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A. Hybridisation
1 (a) A σ bond is formed from the end-on/head-on overlapping of orbitals.
H H
H
H H
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
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)
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
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.
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.
14
15
16 (a) (i)
H
H2N C COOH
CH2COOH
(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)
Nucleophilic Substitution
H H H O
H C N C C OH
H CH3
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.
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
(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
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
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
(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
40 a) A is
CH3
CH3C CHCH2CH3
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
J is
O
HC CH2CH2OH
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
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. H+ C
Na
H2
B C must have an OH group
C2H5OH diester
diacid
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
c) Diol product is formed. Purple manganate(VII) solution is decolourised, brown MnO2 ppt is
formed.
H H
C C CH3
OH OH
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
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
H
C
O
C H
H3C
C
O
C CH3
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
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
H P
OH
H3C C H CO2H
CH3 CO2H
J Q
CH3
H3C C OH CO2H
L R
CH3
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
H3C C C CH3
*
H3CH2C and
X
H OH H OH
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
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
NH2
Since Z is soluble in HCl Z contains
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
A is
NH3+ NH3+
Not COOH
[see eq. (i) below]
COOH
X Y Z
i) NH2 Br NH2
H
CH=CH2 + 2Br2(aq) C CH2 + 3HBr
OH Br
Br
ii) NH2 NH2
iii)
NH2 NH3 +
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-.
KOH(alc.) heat
P S (C5H10O)
- +
MnO4 /N
S CO2 S has a terminal alkene group
H3C C C Br H3C C C OH
OH H OH H
P Q
CH3 O CH3
OH OH H
R S
i)
CH3 O CH3
OH OH
ii) CH3 O CH3 O
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
NO2
O2N
O2N NH H
N NO2
N N
+ 2H2O
C2H5OOC C C COOC2H5
OH OH Cl Cl
+ 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 Cl O
% mass 44 6.6 26 23.4
Ar 12 1 35.5 16
No. of mol 3.67 6.6 0.732 1.46
Mole ratio 5 9 1 2
Information given Deduction
1 % composition of each G has empirical formula of C5H9ClO2
given elements in G G has molecular formula C5H9ClO2
2 G is soluble in aq NaOH, 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)
3 When G is heated with aq G, contains alkyl halide, undergoes nucleophilic
NaOH followed by addition of substitution with aq NaOH to give H.with alcohol.
aq HCl, H, C5H10O3 is
obtained.
4 H gives a positive iodoform H has a CH3CH(OH)- structure.
test.
5 H when refluxed with conc J is an ester / H undergoes internal
H2SO4, give J which is a esterification, hence H must contain both –
sweet smelling liquid. COOH and –OH group.
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
Cl O H3C
O
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
P undergoes basic hydrolysis with hot, aqueous sodium hydroxide to form Q and
sodium ethanoate.
⇒ P is an ester
⇒ Q is an alcohol
T is optically inactive
⇒ T does not contain a chiral carbon.
O O
H 3C C O CH2 CH2 O C CH3
P:
64 ● Mole ratio of C:H ratio ≈ 1:1 in A => A probably contains benzene ring
● 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+
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
(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.
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.
O C CH3 O C CH3
• V: CH3 • W: CH3
• X: CH3CH2OH
(ii) Z:
OH OH
Br Br
• Y: CH3 Br CH3
69
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
71
A: C:
NO2 CH=CH 2 NO2 CH=CH2
H2 N
A:
NO2 CH(OH)-CH 2Br
(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
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
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
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
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)
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
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
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
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
(c)(ii) Fe in the presence of excess Cl2 gives FeCl3 and Cl2 (not necessary)
FeCl3 + Cl2 → Cl+(FeCl4)- (not necessary)
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
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
C4H9
O
HO NH+
2
S
C
- -
O O O
O
Organic Compound B
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