Class 12 Organic Chemistry Important Topics
Named Reactions
Sandmeyer Reaction:
The Sandmever reaction is a chenical reaction which is used to synthesize aryl halides from aryl
diazonium salts. This reaction is a method for substitution of an aromatic amino group by
preparing diazonium salt that is followed by its displacement and copper salts often catalyze it.
CuCVH1
ArCl + N,
CuBrHBr
ArBr+ N;
CuCNKCN ArCNt N;
Gattermann Reaction:
Bromine and Chlorine can be present in the benzene ring by preparing the benzene diazonium
salt solution with similar halogen acid present with copper powder. This is the Gattermann
Reaction.
A m aD
n hattarwal
Cutli
ArCl+ N, +CuX
CuHBr ArBr + N, +CuX
Balz-Schiemann Reaction:
When arene-diazonium chloride is prepared with fluoroboric acid, arene diazonium fluoroborate is
precipitated and decomposes to yield aryl fluoride which on heating.
Ar N,CI +HBE, Ar- N,BrF, HentAr-F+BF; +N;
Fluoroboric acid
Finkelstein Reaction:
In the Finkelstein Reaction Alkyl iodides are prepared easily by the reaction of alkyl chlorides with
Nal in dry acetone.
R-X+ Nal ’R-1+NaX
(X=Cl,Br)
Swarts Reaction:
When alkyl chloride is heated in the presence of a metallic fluoride like AgF, Hg2F2, SbF3 or CoF2,
we get alkyl fluorides.
H,C-X +AgFH,C-F+AgX
(X=C1,Br)
Wurtz Reaction:
When Alkyl halides get reacted
with sodium with dry ether, we get hydrocarbons that
include the
double number of carbon atoms present in the halide. This is known as the Wurtz ReactiOn
CH,Br +2Na+BrCH, dy ethe,CH,-CH, +2NaBr
Bronomethane Ehane
C,H,Br+2Na+BrC,H, Yethet, C,H, -C,H,
Bromoethane n-Butane
Wurtz-Fittig Reaction:
When a mixture of alkyl halide and aryl halide gets treated with sodium in dry ether, we
alkyl arene.
get an
-R
+ Na + RX Ether ) aD
n+h attarwal
NaX
Fittig Reaction:
Aryl halides prepared with sodium in dry ether to give
groups joined. scompounds where two aryl
2 + Na Ether
+ 2NaX
Friedel-Crafts alkylation Reaction:
Benzene is prepared with an alkyl halide in the presence of anhydrous
Alkylbenzene. aluminum chloride to give
CH.
Anhyd. AICI,
CH,CI + HC)
Toluene
(13.75)
AnhydAlCL CH,
+ C,[Link] + HCI
Ethyibenzene
Friedel-Crafts acylation reaction:
We get acyl benzene when an acyl halide is reacted with benzene in the
presence of Lewis acids.
COCH,
+CH,COC1 Anhyd. AICI, + HCI
Acetylchloride
Acetophenone
(13.77)
COCH,
CHCO,o Anhyd. AIC
Acetic anhydride
CH,COOH
Stephen reaction: acid reducod to the Coresponding
the presonco of hvdrochloric
Nitriles with stannous chlorido in aldehyde aftor hydrolysis.
imine and give the corOsponding
RCN +SnCl, + HCIRCH= NI |0->RCHO
Etard reaction:
on hydrolys0s provides
Chromylchloride oxidizes methyl group to get chromlum complex which
corresponding benzaldehyde.
CHO
Cl, CH(OCOHC),
+Cro.C,,
Tolucne Benzaldehyde
Chromum connplex
Gatterman - Koch reaction:
Benzene is prepared with carbon monoxide and hydrogen chloride in the presence of anhydrous
aluminum chloride to give benzaldehyde. AmaDnhattarwal
CHO
CO. HCI
Anhyd. AICI,/CuCÍ
Benzene Benzaldechyde
Clemmensen Reduction:
In Clemmensen reduction, Carbonyl group of aldehydes and ketones on treatment with zinc
amalgam and concentrated hydrochloric acid reduced to CH2 group.
C=0,c, + H0 (Clemmcnsen reduction)
Wolff Kishner Reduction:
Carbonyl group of aldehydes and ketones on treatment with hydrazine which on heating with
sodium hydroxide in a high boiling solvent (ethylene glycol) reduced to CH2 group.
KOH/ethylene glycol
c=o-=NNH, heat + N,
(Wolff-Kishner rduction)
Tollens' test:
Heating an aldehyde with fresh prepared ammoniacal silver nitrate solution produces a bright
silver mirror due to the formation of silver metal.
RCHO + 2|Ag(NH)J + 3OH’ RCOO + 2Ag + 2H,0 + 4NH,
Fehling's test:
rening sSOlution A(aqueous copper sulfate) and Fehling solution B(alkaline sodium potassium
lartrate)are mixed in equal amounts before the test. Areddish brown precipitate is obtained when
an aldehyde is heated with Fehling's reagent.
R-CHO + 2Cu" + 5ÖH ’RCO0 + Cu,0 + 3H,0
Red brown ppt
h p h a t t a a
Aldol reaction:
Aldehydes and ketones havingone a-hydrogen undergo a reaction in the presence of alkali
as the catalyst to produce B-hydroxy aldehydes or B-hydroxy ketones.
Aldol condensation:
are aldol
Aldol and Ketol lose water to provide a,ß-unsaturated carbonyi compou
condensation products.
2CH,-CHO Æ
Nao CH-CH-CH-CHO -H0 CH,-CH=CH-CHO
But-2-enal
Ethanal
3Hydroxybutanal (Alclol condensation
(Aldol) product)
CH, CH,
2CH,-CO-CH, Balo CH--CHCO-CH, 3-H0
ACH--CH-CO-CH,
Propanone OH 4-Methylpent-3-en 2-one
(Ketol) (Aldol condensation
4 Hydroxy-4-methylpentan-2-one product)
Cross aldolcondensation:
Aldol condensation is carried out between two different aldehydes and [Link] gives a mixture
of four products if both of them includes a-hydrogen atoms.
CH,CH,-CH=CHCHO
CH-CH-ç-CIO
H,
2-Methylbut-2 enal Pent-2-enal
CH,CHO 1. NaOH CH,-CH-CH-CHO + CH,CH,-CH-C-ÇHO
But-2-enal
CH,CH,CHO
Cannizzaro reaction:
Aldehydes without a-hydrogen atom undergo self-oxidation and reduction reaction when
prepared with concentrated alkali.
C=0 + + Cone. KOH H-C-0H + H-C
OK
H
Formaldehvde Methanol Potassium formate
-CHO + Conc. NaOH CHOH -coONa
Benzaldehyde Benzyl alcohol Sodiumn benzoate
Kolbe electrolysis:
in Kolbe elactroiys s, An aqueous solution of sodium or potassium salt of acarboxylic acid gives
alkane containing an even number of carbon atoms on electrolysis.
2CH,CO0 Na' + 2H,0
Sodium acetale
Electroyss
CH, -CH,+2C0, +H, +2NaOH
Hell-Volhard-Zelinsky (HVZ )reaction: val
Carboxylic acids having a a-hydrogen are halogenated at the a-position give a-halo carboxylic
acids on treatment with chlorine or bromine in the presence of
small amount of phosphorus.
() X/Red phosphorus
RCH,-COOH
(1) H,O
X= Cl, Br
a- Halocarboxylic acid
Gabriel phthalimide synthesis:
Phthalimide prepared with ethanolic potassium hydroxide produces potassium salt of phthalimide
when heated with alkyl halide followed by alkaline hydrolysis forms the
amine. corresponding primary
CN-| KOH, NK RX
Phthallmide
N Alkylphthalimide
N -R NaOH{aq) C-ONa
+R-NH,
C-ONa (1' amine)
Hoffmann bromamide
An amide with bromine indegradation reaction:
an aqueous solution of sodium hvdroxide produces
primary amines.
Migration of an alkyl or aryl group takes place from carbonýlcarbon of the amide
atom. The amine so produced include one carbon less than to the nitroge
that present in the amide.
R-C- NIL, + Br, + 4NaOH ’ R-NH, + Na,CO, + 2Nalir + 211,0
Carbylamine reaction:
Aliphatic and aromatic primary amines when heated with chloroform and ethanolic potassium
hydroxide produces isocyanides or carbyl amines which are foul smelling substances.
R-NH, + CHCI, + 3KOH enl, R-NC + 3KCI + 3H0
Hinsberg's Test:
Benzenesulfonyl chloride (C6H5SO2C) reacts with primary and secondary amines
sulphonamides.
chloride with e r i o . .
1.
amion of benzene-sulfonyl
amide. The hydrogen attached to the nitrogen iF sulphonamide is strongly acidic due to the
presence of strong electron withdrawing sulfonyl group. Hence, it is soluble in alkali.
+ HCI
H ) H
N Ethylbenzenesulphonamide
(soluble in alkali)
2. In the reaction with a secondary amine, N, N-diethyl- benzenesulfonanide is formed. Since N,
N- diethyl benzene sulphonamide does not contain any hydrogen atom attached to a nitrogen
atom, it is not acidic and hence insoluble in alkali.
+ H-N-CH,’ HC -$-N-CH, +HCI
C,H, C,H,
N.N-Diethylbenzenesulphonamlde
3. Tertiary amines do not react with benzene-sulfonyl chloride.
Coupling Reactions:
Benzene diazonium chloride gets reacted with phenol in which the phenol molecule at its para
position is mixed with the diazonium salt to give p-hydroxyazobenzene.
-OH +C1* H,0
p-Hydroxyazobenzene (orange dye)
