Points to be remember for MCQ

(a) Allylic halides : If halogen atom is bonded to an sp3-hybridised carbon atom next to carbon-carbon double bond (C=C) i.e. to an allylic carbon.

c) Benzylic halides: in which the halogen atom is bonded to an sp3-hybridised carbon atom next to an aromatic ring.

Compounds Containing sp2 C—X Bond :

(a) Vinylic halides : if halogen atom is bonded to an sp2-hybridised carbon atom carbon-carbon double bond (C = C).

(b) Aryl halides : These are the compounds in which the halogen atom is bonded to the sp2- hybridised carbon atom of an aromatic ring.

The dihaloalkanes having the same type of halogen atoms are named as alkylidene or alkylene dihalides. The dihalo-compounds having same type of
halogen atoms are further classified as geminal halides (halogen atoms are present on the same carbon atom) and vicinal halides (halogen atoms are
present on the adjacent carbon atoms). In common name system, gem-dihalides are named as alkylidene halides and vic-dihalides are named as
alkylene dihalides. In IUPAC system, they are named as dihaloalkanes.

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 1. Reactivity and stability of carbocation: Benzylic > allylic > alkyl > vinyl

2. Allyl chloride is more reactive than n-propyl chloride towards nucleophilic substitution: Because of greater stabilization of
allylic carbocation intermediate formed by resonance.

CH2= CH CH2 CH2-CH=CH2

3. Vinyl chloride less reactive than ethyl chloride: Because in vinyl chloride, the electron pair on chlorine atom conjugates with
the Pi electron pair of the double bond. As a result, there is partial double bond character in C-CI and its bond strength increases.
Consequently, it becomes difficult to cleave C-CI bond as compared to the bond in ethyl chloride where no such conjugation is
possible.

CH2= CH-CI CH2-CH=CI

4. Boiling point of dichlorobenzene: ortho > para > meta
5. Melting point of dichlorobenzene: para > ortho > meta
(due to symmetry p-isomer easily fit into crystal lattice)

6. The para-isomers are having high melting as compared to their ortho and meta-isomers. It is due to symmetry of para-
isomers that fits in crystal lattice better as compared to ortho- and meta-isomers.

7. Boiling point order: Carboxylic acid > alcohol > Ketone > aldehyde > Haloalkane > hydrocarbon

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 8. X2 / sunlight(hv) or presence of peroxide always go for Free radical substitution: always do α- halogenation.
Br2 / Sunlight
(i) CH3-CH=CH2 Br-CH 2-CH=CH2
Prop-1-ene 3-BromoProp-1-ene

9. Haloarene or any alkyl benzene like toluene always prefer Electrophilic substitution with catalyst. Means like nitration,
halogenation, sulphonation , alkylation, acylation of toluene and haloarene always electrophilic substitution.
CH2Cl

Cl2/ U.V. In presence of UV rays its free radical substitution

+ HCl
CH3
Bezylchloride

CH3 CH3
Cl
Cl2 / Anhyd. AlCl 3
Toluene IN presence of catalyst its electrophilic substitution
o-Chlorotoluene
Cl

10. Markownikov`s rule: Electrophilic addition(normally all alkene or alkyne in absence of peroxide follow +E effect and undergo
electrophilic addition reaction.
Br
H3C CH CH3
-
H3C CH CH2 + +
H -Br Absence of Peroxide⎯
⎯⎯⎯⎯⎯⎯⎯⎯⎯ → 2-bromopropane

11. Antimarkownikov`s : Free radical addition

-
Peroxide
H3C CH CH2 + H+-Br H3C CH2 CH2 Br
1-bromopropane

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 11. Lucas reagent: anhyd ZnCl2 + conc. HCl(help in finding the nature and reactivity of alcohol)
12. Reactivity of alcohol: Tertiary alcohol > Sec. Alcohol > primary alcohol (due to more stability of 30 carbocation.)

13. Grignard reagent always gives alkane with H2O as well as Alcohol:

Q: If CH3CH2MgBr react with 2-Methyl propan-2-ol then what happens?

Ans : CH3CH3 (Ethane will form only because alcohol will give only hydrogen to alkyl of Grignard.

14. Whenever in any reaction elimination takes place, it means in that reaction nucleophile will act as a strong base and strong base
always abstract a H+(proton) from the compound.( These reactions follow SN1 mechanism).
15. Whenever in any reaction substitution takes place, it means in that reaction nucleophile will act as a nucleophile only.
( These reactions follow SN2 mechanism)
16. Alcoholic and aqueous KOH give different product :
because Aqueous KOH is almost completely ionized to give OH- ions which being a strong nucleophile brings about a substitution
reaction on alkyl halides to form alcohols. In contrast, an alcoholic solution of KOH contains aikoxide (RO-) ions which being a much
stronger base than OH- ions preferentially eliminates a molecule of HCl from an alkyl halide to form alkenes .
KOH K + OH RO means alkoxide ions is a strong nucleophile as
well as strong base, So when it behave as a strong
base it will go for elimination process.
H2O(aq.) H + OH
* OH is only act as a nucleophile so always go
ROH(alc.) H + RO for substitution.

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 14. C6H5CHClC6H5 is hydrolyzed more easily than C6H5CH2Cl by aqueous KOH: C6H5CH2+ forms 1°-carbocation, while C6H5CH+C6H5
forms 2°-carbocation, which is more stable than 1°-carbocation.
15. Thionyl chloride is more preferred over concentrated halogen acid for the formation of alkyl halide from alcohol: because
the other two products are escapable gases. ROH + SOCℓ2 → RCℓ + HCℓ(gas) + SO2(gas)

16. Reactions of alkane with iodine are reversible in nature :So require the presence of an oxidising agent (HNO3, HIO4) to oxidise
the HI (good reducing agent): CH4 + I2 ⎯⎯⎯⎯→
Conc. HNO3
CH3 -I + HI ;

2HNO3 + 2 HI → I2 + 2NO2 + 2H2O

17. Detection of unsaturated hydrocarbon: Reddish brown colour of bromine change to colourless with alkene/alkyes.

18. KCN and AgCN gives different product with haloalkanes :

𝐴𝑙𝑐𝑜ℎ𝑜𝑙𝑖𝑐 𝐾𝐶𝑁 𝐴𝑙𝑐𝑜ℎ𝑜𝑙𝑖𝑐 𝐴𝑔𝐶𝑁
CH3 − CH2 − X → CH3 − CH2 − CN + KX Where X = Cℓ or Br ; CH3 − CH2 − X → CH3 − CH2 − NC + KX

KCN is predominantly ionic and provides cyanide ions in solution. Although both carbon and nitrogen atoms are in a position to
donate electron pairs, the attack takes place mainly through carbon atom and not through nitrogen atom since C—C bond is more
stable than C—N bond. However, AgCN is mainly covalent in nature and nitrogen is free to donate electron pair to form isocyanide.
19. Finkelstein reaction: Alkyl iodides are often prepared by the reaction of alkyl chlorides/ bromides with NaI in dry acetone. This
reaction is known as Finkelstein reaction

20. Use of dry Acetone in Finkelstein reaction: The Dry Acetone in the medium doesn't allow NaX to dissolve because NaX is a polar
compound whereas Acetone is an important organic non-polar solvent, which results in precipitation of NaX in Acetone
which facilitates reaction in forward direction.

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 21. Swarts reaction: The synthesis of alkyl fluorides is best accomplished by heating an alkyl chloride/bromide in the presence of a
metallic fluoride such as AgF, Hg2F2 , CoF2 or SbF3 . The reaction is termed as Swarts reaction.

22. Formation of haloalkane through free radical halogination of alkane is not a suitable process: because we will get a mixture of
haloalakne which is not easy to separate.

23. Ambidentate Nucleophiles: Groups like cyanides and nitrites possess two nucleophilic centres and are called ambident
nucleophiles.

24. boiling points of chlorides, bromides and iodides are considerably higher than those of the hydrocarbons of comparable
molecular mass: the intermolecular forces of attraction (dipole-dipole and van der Waals) are stronger in the halogen derivatives.
the boiling points of alkyl halides decrease in the order: RI> RBr> RCl> RF.

25. SN1: Reactivity depends upon stability of carbocation , ( Racemisation and inversion both takes place).
26. SN2: Reactivity depends upon steric hindrance ( only inversion takes place)
SN2 : Primary halide > Secondary halide > Tertiary halide. ( When halogen is same )
SN1 : Primary halide < Secondary halide < Tertiary halide. ( When halogen is same )
27. If halogens are different than in both case reactivity order is : R–I > R–Br > R–C l > R–F.
Eg: i) CH3CH2CH2CH2Br < (CH3)2CHCH2Br < CH3CH2CH(Br)CH3 < (CH3)3CBr (SN1)
ii) CH3CH2CH2CH2Br > (CH3)2CHCH2Br > CH3CH2CH(Br)CH3 > (CH3)3CBr (SN2)
28. Aryl halides are extremely less reactive towards nucleophilic substitution reactions :
➢ Due to Resonance effect : bond cleavage in haloarene is difficult than haloalkane
➢ Difference in hybridisation of carbon atom in C—X bond : in haloarene sp2 hybridised carbon with a greater s-character is
more electronegative and can hold the electron pair of C-X bond more tightly than sp3-hybridised carbon in haloalkane .
➢ Instability of phenyl carbocation.

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 29. Electron withdrawing group like: NO2(Nitro) , F , Cl , Br etc, always increase the reactivity as well as acidic nature.
30. Electron donating group like: Any alkyl(methyl, ethyl etc.) or alkoxy(methoxy, ethoxy etc.) always decreases the reactivity.

Acidic nature : Propan-1-ol < 4-methylphenol < phenol < 3-nitrophenol < 3,5-dinitrophenol < 2,4, 6-trinitrophenol.

31. Although chlorine is an electron withdrawing group, yet it is O/P directing in electrophilic aromatic substitution reactions :
because
➢ Chlorine withdraws electrons through inductive effect and
➢ releases electrons through resonance.
➢ The inductive effect is stronger than resonance and causes net electron withdrawal and thus causes net deactivation.
➢ The resonance effect tends to oppose the inductive effect for the attack at ortho- and para positions and hence makes the
deactivation less for ortho- and para-attack.
➢ Reactivity is thus controlled by the stronger inductive effect and orientation is controlled by resonance effect.

32. The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride:

➢ In chlorobenzene, sp2 hybridized carbon has more s-character than sp3 hybridized carbon atom in cyclohexyl chloride.
➢ Moreover, the Resonance effect in chlorobenzene decreases the electron density of the C−Cl bond. As a result, the polarity of
the C−Cl bond in chlorobenzene decreases.
33. Chirality: Compounds which are non-superimposable on their mirror image are said to be chiral and this property is known as
chirality.
34. Sulphuric acid not used during the reaction of alcohols with KI : because In the presence of sulphuric acid (H2SO4), KI produces
HI then HI oxidise to I2.

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 35. Enantiomers: Those stereoisomers which are non-superimposable on their mirror images.

36. Butan-2-ol: has four different groups attached to the tetrahedral carbon and as expected is chiral so no possibility for
superimposable on each other.
37. propan-2-ol: Does not contain an asymmetric carbon, as all the four groups attached to the tetrahedral carbon are not different.
Thus it is an achiral molecule.

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 38. Haloalkanes though polar but immiscible with water: Because energy is required to overcome the attractions between the
haloalkane molecules and break the hydrogen bonds between water molecules. Less energy is released when new attraction forces
are created between the haloalkane and the water molecules which are not enough to overcome the older forces.
39. Organic halogen compounds used in industry as solvents are chlorides rather than bromides and iodides: because chlorides
are more volatile than bromides and iodides.
40. Use of chloroform as anesthetic is decreasing: Because in some cases, CHCℓ3 causes cardiac and respiratory problems.
41. Retention: It means initial configuration of molecule remain same after the reaction.
42. Inversion: If the initial configuration of molecule do not remain same after the reaction.
43. racemic mixture or racemic modification: A mixture containing two enantiomers in equal proportions will have zero optical
rotation, as the rotation due to one isomer will be cancelled by the rotation due to the other isomer.

CH3
CH3
Step-1
H3C C Br C
+
+ Br
H3C CH3
CH3
CH3 CH3
CH3
Step-2 or HO C CH3
C
+
+ OH H3C C OH
H3C CH3
CH3 CH3
Retention Inversion

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Complete the following name reaction
Fittig reaction:

Wurtz fittig reaction:

Diazotisation:

Sandmayer reaction:

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