2010 H2 Revision Package for BT2 Part 1 Solutions

A. Hybridisation
1 (a) A σ bond is formed from the end-on/head-on overlapping of orbitals.

A π bond is formed from the side-on overlapping of p-orbitals.

b)i) sp2 and sp3 hybridisation

H
ii)

H H
H
H H

8 σ bonds and 1 π bond

2
Carbon atom CX

Type of
hybridisation sp2

Description of One s and two p orbitals take part in the mixing process
hybridisation
Three sp2 hybridised orbitals are formed.

Carbon atom CY

Type of
hybridisation sp3

Description of One s and three p orbitals take part in the mixing process
hybridisation
Four sp3 hybridised orbitals are formed.

3 sp2: 5
 sp3: 3

4 i) sp2 hybridisation

ii) 120o

B. Explanation Based Questions

I Comparison of acidity and basicity

5 OH OH OH
TJC H3C CH3 O2N NO2
2006
< <
CH3 NO2
CH3 alkyl groups are electron donating groups which increases the strength of the O-H
bond hence a proton is lost less easily. Furthermore, the phenoxide ion (conjugate base)
is destabilised as the electron density on the O atom is increased.

NO2 groups are electron withdrawing groups which decreases the strength of the O-H
bond hence a proton is lost more easily. Furthermore, the phenoxide ion (conjugate
base) is stabilised as the electron density on the O atom is effectively dispersed.

6 (a) Lone pair of electrons on N atom interacts with the pi electrons of the adjacent C=O
RJC bond and the benzene ring. Thus, the lone pair of electrons are not available for
2006 coordination to a proton.

(b) The acidity of an acid is determined by the stability of the conjugate base (anion).
CH3COOH + H2O CH3COO- + H3O+ (eqm 1)

C6H5OH + H2O C 6 H5 O- + H3O+ (eqm 2)

In phenoxide ion, the negative charge is delocalised into the benzene ring, hence
stabilising the conjugate base.
 In CH3COO-, the negative charge on oxygen is delocalised into the two
electronegative O atoms resulting in a resonance effect. Thus, the ethanoate ions
are more resonance stabilised than the phenoxide ion.

Hence, the position of equilibrium 1 shifts more to the right to produce more H3O+
ions.
7
IJC
2007

8 Tertiary amines are less basic than primary amines due to the bulky substituents
NYJC hindering the formation of dative bond.
2008
The lone pair on N of the heterocyclic aromatic ring is found in sp2 orbital which is
planar with the aromatic ring. Hence it is not delocalised into the aromatic ring.

The lone pair on N of phenylamine is delocalised into the aromatic ring, hence
less available to accept protons.
9 CH2CH3
DHS
HOCH2CH2N CH2CH3
2008 (i)

CH2CH3
H2N COOH
HOCH2CH2N CH2CH3
(ii) is more basic than

Presence of electron–donating alkyl group increases the availability of lone pair of

electrons on the nitrogen atom for dative bonding with proton. The positive charge
on the conjugate acid is dispersed hence stabilising the cation relative to the base.

In 4–aminobenzoic acid, the lone pair of electrons on the nitrogen atom is

delocalised into the π electron cloud in benzene. This reduces the availability of
lone pair of electrons for dative bonding with proton, making it less basic.

10
TPJC NH2 < NH2 < CH2NH2
2007

CH3CO

The stronger the base, the larger the Kb value. Basicity depends on the
availability of the lone pair of electrons on N atom for donation to a proton.

II Comparison of ease of hydrolysis

11 Rate will increase when 2-iodobutane is used. C- I bond is weaker than the C – Cl bond
RJC due to less effective atomic orbital overlap in the former. Rate of reaction is dependant
2006 on the ease of breaking of the carbon – halogen bond.

12
HCI
2006
13 Iodocyclohexane is the most susceptible to hydrolysis as the C – I bond is weaker than
AJC the C – Cl bond in cyclohexane due to less effective atomic orbital overlap in the former
2001 (Iodine is bigger in atomic radius than chlorine). Hence the C-I bond is easier to break
than C-Cl bond.

In Chlorobenzene, the one pair of electrons on Cl is delocalised into the benzene ring as
the p orbitals of Cl overlaps with the pi electron system of the benzene ring. Hence, the
C-Cl bond is stronger and making the carbon of the C-Cl bond less electron deficient.
Hence, substitution is very difficult.

III. Nitrogen Compounds

14
15

16 (a) (i)
H
H2N C COOH
CH2COOH

(ii) Side chains of amino acid A are most likely to be involved.

An increase in pH causes –CH2COOH to be deprotonated to form –
CH2COOH + OH- à -CH2COO- + H2O

(iii) amino acid B: The side chain in B forms disulhide bridge, -CH2-S-S-CH2-

amino acid D: The side chain in D forms hydrogen bonding between –CH2OH and other
suitable R groups that are also capable to form hydrogen bonds (e.g.: -CH2OH or –
COOH).

(b)à Protein undergoes denaturation in which there is a major change in the secondary,
tertiary and quaternary structure of proteins.
à This is because during cooking, hydrogen bonds, electrostatic forces of attraction
and Van der Waals forces are disrupted by heat.
17

18
19 (a)

(b) β-pleated sheet consists of adjacent polypeptide strands stabilised by hydrogen

bonds between the backbone C=O group of one strand and the backbone N-H
group of the adjacent strand.

(c) Asparagine : Hydrogen bond; Glutamic acid : Ionic bond

(d) (i) (ii)

 (e)

Nucleophilic Substitution
H H H O

H C N C C OH

H CH3

20 (a)(i) Students can draw parallel or anti-parallel sheets.

Sketch showing
- Mirror image of pleated sheets, with C=O mirroring N-H
- Show and label hydrogen bonds
State
• R groups (side chains) project above or below the sheet and are 90º to the plane of
the pleated sheet.

(ii) In alkali medium, the some of the R groups are deprotonated which affect the
electrostatic interactions between them, causing unfolding of the protein
chain
(OR for mentioning the disruption of tertiary structure of protein)
(iii) leu-ser-pro-ala-asp

(iv)
 O O-Na
C O H
-
H H C H ONa+
-
H H C H ONa+
N C N C
H O H O
H H
asp residue ser residue

21 ai) CH3 O H
H2N CH C N CHCOOH
CH2

H N [1]
N
ii) H
H N CHCOOH
CH2

H2N CH C N [1]
CH3 O
N

b) Ala-His-His-Pro-Ser
ci) Hydrogen Bonding
O
C N
H
Diagram: [1]
O
C N
H

ii) At pH above and below 2, pepsin has denatured as the side chain groups with opposite
charges / the ionic interaction between the side chain residues of the amino acids are
broken which disrupts the tertiary structure / causes unfolding of the polypeptide
chain.

C. Distinguishing Test Questions

2
2

2 (i)
3

(ii)

(iii)

2 A and B
Reagent Solid sodium carbonate / PCl3
4
Condition Room Temperature
Observations Effervescence is observed in B which will form a white ppt in
limewater when the gas evolved is bubbled through. No
 effervescence is observed in A and no white ppt is formed with
limewater. / White fumes are evolved in B while A will have not
form white fumes.

B and C
Reagent Solid sodium carbonate
Condition Room Temperature
Observations Effervescence is observed in B which will form a white ppt in
limewater when the gas evolved is bubbled through. No
effervescence is observed in B and no white ppt is formed with
limewater.

A and C
Reagent NaOH (aq), followed by HNO3 (aq) and AgNO3 (aq)
Condition Heat
Observations White ppt observed in A whilst C has no white ppt formed.

2 (i) Left (A), Right (B)

Reagent NaOH (aq)
5
Condition Heat
Observations Pungent gas evolved in A that will turn moist red litmus paper
blue while B will has no effect on moist red litmus paper.
White ppt formed in A while B has not white ppt formed
(Benzoic acid is a white ppt).

(ii) Left (A), Right (B)

Reagent I2, NaOH (aq)
Condition Heat
Observations Yellow ppt formed in A while no yellow ppt formed in B.

(iii) Left (A), Right (B)

Reagent NaOH (aq)
Condition Heat
Observations Pungent gas evolved in A that will turn moist red litmus paper
blue while B will has no effect on moist red litmus paper.

(iv) Left (A), Right (B)

Reagent KMnO4 (aq) followed by I2, NaOH (aq)
Condition Acidified and Heat followed by heat
 Observations Both A and B will decolourise purple KMnO4 (aq) (double bond
is cleaved). On reaction with I2 / NaOH, yellow ppt is observed
in A but no yellow ppt formed with B.

(v) Left (A), Right (B)

Reagent KMnO4 (aq)
Condition Acidified and Heat.
Observations B will decolourise purple KMnO4 (aq) but purple KMnO4 (aq)
remains with A.
(vi) Left (A), Right (B)
Reagent H2O
Condition Cold
Observations A will form white fumes while B does not form white fumes

2 A: C6H5CH(OH)CH3 and B: phenylethanone

Reagent I2 / NaOH (aq)
6
Condition Heat
Observations Both A and B will form yellow ppt. (Iodoform test)

A: C6H5CH(OH)CH3 and B: phenylethanone

Reagent 2,4 dinitrophenylhydrazine
Condition Heat
Observations Orange ppt formed in phenylethanone whilst no orange ppt in A.

2
(a) Phenol and benzoic acid can both react with NaOH (aq) whilst Phenylmethanol and
7
cyclohexanol cant.
OH O-Na+
+ NaOH
+ H 2O

COOH COO-Na+
+ NaOH
+ H 2O

(b) A: phenol and B: benzoic acid

Reagent Solid sodium carbonate / aqueous bromine
Condition Room temperature
Observations Effervescence is observed in B which will form a white ppt in
limewater when the gas evolved is bubbled through. A will not
form effervescene and no white ppt formed in limewater. /
Brown bromine decolourises and white ppt formed in A while
brown colour remains in B.
 Br
OH OH
+ 3Br2(aq)
+ 3HBr
Br Br
white ppt
COOH COO-Na+
+ Na2CO3 2 + H2O + CO2

CO2 + Ca(OH)2 CaCO3 (s) + H2O

white ppt

A: phenylmethanol and B: cyclohexanol

Reagent K2Cr2O7 or KMnO4
Condition Acidified and Heat
Observations Both A and B will turn orange dichromate to green. However, A
will give a white ppt but B does not.
OH O

CH2OH COOH

NO2
NH=NH2
O NO2 N=N
+ + H2O

NO2
NO2
Orange ppt
2
8
2
9

3
0

3
1
3 (a)
2

(b)

(c) Add aqeous bromine at room temperature. Compound A decolourises brown bromine water
with the formation of a white ppt whilst Compound A does not decolourise brown bromine water
and white ppt is not formed.

(d)
3 Test:
Add KMnO4 in H2SO4(aq) to both compounds separately and heat. To the oxidised products,
3
add 2,4-DNPH and warm.

A: orange ppt
B: no ppt

Alternative:
(1)Use alkaline aqueous iodine, warm.
(2)Cold alkaline KMnO4, followed by Cr2O72-
(3)H3PO4, 300oC, 70atm, followed by Cr2O72-
(4)KMnO4 in H2SO4, passed CO2 gas produced into Ca(OH)2(aq), white ppt for A.
3 Reagent(s) and Condition(s): ………… Na metal …………………...
Observations for :
4
Compound Y: …… no effervescence observed.
Compound X: …… effervescence of hydrogen gas observed and it will extinguished burning
splint with a ‘pop’ sound.…………
3 (i) Use aq I2, aq NaOH, warm.
CCl3CH2COCH3: Yellow ppt formed. CCl3COCH2CH3: No ppt formed.
5
(ii) Use alcoholic AgNO3 or silver ethanoate, warm. (Aqueous AgNO3 not allowed)
CH3 CH2Cl
Cl

No ppt formed. : White ppt (of AgCl) formed

3 Add aq Br2 to both compounds separately.
salicylic acid: reddish brown aq Br2 will decolourise.
6
aspirin: reddish brown aq Br2 will not decolourise.
3 Add dilute HCl(aq) and heat each mixture.
Add excess NaOH(aq) followed by I2(aq) to each mixture and heat .
7
For G, a yellow ppt of CHI3 is formed.
For H, no yellow ppt of CHI3 is formed.

O O
CH3 - +
CH 2 O CH 2 C O Na
O C
C C C CH 2 C
CH 2 + 4 I2 + 7NaOH C IH3 + 5 N I a + + 6H 2O
H - +
OH HO O Na O

3 (i) Add Tollens’ reagent to both compounds separately with warming.

For the 1st compound (aldehyde), there would be a silver mirror formed.
8
For the 2nd compound, there would be no silver mirror formed.

(ii) First, add dil H2SO4 (aq) to both compounds separately, and heat.
Then, cool and add aqueous bromine to both samples.

For the 1st compound, the reddish-brown bromine remains, with the absence of the
formation of any ppt.
For the 2nd compound, there would be a decolourisation of reddish-brown bromine,
with the formation of a white ppt.
Or
Add K2Cr2O7 (aq), dil H2SO4, heat
For the 1st compound, orange solution turns green.
For the 2nd compound, orange solution does not turn green.

3 (a)
To each compound in separate test tubes, add NaOH(aq) and heat. Add Br2(aq) after cooling the
9
mixture.
The test-tube containing A will decolourise reddish brown aqueous bromine with the formation
of a white precipitate. Reddish brown aqueous bromine remains for test tube containing B.
 NHCOCH2CH3 NH2

H3C H3C

+ NaOH(aq) + CH 3CH2COO-Na+

CH3 CH3

NH2 NH2

H3C H3C Br

+ Br2(aq) + HBr

CH3 CH3

(b)
To each compound in separate test tubes, add 2,4-dinitrophenylhydrazine.

An orange precipitate will form in test-tube containing D and no precipitate observed for test
tube containing C.

H
H N H
O N H
N N NO2
NO2

+ + H 2O
NH
N
NO2 H NO2

D. Structure Elucidation Questions

40 a) A is
CH3

CH3C CHCH2CH3

b) CH3 CO2H CO2CH3

CH3 CO2H CO2CH3

B C D
(Note: The positions of the side chains does not matter.)
Since C reacts with methanol and hot conc. H2SO4 to give D which has sweet smell, D must
be an ester and C must contain COOH.

c) E is CH3CONH2
Since E is neutral and has no reaction with aq alkali, it is not amine.
 d) F is

H3CCONH

Since upon hydrolysis, the compound C6H7N gives a white ppt with aq Br2, it must be
phenylamine.

e) G is cyclohexane

Since G does not react with Br2 in CCl4, it must not contain any C=C.

41 i) A solution of H turns damp blue litmus paper red  H is acidic, either RCOOH or phenol is
present.
H gives a yellow ppt. with iodoform test  H contains methyl carbonyl.

H is
CH3
O

HO CH2CCH3 or HO COCH3

ii) When PCl5 is added to J, dense white fumes were observed  J contains -COOH or

–OH, but not phenol

J forms a silver mirror with ammonical silver nitrate  J contains aldehye

J does not form any ppt. when Fehling’s solution  J is a benzaldehyde
J does not form a yellow ppt. with aq. alkaline iodine  J does not contain methyl carbonyl
gp or methyl alcohol gp.

J is
O

HC CH2CH2OH

42 i) Alcoholic sodium hydroxide and reflux/heat.

ii) D B
 H H H H H H H

H C C C C CH3 H C C C C CH3

CH3 H H CH3 H
Or

H CH3 H H CH 3 H H

H C C C C CH3 H C C C C CH 3

H H H H H
D B

iii) C

Br H H Br Br H Br H

H C C C C CH3 H C C C C CH3

H H CH 3 H H H CH3 H

H Br Br H H Br H Br

H C C C C CH3 H C C C C CH3
any two
H H CH3 H H H CH3 H
Or

Br CH 3 H Br Br CH3 Br H

H C C C C CH3 H C C C C CH3

H H H H H H H H

H Br Br H H Br H Br

H C C C C CH3 H C C C C CH3
any two
H CH3 H H H CH3 H H

43 a) A has chiral carbon as it can rotate plane-polarised light.

A contains alcohol / carboxylic acid as it reacts with PCl5.
Since there are two Cl atoms in B, there must be two OH groups in A that are substituted.
Since B reacts with water to give C, losing one Cl atom, there must be an acid chloride in B,
hence A must contain one carboxylic acid and one alcohol.
 H H H

PCl5 H2O KCN(alc)

C C C
H3C COOH H3C COCl H3C COOH
OH Cl Cl
A B C

H H
+
dil. H
C C
boil H3C COOH
H3C COOH
CN COOH
D E

Conversion of C to D
Nucleophilic substitution
H H
slow + Cl-
C C
H3 C COOH H3 C COOH
Cl

H H

C f ast
C
H3 C COOH H3 C COOH
CN
CN-
b) Optical isomerism: Non superimposable mirror images which rotate plane-polarised light.
CH3 CH3

C C
H H OH
HO HOOC
COOH

44 a)
Atom C H O
35.8/12 4.5/1 59.7/16
Mole ratio 2.98 4.5 3.73
1 1.5 1.25
4 6 5

E.F. = C4H6O5

b) The formula of B shows it contains five O. B besides being is a diacid, must contain ether or
alcohol.
Since B is a diacid, it reacts with ethanol to form diester with eight carbon atoms, B must
have started with 4 carbon.

Since compound C reacts with sodium metal producing H2, it must contain –OH group.
Hence B is a diacid + alcohol.
 D must be a ketone since it gives positive test with 2,4-DNPH but negative test with
Fehling’s solution or Tollens’ reagent.

C must contain secondary alcohol which is oxidized to ketone in D.

c. H+ C
Na
H2
B C must have an OH group
C2H5OH diester
diacid

2,4-DNPH Orange ppt D is a carbonyl

D

Tollen's and Fehling's

N.R. D is not an aldehyde but a ketone

O H H O O H H O

HO C C C C OH H3CH2CO C C C C OCH2CH3

OH H OH H
B C

O H O

H3CH2CO C C C C OCH2CH3

O H
D

45 ai) H H H CH3

C C C C

CH3 H

K L

H H H H H H

C C C H C C C H

H OH H H

J M K and L are interchangeable

aii) K & L exhibit geometric/cis-trans isomerism.

K , L and M exhibit structural/positional isomerism.

 b) Electrophilic addition
As bromine molecule approaches the π electrons in the C = C bond, it becomes polarised.
δ
The Br + atom acts as an electrophile and adds to one of the C atoms forming a
carbocation intermediate which then attracts the Br- ion forming the product

c) Diol product is formed. Purple manganate(VII) solution is decolourised, brown MnO2 ppt is

formed.

H H

C C CH3

OH OH

46 ai) Carbonyl compound

aii) Aliphatic aldehyde
aiii) –OH group in alcohol and carboxylic acid (not phenol)

bi) Q is
H

C O
C
C
C H
O H H H
H
H H
Displayed formula ≡ Full structural formula

ci) Orange or brown Br2(aq) is decolourised, steamy fumes evolved and white ppt. formed.
 cii) H

Br C O
C
C
C H
O H H H
H
H H
Br
ciii) Electrophilic substitution

47 ai)
Atom C H O
Mole ratio 40.0/12 6.65/1 53.3/16
1 2 1

E.F. = CH2O

b) i) A contains chiral carbon present

ii) A is acidic, contains carboxylic acid
iii) A contains
H

CH3 C or CH 3 C

O OH
group

c) H

H C H

C O
HO C
H
O
H

d) H O O

H C C C O H

e) Ester functional group present

O

H
C
O
C H
H3C
C
O
C CH3

f) Ethanamide, CH3CONH2(s) and ammonium ethanoate, CH3CO2NH4(s)

 Dissolve the unknown solids in deionised water respectively.
Add neutral FeCl3 solution to each solution in a test tube followed by boiling.
The test tube which shows red colouration followed by brown precipitate on boiling is
ammonium ethanoate, CH3CO2NH4.
The test tube which shows no visible reaction is ethanamide, CH3CONH2.
Cl
48 ai)

H3CH2C OH

Cl

aii) F would be more acidic than phenol because the two electron-withdrawing Cl atoms
stabilise the phenoxide ion formed. They do this by drawing the electrons from the oxygen
atom of the phenoxide ion into the delocalised π electron system in the benzene ring. This
makes the O—H bond more polar (weaken O- H bond) and easier to donate a proton and
hence the acid strength increases.
bi) Since G reacts with NaOH(aq) losing both Cl atoms to form H, it must have hydrolysed and
hence the two Cl atoms must be on aliphatic chain (not on benzene ring).
J is insoluble in water but it dissolves in NaOH(aq)  J must be acidic, still contains phenol.
J reacts with 2,4-dinitrophenylhydrazine and with alkaline aqueous iodine, but not with
CH3 C
Fehling’s solution  J is a methyl ketone or contain
O

Cl OH
aq. NaOH -H 2O
H3C C OH H H3C C OH H3 C C OH J

G O
Cl OH

bii) Cl2, u.v. light

49 F is insoluble in water, but dissolves in NaOH(aq)  F contains phenol

F reacts with 2,4-dinitrophenylhydrazine but not with Fehling’s solution  F contains ketone or
benzaldehyde
With bromine water, F gives G, C8H6O2Br2 (disubstitution)  F contains phenol and has one of
the positions 2 or 4 occupied.
F reacts positively with iodoform test to give H, C7H6O3  F has methyl cabonyl group, CH3CO-
H dissolves in both NaOH(aq) and Na2CO3(aq)  H contains carboxylic acid
 Br

OH
OH OH

O
CH3 CH3 H
C
C Br C

O
F O G O H

OH OH

OH O-Na+ 2,4-DNPH
aq NaOH
CH3 CH3
CH3 C C O2N
CH3
C C
O N
O
O F N NO2
F H

Br

OH OH OH
OH
aq I2, NaOH,
aq Br2
followed by H+ H
CH3 G CH3 OH
CH3
Br C C C
C

O O O
O
F F

OH O-Na+
aq NaOH or
H
aq Na2CO3
OH O-N a+
C C

O O
H

OH O-Na+ OH

hot H2SO4
NaOH(aq)
CO2CH3 COO- Na+ COOH
J
+ CH3OH

50 K is not very soluble in water, but dissolves in HCl(aq)  K is basic, contains an amine.
K dissolves in NaOH(aq), but not in Na2CO3(aq)  K is acidic, it contains phenol but not
carboxylic acid.
L is no longer soluble in HCl(aq), but is still soluble in NaOH(aq)  L is no longer basic, but is still
acidic, the phenolic group is still present.
N reacts with bromine water with 2 Br substituted  L is phenolic and has its 2 or 4 position
occupied.
N is not soluble in either HCl(aq) or NaOH(aq)  N is neutral, amine and phenol is no longer
present.
 OH OH OH
Nitration Reduction

NO2 NH2

K
Br

OH OH
bromination
K + CH3COCl

NHCOCH3 Br NHCOCH3

L M

OH OCOCH 3

+ 2CH3COCl

NH2 NHCOCH3

K N
51 H, J, K and L all show positive reactions with Na  All four contain OH gp
K reacts with NaOH: K is a phenol or is acidic
K reacts with Br2(aq): K contains a phenol.
K & L have no reaction with acidified K2Cr2O7: K & L are neither 10 ROH nor 20ROH, could be 30
ROH
H reacts with acidified K2Cr2O7 to give M (C9H10O2): 10 ROH oxidised to acid
J reacts with acidified K2Cr2O7 to give N (C9H10O): 20 ROH oxidised to ketone
+ve reaction of J & I2/OH-: J has CH3CH(OH)- gp.
H, J, & L have side-chain alkyl gp oxidised by hot alkaline MnO4-
CO2H CO2H

H3C CH3 HO2C CO2H

H P

OH

H3C C H CO2H

CH3 CO2H

J Q
 CH3

H3C C OH CO2H

L R

CH3

H3C CH3 CH2CH2CH3

OR

OH OH

K
52 bi) No. of moles of NaOH = 0.1 x 6.85/1000 = 6.85 x 10-4 mol
Z is a monobasic acid.
No. of moles of Z = 6.85 x 10-4 mol
Mr of Z = (1.0 x 25/250) / 6.85 x 10-4 = 146
If Z is RR’C(OH)CO2H
C(OH)CO2H has Mr of 74, so R + R’ has Mr of 146 – 74 = 72
R and R’ could be C5H11/H or C4H9/CH3 or C3H7/C2H5

bii) [H+] = 10-2.73 = 0.00186 mol dm-3

[Z] = 6.85 x 10-4 x 1000/25 = 0.0274 mol dm-3
[H + ] 2 (0.00186) 2
Ka = = = 1.26 x 10-4 mol dm-3
[Z] 0.0274

biii) X is chiral  X contains a C atom joined to 4 different groups/atoms

X has no reaction with Na  X has no –OH group (or not alcohol or acid)
X has no reaction with Fehling’s solution  X is not an aldehyde
X forms ppt. with 2, 4-DNPH  X must be a ketone
X forms yellow ppt. with I2/OH-  X contains CH3CO- group
Since X is chiral and it contains CH3CO-, X must be
H O

H3C C C CH3
*
H3CH2C and
X
 H OH H OH

H3C C C CH3 H3C C C CH3

* * * *
H3CH2C CN H3CH2C COOH
53 i) Since D is basic,
Y D must contain an amine group. Z
NH2
Since D forms a white ppt. With Br2(aq), D must be phenylamine,

G + OH- à D

NH3+
∴ G must be an ammonium salt:

ii) OH-(aq)
CH3CH2CN H
heat
∴ H must be CH3CH2COO-

I2(aq)/OH
E CHI3 + H
∴ E must be CH3CH2COCH3

iii) No. of moles of NaOH = 0.50 x 20/1000 = 0.01 mol

0.693
No. of moles of F = 0.005 mol
138.5

No. of moles of NaOH = 0.01 = 2

No. of moles of F 0.005 1

∴ F must be a dibasic acid.

Since B à E + F + G
B = C13H16NOCl, E = CH3CH2COCH3, G = C6H5-NH3+, (E + G: 9 carbon atoms)
F must contains the 4 carbon atoms with 2 COOH groups According to the Mr of F = 138.5.
H

HOOC C COOH

F must be
Cl
iv) B à CH3CH2COCH3 + HOOC – CHCl – COOH + C6H5-NH3+
B is
 H H CH3 H H O H

H C C C C C C N

H H Cl

v)
NH2
B undergoes alkaline hydrolysis to form C and

C is
H H CH3 H H O

H C C C C C C O-Na

H H OH

54 a) Since mole ratio of C:H in Z ≈ 1:1, Z contains benzene ring.

NH2
Since Z is soluble in HCl  Z contains

Since Z reacts with Br2(aq)  C6H5NH2 is confirmed.

Z is either
NH2 NH2

or R

R
Z + fuming H2SO4 + H2O  X + Y
optically active optically inactive
+ve iodoform test

X
Y + MnO4-/H+  A, C7H8O2N
Z heat

X, Y & Z must have the same C number.

A is
 NH3+ NH3+

Not COOH
[see eq. (i) below]

COOH

NH2 NH2 NH2

CHOH(CH3) CH2CH2OH CH=CH2

X Y Z

i) NH2 Br NH2

H
CH=CH2 + 2Br2(aq) C CH2 + 3HBr

OH Br
Br
ii) NH2 NH2

CHOH(CH3) + 4I2 + 6NaOH COO-Na+ + CHI3 + 5NaI

+ 5H 2O

iii)
NH2 NH3 +

CH 2CH 2OH + 5[O] + H + COOH + CO2 + 2H2O

55 a)
heat
Q (C5H12O2 )
∴PP(C H11
is 5an BrO)
alkyl + NaOH(aq)
bromide that undergoes alkaline hydrolysis to give an alcohol group in Q.
acidified K2Cr2O7
Q R
∴ Q contains an aldehyde group or 10 or 20 alcohol which undergoes oxidation by Cr2O72-.

R reacts with alkaline iodine to form yellow precipitate.

R must contain CH3CO - group which gives a positive test with iodoform test.
 R + PCl5 à dense white fumes
R must have a 30 alcohol since it has already been oxidised.
∴ Q must contain 20 and 30 alcohols.

KOH(alc.) heat
P S (C5H10O)
- +
MnO4 /N
S CO2 S has a terminal alkene group

CH3 CH3 CH3 CH3

H3C C C Br H3C C C OH

OH H OH H
P Q

CH3 O CH3

H3C C C CH3 H3C C C CH2

OH OH H

R S
i)
CH3 O CH3

H3C C C CH3 + 3I2 + 4NaOH H3C C COO-Na+ + CHI3 +3NaI + 3H 2O

OH OH
ii) CH3 O CH3 O

H3C C C CH3 + PCl5 H3C C C CH3 + POCl5 + HCl

OH Cl

56 a) Since Q has a positive iodoform test and negative test with Tollen’s reagent, Q must be
contain

OH O

R C CH3 Or R C CH3

H
Since Q can be oxidised, Q is not a ketone and thus a methyl alcohol.
Q is CH3CH2CH(OH)CH3
CH3CH2CH(OH)CH3 + 3I2 + 4NaOH à CH3CH2COO-Na+ + CHI3 + 3NaI + 3H2O
 b) Dehydration

c) H H O H H H CH3

H C C C CH3 C C C C

H H H3 C CH3 H3C H

R S T

H H H H H

H C COOH C C H C C COOH

H H CH2CH3
H H
V U W
d) Electrophilic addition
As bromine molecule approaches the π electrons in the C = C bond, it becomes polarised.
δ
The Br + atom acts as an electrophile and adds to one of the C atoms forming a
carbocation intermediate which then attracts the Br- ion forming the product

57 i) Since J reacts with aqueous Cl2 forming K with 3 H substituted by 3 Cl, J must be contain a
phenol with 2,4 and 6 positions unoccupied.
J undergoes monosubstitution with Cl2 in CCl4 forming L,
Since J contains 7 carbon and besides phenolic group, J must contain an aldehyde
substituted on 3 position.
J contains aldehyde which undergoes reduction with LiAlH4 in dry ether to give a primary
alcohol which will react with PCl5 to give an alkyl halide.
Since L does not undergo substitution with NH3 while M does, Cl in L will be on the ring
while Cl in M is on aliphatic chain.
 ii) K is acidic as the conjugate base formed is stabilized when the lone pair electrons on
oxygen delocalised into the benzene ring.
Furthermore, the 4 substituted groups on the ring are all electron withdrawing, further
enhancing the stability of the conjugate base.

iii) The Cl in M pulls electrons away from the C bonded making the C electron deficient and
hence attracts the lone pair electrons on NH3. Cl then leaves and nucleophilic substitution
occurs.

The lone pair electrons on Cl in L delocalized into the benzeme ring, hence strengthening
the C – Cl bond. Cl does not leave easily and hence substitution by NH3 is difficult and only
occurs under harsh conditions (high P)

58 i)
Atom C H O
32/12 4/1 64/16
Mole ratio 2 3 3
Empirical formula. = C2H3O3
Since molar mass of P is 150 g mol-1, let molecular formula of P be (C2H3O3)n
(12x2+3+16x3) n = 150
n=2
Molecular formula = C4H6O6
ii)
Since P with 4 carbon, undergoes esterification with ethanol forming Q with 8 carbon, there
should be two COOH groups in P.

Since Q is oxidisable by Cr2O72- to give R, which reacts with 2,4 DNPH to give orange ppt, Q
should contain 2o alcohol to give carbonyl. Since R has no reaction with Tollen’s reagent, R
should not contain aldehyde.

Since Q evolves 2 moles of HCl with PCl5 to form S, Q contains 2 alcohol groups.
Since S reacts with ethanolic KOH to give product which reacts with 2 moles of H2 during
hydrogenation, the product must have two C=C double bonds and hence S must contain 2
Cl groups which can undergo elimination.

OH OH OH OH
conc H2SO4
HOOC C C COOH + 2C 2H5OH C2H5OOC C C COOC2H5
reflux
H H H H
P Q
OH OH O O
K2Cr2O7/H+
C2H5OOC C C COOC2H5 + 2[O] C2H5OOC C C COOC2H5
reflux
+ 2H 2O
H H
Q R
O2N

O O

C2H5OOC C C COOC2H5 + 2 H2NHN NO2

R

NO2
O2N

O2N NH H
N NO2
N N
+ 2H2O
C2H5OOC C C COOC2H5
 OH OH Cl Cl

C2H5OOC C C COOC2H5 + 2PCl5 C2H5OOC C C COOC2H5

+ 2POCl3 + 2HCl
H H H H
Q S

Cl Cl
KOH(alc)
C2H5OOC C C COOC2H5 C2H5OOC C C COOC2H5

H H
S

H H
Ni
C2H5OOC C C COOC2H5 + 2H2 C2H5OOC C C COOC2H5
iii) T
H H
59
60
O CH 3

H3 C O
O CH3

CH 3 O
Compound A
 H
O O

H 3C OH
OH
HCompound
3C B H3 C CH3 HO
Compound C
O
Compound D

H CH3 O

HCl Compound F
Compound E H H Compound G
H3 C OH

NH 2
Compound
H 3C H Compound I
Cl H3 C
H
Each structure carries 1 mark; total [9] ; max [8]

• A must be an ester which undergoes alkaline hydrolysis with aqq NaOH to give carboxylate
salt and alcohol.
• B must be the alcohol and since it is positive towards iodoform test, it must contain methyl
alcohol CH3CHOH-
• B is oxidized by Cr2O72- producing C. B must be a 2o alcohol CH3RCHOH which is oxidized to
C which contains ketone which reacts with 2,4 DNPH
• is can be oxidized to a carbonyl, B is a secondary alcohol with CH3RCHOH
• D is ethanedioic acid since it is oxidized to CO2 and H2O by MnO4-.
• D contains COOH which is converted to acid chloride with PCl5, forming HCl fumes E.
• B undergoes dehydration to form F which contains C=C.
• Vigorous oxidation of F brings about the double bond cleavage to form acid G.
• Reduction of acid G by LiAlH4 produce a primary alcohol, which undergoes substitution with
SOCl2 to form alkyl halide H.
• Alkyl halide H undergoes nucelophilic substitution with alcoholic KCN to form a nitrile, which is
reduced to give an amine I.
61 ● mole ratio of C:H ratio ≈ 1:1 in X => X probably contains benzene ring

● X contains 3 O atoms but is neutral => X does not contain phenol or carboxylic acid
groups

● X does not react with 2,4 DNPH => X is not a carbonyl compound

● X does not react with Br2 dissolved in CCl4 => it does not contain an alkene group

● Since X gives two products when it is oxidized under acidic conditions, but is not an
alkene, it must have an ester linkage (heating with acid produces benzoic acid and
alcohol, but the alcohol is further oxidized to a carboxylic acid)

● Y has positive tri-iodoform test and is a product of oxidation => Y has a methyl
carbonyl group,

CH3 C
● Y reacts with Na2CO3 to give CO2 gas => Y has –COOH group
O
● Y is

CH 3 C C
● Since one of the products
OH is benzoic acid,
X must be
O

H H

C O C C CH3

O H OH
62
C H
% mass 44
Ar 12
No. of mol 3.67
Mole ratio 5 9
Information given
1 % composition of each
given elements in G
2 G is soluble in aq NaOH,
3 When G is heated with aq
NaOH followed by addition of
aq HCl, H, C5H10O3 is
obtained.
4 H gives a positive iodoform
test.
5 H when refluxed with conc
H2SO4, give J which is a
sweet smelling liquid.
Cl O
6.6 26 23.4
1 35.5 16
6.6 0.732 1.46
1 2
Deduction
G has empirical formula of C5H9ClO2
G has molecular formula C5H9ClO2
G contains –COOH group.
(Phenol is not possible as only 5 C is present)
Note: When no heating is involved for addition of
acid/alkali, its purpose is to test for presence of
basic/acidic/neutral compound)
G, contains alkyl halide, undergoes nucleophilic
substitution with aq NaOH to give H.with alcohol.
H has a CH3CH(OH)- structure.
J is an ester / H undergoes internal
esterification, hence H must contain both –
COOH and –OH group.

6 H also forms K when refluxed H undergoes elimination or dehydration to form

with conc H2SO4.
7 K exhibits cis-trans.
8 Since K reacts with bromine
to give on a product with Br
on adjacent C atoms,.
9 K reacts with acidified KMnO4
forming L, C3H4O4.
K.
K must contain C=C with each C bonded to
different atoms or groups of atoms.
K must contain C=C which undergo electrophilic
addition with Br2.
K undergoes strong oxidation, C=C is cleaved.

Structure of K (pt no 8) is

H3C
Therefore C CH
structure of H (ptCH C 4) and
no2 5 and OH L (pt no 9) are
H
K

OH O O O

H3C C CH2 CH2 C OH HO C CH2 C OH

H
H L
 Structure of G (pt no 3) is Structure of J (pt no 6) is

Cl O H3C
O

H3C C CH2 CH2 C OH O

Explanations
H required are:
• Functional group
G possible for such reaction or any unique structure is present
• Type of reaction undergone
• Whether acid/basic/neutral compound is present
• Write balanced equations if asked by the question.

63 C H O
% mass 49.3 6.85 43.85
Ar 12 1 16
No. of mol 4.108 6.85 2.741
Mole ratio 1.5 2.5 1
3 5 2

Empirical formula of P: C3H5O2

 P undergoes basic hydrolysis with hot, aqueous sodium hydroxide to form Q and
sodium ethanoate.
⇒ P is an ester
⇒ Q is an alcohol

 Q undergoes nucleophilic substitution with HCl and ZnCl2 to form R.

⇒ Q is an alcohol
⇒ R is a halogenoalkane / chloroalkane

 R undergoes nucleophilic substitution with ethanolic KCN to form S.

⇒ S is a nitrile

 S undergoes acid hydrolysis with aq. HCl to form T.

⇒ T is a carboxylic acid

 T is optically inactive
⇒ T does not contain a chiral carbon.

 U undergoes electrophilic addition with aq. bromine.

⇒ U is an alkene / contains C=C bond
 • T undergoes oxidation to form V
⇒ T contains an –OH group
⇒ V is a carboxylic acid

Structures (displayed formula not required):

O O
H 3C C O CH2 CH2 O C CH3
P:

HO CH2 CH2 OH HO CH2 CH2 Cl

Q: R:

HO CH2 CH2 CN HO CH2 CH2 COOH

S: T:

CH2 CH COOH HOOC CH2 COOH

U: V:

64 ● Mole ratio of C:H ratio ≈ 1:1 in A => A probably contains benzene ring

● A undergoes elimination with ethanolic NaOH forming B which decolourises aq

Br2 => A probably contains alkyl halide
=> B probably contains C = C

● A contains alkyl halide which undergoes nucleophilic substitution with aq NaOH

forming C, which contains alcohol and undergoes dehydration easily to form D.

● D gives orange ppt with 2,4 DNPH => D contains carbonyl

● A undergoes oxidation with MnO4- forming E with two O, very likely side chain
oxidation occurs to A, forming benzoic acid in E.

Cl

CCl2CH3 C CH2

CH3
A is (CH3 can be anywhere on ring) B is

CH3
 COCH3 CCl2CH3

CH3 COOH
D is E is
65 • R has a C=C. On vig oxidation, 2C must have been converted to CO2
• S has a carboxyl fg (reaction with NaHCO3) and a ketone with the group CH3CO
• R to T is a nucleophilic substitution ( note same no. of H-atoms)
• T is reduced to U, a saturated amine
• V is a salt from neutralistion with HCl
• T is hydrolysed to a diacid.

R S
H3C
H3C CH2Cl C O
C C
CH2
CI(CH2)2 H HOOC

U
T
CH3 H
H3C CH2CN H C C (CH2)2NH2
C C
( CH2 )3 H
CN(CH2)2 H
NH2

V W
CH3 H
H C C (CH2)2NH3 Cl

( CH2 )3 H

NH3 Cl

H3C CH2COOH
C C
HOOC(CH2)2 H
(c)
H3C CH2Cl
(ii)
C C H3C
C O
CI(CH2)2 H
CH2
HOOC

+ 3OH- + 4[O]
+H+

+2CO2 + 2H2O + 2Cl-

H3C CH2CN
C C
CN(CH2)2 H

+ 2NH4+
CH2COOH
+ 2H+ + 4H2O H3C
66 C C
HOOC(CH2)2 H

67 (a)
Mole ratio of C to H to N in compound Q
= 61.0/12.0 15.3/1.0 23.7/14.0
= 5.08 15.3 1.7
= 3 9 1

Hence the empirical formula of Q is C3H9N.

 The Mr of Q is 59.
Let Q be (C3H9N)n. Then Mr of Q = (3n)(12.0) + (9n)(1.0) + (n)(14.0) = 59
59n = 59 i.e. n = 1
Hence the molecular formula of Q is C3H9N.

(b)

Description Deductions
P, C15H20O3NCl 6 degrees of unsaturation / high C:H ratio.
Benzene ring may be present since P has at least 6 C atoms
P is neutral compound Amines, carboxylic acids, phenols absent OR amides, esters
present
Q reacted with excess T is a quarternary ammonium iodide OR quarternary
iodomethane to give T (Mr = ammonium salt
−
229). T can be [CH3CH2CH2N(CH3)3]+I
T gives a yellow precipitate with T has Mr = (6)(12.0)+(16)(1.0)+(1)(14.0)+127 = 229 which agrees
aqueous silver nitrate. Q is with the given value (show working) OR
straight−chain. Since Mr of T is 229, three −CH3 groups must be substituted on Q
(show working : 229−127−57 = 45 = 3 x 15)
Hence Q is a primary amine
Since Q is a straight−chain amine, Q can be CH3CH2CH2NH2.

R on acidification yields U, R is the sodium carboxylate

which is also obtained from
acidic hydrolysis of P.
U reacts with a small amount of
concentrated sulphuric acid to
give γ-butyrolactone
S (C8H7O3Na), reacts with
acidified potassium
dichromate(VI) and heating with
immediate distillation, to give
V.
Treating V with 2,4-DNPH gives
an orange precipitate which has Since V is obtained from (controlled) oxidation of S
the following structure:
U is a carboxylic acid
U undergoes esterification (or intra-esterification)
U must be a hydroxy acid
U must be HO2C−CH2CH2CH2OH
−
R must be Na+ O2C−CH2CH2CH2OH
Since V undergoes condensation with 2,4−DNPH to give the
hydrazone,
V must be an aldehyde with the structure
HOOC CHO
S must be a primary alcohol with the structure

H H O
O 2N N N C COOH
Na+O- C CH2OH
NO2

When P is refluxed with aqueous P undergoes alkaline hydrolysis of the ester and amide groups
sodium hydroxide, three and nucleophilic substitution of the Cl.
compounds Q, R and S are P must be an ester, amide and chloroalkane.
obtained. O O
CH3CH2CH2 N C CH2CH2CH2O C CH2Cl
P:
H
68
• V has a high C:H ratio, it is likely to contain a benzene ring.

• V does not dissolve in NaOH, hence it is not acidic (It does not contain a carboxyl group or a
phenol group).

• V does not give orange precipitate with Brady’s reagent, hence V is not a carbonyl
compound.

• V reacts with cold, dilute acidic KMnO4, therefore V is an alkene and W is a diol.

• V undergoes reduction with LiAlH4 to give 2 products. V is an ester. X and Y are primary
alcohols.

• X gives a positive triiodomethane test, it contains – CH(OH)CH3 group.

• Y decolourises aqueous bromine to give a whit precipitate Z (C10H10Br4O2). Y is a phenol and

only the 3rd carbon with respect to the –OH group is substituted. Y is also an alkene.

• V, W, Y and Z have chiral carbons, non-superimposable mirror images and no plane of

symmetry.
O O

O C CH3 O C CH3

CHCH CH2 CHCH(OH)CH2(OH)

• V: CH3 • W: CH3
• X: CH3CH2OH
(ii) Z:
OH OH

Br Br

CHCH CH2 CHCH(OH)CH2Br

• Y: CH3 Br CH3
69

E. Conversion Based Questions

70
 O NO2
C CH2Cl N NH
A: B: C CH2Cl
NO2
O2N
H O2N
C CH2Cl
D: OH H
H2N C CH2Cl
E:
OH
O - +
Cl H3N
C CH2COOH
C:

O2N

(b) C2H5OH + conc. H2SO4, heat

(c) CH3CONH2 + NaOH(aq)  CH3COOH + NH3(g)
heat
NH3 gas turns moist red litmus paper blue and forms white fumes with a glass rod
dipped in concentrated HCl.

CH3CH2NH2 + NaOH(aq)  No reaction.

Heat
Moist red litmus paper remains red and no fumes are formed with concentrated HCl.

71

A: C:
NO2 CH=CH 2 NO2 CH=CH2

H2 N

A:
NO2 CH(OH)-CH 2Br

Step 1 = KOH (ethanolic), heat

Step 4 = Sn, conc. HCl, followed by excess NaOH

72 (a) Stage 1 = CH3Cl, AlCl3, warm

Stage 2 = CH2COCl, r.t.p.
Stage 3 = Cl2, U.V. light
 Stage 4 = KMnO4, H+(aq), heat
Stage 5 = C2H5OH, conc. H2SO4, heat

(b) Y are
+
Na-O COO-Na+
+ CH3CH2OH
(c) Free radical substitution reaction.
RCH3  RCH2Cl where R = C6H5-OOCCH3

Initiation: Cl Cl  2Cl•
Propagation:
Cl • + RCH3  RCH2• + HCl
RCH2• + Cl2  RCH2Cl + Cl •
Termination:
Cl • + Cl •  Cl2
Cl • + RCH2•  RCH2Cl
RCH2• + RCH2•  RCH2CH2R

73 (a) Step 1= KMnO4, dilute H2SO4, heat

Step 2 = PCl5, r.t.p.
Step 3 = HO-(CH2)2N(C2H5)2, r.t.p.
Step 4 = Sn, conc. HCl, heat followed by excess NaOH
(b)

NO2 COOH

74 (i)
O2N CH(OH)-CH-NHCOCHCl2
+ CHCl2COCl
CH2OH
NO2 CH(OH)CHNH2

CH2 OH

(ii)

NO2 CH(Br)CH-NHCOCHCl2

CH2 Br
 iii)
OH

NO2 CH-CH-NHCOCHCl2

CH 2OH

OH OH

NO2 CH-CH-NHCOCHCN2 NO2 CH-CH-NHCOCH(Ch 2NH2)2

CH 2OH CH2OH
(iii) Add Br2(aq) at r.t.p. to chloramphenicol and X respectively. X will form a white ppt,
steamy fumes evolved and Br2(aq) is decolourised whilst chloramphenicol does not
give a white ppt. Type of reaction involved is electrophilic substitution.

(b)
H Cl CN
Cl2, KCN (alc)
HO C CH3 HO C CH3 HO C CH3
CH3 UV light CH3 heat CH3

Dilute H+, heat

COOH
COOCH3 CH3OH
HO C CH3
HO C CH3
conc. H2SO4 CH3
CH3 heat

75 1: NaOH(alcoholic), heat
2: conc. H2SO4 ( at 0 oC followed by boiling with H2O )
3: NaOH(aq), heat.

76 (a) To synthesize compound B via 2 steps: Step 1: Sn, Conc. HCl, heat followed by
excess NaOH, step 2: CH3Cl (alcoholic), heat.
To synthesize compound C via 3 steps: Step 1: acidified KMnO4 solution, heat, step 2:
PCl5, r.t.p. step 3: NH2CH2CH2CO2H, r.t.p.
 (b)(i)
CH3 CH3
Cl N CH2 N CONH(CH2)2COOH

(ii)
CH3 CH3
H N CH2 N COO-K+ + NH2CH2CH2COO-K+

(iii)
CH3 Br CH3 Br
H N CH2 N CONHCH2CH2COOH

Br Br Br Br
77 (a) Let R = CH3O-C6H5

LiAlH4 in dry ether PCl5 at rtp KCN(alc)

R – CHO ============> R – CH2OH =======> R – CH2Cl =====> R –

CH2CN

Rtp heat

(b) (i)

CN
CH3O C H
OH
C
 (c) C is a racemic mixture where the d isomers and l isomers are in 50:50 ratio.

2, 4-dinitrophenylhydrazine at rtp.

Condensation reaction.
H C
NHNH2 NH N
+ OCH3 + H2O
CH3O C H O 2N NO2 O2N NO2
O

78 (a)

I CH3CH2Cl, AlCl3, warm V dilute HCl, heat

II Cl2, U.V. VI NaOH(alcoholic), heat
III KCN(ethanolic), heat VII NaOH(aq), heat
IV NaOH(aq), heat VIII KMnO4, dil. H+, heat
(b) Oxidation with K2Cr2O7, dilute H+, heat. Compound 2 does not turn orange
Cr2O72-/H+ to green .Compound 2 changes the orange Cr2O72-/H+ to green.
Compound 1 is oxidised to C6H5CH2COOH.

79 (i) Compound J to Salbutamol

O O
H+(aq)/heat
3HCCOOH2C C HOH2C C
CH2Cl CH2Cl

H3CCOO HO
J LiAlH4/dry ether

H H
conc. NH2C(CH3)3
HOH2C C HOH2C C
CH2NHC(CH3)3 CH2Cl
OH OH
heat in a
HO sealed tube HO
Salbutamol

(ii)
 OH OH
+
NaOH(aq) H (aq)/heat
CH3CHO + HCN H C CN H C COOH
10 - 20oC
CH3 CH3

OH O
C
2 H C COOH conc. H2SO4 O CHCH3
heat 3HCHC O
CH3 C
O

80 .(a) (i) L: P:
H O
O
C O C
CH3 O C
H

(ii)

CH3 OH

O O
COOH Q
PCl5 C Cl
rtp CH3 O C

N Or PCl3/SOCl2 P

(iii) acidified aq. KMnO4, reflux/heat.

81 A is CH2BrCH2Br F is CH3CH2COOCH2CH3
B is CH2OHCH2OH G is CH3CH2COCl
C is CH2BrCH3 H is CH3CH2CONH2
D is CH3CH2CN K is CH3CH2COOH + NH4+
E is CH3CH2COOH I is CH3H2CH3
L is CH3CH2COO- + NH3 J is CH3CONHCH2CH3
82 O2N NO2
(a)(i) H N (ii) HO (iii) O (iv) O
N

O HO O
Br
O
O O O
O-Na+ H
O

conc. KMnO4
(b) CH3CH2CHCH3 CH3CH=CHCH3 CH3COOH
H2SO4 H+(aq)
Cl reflux
170oC Conc. H2SO4
C2H5OH
reflux
CH3COOCH2CH3

(c) CH3CH2COOCH3 + NaOH(aq)  CH3CH2COO-Na+ + CH3OH

methyl propanoate heat distillate

CH3OH + I2 + NaOH(aq)  No reaction (no yellow ppt formed)

heat

CH3CH2COOCH2CH3 + NaOH(aq)  CH3CH2COO-Na+ + CH3CH2OH

ethyl propanoate distillate

CH3CH2OH + I2 + NaOH(aq)  CHI3 yellow ppt.

heat

83 (i)
COOH COCl
E F G CH2CH2NH2

HO HO HO
(ii)
 CH2OH CH2Cl CH2CN
D

HO PCl5 KCN(alc) HO
HO
rtp heat
LiAlH4
dry ether

G CH2CH2NH2

HO
(iii) Amide and phenol
(iv)

COO CH2CH2NH2

HO

84 (a) Condensation
(b)
Cl

CH=CHCOOD Cl

P R COO-Na+ Q or
OH O O O O
OH

COOH
S T
COOH
OH OH

(c) React both X and Coumarin respectively with: 2, 4 DNPH at r.t.p.

X gives an orange ppt. whilst Coumarin has no orange ppt formed.
React both Y and Coumarin respectively with: Br2(aq) at r.t.p.
Y gives a white ppt with brown Br2(aq) decolourised and evolution of steamy fumes,
whilst Coumarin does not decolourise brown bromine to form a white ppt.
85 O-Na+ O-Na+ OH
OH
Br Br
A B C D

CH2CH2OH CH2CH2OH CH2CH2COCl

CH2CH N NH
NO2

NO2
I = K2Cr2O7, dil. H+, heat with distillation [controlled oxidation]
II = KCN (ethanolic), reflux
III = dilute HCl(aq), heat
IV = PCl5, r.t.p.

86 (c)(i)
OH
Cl Step 2
Step 1
Cl2, UV light NaOH (aq)
heat
cyclohexane cyclohexanol
Cyclohexene has only 1 isomer as the molecule only exhibits cis isomerism. The trans
form would distort the ring with great strain and hence is not stable and non-existent.

Hex-3-ene has geometrical cis-trans isomerism due to the restriction of rotation caused
by the C=C double bond.
H H H CH2CH3
C C C C
H3CH2C CH2CH3 H3CH2C H

Cis isomer Trans isomer

(d)(i) concentrated NH3, heat in sealed tube.

(ii) Ethanolic KCN, reflux
(ii) Alcoholic NaOH, heat

87 Step II : KCN in ethanol, reflux

(c)(i) Step III : dilute acid or H+(aq), boil under reflux

(c)(ii) Fe in the presence of excess Cl2 gives FeCl3 and Cl2 (not necessary)
 FeCl3 + Cl2 → Cl+(FeCl4)- (not necessary)

Electrophilic substitution of methyl benzene with Cl+

+
Cl
H Cl Cl
H3C H3C H3C
s l o w +
+
f a s t
+ H

I n t e r m e d i a t e
Arrows [1]
Intermediate [1]

(c) P = C6H5CH2COOH
(iii)
(c) Step III : acidic hydrolysis
(iv) Step IV : reduction

88 Reaction I: Concentrated HCl, Sn, heat under reflux, then add NaOH(aq)
C4H9

N
Cl

Reaction II: O , room temperature

 1 mark for any one of the 6 acceptable structural formulae for Organic Compound A
Structural formulae is acceptable if anion Cl- is omitted.
C4H9 C4H9
CH3 CH3
H H
N
N ICl N I Cl
I N
OR
C C

CH3 O CH3 O
I Organic Compound A1 Organic Compound A2

C4H9 C4H9
CH3 CH3
H H
N
N HCl N HCl
I N
OR
C C

CH3 O CH3 O
I Organic Compound A3 Organic Compound A4

C4H9 C4H9
CH3 CH3
H H
N
N HCl N I Cl
N
OR
C C
I O I
CH3 CH3 O
Organic Compound A5 Organic Compound A6

Structural formula of B is acceptable if either SO42- or its structural formula is omitted

C4H9
O
HO NH+
2
S
C
- -
O O O
O

Organic Compound B

89 ci) Al-H bond is weaker than the B-H bond.

ii) H- acts as nucleophile. Alkenes are not attacked by nuclephiles as they are
electron-rich.
 iii)

iv) reaction II: NaCl, conc. H2SO4, reflux / PCl5, room temp / SOCl2, room temp.
reaction III: KCN in ethanol, reflux
reaction IV: dilute H2SO4 (or dilute HCl), reflux
90
91

CH3
CH3

KMnO4/
dil H2SO4, [1] H+ (aq)
heat
H3CCO(CH2)4COCH3 I2(aq), − −
Na+ O2C(CH2)4CO2 Na+
NaOH(aq),
[1]
heat

92
●Nucleophilic addition [1]
●CH3CH2MgBr
●CH2O (methanal) [2]

●
CH2CH3 [1]

93
O
[1]
H3CCCH2CHCCH2CO2H

O CO2H [1]
Br

H3C OH HO
OH
CH3
E: CH2OH F: CHO
[2]
 δ_ Cl δ+H H

_
Slow CH3 OH +
CH3 OH + Cl :

CHO
CHO

H H

fast Cl
CH3 + OH OH
CH3
CHO CHO
_
: Cl

94
•L Cl •K
H2NCH2CH CH2 Cl
COCl
OH
[2]
Step 1
Cr2O72-/ H+
Cl CH2CH2OH Cl CH2C H
Heat to distill O

J
KCN(s)/ dil H2SO4
Step 2
10 - 20oC

Step 3
H H
Cl CH2 C CH2NH2 anhydrous LiAlH4 Cl CH2 C CN
OH ether solvent OH
at room temp
K

[5]

• optical isomerism
•2 [2]

• Cl O
C O CH CH2 Cl
CH2
NH2
 • Esterification takes place in the reaction between –COCl and –OH functional
groups [2]

• I : reduction
• II : electrophilic addition [2]

95

96
97