Chemistry HIT4 Integrated Organic Chemistry Revision

Additional Questions

Reaction Mechanism & Other Interesting Questions

Solutions HCI 2010/P3/3e 1 (i) Nucleophilic addition (ii) I : ethanolic KCN, heat II : dilute H2SO4, heat III : PBr3, heat OR OR dilute HCl, heat red phosphorus with Br2, heat

O CH3
H:

C CH2CH3

NJC 2010/P3/5a 2 (i) Electrophilic Substitution Mechanism Generation of electrophile

CH3CH CH2 +

H OPO3H2

CH3CHCH3

H2PO4

5 (ii) Add aqueous NaOH to a separating funnel containing the mixture of phenol and propanone. Shake thoroughly and drain off the aqueous layer. Acidify the aqueous layer with dilute HCl to recover the phenol.

NJC 2010/P3/4c, d, e 3 (a) (i) Only a few Cl radicals are required to initiate/kick-start the propagation reaction, hence short duration of radiation will be sufficient. (a) (ii)
CH3 C H H C CH2 H CH3 C CH2 C H CH3 C H H C CH2 H C CH2 C H CH3

CH3 C H C

CH3

H C CH2 Cl

+
CH2

Cl

Cl

C H

Cl

Chemistry HIT4 Integrated Organic Chemistry Revision

CH3 C C CH2 H

Additional Questions

When

radical reacts with Cl2, 1-chlorobut-2-ene is formed.

(b) 1-chlorobut-2-ene undergoes nucleophilic substitution/hydrolysis with NaOH(aq) to form AgCl white ppt. 2-chlorobut-2-ene does not undergo nucleophilc substitution. The C-Cl bond is harder to break due to overlap of Cl p orbital with the adjacent C=C bond. Hence no free Cl ions is formed to react with Ag+ to form AgCl white ppt. (c)

Cl

DHS 2010/P3/2b,c 4(a) (i) CH3OH + O2 HCHO + H2O (ii) (iii) CH3OH: HCHO: K2Cr2O7 in dilute H2SO4, heat with distillation

sp3 (b) (i) Initiation: SO2Cl2 Cl + SO2Cl SO2Cl Cl + SO2 Propagation: CH4 + Cl CH3 + HCl CH3 + SO2Cl2 CH3Cl + SO2Cl SO2Cl and CH3

sp2

(ii)

(iii)

[5]

Chemistry HIT4 Integrated Organic Chemistry Revision

Additional Questions

Structure Elucidation
Solutions MJC 2010/P3/2ciii 5 (1) (2) C2H6. PV = nRT =

m RT Mr
0.25 x 8.31 x (127 + 273) Mr

101000 x 142 x 10-6 = Mr = 57.9 58.0 V is C4H10. (3) CxHy + ( x +

y ) O2 4

xCO2

y H2O 2

Volume of excess O2 + CO2 = 180 cm3 Since NaOH absorbs acidic CO2 gas. Volume of excess O2 =60 cm3 Volume of CO2 = 180 60 = 120 cm3 Volume of O2 used for combustion = 250 60 =190 cm3

120 =x 20
x=6 W is C6H14.
H H H H C H C H H C H H C

190 y = (x + ) 20 4
y = 14

H C H H

C H

H
(4) S is CH3COOH, T is

H3C

C CH3

COOH

Chemistry HIT4 Integrated Organic Chemistry Revision RVHS 2010/P3/3b 6 (i)

Additional Questions

The reaction is autocatalytic as the Ag produced catalyses the reaction. The rate of reaction increases at first due to the formation of the Ag autocatalyst, then decreases as the reactants are used up. Z undergoes condensation with 2,4-DNPH Z is a carbonyl compound / contains ketone or aldehyde functional group 1 molar equivalent of Z undergoes electrophilic addition with 2 molar equivalents of Br2 Z contains two alkene functional groups Z undergoes oxidation with hot acidified KMnO4(aq) to give two identical compounds Z contains a plane of symmetry Y is insoluble in water (due to large hydrophobic benzene ring) but can undergo acid-base reaction with NaOH(aq) Y contains phenol or carboxylic acid group Y does not undergo acid-carbonate reaction with Na2CO3 Y is not a carboxylic acid, so Y contains phenol group Y undergoes acid-metal reaction with Na Y contains phenol group
HO OH O O

(ii)

HCI 2010/P3/4d 7 J

K
CO2H

C CH3

Chemistry HIT4 Integrated Organic Chemistry Revision VJC 2007/P3/5c Question 8

Additional Questions

Chemistry HIT4 Integrated Organic Chemistry Revision

Additional Questions

Chemistry HIT4 Integrated Organic Chemistry Revision 9 ACJC 2006/P3/7a D has C:H = 1:1 and no of C> 6, D is basic and D undergoes electrophilic substitution with aq Br2 to give white ppt D is NH
2

Additional Questions

G undergoes neutralisation with aq NaOH to give D G is NH +

3

(ii)

H is obtained from basic hydrolysis of CH3CH2CN CH3CH2CN + OH- + H2O CH3CH2COO- + NH3 H is CH3CH2COOE reacts with aq alkaline iodine to give yellow ppt,CHI3 and H O E must be a methyl ketone or has the structure CH3 C E is CH3CH2COCH3 No of mol of F is 0.693/138.5 = 0.005 No of mol of NaOH required = 20.00/1000 x 0.50 = 0.01 F is a dibasic acid or F has 2 COOH groups

(iii)

F is HOOC-CHCl-COOH (iv) B undergoes oxidation and hydrolysis with hot aq KMnO4 to give E (ketone), F (acid) and G (amine salt) B must be an amide with C=C functional group B is B is C is

CH3 H CH3CH2 C
CH3 H CCHOH

CCHCl C NH
refluxed with aq NaOH to give salt C

O C O- Na+

CH3CH2 C