
12

AS/AL-CHEM (1997-2002)

Part XI

Chemistry of carbon compounds

Marking Scheme 5. (d) (i) G:

O

2000-AL-CHEM 2
O C O(CH2)5O C

Mark
O C O(CH2)5OH

H:

1,1

G is less polar than H (or H has a polar OH group) and is therefore less tightly bound to the stationary phase and hence moves faster. (ii) or, or, or, (iii) Reagent: PCl5 / PCl3 / SOCl2 Only H will give misty fumes of HCl
NOTE: ROH + SOCl2 RCl + SO2 + HCl

1,1 1 1 (1) (1)

Reagent: Na Only H will react with Na to give gas bubbles (H2)

2+

NOTE: 2ROH + 2Na 2RO-Na+ + H2

Reagent: Cr2O7 /H Only H will induce a colour change from orange to green Reagent: MnO4-/H+ Only H will induce a colour change from purple to colourless Compound H shows an IR absorption at 3200-3700 cm-1 but G does not, because H has an OH functional group whereas G does not. 1, [8]

-------------------------------------------------- Take a break ----------------------------------------------------6. *(d) The conversion below can be completed in not more than four steps.

Use equations to show how you would carry out the conversion in the laboratory. For each step, give the reagent(s), conditions and structure of the product.

(4 marks) (e) Identify L, M, N, and P in the following reactions:

(4 marks)
13

Exam Practice Marking Scheme 6. (d)

Functional groups

Do Brilliantly Mark 4

2000-AL-CHEM 2

heat

heat

4 marks

6.

(e)

(i) (ii) *(iii)

L: M: N:

Cl2 and light or hv / N-chlorosuccinimide (NBS) and light H2 and transition metal catalyst (e.g. Pt or Ni) + pressure

1 1 1

(elimination reaction) *(iv) P: HOOC(CH2)4COOH (hydrolysis of ester group and nitrile group (CN) 1
5 marks

-------------------------------------------------- Take a break ----------------------------------------------------7. (a) An acyclic compound R (C7H12O) has a linear structure. R can be converted to S and then to T:

Given that R exists as a mixture of geometrical isomers, S has a chiral carbon centre, and T does not have any chiral carbon centre, deduce all possible structures of R, S and T. (8 marks) 7. (b) Aspartame, a sweetener, has the structure below:

(i) (ii) (iii)

Name all functional groups in aspartame. Upon hydrolysis, aspartame gives two amino acids. Draw their structures. Two electrodes are dipped into an aqueous solution containing the two amino acids in a pH 12 buffer, and are connected to the two poles of a battery. Which species derived from these amino acids will move faster towards the anode? Explain your answer. (7 marks)

14

AS/AL-CHEM (1997-2002)

Part XI

Chemistry of carbon compounds

7.

(c)

The compounds below are the monomers of some polymers.

O2N

COCl

H2N

CO2H

These compounds react in the presence of an inorganic reagent U to give compound V.

(i) (ii)

What is reagent U? The flow diagram below illustrates the reaction sequence for the transformation of V to compound W with four aromatic rings. What are reagents X and Y?

In the reaction sequence as in (ii), V is replaced by W, i.e., W is allowed to react with reagents X and Y, and the products react in the presence of U to form a polymer Z. Draw the structure Z. (5 marks) Marking Scheme 2000-AL-CHEM 2 Mark 7. (a) T (C7H16O) is an alkanol / alcohol. 1 R has 2 double bonds and S has 1 double bond. 1

(iii)

R can be reduced by LiAlH4 and S can undergo catalytic hydrogenation. R possesses the >C=O and >C=C< functional groups and S is an unsaturated alcohol. ,

S has a chiral carbon centre while T has not. Possible structures of R:

O
or Possible structures of S:

O
2

OH *
T is heptan-4-ol:

OH * or 2+1 (2 marks for structures; 1 mark for a clear indication of the chiral centre.)
OH
1 (For each of R, S and T, deduct marks for each additional structure.)
8 marks 15

Exam Practice 7. (b) (i)

Functional groups

Do Brilliantly

(max. 4 guessing, phenyl group not counted as a guess) amine/amino carboxylic acid/carboxyl/alkanoic acid amide/peptide (link) ester/alkyl alkanoate
COOH H2N COOH
H2N COOH

(ii)
(iii)

1+1 (accept structures in form of Zwitterion.)

At pH 12, the amino acids exist as anions:

COO H2N COO

-

H2N

COO-

1+1 ,
7 marks

(I) (II) (I) is doubly (more highly) charged, and will moves faster towards the anode. 7. (c) (i) (ii) U: X: Y: (iii) Z:
O O 2N C N H 7 COOH

NaOH/KOH/Na2CO3/K2CO3 SOCl2 / PCl3 / PCl5 Sn/HCl or Fe/HCl, or Zn/HCl or H2/Pd-C or H2/PtO2 or Na + alcohol or

1 1 1

O O 2N C N H COOH 7
2
5 marks

2001-AL-CHEM 1
5. (b) Give the structures of the organic compound E.

(ii) (1 mark) 6. (b) After some lessons in organic chemistry, a student remarked, Alkanes are more stable than alkenes, therefore alkanes do not react with chlorine but alkenes do. Do you agree with the student ? Explain. (3 marks)

Marking Scheme
5. (b) (ii) E:

2001-AL-CHEM-1

Mark
1

NOTE: IT is a condensation polymerisation reaction. 6. (b) or, Alkanes are thermodynamically/energetically more stable than alkenes because hydrogenation of alkenes is exothermic.

[1] 1 (1)

H2

Pt C C
H < O

H H
Alkanes do react with chlorine under sunlight to give chloroalkanes. 1

16

AS/AL-CHEM (1997-2002)

Part XI

Chemistry of carbon compounds

e.g.

CH3CH3 + Cl2

hv

CH3CH2Cl + HCl

Comment on the relationship of the first and second statement.

(1) 1 [3]

2001-AL-CHEM 2
5. (a) Compound A has the following structure :

*(i)

The carbon atom indicated by arrow a is more reactive towards nucleophilic substitution (SN2) reaction with C2H5ONa than that indicated by arrow b. Explain. 5.56 g of A is treated with 1.36 g of C2H5ONa. B. 5.56 g of A is treated with 3.00 g of C2H5ONa. molecular formula C11H14O. (I) (II) (III) Give the structure of D. If the yield of D is 82%, calculate the mass of D that can be obtained. Give the structure of E and name the types of reactions involved in the formation of E. (8 marks) Mark 1 Deduce the structure of the major substitution product

(ii)

(iii)

The reaction gives two products, D and E.

E has the

Marking Scheme
5. (a) (i) (ii)

2001-AL-CHEM 2

The reaction involves the attack of C2H5O- on the C atom of the substrate. Carbon atom b is more crowded. it is less reactive. (Accept equivalent answers, such as steric hindrance, etc.) No. of moles of A =

5.56 = 0.02 (12.01 9 + 1.008 10 + 79.9 2) 1.36 = 0.02 (12.01 2 + 1.008 5 + 16 + 22.99)

No. of moles of C2H5ONa =

A : C2H5ONa = 1 : 1
Structure of B:
Br O

(iii)

(I)

Structure of D:
O

(II)

C2H5ONa is in excess. Molar mass of D (C13H20O2) = 12.01 13 + 1.008 20 + 16 2 = 208.3 g mol-1 Mass of D obtained = 0.02 208.3 0.82 = 3.42 g
(Deduct marks for wrong/no unit.)

1 1 1

(III)

Structure of E:

Types of reactions: elimination and substitution

, [8]

17

Exam Practice

Functional groups

Do Brilliantly

-------------------------------------------------- Take a break ----------------------------------------------------5. (b) *(i) Give the reagent(s) and conditions for Step 1 and Step 2 in the reaction sequence below :

(ii)

4-nitrobenzoic acid can be converted to benzocaine, an anaesthetic, in not more than three steps.

Marking Scheme
5. (b) (i)

Use equations to show how you would carry out the conversion. In each step, give the reagent(s), conditions and structure of the product. (5 marks) 2001-AL-CHEM 2 Mark Step 1: conc. HNO3 + conc. H2SO4 (); 0-60C / heat/warm () Step 2: MnO4-/H3O+ (); heat () ( marks for reagents; marks for conditions.) 1 1 3

(ii)

c:
Alternative answers:

H2/Pt, or Na/EtOH, or NaBH4 (1) (3)

d: H2/Pt, or Sn/HCl + heat

e: EtOH/H3O+ + heat

f: OH-(aq)

-------------------------------------------------- Take a break ----------------------------------------------------5. (c) Consider the information below concerning the production of low density polyethene from ethene.

*(i) (ii) (iii) (iv)

Outline a mechanism for the polymerization and name each mechanistic step. Explain why benzoyl peroxide is used. Why is high pressure needed for the polymerization ? Is the product a single compound ? Explain. (7 marks)
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AS/AL-CHEM (1997-2002)

Part XI

Chemistry of carbon compounds

Marking Scheme 5. (c) (i)

2001-AL-CHEM 2
Initiation ( )

Mark 2

Propagation ( )

Termination ( )

(Fish-hooks should be shown in the mechanism; otherwise max. deduction 1 mark) (ii) or, (iii) Benzoyl peroxide readily undergoes homolytic cleavage / decompose to give free radicals Benzoyl peroxide is a free radical initiator Concentration of reactants is high. 1 (1)

chance of collision between ethene and free radical increases /higher reaction rate.
(iv) No, because the product is a mixture of polymer molecules with different chain lengths.

1 1

-------------------------------------------------- Take a break ----------------------------------------------------7. (a) For each of the following reactions, suggest a possible reactant :

19

Exam Practice Marking Scheme

7. (a) (i)

Functional groups

Do Brilliantly Mark
1

2001-AL-CHEM 2

O
(ii)
O

COCl
(iii)

COOCOR
(iv) (v)
O OH
CO2CH3

OH Cl

Each: 1 mark

-------------------------------------------------- Take a break ----------------------------------------------------7. (b) Study the following information: Aromatic compounds T and U have the same molecular formula C10H12O.

T gives positive result in iodoform test. U reacts with hydrogen in the presence of a palladium catalyst to give compound V (C10H14O). obtained from the reaction of T with LiAlH4. V can also be

Treatment of U with ozone followed by acidified KMnO4 gives two products, one of which is benzoic acid. (i) (ii) Deduce the structures of T, U and V. For each compound, give all possible stereoisomers.

Suggest how infra-red spectroscopy can be used to distinguish between T and U.

Marking Scheme
7. (b) (i)

2001-AL-CHEM 2
T gives positive result in the iodoform test and has the structural characteristic

(9 marks) Mark 1

O C CH3 or

OH CHCH3
( marks for each characteristic.)

U reacts with H2-Pd U is an alkene / has a C=C group T can be reduced by LiAlH4 T is a ketone / has a C=O group Reaction of U with O3 following by KMnO4 gives benzoic acid. The double bond in U is adjacent to the benzene ring. Structures: (Four possible structures; 1 mark each for the 1 and 2 structures, and marks for each of the 3rd and 4th structures) T:
st nd

U:

OH *

1,1

V:

OH *
(two stereoisomers; marks for each structure)

NOTE:

Also accept the following structures for T, U and V:

(ii)

T has a sharp absorption peak in the wavenumber range from 1680 to 1750 cm-1 but U has not. U has a broad absorption peak in the wavenumber range from 3230 to 3670 cm-1 but T has not.

, , [9]

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AS/AL-CHEM (1997-2002)

Part XI

Chemistry of carbon compounds

2002-AL-CHEM 1
5. (a) Two acyclic structural isomeric compounds have the molecular formula C3H6O3. Both are optically active and have infrared absorptions at 3400 cm-1 and 1700 cm-1. Neither possesses an alkoxy group. (i) (ii) Draw the structure of each of the compounds. Label one of these structures A and the other B.

Suggest a chemical test, giving the expected observation, to distinguish between the compounds represented by A and B. Give the structure of the major organic product formed when the two compounds are treated separately with excess LiAlH4. Product from the compound represented by A Product from the compound represented by B

(iii)

(6 marks)

Marking Scheme
5. (a) (i)
CO 2H OH HO

2002-AL-CHEM 1
CHO OH

Mark
1,1

(ii)

Treat compounds with Na2CO3(aq). Only the carboxylic acid will give colourless gas bubbles, CO2(g). Treat compounds with 2,4-dinitrophenylhydrazine / Fehlings solution Only the aldehyde will give a yellow precipitate / red precipitate (Accept other tests for the carbonyl group and the corresponding expected observations)

1 1 (1) (1)

(iii)

product from the carboxylic acid OH

OH

product from the aldehyde OH

HO OH

1,1

[6]

-------------------------------------------------- Take a break ----------------------------------------------------5. (b) Suggest reagent(s) to accomplish each of the following single-step transformations:

O
(i)

OH

CH3C(CH2)4COCH3
CHO

CH3CH(CH2)4COCH3
CO 2H

(iii)

COCH3 OH
Marking Scheme
5. (b) (i) (iii)

COCH3 OH
2002-AL-CHEM 1
(3 marks) Mark 1 1

NaBH4

or

H2/Pt (Accept other correct answers.)

Cr2O72-/H3O+

3 marks 21

Exam Practice

Functional groups

Do Brilliantly

2002-AL-CHEM 2
5. (b) Suggest a synthetic route, in not more than four steps and using LiAlD4 or NaBD4 as a source of deuterium (isotope of hydrogen), for the following transformation.
OH D

Marking Scheme

2002-AL-CHEM 2

(4 marks) Mark

-------------------------------------------------- Take a break ----------------------------------------------------5. (c) Consider the substances listed below: butane ethanoic acid propanone benzoic acid hexane tetrachloromethane dichlorodifluoromethane polystyrene triethylamine

For each of the descriptions of physical properties from (i) to (viii) below, choose from the above list, one substance which best fits the description. (i) (ii) (iii) (iv) (v) (vi) (vii) (viii) a colourless, flammable gas a colourless liquid with a sour odour a colourless, water miscible, flammable liquid a colourless, non-flammable liquid a colourless liquid with a fishy smell a colourless, water immiscible, flammable liquid a white solid which is insoluble in both cold and hot water a white solid which is insoluble in cold water, but soluble in hot water (8 marks)
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AS/AL-CHEM (1997-2002)

Part XI

Chemistry of carbon compounds

Marking Scheme
5. (c) (i) (ii) (iii) (iv) (v) (vi) (vii) (viii)

2002-AL-CHEM 2 butane - a colourless, flammable gas ethanoic acid - a colourless liquid with a sour odour propanone / ethanoic acid - a colourless, water miscible, flammable liquid tetrachloromethane - a colourless, non-flammable liquid triethylamine - a colourless liquid with a fishy smell hexane - a colourless, water immiscible, flammable liquid polystyrene - a white solid which is insoluble in both cold and hot water benzoic acid - a white solid which is insoluble in cold water, but soluble in hot water

Mark
1 1 1 1 1 1 1 1 [8]

-------------------------------------------------- Take a break ----------------------------------------------------7. (b) For each of the following pairs of molecules, identify their relationship as identical, enantiomeric, geometrical isomeric or structural isomeric.

Marking Scheme
7.

2002-AL-CHEM 2

Mark

23

Exam Practice

Functional groups

Do Brilliantly

-------------------------------------------------- Take a break ----------------------------------------------------7. (c) A mixture of 2.8 g of butane-1,4-diol and 6.3 g of benzene-1,3-dicarbonyl chloride was heated at 215C for 30 minutes to give 6.4 g of a polymer M.

(i) (ii) (iii)

Draw the repeating unit of M. What type of polymerization is involved in the formation of M ? Calculate the percentage yield of M.

Marking Scheme
7.

2002-AL-CHEM 2

(5 marks) Mark

-------------------------------------------------- Take a break ----------------------------------------------------7. (d) Suggest a synthetic route, in not more than three steps, for the transformation of 3-methylbenzoic acid to N,N-diethyl-3-methylbenzamide, a substance commonly used in mosquito repellent.

Marking Scheme
7.

2002-AL-CHEM 2

(2 marks) Mark

24