1

HYDROXYLATION
CH3 CH = CH2
Cold
,dil , alkaline

CH3 CH CH2

KMnO4

1. O O

5 4

(syn)

OH OH

2. NaHSO3
1. peracid

OH

2. H / H 2O

CH3 CH CH2

(anti)

OH
(i)

Case of KMnO4 :

Electrophilic addition

MnO4 is electrophile.

No rearrangement.

CH2

O+

O
Mn
O

CH2 O

O
CH2 O MH

(ii)

Case of O5O4.

O
CH2 O OH / H2O
4

CH2
CH2

CH2OH + Mn O2

CH2OH

O3
O

O
O5

(iii)

NaHSO3

CH2 OH
CH2 OH

Epoxidation:
CH3CO3H

Peracitic acid

PhCO3H

Perbemoic acid

CH3 C

OH

(peraciticacid)

O
CH3 C = O

O H

electrophile.

+ O5O2

**

CH2 = CH2
peracid

Mech:

CH2 CH2

CH2 = CH2
CO2H

CH2 = CH2
COOH
H

Cl
O

Cl

Eposide opening:

If can be either acid or base catalyse

Note that products may be different

O
C
CH3

HO
CH2 CH2 + O = C CH3
O

in both catalysis.
CH3

Na+/CH3OH

CH3 CH CH2
O
OCH3

OH

CH3 CH CH2

CH3 CH CH2

OH

OCH3
CH3 CH CH2
CH3 OH

CH3 CH CH2

O+

OCH3

H
Other

CH3 CH CH2

O CH3

OH

CH3 CH CH2

OCH3

CH3 CH CH2
OH
Hot KMnO4

Cold KMnO4
OH

OH

OH

OH

OH

i, e
OH

OH

OH

OH

**

Case of hot KMnO4 : - If high tempn KMnO4 oxidatively cleaves. {C = C bond}.

C = CH2 CO2

R CH = CH R

H
C=C

RCOOH

[0] hot alk. KMnO4.

2 ROOH.

C=CR
R

C=O
R

C = C = C CO2
R
C = CH CH = CH R
KMnO4 / OH,

R
R

C = O + HOOC COOH + RCOOH.

R
Q.

A hydrocarbon
oxidative cleavage
O

Ans.
Q.

+ CH3 COOH

CHCH3

A hydrocarbon (6c)
oxidative cleavage
COOH
2 CH2
COOH

Ans.
Explanation: -

COOH

HOOC

CH2

CH2
COOH

CH = CH

HOOH

4
CH2

CH2

CH = OH
: Ozonalysis :
CH2 = CH2 1 .O3 / ZnH 2O 2CH2O
CH2 = CH2

CH2 CH2

CH2

CH2

O CH2

CH2

Ozonide
Explosive

CH2 O

[Mo/zonide not stable]

O Zn / H2O 2H2O.

O CH2

Ozonolysis also oxidatively cleaves C = C the product depends upon the constituents of C
= C as well as reaction condition.
Ozonolysis
Reductive

Oxidative

Zn / H2O

O2

HiAlH4(strong)

H2O2,

NaBH4

Ni/H2

Zn/H2O

HiAlH4

H2O2

C = CH2

CH2O

CH3OH

RCOOH

CH = CH R

RCHO

R CH2OH

R COOH

R
C=C

C=O
R

CH OH

C=O

C=C=C

CO2

CO2

CO2.

Q.

CH3 CH = CH CH3

1. O3
2. LiAlH4

2CH3 OH2OH

1. O3
2. Zn/H2O

1. O3
2. H2O2

2CH3CHO

CH3COOH.
CHO

5
Q.

2 CH2 + CHO

Ozanolysis

**

(A)

(B)

CH3

(C)

CH3

CH3

Ozonolysis

CHO

CH3
Ozonolysis

CH3

CH3

CH3

CH3

CH3

CHO

2CHO + CH3 C CH3

CH = CH2

Q.

: Allytic halogenation :

Ozonolysis

PhCHO + CH2O

O
N Br

NBS
CCl
4

N.B.S
O

(a)

2CHO + 2CH3 C CH3

CH2 = CH CH3
Allylic

CH3
Ozonolysis

CH3 CH = CH CH2 CH3

N.B.S
CH3 CH = CH CH CH3 (Major)
Br

Case. CH2 CH = CH = CH2 CH3 (L.S)

CH3 CH = CH CH CH3 (M.S)
so attack here.

ALKYNES
1.

By hydrohalogenation: CH3 CH CH NaNH 2 CH3 C CH

Br

Br

Mech:-

CH3 CH CH2
Br

Br
Base

Can be isolated because HBr elimination is difficult since C Br bond is stronger due to
resonance.
CH3 CH = CH Base CH3 C CH

Br
eg.

difficult.

Br
CH3 C CH2 CH3
NaNH

Br

CH C CH2 CH3

Horeacidic H.
2.

From alkynides:
R C CH
Ag ( NH ) NO

R C C Ag

Cu ( CH ) NO

R C CCu

Amuconical silver nitrate.

3 2 3

(Tollenlseagent

3 2 3

NaNH 2

R C C Na

Silver and copper alkynides being nonpolar are insoluble in H 2O therefore it is used to
distinguish terminal and internal alkynes.
*

Some inorganic compds of importance.

Li LiI
CsI polar

CB

1
Li
cov alentiation

Ionic bond Always polar Li I I polarized towards Li+ therefore Li

as well on I decreases.
Size of atom 1/ polarizing
CH3 H

decreases

7
sp3
Nodal plane.
(a)

CH3 CH2 C CH
Ag

(Mean & tollens regent)

CH3 CH2 C C Ag colourless

(b)

CH3 C C CH3 + Ag

(c)

RCC

(NO ppt (Internalalkyne)

Na + CH3 CH2 CH2 I

SN2

Strong Nu

(1o) = SN2

R C C CH2 CH2 CH3

C is a very strong Nu.

SN1 SN2
(d)

RCC

Na

+ CH3
2o

CH I
SN2

CH3

CH3
R C C CH
CH3
(e)

CH3
RCC

Na + CH3 C I

E2

CH3

3o.

CH3
R C CH +

C = CH2.
CH3

: Properties :
(1)

Isomerisotion:
CH3 C C CH3

Base

CH3 OH2 C CH

If base is alc. kon internal alkyne.

If base is NaNH2 in non polar solvent then terminalakyne is preffered even though it is
less stable than internal alkyne.

Cause:- NaNH2 form ppt of Na alkynide from terminal alkayne and thereby disturb the equlm.
CH3 C C CH3

8
base
CH3 C C CH3

CH3 CH2 C H
NaNH2

Base.
CH3 C C = CH2

CH3 CH2 C C

Na

CH3 C = C = CH2

H 2O

CH3 CH = C = CH2
Base

CH3 CH C CH

CH3 CH = C = CH

H2O
2.

Addition of HX.
Ch3 C CH HCl CH3 C = CH2

Imp: Orientation
1st addition is equivalent to

Cl vinylic chloride.

orientation of 2nd addition

HCl
CH3 C CH3

CH2 = CH Cl

I.

II

CH2 = CH OCH3

+M

III

CH2 = CH2

Cl

Reactivity towards E II > III > I.

CH3 C CH
(fast)

HCl
CH3 C = CH2

can be isolated.

Cl
(slow)

HCl
Cl
CH2 C CH3
Cl.

3.

Addition of X2
Br
Br

CH3 C CH fast2 CH3 C = CH

Br2 (slow)
Br
CH3 C CH

Br

9
Br
(4)

Br

Addition of HOX
CH3 C CH
HO Cl
OH

OH

Cl

CH3 C CH HOCl CH3 C CH

Cl

OH

HOCl OH + Cl

Cl

H2O
O

Cl

CH3 C CH
Cl
Imp:
(5)

Addition of H2O
R C CH

HgSO / H SO

4 2 4 R C CH3.
( H O)
2

Mech: R C CH
Hg2+
Hg

R C = CH

R C CH3

H2O

OH2

R C = CH

OH

Hg
H

R C = CH2

OH
R C = CH

Hg

OH
H

R C CH2

R C CH2

Hg

Hg
O
Hg

(a)

Ph C CH di / H 2SO
Ph C CH3
4

(b)

CH3 C C CH2 CH3

10
Hg2+ / di/H2SO4
O

CH3 C CH2 CH2 CH3 + CH3 CH2 C CH2 OH3.

(6)

KMnO4 oxidation

CH3 C C CH3 AlK .KHnO

4 CH3 C C CH3

Can be isolated.

2 CH3 COOH
C CH CO2 ,
C C R RCOOH , C HCOOH
COOH
COOH

HC CH [o]
(7)

Ozonolysis:

R C C R O3
RCOOH
(a)

RC

Zn / H O

CR
O

Ozohido.

CH3 C C CH2 CH = CH CH3

Ozonolysis
COOH
CH3 COOH + CH2

+ CH3 CHO
CHO

CH C CH3
CCl4. N.B.S

CH = C CH2 Properly / grp.

CH C CH2
Br.
(b)

CH3 C CH
BH3
CH3 CH = CH BH2
H2O2 / OH
CH3 CH2 CHO CH3 CH = CH OH
B

(c)

CH3 CH = CH BH2 BH 3 CH3 CH2 CH

H2O/OH

11
OH
CH3CH2 CHO H 2O CH3 CH2 CH
OH
Note: - When enol comes in the product charge it ino keto form. But during mechanism charge
keto to enol for clear reacn eight.

HALOGEN DERIVATIVES
R OH
HCl

R Cl + H2O

PCl3

R Cl + H3PO3

PCl5

R Cl + POCl3

Case of HX.
1o alc follow SN2 while 2o and 3o alcohols

R OH
H+

follow SN1.

R OH2
SN1

(1) CH3 CH2 CH2 OH

HCl.

SN2
R

RCl + H2O

CH3 CH2 CH2 Cl

Cl

(2) CH3 CH CH CH3

R Cl + H2O

CH3 OH
HCl
CH3 C CH2 CH3
CH3

(Major )

+ CH3 CH CH CH3
CH3 Cl
Reactivity of HX.
H I > HBr > HCl > HF. Because H I is the strongest acid I is the best Nu . Among HX,
HCl is less reactive, therefore lucas reagent this is (ZnCl2 . HCl) is often taken.
R OH

[HOZnCl2]

H2O + 2HCl2

HCl ZnCl2
RO

ZnCl2 R Cl + [HOZnCl2]

--------------------------------Reactivity of alcohols 3o R OH > 2o R OH > 1o R OH.

3o, 2o and 1o alc. can be distinguish by lucas reagent.
CH3 OH > CH3 CH2 OH

12
Reactivity order

(Here more sterichindr.)

3o R OH

2o R OH

1o R OH

Cone HCl

HCl

HCl

ZnCl2

ZnCl2

ZnCl2

Turbidity just app(atance) Turbidity in 5min.

No Turbidity

H I is also a R.A BO H I often avoided. Iodides are best prepared through halogen
exchange reacn also known as finkghtein reacn.
R OH + H I RI HI RH + I2
R I + KCl
R Cl + K I Acetone

is a good Nu

and acetone fovours SN2.

R Cl R I

Note: that in acetone K I is soluble but other KCl, KB are insoluble. That is why acetone is used
since KCl/KBr precipitates and reversible reacn doesnt occur.
Imp
Q.

An optically active solution of 2 iodo butane is treated with K I in acetone after some
time solution becomes optically inactive

Soln

CH3

Acetone

I
C2H5

C2H5

KI

I +KI
H3

II

(I)

Conc. of K I doesnt change

(II)

Initially only I is present therefore soln is active as reacn proceeds conc. of II increases. As
II forms backward reaction begins.

(III)

After some time Kf = Ko. therefore solution contains a remain mixture after some time
solution becomes inactive.

: Case of PX3 :

R OH +

PX
X

ROP

R X + HO P

X
o

It is SN2. only 1 and 2 alcohols reactions.

: Case of PX5 :
R

H
P

X
X

X
X

HX + POX3.

13

ROP

RX + H O R

X
X

X
X

SN2 only 1o and 2o alcohols react.

OH

Q.

CH3 CH CH CH3

CH3

PCl5 / or PCl3

CH3 CH CH CH3
CH3
Imp.

Cl

Case of SOCl2 :
Cl

OH

+ S=O

RCl + SO2

Cl

SN2 SNi
O

R O S Cl R O S = O

Front side attack occurs this path is called SNi which leads to retension of confugration.

If pyridine is used SN2 occurs.

Cause:

R O S Cl

R O S Cl

N
Cl
O

R Cl + SO2 +
Imp.

S 2

ROSN

CH3
H

OH
C2H5

PCl5

SOCl2
SOCl2

14
CH3

CH3

Cl

OH

Cl

CH3
H

C2H5

C2H5

: Properties :
RCl
Ag NaOH

ROH

Most Ag2O

ROH

Dry Ag2O

ROR

NaO Et

R O Et

NaCN

RCN

AgCN

RNC
COOEt

COOEt

CH2

R CH
COOEt

COOEt

Base

Case of alcoxides (EtO)

(Williamsons synthesis of ethers)
R Br S N 2 R Oet.

EtO

O C2H5

+ C2H5I
ONa

SN1
SN2

+ C2H5O Na

(Here unsaturation is available)

I
SN1

O CH3

SN2

I + CH3ONa.

O Na + CH3 I

Cause: unsaturation is available here also.

**
Ag O

+(CH3)3N.

N
CH3 CH3

CH3

Case of diethyl malonate : COOEt

COOH

Cl
C2H5.

15
CH2

hydrolysis

CH2

COOEt

CH3COOH

COOH

base

Mech:

[?]

COOEt
CH

R CH2COOH
COOEt

RI

COOEt

COOH
HO

R CH

R CH

COOEt

COOH

Starting from DEM anumber of acids of the type R CH2 COOH

R

R
CH COOH

CH COOH

Can be prepared.
Q.

O
CH3 C CH2 COOEt
O
conversion

CH3 C CH2 CH2 Ph.

O
CH3 C CH2 COOEt
Basic ethylaeetoaectate.
O

C CH3 PhCH 2I CH3 C CH COOEt

CH
C OEt

CH2 Ph
Hydrolysis

O
O

CH3 C CH2 CH2 Ph CH3 C CH COOH

CH2 Ph
Starting from EAA a number of ketones of the type
O

16
R CH2 C CH3
R

O
CH C CH3

R
R

O
CH C CH3 can be prepared

CN Ambident Nu

[AgCN / NaCN]
NaCN Nu

C more active

CN {Ionic compd}

R Br + CN RCN.
AgCN (covalent)
It doesnt dissociates, so attack occurs through N. giving R NC.
O

CH3 C CH2 CH2 C CH3

CH3 C CH2 COOEt Conversion

Base.

another method

CH3 C CH COOEt

CH3 C CH2 COOEt

II

Base

CH3 C CH C Oet

C CH3

I
O

CH
O

CH2 C OEt

CH3 C CH C OEt
O

Cl CH2 COCH3

CH3 C CH C OEt

CH3 C CH C OEt

CH3 C CH C OEt
O

CH2 C CH3

H3O
O

H3O
O

CH3 C CH2 CH2 C CH3

CH3 C CH C OH
CH2 C CH3

CH3 C CH2 CH2 C CH3.

17

Haloform reacn : O
I

2 CH3 COO Na + CH I3.

CH3 C CH3 NaOH

NaOH (r. d. s)

CH3 C C I3

CH3 C CH2 CH3 C = CH2

[r.d.s]

OH

OH (hydrolysis)

II

O
CH3 C C I3

I2

CH3 C OH + C I3

CH C CH2

CH3 C C

Base

Base

O
I

CH3 C CH I

CH3 C CH
I

Halofrom reacn involves three enolisation and three halogenation and finally hydrolysis.
Each enolisation is followed by one halogenation. First enoligation is r.d.s because it
involves least acidic hydrogen (H)
O
r .I

2 CH I3
CH3 C CH3 KOH

O
r . Br

2 2
CH3 C CH3 KOH
CH Br3

O
r Cl

3 2
CH3 C CH3 KOH
CHCl3

r1 = r 2 = r 3

Which of the following give haloform reacn.

O

(I)

NaOH
CH3 CHO I2 H C ONa + CH I3

18
O
(II)

NaOH
CH3 CH2 C CH3 I2 CH I3 + CH3 CH2 - COONa

(III)

NaOH
CH3 CH2 CHO I2 CH3 CH CHO

O
(IV)

CH3 CH2 C CH2 CH3

NaOH I2
O
CH3 CH C CH2 CH3
I
O

(V)

CH3 C CH2 C CH3

(M. Acidic)
O

CH3 C CH C CH3
I
O

(VI)

NaOH
Ph C CH3 I2 Ph C C Na + CH I3.

1o CH3 CH2 OH

2o OH

[o] NaO I

CH3 CH CH3

CH3 CHO

CH3 C CH3
Br2 / NaOH

CH I3 + HCOONa

CH Br3 + CH3COONa
Q.

A comd molecular formula

C8 H10 C

Ans.

Ph CH CH3
H (only)
O
Ph C CH3 (V. F 5)
O
Ph C CH3 X

(V. F = 4)

I2 / NaOH
PhCOONa + CH I3

19
(a)

(b)

OH

Ph C CH3

Ph CH CH3

H2O Ca(OCl)Cl

H2O Ca(OCl)Cl

CHCl3 + (PhCOO)2CaPh(COO)2Ca + CHCl3

Mech:

H2O

or,

Ca(OCl)Cl + H2O

Ca OCl
Cl

Ca(OH)2 + Cl2

Ca OCl
OH2

Ca O Ca OH
OH2

OH

CHCl3
O

COCl2 EtO 4 EtO C OEt

O
CH3 C CH3

diethyl carbonate.
CH3

Base

OH
C

CH3
O

CCl3
O

Ph C CH3
PCl5

CH3 C H
PCl3

Cl

CH3 CH Cl2

Ph C CH3
Cl
Imp.

+ Cl2

O
CH3 C CH2Cl
Cl2 / K2CO3
O
CH3 C OK + CHCl3

20

ALCOHOL
: Preparation :
(1)

By hydrolysis of ester
O

CH3 C OET

HO

CH3 C OH + EtOH.

NaOH
H2O
O
CH3 C ONa + EtOH.
i.e ester can be hydrolysed either through acid catalysis or through base catalysis.
Mech:
O
CH3 C OEt
r.d.s

H3O
OH

CH3 C OEt

H2

OH H
CH3 C OEt
H2O
O
CH3 C + EtOH + H

This reacn exist in equiln so if

H2O is excess then acid is formed
and alcohol is access then ester is
formed. But base catalysed
hydrolysis of ester is not
reversible. Hence hydrolysis of
ester can be both acid and base
catahesed but esterification of
can be only acid catahesed of
base a catahesed

21
OH
O
CH3 C OEt
but

OH

r.d.s

CH3 C O Et

H2O18

CH3 C OEt

OH

CH3 C O18 H + EtOH

since acyl O bond

is generally cleaved retension

CH3 C OH + EtO

of confugration occurs on both side.

CH3 C O + EtOH.
CH3

CH3
O

Ph

CH3
C2H5

H O

CH3
COOH + OH

Ph

Et
H

In some cases: - Alkyl O bond is cleaved.

CH3
C2H5

O
C

Ph

CH3
O
H

CH3
H

C2H5

OH2

CH3
COOH + H

Ph

OH
D

However it of is not formed by the Inestion then acyl o bond cleavage should be
bone.
CF3 COOEt, CH3COOEt, (CH3)2COOEt, (CH3)3 C COOEt
I.

II.

III.

IV.

Ease of hydrolysis: I > II > III > IV

[Here see the position character of carbonylic carbone]
(2)

From amines:
R NH2

a.q.NaNO2
HCl
R N2Cl
H2O{0oC}
ROH

Diazotisation, this can not be escalated alkyl diagonium

chloride. Became N2 is an excellent leaving group.

22
[Generation of NO ] NaNO2 + HCl HNO2.
HCl
H O N = O i. eH H2O NO H2O + NO

Mech:

N H2

R NH N = O

NO

R OH
Cl

H2O:

RNN
R

N = N OH2

N N O
H

Tautomerise.

= N OH

R
AqNaNO

2 R2N NO (N nitrosoamine An yellow oil)

NH HCl

R
AqNaNO

2 ROH + N2
R NH2 HCl

R3N

"

R3N HCl

(salt)

{clear solution no evolution of gas}

AqNaNO

2
Ph NH2 HCl 0o C Ph N2 Cl
o

0 C

H 2O

can be isolated

H2O..SN1
Ph OH + N2

Coupling reaction: -

Ph N2 Cl

PhN2 Cl
(a)
(c)

OH
CH3

(b)
(d)

NH2

KI

Ph I

CuSCN

Ph SCN

KNCO

Ph NCO

NO2

O
RCOOAg

R C O Ph

H3PO2

PhH

HBF4

PhF

23
Case: PHN2 is
A weak E therefore it couples only with strongly activated Ph grp.
OH

OH
NN

OH

NN

Coupling with phenol occurs in basic medium.

Causes: - In basic medium phenoxide ion is generated which is more reactive towards E than
phenol itself
O

OH
base

However it should be only mildly basic.

Cause: - In strongly basic condition diagotate ion is formed which doesnt couple.
Ph N = N

OH

Ph N = N OH

Digotate ion.

Ph N = N O
N NCl

NH2

Coupling reaction occurs in mild acidic condition

cause: acidic condition avoids N N coupling.

General rule
NH - G

NH2

N=N
(something missed)

NH2

However medium should be strongly acidic

Cause: NH2

gets protonated and becomes deactivated towards E

NH3

NH2
H (excess)

Generally P coupling occurs. It P position is blocked then O coupling occurs.

Multiple coupling is also possible.
OH

OH
PhN2 Cl

N = N Ph

24
OH

CH3
OH

CH3
OH

PhN2 Cl
N = N Ph

NH2

NH2
OH
PhN2 Cl

N = N Ph

OH

NH2

: By reduction of alds, and ketones :

R CHO

R
C=O
R

NaBH4

R CH2 OH

LiAlH4

R
CH OH
R

B2H6

R CH2 OH

H2O
Na AlC

Zn/CH3COOH

CH OH
R

Zn/NaOH
Imp:

NaBH4,

weak RA while

LiAlH4,

consequently

BH4

redness only

AlH4

While LAH
(1)

H + BH3

many

R CHO

NaBH

R2CO

NaBH

NaBH4
four groups
reduces

H + AlH3
R- CH2 OH
R

(2)

strong R.A.

CH OH

groups.

25
O

R
NaBH

R CH2 OH

NaBH

RH

RCH2OH

LAH

R CH OH

(3)

R C Cl

(4)

R Cl
R CHO

LAH

R
C=O
R

R CO Cl

R CH2 OH

RX

LAH

RH

R NO2

LAH

R NH2

R COOH

LAH

R CH2 OH

LAH

R CO NH2 LAH

R CH2 NH2

O
R C OH1

LAH

R CH2 OH + R1 OH
O

NaBH4

NaBH4
COOCH3

OH

COOCH3

OH

CH2 OH

Property : Oxidation : - Gen. O.A KMnO4 ; K2Cr2O7

R CH2 OH

HNO3 with there oxidizing

[o]

agent stopping oxdn at

R CHO
[o]

aldchylic stage is difficult

RCOOH

because their oxidizing agent

Work on H2O in which aldchydes kept in a form of hydrates which oxidn is easy
O
RCH

OH
HO

R CH
OH

26
However some amount of aldchyde can be obtained, if reacn is fractionally distilled
during the reacn.
Imp:

Cause BP of ald is lower than corresponding alcohol and acid.

R CH2 OH
0oC

PCC (Pyridinium chloro chromate)

PCC
CrO3Cl

CH2Cl2
R CHO

Cause of 2o alcohol

OH
3C

CH3 CH CH3

+ CrO3 + HCl.

[o]

O
3C

CH3 C CH3

[o]

CH3 COOH (2C)

So, oxdn of ketones is difficult, hence oxdn of 2o also can be stopped

At ketonic stage even when K2Cr2O7 / H+OR
KMnO4 / OH is used.
O
CH3 C CH3
OH
CH3 C = CH2
OH

KMnO4
O

CH3 C OH + CO2
Case of 3o alc : CH3

CH3
KMnO

CH3 C OH H 4
CH3
KMnO4/OH

C=O
CH3

mech:

CH3
CH3 C OH
CH3

CH3

CH3

OH2
H

CH3 C CH2
CH3 H

27
CH = CH2 + H2O

C = O + CO2

K2Cr2O7/H+

CH3

CH3

3o alcohols are oxidized through dehydration in acid catalysed so, 3o alc are highly reluctant to be
oxidised in neutral basic medium.
OH
PCC mild oxdn

vigorous oxdn. (KMnO4 Cag)

O

COOH
COOH

[o]

OH

Hydrates:
Nu addition of H2O on aldehydes and ketones gives hydrates. It can be both acids or base
catalysed.
R CH = O
H+/H2O

OH

OH

H2O

R CH
OH

OH
R CH

Mechanism
OH

R CH = O

R CH = O

H+

OH

R CH OH

R CH O

H2O

OH

HOH

OH

OH

R CH

R CH
OH2

OH + OH

OH
R CH
OH

Base or acid both catalyse nucleophilic add-product are generally not stable but it survive
in the water.
R

OH
C

OH
C

CCl3

OH
C

28
R

OH

Stability : - III > II > I

OH

So stable that survive even without water

OH

sp3

OH
>

OH

OH

OH

---------------------------------------------------In

OH
OH

Angle strain = 49/2

Angle strain

sp2

60/2 = 30o.

: Hemiacetals/ Hemiketals :
R

R
C=O

C=O

CH3OH / H

CH3O
CH3OH

R
C = OH

C=O

CH3O

CH3

OH

O
C

OH

HO CH3

OCH3

OH

CH3
R

OH
C

C
OCH3

OCH3

: Hemiketas :
Acctals / Ketals
R

OH
CH OH

C
H

OCH3

OH2

OCH3

29
R
C = OCH3
R

CH3

OCH3
C

O
H

OH
C

CH3

OCH3

H
R

O CH3 / CH3OH

OCH3

O
C

OCH3

Acetal

OCH3

R
C = O + CH3O
H

Imp:

R
CH3OH

H
R

OH

H
OCH3

OCH3

C
H

H2O
C=O

OCH3

Note: (a) It is clear from the mechanism that acetals and ketals are formed only by acid
catalysed from hemiacetal to acetal is Nu substitution. Therefore to make OH group is a
good leaving group H+ catalysis is required.
(b) If we take a lot of alcohol then acetal / ketals one obtained otherwise if we take a it a
water then aldsehydes are formed.
R

OH CH2
C=O

+
OH CH2

SH CH2

cyclic ketal

SH CH2

O
C

R
C=O

cyclic this ketals.

30

: Decomposition :
(1)

OH

(2)

OH

OH

OH
OH

H
R

OH2

OH

OH

R
C=O

C=O

R
(3)

OH
C

H / H2O

OCH3

H / CH3OH

C=O
R

OCH3
C

OCH3

Acetal / Ketal.
R

OCH3
OH / H O

C
R

OCH3

H / H2O
R
C
R

OCH3
H

H2 O
R

OH2

Ketals / acetal are stable in

basic medium since its both
formations decomposition are
only
acid
catalysed
consequently acetals and ketals
are used as protecting groups of
aldehydes / ketones for reaction
in basic medium..

31
C
R

OCH3
H

OH

R
C
R

OCH3H

C = OH

R
Q.

convert

Br

COOH

R
C=O
R
R Mg Br

Hg ether

O=C=O

Br

O
RC

HgBr

H2O

Cho3/T2O
HgBr

32

Aldehydes and ketones

(1)

(a) By the pyrolysis of acid salt :

O
R C OCl

O
Ca (OH )2

(R C O)2 Ca R C R

(H C O)2 Ca H C H
O

R C O Ca2+ O C R R C R + CaCO32
(b) Cross pyrolysis :
O
(R COO)2 (HCOO)2 Ca R C R
O
HCH
O
(cross product will be major)
O

R C H (Maj)

33
R C O Ca++ O C R
O

chance of formation of cross product-twice

hence will be major

H C O Ca++ O C H
Reduction of acid and acid derive :

(2)

R CH2OH

BY reduction of acid

[O]

[H]

RCHO
[H]
not easy

R C H cannot be prepared. This is because

[O]

reduction of acid requires vigsons condition

R COOH

under which -------

can not survived.

O

R C OH

R C H > R C OH > R C O
ease of reduction

LiAlH4

O
R C O Li
H
Q.

Aldehydes can be prepared from

(a) acid

But:

(b) Acid halide

(c) Ester

(d) Ketone

(Lithium triter butoxide almunium hydride)

O

R C OH PCl 5 R C Cl Li (tB 4O )3 AlH

R C H
O
(only redness)
O
RC
OH

NaBH4

[R C Cl , R X, R C H

LiAlH4

R CH2OCl

(1) B2H6

R CH2OH

(2) H3O
(1) NaBH4,BF3

R CH2OH

(2) H3O

NaBH4 + BF3

B2H6

O
RCR]

34

1. B2H6

CH3CH2OH

2. H2O2/OH
CH2 = CH2
1. NaBH4/BF3

CH3CH2OH

2. H2O2/NH
(3)

(a)

R CN

1.CH3HgBr

2.H O
3

O
RC
CH3
N MgBr
Mech: -

RCN

RC

CH3 MgBr

CH3
H+

NH

1.CH MgBr

3
(b) R NC 2 .H ( H O) CH3 C + R NH2.

RC

CH3

1.PhLi
(c) R CN 2.H R C Ph

O
1.PhLi
(d) R NC 2.H Ph C

H2O:

+ RNH2.

R C = NH2

CH3

H.W (write mechanism)

NH2
C

CH3

OH

*** NH2 removed since H2O.

If NH3 taken OH removes

35
C = OH
H

CH3
O

R C CH3
[Properties] hanig no func. grp.
(keto form)

deactived grp.

O
R C CH3

Br2

OH

CH3COOH

NaCN

R C = CH2 (enol)

H2SO4

R C CH2

XX

Br

OH
C

Nu

CH3

CN

cyanohydrin
*

Reaction site in,

CH2 = OH OH

C = O group

Br2

CH2 CHO

R C CH3

Nu

Br

R carbon

Mech:

CH2 = CH O H

Br Br
H
CH2 C = O + H
Br

As seen, there are two sites of reaction in RCHO and ketones - carbonyl carbon and
carbon Nucleophilic attack on carbonylic carbon and electrophile attacks on carbon.
The reaction on position occurs through enolisation.
O
Ph C CH3
OH

1. NaCN

Ph C CH3

2. H

CN
Ph
CN

Ph
OH

CH3

HO

CN
CH3

36
(b)

RNC

[ E and Nu ]

E+

Attacked to the same carbon atom (only one

RNCE

of its type just different from other)

Nu
E

**

CH 2 N H polar bond

RN=C

Breaking Easy
Nu

CH2 = O [*]

H+/H2O
E
R NH2 + O = C
Nu
RNC
CH3MgBr

CH3

[Hydrolysis of imines very easy]

MgBr

[Ionic bond]

RN=C
H

H2O
CH3

O
HO

RN=C

R NH2 + CH3 C H

H
(4)

Rosenmund Reduction: O

RC

H 2 / Pd / CaCO3

RC

Cl
(5)

Stephum Reduction : 1.SnCl / HCl

2
R CN 2 .H O
2

RCH

CHO

CN

1. PhLi

1. SnCl2/HCl

2. H3O

2. H2O

O = C Ph

1. MeMgBr
2. H3O

37
O = C = CH3

R C R

1. NH3

C = NH

H+

(ald. Or ketone)
Hydragine

2. NH2 NH2

I mine

H+
Phenyl hydrazine

C = N = N NH2

3. PhNHNH2

R
C = N NH2 Ph

NHNH2
S

phenyl hydrogone

C = N NH C NH2
R

NO2

O2N

hydrogone

O
H2N NH C NH2
H

All these reactions are acid catalysed but only a small amount of acid should be used,
because, excess acid will protonate NH3 and its derivative and thereby retards thereacn.
NH3 + H

NH4

OH

N H 3 R

NH2

N H2

C=O

R
C = NH

C = NH2

Aldehydes/ketones
Base
Aldol
or Acid

O
1)

CH3 C CH3 Na2 CO 3 CH3 C CH2 C CH3

O

2)

OH
O

CH 3 ONa
CH3 C O CH3 CH OH CH+ C CH+ C OCH3
3

38
O
3)

CH O Na

3
CH3 C O CH3 CH OH CH2 CH2 COOCH3
3

OH

HCH
O
4)

CH3 C CH3 + CH2O

OH

OH

CH3 C CH2 CH2

CH2

CH3

O
C

CH ONa

3
+ HCOOCH3 CH OH
3

NO2

NO2

COOEt
6)

CH2 COOEt
EtoNa
? H3O
EtOH

+ CH2
COOEt

CH2 COOEt
EtO

Mech:

CH COOEt

C = O Et

CH2

C O Et

CH COOEt

O
COOEt

O
C

COOH
H O
3

COOH

O
7)

Ph C CH3

CH3 C H

H Peracid

H peracid

Ph O C CH3
Imp:

CH3 C O H

O
peracid

H

C
COOEt

39

Aldol condensation

OH
CH3CHO or, H CH3 CH CH2 CHO

OH
By base catalysed:
O

OH

CH3 C H

CH3 CH CH2 CHO

OH

O
CH 3 CH O

CH2 C H

CH3 CH CH2 CHO

CH2 = C H (enolisation)
By acid catalysed:

OH
CH2 C H

O
CH2 = C H

CH3 CH = O

CH3 CH CH2 CHO

O
H
CH3 CH CH2 CHO
OH
Bayer villager oxdn.
O

O
CH CO H

3 3
R C R H R C O R

Mech:
O
RCR
H
OH

40
RCR
H

O C CH3

OH
RCR
O O C CH3
OH
OH

Note: Migsatory aptitude should be followed

RCR
O

in case of unsymmetrical ketones.

Migrate.

CH3

CH3 C CH

OH

CH3
percied

RCOR

RCOR

CH3

CH3 C O C
CH3

Br

COOH

H3O

OH CH2
OH CH2
O

Br

: CANNTZZARO REKN :
Aldehyde without

Mg

Mg Br

CO2

C
O

O Mg Br

41
hydrogen
CH2O

OH

OH

C. R

HCOO + CH3OH
H (Acidification)
HCOOH

Mechanism : - One molecule is oxidised to acid and other molecule is reduced to alcohol,
therefore conniggaros reacn is a disproportional reacn.
eg.

(1)

CH3 CHO
OH

Aldol cond. (easier)

Cannizzaro reacn
*

If concentration of OH is increased rate of canniggaros reacn increases.

O

Reason

HCH

HCH

[*] OH

OH [ I ]

[*]
Oxidn

OH

O
H C H CH2 = O
r.d.s

OH
O

HC

+ CH3O

H C H easy to remove

OH

[II] Dianion

O
HC

+ CH3OH
O

Monoanion I. is converted into dianion II. from which H transfer is easier.

eg

CHO

OH

COO

CHO

CH2OH

(Intramolecular)

eg

Ph CHO + CH2O

eg

OH
CH3 CHO + CH2O (excess) Aldo CH2 CH2 CHO

OH

PhCH2OH + HCOO

OH
CH2OH
CH2 C CHO

{ cross C. R

42
OH

2CH O

CH2OH + CH2O Aldol 2

OH
OH

OH + HCOO
OH

OH

CH2O

CH3OH + CH2O

CH3OH + HCOO

(?)

OH

Reformat sky reacn

O

CH2 C

+ CH3 C

Br

OEt

CH3
1. Zn

Mechanism

2. H2O
Zn

OH
CH3 C CH2 COOEt
hydroxy ester

CH3

OH

CH2 C
ZnBr

CH3 C CH2 COOEt.

OEt

CH3

H2O

OZnBr

OZnBr

CH2 = C OEt

CH3 C CH2 C OEt

CH3 C CH3

CH3

O
Imp:

COOEt
O

OH

Br 1. Zn/2.H2O

COOEt

: Beckman Rearrangement :
R

R conc H2SO4

43
NH OH HCl

O (ketoxime)
eg

or

N OH or SoCl2
H

CH3 ( rearrange)

Ph

R C NHR

P2O5

N OH

H2SO4/

O
eg

OH2

CH3 C NH Ph

CH3

RC=NR

Ph

H2O

N OH
conc H2SO4 /

RC=NR

OH2
H

Ph C NH CH3

RC=NR
The group anti to OH

OH

migrates. Migratory aptitude has

no role in Backmann he arrangement.

O
R C NH R

Geometrical isomers of oximes can be distinguished by help of Backmann

rearrangement.
O
CH3 C Ph
1. NH2OH HCl
2. H2SO4/
O
CH3

NH

PH
1. NH OH HCl

2
2.H 2 SO4 /

: Witting Reaction :
CH3 1.
: PPh3
CH3 PPH3

PH3 > NH3

I > Br
(witting reagent)

NH

44
CH3Li
CH2 PPH3
eg

phosphorous ylide

CH2 = PPH3

CH2 O

CH2 = CH2 + Ph3PO

CH2 PPH3
CH2 O

CH2 O

CH O CH2

CH2 - ---

Batain intermediate

eg

CH2 = O
+

CH2 = CH2

CH2 = PPh3

+ Ph3PO
CHO

eg

Ph CH = PPh3 +
Ph CH PPh3
Ph CH = CH Ph

Test

RCHO

PhCHO

Ketone

1. DNP test
2. Fehling soln test
3. Benedict soln test
4. Tollens reagent
5. Schiffs reagent
DNP test

F.S. test

C=O

NH NH2

H ,

NO2

Soln A

Soln B

AgCnSO4

Na/K tartrate

NO2
Cu2+ tartrate
C = N NH

complex a weak O.A.

RCHO

NO2
NO2

R COO + CH2O

Yellow ppt.
Benedict reagent test: -

Brick red ppt.

schiffs test : -

It is same as F. S
test except that is
replaced by citrate

NH2
ClH2N =

=C

CH3
NH2

45
Rosaniline hydrochloride [Blood red soln]
SO2 (g)

Tollens reagent
R CH = O

colourless

Ag(NH3)2NO3

RCHO

R COO + Ag

colour comes back

(silver mirror)

Chemistry of this test is not clear.

CARBOXYLIC ACIDS & THEIR DERIVATIVES

1)

RCOOCH3

H O

RCOOH + CH3OH

O
2)

R C Cl H2 O RCOOH
O

3)

NaOH
R C NH2 H2 O RCOONa + NH3

H2O
RCOOH
O
4)

RCOCR

H O

2 RCOOH

46
H O

RCOOH

H O

R NH2 + HCOOH

5)

RCN

6)

RNC

7)

2
RMgX 2. H O RCOOH

8)

2
CH2 = CH2 H CH3 CH2 COOH

(3)

1.CO
3

CO / H O

O
NaOH ( excess )
R C NH2 H 2 O RCOO

H2O NaOH

+ NH3

very first

O
RC

+ H2O
ONa
O

Canc:

R C NH2 R C
OH

+ NH2
OH

OH
O

R C NH2

RC

O
(8)

CH2 = CH2

Ph CH = CH2

1. CO/H2O

=?

2. H+

CH3 CH2
:CO

Ph CH CH3

CH3 CH2 C = O
H2

+ NH2

(Markonikoffs rule)

O
O

R COOH
NaOH

CH3 CH2 C
OH2
H
O
CH3 CH2 C

COOH

O
R C O Na.

47
OH
Properties: R COOH

NH3

R C O NH2 R C NH2 + H2O

Na

RCOO Na + H2
O

NaHCO3

RCO

Na + H2O + CO2

O
PCl5

R C Cl

R C Cl/Py(?) R C O C R
O
P2O5

RCOCR

R C Cl

CH3 C OH
PCl5

HO C R
O

OH

x : CH3 C Cl

Br2

RCOCR

CH2 = C Cl

B r Br

H
O
O

y : CH2 C Cl (Hell-vollhard zehin sky recn )

RCOCR

H2O

Br
O

z : CH2 C OH
Br
HCl

+ Cl

N
H
O

R C Cl

O
NH3

R O NH2

48
CH3

O
NH

CH3

RCN

CH3

CH3

O
R C NH2
LiAl H4

R CH2 NH2

Br2/NaOH

R NH2

P2O5

RCN

RCOCR
H

LAH

2RCH2OH
O

CH3OH / H+
Imp:

R C OCH3 + RCOOH

O
R C NH2
H
OH
R CH NH2
H2O
R CH = NH
H
RCH2 NH R CH2 NH2

**

Hofmann bromide reaction: O

Br

2 R NH2
R C NH2 NaOH

Mech:

R NH2

R C NH2
NaOH

H2O
R NH + CO2

O
R C NH
Br Br

O
R NH C O

49
O

RCN

O
Br

R N C OH

NaOH

RC

How

R N = C = O H2 O R N = C
OH

**

O
Formic acid (H C OH)
O
Fehling
H C OH sol n CO32 + CH2O

CO32 + Ag

COOH

CO2 + H2

COOH

H2SO4/

CO + H

NaOH

sodaline
HCOONa COONa

Tollens reagent

v.v.i
Imp:

COONa
O

O
C O H H2SO 4

C OH2

COH
O

CO + CO2 + H2O
Imp:

C
O

OH

CO + H2O + CO2 + H
O

HCOH

H2 + CO2

H C OH2

H + CO + H2O

ETHER

50
ROR
HI

ROR

R OH + RI

HI

HI

leg

ROR

2H I
2RI

RI

R I + ROH

R OH + RI
CH3

CH3 O CH2 CH3

O
HI

1o
HI

+ CH3

CH3I + CH3CH2OH

OH

CH3

HI

CH3 O CH
HI

CH3

CH3I + CH3CH OH
(Major pair)

SN2

SN1
CH3

CH3 O C CH3

CH3
HI

CH3OH + CH3 C CH3

CH3

BENZENE
1)

Sodalim e
Decarboxylation of benzoic acid, R COOH R H

Base catalysed
(B)

COOH

Sodalim
e

(A)

Benzoic acid can be decarboxylated either by acid or by base catalysis.

Mech: -

(A)

(B)
O Na

O = C OH

O
O

O
C

+ CO2
+ CO2

51
H2O

COOH

COOH

COOH

Ease of acid cat. decarboxyl. III > I > II.

Imp.
I

II NO2

Ease of baoecat: II > I > III.

III CH3

If catalysis is not mentioned then (i.e base cat. taken) II > I > III.
H PO

3 2

N2Cl
OH

Zn
CHO

CO/HCl/AlCl3
H2O

Gatterman KOCH reacn;

CHO

HCl/HCN/AlCl3
H2O
HCl/HCN/AlCl3

Mech: -

CH2 OH

HCl/ZnCl2

(CO + HCl + AlCl3)

H C O + AlCl4
O
CH.

AROMATIC HYDROCARBON
R
I

+ CH3CH2I Na ,

Wurtz fitting reaction.

CH2 CH3

Cl

52
3HC CH
Red hot Cu tube

Oxidation of side chain

Imp.

KMnO4

Cr2C2Cl2

(Chromyl chloride)

CH3
COOH

CHO

Mechanism is not very clear. However it has been speculated that occurs through the
formation benzylic radical or benzylic cation. This speculation is supported by following
evidences.
(a)

Oxdisability of the side chains is in the order

CH3
as CH2 Ph > CH

>
CH3

CH2 CH3 > CH3

r

CH2 Ph

C H Ph

[o ]

CH3

CH3
r

CH

[o]

C H2

CH3

CH3
r

CH3

[o]

C H2

r1 > r 2 > 43
(b)

There should be at least one benzylic H.

I.

H3PO2
N2+Cl

II.

Zn
OH

CHO

CO/HCl/AlCl3
CHO
ZnCl
CH
1.HCl/HCN/AlCl
/HCl.
2O/HCl/ZnCl
22.H
2O
23

Cl

53
III.

Gattermann KOCH reaction

IV.

V.

Mechanism
(III)

CO + HCl + AlCl3

H C O + AlCl4

(IV)

CH2 = O + HCl + ZnCl2

CH2 = OH + ZnCl3

**

CH3

COOH

[o]

C CH3
CH3
Additionally note that irrespective of the length and structure of side calkyl chain,
oxidation by KMnO4 yields benzoic acid. only condition is that there should be at least
benzylic hydrogen.

CH2 CH3
CH3
CH

KMnO4
[o]
CH3

CH
CH3

COOH

54
We can use KMnO4 K2Or2O7 , HNO3.

It becomes impossible to shave the ring if it bears OH or NH2 group.

COOH

COOH

KMnO4
[o]

e rich species.
OH

OH

CH3

COOH

KMnO4
[o]

e rich species.

NO2

NO2

COOH

CH3

[o]
OCH3

OCH3

ARYLHALID
Fe
+ X2

X
AgClO4

+ I2
OH

I
SeCl

2 X

Cl
Cl

55
PCl

3 X

HCl
X

Cl

PCl
5 X

Cl

Cl

Cl

+ HOPCl4

(vary poor yield)

POCl3 + HCl.
Cu

Cl

OH

NaOH

NH2

NH

CN.

MgCl.

Mgnether

Li

PhLi.

PhLi

Ph Ph.

ANILINE
O
(1)

Ph C Cl

O
(2)

NaOH Br2

1. NaN3 (sod. azide)

2.

Ph NH2

3. AgNaOH
Ph NH2
(3)

Ph N = N Ph

Ph C NH2

O
(4)

NHR / NH C R
*

56
Ni / H2

HCl

2Ph NH2

NH2

NH2

R[*]
R/[*]
(5)

Zn / HCl

NO2

NH2

Acidicmed .

Zn / NH Cl

Ph NH OH

Zn
/ NaOH

Ph N = N Ph (A = 0 benzene)

neutralmed .

basicmed .

(6)

CHCl / NaOH

NH2

Ph NC

3
KMnO

=O

4
Peracid

NO2.

or ,

(7)

NH2

CH Py

NH CH3

CH 3OH / H

NH CH3

CH 2O / Ni / H 2

NH CH3

CH O ( Excess )

2
Ni / H 2

O
N=N=N
2

N N N

CH3
N

NH C R

R COCl
/ Py

Mech: -

CH3

R NH2

R C N N2
Acyl azide

R NH + CO2

O
RC

H2O

N:

RN=C=O
H2O/NaCH

R NH C O
O
RNC
OH

57
O
RN=C
OH
Benzidene rearrangement
NH R

NH NH
HCl

HCl
NH R

NH R
NH2

NH2

HCl

NH2
R

NH2

NH

NH2

+
R

(1)

Semidine

(2)

Benzidine

(1)

NH2

(2)

HO

Ph N2Cl 2 PhOH
H O /H

2 2

PhOH

(3)

NaOH
SO3H H PhOH

(4)

2
MgBr 2.H O PhOH

1.O

+
G

(2)

PHENOL
(1)

NH2
G

58
OH

Na

PhO Na + H2

NaOH

PHONa + H2O

Na2CO3
NaHCO3

OCH3

CH3I/NaOH

ROCl / Py

CCR

FeCl3

Coloured complex

Na2Cr2O7/H
O

OR

OH

OH
R +

AlCl3

AlCl3

O C CH3

OH
COOH
OH

OH
+
COCH3

OH

OR
O

CHCl3
Base,
Reimer tieman reaction

OH

CHO

CHO

OH

OH

OG

AlCl3 /

+
G

Reimer Tieman reaction: x

CHCl3 + NaOH x CCl2
OH

+ NaOH
O
x
x CCl2

+ H2O
O
CCl2
H

CHCl2

59
O
OH

OH

OH

CHO

CH
OH
OH

OH

NaOH
+ CCl4

OH

COO

COOH
Salicylic acid.

CCl3
H

CCl3
1. NaOH

OH
(1)

CCl3.
O

2. CO2/150oC
3. H3O Kinetic product.
OH

C
O

OH

H3O

COOH

OH

OH

H+

COO Na
OH

1. NaOH

Thermodynamic.
o

2. CO2/200 C
3. H3O

OH
Br2/H2O

COOH

Br

OH
Br
Br

Br2/CS2

OH

Br

O O
C
O Na
H

60
Here, CS2, a nonpolar solvent in which phenol is not ionized to phenoxi debut. H2O is a
polar solvent in which phenoxide is generated, therefore polybrominated occurs.
Q.

An aromatic compd. A containing one O atom has C = 76.6% and H = 6.38%. It is

solb in caustic alkali and gives characteristic colour with FeCl3 sol. When treated with
NaOH and CO2 at 140oC under pressure A gives B which after acidification give C.
Acetylation of C gives D which is used on a pain killer(?).

Sol.

A ag NaOH solb
Aromatic FeCl 3 colour A O atom + 76.6% C + 6.38% H
A

Soln

NaOH / CO2
B
140 o C

H O

3 C Acetylatio
n

OH

D painkiller
Ph OH

OH

CH3 C Cl

COO Na
Acetylation
OH
94 72
300

72
100
94

= 76.6%

COOH
O
O C CH3

COOH
O acetyl salicylicaid (Aspirine)

O
Ph O C CH3
O acetylation