Organic Reactions & Mechanisms Suggested Answers

Topic 10.1 : Organic Reactions & Mechanisms

1. CJC/2009/P2/Q2c

2.

CJC/2009/P3Q2a

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Organic Reactions & Mechanisms Suggested Answers

3.

AJC/2009/P3/Q5d

4.

IJC/2009/P2/Q3b

5.

IJC/2009/P3/Q1a

6.

HCI/2009/P2/Q2b

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Organic Reactions & Mechanisms Suggested Answers

7.

IJC/2009/P3/Q2(c)(iv)

8.

AJC/2009/P2/Q1e

9.

IJC/2009/P3/Q5d(i)

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Organic Reactions & Mechanisms Suggested Answers

10.

JJC/2009/P2/Q2c

11.

JJC/2009/P2/Q6(a),(b) (a) Phenol and secondary alcohol (b) (i) (ii)

(iii)

12.

JJC/2009/P3/Q1c

13.

JJC/2009/P3/Q2c

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Organic Reactions & Mechanisms Suggested Answers

14.

MI/2009/P2/Q5
Lone pair of electrons from O is delocalized into the ring, increasing the electron density of the ring; making it more susceptible to electrophilic attacks.; Or electrophiles are more attracted to the ring.

15.

MJC/2009/P2/Q4e

16.

MJC/2009/P3/Q1d

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Organic Reactions & Mechanisms Suggested Answers

17.

SAJC/2009/P3/Q1e

18.

NJC/2009/P3/Q4b(iv)

189

Organic Reactions & Mechanisms Suggested Answers

19.

RJC/2009/P3/Q4c

20.

SAJC/2009/P3/Q2c

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Organic Reactions & Mechanisms Suggested Answers

21.

SAJC/2009/P3/Q3c

22.

191

Organic Reactions & Mechanisms Suggested Answers

23.

TJC/2009/P2/2c

24.

TPJC/2009/P3/Q3c

25.

VJC/2009/P2/Q1e

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Organic Reactions & Mechanisms Suggested Answers

YJC/2009/P2/Q3b 26.

CJC/2009/P3/Q5b,c 27. Condensation (i) (ii) methanol, propanol ethanol

IJC/2009/P3/Q4c,d 28. (c) (i)

(ii)

(d)

(i) (ii)

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Organic Reactions & Mechanisms Suggested Answers

(iii)

(iv)

(v)

JJC/2009/P3/Q4c 29. (c) (i) R + C O + :CN R R

R CO CN + HCN R R COH CN + CN-

(ii)

The first step is the rate determining (slow) step. Step 1 involves breaking the C=O bond.

(iii)

HCN is a very weak acid, almost completely un-ionised OR

CN is a stronger nucleophile than HCN.

O C

(iv)

Nucleophilic addition is dependent on + on the carbon of C=O, but this is neutralised by the oxygen, with delocalisation
O CH 3

(v)

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Organic Reactions & Mechanisms Suggested Answers

CH3CH2 C H O

HCN

CH3CH2 C H

OH CN

LiAlH 4, dry ether or H2, Ni, heat

CH3CH2 C H

OH CH2NH2

traces of NaCN or NaOH

[1]

[1]

NJC/2009/P2/Q4a,b 30. (a) (i) K2Cr2O7, dil. H2SO4, heat with distillation (ii) (iii) 2,4-dinitrophenylhydrazine. Positive observation: orange ppt Cyanide ions can attack the trigonal planar carbonyl carbon from top and

bottom with equal probabilities. Hence a racemic mixture is formed. The optical activity of one enantiomer cancels out the optical activity of the other hence the product mixture does not exhibit any optical activity. (b) (i) (CH3)2CHCH2CH2OCOCH3 + NaOH NYJC/2009/P3/Q3c 31.
CH3 NC __ C CH3 OH H (aq), 2H2O reflux CH3
+

(CH3)2CHCH2CH2OH + CH3CO2Na

CH3 HOOC C OH

H H C H C H H C C H
CH3

conc. H2SO4, 180oC

H O N
H2C C C O O CH3 CH3OH, conc. H2SO4 reflux H2C C

CH3 COOH

RI/2009/P3/Q4d 32.

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Organic Reactions & Mechanisms Suggested Answers

(i) Ca has a bigger atomic radius/ more diffuse electron cloud than Mg so that it does not form strong covalent bond with R and X. Thus, it is not able to form organometallic compounds with halogenoalkanes. Lithium/ copper gives a similar reaction with halogenoalkane as magnesium. (ii) Being a very strong base, R in RMgX reacts with water to form an alkane, RH which would prevent it from acting as a nucleophile. (iii) The reaction between Mg and RX requires breaking of the CX bond. CX bond gets weaker in the order CF > CCl > CBr > CI due to decrease in efficiency of overlap of C and X orbitals as valence orbital of X becomes more diffuse as halogen increases in size/ decrease in polarity of CX bond as X decreases in electronegativity down the group. Hence reactivity between RX and Mg is in the order: iodoalkane > bromoalkane> chloroalkane > fluoroalkane. (iv)

(v)

(vi) One mole of RMgBr reacts with one mole of CH3COBr via nucleophilic substitution mechanism to form one mole of the ketone CH3COR. The one mole of CH3COR formed then reacts with another mole of RMgBr to form CH3CR2OH. (vii) Ratio of alcohol A: =
= SAJC/2009/P3/Q1e 2 2 x 3 3 4 : :

alcohol B:
2x 4

alcohol C
1 1 x 3 3

2 1 x : 3 3 : 1

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Organic Reactions & Mechanisms Suggested Answers

33.

(e)

SRJC/2009/P2/Q2a-c 34. (a) Cis-trans isomerism

(b) HCN with traces of NaCN, 10-200C Describe the nucleophilic addition mechanism.
H C O + CH3CH2CH2CH=CH CNSlow Step H CH3CH2CH2CH=CH C OCN

H CH3CH2CH2CH=CH C O CN

+ H CN

Fast Step

H CH3CH2CH2CH=CH C OH CN + CN-

(c)
H C CH3CH2CH2CH=CH OH CN HO CN H C CH3CH2CH2CH=CH

(ii)

H C O CH3CH2CH2CH=CH - Carbonyl carbon of compound B is trigonal planar [1/2 M] or Carbonyl carbon atom in compound A is sp2 hybridised. Hence, the C atom and the three atoms attached to it lie on the same plane.
- Nucleophilic attack on the carbonyl carbon can occur from either above or below the plane [1/2 M] and the chance is 50%-50%[1/2 M] (equally likely)

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Organic Reactions & Mechanisms Suggested Answers

- Racemic mixture is formed[1/2 M] which is optically inactive. or Both optical forms of compound B will be formed in equimolar which is optically inactive.

SRJC/2009/P3/Q4c 35. (c)

CHO

CH2COO-

CH2CH2COO-

Nickel has partially filled 3d orbitals which allow the reactants molecules to be adsorbed onto the catalyst surface. This adsorption lowers the activation energy and allowing reaction to occur. H

H C OH H H H HO C C C H H H H H C C OH H H

TJC/2009/P3/4c 36. (ii) (iii)

CH3CH2CHBrCH3 NaOH(aq), reflux CH3CH2CH(OH)CH3 Acidified KMnO4, reflux CH3CH2C(CH3)(OH)CH3 CH3 Li, H2O CH3CH2COCH3

Nucleophilic addition

RI/2009/P2/Q4a,b,f 37.
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Organic Reactions & Mechanisms Suggested Answers

(a) (b)

Structural/positional isomerism Geometric isomerism H C C HO OCH3 cis trans H CH3 CH3O H C C HO H CH3

O
(f)

O OCH3

RI/2009/P3/Q1b 38. (b)(i)

    +   !

&22+ & &+  2+

Samples A and B contain lactic acid but the lactic acid in B is the enantiomer/ optical isomer of the lactic acid in A. Hence A and B behave differently towards planepolarised light. (ii) Sample C is a racemic mixture of the two optical isomers of lactic acid (contains equal amounts of the two optical isomers of lactic acid) and hence does not exhibit optical activity. Due to the mixture of the optical isomers, the packing of lactic acid molecules in C is not as regular as the packing of lactic acid molecules in A where only one optical isomer of lactic acid is present. Hence melting point of sample C is lower than that of A.

AJC/2009/P3/Q1c 39. (c) Add 2,4-dinitrophenylhydrazine to 4 compounds. 2 give orange ppt- CH3COCH3 and

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Organic Reactions & Mechanisms Suggested Answers

C4H9CHO. To these 2, add Tollens reagent and warm. C4H9CHO gives silver mirror but not CH3COCH3. To the remaining 2 that give negative test with 2,4-DNPH, add aq NaOH and warm. The substance that give out NH3(g) is CH3CH2COO- NH4+

To the last substance add bromine in the dark. It rapidly decolourises brown Br2.

AJC/2009/P3/Q4c 40. (c) In aqueous solution, in increasing pH II, I, lactic acid. CJC/2009/P3/1e 41. Step I : add alcoholic KCN to (choromethyl)benzene and heat under reflux. Intermediate product is CH2CN

Step 2 : add dilute hydrochloric acid and heat. Product is formed

NJC/2009/P3/Q3d 42. (d) (i) Draw the structural formulae of ester G and H.
O H3C C O H C H OH

G
O H3C C O

H C H O

O C CH3

(ii)

In the presence of NaOH, the phenol group is deprotonated to give O-/ phenoxide ion, which is a stronger nucleophile.

AJC/2009/P3/Q4d 43. (d) (i) Concentrated nitric acid and concentrated sulfuric acid. 500C
(ii) (iii) Electrophilic substitution J COOH COCl, rest no change K- COCl + -NH2 -CONHL:

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Organic Reactions & Mechanisms Suggested Answers

ONa COONa

NH2

NH2

HCI/2009/P2/Q4b 44. (b) Q: CH2=CHCH(Br)CH=CH2 R: CH2=CHCH(OH)CH=CH2 I: excess conc H2SO4, 170 C ; II: NaOH(aq), heat ; H2SO4, heat YJC/2009/P3/Q2a,b 45. III: KMnO4(aq), dilute

IJC/2009/P3/Q5e 46. e (i) HCl(aq), heat under reflux (ii)

(iii)

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Organic Reactions & Mechanisms Suggested Answers

JJC/2009/P2/2c 47. [ ] arrow pointing fr

the + CO ring to CH 3

[ ] arrow pointing fr C-H bond to +ve

[ ] correct arenium ion

4 [ ]: 2m 2-3 [ ]: 1m

[ ] balanced eqn with FeCl4- and regeneration of catalyst

NYJC/2009/P2/Q5a-e Ester, secondary alcohol, primary alcohol, alkene 48. (a)

(b) (c)
CH2 O O C C HO C OH HO C H H C OH

The molecule has many OH (or alcohol or hydroxy groups) that allows it to form (intermolecular) hydrogen bonds with water molecules
OH O O C C C O
-

CH2 H C H C OH

OH

H2O

H3O

Loss of H+ - must be from OH group attached to C=C (either one or two H+ ) The p orbital of oxygen atom overlaps with the electron cloud of the C-C double bond. The negative charge on oxygen is delocalized over the 2 carbon and the oxygen atoms. The negative charge is dispersed and the conjugate base stabilized, making ascorbic acid acidic.

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Organic Reactions & Mechanisms Suggested Answers

(d)

O C O O C C HO C OH C H C N

OH H N NO2

NO2 For changing primary alcohol to carboxylic acid. For reacting resultant ketone with 2,4-DNPH (i) Condensation (or esterification) Intermediate product 1 circle COOH and 4th C-OH (ii) Elimination [1] [1]

SAJC/2009/P2/Q2a-c 49. (a) (b) (c)

TJC/2009/P2/Q2c 50. (c) (i)

(ii)

CH3COCN

NYJC/2009/P2/Q6a
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Organic Reactions & Mechanisms Suggested Answers

51. (a)

(b)

CO2H

OH

(c)
H H

Reactant
O C Cl C
H

Reagents/Conditions

Room Temperature

SAJC/2009/P3/Q2c 52. (c) (i)

(ii)

Optical isomerism due to the presence of a chiral carbon Exists as a pair of non superimposable mirror images

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Organic Reactions & Mechanisms Suggested Answers

(iii) A has a higher pKa as A is a weaker acid. Ibuprofen contains a carboxylic acid. Carboxylate anion stabilized by
delocalization of the electrons over the carbon atom and both oxygen atoms / distribution of negative charge over the C and 2O atoms

RI/2009/P3/Q5a 53.

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Organic Reactions & Mechanisms Suggested Answers

HCI/2009/P3/Q5d 54.

AJC/2009/P2/Q5a-c 55. (a) Step I concentrated NH3 in sealed tube and heat Step II- CH3COCl, r. t Step III CH3Cl, heat (b)
F
NH2

NH2

G
NHCOCH3

NH2

(c) (i)

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Organic Reactions & Mechanisms Suggested Answers

(ii)

MJC/2009/P2/Q6d 56. Group 1. Electronegativity of F > Br hence electron-withdrawing effect on carboxylate

ion for: F > Br . Extent of stabilisation of the conjugate base relative to the acid for : Group 1 > Group 2

VJC/2009/P3/Q2c 57. (i) The carboxylic acid group has higher acid strength than alcohol. On dissociation, the
carboxylate ion is more stable than the alkoxide ion due to resonance effect which disperses the negative charge on the ion, unlike alkoxide ion which does not have resonance effect.

CH3CH2CONH CH CO2 Na

CH2OH

CH3CH2COCl
(ii)

NH2CH CO2H

CH2OH

HCl
Isomer of P

CH3CH2CONH CH CO2H

CH2OH

H2N CH CO2H

CH2O

C O

CH2CH3

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Organic Reactions & Mechanisms Suggested Answers

TPJC/2009/P2/Q4a,b 58.
4.19- tertiary amine ; 9.37 phenylamine

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Organic Reactions & Mechanisms Suggested Answers

CJC/2009/P3/Q4c-f 59. % N = 6/Mr X 100 %

(i) (ii) (iii) Compare the %N among the compounds given. Highest % is best Lone pairs of electrons on nitrogen atoms are available to accept H+ Melamine more basic, presence of greater number of lone pairs of electrons on nitrogen. d(i) any of NH2 convert to NHCOCH3 d(ii) any of NH2 convert to NH3+ -COOCH3 d(iii) any of NH2 convert to NHBrC2H5

NH2 N H2N
f

N N N(C2H5)3+Br

cyanuric acid and melamine undergoes neutralization.

NH3+ N NH3+ N N NH3+ O N N O N O

YJC/2009/P2/Q5a,b 60.

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Organic Reactions & Mechanisms Suggested Answers

VJC/2009/P3/Q5c 61. Trimethylamine, is less basic than methylamine, due to presence of three bulky CH3 substituents which reduces the availability of the lone pair of electrons on nitrogen of trimethlyamine for donation to acid. [1] ammonia and hydroxylamine;
Hydroxylamine, is less basic than ammonia, due to electron-withdrawing inductive effect of the OH group which makes the lone pair of electrons on its nitrogen less available for donation to acid. [1] pyridine and phenylamine. Phenylamine is less basic than pyridine as the lone pair of electrons on nitrogen of phenylamine is delocalised into the aromatic ring, hence less available for donation to acid. 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.

JJC/2009/P3/Q1c 62. (c) (i)

OH NO2

(ii)

Step I: dil HNO3 / HNO3(aq) [1] Step II: Sn, conc HCl, heat [1] Bulky non-polar group in 1-naphthol hinders the formation of hydrogen bonding.

(iii)

SAJC/2009/P3/Q3c 63. c (iv) R has higher pKb.

Br atom in R is electronegative/electron withdrawing Lone pair of electrons on N less available for protonation. R is less basic.

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Organic Reactions & Mechanisms Suggested Answers

IJC/2009/P2/Q5a-e 64. (a)

(b)

(c)

(d)

(e)

(i) (ii)

Nucleophilic substitution

PJC/2009/P3/Q3b,c 65.

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Organic Reactions & Mechanisms Suggested Answers

MJC/2009/P2/Q5a-d 66. (a)THC consists a large hydrophobic groups hence can form hydrophobic interactions with benzene molecules. (b)i Dilute H2SO4* accept any other possible reagent
(ii) Br2 in CCl4 ,rtp * accept any other possible reagent

(iii) H2 with Ni catalyst at high temperature and pressure or Br2 , heat with FeBr3 catalyst *accept any other possible reagent (c)
CH3 O NH2

N H

and CH3COCl
Br NH2

(d)
OCH3

Br O NHCH2COBr

It is easiest to hydrolyse the acyl bromide as the electron deficient carbon atom/carbonyl carbon in COBr is bonded to two electronegative atoms, O and Br. Hence, COBr group is most susceptible to nucleophilic attack, thus it is most reactive. In Br (1) , the p-orbital of the bromine atom interacts with the electron cloud of the benzene ring. bromide. Thus,

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Organic Reactions & Mechanisms Suggested Answers

rendering nucleophile substitution difficult in aryl bromide. Hence, Br (1) is the least reactive.

MJC/2009/P3/Q3a-i 67. (a) alkene, ester,amine ,amide, ether-any 4 out of 5

(b) The phosphate salt is more soluble in water hence more easily absorbed. (c)
O O O H2N NH2
-

CH3COOOH O O OH COOH

CH3CH2OH

(h) (i)

Unusual : The alkene group would have been expected to undergo reduction. CH3Br , heat under high pressure Compound G would be more basic due to the electron-donating group which increases the electron density on the lone pair of the N atom hence making the lone pair more available to accept a proton.

SRJC/2009/P3/Q5b,c 68. (b) (i)

Hot, dilute hydrochloric acid
COOH

H3 N+

H HOCH2CH2N+(C2H5)2
(ii)
Aqueous bromine

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Organic Reactions & Mechanisms Suggested Answers

CO2CH2CH2N(C2H5)2

Br NH2
(c)

Br

Procaine is more basic Electron-withdrawing group Cl in M reduces the availability of the lone pair on N atom to accept a proton via a dative bond OR Electron-withdrawing group Cl in M intensifies the positive charge on the conjugate acid ion hence destabilising it

NYJC/2009/P3/Q2c,d 44. (c) (i)

N: N .. CH3

The nitrogen atom (circled) is attached to the three alkyl groups which are electrodonating, making the lone pair more available for bonding to H+/ hence stabilizing the conjugate acid by dispersing the positive charge on the nitrogen atom.

(ii)
N: ||||||||||||||| H+ CH3

..
O H

..

N ..
+

(d) (i)
CH3CH(NH2)CH2CONH2

..

|||||||||||||||

H O

..

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Organic Reactions & Mechanisms Suggested Answers

(ii)

Cl- NH3+CH2CH2CH2COOH

SAJC/2009/P2/Q8a-d 45. (a) Phenylamine; Ester ; Tertiary amine (b) (i)

Draw the structural formulae of the compounds A and B:
O

Cl

HO
(ii)
(c)

N
H2 N

NH(CH2CH3)2, heat Reagent and condition: any acid except HNO3 OR hot acidified KMnO4 OR Br2 with halogen carrier, heat Observation: miscible layer OR purple KMnO4 decolourise OR brown Br2 decolourised

(i)

(ii)

Reagent and condition: aqueous bromine, room temperature/heat OR acid chloride Observation: Procaine decolourises brown bromine with formation of white ppt. OR white fumes

(d)

CH3

H N C O CH3

H N

COO-

Cl

NH2
-

OOC

COO-

TJC/2009/P2/Q5a 46. (a) (i) Tertiary amine ;Substituted amide

(ii)

4 chiral centres in coaine 0 chiral centre in lignocaine

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Organic Reactions & Mechanisms Suggested Answers

COOCH3 N H3C

H CH3CH2 C N CH2 N C

CH3

* *

O O

CH2CH3 O H3C

cocaine

lignocaine

(iii)

X
CH3CH2 N CH2

Y
O
C

H N H H3 C

CH3

CH2CH3 O

(iv)

X is an ionic salt and it can form ion-dipole attractions with water molecules. The energy released from the ion-dipole attractions is sufficient to overcome the ionic bonds in X as well as the hydrogen bonding between water molecules. As a result, X is soluble in water. (NB : hydrogen bonding between X and water is possible due to presence of electronegative N in X but is not extensive enough to explain solubility of X in water)

Although Y has an amine group, it has a large hydrophobic benzene ring. The attraction between molecules of Y and water is mainly weak van der Waals forces and the energy released from these attractions is insufficient to overcome the strong hydrogen bonding between water molecules and the van der Waals forces between molecules of Y. Hence Y cannot intermingle with the water molecules and it is insoluble in water.

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Organic Reactions & Mechanisms Suggested Answers

TJC/2009/P2/Q5b 47. (bi)

O C Cl H C H Cl
H H C H xx H H N C C H H H H C H H

(bii) Intermediate U is a stronger nucleophile compared to NH3 due to the positive inductive effect from the two alkyl groups attached to the nitrogen atom. U can react with excess CH3CH2Cl to form 3 obtained. (biii)
CH3 NH2

amines or quaternary salt eg.

(CH3CH2)3N or (CH3CH2)4N+Cl-. Hence a mixture of substituted products is

CH3

(biv) Br2(aq), room temperature

TJC/2009/P3/Q3b 48. dilute HCl or dilute H2SO4 , reflux (b) (i) NaOH(aq) , reflux (ii)
In acid hydrolysis H3C
CH H3C OH
F

and

HO

P O

CH3

OR

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Organic Reactions & Mechanisms Suggested Answers

In alkaline hydrolysis
H 3C CH H 3C
+

OH and

Na-O

P O

CH3

(iii)

Less resistant P-O bond length is longer than C-O, lower bond energy and easier to break OR P is more susceptible to nucleophilic attack due to the highly electronegative F. Carbon, being a period 2 element does not have energetically accessible vacant d-orbitals to allow it to expand its octet structure and accommodate the electrons from fluorine. Any 2 of the following structures (CH3O)PCl2 (CH3O)2PCl (CH3O)P(Cl)(OH) (CH3O)P(OH)2 (CH3O)3P P(Cl2)(OH) P(OH)3 OR OR OR OR OR OR

(iv)

(v)

218