Alcohol Ether

Chemistry
ALCOHOL & ETHERS

Hydroxy derivatives
Aliphatic hydroxy derivatives Aromatic hydroxy derivatives
(I) Aliphatic hydroxy derivatives :

Hydroxy derivatives in which —OH is directly attached to sp3 C (Alcoholic compounds).
(II) Aromatic hydroxy derivatives :

Hydroxy derivatives in which —OH is directly attached to sp2 C of benzene ring (Phenolic compounds).
Aliphatic hydroxy derivatives :
(a) Classification according to number of —OH groups :

(i) Monohydric [one –OH] ¾¾¾¾® CH3CH2—OH
CH2 CH2
(ii) Dihydric [two –OH] ¾¾¾¾® OH OH

Glycol
CH2 CH CH2
(iiii) Trihydric [three –OH]¾¾¾¾® OH OH OH
Glycerol
D:\TEACHING NOTES-2016-17\CHEMISTRY\OC\FINAL\ALOCOHAL & EITHER\1. ALOCOHAL & EITHER.p65
CH2–OH
(iv) Polyhydric [n –OH] ¾¾¾¾® (CHOH)4

CH2– OH
Sorbitol
(b) Classification according to nature of carbon :

(i) p or 1° – alcohol ¾¾¾¾® CH3CH2 – OH
(ii) s or 2° – alcohol ¾¾¾¾® (CH3)2CH – OH
(i) t or 3° – alcohol ¾¾¾¾® (CH3)3C – OH :O :
3
sp
sp
Structure of alcohol :
3
108 .5° 1s
3
sp
Alcohols are bent molecules. The carbon atom (linked with

H 3C 3 H 1s
'O' atom of –OH group) is sp3 hybridised. The central 'O' atom is also sp
S tr ucture of C H 3 O H
in sp3 state of hybridisation. The bond angle is 108.50 . In sp3
hybridisation of O - 2s2,2px2 2py1 2pz1
orbitals hybridised to form sp3 orbitals
O ® ¯ ¯
2s 2p x 2p y 2p z
sp 3 hybridisation
E 1
Lecture notes JEE - Advance
In these four orbitals two containing one electron each N on - b o nd ing e — pair
and two co ntaining two electrons each . Orbitals

containing two electrons do not take part in bonding. Other
s bo nd O ato m
two half f illed o rbit als form s bond with s bo nd
s-orbitals of H -atom and hybridised orbital of C-atom sp 3 +. .×
S
(O—C). h ybrid ised 108 .5° H ato m
3
o rbitals sp C ato m
Due to lone pair effect the bond angle of tetrahedral oxygen atom
.× .×
is lesser than normal tetrahedral structure (109028'). S .× S
H S H
H
Ex.1 Classify the following as primary, secondary and tertiary alcohols :
CH 3
(i) CH3–C–CH2–OH (ii) H2C = CH – CH2OH (iii) CH3–CH2–CH2–OH

CH 3
OH
CH–CH3 CH3
C H 2 –C H – C H 3 CH2=CH–C–OH
(iv) (v) (vi)
OH CH3
GENERAL METHODS OF PREPARATION

(1) From alkenes :
(i) By hydration :

Å
CH3—CH CH2 ¾¾
H
® CH3 CH CH3
H 2O
(ii) By hydroboration oxidation : OH
CH3—CH CH2 ¾¾¾¾¾

(i) B2H 6 / THF
1
® CH3 CH2 CH2 (1° alcohol)
(ii) H 2O 2 HO
Mechanism : OH
Takes place by Anti Markownikov Rule in presence of H2O2
Firstly formed trialkyl borane by Cis cyclic addition which convert in alcohol by oxidation with
H2O2 /OH–
B2H6 ® BH3 + BH3
H H
H B H B
Me Me Me H H
H H H
C=C + H– B– H Hydroboration C C C C
H H H H H
H Me H
2 C=C
H H
H
H2O2 Me a
3MeCH2CH2OH + H3BO3 C–C B
Oxidation H b 3
(iii) By oxymercuration demercuration :
(i ) Hg(OAc)2 , H2 O
CH3—CH CH2 ¾¾¾¾¾¾¾ ® CH3 CH CH3
(ii) NaBH 4 ,HO1
OH
Mechanism
Take place by Markonikoff rule. No carbonium is formed during reaction hence no rearrangenment takes
place. Mercuration by Hg(AcO)2 and demercuration by NaBH4/OH–
2 E
Chemistry
O
a H O – C – CH3
C C + Hg
b H O – C – CH3
Mercuration O
O
–
T.H.F – [ O– C– CH3]
O
a H a H
C C H H C C
b Å H b H
O Hg
Hg Å
H H O – C – CH
O – C– CH3 3
O
O
deprotonation
O O +
–[H ]
CH3 – C – O + H ® CH3 – C –OH
– +
a H Demercuration a H
C C + Hg + CH 3– COOH C C
b H NaBH4/OH
–
b H
OH H OH Hg–O – C – CH3
O
If a= b = H Þ 1º alcohol
a = R b = H Þ 2 º alcohol
a = R and b = R Þ 3· alcohol
(2) From alkyl halides (By hydrolysis) :
Aq. KOH
¾¾¾¾¾ ®
CH3—CH2—Cl or Moist Ag2O CH3CH2—OH
(3) From ethers :

R—O—R ¾¾¾¾
dil.H 2SO 4
® R—OH + R—OH
CH3—O—CH2CH3 ¾¾¾¾
dil.H 2SO 4
® CH3—OH + CH3CH2—OH
(4) From carbonyl compounds (By reduction) :
Reducing agent
>C O ¾¾¾¾¾¾ ® >CH—OH
u Reducing agents may be,
LiAlH4/protic solvent, NaBH4/protic solvent
Na + EtOH [Bouveault-blanc Reduction]
NaH [Darzen reduction]
Ni/H2
R—CHO ¾¾¾
LiAlH 4
® R—CH2—OH
proticsolvent
R C R ¾¾¾
NaBH 4
® R CH R
protic solvent
O OH
CH3 C CH3 ¾¾¾

LiAlH 4
® CH3 CH CH3
proticsolvent
O OH
E 3
Mechanism :
LiAlH4 ® Li+ + AlH4–
AlH4– ® AlH3 + H–
H H
1 Å
H H
CH3 C C H 3 ¾¾¾¾® C H 3 C C H 3 ¾¾¾¾®
F ro m H O
CH3 C CH3
2
1
O O OH
OD
H
LiAlH 4
O
DÅ
OH
D
NaBD 4
Å
H
CH3—CH CH—CHO ¾¾¾

LiAlH 4
Å
® CH3—CH CH—CH2—OH
H
Crotonaldehyde
Ph—CH CH—CHO ¾¾¾

LiAlH 4
Å
® Ph – CH2 – CH2 – CHO
H
Cinnamaldehyde

(5) From acid and derivatives (By reduction) :
R—COOH ¾¾¾
LiAlH 4
Å
® R—CH2—OH + H2O
H
R C Cl ¾¾¾
LiAlH 4
Å
® R—CH2—OH + HCl
H
R C OR ¾¾¾
LiAlH 4
Å
® R—CH2—OH + R—OH
H
R C O C R ¾¾¾
LiAlH 4
Å
® R—CH2—OH + R—CH2—OH
H
O O
** R C NH2 ¾¾¾
LiAlH 4
Å
® R—CH2—NH2 +H2O
H
O
** Amide gives amine (not alcohol) with LiAlH4
4 E
Chemistry
Chart-1
REDUCING AGENTS AND THEIR ROLE
Group Product LAH in NaBH4 B2H6 H2 /

Ether in EtOH in T H F Cat alyst D
–CHO –CH2OH + + + +
>C = O >CH – OH + + + +
–CO2H –CH2OH + – + +
–CO2R –CH2OH + – + +
–COCl –CH2OH + + – +
–CONH2 –CH2NH2 + – + +
(RCO)2O RCH2OH + – + +
–CN –CH2NH2 + – + +
>C = NH –CH2NH2 + + – +
>C = C< >CH – CH< – – + +
–C º C– –CH = CH– – – + +
1° RX RH + – – +
E 5
Name Reagent Function

H
Wolf Kishner Reduction (i) N2H4 / (ii) KOH, O
H
H
Clemenson Reduction Zn–Hg / HCl or O
Na–Hg/HCl H
SH H
Mozingo Reduction Dry HCl, followed
O
by Raney Ni
SH H
SnCl2 / HCl followed
Stephen's Reduction + R–C N R–CH=O
by H3O
CH3 CH3
MPV Reduction Al –O–CH HO–CH O OH
CH3 3 CH3
C=C C—C
H H
Hydroboration Reduction B2H6 / AcOH, H2O
O O
H H
Bouvoult Blank Reduction Na / EtOH R–COO–R RCH2OH +ROH
Transfer Hydrogenation N2H4 / H2O2 C=C C—C

H H
O O
Rosenmund Reduction H2, Pd–BaSO4 R—C—Cl R—C—H

* —C C— —C C—
H H
H
Birch Reduction Na / Liq. NH3 —C C— —C C—
H
—COOR
H–Al –CH2–CH–CH3 —C N –78°C
—CHO
CH3 2 —COCl
DIBAL-H —COOH
followed by H3O+
—CHO —CH2OH
R–CH=O RCH3
Red phosphorus in R–C–R RCH2R
presence of HI Red P + HI
O
R–OH R–H
6 E
Chemistry
(6) From hydrolysis of ester
O
OH R C O + R'OH (irreversible)
R C OR' + H2O +
H (acidic hydrolysis is reversible)
R C OH + R'OH
O
O
Note : (i) Hydrolysis of ester can be catalysed by acid/base.

(ii) Acid cataalysed hydrolysis of ester is reversible.
(iii) Base catalysed hydrolysis of ester is called saponification
(iv) Following bond breaking may take place during hydrolysis :
R C O R'
O
Acyl (AC) alkyl (AL)
(v) For hydrolysis of ester following mechanisms are possible
(a) BAC2 (Base catalysed bimolecular acyl-oxygen bond cleavage mechanism)
(b) BAL1
(c) BAL2
(d) AAC2
(e) AAC1
(f) AAL1
Note : Most common mechanism in acidic medium is AAC2 and in basic medium is BAC2
OH
18 r.d.s 18
1. BAC : R2
C O R' OH
R C OR' R C OH + R'–O
18
O O
O
18
R C O– + R'OH
O
18 Å OH
2. BAL1 : R' O C R R' + R'OH + R C O–
R C O 18
O 18 O
O
18 OH 18
3. BAL2 : R C O R' R C O + R'OH
O O
E 7
OH
H
4. H
+ 18 OH2 +
AAC : R C 18 OR'
2
R C O R' R C O
r.d.s H
18
OH O O
+ OR'
H
R C OH Å
–H
O Å R'OH + R C OH R C OH + R'OH
18 18 18
H R' +
OH O
H
+ Å
H
5. AAC1 : R C OR' R C Å
O R' R C O + R'OH
O O
O
OH2 Å –HÅ
R C OH2 R C OH
O
+ 18 r.d.s OH 2
H Å
R C OR' R C O R' R' + R C OH
6. AAL1 :
O OH
Å
18
O
Å 18 Å 18
–H
R' OH2 + RCOOH R'OH + RCOOH
Examples based on above reactions :

+
H /HOH
2
18 AAC
Ex.2 CH3 C OC2H5
OH /HOH
2
BAC
O

+ 18
18 H /HOH 2
CH3 C O C2H5 CH3 C OH + C2H5OH (AAC)
Sol.
O O
18
18 OH/HOH
CH3 C O C2H5 CH3 C O + C2H5OH (BAC)2
O O
+
H /HOH
18
Ex.3 Ph C OCH3
OH/HOH
O
+ 18
18 H /HOH 2
Ph C O CH3 Ph C OH + CH3OH (AAC)
Sol.
O O
18 OH/HOH 18
Ph C O CH3 Ph C O + CH3OH (BAC)2
O O
O H+/HOH
C CH3
O OH/HOH
Ex.4
Sterically hindered group gives BAL2
8 E
Chemistry
O O
C C
O HOH/H OH 18
Sol. 18
+ CH3OH (AAC 1)
O
18
C CH3 COO + CH3OH(BAL2)
18 O H2O/OH –
O
+
H /HOH
C AAL1 mechanism
OCPh3
Ex.5 OH/HOH
BAL1 mechanism
It gives stable
1 1
carbocation, so it follow AAL & BAL
O
C COOH
OCPh3 HOH/H
+ CPh3OH (AAL1)
O
C COOH
OCPH3 H2O/OH
+ CPh3OH (BAL1)
O
+
H /HOH
Ex.6 O
OH/HOH
O O
O OH
HOH/H OH (AAC2)
O O
Sol.
O OH– OH
OH (BAC2)
HOH
O
C CH3
Ex.7 O NaOEt
18
SN2
O O
C CH3 C
Sol. O NaOEt O
18 18 + Et – O – Me
SN2
E 9
O R Aq.NaOH
Ex.8
O D
HO
S
Sol. C O R Aq.NaOH C ONa+
BAL2
O D O
D
(8) From primary amines :

NaNO + HCl
R—NH2 ¾¾¾¾¾¾
2
® R—OH + N2 + H2O
or HNO2
Mechanism :
NaNO2 + HCl ® H – O – N = O+ NaCl
H+ – H2O NºO
+
H–O–N=O H–O –N=O
+
N+ = O
H H
R – N + N+ = O R – N+ – N = O
H H
– H+
R–N=N–O–H R – N –N = O

H
H+
R – N = N – O +– H – H2O
R – N = N+
H
Å H – H2O –N2
R–O R+ R – N+ º N
H
R–O–H
–H+
Example : CH3CH2—NH2 HNO

¾¾¾¾
2
® CH3CH2—OH + N2 + H2O
Ex. CH3CH2CH2—NH2 ¾¾¾¾¾¾

NaNO + HCl CH3 CH CH3
® 2
OH
Exception : CH 3 – NH 2 ¾¾¾
HNO 2
® CH 3 – O – CH 3
10 E
Chemistry
GRIGNARD REAGENT RMgX

(7) From Grignard reagent :
Now we need to learn chemistry of Grignard reagent
(A). Organometallic compounds
Organometallic compounds are the organic compounds in which a metal atom is directly attached
to carbon of organic molecules through covalent bond or ionic bond. For example
C – M or
(Where C is a carbon atom of an organic molecule and M is a metal atom)
If the metal atom is attached to oxygen, nitrogen. sulphur, etc., then such an organic compound is
not regarded as an organometallic compound. The following structural formula do not belong to
the family of organometallic compounds.
RONa (Sodi um al koxi de). CH 3COONa (Sodium acetate), CH3COOAg(Silveracetate),RSK
(Potassium mercaptide) RNHK
(N-Alkylpotassamide), (CH3COO)4Pb (Lead tetraacetate), etc.
Note : It should be noted that (CH3)4Si (Tetramethylsilane, TMS) is also not an organometallic compound
because silicon is a nonmetal.
Most important examples of organometallic compounds are Grignard reagents. In Grignard reagent,
the carbon and magnesium atoms are bonded with each other through polar covalent bond and
magnesium atom is attached to halogen by ionic bond.
(Functional part of a Grignard reagent molecule)

In organometallic compounds, the metal atom can be bonded to carbon atom of a hydrocarbon
parts (Saturated, unsaturated, aliphatic, alicyclic or aromatic) or carbon atom of a heterocyclic
part. Some examples are given below.
Saturated Aliphatic Grignard reagent :- CH3 – MgI (Methylmagnesium iodide)
Unsaturated Aliphatic Grignard reagent : -
(i) Alkenyl Grignard reagent : - CH2 = CH – CH2 – MgX (Allylmagnesium halide)
(ii) Alkynyl Grignard reagent : - CH º C – CH2 – MgX (Propargylmagnesium halide)
Alicyclic Grignard reagent : - (Cyclohexylmagnesium halide)
Aromatic Grignard reagent : (Phenylmagnesium halide)
Heterocyclic Aromatic Grignard reagent :- (Pyridine-4-magnesium halide)
E 11
(B) Preparation of Grignard Reagent
Dry and pure
RX + Mg ¾¾¾ ¾ ¾¾
¾® RMgX
Ether
Ether is used as a solvent because it is a Lewis base that coordinates its lone pair of electrons to
electron-deficient magnesium atom, therefore providing stability to the Grignard reagent.
¾¾®
(C) Reactions of Grignard reagents

It has been found out by estimation that there is 35% ionic character in carbon-magnesium bond
of Grignard reagent. Therefore, there is a tendency of forming carbanion by heterolysis of this
polar coordinate bond as follows.
¾¾® +
The carbanion (a nucleophile) formed as shown above, attacks the positively charged electrophilic
centre of other compound. Therefore. It can be said that if a Grignard reagent is regarded as the
substrate, then electrophile displaces MgX, i.e. electrophilic substitution (SE) reaction takes place.

R – MgX ¾¾® R – E (SE Product)
Grignard reagents form adducts by addition on the following types of pi bonds.
, , and C º N , – N = O,
|
eg. R – MgX + ¾¾® R - C - OMgX
|
Adduct
On having same hydrocarbon radical, the order of reactivity of Grignard reagents will be as follows:
RMgI > RMgBr > RMgCl
(D) Synthetic importance of Grignard reagents
(a) Synthesis of Alkanes
(i) With compounds having reactive hydrogen atom
General reaction :
R – MgX + H – Z ¾¾® R – H + ZMgX
CH3 – MgX + H – OH ¾¾® CH3 – H + Mg(OH)X
C2H5 – MgX + H – OR ¾¾® C2H5 – H + Mg(OR)X
C3H7 – MgX + H – OC6H5 ¾¾® C3H7 – H + Mg(OC6H5)X
12 E
Chemistry
C2H5 – MgX + H – NH2 ¾¾® C2H5 – H + Mg(NH2)X
CH3 – MgX + H – NHR ¾¾® CH3 – H + Mg(NHR)X
C2H5 – MgX + H – NR2 ¾¾® C2H5 – H + Mg(NR2)X
CH3 – MgX + H – NHC6H5 ¾¾® CH3 – H + Mg(NHC6H5)X
C2H5 – MgX + H – SR ¾¾® C2H5 – H + Mg(SR)X
CH3 – MgX + H – C º N ¾¾® CH3 – H + Mg(CN)X
C2H5 – MgX + H – C º CH ¾¾® C2H5 – H + HC º C – MgX (Ethynylmagnesium halide)
CH3 – MgX + H – C º CR ¾¾® CH3 – H + R – C º C – MgX (Alkynylmagnesium halide)
Methane gas is released on reacting methylmagnesium iodide with a compound containing reactive
hydrogen atom. The reaction is used for estimation of reactive hydrogen atoms present in a molecule.
This method is called Zerewitnoff's method of estimation of reactive hydrogen atoms.
(ii) With alkyl halide (coupling) :
R – MgX + X¢ – R¢ ¾¾® R – R¢ + MgXX¢
(b) Synthesis of alkenes
R – MgX + X¢ -CH2 - CH = CH2 ¾¾® R – CH2 – CH = CH2 + MgXX¢

Allyl halide
(c) Synthesis of higher alkynes

Non-terminal alkynes
RMgx ¢¢ X R
R¢ C º C – H ¾¾ ¾¾® R¢ – C º CMgX ¾¾¾® R¢ – C º C – R¢¢
- MgX
- RH 2
(d) Synthesis of other organometallics

4R – MgCl + 2PbCl2 ¾¾® R4Pb + Pb + 4MgCl2
Two important antiknocking compounds, tetraethyllead (T.E.L.) and tetramethyllead (T.M.L.)
are manufactured by the above reaction.
2R – MgCl + HgCl2 ¾¾® R - Hg - R + 2MgCl 2
Diallkylmercury
2R – MgCl + CdCl2 ¾¾® R - Cd - R + 2MgCl 2

Diallkylcadmium
4R – MgCl + SnCl4 ¾¾® R 4 Sn + 4MgCl 2

Tetraalkyl tin
(e) Synthesis of Alcohols
There are following methods to obtain alcohols from Grignard reagent.
(i) From carbonyl compounds
| |
R – MgX + ¾¾® R - C - OMgX HOH
¾¾¾¾® R - C - OH
| |
alcohol
This is nucleophilic addition reaction
E 13
Primary or 1° Alcohols
Primary alcohols are formed on taking formaldehyde
H H
| |
HOH
R – MgX + ¾¾® R - C - OMgX ¾¾¾¾® R - C - OH
| |
H H
1° Alcohol
Secondary or 2° alcohols :
From RCHO Secondary alcohols are formed by the reaction of any aldehyde other than
formaldehyde.
R¢
|
R – MgX + ¾¾® R - C - OH
|
H
2° Alcohol
Tertiary or 3° alcohols
Tertiary alcohols are formed by taking any ketone
R¢ R¢
| |
R – MgX + ¾¾® R - C - OMgX R - C - OH
| |
R¢¢ R¢¢
3° Alcohol

(ii) From Ester :
Secondary alcohols are obtained on hydrolysis of the product obtained by taking excess
of Grignard reagent and adding formic ester to it.
H H H
| | |
RMgX
R + C - OEt ¾¾® R-C ¾¾ ¾ ¾® R - C -R
| || H2O |
||
MgX O O OH
Tertiary alcohols are also obtained on hydrolysis of the product obtained by taking
excess of Grignard reagent and an ester of a higher homologue of formic acid.
R R R
| | |
R + C - OEt ¾¾® RMgX
R - C ¾¾ ¾¾® R - C - R
| || || H2O |
MgX O O
OH
Various alcohols can be prepared by changing R in the above synthesis.
(iii) From Epoxides
¾¾® R - CH2 - CH2 R - CH2 - CH2
| |
OMgX OH
1° Alcohol
having two more C
14 E
Chemistry
(iv) From Oxygen
Synthesis of alcohol
R – MgX + O = O ¾¾® R – O – O – MgX
R – O – O – MgX + R – MgX ¾¾® 2R – O – MgX
R – O – MgX + HOH ¾¾® R – O – H + Mg(OH)X
Primary, secondary and tertiary alcohols can be obtained by above reaction
Synthesis of phenols
Phenol is obtained on hydrolysis of the product obtained by reaction of
arylmagnesium bromide with oxygen.
C6H5MgBr + O = O ¾¾® C6H5O – OMgBr
C6H5O – OMgBr + C6H5MgBr ¾¾® 2C6H5 – OMgBr
C6H5 – OMgBr + H2O ¾¾® C6H5 – OH + Mg(OH)Br
(f) Synthesis of Aldehydes
Corresponding aldehyde is obtained on hydrolysis of the product obtained by reacting of
formic ester and Grignard reagent in equimolar ratio.
H H
| – |
–EtO
R + C - OEt ¾¾® ¾¾ ¾¾® R - C
| || ||
MgX O O
Tetrahedral intermediate
In this reaction tetrahedral intermediate is fromed so this mechanism is called SN2 Th
mechanism
(g) Synthesis of Ketones

From Acid derivative
R¢
– MgOG |
¾¾® ¾¾ ¾ ¾¾® R - C
||
O
Where G = -OEt, – Cl
The above reaction sequence can be simplified as follows for convenience.
R – MgX + G - C - R¢ ¾¾® R - C - R¢ + G – MgX
|| ||
O O
eg. R – MgX + EtO - C - R¢ ¾¾® R - C - R¢ + EtO – MgX

|| ||
O O
eg. R – MgCl + Cl – CO – R¢ ¾¾® R – CO – R¢ + MgCl2

From Alkyl Cyanides
A ketimine is formed on hydrolysis of the adduct obtained by the reaction of Grignard
reagent and an alkyl cyanide, which gives ketone on further hydrolysis.
E 15
HOH HOH
RMgX + RCN ¾¾® R2C = NMgX ¾¾¾¾® R 2C = NH ¾¾¾
¾® R 2C = O
Keti min e Ketone
(h) Synthesis of Carboxylic acids
A carboxylic acid is formed on hydrolysis of the adduct formed by passing carbon dioxide
in the ethereal solution of a Grignard reagent.
HOH
R - MgX + C = O ¾¾® R - C - OMgX ¾¾ ¾ ¾¾® R - C - OH
|| -Mg(OH) X
|| ||
O O O
(i) Synthesis of Carboxylic acid esters

Esters are formed on reacting the ethylchloroformate with Grignard reagent.
RMgCl + ClCOOEt ¾¾® RCOOEt + MgCl2
(j) Synthesis of Ethers
Higher ethers can be synthesised by reacting a lower chlorinated ether with Grignard reagent.
R – MgCl + Cl – CH2 – O – R ¾¾® R – CH2 – O – R + MgCl2
CH3MgCl + Cl - CH2 - O - C 2H5 ¾¾® CH3 - CH2 - O - C2H5
Chlorometh yl ethyl ether Diethyl ether
(k) Synthesis of Mercaptans

Alkanethiols, i.e. mercaptan is formed on hydrolysis of the product obtained by adding
sulphur to the ethereal solution of Grignard reagent.
HOH
R – MgCl + S ¾¾® R – S – MgCl ¾¾¾¾® R – S – H + Mg(OH)Cl

Ex.9 Which of the following formula represents Grignard reagent ?
(A) H2NMgX (B) HC º CMgX (C) RMg (D) Mg(OH)Br
Ex.10 Which of the following is not a Grignard reagent ?
(A) (CH3)2CHMgCl (B) CH3COOMgI (C) C6H11MgBr (D) C2H5MgCl
Ex.11 The reaction of an alkyl halide and magnesium is initially very slow, but later becomes very fast,
because
(A) The reaction is autocatalytic
(B) The Grignard reagent formed is ether-soluble
(C) The reaction is endothermic
(D) The reaction is exothermic
Ex.12 Primary alcohol cannot be obtained by the reaction of a Grignard reagent with
(A) The simplest alkanal (B) Dimethylene oxide
(C) Ethylene glycol (D) Oxygen
Ex.13 Primary, secondary and tertiary alcohols can be obtained by hydrolysis of the products formed on
reaction of a Grignard reagent with
(A) Isobutyraldehyde (B) Butanone (C) Oxygen (D) Oxirane
Ex.14 Which of the following is formed on the reaction of one mole of acetyl chloride with one mole of
methylmagnesium chloride ?
(A) 2-Butanol (B) Acetone (C) Isobutyl alcohol (D) t-Butyl alcohol
16 E
Chemistry
PHYSICAL PROPERTIES :
(i) C1 to C11 are colourless liquids and higher alcohols are solids.
(ii) Density of monohydric alcohol is less than H2O.
(iii) Density µ mol. wt. (for monohydric alcohol).
(iv) Solubility : C1 to C3 and t-butyl alcohol is completely soluble in H2O due to H–bonding.
1
solubility µ No. of side chain µ molecular weight
Order of solubility :
C4H9OH > C5H11OH > C6H13OH
CH 3
CH3CH2CH2CH2OH < C H 3C H 2C H OH < CH3 C OH
CH3 CH 3
CH3CH2CH2 < CH3 CH CH2 < CH2 CH CH2
OH OH OH OH OH OH
[Number of —OH increases, H-bonding increases]
(v) Boiling points : B.P. µ molecular weignt
1
If molecular wt. is same then B.P. µ
branching
Order of BP : C4H9OH < C5H11OH < C6H13OH

CH3
CH3CH2CH2CH2OH > CH3CH2CH OH > CH3 C OH
CH3 CH3
CH3CH2CH2 < CH3 CH CH2 < CH2 CH CH2
OH OH OH OH OH OH
[Number of OH increases, H-bonding increases]
Ex.15 Boiling point of alcohol is more than corresponding ether. Why ?
Sol. Reason : H-bonding in alcohol.
O H ---------- O H ------------- O H ------------- O H ----------
R R R R
Ex.16 Boiling point of alcohol is less than corresponding carboxylic acid. Why ?
O H O
Sol. Reason : Dimer formation in carboxylic acid. R C C R
OH O
KEY POINTS
1. Diols and triols have higher b.p's and are more water soluble
2. In Thiols ,Hydrogen bonding is much weaker than that in alcohols.
3. Thiols have Lower boiling points than similar alcohols.
4. Thiols are much more acidic than similar alcohols
E 17
CHEMICAL PROPERTIES :
Monohydric alcohol show following reactions
(A) Reaction involving cleavage of O H
(B) Reaction involving cleavage of C OH
(C) Reaction involving complete molecule of alcohol
(A) Reaction involving cleavage of O H : Reactivity order (Acidic nature) is
CH3—OH > CH3CH2—OH > (CH3)2CH—OH > (CH3)3C—OH

(i) Acidic nature :
H2O > R—OH > CH CH > NH3 (Acidic strength)
Alcohols are less acidic than H2O and neutral for litmus paper and gives H2 with active metals (Na, K)
1
R—OH + Na ¾¾® R—ONa + H2
2
1
R—OH + K ¾¾® R—OK + H2
2
(ii) Reaction with CS2 :
1
R—OH + Na ¾¾® R—ONa + H2
2
R—ONa + S C S ¾¾® R O C S Na
S
Sodium alkyl xanthate (Used as floating agent)
(iii) Alkylation :

R—OH CH 2 N 2 D
¾¾ ¾¾ ® R—O—CH2—H (Chain insertion)
R—OH ¾¾
Na
® R—ONa R -X
¾¾¾ ® R—O—R
(Williamson synthesis)
(iv) Acylation :
R OH + Cl C R ¾¾® R O C R
O O
(Acylation)
R O H + Cl C C H 3 ¾¾® R O C CH 3
O O
(Acetylation) molecular mass increases by 42
OH O O C R
or
CH3–C–Cl O
COOH COOH
O O
CH3–C–O–C–CH3
Salicylic acid Acetoxy benzoic acid

or Acetyl salicylic acid
or Aspirin [Used as analgesic] pain killer
18 E
Chemistry
(v) Benzoylation : (Schotten Baumann's Reaction) :
R OH + Cl C Ph ¾¾® R O C Ph
O O
(Benzoylation)
(vi) Esterification : Conc. H2SO4 is used as catalyst and dehydrating agent.
conc. H2SO4
R C OH + R O H ¾¾¾¾¾¾ ®R C O R + H 2O
O O
u Mechanism :
H2SO4 ¾¾® H+ + HSO4–
: :
+
R—C—O—H + H R—C—O—H
O OH
Å
Å
OH OH OH OH
+
Å Å –H
R—C—O—H + ROH R—C—OH R—C—OH2 R—C R—C R—C—OR'
Å
OH O OR' OR' OR' O
Å H R'
Note : This is a laboratory method to prepare ester i.e. esterification.

Ex.17 CH3 C OH + H

O C 2 H 5
conc. H 2SO 4

CH3 C O C 2H 5 + H 2 O
O O

18 conc. H 2SO 4 18
Ex.18 Ph C OH + H O C 2 H 5 Ph C O C 2H 5 + H 2 O
O O
Ex.19 CH3 C OH + H O C 2 H 5 ¾ ¾¾
Dry. HCl
¾® C H 3 C O C 2H 5 + H 2 O
O O
1
(i) Reactivity for esterification µ Steric hinderence .
(ii) Reactivity of R – OH [If acid is same] : CH3 – OH > 1° > 2° > 3° alcohol
(iii) Reactivity of RCOOH [If alcohol is same] :
CH3
H C OH > CH3 C OH > CH3 CH C OH > CH3 C C OH
O O CH 3 O CH 3 O
E 19
KEY POINTS
1. Esters are obtained by refluxing the parent carboxylic acid with the appropriate alcohol with an
acid catalyst.
2. The equilibrium can be driven to completion by using an excess of either the alcohol or the
carboxylic acid, or by removing the water as it forms.
3. Esters can also be made from other carboxylic acid derivatives, especially acyl halides and anhy-
drides, by reacting them with the appropriate alcohol in the presence of a weak base
(vii) Reaction with CHº CH :

OCH3
CH CH + 2CH3—OH BF3 / HgO
¾¾¾¾¾ ® C H 3C H
D OCH3
Methylal
BF3 / HgO O C 2H 5
CH CH + 2CH3CH2— OH ¾¾¾¾¾
D ® C H 3C H
O C 2H 5
Ethylal
(viii) Reaction with carbonyl compounds :
OR
R—CHO + 2R—OH H
¾¾¾
Å
® R CH
OR
Acetal

R C R + CH2OH H Å R O
¾¾¾® C Cyclic Ketal
R O
O CH2OH
OCH3
CH3CHO + 2CH3—OH ¾¾¾
HÅ
® C H 3C H
OCH3
Methylal
(ix) Reaction with Grignard reagent :
X
R—Mg—X + H—OR ¾ H¾® R Å
H + Mg
OR
(x) Reaction with Ketene : Ketene is used as acetylating agent.
OR OR
CH2 C O + R—OH ¾¾® C H 2 C OH

CH3 C O
O C 2H 5 O C 2H 5
CH2 C O + C2H5—OH ¾¾® C H 2 C

O H CH3 C O
Ethylacetate
(xi) Reaction with isocyanic acid : Ethyl urethane is used in preparation of urea
20 E
Chemistry
O C 2H 5 O C 2H 5
HN =C = O + H—OC2H5 ¾¾® H N C

O H H 2N C O
Ethyl urethane
(xii) Reaction with oxirane :
OR
R OH + CH 2 H+
C H 2 ¾¾® C H 2 CH2
O
OH
(B) Reaction involving cleavage of C O H : Reactivity order or basic nature is
CH3—OH < CH3CH2—OH < (CH3)2CH—OH < (CH3)3 C—OH

(i) Reaction with halogen acid :
ZnCl
R—CH2—OH + HCl ¾¾¾¾
D ® R—CH2—Cl
2
+ H2O
ZnCl
R2CH—OH + HCl ¾¾¾¾
D ® R2CH—Cl + H2O
2
20 alcohol
Reactivity of the acids is HI > HBr > HCl > HF
(ii) Reaction with inorganic acids :
R OH + H O N O ¾¾® R O N O + H 2O
¯ ¯
O O
Nitric acid Alkyl nitrate

R—OH + HHSO4 ¾¾® R—HSO4 + H2O
Alkyl hydrogen sulphate
(iii) Reaction with phosphorous halides :
3R—OH + PCl3 ¾¾® 3RCl + H3PO3
R—OH + PCl5 ¾¾® R—Cl + POCl3 + HCl
(iv) Reaction with thionyl chloride (SOCl2) :
R—OH + SOCl2 ¾¾¾¾
Pyridine ® R—Cl + SO2 + C5H5N+HCl–
(gas)
(v) Reaction with NH3 : Alumina (Al2O3) is used as dehydrating agent.
Al O
R OH + HNH2 ¾¾¾¾
2 3
o
® R—NH2 + H2O
250 C
(vi) Reaction with halogens : Oxidation and chlorination takes place simultaneously.
CH3CH2OH + Cl2(dry) ¾¾® CH3CHO + 2HCl (Oxidation)
CH3CHO + 3Cl2 ¾¾® CCl3CHO + 3HCl (chlorination)
chloral
E 21
(C) Reaction involving complete molecule of alcohol :
(i) Dehydration : Removal of H2O by two type
(a) Intermolecularly removal of H2O [form ether]
(b) Intramolecularly removal of H2O [form alkene]
0°C
(C2H5)2SO4
100°C C2H5HSO4
C2H5 OH + H2SO4
(conc.) 140°C
C2H5 O C2H 5 (Williamson's synthesis)
170°C
CH2 CH2 (Elimination)
250°C
C2H5 OH +Al2O3 C2H 5 O C2H 5
(Alumina) 350°C
CH2 CH2
Ease of dehydration follow the order : 3° ROH > 2° ROH > 1° ROH > CH3OH
(ii) Catalytic Dehydrogenation : This reaction is useful in distinction of 1°, 2° and 3° alcohols.
Cu
CH3CH2OH ¾¾¾
300° C
® CH3CHO + H2
(p- alcohol ) (Acetaldehyde)
Cu CH3 C CH3 + H2
CH3 CH CH3 ¾¾¾
300° C
®
O

OH
(s- alcohol) (acetone)
CH3
CH3
CH3 C OH
Cu
¾¾¾
300° C
® CH3 C CH2 + H2O [dehydration]
CH3
(Iso - butylene)
(tertiary butyl alcohol)
(II) OXIDATION OF ALCOHOLS

Oxidising agents
(1) HÅ/K2Cr2O7, D (Strong oxidising agent)
(2) HÅ/KMnO4, D (Strong oxidising agent)
(3) Jones reagent : CrO3 / H2SO4 treated with alcohol usually taken in acetone (strong oxidising agent)
(4) Cu / 300°C (or Red hot Cu tube)
(5) PCC (Pyridinium chloro chromate) CrO3 Cl or CrO3 + HCl

NÅ N
H
22 E
Chemistry
(6) Collin’s reagent ( (2 mol) + CrO3 + CH2Cl2)

N
(7) Sarett reagent (i.e. PCC in CH2Cl2) + CrO3 + HCl + CH2Cl2

N
(8) PDC 2–
( Pyridinium dichromate ) Cr2O7
N
+ 2
Ts -Cl
(9) TsCl + DMSO + NaHCO3 ¾¾¾® RCH2OTs¾¾¾
RCH2OH DMSO
NaHCO
® RCHO 3
Ts -Cl
¾¾¾® R2CH–OTs¾¾¾
R2CHOH DMSO
NaHCO
® R2CO 3
Ts -Cl
¾¾¾® R3C–OTs¾¾¾
R3COH DMSO
NaHCO
®× 3
MnO 2
(10) MnO2-Oxidises only allylic or benzylic– OH. 1° Allylic or benzylic OH ¾¾¾® Aldehyde
MnO
2° Allylic or benzylic OH ¾¾¾2 ® Ketone
No effect on 3° ROH and on Carbon-Carbon multiple bond.
O
(11) NBS (N-Bromosuccinamide) N—Br
O
(12) Periodic cleavage

A similar oxidation is obtained in case of HIO4 known as periodic cleavage.
O O O
–
R–CH–OH + HO–I=O R– CH — O – I = O R–CH + HIO3
+
R2C–OH O R2C–O–H O R2C = O
But reaction is observed for Vic-diols.
(13) Openaur oxidation
O
Al(OCMe3)3
R – CH – R R–C–R
O
OH CH3 –C – CH3
R2CH–OH + Al(OCMe3)3 Me3COH + Al(OCHR2)3 (R2CH–O)2 Al–O

O CR2
3Me2C H
3R2C=O + (Me 2CH–O) 3Al
Oxidation of alcohol with aluminium tertiary butoxide is Openaur oxidation.
E 23
Ex.20 Different oxidising agents are used to oxidise alcohols in corresponding carbonyl compounds and
carboxylic acids.
R - CH 2 - OH ¾¾¾ ® R - C - OH
1,2,3,
e.g. (I)
1°alcohol ||
O
(II) R - CH 2 - OH ¾¾¾¾¾
4,5,6,7,8,9,10,11
® R - C - H (Aldehyde)
1°alcohol
||
O
OH O
| ||
R - CH - R ' ¾¾¾¾¾¾¾ ® R - C - R ' (Ketone)
1,2,3,4,5,6,7,8,9,10,11
(III)
2° Alcohol
CH 3 CH2
| Cu 300°C
(IV) CH 3 - C - OH ¾¾ ¾¾® C Dehydration takes place.
| CH3 CH3
CH 3
(V) Double bond or Tripple bond is not affected by 4,5,6,7,8,9,10

(VI) No effect on 3° alcohol by 1,2,3,5,6,7,8,9,10,12,13
(a) Oxidation by HIO4 [per iodic acid] :

When diols reacts with HIO4 [Periodic acid]. Those diols/ Polyols in which –OH group attached
to vic C-atom after reaction with HIO4 forms aldehyde and ketone.
This reaction is also used in identification of no. of OH group in polyol.
HIO4 -2H2 O
CH2 CH2 ¾¾¾ ¾
® CH2 OH + HO C H 2 ¾¾¾¾ ® HCHO + HCHO
OH OH OH OH
HIO4 -3H2 O
CH2 CH C H 2 ¾¾¾ ¾
® HO C H 2 +H O CH OH + HO C H 2 ¾¾¾¾ ® HCHO+HCOOH+HCHO
OH OH OH OH OH OH
(G lycero l)
Condition for oxidation by HIO4 :

At least 2 —OH or 2 >C=O or 1 —OH and 1 >C=O should be at adjacent carbons.
CH 3 O
2HIO 4
Ex.21 CH 3 CH CH C CH 3 ¾ ¾ ¾ ® CH 3 CHO + HCOOH + CH 3 C CH 3
OH OH OH
24 E
Chemistry
O
HIO
CH3 C CH CH2 C H ¾¾¾
4
® CH3COOH + CHO CH2 CHO
Ex.22
O OH
Ex.23
CH O CH O CH O
O
O O
2 H IO
¾¾¾®
–H O CO OH
+ HO C O H ¾¾¾®
4 2
OH +H 2 O + C O 2
O
HO CH 2 HO CH 2
OH (H 2 C O 3 ) H O CH 2 CHO
OH OH
O O
Ex.24 R - CH - OH || ||
+ HIO4 ¾¾¾¾
strong
oxidation
® R - C - H + H - C - H + 2H 2 O
CH2 - OH
R
é O ù
R - C - OH ê || ú
¾¾¾¾
strong
® 2 ê R - C = O ú + 2H 2 O
Ex.25 R - C - OH
oxidation
êë úû
R
R - CH - OH
Ex.26 CH2 + HIO4 ¾¾¾¾

strong
® No reaction (due to absence of vic diols.)
oxidation
R - CH - OH
KEY POINTS
1. 1,2- or vicinal diols are cleaved by periodic acid, HIO4, into two carbonyl compounds.
2. The reaction is selective for 1,2-diols.
3. The reaction occurs via the formation of a cyclic periodate ester .
4. This can be used as a functional group test for 1,2-diols.
5. The products are determined by the substituents on the diol
KEY POINTS
1. The product of alcohol oxidation depends on whether the starting alcohol is a primary, secondary
or tertiary alcohol.
2. Oxidation of methanol is unique amongst alcohols as the eventual products of methanol oxida-
tion are water and carbon dioxide.
3. A common reagent that selectively oxidizes a primary alcohol to an aldehyde (and no further) is
pyridinium chlorochromate, PCC.
4. 3º alcohol are resistant to oxidation because they have no hydrogen atoms attached to the oxygen
bearing carbon (carbinol carbon).
E 25
5. Potassium permanganate is a cheaper but stronger oxidizing agent, and conditions must be con-
trolled carefully.
(iv) Reaction with phosporous pentasulphide :

R—OH + P2S5 ¾¾® R—SH + P2O5
Thio alcohol
(v) Reaction with salts :
CuSO 4
CuSO4. 2CH3OH
CaCl2
CH3OH CaCl2. 4CH3OH
MgCl2
MgCl2 . 6CH3OH
(b) Pinacole - Pinacolone Rearrangement :

CH 3 CH 3 CH 3
CH3 C C CH3 ¾¾¾¾¾

®conc. H 2SO 4
CH3 C C CH3
- H2 O
OH OH O CH 3
Pinacole Pinacolone
Mechanism : Four steps involved
(a) Protonation (b) Dehydration (c) 1, 2 Methyl shift (d) Deprotonation
CH3 CH3 CH3 CH3 CH3

CH3

Å
HÅ –H O
CH3 C C CH3 CH3 C C C H 3 ¾¾¾® 2
CH3 C C
Å
CH3
OH OH OH OH2 OH
CH3 CH3 CH3 1, 2 m ethyl sh ift

Å
CH3 C C C H 3 ¬¾¾
Å
CH3 C C C H 3 ¬¾ C H 3 C C C H 3 ¬¾¾
–H
Å
O CH3 OH CH3 :O
.. H CH3
(C om p lete octet m ore stable)
TEST OF ALCOHOLS :
(1) Lucas test : A mixture of HCl(conc.) and anhydrous ZnCl2 is called Lucas reagent.
p-alcohol ZnCl2 + HCl
¾¾¾¾¾ ® No turbidity at room temp. [On heating within 30 minutes.]
s-alcohol ZnCl2 + HCl
¾¾¾¾¾ ® Turbidity appears within 5 minutes.
t-alcohol ZnCl2 + HCl
¾¾¾¾¾ ® Turbidity appears within 1 minute.
This test is used to differentiate 1º, 2º and 3º alcohols,
(2) Victor - Meyer test : This is colour test for alcohol (primary, secondary & tertiary) .
p-alcohol ¾¾® Red colour
s-alcohol ¾¾® Blue colour
t-alcohol ¾¾® No colour
This test is used to differentiate 1º, 2º and 3º alcohols,
26 E
Chemistry
R—CH2—OH [1°] R2CH—OH [2°] R3C—OH [3°]
¾¾®
¾¾®
¾¾®
P + I2 P + I2 P + I2
R—CH2—I R2CH—I R3C—I

¾¾®
¾¾®
¾¾®
AgNO 2 AgNO 2 AgNO 2
RCH2—NO2 R2CH—NO2 R3C—NO2

¾¾®
¾¾®
¾¾®
HNO2 HNO2 HNO2
R—C—NO2 R2C—NO2 No reaction
N OH N
¾¾¾¾¾¾®
Blue
NaOH
¾¾®
¾¾®
NaOH NaOH
Soluble (Red) Insoluble (Blue) Colourless or White

(3) Other test of alcohols :
(a) Dichromate test :
Å
1° Alcohol ¾¾¾¾¾ ®
H K 2Cr2O 7
orange [Cr +6 ]
Acid + Cr+3
[green]
Å
2° Alcohol ¾¾¾¾¾ ®
H K 2Cr2O 7
orange [Cr +6 ]
Ketone + Cr+3
[green]
Å
3° Alcohol ¾¾¾¾¾ ® No oxidation, No green

H K 2Cr2O 7
orange [Cr +6 ]
(b) Test of alcholic group :

1
R—OH ¾¾
Na
® R—ONa + H
2 2
[effervesence of H2]
R—OH ¾¾¾
PCl5
® R—Cl + POCl3 + HCl ¾¾¾
NH3
® NH4Cl
[White fumes]
R—OH ¾¾¾¾¾¾¾
Cerric ammonium nitrate
® Red colour
(c ) Distinction between CH3 – OH and C2H5OH
CH3OH CH3CH2OH
I2 + NaOH No ppt Yellow ppt of CHI3
Cu/300°C Smell of formalin [HCHO] No smell
E 27
Salicylic acid Smell of oil of wintergreen No smell
Synthesis of oil of wintergreen and other related reactions are as following :
OH
CH3OH COOH3 Methyl salicylate
(Oil of wintergreen)
OH
OH
COOH
COOPh Phenyl salicylate
Ph—OH Salol (Internal antiseptic)
Salicylic
acid
KEY POINT
1. Alcohols are very weak acids (somewhat weaker than water) but may loose H+ from the OH group if
sodium or a sufficiently strong base is present
2. Phenol is more acidic than alcohols and H+ may be removed with sodium hydroxide solution. It is
less acidic than carboxylic acids.
3. Normally an alcohol cannot be directly reduced to an alkane in one step. The –OH group is a poor
leaving group so hydride displacement is not a good option - however the hydroxyl group is easily
converted into other groups that are superior leaving groups, and allow reactions to proceed.
4. The -OH is a poor leaving group, but –OH2+ is an excellent leaving group, and once the –OH is
protonated, the molecule may take part in a variety of substitution and/or elimination reactions.
5. The ZnCl2 coordinates to the hydroxyl oxygen, and this generates a far superior leaving group.

Ex.27 Give structures of the products you would expect when each of the following alcohol reacts with
(a) HCl-ZnCl2 (b) HBr and (c) SOCl2.
(i) Butan-1-ol (ii) 2-Methylbutan-2-ol
Ex.28 Predict the major product of acid catalysed dehydration of
(i) l-methylcyclohexanol and
(ii) butan-1-ol
Ex.29 Give equations of the following reactions :
(i) Oxidation of propan-1-ol with KMnO4 solution.
(ii) Bromine is CS2 with phenol.
(iii) Dilute HNO3 with phenol.
Ex.30 When 3-methylbutan-2-ol is treated with HBr, the following reaction takes place :
Br
HBr
CH3–CH–CH–CH3 CH3–C–CH2–CH3
CH3 OH CH3
Give a mechanism for this reaction.
28 E
Chemistry
ETHER
R—O—R (Dialkyl ether), alkoxy alkane. It's General formula is CnH2n + 2O.
CH3—O—CH2CH3 (Methoxy ethane) or ethyl methyl ether or 2–oxa butane
Ether is monoalkyl derivative of R–OH and dialkyl derivative of H2O
-H -2H
R—OH ¾¾¾
+R ® R—O—R ¬¾¾¾
+2R
H—O—H
Classification : They may be classified as :
(a) Simple or symmetrical ether. e.g. R–O–R
(b) Mixed or unsymmetrical ether e.g. R–O–R'
Structure :
The molecule of ether is bent due to lone pair of electron on
: O : sp 3 hybridized
oxygen atom- bond electron repulsion. The bond angle is 1100.
It is greater than that of water 1050 due to the repulsion between bond s s bond
110°
bulky alkyl groups.
R R
Due to bent structure, it posses dipole moment and hence are polar
molecules.
GENERAL METHODS OF PREPARATION :
(A) From alkyl halides :
(i) By Williamson's synthesis :
R—X + Na—O—R ¾¾® R—O—R + NaX [ SN2 Reaction]
Ex.31 CH3—I + C2H5 O– Na+ ¾¾® CH3—CH2O—CH3 + NaI
Mechanism : [ SN2 Reaction]
Å Å
C2H5O Na C2H5O + Na
H H H H
S low Fast
C 2H 5 O C— I C 2 H 5 O ------ C ----- I C 2 H 5 —O —C H 3 + I
H H
Å
Na + I N aI
CH3 CH2
Ex.32 CH3 C Cl + CH3ONa ¾¾® H3C C

CH3 CH3
CH3 CH 3
Ex.33 CH 3 C ONa + CH 3 CH2 Cl D
¾¾® CH 3 C O CH2 CH 3
CH3 CH 3
E 29
Ex.34 CH2 CH—Cl + CH3CH2—ONa ¾¾® No reaction
[Stable by Resonance]
(ii) Reaction with Dry Ag2O :
2RX + Ag2O D
¾¾® R—O—R + 2AgX
Ex.35 2CH3—CH2—Cl + Ag2O ¾¾®

D CH3CH2OCH2CH3 + 2AgCl
(B) From R–OH:
(i) By dehydration : R—OH ¾¾¾¾®

Con. H 2SO 4
D
?
250°C 140°C
CH 3 CH 2 O CH 2CH 3 CH 3 CH 2 O CH 2 CH 3
Al2 O 3 conc. H 2 SO 4 (Williamson's synthesis)
¬ ¾ ¾ ¾ CH 3 CH 2 OH ¾ ¾ ¾ ¾ ®
350°C 170°C
CH 2 CH 2 CH 2 CH 2
(Elimination)
(ii) Reaction with CH2N2 (diazomethane) :

D
R—OH + CH2—N2 ¾¾¾
BF
® R—O—CH2—H + N2
3
PHYSICAL PROPERTIES :
(i) CH3OCH3 , CH3OCH2CH3 are gases and higher are volatile liquids.

(ii) Ether are less polar [m=1.18D].
(iii) Ethers are less soluble in H2O.
(iv) Ethers have less BP then corresponding alcohol.
Ex.36 Ethers are less soluble in H2O . Why ?
Sol. Reason : Due to less polar, it forms weaker H–Bonding with H2O.
Ex.37 Ethers have less BP then corresponding alcohol. Why ?
Sol. Reason : No H–Bonding in ether molecules.
CHEMICAL PROPERTIES :
Ethers are less polar so less reactive and do not react with active metals [Na,K], cold dil. acid,
oxidising and reducing agent.
Reason : They do not have any active functional group.
1. Basic nature : Due to presence of l.p on oxygen atom ether behave as lewis base
Ethers react with cold conc. acid and form oxonium ion
.. c o ld ; co nc. H C l Å
Ex.38 C 2 H 5 O..C 2 H 5 ¾¾¾¾¾¾® C 2 H 5 O C 2 H 5 C l 1 (diethyl oxonium chloride)
H
30 E
Chemistry
.. co ld ; co nc. Å
C 2 H 5 ¾¾¾¾®
1
Ex.39 C 2H 5 O
.. H SO
2 4
C 2H 5 O C 2 H 5 H S O 4 (diethyl oxonium hydrogen sulphate)
H
Ether form dative bond with Lewis acids like BF3, AlCl3, RMgX etc.
R R
..
O..
R .. F
O: B F R Mg X [Ether is used as solvent] for Grignard reagent.
R F ..
O..
R R
2. Halogenation :
C l 2 /da rk
C H 3C H O CH CH3
Cl Cl
C H 3C H 2 O C H 2C H 3
a,a' – D ichlo ro diethy l e the r
1 0 C l 2 ligh t
C 2 C l5 O C 2 C l5 + 10 H C l
Perchloro d iethyl ether
3. Formation of peroxides : Ether add up atmospheric oxygen or ozonised oxygen. It is explained

by Free radical mechanism as intermediates is free radical.
O2 (nonpolar )
C2H5—O—C2H5 ¾¾¾¾¾¾
Long contact ® C H 3C H 2 O CHCH3
(Non polar) sunlight or UV O O H

.. .. ..
C 2 H 5 O..C 2 H 5 + O .. ¾¾® C 2 H 5 O..C 2 H 5 or (C 2 H 5 ) 2 O ¾® O
..¯
:O .. :
O2 ·
CH3CH2—O—CH2—Ph ¾¾¾¾¾
long contact
¾
® CH —CH —O— CH —Ph ¾¾¾
3 2
O2
® CH3 CH2 O CH Ph
stable by resonance O O H
Peroxides are unstable and explosive.
Test for peroxides

ether (peroxide) ¾¾¾¾¾
FeSO4 / KCNS
® Red colour
ether (Peroxides) + Fe +2 ® Fe +3 ¾¾¾
CNS
® Fe(CNS)3
(Red)
hot dil
4. Reaction with hot dil. H2SO4 : R—O—R ¾¾¾¾
H2 SO4
® 2R—OH
E 31
5. Reaction with hot conc. H2SO4 : R—O—R ¾¾¾¾¾¾¾
hot conc. H2 SO 4
® 2RHSO4
cold dil.
No Reaction
cold conc.
Oxonium salt
H2SO4
CH3 CH2 O CH2 CH3
hot dil.
Ethyl alcohol
hot conc.
Ethyl hydrogen sulphate
6. Reaction with PCl5 : ROR + PCl5 heat
¾¾¾ ® 2RCl + POCl3
7. Reaction with BCl3 : 3ROR + BCl3 ¾¾® 3RCl + (RO)3B
AlCl3
8. Reaction with RCOCl : ROR + RCOCl ¾¾¾¾ ®
ZnCl2 heat RCOOR +RCl
BF / HgO 500 atm
9. Reaction with CO : ROR + CO ¾¾¾¾¾¾¾
3
150°C
® RCOOR
¾
1
10. Reaction with C2H5Na : C H 2 C H 2 O C H 2C H 2 + C 2H 5 ® CH3CH2OH + CH2 CH2+C2H6
H H S tro ng e r
ba se
11. Dehydration : C H 3C H 2 O C H 2C H 3 Al O
¾¾¾® 2 3
2CH2 C H 2 + H 2O
Re d P + HI
12. Reduction : CH3CH2OCH2CH3 ¾¾¾¾¾
heat
® 2CH3CH3
13. Oxidation :
CH3CH2—O—CH2CH3 ¾¾¾¾¾¾
H / K Cr O
® 2CH3CH2OH ¾¾¾
+
[O]
® 2CH3CHO ¾¾¾
2 2 7 [O]
® 2CH3COOH
14. Combustion : C2H5OC2H5 + 6O2 ¾¾® 4CO2 + 5H2O
(explosive mixture)

15. Reaction with HX : Reactivity of HX HI > HBr > HCl
Reaction with cold conc. HX :
Ethers forms oxonium salt with cold and conc. HCl (less reactive)
Cold conc. HI and HBr (more reactive) break C–O bond.
CH3
C H 3 ¾¾¾¾¾ ® ?
Cold and conc.
Ex.39 CH3 C O CH 2 HI
CH3
Sol. Mechanism
CH3 CH3 CH3
..
CH3 C O CH2CH3 H+ CH3 C O
Å
CH2CH3 ¾¾® CH3
Å
..
CH3 CH3 H CH3
(Oxonium ion)
CH3 I1
CH3 C I + CH3CH2OH
CH3
Å Å Å
u If oxonium ion gives more stable carbocation [ Ph CH2, CH2 CH— C H2, (CH3)3 C ] then SN1
reaction occurs.
Å Å Å
u If oxonium ion gives less stable carbocation [P h , CH2 C H, CH3 C H2] then SN2 reaction occurs,
and X attacks at less hindered carbon.
32 E
Chemistry
Cold con.
Ex.40 CH3CH2—O—CH2Ph ¾¾¾¾HI ¾ ® CH3CH2—OH + PhCH2—I, write mechanism of given reaction.
Sol. Mechanism :
.. HÅ Å
C H 3 C H 2 O..C H 2 Ph C H 3C H 2 O C H 2P h CH3CH2OH
H
Å
+ Ph CH2 ¾¾® PhCH2I + CH3CH2–OH
1
I
anhy.HI
Ex.41 CH3CH2—O—CH3 ¾¾¾¾ ®?
.. HI Å I1
Sol. CH3CH2 O CH3CH2 O CH3 CH3I + CH3CH2OH
.. CH3
H
Oxonium ion gives less stable carbocation
SN2 reaction I attacks at less hinderd carbon.
(aq.)HBr
Ex.42 CH3—CH2—O—Ph ¾¾¾¾ ® ?
¾
.. Å
Sol. Mechanism : CH3 CH2 O H+ Br 1
.. Ph ¾¾® CH3 CH2 O Ph ¾¾® CH3CH2Br + PhOH
H
u If excess of HI is used then two moles of alkyl hallides are formed.

u CH3CH2—O—CH2Ph ¾¾¾
HI
® CH3CH2OH+PhCH2I ¾¾¾
HI
® CH3CH2 — I + PhCH2 — I
(B) Reaction with hot and conc. HX :
CH3CH2—O—CH3 ¾¾¾¾¾¾¾
hot and conc HI
® CH3CH2—I + CH3—I
Ex.43 C2H5—O—C2H5 ¾¾¾¾¾¾¾
hot and conc. HBr
¾
® ?+?
Sol. C2H5—Br + C2H5 — Br
USES OF ETHER :
(i) General anaesthetics agent.
(ii) Refrigerant a mixture of ether and dry ice gives temperature as low –60°C.
(iii) Solvent for oil, fats, resins, Grignard reagent.
(iv) For providing inert & moist free medium to organic reaction example : Wurtz reactions.
(v) In perfumery.
(vi) Mixture of alcohol and ether is used as a substitute of petrol. Trade name "Natalite"
(vii) Halothane (CF3CHClBr) used as an anaesthetic because it produces unconsciousness without
affecting lung and heat.
E 33
EPOXIDES :
Preparation of Epoxides :
(i) Epoxidation of alkenes by reaction with peroxy acids
(ii) Base-promoted ring closure of vicinal halohydrins
(iii) Epoxidation of alkenes by reaction with peroxy acids
u Epoxidation of alkenes by reaction with peroxy acids :
O O
C =C + R– C – O O H C —C + R– C – O H
O
Peroxy acid E poxide
Ex.44
O O
(a) C H 2 = C H – ( C H 2 )9 – C H 3 + C H 3 – C – CO O H C H 2 – C H (C H 2 ) 9 C H 3 + C H 3 –C –O H
O
O O
(b) + C H 3 – C– O O H O + C H 3 – C –O H
(c) Epoxidation is a stereospecific syn addition :
C6H5 O O
H C 6H 5 H
C =C + C H 3 – C –O O H + C H 3 – C –O H
H C 6H 5

H O C 6H 5
(E ) -1,2 -diphenyl e then e trans -2 ,3-diphe nyl oxira n e
Mechanism :
H
O C O O O
C
CH 3 –C O CH 3 –C H + C C
C CH 3 –C O
O
O C O Epoxide
transition state
u Base-promoted ring closure of vicinal halohydrins :
–
HO
R2C = CR2 ¾¾¾
x2
H o
® R 2C––CR 2 R 2C–––CR 2
2
O
HO X
Vicinal halohydrin Epoxide
Mechanism :
R X R X
R C––C R R C––C R + HO—H
Step I O
.. –O
..
..
R
..
..
.. – R
HO
.. H
34 E
Chemistry
R X R R
Step II –
..
R C C R R C––C R + X
..
..
..
–O
.. O
..
..
R
..
..
Ex.45
H H
OH
Na O H
O
(i)
OH
Br H
tra n s -2 -b ro m o c yclohex a n ol 1, 2-epoxycyclohexane
H 3C Br
H 3C
H H
H 3C H
Br2 /H 2 O inversion of
Anti addition configuration H 3C O
(ii) H 3C H 3C H H
H
OH
cis-2-butane cis-2, 3-epoxybutane
H Br
H
CH3
H CH3
Br2/H2O
CH3
inversion of
Anti addition configuration H 3C
(iii) H3C H3C H H
H
OH O
trans-2-butane trans-2, 3-epoxybutane
u Reaction of Epoxides :
u With Grignard reagent :
RMgX + H2C––CH2 (1) diethylether
¾¾¾¾¾ ® RCH2CH2OH (primary alcohol)
¾
(2) H O+
3
(i) diethylether
CH 2 MgCl + H 2 C––CH 2 + CH 2 CH 2 CH 2 OH
(ii) H 3O
O
Benzyl magnesium Ethylene 3-phenyl-1-propanol
chloride oxide
u Nucleophilic ring opening reactions of epoxides :
Y Y
Y: – + R 2C– –––CR 2 R 2C– ––CR 2 ¾¾¾

H2O
® R 2C– ––CR 2
O O OH
..
..
..
..
..
..
H2C–––CH2 ¾¾¾¾¾¾
KSCH 2 CH 2 CH 2 CH 3
ethanol water , 0° C
¾
® CH3––CH2CH2––CH2SCH2CH2OH
O
2-(butylthio) ethanol
E 35
Note : Nucleophilic ring opening reactions of epoxides is the characteristic feature of SN2 reaction.
H OCH 2CH 3
NaOCH2CH 3 H
(i) O ¾¾¾¾¾
CH3 CH2OH
®
H
H OH
CH3
H 3C H
H OH
H NH3 /H 2 O
O H 2N
H 3C H
CH3
H 3C CH3 C H 3O CH3
NaOCH 3
(ii) C – – –– C ¾¾¾¾® C H 3 – – C H –– C – – C H 3
CH3OH
H O CH3 OH
u Nucleophilic ring opening of epoxides :
C6H5MgBr + H 2C –––CH CH 3 ¾¾¾¾¾ ® C 6H 5CH 2CH– –CH 3

1, diethyl ether
2, H3O +
O OH
R R
R R
.. – ..

O.. O.. H
..
–
Y: d– .. d– Y
Y O Y
O ..
ep oxid e tra nsit ion state alkoxide b-s ubstitute d alcoh ol
CH 2–––CH(CH 2) 7CH 3 ¾¾¾¾®

1. LiAlH4
CH 3 – –CH––(CH 2) 7CH 3
2, H2 O
O OH
(i) H 2C –––CH 2 ¾¾¾

HBr
® BrCH CH OH
10°C 2 2
CH3 CH2OH
(ii) H 2C –––CH 2 ¾¾¾¾¾ ® CH3–CH2OCH2CH2OH
H2SO4 , 25° C
(iii) H 2C –––CH 2 + H2O ¾¾¾®

H O HOCH2CH2OH 3
+
Mechanism
+ H ..
H 2 C – –– C H 2 + H —O : H 2C – – – C H 2 + H 2O :
Step-1 :
H :O +
:O :
H
36 E
Chemistry
H 2 C – – –C H 2
H .. H
Slow +
:O : + O+ H —O.. ..
..
Step-2 : H C H 2 – C H 2 – O..– H
H
+ H
H —O .. .. ..
..
H C H 2 – C H 2 – O..–H H +
Step-3 : :O : + O —H + H O C..H 2 C H 2 O H..
..
H H
H
Ex.46 H
OH
HBr
O
H
H Br
1,2-Epoxycyclohexane trans -2-bromo cyclohexanol
H 3C CH 3 OCH3
C – – –C CH 3OH
¾¾¾¾ ® C H 3 – – C H –– C – – C H 3
H2 SO 4
H O CH3 HO CH3
2,2,3-trimethyl oxirane 3-methoxy-3-methyl-2-butanol
Problems :
Ex.47 Which of the following is an appropriate set of reactants for the preparation of
ether and why ?

Br ONa
(i) + CH3ONa (ii) + CH3Br
Ex.48 Write the equation of the reaction of hydrogen iodide with :

(i) 1-propoxypropane (ii) Methoxybenezene and
(iii) Benzyl ethyl ether
Ex.49 Explain the fact that in aryl alkyl ethers
(i) The alkoxy group activates the benzene ring towards electrophilic substitution and
(ii) It directs the incoming substituents to ortho and para positions in benzene ring.
Ex.50 Explain the following with an example.
(i) Williamson ether synth (ii) Unsymmetrical
E 37
FLOW CHART FOR ALCOHOL
R +
H2O, LAH, SBH, DiBAL–H,Na/EtOH H /D
C O R–CH= CH2
Grignard, MPV, H2Pt,B 2H6, Na, Liq,NH3
R/H pinacole –
C C
LAH, Grignard, H2/Pt(D) pinacolone O
R-COOH +
R'
R–CH=CH–R' H
dil H2SO 4 C
R–CH CH–R PCl3 R–CH2 OR
OMDM R–Cl
R–CH CH–R PCl5
R–Cl
HBO SOCl2
R–CH CH–R R–Cl (SN1)
Lucas
R–Cl
SOCl 2/Pyridine
R–Cl (SN2)
hydrohysis
R – C – O – R' ALCOHOL NBS
R–CHO/(1°/2°)
R
O Aq. KOH C O
R–X Grignard R
LAH, grignard, DiBAL–H R–OMgX (acid base)
R –COOR Red P/HI
B 2H6, Na/EtOH R–CH2–H
LAH, SBH, Grignard R– COOH R–C–O–R (esterification)
R– C – X
Å
H , K2Cr2O7 O
O R–COOH
Bayer Reagent
R – CH = CH R Jones R–COOH
m-CPBA, H2OÅ
R – CH = CH R O
OsO4 PCC
C
R – CH = CH R

SeO2 PDC
O
R – CH = CH R C
AlK H2O2 Cu/D O
R – CH = CH R C
Ag2O O
Collin/sarett
Conc. NaOH C
HCHO
Cannizaro HÅ, KMnO4
RCOOH
TSCl/DMSO
R–CHO/Ketone (1°/2°)
R'–C–O–C–R' O
O O R–O–C–R'
Anhydride ester
Acylation
R–C–O–R'
O
Haloform
CHX3
openaur oxidation
C O (Only for 2°)
MnO2 O (Allylic only)

R
38 E
Chemistry
FLOW CHART FOR ETHERS
RONa/Williamson ether synthesis

R X Cold HI
OMDM/CH3OH R OH + RI (ether cleavage)
C C hot HI excess
ROH, H
+ R I+R I (ether cleavage)
Alkene dil H2SO4
R OH (hydrolysis)
(i) NaOH
PhOH
(ii) Me2SO4 ETHER R Cl
PCl5
413K, H2SO4
ROH O2 O
m – CPBA hn
Alkene O
H
O
E 39

Alcohol Ether

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Alcohol Ether

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Chemistry

ALCOHOL & ETHERS

Aliphatic hydroxy derivatives Aromatic hydroxy derivatives

(I) Aliphatic hydroxy derivatives :

(II) Aromatic hydroxy derivatives :

(a) Classification according to number of —OH groups :

(ii) Dihydric [two –OH] ¾¾¾¾® OH OH

(iv) Polyhydric [n –OH] ¾¾¾¾® (CHOH)4

(b) Classification according to nature of carbon :

Alcohols are bent molecules. The carbon atom (linked with

and two co ntaining two electrons each . Orbitals

Ex.1 Classify the following as primary, secondary and tertiary alcohols :

(i) CH3–C–CH2–OH (ii) H2C = CH – CH2OH (iii) CH3–CH2–CH2–OH

GENERAL METHODS OF PREPARATION

D:\TEACHING NOTES-2016-17\CHEMISTRY\OC\FINAL\ALOCOHAL & EITHER\1. ALOCOHAL & EITHER.p65

(ii) By hydroboration oxidation : OH

CH3—CH CH2 ¾¾¾¾¾

CH3—CH2—Cl or Moist Ag2O CH3CH2—OH

(3) From ethers :

CH3 C CH3 ¾¾¾

LiAlH4 ® Li+ + AlH4–

CH3—CH CH—CHO ¾¾¾

Ph—CH CH—CHO ¾¾¾

D:\TEACHING NOTES-2016-17\CHEMISTRY\OC\FINAL\ALOCOHAL & EITHER\1. ALOCOHAL & EITHER.p65

Group Product LAH in NaBH4 B2H6 H2 /

>C = C< >CH – CH< – – + +

Name Reagent Function

Bouvoult Blank Reduction Na / EtOH R–COO–R RCH2OH +ROH

Transfer Hydrogenation N2H4 / H2O2 C=C C—C

D:\TEACHING NOTES-2016-17\CHEMISTRY\OC\FINAL\ALOCOHAL & EITHER\1. ALOCOHAL & EITHER.p65

Rosenmund Reduction H2, Pd–BaSO4 R—C—Cl R—C—H

Note : (i) Hydrolysis of ester can be catalysed by acid/base.

(v) For hydrolysis of ester following mechanisms are possible

(a) BAC2 (Base catalysed bimolecular acyl-oxygen bond cleavage mechanism)

Examples based on above reactions :

D:\TEACHING NOTES-2016-17\CHEMISTRY\OC\FINAL\ALOCOHAL & EITHER\1. ALOCOHAL & EITHER.p65

Sterically hindered group gives BAL2

(8) From primary amines :

NaNO2 + HCl ® H – O – N = O+ NaCl

D:\TEACHING NOTES-2016-17\CHEMISTRY\OC\FINAL\ALOCOHAL & EITHER\1. ALOCOHAL & EITHER.p65

Example : CH3CH2—NH2 HNO

Ex. CH3CH2CH2—NH2 ¾¾¾¾¾¾

GRIGNARD REAGENT RMgX

(Functional part of a Grignard reagent molecule)

(ii) Alkynyl Grignard reagent : - CH º C – CH2 – MgX (Propargylmagnesium halide)

Alicyclic Grignard reagent : - (Cyclohexylmagnesium halide)

Aromatic Grignard reagent : (Phenylmagnesium halide)

Heterocyclic Aromatic Grignard reagent :- (Pyridine-4-magnesium halide)

(C) Reactions of Grignard reagents

D:\TEACHING NOTES-2016-17\CHEMISTRY\OC\FINAL\ALOCOHAL & EITHER\1. ALOCOHAL & EITHER.p65

R – MgX + X¢ -CH2 - CH = CH2 ¾¾® R – CH2 – CH = CH2 + MgXX¢

(c) Synthesis of higher alkynes

(d) Synthesis of other organometallics

2R – MgCl + CdCl2 ¾¾® R - Cd - R + 2MgCl 2

4R – MgCl + SnCl4 ¾¾® R 4 Sn + 4MgCl 2

D:\TEACHING NOTES-2016-17\CHEMISTRY\OC\FINAL\ALOCOHAL & EITHER\1. ALOCOHAL & EITHER.p65

(g) Synthesis of Ketones

eg. R – MgX + EtO - C - R¢ ¾¾® R - C - R¢ + EtO – MgX

Ex.17 CH3 C OH + H

CH2 C O + R—OH ¾¾® C H 2 C OH

CH2 C O + C2H5—OH ¾¾® C H 2 C