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Basic Principles of Organic Chemistry

EXERCISE 1 JEE MAIN/BOARDS

Q.1 Explain tetravalency of carbon. CH2=CH–C2H5,CH3CH=CHCH3,

CH2=CHCH=CH2,
Q.2 Why does carbon undergo hybridization CH2=C–––C=CH2
prior to bond formation.
CH3–CH=CH–CH=CH2 and CH3 CH3
Q.3 Draw the orbital diagram of methane and
ethane molecules indicating the hybridization Q.13 What is homologous series? Given its
involved. important characteristics. Write the first four
homologues of alcohols and give their IUPAC
Q.4 Which of the following has higher melting
names.
point and why?
(a) Fumaric acid (b) Maleic acid Q.14 Explain in the following terms with one
example in each case, (i) word root (ii) primary
Q.5 What is the effect of type of hybridization
and secondary suffixes and prefixes.
on (i) bond length (ii) bond
strength. Q.15 0.2018 gm of silver salt of dibasic acid
gives 0.1073 gms of silver on complete ignition.
Q.6 Draw bond-line formulae for (a) tert-
What is the molecular weight of the acid?
butylcyclopentane, (b) cyclohexanone.
Q.16 List the different methods used for the
Q.7 Which is more soluble and why?
purification of organic compounds.
OH OH
NO2 Q.17 Explain inductive and electrometric effect
with examples.

NO2 Q.18 What is resonance? How does resonance

explain that all the carbon-carbon bond lengths
(a) (b)
in benzene are equal (139) pm?
Q.8 Write condensed and bond-line structural
Q.19 What is resonance effect? What are its
formulae for all the possible isomers of
various types? In what respects, does the
molecular formula
resonance effect differ from inductive effect?
(a) C6H14 (b) C6H10 (c) C8H10
(d) C8H18 (e) C3H8O (f) C3H8O Q.20 Common upon the statement: 'Usual
(g) C3H8O2 (h) C6H11NO2 order of inductive effects of the alkyl groups is
often reversed when attached to a double or a
Q.9 What is a functional group? Write the
benzene ring.' Name the electronic effect and
functional groups of the following:
illustrate your answer with suitable examples.
(i) Thioalochol (ii) Isothiocyanate
(iii) Thiocyanate and (iv) Sulhponic acid Q.21 Explain hyperconjugation effect.
(v) Sulphoxides
Q.22 What is principle of column
Q.10 What are homocyclic and heterocyclic chromatograph?
compounds? Given two examples with their
names. Q.23 Explain the principle of steam
distillation.
Q.11 Hydrazine does not show a positive test
for Lassaigne's test of nitrogen. Why? Q.24 When is the process of fractional
distillation employed?
Q.12 Giving reason arrange the following in Q.25 When is the process of fraction
increasing order of reactivity towards HBr. crystallization employed?

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Basic Principles of Organic Chemistry

Q.26 0.3168 gms of the platinic chloride of a

mono acidic base gave 0.1036 gms of platinum,
what is the molecular weight of the base?

Q.27 How will you separate two components

when: (a) their boiling points differ by a few
degrees,
(a) They are soluble in the same solvent.
(b) They are almost immiscible in water but are
volatile in steam?

8.2
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Basic Principles of Organic Chemistry

EXERCISE 2 JEE MAIN

Q.1 Which of the following species have a O O–

••
trigonal planar shape? H–C–OH H–C–O–H
 ••

(A) :CH3– (B) CH3+ (I) (II)

–
(C) BF4 (D) SiH4 – 
O O
Q.2 A nucleophile must necessarily have - H–C=O–H H–C=O–H
 –
(A) an overall positive charge
(III) (IV)
(B) an overall negative charge
Which of the following order is correct for the
(C) an unpaired electron
stability of the four contributing structures?
(D) a lone pair of electrons
(A) I > II > III> IV (B) I > II > IV > III
Q.3 Which of the following has a bond formed (C) I > III > II > IV (D) none of these
by overlap of sp3–sp2 hybrid orbitals?
Q.10 Examine the following 
(A) CH3– –CH3 (B) CH3–CH=CH–CH3 NH3 NH3
two structures for the
(C) CH2=CH–CH=CH2 4 
. anilinium ion and choose
Q.4 The bond between carbon atoms (1) and the correct statement from
1 the ones given below. (I) (II)
CN
2 (A) II is not an acceptable
canonical structure because carbonium ions
are less stable than ammonium ion
carbon atom (2) in compound,
(B) II is not an acceptable structure because it
(A) sp3 and sp2 (B) sp2–sp3
is non-aromatic
(C) sp and sp2 (D) sp and sp
(C) II is not an acceptable canonical structure
Q.5 In the compound CH2=CH–CH2–CH2– because the nitrogen has 10 valence electrons
CH2– 2–C3 bond is of the type is - (D) II is an acceptable canonical structure
(A) sp – sp2 (B) sp3 – sp3
Q.11 Resonance structure of a molecule
(C) sp – sp2 (D) sp2 – sp3
should have –
(A) identical arrangement of atoms
Q.6 Which of the following species has a
(B) nearly the same energy content
trigonal planar shape?
(C) the same number of paired electrons
(A) CH3– (B) CH3+
•
(D) identical bonding
(C) BF4– (D) C H3
Q.12 HC≡CH  (A)  (B).

HgSO 4 dil. OH
   
H2SO 4 5ºC
Q.7 The stability order of alkenes is given as
Give the IUPAC name of B.
CH3–CH=CH2 > CH2=CH2, the reactivity order
(A) 2-butenal B) 3-
towards electrophilic addition reaction is
hydroxybutanal
given by
(C) 3-formyl 2-propanol (D) 4-oxo-2-
(A) CH2=CH2 > CH3–CH=CH2
propanol
(B) CH3–CH=CH2 > CH2=CH2
Q.13 Geometrical isomerism is shown by
(C) CH3–CH=CH2 equal to CH2=CH2
H H H F
(D) None of these
(A) C=C (B) C=C
Q.8 Carbanion is H H H3C I
(A) an electrophile (B) a nucleophile H3C Cl H Br
(C) a zwitter ion (D) a free radial (C) C=C (D) C=C
Q.9 Formic acid is considered as a resonance H3C I H3C Br
hybrid of the four structures.

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Basic Principles of Organic Chemistry

Q.14 Polarisation of electrons in acrolein may Q.19 In the identification of phosphorus, the
be written as phosphorus in the organic compound is
 
converted to PO43– using
(A) C H2  CH  C H  O (B)
 
(A) NaOH (B) Na2O
C H2  CH  CH  O (C) Na2O2 (D) NaO2
 
(C) C H2  C H  CH  O (D) Q.20 The correct reactivity order(s) for SN1
  reaction is/are
C H2  CH  CH  O
1. Ph–Br < Ph–CH2–Br
Q.15 What is the basic strength order 2. Ph–Br > PhCH2Cl
H 3. O2N CH2–I > CH3 CH2–I

N: N:
A. B. > Br
4. Br
••
NH2 (A) 1, 2, 3 (B) 2, 4
•• (C) 1, 4 (D) 2, 3, 4
C. CH– : D. C=NH
••
NH2 Q.21 The incorrect statement about SNI
(A) A > B > C > D (B) D > A > B > C -C atom is chiral)
(C) D > C > A > B (D) C > D > A > B (A) a stereoisomer is formed
(B) two step reaction
Q.16 The leaving group ability of the following (C) rearrangement takes place
will be expressed in the order (D) the rate is independent of concentration of
O O nucleophile
+
H3C S–O H3N S–O
Q.22 The acidic strength of chloro substituted
O O
1. 2. benzoic acid is
O (A) Benzoic acid>o-chloro > m-chloro > p-
H3C C–O H3N O hloro
(B) o-chloro > m-chloro>p-chloro>benzoic
3. 4. acid
(A) 1 > 2 > 3 > 4 (B) 2 > 1 > 3 > 4 (C) m-chloro>o-chloro> p-chloro >benzoic
(C) 4 > 3 > 2 > 1 (D) 2 > 4 > 3 > 1 acid
(D) none of these
Q.17 The rearrangement of following
carbocation will Q.23 The major product of following reaction
occur with the (p) is
Me O
shifting of group … Me(r) Ph (A) CH3–NO2 (B)
C
to yield the most + Me Ph NO2
stable carbocation (q)

(A) Me – (p) (B) Me – (q) (C) NN (D) CH3CONH2

(C) Me – (r) (D) bond – (s)

Q.18 Which of the following is aromatic CH3

(A) (B) Br H
Q.24 + NaI  Products
H CH3

CH2–CH3
(C) (D) H H
Product of reaction is -

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Basic Principles of Organic Chemistry

CH3 CH3 (B) Singlet carbene = Triplet carbine

(C) Singlet carbene < Triplet carbine
I H H I
(A) (B) (D) Cannot be predicted
H CH3 H CH3
CH2–CH3 CH2–CH3
Q.31 The number of isomeric chloro butanes
formed by the monochlorination of n-butane
are -
CH3 CH3
(A) 1 (B) 2 (C) 3 (D) none of these
I CH3 I H
(C) (D) Q.32 The reactivity order of HCHO, ArCHO,
H CH3 CH3 H
ArCOAr, ArCOR, RCOR is towards nucleophilic
CH2–CH3 CH2–CH3 attack is -
(A) HCHO > ArCHO > ArCOAr > ArCOR >
Q.25 Which of the following is most reactive RCOR
towards SN2 reaction? (B) HCHO > ArCOAr > ArCHO > ArCOR >
Cl
Cl Cl Cl RCOR
(A) (B) (C) (D) (C) HCHO > ArCHO > RCOR > ArCOAr >
RCOAr
CH3 (D) None of these
Cl NO2
Q.33 The number of meso forms for glucose
Q.26 Magnesia mixture used during
are
estimation of phosphorous is -
(A) 1 (B) 2
(A) MgCl2 + NH4Cl
(C) 3 (D) none of these
(B) HgCl2 + NH4Cl + little of NH3
(C) HgCl2 + NH4Cl Q.34 The Lassaigne's extract is boiled with dil.
(D) MgCl2 + NH4Cl + little of NH3 HNO3 before testing for halogens such that -
(A) AgX is soluble in HNO3
Q.27 In the Kjeldal's estimation of nitrogen in
(B) Na2S and NaCN are decomposed by HNO3
the form of NH3 small amounts of K2SO4 is
(C) Ag2S is soluble in HNO3
added to the system -
(D) AgCN is soluble in HNO3
(A) Here K2SO4 acts as a catalyst
(B) To provide common ion effect for Passage (Q.35 to 37)
dissociation of CuSO3 Those compounds which rotate plane
(C) K2SO4 is responsible for converting NH3 to polarised light are optically active compounds.
(NH4)2SO4 They must be chiral, i.e. should not have any
(D) K2SO4 raises the boiling point of H2SO4 plane of symmetry. They should have chiral
carbon atom. Meso compounds have internal
Q.28 The compound having maximum enol
plane of symmetry.
content -
(A) CH3CH2CHO (B) CH3COCH3 Q.35 Which of the following alkane shows
(C) CH3CHO (D) CH3COCH2COCH3 optical isomerism?
(A) 2-methyl pentane (B) 3-methyl pentane
Q.29 In which of the following pairs the
(C) 2,3-dimethyl pentane (D) Both (B) and (C)
difference in dipole moment is maximum -
(A) cis and trans 1,2-Dichloro ethane Q.36 (A) d-glucose and l-glucose
(B) cis and trans 1-chloropropene (B) Glucose and L-glucose
(C) o-Xylene, m-xylene (C) Racemic-tartaric acid
(D) Dipole moment does not change with (D) Meso-tartaric acid
configuration
Q.37 Which of the following is meso
Q.30 The stability of carbenes is - compounds?
(A) Singlet carbene > Triplet carbine

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Basic Principles of Organic Chemistry

COOH COOH Matching Column:

(A) H OH (B) H OH Q.42 Match the following:
HO OH H OH Column-I Column-II
COOH COOH (A) (CH3)2C=CH2 + (P) 1º
CHO HBr carbocation
CHO
(B) + CHBr3 + (Q) 2º
(C) H OH (D) H OH
HO H carbocation
(CH3)3COK
CHO CH2OH
(C) CH2OH (R) 3º
+ H–
Assertion and Reason: carbocation
Each of the questions given below consists of (D) OH (S) Carbene
two statements, an assertion (A) and reason
(R). Select the number corresponding to the
appropriate alternative as follows Q.43 Match the following:
(A) If both A and R are true and R is the correct Column-I Column-II
explanation of A. (A) Carbocatio (P) Reaction with
(B) If both A and R are true and R is not the n ethylene
correct explanation of A. (B) Carbanions (Q Reaction with
(C) If A is true but R is false. ) opposite species
(D) If A is false but R is true. (C) Carbenes (R) Rearrangement
(D Free (S) Disproportionatio
Q.38 A: Trophylium cation is more stable than ) adicals n
(CH3)3C+.
R: It is stabilized by both resonance effect and Q.44 Match the following:
inductive effect. Column-I Column-II
O
(A) (P) E2(Major)
Q.39 A: In benzyne, two out of six carbon 
OH
atoms are sp-hybridised. 
H3C Br
R:
(B) O (Q) E1(Major)
Q.40 A: PH3 is stronger nucleophile than NH3. Ph Br PhSNa
Ph  

R: PH3 is stronger base than NH3.

Q.41 A: The carbocation CF3  CH2 is less
(C) Me3C (R) SN1
 O
stable than CF3 . Br
HBr
(Major)
 
R: In case of CF3  CH2 , CF3 is strong electron
withdrawing, therefore increases +ve, charge (D) OH (S) SN2
 H3PO4
whereas in CF3 , lone pair of F overlap with  
D
(Major)
vacant p-orbital of carbon reducing +ve (T) E1CB
charge by p-p bonding or back bonding.
(Major)

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Basic Principles of Organic Chemistry

PREVIOUS YEARS’ QUESTIONS JEE MAIN

Q. 1 O– O–
O O
HOOC
N
OH
(A) N+ (B)

O2N
O–
CH – –
O O O O–
OH (2003) N +
N +

2 moles of NaNH2
   (C) (D)
The product A will be -
–OOC
(A) OH
(B) –OOC O– O
OH

O2N
Q.6 The correct stability order of the
O2N
CH
C–
following resonance structures is - 2009)
O– OH + – + –
H2C=N=N H2C–N=N
HOOC HOOC (I) (II)
(C) O– (D) OH

– + – +
O2N O2N
H2C–NN H2C–NN
CH C–
(III) (IV)
O– O–
(A) (I) > (II) > (IV) > (III)
Q.2 The correct order of basicity of the (B) (I) > (III) > (II) > (IV)
following compounds is - (2001) (C) (II) > (I) > (III) > (IV)
NH (D) (III) > (I) > (IV) > (II)
(1) CH3—C (2) CH3CH2NH2 Q.7 In the following carbocation, H/CH3 that
NH2
is most likely to migrate to the positively
(3) (CH3)2NH (4) CH3CONH2
charged carbon is – (2009)
(A) 2 > 1 > 3 > 4 (B) 1 > 3 > 2 > 4 H H
(C) 3 > 1 > 2 > 4 (D) 1 > 2 > 3 > 4
1 2 + 4 5
H3C––C––C––C––CH3
Q.3 Arrange in order of increasing acidic 3

strength (2004)
 HO H CH3
H3N + NH3 (A) CH3 at C-4 (B) H at C-4
Z Y (C) CH3 at C-2 (D) H at C-2
COOH
X Q.8 Hyperconjugation involves overlap of the
(A) X > Z > Y (B) Z < X > Y following orbitals – (2008)
(C) X > Y > Z (D) Z > X > Y (A) - (B) -p
(C) p-p (D) -
Q.4 Which of the following, has the most
acidic hydrogen? (2000) Q.9 Amongst the following, the total number
(A) 3-hexanone (B) 2,4-hexanedione of compound soluble in aqueous NaOH is –
(C) 2,5-hexanedione (D) 2,3-hexanedione (2010)
NO2 OH
H3C CH3
Q.5 The most unlikely representation of N COOH

resonance structure of p-nitrophenoxide ion is H3C

N
CH3
(1999) OCH2CH3 OH
CH2CH3 COOH
CH2OH CH2CH3

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Basic Principles of Organic Chemistry

Q.10 The total number of contributing (C) Trans-1,2dichloro-2-pentene

structures showing hyper conjugation (D) Trans-1,2dichloro ethene
(involving C-H bonds) for the following Q.16 The molecules that will have dipole
carbocation is (2011) moment are – (1992)
H3C 
CH2CH3 (A) 2,2-dimethyl propane
(B) Trans-2-pentene
(C) Cis-3-hexene
(D) 2,2,3,3-tetramethyl butane
Q.11 The optically active tartaric acid is
Q.17 Only two isomers of monochloro
named as D-(+)-tartaric acid because it has product is possible of - (1986)
positive - (1999) (A) n-butane
(A) Optical rotation and is derived from D- (B) 2,4-dimethyl pentane
glucose (C) Benzene
(B) pH in organic solvent (D) 1-methyl propane
(C) Optical rotation and is derived from D(+)
Q.18 Assertion: Carbon-oxygen bonds are of
glyceraldehydes
equal length in carbonate ion.
(D) Optical rotation only when substituted by
Reason: Bond length decreases with the
deuterium multiplicity of bond between two atoms.
Q.12 Dehydrohalogenation in presence of Q.19 Assertion: Boiling points of cis-isomers
OH is correctly represented by – (2004) are higher than trans-isomers.
Br Reason: Dipole moments of cis-isomers are
Br
higher than trans-isomers.
(A) (B)
H H Q.20 Assertion: Diastereoisomers have
OH– OH–

different physical properties.
(C) Br OH (D) Reason: They are non-superimposable mirror
images.
H
 Br Q.21 Assertion: The presence of nitro group
OH
facilitates nucleophilic substitution reactions
H in aryl halides.
Reason: The intermediate carbanion is
Q.13 Which one of the following species is stabilised due to the presence of nitro group.
most stable - (1995)

(A) p  O2N  C6H4  C H2

(B) p  CH3O  C6H4  CH2

(C) p  Cl  C6H4  C H2

(D) C6H5  C H2
Q.14 Which of the following has the highest
nucleophilicity - (2000)

(A) F (B) OH

(C) CH3 
(D) NH2

Q.15 Dipole moment is shown by - (1986)

(A) 1, 4-dichloro benzene
(B) Cis-1, 2-dichloro ethene

8.8
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Basic Principles of Organic Chemistry
EXERCISE 1 JEE ADVANCED
Q.1 Explain the term hybridization. Why does
carbon undergo hybridization ? Explain the
different types of hybridizations carbon atom
can undergo?
Q.2 In terms of hybridization of carbon atom,
discuss briefly the shapes of methane, ethane,
ethane and ethyne?
Q.3 Explain?
(a) Although boron trifluoride is insoluble in
trimethylamine, it is soluble in triphenylamine.
(b) Which CX2(X = F, Cl, Br, I) is the most stable
radical and why ?
Q.4 Discuss classification of hydrocarbons into
various types and illustrate each class by
taking two examples?
Q.5 Explain the following giving examples?
(i) Functional group
(ii) Homologous series and its characteristics
Q.6 Sulphanilic acid although has acidic as
well as basic group, it is soluble in alkali but
insoluble in mineral acids. Explain.
Q.7 What is the meant by hybridization ?
Discuss its various type giving at least one
example in each case.
Q.8 Define tautomerism. Discuss briefly keto-
enol tautomerism in aldehydes and ketones.
Also discuss the conditions under which enol
form predominates.
Q.9 Give a brief description of the principles of
the following processes taking an example in
each case,
(i) Filtration, (ii) Recrystallisation,
(iii) Sublimation,
(iv)Distillation under reduced pressure
(v) Steam distillation
(vi)Extraction with solvent.
Q.10 Discuss the reactions and the principle
underlying the estimation of the following:
(i) Carbon and hydrogen
(ii) Duma's method for estimation of nitrogen
(iii) Kjeldahl's method for the estimation of
nitrogen
(iv) Carius method for the estimation of
halogens and sulphur
(v) Phosphorus
Q.11 Write equations for the acid base
reaction that would occur when each of the
following compounds of solution are mixed. In
each case label the stronger acid and stronger
base and the weaker acid and weaker base.
(a) NaNH2 is added to acetylene
(b) gaseous NH3 is add to ethyl lithium in
hexane

(c) C2H5OH is added to a solution of CN a
in liquid NH3.
(d) NaH is added to H3COH.
Q.12 Give a brief account of the various
types of electronic effects in a covalent
molecule.
Q.13 Define and explain the term resonance
with suitable examples. Comment upon the
relative contributions of the various resonance
structures.
Q.14 What is hyperconjugation effect? How
does it differ from resonance effect. Briefly
discuss the significance of hyperconjugation
effect.
Q.15 How are free radicals, carbocations and
carbanions produced? Discuss their relative
stabilities.
Q.16 Cyclohexanol is more soluble in water 1-
hexanol why?
Q.17 1, 5-Pentanediol is soluble and 1-
pentanol is slightly soluble in H2O. Justify the
statement.
Q.18 1º and 2º amides tend to exist as dimmer
in solid and pure liquid state.
Q.19 Give an account of common types of
organic reactions with suitable examples.
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Basic Principles of Organic Chemistry

Q.20 Explain the following with one example Q.30 Discuss the chemistry of Beilstein test
in each case. for the detection of halogens. Why is this test
(i) Homolytic fission not dependable?
(ii) Heterolytic fission of covalent bonds.

Q.21 What are electrophiles and nucleophiles?

Explain with examples.

Q.22 What are reactive intermediates? How

are they generated by bond fission?

Q.23 Discuss the stability of carbanions on the

basis of inductive effects.

Q.24 Explain the following:

(a) p-chlorobenzene is more soluble in n-
propyl alcohol than methyl alcohol, while o-
dichlorobenzene is less soluble in n-propyl
alcohol than methanol.
(b) Heterolytic cleavage requires more energy
than homolytic cleavage.

Q.25 How many isomers of molecular formula

C3H7NO are possible when all isomers have
'amide' group. If one of the isomer has
different properties, name that isomer and
give reason of different characteristics.

Q.26 Write down the all possible amides of

formula C3H7NO and show one among these
isomers and give reason for this exception.

Q.27 Explain the following reactions:

(i) Substitution (ii) Addition
(iii) Elimination (iv) Rearrangement
(v) Isomerization (vi) Condensation
(v) Pericyclic.

Q.28 Explain:
(a) Although boron trifluoride is soluble in
trimethylamine, it does not dissolve in
triphenylamine.
(b) Which CX2(X = F, Cl, Br, I) is the most stable
radical and why?

Q.29 Sulphanilic acid although has acidic as

well as basic group, it is soluble in alkali but
insoluble in mineral acids. Explain.

8.10
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Basic Principles of Organic Chemistry

EXERCISE 2 JEE ADVANCED

Q.1 The major product of the following OH

O

reaction is - (A) (B)

Me Br
F
CHO OH
O
OH
NO2
 (C) (D)
Ph S N a

dimenthyl formamide

O OH
Me SPh
Me SPh
F Q.6 Reaction A:
(A) (B) F
Me
H I
NO2 NO2 KSH
S H
Me Br Me Br
SPh SPh Et
(C) (D) Reaction B:
Me
NO2 NO2 I H
KSH
S H
Q. 2 The correct stability order for the following
   Et
O O  (A) Products are same and mechanism is also
species is - I II III IV
same
(1) II > IV > I > III (2) I > II > III > IV (B) Products are same but mechanism is
(3) II > I > IV > III (4) I > III > II > IV different
(C) Products are different but mechanism is
Q.3 The most unlikely representation of
same
resonance structure of p-nitrophenoxide ion is
O  O O O (D) Products are different and mechanism is
N N also different
(A) (B)
Q.7 The stability order of the compounds

O– O A. B.
O O
O O
O O N (A) A < B (B) A > B
N
(C) A = B (D) Stabilities cannot be compared
(C) (D)
–
Q.8 The acidic strength of chloro substituted
O O benzoic acid is
(A) benzoic acid>o-chloro>m-chloro>p-chloro
Q.4 Which of the following is an electrophile?
(B) o-chloro>m-chloro>p-chloro>benzoic acid
(A) AlCl4– (B) BCl3
(C) m-chloro>o-chloro>p-chloro>benzoic acid
(C) NH3 (D) CH3OH
O (D) none of these
C–Cl
Q.9 The major product of following reaction is
( i) CdMe2
OH
Q.5   Product is -
( ii ) H O
2
HBr

CHO

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Basic Principles of Organic Chemistry

Br Me Me
Br Me
(A) (B)
(A) (B)
Me
Me Et

(C) (D) (C) (D)

Br
Br Me

CH3 Q.14 Select the incorrect option amongst the

Q.10 Br H + NaI  Product of following statements
H CH3
(A) Bimolecular elimination of alkyl halides is a
CH2–CH3
stereospecific reaction
reaction is - (B) In SN2 reaction a single isomer is the only
CH3 CH3
product
(A) I H (B) H I (C) n-Propyl alcohol dehydrates in strongly
H CH3 H CH3 basic conditions by E1cB mechanism
CH2–CH3 CH2–CH3 (D) 3-Hydroxypropanal dehydrates in strongly
CH3 basic conditions by E1cB mechanism
CH3
I H Q.15 Which of the following S
(C) I CH3 (D) is the most likely product Cl O
H CH3 CH3 H
from the reaction illustrated
CH2–CH3 CH2–CH3 by the curved arrows in the
formula?
Q.11 Which one among the following geminal
O
dihydroxy compound is most stable -
OH Cl S O
CH3–CH (A) CH3 (B)
(A) OH (B) CH3–C(OH)2–CH3
Cl
CH(OH)2 +SO2
(C) CCl3–CH(OH)2(D) Cl
(C) Cl (D)
+SO Cl
Q.12 Which of the following can undergo
decarboxylation reactions most easily 
CH3 H
(A) CH–C–CH–COOH (B) CH3–CH–COOH Q.16 •• ••
OH +••O=C   X[ X ] is -
•• CH3
O OH CH3
CH2–C–COOH
(A) HO C–CH3
(C) (D) CH3–CH–COOH
O CH3
NH2 CH3
(B) HO ••
O C–CH3
Q.13 Write the product of the following ••
CH3
reaction: CH3

H
OH 
 (C) HO C C–CH3
D
O •• OH
Me ••

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Basic Principles of Organic Chemistry

CH3 conformation is more stable than eclipsed

(D) HO C OH conformation.

CH3 Q.22 The total number of possible

conformation of ethane are -
Q.17 In the following H H (A) 2 (B) 3
carbocation, H/CH3 that is 1 2 + 4 5
H3C––C––C––C––CH3 (C) infinite (D) zero
most likely to migrate to 3

the positively charged OH H CH3 Q.23 Which conformation of cyclohexane is

carbon is most stable?
(A) CH3 at C-4 (B) CH3COCH3 (A) Chair (B) Boat
(C) CH3CHO (D) CH3COCH2COCH3 (C) Half-chair (D) Half-boat

Q.18 The compound having maximum enol Q.24 Which of the following is correct?
content - (A) Conformations cannot be isolated due to
(A) CH3CH2CHO (B) CH3COCH3 less difference in their energy
(C) CH3CHO (D) CH3COCH2COCH3 (B) Conformations can be isolated
(C) Conformations are obtained by breaking
Q.19 Which of the following statement is
and remaking the bonds
correct?
(D) Conformations are same as configurational
(A) Trimethylmenthyl and triphenylmethyl
isomers
radicals, both being 3º free radical, equally exist
in solution Q.25 Match the following:
(B) Stability order of carbanions always follows Column-I Column-II
reverse order to that of corresponding (A) Carbocations (P) E1
carbocations (B) Tetrahedral (Q) Nucleophilic-
(C) Among the simple alkyl carbocations, the

transition state addition
most stable one is C H3 because here the (C) Pentavalent (R) SN2
positive charge is dispersed only to small extent transition state
(D) none of these (D) Carbonyl (S) C=C + HX
Q.20 The heat of hydrogenation of benzene is compounds
49.8 Kcal/mole while its resonance energy is
36.0 Kcal/mole. Then the heat of hydrogenation Q.26 Match the compounds given in
of cyclohexene is - column-I with their reactions given column-II
(A) 28.6 K cal/mole (B) 13.8 K cal/mole Column-I Column-II
(C) 85.8 K cal/mole (D) 36.0 K cal/mole (A) Cl (P) Halogenatio
Q.21 Which carbocation among the n
following is most stable -
+ +
(A) CH3–C–CH3 (B) C2H5–C–C2H5 (B) (Q Electrophilic
CH3 C2H5 ) addition
+ reactions
(C) C2H5–C–H (D) CH2–CH–CH2+
(C) Me H Me (R) Nucleophilic
C2H5 addition
Ph OH Ph reactions
Passage (Q.22 to 24)
Conformation are structures obtained by (D (S) Elimination
OTs
rotation around  bonds without breaking ) reaction E1 or
and remaking the bonds. Ethane has staggered E2)
and eclipsed conformations. Staggered

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Basic Principles of Organic Chemistry

(T) Formation of
carbocation
intermediate

Q.27 Match the compounds given in

column-I with the reaction(s), that they

can undergo, given in column-II

Column-I Column-II

(A) Br (P) Nucleophilic

substitution
O

(B) OH
(Q) Elimination

(C) CHO (R) Nucleophilic

OH addition

(D) Br (S) Esterification

NO2 with acetic

anhydride

(T) Dehydrogenati
on

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Basic Principles of Organic Chemistry

PREVIOUS YEARS’ ADVANCED QUESTION

Q.1 For 1-methoxy-1, 3-butadienem which of Q.6 The compound in which C uses its sp3-
the following resonating structure is least hybrid orbitals for bond formation is [2000]
stable? (A) HCOOH (B) (H2N)2CO
[2005] (C) (CH3)3COH (D) CH3CHO
 
(A) C H2  C H  CH  CH  O  CH3
Q.7 Amongst the given options, the
Θ 
(B) C H2  CH  CH CH  O CH3 compound(s) in which all the atoms are in one
  plane in all the possible conformations (if any),
(C) CH2  CH2  C H  C H  O  CH3 is (are) [2011]
 
(D) CH2  CH  C H  CH  O CH3 H H H
(A) C–C (B) H–CC–C
Q.2 Which of the following is obtained when 4- H2C CH2 CH2
methylbenzene sulphonic acid is hydrolysed (C) H2C=C=O (D) H2C=C=CH2
with excess of sodium acetate ? [2005]
Q.8
(A) H3C COONa Column-I Column-II

+ SO3 (A) (P) Racemic

(B) H3C N2Cl + OH
mixture
   
NaOH / H O
(C) H3C
2
SO3Na + CH3COOH 0 C

N=N OH
(D) H3C SO2OCOCH3 + NaOH
(B) OH OH (Q) Addition
Q.3 When benzene sulphonic acid and p- H3C – C – C – CH3 reaction
nitrophenol are treated with NaHCO3, the gases H
 

2SO4

CH3 CH3
released respectively are - [2006]
O
(A) SO2, NO2 (B) SO2, NO
C CH3
(C) SO2, CO2 (D) CO2, CO2 C
H3 C
CH3
Q.4 Among the following least stable CH3
resonance structure is – [2007] (C) O (R) Substitution
 O  O C 1 
.LiAlH4
 reaction


 CH3
2. H 3 O
(A) N (B)  N
 OH
O O CH
  CH3
 (D) (S) Coupling
 O O HS Cl Base

  reaction
(C)  N (D)  N
S
O O
 
(T) Carbocation
Q.5 Phenol is less acidic than - [1986] intermediate
(A) acetic acid (B) p-methoxy phenol
(C) p-nitrophenol (D) ethanol Q.9 Match the reactions in column I with
appropriate type of steps/reactive intermediate
involved in these reactions as given in column
II

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Basic Principles of Organic Chemistry

Column-I Column-II
(A) H3C
O O (P) Nucleophilic
substitution

aq NaOH

O
(B) (Q) Electrophilic
CH2CH2CH2Cl substitution
CH3MgI

CH3

O
(C) (R) Dehydration
18
CH2CH2CH2OH

H2SO4

18 O

(D) CH2CH2CH2C(CH3)2
(S) Nucleophilic
OH
H2SO4
addition

H3C CH3

(T) Carbanion

Q.10 Give reasons for the following

CH2=CH– is more basic than HCC–. [2000]

Q.11 Match the following with their Ka values

Benzoic acid 4.2 × 10–5
p-nitrobenzoic acid 3.3 × 10–5
p-chlorobenzoic acid 6.4 × 10–5
p-methylbenzoic acid 36.2 × 10–5

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Basic Principles of Organic Chemistry

PLANCESSESSENTIAL QUESTIONS

Exercise 1 JEE Main/Boards

Q.1(iii) Q.3 Q.12(iii) Q.17(vi,ii) Q.19(iv) Q.22(ii) Q.27

Exercise 2 JEE Main

Q.2 Q.11 Q.15 Q.20 Q.28

Previous Years’ JEE Main

Q.1 Q.5 Q.10

Exercise 1 JEE Advanced

Q.2 Q.6(4) Q.7(4) Q.14 Q.23 Q.29

Exercise 2 JEE Advanced

Q.8 Q.19 Q.21

Previous Years’ JEE Advanced

Q.2 Q.4

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Basic Principles of Organic Chemistry

ANSWER KEY

EXERCISE 1 JEE MAIN/BOARDS

Q.15 192 Q.26 93.14 g

EXERCISE 2 JEE MAIN

Q1. B Q7. B Q13. B Q19. C Q25. D Q31. B Q37. C

Q2. D Q8. B Q14. D Q20. C Q26. D Q32. D Q38. A

Q3. B Q9. B Q15. B Q21. A Q27. D Q33. D Q.39. A

Q4. C Q10. C Q16. B Q22. B Q28. A Q34. B Q.40. C

Q5. D Q11.ABC Q17. D Q23. B Q29. A Q35. C Q.41. A

Q6. B Q12. B Q18. C Q24. B Q30. C Q36. A

Q42. A  P,R ; B  R,S ; C  P,R ; D  Q,R

Q43. A  P,S ; B  S ; C  P,S ; D  Q,R

Q.44. A T; B P; C R; D T

PREVIOUS YEARS’ QUESTIONS JEE MAIN

Q.14 C
Q1. C Q3. B Q5. Q7. D Q11. A Q.17
B,C,D A,D
Q2. A Q4. C Q8.B Q9. 4 Q.12 A
Q6. C Q10. B Q.13 B

EXERCISE 2 JEE ADVANCED

Q1. A Q4. B Q7. A Q10. B Q13. B Q16. D Q19. D

Q2. B Q5. C Q8. B Q11. C Q14. C Q17. D Q20. A

Q3. C Q6. C Q9. C Q12. A Q15. A Q18. A Q21. A

Q.22 C Q.23 A Q.24 A

Q25. A  P,S ; B  Q ; C  R ; D  S

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Basic Principles of Organic Chemistry

Q26. A  P,R,S,T ; B  P,R,S,T ; C  P,S,T ; D  P,R,T

Q27. A  R,S ; B  T ; C  R,S ; D  P

PREVIOUS YEARS’ QUESTIONS JEE ADVANCED

Q1. C Q2. C Q3. D Q4. A Q5. B,D Q6. C,D Q7. B,C

Q8. A  R,S ; B  T ; C  P,Q ; D  R

Q9. A  R,S,T ; B  P,S ; C  R,S ; D  Q,R

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Basic Principles of Organic Chemistry

SOLUTIONS
Sol.5 (i) Bond length: Bond length decreases
EXERCISE – I JEE MAIN with increasing s character in overlapping
orbitals for ex., sp3 has the largest bond length
Sol.1 Configuration of C: [He] 2s22p2 and sp has the least (for carbon compounds)
It has four electrons in its outermost shell (ii) Bond strength: Bond strength follows
Ground state : opposite order to bond length

2s 2p
Sol.6 (a) Tert-butylcylopentane
Excited state :

2s 2p
Thus, it has 4 unpaired electrons which its uses
in bond forming thus making it tetravalent. (b) Cylohexanone
O
Sol.2 Carbon undergo hybridization due to
following reasons
(i) Hybridised orbitals are equivalent in energy
(degenerate) and have more effective
overlapping Sol.7 (b) (p-nitrophenol) is more soluble than
(ii) Hybridised orbitals are directional in nature (a) (o-nitrophenol) as the extent of hydrogen
bonding with solvent will be less in (a) due to
Sol.3 Methane: steric hindrance by a bukly NO2-group
H
Sol.8 (a) C6H14
C sp3 hybridisation Condensed Bond line

H H CH3CH2CH2CH2CH2CH3
H
Ethane:
sp3–sp3 overlap CH3CH2CH2CHCH3CH3
CH3CH2CHCH2CH3

C + C CH3

H H H H CH3CH––CH–CH3
H H
CH3 CH3
Both carbon sp3
CH3
CH3C–CH2–CH3
Sol.4 Fumaric acid has higher metling point as
maleic acid has intramolecular H-bonding CH3
whereas fumaric acid has intermolecular (b) C6H10
bonding Condensed Bond line
H
O O CHCCH2CH2CH2CH3
Maleic acid : HO–C C=O
CH3CCCH2CH2CH3
C=C
H H CHCH2CCCH2CH3

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Basic Principles of Organic Chemistry

Condensed Bond line

CHCCH2CHCH3CH3
CH3CH2CH2OH
OH
CH3CCCHCH3CH3 OH OH
CHCCHCH2CH3
CH3CHCH3
CH3
(b) C8H10 CH3OCH2CH3
O
Degree of unsaturation
10 (f) C3H6O2
=8– +1=4 Degree of unsaturation = 1
2
I am drawing those isomers only which contains Condensed Bond line
a benzene ring.
CH3 O O
Condensed Bond line
C
CH3 O O
CH3
CH CH2
CH C–CH3 O O O O

CH C–H CH2 CH2

C O O
H CH OH
CH3 CH2 CH2OH

C O

CH CH CH3CH2OCHO
H O
CH C CH3CH–CH=O
CH3
CH O
OH
CH3 OH
CH O O

CH CH CH3COCH3
O
CH CH O
C CH3CH2COOH
OH
CH3
(g) C4H10O
CH2CH3
Condensed Bond line
CH
CH3CH2CH2CH2OH
CH CH
OH
CH CH CH3CH2CHCH3

CH OH
OH
(d) C8H18
CH3
18 isomers
OH
(e) C3H8O CH3CHCH2OH

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Basic Principles of Organic Chemistry

CH3 
CH3CH2 C HCH3 +
CH3CHCH3 
OH CH3 C HCH2CH3
OH HBr
O (iii) CH2=CH–CH=CH2 
CH3CH2CH2OCH3

O CH3 C H2–CH=CH2
CH3CH2OCH3

CH3 
CH3CH2OCH2CH3 CH3CH2=CH– C H2 + Minor
O
HBr
(h) C6H11NO2 (iv) CH3–CH=CH–CH=CH2 
More than 20 molecules 
CH3CH2– C H–CH=CH2
Sol.9 Functional group is a specific group of
atoms or bonds within molecules that are 
CH3CH2–CH=CH–CH2
C
responsible for the characteristic chemical
reaction of those molecules. + minor but stable
(i) Thialcohol:–SOH than III minor
(ii) Isothiocyanite:S=C=N– HBr
(iii) Thicyanate:–S=C=N– (v) CH2=C–––C=CH2 
(iv) Sulphonic acid: –SO3H CH3 CH3
O O

(v) Sulphones: S CH3C
C–––CH=CH2

O CH3 CH3

(vi) Sulphoxide: S

CH3–C CH–CHC
2 + minor
Sol.10 Homocyclic compounds is a cyclic
compound that has only one single element as CH3 CH3
its constituent. Thus, we see on the basis of resonance and
inductive effects
eg: Cyclopentane: (v) > (iv) > (iii) > (ii) > (i)
Heterocyclic compounds is a cyclic compound
that has atoms of atleast two different elements Sol.13 Homologous series is a series of
as members of its ring (s) compounds with a similar general formula,
usually varying by a single parameter such as
eg: Pyridine: the length of the chain.
Members of a homologous series usually have
..
N
similar physical and chemical properties
Sol.11 Hydrazine (H–N=N–H) does not give a Many physical properties, eg. Boiling point
+ve test for Lassaigne’s test of Nitrogen gradually increase with molecular mass
because it cannot produce NaCN. Alcohol series:
HBr Methyl alcoholCH3OH
Sol.12 (i) CH2=CH–C2H5 
 Ethyl alcoholC2H5OH
CH3– C H–C2H5 + Propyl alcoholC3H8OH
 Butyl alcoholC4H10OH
C H2–CH2CH2C2H5
HBr
(ii) CH3CH=CHCH3  Sol.14 Question from nomenclature chapter

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Basic Principles of Organic Chemistry

given organic mixture between two medium.

One of which is stationary and other is mobile.

Sol.15 R1Ag2  2Ag + other Sol.23 Refer text

Let molecular weight of salt be M.
Then 1 mole of R2 Ag gives 2 moles of Ag Sol.24 Fractional distillation is employed when
0.2018 0.1073 the liquids which have to be separated have
2 × =
M 108 very little difference in their boiling point
M = 406.23 temperatures (~10 – 15K)
Molecular weight of organic compound =
406.23 – (2 × 108) × 2 Sol.25 Fractional crystallization is a method of
= 192.23 refining substances based on difference in
solubility (especially when the difference in
Sol.16 Refer text solubility is low)

Sol.17 Refer text Sol.26 For platinic chloride method, we have

w x
=
Sol.18 Refer text 2M  410 195
w 0.3168 0.1036
=
Sol.19 For definition and types of resonance 2M 2M  410 195
effect refer text. 2M + 410 = 596.3
It differs from inductive effect as resonance M = 93.14 g
effects involves actual movement of electrons
contrary to inductive effect in which there is no Sol.27 (a) Fractional Distillation
actual movement but just development of (b) Crystallisation
polarity. (c) Steam Distillation
Because of this, resonance effect is more
stronger than inductive effect.

Sol.20 The reversal occurs due to

hyperconjugation effect, which is an extension
of the resonance effect. The inductive effect will
depend on the number of hyperconjugation
structures which will depend on the number of
–H
For H3C– max inductive effect (3H)
H2CH3C–2  H
(CH3) CH–1  H
(CH3) 3C–0  H
Thus order of hypercongugation effect
CH3– > CH3CH2– > (CH3) 2C– > (CH3) 3C–
Whereas inductive effect follows reverse order

Sol.21 Refer text

Sol.22 Chromatography is based upon the
principal of distributing the components of a

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Basic Principles of Organic Chemistry

EXERCISE – II JEE MAIN

Sol.1 (B) In CH3+, C has a sp2 structure, making

its shape trigonal planar Sol.12 (B)
O
HgSO4
Sol.2 (D) A nucleophile must have a lone pair of HCCH CH3CH
H2SO4
electons
dil OH– Aldol
5ºC
Condensation
Sol.3 (B) CH3 – CH = CH – CH3

sp3 sp2 sp2 sp3 OH

CH3–CH–CH2–CHO
2
Sol.4 (C) C1 is sp and C2 is sp (3-hydroxybutanal)

Sol.5 (D) CH2 = CH – CH2 – CH2 – C  CH H F

Sol.13 (B) C=C and
2 3 H3C Br
sp sp
H3C Br
C=C
Sol.6 (B) same as Q.1 H F
Are geometric isomers
Sol.7 (B) For rest cannot show geometrical isomerism as
+ they contains same group on C atom.
CH3–CH=CH2 + X+ CH3–CH–CH2X

+ Sol.14 (D)
CH2=CH2 + X+ CH2–CH2X O O–
+
The resulting carbocation is more stable for H2C=CH–C–H CH2–CH=C–H
CH3–CH=CH2 due to more number of + –
hyperconjugation structures  CH2–CH=CH=O

Sol.8 (B) Carbanion is a nucleophile as its has a Sol.15 (B)

negative and lone pair of electrons.
Sol.9 (C)
In (I)  No charge separation.
(II)  Complete octet on every atom
(III)  Positive charge on Carbon atom
(IV)  Negative charge on Carbon atom
(D) is most stable because of the enhanced
stability of resulting carbocation due to
conjugation.
In (A) lone pair of N is not conjugated and also
CH2C–N single bond have more +I effect than
C–N double bond making it basic than (B)
CH3–C has least +I effect

Sol.10 (C) In II, N has 10 valence electrons which Sol.16 RSO3– group is the best leaving group. In
is not possible, as N is period 2 element 1 and 2, 2 will be
more stable due to more – I effect
Sol.11 (A) , (B) , (C) of NH3+ and 3 > 4 in stability
These are the characteristics of resonance 2>1>3>4
structures

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Basic Principles of Organic Chemistry

Sol.17 (D) CH3

Br H I–
O H CH3
Me Ph CH3
CH2CH3
C
Me + Me Ph H I
O
H CH3
CH2CH3
Me Ph O
Me Sol.25 (D) For a compound to be reactive
Ph
towards SN2 reaction, the resulting carbocation
+ should be least stable. Here, the resulting
O Me
carbocation is least stable in (d) due to strong
–M effect of –NO2 group.

Me Ph O Sol.26 (D) Magnesia mixture is

Me
Ph MgCl2 + NH4Cl + little of NH3

+
O Me Sol.27 (D) K2SO4 raises the boiling point of
Here the positive charge is greatly Stabilise as water
all the atoms have complete octet.
Sol.28 (A)
Sol.18 (C) Its ring ontains 2 electrons, so it O H O
follows huckel s rule
H3C–––C–––C–––C–––CH3
fuse
Sol.19 (C) 5Na2O2+2P  H
2Na3PO4 + 2Na2O Enol ate form is
O O
Sol.20 (C) Reactivity order for SN1 reaction –
depends upon the stability of resulting H3C–––C–––CH–––C–––CH3
carbocation.
Ph.CH2+ > Ph+, since Ph–CH2+ is a benzyl cation
O– O
+
NO2 CH2
H3C–––C–––CH–––C–––CH3

< CH3 CH2+

O O–
(due to –I and –M effect of NO2–)
H3C–––C–––CH–––C–––CH3
+ >
This structure is stabilised most by resonance
( tertiary carbocation > secondary
carbocation) Sol.29 (A) For trans 1,2-Dichloroethene, dipole
moment is 0
Sol.21 (A) SN1 reaction yield a racemic mixture H Cl
C C
Cl H
Sol.22 (B) –Cl group have –I effect which Which causes maximum difference in dipole
stabilizes the anion and it decreases with moment between its cis
distance. and trans form. For others,
trans form also has some dipole moment.
Sol.24 (B)

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Basic Principles of Organic Chemistry

Sol.30 (C) Triplet carbene is more stable than 

singlet carbene because of the more repulsion
between electrons in singlet carbene compared
to triplet carbene.
This cation is aromatic and hence very stable
Sol.31 (B) due to resonance
(i) hv (CH3) 3C+ is stabilized only by +I effect
(ii) Cl2
Cl2 Sol.39 (A) Benzyne:
1
Cl
2
Cl
C1 and C2 are sp hybridized as C1–C2 is triple
Total number of isomeric chloro butanes = 2 bond

Sol.32 (D) Reactivity will be most for the
compound which has most positive charge
density on carbonyl carbon. Noting this, order
will be:
ArCOAr > ArCHO > ArCOR > HCHO >ArCOAr>
Sol.40 (C) PH3 is stronger nucleophile than NH3
due to big size of P and increased polarisability
PH3 is weak base than NH3 as lone pair density
is more in NH3 due to its small size making it a
better electron donor and hence better base

Sol.33 (D) There are no meso forms for glucose Sol.41 (A) R is the correct explanation for A

Sol.34 (B) Its necessary to remove S and N Sol.42 (A) (P), (R)
before testing for halogens CH3 H
C C + H–Br
Comprehension-2
CH3 H
Sol.35 (C) CH3 CH3
+
+
C CH3 + HC CH2
(A) : No chiral carbon
CH3 CH3
(B) : : No chiral carbon
3º 1º
Carbocation Carbocation
(A) : * : * C is chiral (B) (R), (S)
chiral carbon H
Making it optially active (CH3)3CO– –
Br–C–Br Br–C–Br CBr2
Br Br
Sol.36 (A) d-glucose and -glucose are Br
enantionmers
C–Br
CBr2
+
Sol.37 (C) Meso compounds contain internal
plane of symmetry which is only in C 2º carbocation
COOH (C) (P), (R)
H OH
H OH
COOH

Sol.38 (A) Tropylium cation:

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Basic Principles of Organic Chemistry

CH2OH
H+

+ (B) (P)
CH2CH2O
O O
Ph Ph
Br Ph
Cl PhSNa+ Ph S
+
CH2 + CH3
Will undergo E2 because of sterical hindrance
1º 3º
and nucleophile PhS–
(D) (Q), (R) (C) (R)
+ Me3C
OH O OCMe3 OCMe3
+
H +
2º Br +

+ +
+ OCMe3
3º 2º

Sol.43 (A) (P), (S) very stable

Carbocations can undergo reaction with Will undergo SN1 due to stability of carbocation
ethylene and rearrangement. and weaker nucleophile
(B) (S) (D) (T)
Carbanions undergo disproport-ionation OH
+
(C) (P), (S) +
H+
2 carbenes can combine to form ethane 
Carbenes can also react with ethylene
(D) (Q), (R)
Free radicals can combine and they also
undergo rearrangement.

Sol.44 (A) (T) Can’t undergo Ecb as no acidic hydrogen.

E1 CB mechanism
O O

H – –
OH

H3C Br H3C Br

O O–

H3C Br H3C Br

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Basic Principles of Organic Chemistry

PREVIOUS YEARS’ QUESTIONS JEE MAIN

Sol.1 In general, the order of acid strength is Sol.4 A methylene (-CH2 -) with
C  CH  ROH  H2O  PhOH R  COOH carbonyl on both side is highly acidic.

Therefore, during stepwise neutralisation of

given acid, -COOH will be neutralised first. In
the second step, the phenolic –OH, assisted by
–I effect of –NO2 at Meta position will be
neutralised.
Sol.5 octet of nitrogen is
violated.

Sol.6 I is most stable because it has more

covalent bonds and negative charge on
electronegative nitrogen. III is more stable than
II and IV due to greater number of covalent
bonds. Between II and IV, II is more stable since,
it has negative charge on electronegative atom
and positive charge on electropositive atom.
Hence, overall stability order is I > III> II > IV

Sol.7 H at C-2 will migrate giving resonance

Sol.2 I is most basic due to formation of
stabilized carbocation
resonance stablised conjugate acid
IV is amide, least basic

Sol.8

The  -electrons of C-H bond is delocalized

Also, among alkyl amines, 2° is more basic than
1° amine.
Hence , Overall order of basic strength is 1 > 3
>2>4
with p-orbitals of  -bond.
Sol.9 Aromatic alcohols and carboxylic acids
forms salt with NaOH, will dissolve in aqueous
NaOH:

Sol.3 Carboxylic acid is stronger acid than

ammonium ion, hence –COOH(X) is most
 
acidic. Z(NH3 ) is more acidic than Y(NH3 )
due to –I effect of –COOH on Z. Hence, overall
acid strength order is X > Z > Y

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Basic Principles of Organic Chemistry

Sol.10 These are total 6  H to sp carbon

2 Chlorine is also electron withdrawing but its
effect is less than  NO2 group.
and they all can participate in hyper
conjugation. Hence, correct order of stability.
   
CH2 CH2 CH2 CH2

O Cl NO2
| Least
CH3 stable
Most stable

Sol.14 CH3 has the highest nucleophilicty.

Sol.15 Due to presence of two chlorine atoms

on the same side of carbon atom produces
Sol.11 D(+)-tartaric acid has positive optical
dipole moment in molecule.
rotation and is derived from D(+)
glyceraldehyde.
Sol.16 (A) and (D) are symmetric alkanes, hence
these are non polar, while (B) and (C) are
Sol.12
symmetric alkenes hence they posses dipole
Br
momnet.
H–
OH Sol.17 n-butane has following two isomeric
CH3 Br CH3 monochloro derivatives
| | |
Br
H  C  C H   H  C  C H Br  H2 O CH3–CH2–CH2–CH2Cl
| |  |
H 1-chloro butane
H CH3 CH3
OH and CH3  CH2  CH  CH3
Sol.13 |

Cl
CH2 2 chloro bu tan e

2-methyl propane as following two isomeric

monochloro derivatives.
CH3
NO 2 | and
Nitro-group is electron withdrawing therefore CH3  CH  CH2Cl
2 methyl, 1 chloro propane
decreases stability.
 CH3
CH2
CH3–C–CH3
Cl
2-methyl, 2-chloropropane
O
| Sol.18 CO32 shows resonance and thus all the
CH3
three bonds are of identical bond length.
Methoxy group is electron releasing. O  C  O  O  C  O  O  C  O
Therefore increases stability by donating | | ||
O O O
electron.
 Sol.19 Boiling points of isomeric compounds
CH2 depend on dipole-dipole interactions and cis-
isomers have greater dipole moment (more
polar) than trans-isomers (less polar).

Cl Sol.20 Diastereoisomers are mirror images.

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Basic Principles of Organic Chemistry

EXERCISE – I JEE ADVANCED

Sol.1 Refer text pg. 4 Now,

NH3+ NH2
3
Sol.2 Methane: In methane, carbon is sp
OH–
hybridised making the shape tetrahedral. (Soluble in base) (as
Ethane: In ethane, both the carbon atoms are
sp3 hybridised making its shape tetrahedral SO3– SO3
with respect to each carbon atom OH– is more basic than –NH2)
Ethene: In ethene both are carbon atoms are NH3+
sp2 hybridised making its shape trigonal planar
with respect to each carbon atom. H+ (H+
No reaction (insoluble)
Ethyne: In ethyne both carbon atoms are sp
hybridized making its geometry linear.
SO3–
is less acidic the –SO3H)
Sol.3 (a) Boron trifloride
F
Sol.7 Refer Exercise-2 Q.1

B
Sol.8 Tautomers are constitutional isomers of
F F organic compounds that readily interconvert by
Here, B has only 2 electrons in its valence shell chemical reaction called tautomerisation. This
making is a lewis acid. reaction commonly results in the formal
On the other hand, nitrogen has a lone pair of migration of a hydrogen atom or proton,
electron in both (CH3) N and (PH) 3N making accompanied by a switch of a single bond and
them Lewis base. adjacent double bond, The concept of
But, in (PH) 3N lone pair is resonance stabilised tauromerization is called tautomerism
by conjugation with three phenyl rings making Keto-enol tautomerism refers to a chemical
availability for lone pair towards co-ordination. equailibrium between a keto form (a ketone or
(b):CF2 is the most stability due to the back an aldehyde) and an enol (an alcohol)
bonding between vacant orbital of C and the O OH
1 1
filled p orbital of F reducing the electron R R
deficiency on C carbon. 3 R
 R 
2
2
R H R
Sol.4 Refer hydrocarbon chapter
Keto enol
Sol.5 (i) refer exercise-I Q.9 Conditions:
(ii) refer exercise-I Q.14 (i) Presence of conjugated double bonds in
enol form
NH2 (ii) Due to favourable hydrogen bonding
interactions
Sol.6 Sulphanilic acid
H
O O O O
SO3H

NH3+ Keto form

exist as a Zwitter ion (24 %)
(iii) Sometimes under slightly acidic or basic
SO3– conditions

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Basic Principles of Organic Chemistry

Sol.9 Refer text pg 25 (a) is more soluble than (b) because of greater
extent of H-bonding in (a) due to 2-OH groups
Sol.10 Refer text pg 30 compared with 1 in (b)

Sol.11 (a) NaNH2 + C2H2  Sol.18 1º and 2º amides tend to exist as dimer
NH2–CHC–NH2 + Na+ + NH3 in solid and pure liquid state, because of H-
Strong acid: NH2– bonding between them.
Weak acid: C2H2 R R
Weak base: NH3 C O C O
H N N
Strong base: H–CC– H
NH R R
(b) EtLi 
3
 LiNH2 + Et (C2H6)
hexane
But this cannot happen in 3º amides as there
Strong base: Et– (C2H6) is no hydrogen available for H-bonding
Weak acid: NH3
Strong acid: Li+
Sol.19 Refer text
Weak base: NH3
HC CNa
 C2H5O–Na+ + HCCH
(c) C2H5OH    Sol.20 Refer text
NH3

Strong acid: Na+

Sol.21 Electrophile: The species which carry +ve
Weak acid: C2H5OH
charge or are electron deficient are called
Strong base: HCC–
electrophiles these species attack regions of
Weak base: HCCH
high electron density in a molecule.
(b) NaH + CH3OH  CH3O–Na + H2 Two types
Strong acid: Na+ (i) Positively charged electrophile: H+, CH3+
Weak acid: CH3OH (ii) Netral electrophiles: SO3, RCOCl
Strong acid: H– Nucleophiles: Those species which carry a
Weak base: H2 negative cleavage / electron rich species or
which have some pair of electrons are called
Sol.12 Refer Text nucleophiles. They attack regions of low
electron density.
Sol.13 Refer Text Two types
(i) Negatively charged: Br–, CH3–
Sol.14 Refer Text (ii) Neutral electrophiles: NH3, ROH

Sol.15 Refer Text Sol.22 Refer text

OH
Sol.23 Carbanions will be more stable if they are
Sol.16 Cyclohexanol: (a) attached to a group which withdraws go
electrons (–I) .
1-hexanol: (b) Therefore, the more the –I effect of surrounding
OH
atoms, the more stable the carbanion will be
(a) is more soluble than (b) due to greater Cl
extent of H-bonding due to its compact +
structure and less steric hindrance Sol.24 (a) p-dichlorobenzene has a

Sol.17 1,5 pentanediol: OH +

OH (a) Cl
1 pentanol: (b) dipole moment which make this compound
OH
non-polar and therefore, its solubility will be
more in a polar solvent compared to a non-

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Basic Principles of Organic Chemistry

polar one. Now polarity of methyl alcohol O O

(CH3OH) > n-propyl alcohol OH . CH3
H N H N
 its solubility is more in n-propyl alcohol than CH3 H
methyl alcohol. (iii) (iv)
Cl
Out of these four isomers, only (iii) cannot do
Cl hydrogen bonding and therefore exhibits
o-dichrolobenzene has a non zero
different characteristics than the other three.
Name of (iii): Dimethyl formamide
dipole moment and therefore its solubility will
be more in a polar solvent.
Sol.26 Refer previous
(b) A: B  A  + B 
Heterolytic bond fission requires higher energy Sol.27 (i) Refer Text
compared to homolytic bond fission as it
(ii) Refer Text
involves separation of opposite charges which (iii) Refer Text
will be hindered by electrostatic force of (iv) Refer Text
attraction between ions.
(v) Isomerisation: The chemical process by
If we study heterolytic cleavage step wise
which a compound is transformed into any of
If is first homolytic cleavage and then
its isomeric forms
Ionisation of atom
(vi) Condensation: It is a chemical reaction in
A –– B A + B
which two molecules or functional groups
+e– –e– combine to form a large molecule, together
with the loss of a small molecule.
A– B+
(vii) Pericyclic: It is a chemical reaction where in
w x
= the transition state of the molecule has a cyclic
2E  410 for 195
geometry, and the reaction progress in a
concerted fashion.
Sol.25 4 isomers are possible
O O Sol.28Refer Q.3
H CH3
N N Sol.29 Refer Q.6
H H
(i) (ii) Sol.30 Refer Text

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Basic Principles of Organic Chemistry

EXERCISE – II JEE ADVANCED

Sol.1 (A) Ph S– will attack C–Br bond (because Me Me

carbocation formed from this carbon will have I H KSH H SH
most stability due to conjugation with the ring)
S H S H
and from opposite side of Br
Et Et
Sol.2 I and III are stabilized by +M effect of O, I Sol.7 (A)
is further stabilized as it is tertiary carbocation. (A) is antiaromatic (4  electrons)
II is secondary carbocation (B) is aromatic (6  electrons)
IV is primary carbocation.
Sol.8 (B) –Cl group have –I effect which
Sol.3 (C) Here, O contains 10 valence electrons, stabilizes the anion and it decreases with
which is not possible distance.
OH
Sol.4 (B) BCl3 is an electrophile as B has only 6
valence electrons and needs electrons to Sol.9
complete its octet. HBr

Sol.5 (B) H2O+

O O
|| ||
C–Cl C–CH3
–
(i) Me
(ii) H2O
+
CHO C–H +

(i) Me– (ii) H2O

O
|| +
C–CH3 Br–

Br
HC–CH3
OH Sol.10 (B)
Sol.6 (C) Mechanism is same for both CH3
(nucleophilic substitution) , But products will be Br H I–
isomers
H CH3
Me Me
CH2CH3 CH3
I H KSH SH H
H I
S H S H
H CH3
Et Et
CH2CH3

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Basic Principles of Organic Chemistry

Sol.11 (C) CCl3–CH (OH) 2 is most stable as it can Sol.16 (A)

form hydrogen bonding most effectively due to
CH3 H+ CH3 +
more –I effect of CCl3– group C=O C=OH
CH3 CH3

Sol.12 (A) CH–C–CH–COOH has most reactivity

O OH CH3 +
C–OH
as the resulting carbanion: CH3
CH–C–C– CH–C=C CH3
– +
O O HO–C–– OH
This is stabilized by resonance
CH3
CH3
Sol.13 (B) H+ +
HO–C–– OH
Me H+
OH  CH3
Me CH3

 + H2O+–C–– OH
Me OH2
CH3
Me CH3
+ OH
Me C––
H CH3
Me + OH

Me Me + CH3
+
HO= C–– OH

H
Me Me CH3

 CH3
Me Me HO– C–– OH
CH3
Sol.14 (D) n-propyl alcohol will dehydrate by E2 Sol.17 (D)
mechanism. Rest statements are correct) H H
+
S H3C–––C–––C–––C–––CH3
Cl O Cl
OH H CH3
Sol.15 (A)
CH3
H H
+
H3C–––C–––C–––C–––CH3

OH H CH3

H H

H3C–––C–––C–––C–––CH3
+
OH H CH3
(This is very stable as it contains octet for all
elements)

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Basic Principles of Organic Chemistry

Sol.18 (A) Sol.23 (A) Chair forms has least strain

O H O
Sol.24 (A) Conformation have very less
H3C–––C–––C–––C–––CH3
difference in energy and are easily transformed
H into one another at room temperature.
Enol ate form is
O O Sol.25 (A): a, d
– Carbocations are formed in E1 reaction and
H3C–––C–––CH–––C–––CH3 halagenation of alkenes
+
C C +H–X C C
–
O O
H
H3C–––C–––CH–––C–––CH3 (B): b
O O–
R–C–G R–C–G
O O– N–
N
H3C–––C–––CH–––C–––CH3 (Tetrahedral transition state)
This structure is stabilised most by resonance (C): c
H
Sol.19 (D) N–
R–CH2–X R–C–X
(A) Triphyenylmethyl radical is more stable N
than trimethyl radical due to more conjugation H
(increasing stability) in the former. (Pentavalent transition state)
(B) This trend is not always nessarily followed (D): b
(C) +CH3 is the least stable one as the positive Carbonyl compounds undergo nucleophilic
charge needs to be dispersed to increase addition
stability.
Sol.26 (A) a, c, d, e
Sol.20 (A) Heat of hydrogenation of Benzene Cannot undergo electrophillic addition as there
involves hydrogenation of 3 normal  bonds – is electron rich centre except benzene ring
the resonance energy of benzene. which does not undergo addition Nucleophilic
 Heat of hydrogenation of 3 bonds = (49.8 addition can occur
+ 36) K cal./mol due to electron withdrawing effect of Ar–
= 85.8 k cal/mol (B) a, b, c, d, e
Heat of hydrogenation of cyclohexene involves. It can undergo all reaction at different sites
Hydrogenation of 1  bonds, therefore, (C) a, c, d, e
Heat of hydrogenation Cannot undergo electrophilic addition, no 
85.8 bonds which can be broken
= k cal/mole
3 (D) a, c, e
= 28.6 k cal/mole Cannot undergo electrophilic addition reaction
and elimination reaction
Sol.21 (A) + H effect 9  – H in (CH3) 3–C+
Sol.27 (A) – p,q,r,s,t (B) – f (C) – r, s (D) – P
Comprehensive-I

Sol.22 (C) Infinite orientations are possible and

each orientation represents one conformation.

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Basic Principles of Organic Chemistry

PREVIOUS YEARS’ QUESTIONS JEE ADVANCED

 
Sol.6
Sol.1 CH2  CH2  C H  C H  O  CH3
O O
Lone pair of oxygen is not the part of this mode
of delocalisation. H–C–OH H2N–C–NH2
 
Sol.2 A spontaneous neutralisation will occur sp2 sp2
between strong acid and strong base as
CH3 O
H3C SO3Na + CH3COONa
strong base CH3–C–O–H CH3–C–H
strong acid

+
sp3 CH3 sp3
H3C SO3Na + CH3COOH
weak acid
weak base Sol.7 In both (B) and (C), all the atoms are
present in one single plane
Sol.3
2 sp2
H sp H
SO3H + NaHCO3
H–CC–C H C=C=O
straight C H straight
SO3Na + H2O + CO2
H
O2N OH + NaHCO3 In (A) 1,3-butadiene, conformational change is
possible between C2–C3 bond in which atoms
O2N ONa + H2O + CO2 will be present in more than one single plane.
In (D) allene, the terminals H–C–H planes are
perpendicular to one another.
Sol.4 The following structure has like charge on
adjacent atoms, therefore, least stable. Sol.8
 O +
   N2 + OH
 N

 O N=N OH

this is an example of electrophilic substitution
Sol.5 Phenol is less acidic than a carboxylic acid
at para position of phenol, giving a coupling
(acetic acid). Nitro group from para position
product.
exert electron withdrawing resoance effect,
O H O–
increases acid strength. Therefore, phenol is
less acidic than p-nitro phenol. Ph–C–CH3 + H–Al–H Ph–C–CH3
On the other hand, methoxy group from para
H H
postion, donate electrons by resonance effect, nucleophillic addition
decreases acid strength of phenol. Also ethanol OH
is weaker acid than phenol due to resonance
stabilisation in phenoxide ion. Hence, Ph–C–CH3
ethanol < p-methoxyphenol < phenol < p- H
nitrophenol < acetic acid

––increasing acid strength 

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Basic Principles of Organic Chemistry

Sol.9
O O
(A) Ph–C–CH2–CH2–C–CH3 + OH–

•• OH
CH2 O
O Ph
H2O
O
Ph
carbanion
O
H2O Ph

dehydration

O
CH3MgBr
Cl
(B) Ph
O–
S N2 Ph
Ph H3C
CH
Cl
+
O 18 +
OH
H
OH
(C) Ph
••OH
nucleophilic addition

–H
+
Ph –H2O
+

Ph
HO O
18
dehydration

O
+
H
(D) Ph –H2O
OH +

Freidel-
Craft alkylation

Electrophilic
substitution

Sol.10 H–CC–H is more acid than CH2=CH2.

Sol.11 p-methoxy benzoic acid is the weakest

and p-nitrobenzoic acid is the strongest acid
among these acids. Chloro group has overall
electron withdrawing effect on ring, therefore,
increases acid strength of benzoic acid. Methyl
group decreases acid strength of benzoic acid
by +I effect. Therefore,
p-methylbenzoic acid 3.3 × 10–5
p-methylbenzoic acid 4.2 × 10–5
benzoic acid 6.4 × 10–5
p-chlorobenzoic acid 10.2 × 10–5
p-nitrobenzoic acid 36.2 × 10–5

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