SANDMEYERS REACTION

When solution of freshly prepared diazonium salt is mixed with cuprous chloride or cuprous bromide,
then diazonium group is replaced by Cl or Br.

Where X = Cl, Br
Diazonium salt is inturn prepared by reaction by aniline with cold aueous mineral acid ! sodium
nitrite at a temperature of " # $
"
C. %his reaction is called Diazotisation.
Kinetics & Mechanism
&andmeyer's reaction is an example for aromatic nucleophilic substitution.
( (
ArN Y ArY N
+
+ +
%his reaction is found to follow the rate law) *ate =
(
k ArN
+
1
]
%he mechanism is analogous to &+,
%he e-idence for the re-ersible slow step was obtained by the following obser-ation made
FINKELSTEIN REACTION
.l/yl iodides are often prepared by the reaction of al/yl chlorides 0 bromides with +a1 in dry acetone.
%his reaction is called 2in/elstein reaction.
R X NaI R I NaX + +
Where X = Cl, Br
+a1 being more co-alent is soluble in acetone, where as +aCl ! +aBr are relati-ely more ionic than
+a1 ! hence get precipitated in acetone. %his facilitates forwarded reaction according to 3e4
Chatelier's principle.
SWARTS REACTION
%he synthesis of al/yl fluorides is best accomplished by heating an al/yl chloride 0 bromide in the
presence of .g2, 5g
(
2
(
, Co2
6
, &b2
6
. %he reaction is termed as &wart's reaction.
6 6
CH Br AgF CH F AgBr + +
&imilarly
( ( ( (
CH CH CH Cl AgF CH CH CH F AgCl + +
.llyl chloride .llyl fluoride
WURTZ FITTIG REACTION
5aloarenes when treated with al/ylhalide in presence of sodium and dry ether form al/yl benzene
%he reaction is said to proceed through free radical mechanism
FITTIG REACTION
5aloarenes when treated with sodium metal in the presence of dry ether produce diaryl compound
%he reaction is said to proceed through free radial mechanism.
ULMANN REACTION
When iodoarene is heated with Cu powder, diaryl compound is formed.
( (
(
sealed tube
Ph I Cu I Ph Ph Ph Cu I

+ + +
%he reaction is also said to proceed through free radical mechanism
FRANKLAND REACTION
When an al/yl halide is heated with 7n powder, higher al/ane is formed
* # 1 8 7n 8 1 # *

* # * 8 7n1
(
Sme E!am"#es
i9
ii9
SYNT$ESIS OF GRIGNARD REAGENT
:rignard reagents can be obtained by the reaction of al/yl halide with ;agnesium metal in dry ether.
<ther sol-ates and thus stabilizes the :rignard reagent
* # X 8 ;g
EtOEt

*;gX
Carbon # magnesium bond is co-alent but highly polar and magnesium # halogen bond is ionic
%he order of ease of formation of :rignard reagents is
* # ;g1 = * # ;gBr = * # ;gCl
* # ;g2 is difficult to prepare from al/yl fluorides, because the latter don't react with ;agnesium
.ll mono halides except allyl and benzyl halides form :rignard reagents
Reasn% %he :rignard reagent of al/yl and benzyl halides readily react among themsel-es
<x) >h # C5
(
# ;gX
(
Ph CH X

>h # C5
(
# C5
(
# >h
:rignard reagents are highly reacti-e and react with any source of proton to hydrocarbon.

it is
necessary to a-oid traces of moisture from a :rignard reagent
* # ;gX 8 5
(
?

*5 8 ;g@?59X
al/ane
Aiscinal dihalides undergo dehalogenation reaction with ;g instead of :rignard reagent formation
,, 6 # dihalides undergo cyclisation to gi-en cyclopropane when reacted with ;g
Cl # C5
(
# C5
(
# C5
(
# Cl 8 ;g

$YDRO&ORATION'O(IDATION
%his procedure in-ol-es addition of B5
6
to the double bond, with hydrogen being attached to one
doubly bonded carbon and boron to the other. %he al/ylborane is then oxidized during which BB' is
replaced by #?5.
C=C +
H B
C
C
H B
5
(
?
(
0 ? 5
4
C
C
H
OH
Mechanism%
Sta)e I%
5ydroboration is regioselecti-e and it is anti4;ar/owni/off's addition.
%he two B45 bonds of al/yl borane undergo similar additions, finally leading to trial/yl borane.
( ) ( )
( (
( ( ( ( ( ( (
( 6
R CH CH R CH CH
R CH CH BH R CH CH BH R CH CH B


Sta)e II%
?xidation of trial/yl boranes
C5
(
# C5
(
# *
C
* # C5
(
# C5
(
# B # C5
(
# C5
(
# * * # C5
(
# C5
(
# ? # B # ? # C5
(
# C5
(
# *
C
%rial/yl borate ? # C5
(
# C5
(
# *
6?5
4
6* # C5
(
# C5
(
# ?5 8
6
6
BO

?-erall result is D&E+ .DD1%1?+F of 5 ! ?5 groups on the double bond, i.e., the reaction is
stereospecific
.l/anes can be prepared by heating trial/yl borane with C5
6
C??5.
( ) ( )
6
( ( ( 6 6
6 6
CH COOH
R CH CH B R CH CH CH COO B

%he ad-antage of 5ydroboration # ?xidation o-er acid # catalysed hydration of al/enes is that there
is no possibility of any rearrangement.
ACID * CATALYSED $YDRATION OF ALKENES
.l/enes react with water in the presence of dil acid as catalyst to form alcohols.
Mechanism
;echanism of the reaction in-ol-es three steps
&tep 1) >rotonation of al/ene to form DCabocationF
&tep 11) +ucleophilic attac/ of water on carbocation
&tep 111)
.ll the steps are re-ersible and step 1 is rate determining
Because carbocation is in-ol-ed the o-erall addition of 5
(
? onto the double bond follows
;ar/owni/off's rule
<x)
(
(
C
6 ( 6 6 6 (
OH
H H O H
CH CH CH CH C H CH CH CH CH

+ + +

C
6 6
OH
CH CH CH

;aGor product
.cids that ha-e wea/ly nucleophilic anion such as dil 5
(
&?
H
are chosen as catalyst
TRY TO ANSWER
Why dil 5Cl is not preferably used as catalyst in the acid catalysed hydration of al/enesI Can 5
6
>?
H
be
used as the catalystI
%he re-erse of this mechanism is dehydration @<1 mechanism9 of alcohol to get al/ene, which ta/es
place at higher temperature.
Because carbocation is formed in the mechanism, there is always a possibility of rearrangement.
d i l 5
(
& ?
H
+
C 5
6
s h i f t
+
H
2
O
OH

*ing expansions also ta/es place@DemGano- rearrangement9 in certain cases.
<xJ
d i l 5
(
& ?
H
+
+
+
H
2
O
'H' shift
OH
OH
major product
H
2
O
DOWS MET$OD
>henol is obtained by reacting chlorobenzene with fused +a?5 at $(6K and 6""atm followed by
acidification with 5Cl. %his is called Dow's method of preparation of phenol.
L(6
6""
K HCl
atm
PhCl fused NaOH PhO Na PhOH
+
+
KOL&ES REACTION+ a#s ca##e, KOL&ES'SC$MIDT REACTION-
When sodium phenoxide is reacted with C?
(
under pressure followed by hydrolysis then o4
hydroxybenzoic acid is formed.
OH
OH
ONa
COOH
salicylic acid
sodium phenoxide
+ a ? 5 @ i 9 C ?
(
, H , " K , L a t m
@ i i 9 5
8
%he reaction is an example for electrophilic aromatic substitution.
>henol is first con-erted to phenoxide because the later is more reacti-e towards electrophilic aromatic
substitution @especially when wea/ electrophiles li/e C?
(
are used9
Mechanism
?rtho substitution occurs maGorly because of stabilization of intermediate formed in step41 due to
chelation of +a
8
ion.
When potassium phenoxide is used p4substituted product is formed in maGor amounts.
*eason) Due to bigger size and low positi-e charge density on metal ion, chelation does not occur
efficiently.
TRY TO ANSWER
,. What happens when phenol is reacted with CCl
H
in presence of K?5I
(. Complete the following reactions)

OH
D
D
@ i 9 + a ? 5
@ i i 9 C ?
(
@ i i i 9 5
8
@ i 9 + a ? 5
@ i i 9 C ?
(
@ i i i 9 D
8
A major!
B major!
RIEMER'TIEMANN REACTION
>henol when refluxed with C5Cl
6
and al/ali yields ortho and para4hydroxybenzaldehyde. %he ortho
product is the predominant one.
OH
+
CHCl
"
+
a# NaOH
6 H " K
OH
OH
CHO
CHO
CHO
CHO
+
+
H
"
O
+
salicylaldehyde
O
$
O
$
%he reaction is electrophilic substitution where dichlorocarbene is the
electrophile.
Mechanism
&tage 1) :eneration of carbene
&tage 11) <lectrophilic aromatic substitution
O
$
+
%CCl
2
O
$
CCl
2
H
&
O
OH
$
O
$
CHCl
2
CHOH!
2
&
H
2
O
O
$
CHO
H
+
OH
CHO
salicylaldehyde
>yrrole on *iemer4%iemann reaction gi-es an abnormal product due to ring expansion along with
normal product.
N
H
C 5 C l
6
K ? 5 N
H
CHO
normal product
N
Cl
a'normal product
%CCl
2
N
H
C
Cl
Cl
&
Cl
$
+
r
i
n
g

e
x
p
a
n
s
i
o
n
1f one of the ortho positions is occupied, the para substituted product is formed predominantly.
<x)

OH
OCH
"
o$hydroxy anisole
C 5 C l
6
+ a ? 5
OH
OCH
"
CHO
(anillin
?ther example,
OH
@ i 9 C 5 C l
6
, K ? 5
@ i i 9 5
6
?
8
OH
CHO
TRY TO ANSWER
,. >redict the structures of the products formed when indole undergoes *iemer4
%iemann reaction.

N
H
indole!
(. Complete the following reactions)
@i9
OH
D
D
D
C 5 C l B r 1
Bmajor!
C B r
(
1
(
A
@ii9
OH
D
D
D
C 5 C l B r 1
t 4 B u ?
4
C
WILLIAMSONS SYNT$ESIS
1n this method, an al/yl halide is allowed to react with sodium al/oxide. .s a
result, ethers are formed. Both symmetrical and unsymmetrical ethers can be
prepared by this method.
M M R X R O Na R O R NaX
+
+ +
Mechansim)
*eaction in-ol-es SN. attac/ of al/oxide ion on al/yl halide.
Better results are obtained when al/yl halide is primary. 1n case of secondary
and tertiary al/yl halides elimination reaction competes with substitution.
Conseuently, when tertiary al/yl halide is ta/en only elimination product is
formed.
C
CH
"
CH
"
CH
"
Br
+
CH
"
C
CH
"
CH
2 +
NaBr
+
CH
"
OH
)eONa
(4methyl propene
@almost exclusi-ely formed9
1n order to prepare phenyl ethers, phenoxide must be reacted with al/yl halide.
%he otherwise is not feasible under normal conditions because phenyl halides
donot undergo nucleophilic substitution reactions.
OH
+
NaOH ONa
*
4
X
O*
+
Na+
%he reaction is more faster if good lea-ing group is present. Conseuently, the order of
reacti-ity of -arious halides towards Williamson's synthesis is
R I R Br R Cl > >
CLEA/AGE OF C * O &OND IN ET$ERS
<-en though ethers ha-e oxygen atom carrying two lone pairs, they are inert towards substitution
reactions because
R O

@strong base9 is not a good lea-ing group. But if the ethers are protonated, then
they become reacti-e towards nucleophile, because now the lea-ing group is an alcohol which is a -ery
wea/ base.
<ther when reacts with cold conc. 51 or 5Br undergoes clea-age to form alcohol and corresponding
al/yl halide.
0 0
R O R HI ROH R I + +
%he mechanism of the abo-e reaction in-ol-es
@i9 2ormation of oxonium ion
0
C
H
R O R
+
_




,
@ii9 +ucleophilic attac/ of
I

on oxonium ion to produce alcohol and al/yl halide.

Whether the nucleophilic substitution is &+, or &+( depends on
@i9 structure of the ether @ii9 reaction conditions
Case'I
1f both the al/yl groups of ether are primary @or9 one al/yl group is primary and the other one is
secondary, then the nucleophilic substitution ta/es the course of &+( mechanism and the nucleophile
attac/s the less sterically hindered al/yl group.
6 ( 6 6 6 (
@ 9 CH O CH CH HI conc CH I CH CH OH + +
;echanism)
&tep41) 2ormation of ?xonium ion
6 ( ( 6 ( 6
C
CH O CH CH HI CH O CH CH I
H
+

+ +
&tep411) +ucleophilic substitution.
I

acts as nucleophile and attac/s the less sterically hindered C5

6
group.
+ote) 1f excess conc 51 is ta/en then the alcohol so formed further undergoes substitution to form
al/yl halide.
6 ( 6 ( (
CH CH OH HI CH CH I H O + +
%hus in such case the net reaction would be
6 ( 6 6 6 ( (
@ 9 CH O CH CH HI conc CH I CH CH I H O
ecess
+ + +
Case'II
When one of the al/yl groups is primary and the other is tertiary the nature of mechanism is
go-erned by sol-ent.
When aprotic sol-ent is used or anhydrous conditions are maintained &+( mechanism is fa-oured.
When protic polar sol-ent is used &+, mechanism is fa-oured.
Case'III
When one of the al/yl groups of ether is secondary and the other is tertiary, then the mechanism
is &+,.
Case'I/
When phenyl al/yl ethers are ta/en then always phenol is formed because the bond between BC'
of phenyl ring and B?' has double bond character due to resonance.
6 6
Ph O CH HI Ph OH CH I + +
&imilarly,
6 6 6 6
@ 9 @ 9 Ph O C CH HI Ph OH C CH I + +
TRY TO ANSWER
,. %he C4? bond in ether is clea-ed by 5105Br and not by 5+?
6
or 5
(
&?
H
though
all of them are strong acids. WhyI
(. Distinguish between ether and an al/ane of comparable molecular weight.
6. Complete the reaction
@i9
( 6
PhCH O CH HI +
H. :i-e the order of reacti-ity of halogen acids with ethers. <xplain your answer.
ROSENMUNDS REDUCTION
.cyl halides when reacted with 5
(
in presence of >alladium supported o-er Ba&?
H
partially poisoned
by uinoline @3indlar's catalyst9 is partially hydrogenated gi-es aldehyde.
<x)
(
H
H
Pd Ba!O
PhCOCl Ph CHO

*osenmund reduction offers a method for con-ersion of a carboxylic acid into the corresponding
aldehyde -ia acid chloride.
5C5? cannot be prepared by this method as 5C?Cl is unstable at room temperature.
TRY TO ANSWER
,9 Complete the reaction
(
H
6 (
H
Pd Ba!O
CH C C CH COCl


(9 Can acyl halide be con-erted to /etonesI 1f so howI
69 >redict the product formed when acyl halides reacts with * # ;g 4 X
STE0$ENS REACTION
+itriles when reacted with stannous chloride in presence of 5Cl gi-e imine which on hydrolysis gi-es
corresponding aldehyde. %his is called &tephen's reduction.
6
(
H O
R CN !nCl HCl RCH NH RCHO
+
+ +
.lternati-ely, nitriles are selecti-ely reduced by diisobutyl aluminium hydride @D1B.3 # 59 to
imines followed by hydrolysis to gi-e aldehydes
( )
(
(
@,9
@(9
AlH " Bu
H O
R CN R CHO

&imilarly esters are also reduced to aldehydes with D1B.3 # 5
(
@ 9
( $
@ 9
" #IBA$ H
"" H O
R COOC H R CHO

E(AM0LES
Double bond is not reduced
(
(
6 ( ( 6 ( (
@,9 @ 9
@(9
AlH " Bu
H O
CH CH CH CH CH CN CH CH CH CH CH CHO

TRY TO ANSWER
,9 5ow can you prepare /etones from nitrilesI
(9 5ow can you prepare propiophenone from propane nitrileI
69 Can &n 8 5Cl be used instead of &nCl
(
8 5Cl for the reduction of nitriles to aldehydesI <xplain your
answer.
ETARD REACTION
?xidation of %oluene with chromyl chloride in C&
(
as sol-ent followed by hydrolysis gi-es
benzaldehyde. %his is a controlled oxidation method. %his is called <tard reaction.
%he abo-e con-ersion can also be carried out by oxidation of %oluene with chromic oxide in acetic
anhydride followed by hydrolysis
GATTERMANN * KOC$ REACTION
When benzene or its deri-ati-e is treated with carbonmonoxide and hydrogen chloride in the presence of
anhydrous aluminium chloride or cuprous chloride, it gi-es benzaldehyde or substituted benzaldehyde.
Mechanism
Ste" * I % :eneration of <lectrophile
6 H
. CuCl CO HCl AlCl C HO CuCl AlCl
+

+ + + +
Ste" * II % <lectrophilic substitution on benzene ring
GATTERMANN REACTION
When benzene is reacted with 5C+ in presence of 5Cl ! .lCl
6
, aldimine is formed which on
further hydrolysis gi-es benzaldehyde
Mechanism
&tep # 1 ) :eneration of <lectrophile
6 H
HCN HCl AlCl C H NH AlCl

+ + +


&tep # 11 ) <lectrophilic substitution on benzene ring.
&tep # 111 ) 5ydrolysis of benzaldimine
Both :atlermann # Koch and :attermann reactions are electrophilic aromatic substitution reactions.
CLEMENSONS REDUCTION
%he reduction of carbonyl functional group of aldehyde and /etones to methylene group with
amalgamated zinc and conc 5Cl is /nown as Clemenson's reduction.
C=O
*'
* 7 n
4
5 g , 5 C l
r e f l u x
*'
*
CH
2
&imultaneous dehydration of alcohol may ta/e place
<x)

OH
O
@ i 9 7 n
4
5 g
@ i i 9 5 C l
,4unsaturated /etones undergo reduction of both the olefinic and carbonyl groups.
<x)

O
@ i 9 7 n
4
5 g
@ i i 9 5 C l
and 4/eto acids are not reduced, but other /eto acids are reduced.
WOLFF'KIS$NER REDUCTION
1n this method, carbonyl group of an aldehyde or /etone are con-erted to methylene group by
reacting with hydrazine followed by heating with sodium or potassium hydroxide in high boiling
sol-ent such as ethylene glycol.
C=O
*'
*
+ 5
(
+ 5
(
4 5
(
?
*'
*
C=NNH
2
hydra,one
K ? 5 0 e t h y l e n e g l y c o l

*'
*
CH
2
+ N
2
%his method is not suitable for ,4unsaturated carbonyl compounds.
&imultaneous dehydrohalogenation may ta/e place because a strong base is used

CHO
Br
@ i 9 +
(
5
H
@ i i 9 K ? 5 0 g l y c o l ,
NOTE%
Both Clemenson's and Wolff4Kishner reduction do not reduce double bonds@except in case of ,4
unsaturated carbonyl compounds9.
TRY TO ANSWER
1 2ind out .,B,C,D and < in the following scheme of reactions.

O
-!.n/H0
2!DCl
-!N
2
H
1
2!OD
$
-!NH
2
ND
2
2!OD
$
-!ND
2
ND
2
2!OD
$
-!ND
2
ND
2
2!OH
$
A
B
C D
2
TOLLENS TEST
When aldehyde is heated with %ollen's reagent, a white sil-ery ppt is formed. %herefore this test is
also called &il-er ;irror %est.
1n this test aldehyde is oxidized to carboxylate ion by %ollen's reagent. &il-er of %ollen's reagent
gets reduced and precipitated as &il-er metal.
%ollen's reagent is the ammoniacal solution of sil-er nitrate, where sil-er ions exists as
6 (
N @ 9 O Ag NH
+
complex.
%he o-erall reaction can be depicted as below)

6 ( 6 (
(N @ 9 O 6 ( H ( R CHO Ag NH OH RCOO Ag NH H O
+
+ + + + +
FE$LINGS TEST
When aldehyde is heated with 2ehling's reagent, a red ppt is formed.
2ehling's reagent is a solution of 2ehling's reagent B.' and 2ehling's reagent BB' mixed in eual
amounts.
2ehling's reagent B.' contains aueous solution of Cu&?
H
while reagent BB' contains al/aline
solution of *ochelle salt@sodium potassium salt of tartarate9.
2unction of *ochelle salt)
Cu
8(
ions get precipitated in al/aline medium as Cu@?59
(
.
%herefore to /eep Cu
8(
ions in solution it is complexed with tartarate ion forming a soluble
NCu@tartarate9
(
O
4(
complex.
%he o-erall reaction in-ol-ed is

(
( (
( $ @ 9 6 R CHO Cu OH RCOO Cu O redbro%n &&t H O
+
+ + + +
Im"2tant "ints 2e)a2,in) Feh#in)s an, T##enss 2ea)ent%
@i9 Both the %ollen's and 2ehling's reagent cannot oxidize /etones. %herefore /etones do not gi-e
these tests.
@ii9 Both the reagents cannot oxidize olefinic bonds if present in the aldehyde.
@iii9 .romatic aldehydes are not oxidized by 2ehling's solution whereas they are oxidized by
%ollen's reagent.
<x) Benzaldehyde gi-es white ppt when heated with %ollens's reagent and gets oxidized to benzoate
ion, whereas it does not gi-e ppt with 2ehling's reagent.
@i-9 %ollen's test is also gi-en by 4hydroxy /etones.

O
OH
% o l l e n s M s r e a g e n t
O
O
+
Ag
@-9 %ollen's test is also gi-en by al/yl and acyl hydroxylamines.
<x)
NHOH
% o l l e n M s r e a g e n t
N=O
+
Ag
@-i9 2ormic acid gi-es positi-e test with both 2ehling's and %ollen's reagent and
itself is oxidized to C?
(
. Whereas other carboxylic acids do not gi-e these tests.
PPPPPPPP