Practice Questions (Road Map Problems from Organic Chemistry) compiled by- ik gupta

1. Compound ‘A’ with the molecular formula C4H9Br is treated with aq. KOH solution. The
rate of this reaction depends upon the concentration of the compound ‘A’ only. When
another optically active isomer ‘B’ of this compound was treated with aq. KOH solution,
the rate of reaction was found to be dependent on concentration of compound and KOH
both. Write down the structural formula of both compounds ‘A’ and ‘B’. Out of these two
compounds, which one will be converted to the product with inverted configuration?

2. An alkene ‘A’ (Mol. formula C5H10) on ozonolysis gives a mixture of two compounds, ‘B’
and ‘C’. Compound B’ gives positive Fehling’s test and forms iodoform on treatment with
I2and NaOH. Compound C’ does not give Fehling’s test but forms iodoform. Identify the
compounds A, B, and C. Write the reaction for ozonolysis and formation of iodoform from
B and C.
3. An aromatic compound “A’ (Molecular formula C8H8O) gives a positive 2, 4-DNP test. It
gives a yellow precipitate of compound ‘B’ on treatment with iodine and sodium hydroxide
solution. Compound A’ does not give Tollen’s or Fehling’s test. On severe oxidation with
potassium permanganate forms a carboxylic acid ‘C’ (Molecular formula C7H6O2), which
is also formed along with the yellow compound in the above reaction. Identify A, B and C
and write all the reactions involved.
4. When liquid ′A′ is treated with a freshly prepared ammonical silver nitrate solution, it gives
a bright silver mirror. The liquid forms a white crystalline solid on treatment with sodium
hydrogen sulphite. Liquid ′B′ also forms a white crystalline solid with sodium hydrogen
sulphite, but it does not give a test with ammoniacal silver nitrate. Which of the two liquids
is aldehyde? Write the chemical equations of these reactions also.
5. A primary amine, RNH2 can be reacted with CH3-X to get secondary amine, R-NHCH3but
the only disadvantage is that 30 amine and quaternary ammonium salts are also obtained as
side products. Can you suggest a method where RNH2 forms only 20 amines?

6. A hydrocarbon ‘A’, (C4H8) on reaction with HCl gives a compound ‘B’, (C4H9CI), which
on reaction with 1 mol of NH3gives compound ‘C’, (C4H11N). On reacting with NaNO2 and
HCI followed by treatment with water, compound ‘C’ yields optically active alcohol, ‘D’.
Ozonolysis of ‘A’ gives 2 moles of acetaldehyde. Identify compounds ‘A’ to ‘D’. Explain
the reactions involved.

7. An organic compound (A) having molecular formula C3H7Cl on reaction with alcoholic
solution of KCN gives compound B. The compound B on hydrolysis gives compound C.
C on reduction with H2 / Ni gives 1-aminobutane. Identify A, B and C.
8. An alcohol A (C4H10O) on oxidation with acidified potassium dichromate gives carboxylic
acid B(C4H8O2). Compound A, when dehydrated with conc. H2SO4 at 443K gives
compound C. Treatment of C with aqueous H2SO4 gives compound D(C4H10O) which is
an isomer of A. Compound D is resistant to oxidation, but compound A can be easily
oxidized. Identify A, B, C and D and write their structures.

9. An organic compound A having molecular formula C6H6O gives a characteristic color with
aqueous FeCl3. When A is treated with NaOH and CO2 at 400K under pressure, compound
B is obtained. Compound B on acidification gives compound C which reacts with acetyl
chloride to form D which is a popular pain killer. Deduce the structure of A, B, C and D.
What is the common name of Drug D?
10. An ether A(C5H12O) when heated with excess of hot concentrated Hl produced two alkyl
halides which on hydrolysis from compounds B and C. Oxidation of B gives an acid D
whereas oxidation of C gave a ketone E. Deduce the structures of A, B, C, D and E.
11. An organic compound A, molecular formula C9H10O forms 2,4-DNP derivative, reduces
Tollen’s reagent and undergoes Cannizzaro reaction. On vigorous oxidation, it gives 1,2-
benzene dicarboxylic acids. Identify A.
Ans: The compound A will be 2-Ethylbenzaldehyde.

12. A compound X (C2H4O) on oxidation gives Y (C2H4O2). X undergoes haloform reaction.

On treatment with HCN, X forms a product Z which on hydrolysis gives 2-
hydroxypropanoic acid. Write down the structures of X and Y.

13. An alkene (A) with molecular formula (C7H14) on ozonolysis yields an aldehyde. The
aldehyde is easily oxidized to an acid (B). When B is treated with bromine in presence of
phosphorous it yields a compound (C) which on hydrolysis gives a hydroxyl acid (D). This
acid can also be obtained from acetone by the reaction with hydrogen cyanide followed by
hydrolysis. Identify A, B, C and D and write the chemical equations for the reactions
involved.
14. An organic compound A (C2H3N) is used as a solvent of choice for many organic reactions
because it is not reactive in mild acidic and basic conditions. Compound A on treatment
with Ni/H2 forms B. When B is treated with nitrous acid at 273 K, ethanol is obtained.
When B is warmed with chloroform and NaOH, a foul-smelling compound C is formed.
Identify A, B and C.
15. An organic compound A C3H6O2 on reaction with ammonia followed by heating yield B.
Compound B on reaction with Br2and alc. NaOH gives compound C (C2H7N). Compound
C forms a foul-smelling compound D on reaction with chloroform and NaOH. Identify A,
B, C, D and write the equations of reactions involved.
 16. Compound ‘A’ of molecular formula C5H11Br yields a compound ‘B’ of molecular formula
C5H12O when treated with aqueous NaOH. On oxidation, the compound ‘B’ yields a ketone
‘C’. Vigorously oxidation of ketone yields a mixture of ethanoic and propanoic acids.
Deduce the structures of ‘A’, ‘B’ and ‘C’.
17. A compound ‘A’ with molecular formula C5H12O, on oxidation forms compound ‘B’ with
molecular formula C5H10O. The compound ‘B’ on reduction with amalgamated zinc
and HCl gives compound ‘C’ with molecular formula C5H12. Identify A, B and C. Write
down the chemical reactions involved.

18. An organic compound A having the molecular formula C3H8O on treatment with copper at
573K gives B, B does not reduce Fehling solution but gives positive iodoform test. Write
down the structural formulae of A and B.

19. An organic compound a having molecular formula CH4O on treatment with P/I2 gives a
compound B. the compound B on further treatment with KCN and on subsequent reduction
gives compound C. the compound C on treatment with HNO2 gives another compound D,
which responds to the iodoform test. Identify the compounds A, B, C and D. Explain all
reactions.
20. A ketone A, which undergoes haloform reaction gives compound B on reduction. B on
heating with conc. H2SO4 gives compound C, which forms mono-ozonide D. D on
hydrolysis in the presence of Zn dust gives only acetaldehyde. Identify A, B, C and D.
Write the reactions involved.

21. An organic compound A having molecular formula CH3CN on reduction give another
compound B. B on treatment with HNO2 give ethyl alcohol and on warming with
CHCl3 and KOH (alcoholic) gave an offensive smelling substance C. Identify A, B and C.
Write down the equation involved.
22. An optically inactive compound (A) having molecular formula C4H11N on treatment with
HN02 gave an alcohol, (B). (B) on heating with excess of conc. H2SO4 at 440K gave an
alkene (C). (C) on treatment with HBr gave an optically active compound (D) having
molecular formula C4H9Br. identify A, B, C and D and write down their structural
formulae. Also write the equation involved.
{Ans. A=C4H9NH2 B=C6H9OH C=but-1-ene D= 2-bromobutane}
23. An organic compound A on treatment with ethyl alcohol gives a carboxylic acid B and a
compound C. Hydrolysis of C under acidic conditions gives B and D. Oxidation of D with
KMnO4 also gives B. B up to heating with Ca(OH)2 gives E (molecular formulae C3H6O).
E Does not give Tollen’s test and does not reduce Fehling solution, but forms 2,4-
dinitrophenyl hydrazone. Identify A, B, C, D and E.

{Ans. A= (CH3CO)2O B= CH3COOH C= CH3COOC2H5 D=C2H5OH E=CH3COCH3}

 24. Compound A (C6H12O2) on reduction with LiAlH4 yielded two compounds B and C. The
compound B on oxidation gives D, which on treatment with aqueous alkali and subsequent
heating furnished E. The latter, on catalytic hydrogenation gave C. The compound D was
oxidized further to give F, which was found to be a monobasic acid (mol.wt= 60). Deduce
the structures of A, B, C, D and E.

{Ans. A=CH3CH2CH2COOCH2CH3 B=CH3CH2OH C=CH3CH2CH2CH2OH

D=CH3CHO E=CH3CH=CHCHO F: CH3COOH}
25. An alkene A on ozonolysis yield acetone and an aldehyde. The aldehyde is easily oxidized
to an acid B. when B is treated with bromine in the presence of phosphorus, it yield
compound C, which on hydrolysis gives a hydroxyl acid D. This acid can be obtained from
acetone by the reaction with hydrogen cyanide followed by hydrolysis. Identify the
compound A, B, C and D.
26. Compound A(C5H10O) forms phenyl hydrazone, gives negative Tollen’s and iodoform
tests, and is reduced to pentane. What is the structure of compound A?
{Ans. CH3CH2COCH2CH3, Pentan-3-one}

27. A ketone A gives iodoform on reaction with iodine, and sodium hydroxide. A on reduction
gives B which on heating with sulphuric acid gives C. Con ozonolysis gives acetaldehyde
and acetone. Identify A, B and C.

{Ans. A= 3 methylbutan-2-one B= 3-methylbutan-2-ol C= 2-methylbut-2-ene}

28. An organic compound (A) which reduces Tollen’s reagent, on oxidation with potassium
permanganate formed compound (B) which has same number of carbon atoms as (A). (B) reacts
with Na2CO3 to give CO2. (B) on reaction with ethanol in presence of sulphuric acid formed a
compound having molecular formula C4H8O2 (C). Identify A, B, C with suitable reactions and
their IUPAC names.

29. Complete the reaction cycle with suitable reaction conditions.

30. Predict the reagent or the product in the following reaction sequence.

31. A liquid of molecular formula C7H6O forms an oxime, reduces Tollen’s reagent and undergoes
Clemmensen reduction to give toluene. Explain the reaction involved and write the structural
formula of this liquid.
32. Compound ‘A’ C5H12O reacts with K2Cr2O7/H+ to form ‘B’ C5H10 Compound ‘B’ reacts with
2,4-dinitrophenylhydrazine to form a yellow solid but does not give a silver mirror when treated
with Tollen’s reagent or a precipitate of iodoform when heated with basic solution of I2 . Draw the
structures of ‘A’ and ‘B’. Show the reactions involved.
33. An organic compound (A) on catalytic reduction gives (B), (B) on chlorination gives (C), (C)
on heating with sodium metal in presence of ether gives (D), (D) on chlorination gives 2-
chlorobutane as the major product. Give the names for (A), (B) (C) and (D) with reaction.
34. Compound (A), C7H8O, does not react with sodium metal. When (A) is treated with Hl, two
compounds (B) and (C) are formed. Compound (B) reacts with sodium to produce hydrogen, and
also forms a salt with NaOH. Compound (B) can be brominated, and the major product contains
three bromine atoms. Compound (C) contains iodine. Compound (C) reacts with magnesium in
dry ether to form a Grignard reagent. The Grignard reagent reacts with CO2, followed by acid
hydrolysis to form acetic acid. Identify (A), (B) and (C). Show the reactions involved.
35. A hydrocarbon (A) gives a positive Baeyer’s test. When (A) is treated with conc. sulphuric acid
and water, 2-butanol is produced. Ozonolysis of (A) gives propanal and methanol. What is the
structure of (A)? Write equations for all reactions.

36. Compound (A) having molecular formula (C3H602) which upon ammonolysis gives (B). (B)
when heated with Br2 in presence of KOH, gives (C). (C) when heated with Nitrous Acid gives
compound (D) which gives positive iodoform test. (D) again, oxidation gives compound (E) which
when reacted with ethyl alcohol gives pleasant smell. Find (A), (B), (C) (D) and (E).
37. A compound (A) reacts with thionyl chloride to give compound (B). Compound (B) reacts with
magnesium to form a Grignard reagent which is treated with acetone and the product hydrolyzed
to give 2-methyl-2-butanol. What are the structural formulae of (A) and (B)?
38. Compound (A) C6H12 decolorizes bromine but gives no reaction with sodium metal or
phenylhydrazine. Ozonolysis of (A) gives two compounds, (B) and (C), both react with
phenylhydrazine. Compound (B) gives positive Tollens’ and iodoform tests. Compound (C) has
molecular weight of 72. Suggest structures for (A), (B) and (C). Give equations for all reactions.
39. The compound (A), C3H8O, acts as a Lewis base in its reaction with conc. HBr to give (B),
C3H7 On treatment with conc. sulphuric acid, (A) undergoes an elimination reaction to give the
hydrocarbon (C). When (C) is reacted with concentrated HBr the result product (D), C3H7Br, which
is formed in accordance with the Markovnikov’s rule and is isomer with (B). Deduce the structures
of (A), (B), (C) and (D) and explain the reactions.
40. Compound (A), C6H12O, gives the following results:

(a) (A) gives positive test with hydroxylamine.

(b) (A) does not react with Tollen’s reagent.

(c) (A) on catalytic hydrogenation gives (B), C6H14O.

(d) (B) on treatment with conc. H2SO4 gives (C), C6H12.

(e) (C) on ozonolysis gives two compounds, (D)C3H6O and (E) C3H6O.

(f) (D) gives a negative Tollens’ test and +ve iodoform test.
(g) (E) gives a negative iodoform test and +ve Tollens’ test.

What are the structures of (A) to (E)? Explain the reactions.

41. An aliphatic compound (A) reacts with SOCl2 to give (B). The compound (B) is heated with
ammonia to produce (C). The compound (C) is further heated with Br2/KOH to yield (D). The
compound (D) gives (E) when trailed with NaN02/HCI at low temperature. The compound (E) is
primary alcohol which gives positive iodoform test. Identify (A), (B), (C), (D) and (E). Write
reactions involved.
42. An amine (A) has formula C3H9. When (A) is treated with nitrous acid at 0 — 5°C, a reaction
takes place and an oily yellow layer separates from the reaction mixture. What is (A)? Give an
equation for the reaction.

43. An organic compound (A) having molecular formula CH40 on treatment with red phosphorus
and iodine gives a compound (B). The compound (B) on treatment with KCN followed by
reduction gives a compound (C). The compound (C) on treatment with nitrous acid at cold
condition gives a compound (D) which gives positive iodoform test. Identify the compounds (A),
(B), (C) and (D) and give all reactions.

44. An unknown ester C5H1202 was hydrolyzed with water and acid to give carboxylic acid (A)
and alcohol (B). Treatment of (B) with PBr3 gave an alkyl bromide (C). When (C) was treated with
KCN, a product (D) was formed which on acid hydrolysis gave the carboxylic acid (A). Give the
structure and name of the original ester. Identify (A), (B), (C) and (D) and write equations for the
reactions involved.
45. An organic compound (A) when reacts with alc. KOH gives (B) which on ozonolysis gives
(C). This compound on Clemmensen reduction gives propane. The compound (C) also gives
iodoform test. Compound (D) is obtained when (C) undergoes Aldol condensation. On reaction of
(C) with 2,4 -DNP reagent gives compound (E). Identify (A), (B), (C), (D) and (E).

46. An organic compound (A) reacts with HCN to give (B). On hydrolysis of (B) in acidic medium
gives (C). Compound (A) also produces propane when treated with zinc-amalgam and HCI.
Identify (A), (B) and (C) with reaction and give their IUPAC names. What product would you
expect when (A) is treated with trichloromethane in alkaline medium?
47. An organic compound (A) reacts with PBr3 to give (B). Compound (B) produces (C) when
heated with alc. KOH. The compound (C) undergoes ozonolysis to yield ethanal and methanal as
the products. The compound (A) responds to the iodoform test. Identify (A), (B), (C) and write
reactions involved. How is (A) obtained from CH3MgBr?

48. Compound (A), C5H10O gives the following results:

 Treatment with 2,4-DNP gives a coloured precipitate.
 It gives negative Tollen’s test.
 It gives positive iodoform test.
Suggest two structures for (A) that are consistent with these facts.
49. Identify A, B, C, D and E in the following reaction.

50. Prepare a sequence of reactions from the given list with necessary conditions and reagents.