HYDROCARBONS REVISION

1.
O O

heating Zn-Hg/HCl
OH (A) (B)

B is
OH

(a) Methyl cyclohexane (b)ethyl cyclohexane (c) (d)

2.
O

H
NaOH
+ H3C NO2 (A)
con.H2SO4
(B)
O heating

O
Product B is

(a) (b)
NO 2 (B) NO2 (B)
NO2 NO2

HO
HO OH
OH
OH
OH OH
OH
OH
OH
(C) NO2 (D) NO2
(C) NO2 (D) NO 2

O O
O O
O O

O O

(c) (d)
NO2 (B) NO2 (B)
NO2 NO2

HO
OH HO
OH OH
OH
OH
OH OH
(C) NO 2 (D) NO2 OH

(C) NO2 (D) NO2

O O

O O
O O

O O

3.
O
1.HCN
2. LiAlH 4
(A). A is
+
3.NaNO 2/H

(C)
(A) (B)

(D)
 O
1.HCN O

2. LiAlH 4 1.HCN
(A). A is
+ 2. LiAlH4
3.NaNO 2 /H (A). A is
+
3.NaNO 2/H
O
O
(C)
(A) (B) (C)
(A) (B)

O
O

(D) (D)

4. Arrange the following in their increasing order of equilibrium constants for hydration
(1) acetone, (2)acetaldehyde (3)chloroacetone
(4)formaldehyde (5)chloroacetaldehyde
(a)1<2<3<4<5 (b)1<3<2<5<4 (c)1<3<2<4<5 (D) 1<2<3<5<4

5. Compound(a) C6H12O3 when treated with iodine in aqeous sodium hydroxide gives yellow ppt. When A is treated with
tollens reagent no reaction occur. When A is hydrolysed and then treated with tollens reagent, a silver mirror is formed in
test tube. Compound A is
OCH3 OCH3
(A) (B)
H3C H3C
OH CH3
OCH3
O O

OCH3
(C) H3C OCH3 (D)
H
OCH3
O OCH3
O

6. An Optically active compound C6H12O gives positive test with Bradys Reagent but negative test with tollens reagent.
What is the structure of the compound?
(a) 2- hexanone (b)2-methyl pentanal (C)3-methyl-2-pentanone (D)2-methyl-3-pentanone

7. Hexane dioic acid is heated in the presence of Barium carbonate which results in the formation of A. A is treated with
hydrazine to form B. B on heating in the presence of caustic potash forms C. C is
NH2
N

(a) 2-butene (b) cyclohexanone (c)cyclohexane (d)

8.
O
O

CH3

CH3

OH CH3
The above conversion can be achieved by
(a) Dehydration, hydrolysis (b)Retro aldol and further condensation
(c)Perkin condensation and clemmenson reduction (d) Clemmenson and perkin condensation

9. Identify the major product in the following reaction

 O O O aq. NaOH
Product is
+ Cl
H

O
(A) (B) O

O O

Cl O
(C) (D)
O

O
O
Cl

O O O aq.NaOH
Product is
+ Cl
H

O
(A) (B) O

O O

Cl O
(C) (D)
O

O
O
Cl

10.
14
H3C O
base
heat (A) :
I H

(A) is treated with acetaldehyde in the presence of hot alkali which yields B. B is
14 14
H3C (B) O
(A) H3C
H

O
14
(C) H3C Br
(D) H2C O
O
H3C
H3C H
H

11. Identify X in the following reaction

H 2S O 4 ( i) K O H , COOH
X
+
( ii) ( H ) NH2
HO OH
N OH N N
(a) (B) (C) N OH
(D)
12.
CHO X CH 3COONa
MeO H 3 O
MeO CH CHCOOH

The compound (X) is

(a) CH3COOH (b)BrCH2 COOH (c)(CH3CO)2O (d)CHO COOH

13. O
18
Ph C O O H (i) MeMgBr (excess)
COOH (i) Ca(OH)2
X1 X2 X3
COOH (ii) (ii) H 2O

+
H

X4 is
X4
(cyclic compound)

Me OH Me OH
18 18
(a) O (b) O (c) O (d) O

For Q.Nos 14,15,16, use the following information.

Cannizaro reaction involves hydride transfer directly from an aldehyde molcecule lacking alpha hydrogen to a second
molecule of either the same aldehyde(disproportionation) or sometimes to a molecule of a different aldehyde having no
alpha hydrogen (crossed cannizaro). Suitable dialdehydes can undergo intramolecular hydride transfer. The reaction
requires the presence of base. The reaction is believed to follow the pathway as shown below:
OH O-
O
OH
PhC H PhC H PhCHO
CPh
O O
H

O O OH
OH
CPh + H CPh CPh + H CPh

H O H
O
14. Identify the correct statement
(a) the slowest step in this reaction is the attack of OH-
(b)acetaldehyde also undergoes this reaction
(c)hydride transfer is the slowest step in this reaction
(D) low concentration of hydroxide ion is needed for carrying out this reaction.

15. Which one of the following is an example of intramolecular cannizaro reaction?

(a) ortho hydroxyl benzaldehyde with hydroxide ion (b)HOOC-CHO with hydroxide ion
(c)Ethane 1,2- dial with hydroxide ion (D) pentanal with hydroxide ion

16. When benzaldehyde is made to react with hydroxide ion (OD -) in the presence of D2O which of the following compounds
can be produced?
(a) PhCHDOH + PhCOO- (b)PhCH2OD + Ph-COO-
-
(c)PhCD2OH + Ph-COO (d)PHCH(D)OD + Ph-COO-

17. Find the product.

(a) (b) (c) (d) None of these

18. You have two C6H10O ketones, I and II. Both are optically active, but I is racemized by treatment ith base and II is not.
Wolff-Kishner reduction of both ketones gives the same achiral hydrocarbon, formula C 6H12.What reasonable structures
may be assigned to I and II?
(a) I is 3-methyl-4-penten-2-one; II is 4-methyl-1-penten-3-one
(b)I is 2-methylcyclopentanone; II is 3-methylcyclopentanone
(c)I is 3-methylcyclopentanone; II is 2-methylcyclopentanone
(d) I is 2-ethylcyclobutanone; II is 3-ethylcyclobutanone

19. What donor and acceptor reactants should be used to prepare the following
compound by an aldol reaction?
(a) acceptor = formaldehyde; donor = propanedial

(b)acceptor = 1,3-propanediol; donor = ethanal

(c)acceptor = propanal; donor = formaldehyde
(d) acceptor = formaldehyde; donor = propanal

20. A bis-aldol dimerization of 1-phenyl-1,2-propanedione, C6H5COCOCH3, gives which of the following?

(a) (b) (c) (d)

Numerical

N1. How many of the following compounds will answer for haloform test as well as tollens test

Cl O OH

H3C O Br H3C
CH3
CH3

O Br O

O O

CH3 CH3

O N
HO

N2. How many of the following will form stable hydrates. Trichloro acetaldehyde, ninhydrin, cyclopropane,
cyclohexanone, Ph-(CO)3-Ph, Formaldehyde,benzaldehyde,
N3. (3-methylphenyl)acetaldehyde is subjected to simple aldol reaction, how many isomeric products are expected?.

N4. How many of the compounds will undergo cannizaro reaction faster than benzaldehyde 2-chloro-5-nitro
benzaldehyde, nitrobenzaldehyde, para methoxy benzaldehyde,formaldehyde
How many of the following statements are correct?
1. Cyanohydrin formation takes place easier when +I effect groups are present in carbonyl compounds
2. Acetaldehyde in the presence of D2O forms CH3COD
3. Grignard reagent favours conjugate addition in CH2=CH-CHO
4. Formaldehyde does not form imine with ammonia
5. Multiple alkylation on a particular carbon is avoided by the use of LDA

N5. In how many of the following methods carbonyl compounds cannot be synthesised?
i. treatment of nitrile with DIBAL H
ii. treatment of acetyl chloride with lindlars catalyst
iii. treatment of nitrile with SnCl2 in the presence of dil.HCl.
iv. treatment of acetylene with dil.H2SO4 in the presence of HgSO4.

A aromatic stable carbonyl compound(a) of formula C9H6O3 which is optically inactive is treated with
N6. (1)HIO4(2)concentrated sodium hydroxide(3)H+ to yield a product (B). The difference in number of bonds
between A and B are

N7. Select incorrect statements

A. at low concentration of base, formation of enolate ion is the rate determining step in aldol condensation
O

B. to form through aldol, the donor is cyclopentanone and the acceptor is phenyl
acetaldehyde
H3C Br
H3C CH3
CH3

CH2 NaOH

OH OH
C. OH

C=NNH2
COCH3 (i) NH2NH2
product X. X is
D. (ii) alcoholic KOH CH3

N8. The degree of unsaturation present in the benzalacetone is x. The value of x/2.

N9. How many of the following can be reduced by

 O O O O
O
H3C CH3 CH3 H3C
H3C
O CH3

CH3 O

H3C O H3C CH3

CH3 NH

LiAlH4 CH3 O

N10. How many of the following statements correctly points out the difference between acid catalysed halogenation of
ketones with base catalysed halogenations of ketones
1. multiple halogenations happens in base catalysed whereas monohalogenation happens in acid catalysed
2. both forms same intermediate
3. Nucleophilic addition as well as nucleophilic substitution happens in the case of base catalysed halogenation of
acetaldehyde where as only nucleophilic substitution happens in acid catalysed halogenations.

ANSWER KEY:

1. B 2. C 3. A 4. B 5. C

6. C 7. C 8. B 9. A 10. A

11. D 12. C 13.B 14.C 15.C

16. D 17. B 18. B 19. D 20. A

N1. 4 N2. 5 N3.2 N4. 2 N5.1

N6. 0 N7.3 N8.5. N9. 4 N10. 1.