Structure Identification

ORGANIC CHEMISTRY
COURSE CODE : JA, JB, EA & EB
TARGET: JEE (Main+Advanced)

Introduction
The main objective of an organic chemist is the determination of the structure of a new organic
compound which has been obtained in pure state either from a natural source or synthesised in the
laboratory.
In order to establish the correct structure of an organic compound, it is necessary to detect skeleton of
compound, elements and functional groups present in the organic compound.

1. Monohalogenation :
When an alkane or a cycloalkane is treated with halogen (Cl2, Br2, F2, I2), a photochemical reaction
takes place, in which a C–H bond cleaves and a C–X bond is formed. In such reactions if one H-atom is
substituted by one halogen atom, then this is known as monohalogenation reaction.
Applications : If a molecule has more than one type of H-atoms, then on monochlorination, it forms a
mixture of monochloroisomers. All these products (structures) are position isomers.
Conclusion : Hence, it can be concluded that the total no. of position isomers (structural) of
monochloro compounds is equal to the number of different types of H-atoms present in the reactant.
The different type of H-atoms are also known as non-identical Hydrogens or non-equivalent Hydrogens
or chemically different Hydrogens.
Note : In aromatic hydrocarbons, the hydrogen atoms of the side-chain are chlorinated, but H-atoms of
Benzene ring are stable.
Cl , h
Ex. (i) CH4 
2
 CH3Cl + HCl ¼1–Monochloroproduct½
Monochlorination

Cl
Cl , h –
(ii) 2

 + HCl ¼1–Monochloroproduct½
Monochlorination

CH3 CH2Cl
–

Cl , h
(iii) 2

 ¼1–Monochloroproduct½
Monochlorination

Note : Only one monochloro product is formed because aromatic H atoms are inert towards this reaction.
Cl , h
(iv) CH3–CH2–CH2–CH3 
2
 2 Products (structure isomers)
Monochlorination
Cl , h
(v) CH3–CH2–CH2–CH2–CH3 
2
 3 Products (structure isomers)
Monochlorination

Cl , h
(vi) 2
 4 Products (structure isomers)

Monochlorination
CH3
–

Cl , h
(vii) 2
 5 Products (structure isomers)

Monochlorination

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 Structure Identification

2. Catalytic hydrogenation :
Alkenes, Alkynes, polyenes or polyynes can be hydrogenated by using catalysts Ni/Pt/Pd at room
temperature.
All Carbon–Carbon  bonds(C=C, CC) get hydrogenate. The reaction can’t be stopped at any
intermediate stage.

Note: (i) Aromatic  bonds are stable at room temperature but can be hydrogenated at high temperature.
(ii) It can be concluded that the hydrogenation product of an alkene or alkyne or any unsaturated
compound is always a saturated compound.
(iii) The no. of moles of H2 consumed by 1 mole of compound is equal to the no. of  bonds.
(iv) During catalytic hydrogenation carbon skelton does not change.

Application : This reaction gives an information about molecule that the molecule is saturated or
unsaturated.

General reaction :
Ni
(a) R–CH=CH–R + H2   R–CH2–CH2–R
Ni / Pt / Pd
(b) R–CC–R + 2H2   R–CH2–CH2–R
H2

H2
R – CH  CH – R   R–CH2–CH2–R
(Not isolated)
2H2 / Ni
(c) CH2=CH–CH=CH2   CH3–CH2–CH2–CH3
CH = CH2 CH2 – CH3
H2 / Ni
–

(d) 
room temperature
CH2 – CH3
H2/Ni
–

(100 – 150ºC)

3. Ozonolysis :
Ozonolysis reaction is used to determine the position of C=C, CC in a molecule. In this reaction
Alkene, Alkyne and polyalkene on ozonolysis undergo oxidative cleavage. It is of two types.
(i) Reductive ozonolysis
Reagents are : (1) O3 (ozone) (2) Zn or (CH3)2S and H2O or CH3COOH
The products are carbonyl compounds (aldehydes or ketones).

(ii) Oxidative ozonolysis

Reagents are : (1) O3 (ozone) (2) H2O2 or H2O
The products are ketones and/or acids.

Note : (i) Ozonolysis does not interfere with other functional groups.
(ii) At higher temperature, the aromatic double bonds can also undergo ozonolysis reaction.

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 Structure Identification
General reaction :
(i) Reductive ozonolysis
(1) O
3
  R–CH=O + + ZnO + H2O
(2) Zn/H2O

(1) O3
R–CC–H   R–C–C–H + ZnO + H2O
(2) Zn/H2O
OO

(ii) Oxidative ozonolysis

(1) O
R–CH C–R 3
  R–COOH + O=C–R + H2O
(2) H2O2
R R
(1) O3
 R–COOH + HCOOH
R–CC–H 
(2) H2O2

H2O+CO2

(1) O
Ex. (a) CH2=CH2 
3
 CH2=O + CH2=O
(2) Zn/H2O

(1) O
(b) CH3–CH2–CH=CH2 
3
 CH3–CH2–CH=O + O=CH2
(2) Zn/H2O

(1) O
(c) CH2=CH–CH2–CH=CH–CH3 
3
 CH2=O + O=CH–CH2–CH=O + O=CH–CH3
(2) Zn/H2O

(1) O
(d) 3
  2OHC–CH2–CHO (Propandial)
(2) Zn/H2O

(1) O
(e)  3
 O=CH–CH2– C –CH2–CH=O + O=CH2
(2) Zn/H2O ||
O

(1) O (  )
(f) 3
 or (glyoxal)
(2) H2O2

(i)O3
+ CH3CH=O
CH = CH – CH3 (ii)Zn, H2O
–
(g)
2 O=CH–CH=O + O=CH–C–CH=O + CH3CH=O
(ii)Zn, H2O
O

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 Structure Identification

 Marked Questions may have for Revision Questions.

PART - I : ONLY ONE OPTION CORRECT TYPE

1. The degree of unsaturation of following compound C8H12O, C3H5N, C4H8O are respectively :
(A) 4, 3, 2 (B) 3, 2, 1 (C) 2, 1, 3 (D) 2, 2, 3

2. Which of the following hydrocarbons give same product on hydrogenation.

(A) 2-Methyl hex-1-ene & 3-Methyl hex-3-ene
(B) 3-Ethyl hex-1-en-4-yne & 2-Methylhept-2-en-4-yne
(C) 3-Ethylcycloprop-1-ene & 1,2-Dimethylcycloprop-1-ene
(D) 2-Methylbut-2-ene & 3-Methylbut-1-ene

3. Number of moles of hydrogen will required for complete hydrogenation of one mole of following
compound :

(A) 6 (B) 7 (C) 5 (D) 3

4. How many alkenes on catalytic hydrogenation give isopentane as a product (consider only structural
isomers)?
(A) 2 (B) 3 (C) 4 (D) 5

5. If 1 mole H2 is reacted with 1 mole of the following compound.

Which double bond will be hydrogenated ?

(A) c (B) b (C) a (D) d

6. Only two isomeric monochloro derivatives are possible for :-

(A) n-Pentane (B) 2,4-Dimethyl pentane
(C) Toluene (D) 2,3-Dimethyl butane

7. The number of possible monochloro derivatives of 2, 2, 3, 3-Tetramethylbutane is -

(A) 2 (B) 3 (C) 4 (D) 1

8. Which of the following alkene gives four monochloro (structural isomer) products after hydrogenation ?
(A) Pent-2-ene (B) 2-Methylbut-2-ene
(C) 3-Methylhex-2-ene (D) 2, 3-Dimethylbut-2-ene

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SI - 4
 Structure Identification
9. Which of the following compound will give four monochloro (structural) product on monochlorination.

(A) (B) (C) (D)

O3 / Zn
10. X   +

Y.
The IUPAC name of compound Y is :
(A) 2-Cyclohexylbutane (B) 1-Methylpropylcyclohexane
(C) Butylcyclohexane (D) 1-Cyclohexylbutane

11. An alkene give two moles of HCHO, one mole of CO2 and one mole of on

ozonolysis. What is its structure?

(A) (B)

(C) (D)

12. Which of the following compound on reductive ozonolysis does not give glyoxal as one of the product.

(A) (B) (C) (D)

13. Compound A (C6H12) does not absorb H2 in presence of Ni. It forms two monochloro isomers on
photochemical chlorination. Its structure can be :

(A) (B) (C) (D)

14. Which alkyne will give 3-Ethyl heptane on catalytic hydrogenation.

(A) (B) (C) (D)

15. Farnesene is a compound found in the waxy coating of apples. On hydrogenation it gives 2,6,
10-Trimethyl dodecane. On ozonolysis it gives one mole acetone, one mole of formaldehyde, one mole
of 2-Methylpentanedial and one mole of 4-Oxopentanal. The structure proposed for Farnesene may be

(A) (B)

(C) (D)

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 Structure Identification
16. A compound P(C5H6) on hydrogenation form a hydrocarbon B(C5H10) which gives only one monochloro
product. The compound 'P" is:

(A) (B) (C) (D) CHC–CH2–CH=CH2

17. How many products (structural isomers only) are formed by monochlorination of given compound.
CH3

CH3 CH3
(A) 4 (B) 3 (C) 5 (D) 6

Ozonolysis
18. An alkene (A) 
 , A is :

(A) (B) (C) (D)

19.

Compound 'X' is :
(A) 1-Methylcyclopropene (B) 1, 4-Dimethylcyclohexa-1,4-diene
(C) 1, 4-Dimethylcyclohexa-1,3-diene (D) 1, 2-Dimethylcyclohexa-1,4-diene

20. The chemical reactions of an unsaturated compound ‘M’ are given below. Determine the possible
structural formula of ‘M’

(M)

(A) (B) (C) (D)

PART - II : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

21. Which of the following compounds after complete hydrogenation will form three monochloro structural
isomeric products ?

(A) (B)

C  CH
(C) (D) |
HC  C – CH – C  CH

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 Structure Identification
CHO
(1) O3
CH3–CH
(2) Zn/H2O
CHO
22. C8H12
(X) H2/Ni
Y
True statements is/are

(A) Structure of X is .

(B) Structure of X is .

(C) Y on monochlorination produce 3 monochloro structural products.

COOH
(D) Oxidative ozonolysis product of X is CH 3–CH .
COOH

23. Which of the following compound gives 1,4-Dimethyl cyclohexane when undergo catalytic
hydrogenation.
CH2

(A) (B) (C) (D)

CH3

PART - III : SINGLE AND DOUBLE VALUE INTEGER TYPE

24. How many isomeric alkynes on catalytic hydrogenation gives 3-Ethyl-4-methylheptane ?

25. Find the number of structural isomers of fully saturated cycloalkane of molecular formulae C6H12 which
give three monochloro structural products.

26.

Calculate sum of number of products formed in the reaction a, b and c.

27. How many alkenes, alkynes and alkadienes can be hydrogenated to form Isopentane (Including all
structural isomers)

28. ‘n’ number of alkenes yield 2,2,3,4,4-pentamethyl-pentane on catalytic hydrogenation and ‘m’ number
of monochloro structural isomers are possible for this compound.
Report your answer as (n + m).

29. How many isomeric structural alkene on catalytic hydrogenation gives 3-Methyl hexane.

H / Ni Cl / h
30. 2
 P 
2
 Q (Total number of monochloro structural products).

31.^ How many terminal alkynes having molecular mass 68 is possible ?

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 Structure Identification

PART - IV : JEE (MAIN) / AIEEE PROBLEMS (PREVIOUS YEARS)

32. On mixing a certain alkane with chlorine and irradiating it with ultraviolet light, it forms only one
monochloroalkane this alkane could be : [AIEEE 2003, 3/225]
(1) propane (2) pentane (3) isopentane (4) neopentane.

33. Of the five isomeric hexanes, the isomer which can give two monochlorinated compounds is ?
[AIEEE 2005, 3/225]
(1) n-Hexane (2) 2,3-Dimethylbutane
(3) 2,2-Dimethylbutane (4) 2-Methylpentane

34. In the following sequence of reactions, the alkene affords the compound 'B'
O3 H2 O
CH3CH=CHCH3   A   B, compound B is [AIEEE 2008, 3/105]
Zn
(1) CH3CH3CHO (2) CH3COCH3 (3) CH3CH2COCH3 (4) CH3CHO

35. Ozonolysis of an organic compound 'A' produces acetone and propionaldehyde in equimolar mixture.
Identify 'A' from the following compounds : [AIEEE 2011, 4/120]
(1) 1-Pentene (2) 2-Pentene
(3) 2-Methyl-2-pentene (4) 2-Methyl-1-pentene

36. Which branched chain isomer of the hydrocarbon with molecular mass 72u gives only one isomer of
mono substituted alkyl halide ? [AIEEE 2012, 4/120]
(1) Tertiary butyl chloride (2) Neopentane
(3) Isohexane (4) Neohexane

37. Which compound would give 5-keto-2-methyl hexanal upon ozonolysis ? [JEE(Main)-2015, 4/120]
CH3 CH3 CH3
H3C
(1) (2) (3) (4)
CH3 CH3

EXERCISE
1. (B) 2. (D) 3. (C) 4. (B) 5. (D)

6. (D) 7. (D) 8. (B) 9. (D) 10. (B)

11. (B) 12. (A) 13. (C) 14. (B) 15. (C)

16. (C) 17. (B) 18. (C) 19. (D) 20. (C)

21. (CD) 22. (BCD) 23. (ABC) 24. 3 25. 3

26. 5 27. 6 28. 4 29. 6 30. 2

31. 2 32. (4) 33. (2) 34. (4) 35. (3)

36. (2) 37. (2)

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SI - 8