Short-cut Revision Notes

Chapter : H.D.A.
Halo-arene
Cl Cl Cl Cl
NO2 Conc. HNO3 Cl
+ Conc. H2SO4 Cl 2/FeCl 3
+ +
(ESR) (ESR)

NO2 Cl
Ph
Cl Cl
Ph-Br
H3C CH3Cl
Na/Et2O
+ AlCl3 (ESR)
Fittig Reaction
CH3 Cl CH3
Cl O Cl
|| O CH3Br
C || Na/Et2O
H3C–C–Cl
CH3 + AlCl3 (ESR) Wurtz-Fittig Reaction

NH2
C
O CH3 NaNH2
liq. NH3
H
Cl | ArSN
CCl3–C=O
CCl3–C Conc. H2SO4 OH
| (1) NaOH, 623 K
H Cl (ESR) 300 atm
DDT (2) H +
(NSR)

(Dichloro diphenyl trichloro ethane)

Ni-Al Cl O–H
NaOH
O2N NO2 H O O2N NO2
2
warm
Cl Cl
SO3 H NO2
Conc. H2SO4
+
 (ESR)
SO3H
B. Boiling point
RCC * * RCC * * RCC * * RCC * * RCC * * RCC

A. Reactivity toward Nucleophile

F Cl Br I F Cl Br I
i) < < <
> > >
i)
NO2 NO2 NO2 NO2 Cl Cl Cl
Cl
Cl Cl Cl ii) > >
NO2 NO2 O2N NO2 Cl
< < Cl
ii)
NO2 NO2

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 Reactions
PCl5
H3C–CH2–OH
PCl3
KOH(aq)
3H3C–CH2–OH R– OH + KX
alcohol
Red P + Br2
3H3C–CH2–OH Moist Ag 2O
SOCl2
R– OH + AgX
H3C–CH2–OH alcohol
SOCl2 dry Ag 2 O
H3C–CH2–OH R– O – R + 2AgX
2
(SN ) ether
N Dil. acid or alkali
Br2 (Complete
RCOOH
H3C–COAg CCl4 hydrolysis) Carboxylic acid
|| conc. acid or
O KCN (alc.) alkali + H 2 O2
(Hunsdiecker Reaction) R–CN RCONH2
HCl/ZnCl2 –KX Alkyl
(Partial hydrolysis)
Acid amide
H3C–CH2–OH
Lucas Reagent cyanide H 2/Pd or LiAlH 4
or Na/C 2H 5OH
RCH2NH2
NaBr + H2SO4 (Mendius reduction)
1° amine
H3C–CH2–OH
HI AgCN R–N = C
 Na/C2H 5OH
H3C–CH2–OH Reduction
RNHCH3
KI/H3PO4 –AgX Alkyl 2° amine

NBS isocyanide
H3C–CH=CH2
CCl4
(Allylic substitution) R’ONa
(Sodium alkoxide) R–O–R’ + NaX
Cl2/hv
CH3–CH3 (Williamson’s synthesis)

HBr R’COOAg
CH2=CH2 RCOOR’ + AgX
CCl4 Ester
NaI
H3C–CH2–Cl KSH
Acetone
(Finkelstein Reaction) RSH + KX
R–X

AgF or Hg2F2 Thio alcohol (mercaptan)

H3C–CH2–Cl
(Swart Reaction) Na2S
R–S–R + NaX
H3C–CH–CH2–Br

Thio ether
R’C  C–Na+
H3C–CH–CH3

H3C–CH–CH3

R–CC–R’ + NaX
(Sodium alkynide)
Br

Br
Cl

NH3(alc.)
|

RX RX RX + –
RNH2 –HX
R2NH –HX
R3N R4N X
 1° amine 2° amine 3° amine Quaternary
(Hoffmann’s ammonium
ammonolysis) salt
Br2/CCl4
CCl4
HBr

HCl

KNO2
R–O–N = O + KX
Alkyl nitrite
H3C – CH = CH2

O
AgNO2
R–N + AgX
O
Nitro alkane
Corey-House reaction
R–R’
(i)Li (ii) CuX (iii) R’–X

Reduction
Peroxide

Br2/800K

R–H
NBS
CCl4
HBr

LiAlH4 or NaBH4 or Ph3 SnH



R–MgX or RLi or RNa or R2 Zn

or R2CuLi
R–R
H3C–CH2–CH2

CH2–CH=CH2

CH2–CH=CH2
Br

(Organo metallic reagents)

|

R–CH–CH–MgX
R–CH–CH–R
(Streker reaction) Na2SO3
Br

Br

R–SO3Na
|

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Physical Properties
(i) Dipole moment : CH3–Cl > CH3–F > CH3–Br > CH3–I
(ii) Bond enthalpies : CH3–F > CH3–Cl > CH3–Br > CH3–I
(iii) Boiling point : R–I > R–Br > R–Cl > R–F
> >
Br
Br Br
(iv) Density : n–C3H7Cl < n–C3H7Br < n–C3H7I
(v) Solubility :  slightly soluble in water

SN1 Reaction SN2 Reaction

1. It is unimolecular Nu–Subn. 1. It is bimolecular Nu–Subn.
2. Ex. Alkaline hydrolysis of tert. butyl bromide 2. Alkaline hydrolysis methyl bromide
(CH 3)3CBr + aq. KOH (CH3)3–C–OH + KBr CH 3Br + aq. KOH  CH3OH + KBr.
3. Rate of reaction depends upon only one 3. Rate of reaction depends upon both the
reactant. reactant.
R  [ R- X] R  [ R- X] [OH–]
5. It is first order reaction. 5. It is second order reaction.
6. It is two step reaction. 6. It is one step reaction.
7. First step is breaking of C– Br and 7. Breaking of C– Br and formation of C– OH
II step is formation of C– OH . takes place simultaneously.

8. Formation of carbo-cation is slow and R.D.S. 8. Formation of transition state is slow and R.D.S.

9. Product formed has 50% reatention & 50% i n - 9. Product formed has 100% inversion
version configuration i.e. 100 % racemisation. [Walden Inversion]

10. It is not sterioselective & not stereospecific 10. It is sterioselective as well as stereospecific
reaction. reaction.

11. Reactivity of RX : 11. Reactivity :

3°RX > 2° RX > 1° RX 1°RX > 2° RX > 3° RX
12. It has only one T. S.
12. It has two T. S.
13. One energy of activation.
13. Two energy of activation
14. No Catalyst required
14. Catalysed by Lewis acid
15. No Carbonium ion
15. Intermediate = Carbonium ion
16. No rearranged products
16. Rearranged products are formed

E1 E2 E1CB
H
H H
C––C B B B B
• + H C –––C C –––C
C––C • B C=C •
Cl
C–––C Cl Cl
C = C + BH
Cl –Cl

• C Fromed • Two step • One step
• R  (substrate) C=C
• Polar solventROH, H2O, RCOOH • R  (substrate) [ B ] • Poor leaving group
• High temp. • Resonance stablised carbanion
formed

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 SN1 Stable C SN2 - Back side attack
1) Solvolysis [H2O, EtOH, MeOH, RCOOH] 1) 1°/2°  RX

RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * *
2) 2°/3° RX 2) Strong Nu –ve charge aq KOH, C2H5O ,
3) Moist Ag2O NaNH2, O , N3 , CN , I
4) AgNO3
3) Polar aprotic solvent
5) High temper Favours Elimination E1
• DMF, DMSO, acetone, crownethers
solvents having (µ 0, No H–Bonding)

E1 E2
Compare with SN1 two step • Compare with SN2 Nu one step
• C formation
• Strong Base  O , Alc KOH, RO ,
• Dehydration of Alc  H / 
• Pinacol-pinacolone rearrangement NaNH2, EtOH/Et O
• Solvolysis Ethanol / Temp high
• High temp. & Base XoIZm nS>Vm h¡ • Bulky base always gives elimnation O

1. 1°RX • SN 1  Weak nucleophile in polar solvent

• Undergo SN 2 / E2 reaction. [H2O, ROH, HCOOH, RCOOH, H2S, etc.]
• SN2 reaction with almost any nucleophile. E1
•  reaction is favoured with weak base
• Alcoholic KOH alwasy give E2 product with any
halide. at high temperature in polar protic solvents.
– [H2O, ROH, HCOOH, H2S, NH3, etc.]
i. CH3CH2CH2Br CH3O CH3CH2CH2–OCH3
(SN2)
K CN
ii. CH3CH2–Cl CH3CH2–CN (SN2)
+ –
Cl aq. KOH OH
iii. 2
SN

[SN2 – strong Nu  aq. KOH]

+ – OH
aq. KOH
Cl SN2
iv. 3. 3°RX
H2O –
OH
SN1
+
• SN2 reaction cannot take place.
OH • E2 reaction is favoured with the use of strong
aq. KOH base. [EtOH/Et O ]
SN 2 Ph OH
v. Ph Cl CH3OH + .. • SN1 reaction is favoured in polar protic solvent.
CH2 CH3OH CH2
SN 1 Ph [H2O, ROH, RCOOH]
–
CH3O Ph OCH3 • E1 reaction is favoured in polar protic solvent
SN 2
Ph OCH3 at high temperature.
2. 2°RX
• E2  Strong base

[[Link], C2H5 O , NaNH2, (CH3)3C–O , etc.]

• SN 2  Strong nucleophile

[ I , Br , CN, SH , aq. KOH, CH3 COO , etc]

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