1 Aldol condensation

Two molecules of aldehydes or ketones containing a-hydrogen atom, in the presence of dilutealkak a
NaOH, Ba(OH), etc.] undergo condensation to form B-hydroxy aldehydes or B-hydroxyketones. [dil
OH

CH-C+H-CH- -H- Na CH,--CH,--H- CH-CH=CH-C-H

2-Butenal
H H (Crotonaldehyde)
Two molecules of ethanal
3-Hydroxybutanal 9809
CH OH CH H
al
CH,CH-ë+H-CH-CHONaOH
CH,CH,-C-CH-C=0
H H

Two molecules of propanal 3-Hydroxy-2-methylpent-2-enal

| Heat

CH, H
CH,CH,CH=-=0
2 Methylpent-2-enal

Please note this reaction. The second molecule joins only from t-carbon atom.
O QH O O

CH-C+H-CHC-CH BaCH,-CCH- -CH,-aCHc-CH- -CH

CH CH CH
Two molecules of propanone 4-Hydroxy-4- methyl 4-Methylpent-3-en-2-one
2-pentanone (mesityl oxide)
Diacetone alcohol)
Formaldehyde and benzaldehyde which do not have a-hydrogen atom do not undergo aldl condensation.
5 Balz-Schiemann reaction
This reaction involves the decomposition of diazonium fluoroborate to aryl fluorides.

NC N, BF F
HBF 273-278 K
Fluroboric Heat
acid
Benzene diazonium
Benzene diazonium Fluorobenzene
chloride
fluoroborate
6Cannizzaro reaction
Aldehydes which do not contain any aHydrogen atom (e.g.,
axidation and reduction reaction on treatment with conc. solution of benzaldehyde, formaldehyde) undergo self
caustic alkali. In this reaction, one molecude
is Oxidised to acid while another molecule is reduced
to alcohol.
HCHO++HCHO505NaOH
CH,OH HCOO Na*
Formaldehyde Methyl alcohol Sod. formate
CHO CHO CH,OH COONa
50% NaOH +

Benzyl alcohol Sod. benzoate

7 Carbylamine reaction
When a primary amine (aliphatic or aromatic) is warmed with
chloroform and alcoholic KOH, it forms an
isocyanide or carbylamine having extremely offensive smel.

CHCHNH, + CHCl, + 3KOH Warm CH CH NC

Ethylamine (alc.)
3KCl+3H,O
Ethylisocyanide
NH, NC

+CHCl +3KOH Warm

+3KCI+ 3H,O
(alc.)
Aniline Phenyl isocyanide
Claisen condensation
It involves self condensation of two molecules of ester containing
o-hydrogen in the presence of a strong
such as sodium ethoxide to form p-keto ester. base

O O O
CH-COC,H, + H-CH-C-0C,H, CH,ONa
2 molecules of ester CH-CCH-C-OC,H,
Ethylacetoacetate
+C,H,OH
B-keto ester)
Clemmensen reduction
It involves the reduction of aldehydes and ketones to the
and conc. HCI corresponding nyarocarbons with
amalgamated zine
CHCHO + 4H Zn/Hg
conc.
HCI? CHCH + H,O
Acetaldehyde thane
 CH,COCH, + 4H
Zn/Hg
conc, HCICH,CH,CH, + H,OO
Acetone Propane

COCH, CH,CH,
Zn/Hg
O|+ 4H conc. HC
O +
HO
Acetophenone Ethylbenzene
Coupling reaction
The reaction of diazonium salts with phenols and aromatic amines to form azo compounds. 'Th reaction is
carried out in ice cold solution.
273-278 K
ONC OH -HC1 N-N-KO OH

Benzene diazonium Phenol p-Hydroxyazobenzene

chloride (Orange dye)

-N,CI+ NH273-278 K
-HC1 »-N-NONH,
Benzene diazonium Aniline p-Amino azobenzene
chloride (Yellow dye)
Methyl orange which acts as an indicator in the acid alkali titrations is obtained by coupling the diazonium
salt of p-aminosodiumbenzene sulphonate with N,N-dimethyl aniline in the presence of alkali.

NaNO/HCI
Nao,sONH, Na0,8ON,CI
p-Amino sodiumbenzene sulphonate Diazonium salt

Naos O N C I O - N C H , ) , NaOH N a o , s - O N - N O - N I C H ,

N, N-dimethylaniline Methyl orange

11 Diazotisation reaction
The formation of diazonium salt from primary amine in a dilute mineral acid (HCl or H,SO) and treatment
with cold solution of nitrous acid (NaNO, + dil HCI) at 273-278K

NH, N=NCI
NaNO2, HCI
+HONO 273-278K
273-278 K +2H,0
Aniline Benzene diazonium
chloride
13 Etard's reaction
The oxidationoftoluene to benzaldehyde with chromyl chloride (Cr0,C1,) dissolved in CCl, CS or

OCr(OHCl,
CH3 CH CHO

2Cr0Cl2
CCl4 OCr(OHCl, 1,O O
Toluene Brown complex Benzaldebyde
14 Esterification reaction
The reaction of alcohols with carboxylic acids in the presence of a few drops of conc. H,SO, to form esters.

O
conc. H,sO
CHC-OH+ HOCH,CH, CH-C-oCH,CH, H,O
Acetic acid Ethyl alcohol Ethyl acetate
It may be noted that if HCl gas is used as a catalyst in the above reaction, the reaction is known as Fischer-
Speier esterification.
 Fittig'sreaction
This reaction is a modification of the Wurt'z reaction. In this reaction two molecules of haloarene combine
with metallic sodium in the presence of anhydrous ether to give diphenyl.

Cl+2Na +Cl Anhydrous

ether
+2NaCl
Two molecules of Diphenyl
chlorobenzene
I8Finkelstein reaction
or bromoalkanes are
Chloroalkanes
dissolved in acetone.
converted into corresponding iodoalkanes by treating with sodium iodide

CHCHCl + Nal Acetone CH CHI + NaCl

Ethyl chloride Ethyl iodide

CH,CH,Br + Nal Acetone CHCH,I+ NaBr

Ethyl bromide Ethyl iodide
 19 Priedel Craft's alkylation
Benzene and other aromatic compounds react with alkyl halide8 in the presence of anhydrous AICl, to form
rm
involves the addition of alkyl (-R)group to the benzene ring.
alkyl benzene. ThisN reaction

Anhyd AlCla HCI

+CH,C
Methyl
Benzene chloríde Toluene

CH,CH,
+CHCH,Br Anhyd AlCl HBr
Ethyl bromide Ethyl benzene
Benzene
1-i

CH CH CH
CH3
+ CH Cl
Methyl chloride
Anhyd AlCla
O
Toluene 0-Xylene CH3
p-Xylene
acid (as the catalyst)
The alkylation of benzene can also be carried with propene in the presence of phosphoric
when the product formed is isopropyl benzene.
HPOP
+CH,CH=CH H (O-CHCH,,
Isopropylbenzene or Cumene
Benzene Propene
20 Friedel Craft's aeylation
in the presence of anhydrous
Benzene and other aromatic compounds react with acid chlorides or anhydrides
AICl,to form ketones. This reaction involves the addition of acyl (RCO-) group.

COCH
CH,COCI
Anhyd AICl HCI

Acetyl chloride
Benzenee Acetophenone
COCH
Anhyd AlCla + HCI
+CH,COC
Benzoyl chloride
Benzene Benzophenone
COCH
+(CH,CO),0 Anhyd AlCl, CH,COOHH
Acetic anhydride
Benzene Acetophenone
P2Gabriel phthalimide synthesis
This reaction is used to prepare primary amines. In this reaction, phthalimide is converted into its potassium
tby treating with aleoholic solution ofKOH. The aalt is then treated with alkyl halide to give N-alkyl
which
phthalimide, which.on hydrolysis
with dilute hydrochloric acid gives a primary amine as the product.

NHK KOH (ale.)

H,O [OE C O N K
NK
Phthalimide
Potassium phthalimide
-KBr C,HBr

COOH
COOH CHNH, OIN-CH,
coN-C,H,
Phthalic acid
Ethylamine N-Ethylphthalimide
(1)
23 Gattermann reaction
This is a modification of' Sandmeyer's reaction. This
involves the reaction ofbenzene diazonium chloride with
Cu/HCl and Cu/'HBr to prepare
chlorobenzene and bromobenzene
respectively.
N,"C Cl

Cu/HCL O
Benzene diazoniumn
chloride
Chlorobenzene

N Cl Br

Cu/HBr
Benzene diazonium
O Na
Bromobenzene
chloride
24 Gattermann Koch reaction
Benzene is converted to benzaldehyde by passing a mixture of carbon
in the presence of monoxide and hydrochloric acid
anhydrous AlCl, and traces of cuprous chloride. gas

CO + HCl HCOCl
Formyl chloride
CHO
HCOCI AICl3, CuCi HC
Formyl
Benzene chloride Benzaldehyde
This reaction is, thus, a modification to the Friedel-Cralt reaCtIon In which-CHO
group is introduced in .
benzene ring. e

25Haloformreaction
The compounds containingmethyl group bonded to carbonyl group ie. methyl ketones ( C H . C O . .
compounds which can be converted to methyl ketones upon oxidation (eg, CH, CH react with the

OH
carbonate and iodine solution and give yellow precipitates of iodoform. This reaction
reaction is
is also
also called iodofor
reaction. oform
CHCH,OH +4I, + 6NaOH- CHI +HCOONa +
5Nal +
Ethanol Iodoform 5H,O
 CH,CHOHCU, + 41., +GNaOH STAY-AN
2-'ropanol
CH+C1,C0ONa +
5Nul +51,0
CH,COCH, +31, + ANnOH CHL +CH,COONa +3Nal +3H,O
l'ropanone
CH,COCH,CH, + 31, + 4NaOH CHI+CH,CH,COONa + 3Nal +3H,0
2-Butanone
This reaction is commonly used to distinguish betweon methyl ketones or methyl carbinols fron d
ketones and aleolhols. ther
96 Hell Vohlard Zelinsky reaetion
The aliphatie carboxylie acids containing cx-hydrogen reaet with Cil, or Br, in the presence of a small amount
ofred phosphorus to give a-haloacids. With exco8s ofhalogen, all theo-hydrogen atoms of the aliphatic carboxvlio
acids are replaced by halogen atoms,

CH,COOH l .P CH,COOH Cl CI.CHCOOH Cl P CLCCOOH

Acetic acid Dichloroacetie Trichloro acetic
CI acid acid
Monochloro acetic
acid

CH,CH,cOOH CHCHBrCOOOH r CH,CBr,COOH

Propionie acid -Bromopropionic a, a-dibromo propionic
acid acid

The a-halogen in the reaction can be replaced by other groups such as-OH,-CN,-NH2,-COOH, etc.by
suitable reagents.
27Hoffmann bromamide reaction
The amides can be converted into primary amines containing one carbon atom less than the original amide
by heating with a mixture of Br, in the presence of NaOH or KOH. This reaction is also called Hoffmann's
degradation reaction.
CH,CONH, + Br, + 4KOH CH NH,+ KCO+2KBr +2H,O
Acetamide Methyl amine
CH,CONH, + Br, + 4KOH CH NH2 + K,CO, + 2KBr + 2H,O
Benzamide Aniline
The reaction is very useful to convert a higher member in a family to its next lower member.
30 Hunsdiecker reaction
halides are prepared by decomposing the silver salts of carboxylic
acids dissolved in CCl, by bromine
Alkyl
orchlorine.
CH,COOAg BrBr cCCC1 CH,Br +
CO AgBr
Silver acetate Methyl bromide
APPE

CH,COOAg +
Cla CClA CH,CI+ CO + AgCl
Silver acetate
Methyl chloride
Hydroborationreaction
This reaction involves addition of water to a double bond opposite to that of Markovnikov reaction. The
action takes place by addition of borane (BH,) followed by hydrolysis to alcohol.

BH3
CH CH = CH,TH(CH,CH,CH,)B H
OH3CH,CH,CH,OH
Propene
G) BHg, THF
or CH,CH CH () H,O2, OH 3CH,CH,CH,OH
S2 Kolbe's electrolysis reaction
The electrolysis of sodium or potassium salt of a carboxylic acid in aqueous solution, gives alkane, alkene or
alkyne as the product depending upon the nature of the carboxylic acid used.
For example,
() Ethane is prepared by the electrolysis of aqueous potassium acetate.

2CH,COOK 2CH COO-+ 2K

Pot. acetate (Anode) (Cathode)

At anode: 2CH,CO0 -2e2CH,COO- CH,CH+ 2C0

Ethane
At cathode : Both K* and H* ions (obtained by the
electrolysis of water) will be formed but H* ions are
preferentially discharged due to the lesser discharge potential of hydrogen.
2H+2e 2H or H
) Ethene can be obtained by the electrolysis of aqueous solution of the potassium salt of succinic acid.
CH,COOK CH,COO
Electrolysis 2K
CH,COOK CH,COO
Pot succinate (Anode) (Cathode)
At anode: CH,CO0 CH,COO
2e -2C02 CH
CHCOO CH,COO C
Ethene
At cathode: 2H +2e 2H or H,
(ii) Ethyne can also be obtained by the electrolysis of aqueous solution of potassium maleate.

CHCOOK Electrolysis CHCOO + 2K

CHCOOKK CHCOO
Pot. maleate (Anode) (Cathode)
ÇHCO0 CHCOOD CH
At anode CHCO0-
-2C02
CHCOO CH
Ethyne
Atcathode
2H +2e 2 H or Ha
schmidt reaction
33 Kolbe's
m henoxide reacts with t o under pressure (6-7 atm) at 400K to form sodium salicvlate which :
salicylic acid.
acidification with HCl gives
OCOONa
ONa
OH OH

400 K
Rearrangement -COONa [OCOOH
O]+Co, 7 atm.
Phenylsodium Sodium
Sod. phenate carbonate
salicylate
2-Hydroxy benzoic acid
(Salicylic acid)
 Oxymercuration anddemercuration of alkenes
Alkenes react with mercuric acetate in a mixture of THF and water to give (hydroxyalkyl) mercury
compound, involving addition of -OH and -HgOAc to the double bond. This is called Oxymercuration. Then
NaBH, reduces -

HgOAc and replaces with hydrogen. This is demercuration.

CHCHCH-CH HgOAc
THF, H,O
CH,(CH,), ÇH-ÇH,
H.NaBE CH,(CH,), CH-CHH
Pent-1-ene OH
OH HgOAc
Pentan-2-0l
OH CH OH
CH3 CH
HgOAc) XHgOAAc NaBH4
THF, H,O H
1-Methyl cyclopentene 1-Methyl cyclopentanol
 0Rosenmund's reaction
Acid chlorides areconverted to corresponding aldehydes by
catalytic reduction. The reaction is carried out
by passing through a hot solution of the acid chloride in the presence of palladium
(partially poisoned with sulphur or quinoline). deposited over barium sulphate

O
CH--Cl +H Pd,Pd, BaSO4
S CH-C-H + HCI
Acetyl chloride
Acetaldehyde

O
Pd,Pd, BaS0
CH CCl +H, S CH-C-H + HCI
Benzyl chloride Benzaldehyde
The poisoning of palladium catalyst decreases its activity and it does not allow the further reduction of
aldehyde into alcohol._
Reimer Tiemann reaction
Phenols react with chloroform in the presence of
aqueous alkali at 340 K. The hydrolysis of the resulting
product gives 2-hydroxybenzaldehyde (salicylaldehyde).
OH ONa ONa OH
OCHC -NaCT
NaOH
-CHCl 2NaOH -CH(OH)2 HC OCHO
-H20 -2NaCi
Phenol (Unstable) 2-Hydroxy
benzaldehyde
(Salicylaldehyde)
In this reaction, a small amount of p-hydroxy benzaldehyde is also formed.
If instead of chloroform, carbon tetrachloride is used, salicylic acid is formed.

OH ONa ONa OH
|+ CCl, NaOH CCI,
-H,O O 3NaOH
-3NaCl COH) HCI
OCoOH
Salicylic acid
A small amount of p:hydroxy benzoic acid will also be formed.
 AR

Sandmeyer's reaction
Benzene diazonium chloride is converted to chlorobenzene, bromobenzene, cyanobenzéne on treatment with
CuCVHCI, CuBr/HBr and CuCN/KCN respectively.

N,CT Cl

CuCl Na
Benzene diazonium chloride Chlorobenzene

Br
N,CT
OJ CuBr +
No
Bromobenzene

CN
NCT
CuCN + N2
(Pyridine)
Cyanobenzene
44 Schiemann reaction
Pluorobenzene is prepared from benzene diazonium chloride by treating with fluoroboric acid and heating
the product formed.

NCI NBP
HBF
Fluoroboric acid Heat
-HCl OJ
Benzene diazonium Benzene diazonium Fluorobenzene
chloride fluoroborate

45 Schotten Baumann reaction

The reaction involves the benzoylation of phenol, primary or secondary amine with benzoyl chloride in the
presence of aqueous sodium hydroxide.

OH OCOC H
+ CH COCl OH + HCI
Benzoyl chloride
Phenol Phenyl benzoate

NH NHCOC Hs
[O CH COCI OH
+HCl
Benzoyl chloride
Aniline Benzanilide
46 Stephen's reaction
The partial reduction ofalkylor aryl cyanides to the corresponding aldehydes witha suspension of anhydrous
SnCl, in ether saturated with HCI at room temperature followed by hydrolysis.
SnCl+2HCI SnCl +2Nascent
H]
CHC= N+ 2[H] + 2HCI CH,CH=NH HCI HO Bou) CH,CHO +NH CI
Methyl cyanide Acetaldoxime hydrochloride Acetaldehyde
CHC=N +2{H]+2HCI CH,CH= NH HCI H0 (Boil) CH CHO + NH,CI
Phenyl cyanide Benzaldoxime hydrochloride Benzaldehyde
 Cycm
W i l l i a m s o n s y n t h e s i s

dwilliam
This reaction is used to prepare both symmetrical and unaymmetrical ethers by treating alkyl halide with
oxide or sodium phenoxide.
sodium

ither.

CH,Br + CH,ONa
Sod. ethoxide
CH,OC,H, NaBr
Bromomethane Methoxyethane

C,H,Br CH,ONa
Sod. ethoxide
CH,OC,H, NaBr
Bromoethane Ethoxyethane

CH,CI CH OÑa
Sod. phenoxide
CH,OC,H, NaCl
Chloroethane Ethoxybenzene
C,HBr + (CH),CONa (CH),COC,H, + NaBr
Bromoethane Sod. tert. butoxide Ethyl tert. butyl ether
Aryl halides cannot be used for the preparation of alkyl aryl ethers because of their low reactivity.
53 Wurtz reaction HEMSTRY-XH
Alkyl halides react with metallic sodium in the presence of anhydrous ether to form alkanes. This reart.
is used for the preparation of higher alkanes. For example, ction
CH Br +2Na +CH,Br CH CH + 2NaBr
Bromomethane Ethane
CH Br +2Na + CHBr CHCH,CH,CH, + 2NaBr
Bromoethane Butane
Ifwe start with different alkyl halides, then a mixture ofalkanes will be formed. For
CH,I and CHI, a mixture of ethane, propane and butane will be formed.
example, if we start with

CH,I+ 2Na +ICH CH,CH + 2Nal

Methyl iodide Ethane
CH CH,I +2Na+ICH,CH, CH,CH,CH, CH, +2Nal
Ethyl iodide Butane

CH,CH,I 2Na+ ICH, CH,CH,CH + 2Nal

Ethyl iodide Propane
5 Wurtz Fittig reaction
Haloalkanes react with haloarenes in the presence
of sodium and anhydrous ether to form alkyl benzenes.
*****************************^

C1
Chlorobenzene
Cl+2Na + ClCH,
*******************************|
OCH, +2NaC1
Toluenee

*****-******--****---o****-**
Br + 2Na +BrCH,CH
******************************
(o-CH,CH, +2NaBr
Bromobenzene Ethyl benzene

55 Wolff-Kishner reduction
The reduction is done by heating the carbonyl compound with a mixture of hydrazine and KOH in the
presence of ethylene glycol. It is called Wolff-Kishner reduction.

CH,CH=0 NH,NH
-H,0 CH,CH = NNH KOH CH,CH + N2

Acetaldehyde Hydrazone Ethane

KOH
CH-C=0-NH,NH2
H,O CH,-C=NNH, >
CH,CH,CH, + Na
Propane
CH CH
Acetone Hydrazone