588 VATSAL Handbook of Chemistry (CBSE Class Xil

APPENDIX:2

NAME REACTIONS
M. Aldol condensation : Two molecules of an aldehvde or ketone containing a-H atom undergo condensation in
molecule to form unsaturated aldehyde or ketone.
the presence of a base to yield an aldol which loses water
(OHH
Dil. NaOH C-C-H -H,0 CH3 -C=C-C- H
CH,--H +H-CH,CHO ’ CH3 -C
H H H
H
But-2-en-1-al

2. Benzoin condensation : In the presence of KCN, aromatic aldehydes containing no a-H atom, undergo self
condensation to form benzoin.
OH O

Alc. KCN
CH

H
(Benzoin)
. Beror Hunsdicker reaction: Silver salts of acids on treatment with Br, in CCl, yields alkyl bromide.
CCl4 + AgBr
CH,COOAg + Br reflux CH,Br Co,
4. Bouveaut-Blanc reduction : Esters on reduction with sodium in alcohols yield primary alcohols.
Na/CgH50H
CH,COOC,Hs + 4[H) 2C,H;OH
5. Balz-Schiemann reaction : Decomposition of diazoniumfluoroborate upon heating at 150C-160°C yields any
fluoride. +

N,CI N,BE
150°C-160°C
+ HBF4 + BF + Ng
Benzene diazonium Benzene diazonium Fluoro benzene
chloride fluoroborate
v. Cannizzaro's reaction : Aldehydes which do not have an a-hydrogen atom undergo this reaction. When such
aldehydes are treated with concentrated solution of an alkali, they form alcohol and salt of carboxylic acid.
2HCHO + NaOH CH,0H + HCOONa
Conc. Methanol Sodium formate
2C,H,CHO + NaOH CçH,CH,OH + CoH CO0Na
Conc. Benzyl alcohol Sodium benzoate
7.Carbyl amine reaction : When primary amine is warmed with chloroform and an alcoholic solution of KOH, it
forms isocyanide having an extremely unpleasant smell.
CzH,NH, + CHCl, + 3KOH
(alc.)
C,H_N 3KCI + 3H,0
Ethyl amine Ethyl isocyanide

NH, NC

+ CHCI, + 3KOH + 3KCI + 3H,o

(alc.)
Aniline Phenyl isocyanide
 589
Appendices
molecules of ester containing a-hydrogen in the
8. Claisen condensation : It involves self condensation of two
presence of a strong base such as sodium ethoxide to form B-keto ester.
CzH5ONa CH3-C--CH,-C-0C,H, + CzH5OH
CH3--C--0C,Hs + H-CH,-C-0C Hs Ethyl acetoacetate
2 molecules of ester
hydrocarbons
8. Clemmensen reduction : It involves the reduction of aldehydes and ketones to the corresponding
with amalgamated zinc and conc. HCI.
Zn/Hg ’ CH,CH, + H,0
CHCHO + 4H Conc. HCI
Acetaldehyde Ethane

Zn/Hg
+ H,0
CH,COCH, + 4H
Acetone
Conc. HC GHgCHCH3
Propane
A J0. Coupling reaction: The reaction of diazonium salts with phenols and aromatic amines to form azo compounds
in the presence of ice cold solution.
273-278 K, OH -OH
-N,C+ H OH
-HCI
-N=1
p-hydroxyazobenzene
(orange dye)
273-278 K, OH
N,CI + H -NH, -HC)
-N=N -NH,
p-aminoazobenzene
(yellow dye)
t. Diazotisation reaction : The formation of diazonium salt from primary amine in dilute mineral acid and
treatment with cold solution of nitrous acid (NaNO, + dil. HCI) at 273-278 K.
N=NCI
NH2
NaNO,/HCI
+ HONO + 2H,0
273-278 K
Benzene diazonium
chloride

V2. Etard's reaction:The oxidation of toluene to benzaldehyde with chromyl chloride dissolved in CCl, or CS,.
CH
OCr(OH)Cl,
CH, CHO
OCr(OH)Cl,
2Cr0,Cla,
CCl4
H,0+

Toluene Brown complex Benzaldehyde

Y3. Friedel-Crafts alkylation : Benzene and other aromatic compounds react with alkyl halides in the presence of
anhydrous AlCl, to form alkyl benzene.
CH3
Anhyd. AICl3
CHCI + HCI
Methyl chloride
Toluene
The alkylation of benzene can also be carried out with propene in the presence of phosphoric acid.
HzPO4
+ CH,CH=CH, 543 K -CH(CH,)2
Cumene
590 VATSAL Handbook of Chemistry (CBSE Class XII)
UA. medel-Crafts acylation : Benzene and other aromatic compounds react with acid chlorides or anhydrides in
the presence of anhydrous AlCI, toform ketones.
COCH3
Anhy. AlCl, + HCI
CH,COCI
Acetyl chloride
Benzene Acetophenone

ÇOCH3
Anhy. AlCl3 + CH,COOH
+ (CH,CO),0
Acetic anhydride Acetophenone

M5. Finkelstein reaction : It is a halide exchange method and iodoalkanes are best prepared by this method from
or methanol.
the corresponding chloro or bromoalkanes by heating with sodium iodide in acetone
Acetone or methanol
CHCH,-Br + Nal CH,CH,I + NaBr
gets deposited.
Sodium bromide (or NaCl in case of chloroalkanes), being less soluble than Nal inbyacetone,
direct addition of HI to
prepared
This reaction is very useful for preparing such alkyl iodides which cannot be
alkenes.
Cu/HBr to
V6. Gattermann reaction : It involves the reaction of benzenediazonium chloride with Cu/HCI or
prepare haloarene.
CI

Cu/HCI, + Ny
Chlorobenzene

Br

Benzene diazonium
chloride Cu/HBr
+ N2
Bromobenzene
ti.Gatermann Kochreaction: Benzaldehyde is prepared by passing mixture of COand HCl gas to benzene in the
presence of anhydrous AlCl, and traces of CuCl.
CO + HCI HCOCI
Formyl chloride
CHO

+ HCOCI
AlCl,
CuCl
+ HCI

Benzaldehyde
OH

v8. Haloform reaction: The compoundscontaining CH3-C- or CH3 -C group give yellow precipitate of
H
iodoform on reaction with NaOH and l, solution. This known as iodoform reaction.
CH COCH, + 31, + 4NaOH + CH,COONa + 3Nal + 3H,0
Acetone lodoform
(yellow ppt.)
CHgCH,0H + 4l, + 6NaOH CHI, + HCOONa + 5Nal + SH,0
Ethanol lodoform
Appendices 591

9. HellVolhard Zelinsky (HVZ) reaction :Thealiphatic carboxylic acids containing a-hydrogen react with Gl, of,572
in the presence of red phosphorus to give a-haloacids.
Cl,, P Cly, P Cl2, P’
CH,COOH CH,COOH ’ Cl,CHCOOH Cl,cCOOH
HCI -HCI Dichloro
-HCI Trichloroacetic
CI acetic acid acid
Monochloro
acetic acid

L20. Hofmann bromamide reaction :The amides can beconverted to primary amines containing one carbon less
than the amides by heating it with Br, and NaOH or KOH. It is also known as degradation reaction.
CHCONH, + Br, + 4KOH CH4NH, + K,CO, + 2KBr + 2H,0
Acetamide Methyl amine

G6H_CONH, + Br, + 4KOH ’ G7HsNH, + K,C0, + 2KBr + 2H,0

Benzamide Benzamine

L21. Hydroboration reaction : This reaction involves addition of water to alkene according to Anti-Markownikoff's
rule by the addition of borane followed by hydrolysis to alcohol.
BH3
CH,CH=CH, THF (CH,CH,CH,)gB H02,
OH
3CH,CH,CH,OH
Propene Propanol
22. Kolbe-Schmidt reaction :Sodium phenoxide reacts with CO, under 6-7 atm pressureat 400 Ktoform sodium
salicylate which upon acidification with HCl gives salicylic acid. OH
ONa OCOONa OH
COONa COOH
400 K Rearrangement H,0/H*
+ CO, 6-7 atm -NaCl

Sodium
Phenyl sodium Sodium salicylate Salicylic acid
carbonate
phenoxide
23. Mendius reaction:The alkyl or aryl cyanide is reduced to primary amine by amalgamated sodium and alcohol
Na/CzHsOH
CH,CN + 4H CH,CH,NH,
Ethyl amine

anhydride in the presence of sodium acetate fll

4 Perins reaction:Benzaldehyde on heating with acetic
unsaturated acid.
by hydrolysis gives a, B CçHsCH =CHCO,
CGH;CHO + H|CHCO CH,COONa H,o/Bou, CH,COOH +
C7H_CH=CHCOOH
180°C, -H,0 CH,C0
CH,CO Cinnamic acid
Acetic
anhydride
are converted to corresponding aldehydes in the presence of palladium
Rosenmund's reaction : Acid chlorides quinoline.
L25.
BaSO4 partially poisoned with sulphur or
deposited over
Pd, BaSO4
CH3-C--Cl + H Boiling xylene’ CH-C-H + HCI
Acetaldehyde
Acetyl chloride

Pd, BaSO4
C;Hs-C--Cl + H, ’ CçH-C-H + HCI
Benzoyl chloride
S Benzaldehyde
aqueous alkali at 340 K
Phenols react with CHCI3 in the presence of
Reimer-Tiemannreaction: When CCl, is taken instead of CHCI3, salicylic acid is
formed. followed by
L26. salicylaldehyde.
hydrolysis gives
592 VATSAL Handbook of Chemistry (CBSE Class Xl)
OH ONa ONa OH

CHCl, CH(OH), CHO

NaOH, 340 K 2NaOH HCI
+ CHCI, NaCl -2NaCl -H,0
-H,0 (Unstable) Salicylaldehyde
OH ONa ONa OH

CCl3 C(OH)3
HCI
COOH
NaOH, 340 K 2NaOH
+ CCL4 NaCl -3NaCl -H,0
H,0 Salicylic acid
on treatment with
27. Sandmeyer's reaction : Benzene diazonium chloride is converted to chlorobenzene
Cuc/HCI.
N,CI C

CuC/HCI
+ N,‘
Chlorobenzene
Benzenediazonium
chloride
to give alcohol and the sodium
28. Saponification : Hydrolysis of an ester with aqueous NaOH or KOH solution
or potassium salt of the fatty acid is called saponification.
CH,00CR CH,OH R,COONa

CHOOCR, 3NaOH
Heat
CHOH + R,COONa
+

CH,OH RgCOONa
CH,00CRg Glycerol (Sodium salts
Oilor fat of fatty acids)
(Triglyceride)
29. Schotten-Baumannreaction : The treatment of benzoylchloride with the compounds having active hydrogen
example,
like phenol, aniline etc., in the presence of aqueous NaOH is called Schotten-Baumann reaction. For
OH OCOCçHs
CgH;COCl NaOH, + HCI
Benzoyl chloride
Phenol Phenyl benzoate
NH, NHCOCGHs
C6H COCI NaOH, + HCl
Benzoyl chloride
Aniline Benzanilide

La0. Swart's reacion :Alkyl fluorides are easily prepared indirectly by heating suitabie chloro or bromo alkanes
with inorganic fluorides such as Agf AsFa, Hg,Fa etc. This reaction is called Swart's reaction. For example,
2C,H,Cl + HggF 2C,H_R t HgzClz
Chloroeth¡ne Fluoroethane
CH,Br AgF CH,F AgBr
Bromomethane Fluoroethane
31. Transesterification reaction : When an ester is treated with excess af another alcohol (other than one ro
which ester is forned) in the presence of a base such as the corresponding sodium or potassium alkoxide or an aau
as catalyst, a new ester and a new alcohol is formed.
H* or CgHsONa
CH,CO0C_Hg + G2HsOH CH-CO0C,Hs + CaHgOH
n-butyl acetate Reflux n-butyl alcohol
Appendices 593
OL. 1Scneiko reaction : All aldehydes can be made to undergo Cannizzaro's reaction with aluminium ethoXIde
and ester is formed.

2CH,CHO Al(OCzH_)3 CH,CO0C,H,

Acetaldehyde Ethylacetate
L0. Wllamson synthesis : The reaction of alkvi halides with
is called sodium alkoxide or sodium phenoxide to form ethers
Williamson synthesis.
CH,CH,l + CzHONa CzH50C,Hs + Nal
Ethyl iodide Sodium ethoxide
Ethoxyethane
ONa
OCH3
+
CH,I + Nal
Sodium
Methyl iodide
phenoxide Anisole
L34. Wolf-Kishner reduction: The
and KOH in presence of reduction is done by heating the carbonyl
ethylene glycol. compound with a mixture of hydrazine
CH,CH=0 NH,NH2 -H,0CHzCH=NNH, KOH, glycol
Acetaldehyde 453-473 K CH CH3 + Ny
Hydrazone Ethane
H,C NH,NH2 H,C
C=0
H,C -H,0 HgC C=N NH KOH, glycol
Acetone
35: Wurtz reduction :It Hydrazone
453-473 K
Propane CH-CH,CH3 + N2

with metalic sodium in the involves the interaction of two

molecules of an alkyl halide ((preferably
presence of dry ether to form
carbon atoms present in the alkyl halide. symmetrical alkanes containing double bromide or iodide)
the number of
CH3- Br + 2Na +Br -CH Dry ether

However. if twodifferent alkylhalides are a Ethane CH3-CH,

2NaBr
For example, used, mixture of three
alkanes are obtained.
CH,1+ 2Na +ICH, CH, Dry ether
CH,Propane
CH,CH, + 2Nal

CHg-1+ 2Na +ICH, Dry ether

CH3CH3 + 2Nal
Ethane
CH3-CH,1+ 2Na+l-CH,-CH, Dry ether
^38. Wurtz-Fitig reaction : This reaction is a
C4H10
Butane
+ 2Nal

aryl halide and an alkyl halide with metallic variation of Wurtz reaction and
For example, sodium in presence of dry ether toinvolves warming a mixture
prepare homologous of of an
-Br +2Na + BrCH Dry ether
-CH, + 2NaBr
benzene.
Diphenyl and ethane are obtained as by-products. Toluene