Theory PDF

ALCOHOLS & ETHERS Page # 3
ALCOHOL
Introduction
O O
H
H H C H
104.5º 108.9º
water H
H
methyl alcohol
Physical Properties
(1) Boiling point :
(a) Alcohols show increase in boiling point with increase in molecular weight amongst homologues.
(b) Alcohols have higher boiling point than hydrocarbons of the same molecular weight. The reason
for higher boiling point is the intermolecular H-bonding present in alcohols.
H–O H–O H–O
R R R
Intermolecular H bonds in alcohol
(2) Solubility in water :
As molecular weight increases solubility in water decreases. The lower alcohols are miscible with water.
This is due to intermolecular hydrogen bonding between alcohol and water molecules.
H–O H–O H–O H–O
H R H R
Intermolecular H bond between water & alcohol molecules
Preparation of alcohols
(1) From alkenes
(a) By acid catalyzed hydration of alkenes : Formation of carbocation intermediate (Markovnikov
addition, rearrangement possible)
conc.H SO 2 4 Boiling H O
General reacion R–CH=CH2     R–CH–CH3    2
 R–CH–CH3
Markonikof f 's addition
Alkene
OSO3H OH
Alcohol
  Boiling H 2O
H HSO4
e.g. CH3–CH=CH 2 CH3–CH–CH3 CH 3–CH–CH 3
OSO 3H
H2SO4+CH 3–CH–CH 3
OH
(b) By Oxymercuration - demercuration process :

(1) Oxymercuration involves an electrophilic attack on the double bond by the positively charged
mercury species. The product is a mercurinium ion, an organometallic cation containing a
three-membered ring.
(2) In the second step, water from the solvent attacks the mercurinium ion to give (after
deprotonation) an organomercurial alcohol.
(3) The third step is demercuration to remove the Hg. Sodium borohydride (NaBH4, a reducing
agent) re-places the mercuric acetate fragment with hydrogen.
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Page # 4 ALCOHOLS & ETHERS
General reaction
H H
 O 
H H   THF
C=C + H2O + Hg   R–C—C–H + CH 3COOH
R H  O  C  CH3 2 O
OH Hg–(O–C–CH 3)
H H H H O
R–C— C–H + OH + NaBH4 R–C— C–H + Hg + CH3–C–O

O
OH Hg–(O–C–CH3) OH H

Hg(OAc )  OH
e.g. CH3–CH=CH2 
2
  CH 3–CH–CH2   CH 3–CH–CH3
THF / H O NaBH 4
2
Prop-1-ene OH Hg(OAc) OH
Propan-2-ol
(c) By Hydroboration - oxidation process : (Forms anti-markovnikov alcohol, no rearrangement)
(i) BH .THF 3
General reaction R–Ch=CH2 (   R–CH2–CH2–OH
ii) H O , NaOH
2 2
CH3H
H3 C CH3 (i) BH3 .THF
e.g. C=C    
 H 3C–C—C–CH 3
(ii) H2 O2 , NaOH
H3 C H
H OH
Ex. Give the major product of the following reaction
(a) dil H2SO4
CH3–CH–CH=CH2 (b) (i) Hg(OCOCH 3)2 / H 2O

CH3 (ii) NaBH 4 / OH
3-Methyl-1-butene (c) (i) BH3.THF
(ii)H2O2 / OH
Ans. Major product is
CH3
(a) CH3–C–CH2–CH3 because 3o carbocation is more stable.
OH
CH3
(b) CH3–CH–CH–CH3
OH
CH3
(c) CH3–CH–CH2–CH2–OH
(2) From alkyl halides : By nucleophilic substitution reactions

(a) By SN2 mechanism (second-order substitution) : It is given by primary (and some
secondary) halides
KOH
General reaction : R–CH2–Br  
 R–CH2–OH
H2 O
KOH
e.g. (CH3)2CHCH2CH2–Br  
 (CH3)2CHCH2CH2– OH
H2O
H Br HO H
C KOH
C
e.g. CH3 CH2CH3  
 CH3 CH2CH3
SN2
(S)-2-Bromobutane (R)-2-utanol
100% inverted configuration
(b) By SN1 mechanism : It is given by tertiary and some secondary halides
R' R'
Acetone / water
General reaction : R–C–R"      R–C–R"
Heat
Cl OH
CH3 CH3
acetone / water / heat
e.g. CH3–C–CH3    CH3–C–CH3
SN 1
Cl OH
Tert-butyl chloride Tert-butyl alcohol
(3) From Grignard reagents
(a) From air

A Grignard reagent may be used to synthesize an alcohol by treating it with dry oxygen and decomposing
the product with acid :
O 
2 RMgX H O
General reaction RMgX  RO2MgX   2ROMgX   2ROH 3
O2 C 2H5MgX
H O 
e.g. C2H5MgBr  C2H5O2MgX    2C2H5OMgX   2C2H5OH + MgBr(OH) 3
(b) From ethylene oxide

Addition of Grignard reagent to ethylene oxide gives a primary alcohol (with two carbon atoms added)
CH2 
H O 3
General reaction O + RMgX RCH2CH2OMgX   RCH2CH2OH + MgX(OH)
CH2
CH 2 
H O 3
e.g. O + C2H5MgBr C2H5CH2CH2OMgX   C 2H 5CH 2CH 2OH + MgBr(OH)
CH 2 Butyl alchohol
MgBr
O CH2CHOH
(1) CH2–CH–CH3
Cyclohexylmagnesium bromide 
CH3
(2) H3O
(c) From carbonyl compounds : Nucleophilic addition to the carbonyl groups by Grignard reagent
O O MgX OH

H3O
General reaction –C– + R – MgX   –C–
ether   —C— + Mg(OH)X
R R
adduct
(i) Addition of formaldehyde gives a primary alcohol

H Ether
H OMgX H O 
3
General reaction C = O + RMgX   C   RCH2–OH
H H R
(ii) Addition to an aldehyde (other than formaldehyde) gives a secondary alcohol

O
Ether
R OMgX H O  R OH
3
General reaction R–C–H + R'MgX   C   C
H R' H R'
(sec-alcohol)
O H
(1) ether solvent
e.g. MgBr + CH3–C–H      —C—OH
(2) H3O 
acetaldehyde CH3
Phenylmagnesium bromide
1-phenylethanol
(iii) Addition to a ketone gives a tertiary alcohol
R
R (1) ether
General reaction C=O + RMgX    R–C–OH + MgX(OH)
(2) H3O 
R'
R
ketone
O OH
(1) ether
e.g. CH3CH2MgCl +    CH2CH3
(2) H3O 
Cyclohexanone 1-Ethylcyclohexanol
(iv) Addition to an acid halide or an ester gives a tertiary alcohol

Esters on treatment with Grignard ragent first form ketones which then react with second
molecule of Grignard reagent and form tertiary alcohol.
General reaction
O O MgX O
OR'
R–C– OR+ RMgX R–C–OR R–C–R+ Mg
X
R
R
R H2O / H
C=O + R MgX   
 R–C–R
R
OH
tertiaryalcohol

O O MgX O
R–C–X + RMgX R–C–X R–C–R+ MgX2 OH
RMgX X
R R–C–R+ Mg
OH
R'
(4) By reduction of carbonyl compounds

(a) Catalytic hydrogenation of aldehydes and ketones
General reaction H2 / Ni
R–CHO   R–CH2OH
o
Aldehyde 1 Alcohol
H2 / Ni
R2C=O   R2CH–OH
o
Ketone 2 Alcohol
H / Ni 2
e.g. CH3CHO + 2H   CH3CH2OH
Ni
CH2=CHCHO + 4H   CH3CH2CH2OH
Catalyst
(Acrolein)
O H
Ni OH
+ 4H 
(b) Lithium aluminium hydride reduction of aldehydes and ketones

LiAlH4
General reaction (i) R–CHO   R–CH2OH
o
Aldehyde 1 Alcohol
LiAlH4
R2C=O  R2CH–OH
(ii) 
o
Ketone 2 Alcohol
LiAlH 4
(iii) RCOOH + 4H   RCH2OH + H2O
LiAlH 4
(iv) R–C–Cl + 4H   RCH2OH + HCl
O
LiAlH 4
(v) R–C–O–R'   R–CH2OH + R’OH
O
O
LiAlH 4
e.g. CH3–C–O–H   CH3CH2OH
O
C 2H5–C–Cl + 4H C2H5CH2OH + HCl
(c) By NaBH4 (sodium borohydride) : It is insoluble in ether and is used in aqueous ethanolic
solution to reduce carbonyl compounds. It does not reduce esters and acids.
O
NaBH4
R–C–H    R–CH2–OH
O
NaBH 4
e.g. C–H   CH2OH
benzaidehyde benzyl alcohol

NaBH 4
CH3 CH=CHCHO + 4H   CH3CH=CHCH2OH
(ii) Reduction of a ketone gives a secondary alcohol

O H
NaBH4 OH
 
Cyclohexanone Cyclohexanol
(d) Bouveault-Blanc reduction : The reduction of aldehydes, ketones or esters by means of excess
of sodium and ethanol or n-butanol as the reducing agent.
General reaction
Na
(i) Aldehyde RCHO   RCH OH
EtOH 2
Na
(ii) Esters R’CO2R’’   R’CH OH + R’’OH
EtOH 2
Na
(iii) Ketones R2CO   R CHOH
EtOH 2
The Bouveault-Blanc reduction is believed to occur in steps involving transfer of one electron at a
time.
Mechanism
Na •• EtOH Na
R–C–OEt  RC–OEt RCH–OEt R–CH–OEt
O O• O• O
EtOH Na EtOH •• Na
RCH2OH O RCH2–O RCH2–O• RC–O• RCH=O+OEt
Na
e.g. CH3CHO + 2H  CH3CH2OH
EtOH
Na
CH3COOC2H5 + 4H  2CH3CH2OH
EtOH
CH3
Na
CH3–C–CH3+2H  CH–OH
EtOH
CH3
O
Ex. Identify (X) in the following reaction

O
LiAlH4
CH3–CH–CH2–CH   X
OH
Ans. X=CH3–CH–CH2–CH2–OH
OH
Ex. What are the product A, B, C, D and E in the following reactions?

O NaBH4
O O B
OEt LiAlH4 CH4OH
  A
LiAlH4
O C
O
O
OEt NaBH4 NaBH4
  D   E
CH3OH CH3OH
O O
OH
Ans. A: OH + (EtOH)
O O
B: Ester part is not affected by NaBH4
OH
OH OH
C: Ester part and keto parts are affected by LiAlH4
OH
O
OEt
D:
O
E:
OH
(5) By reaction of nitrous acid on aliphatic primary amines

NaNO2 / HCl
General reaction R–NH2+HONO    R–OH + N2 + H2O
Mech.
HNO2
R–NH2   (R N2 )   ROH+ N2+ H
H2O
e.g. (i) C2H5NH2 + HNO2 C2H5OH + N2 + H2O

CH3 CH3
NaNO2 / HCl
(ii) CH3–CH2– C–CH3 + HONO    
 CH3–CH2– C–CH3 + N2+H2O
NH2 OH
Mech.
CH3 CH3 CH 3
HONO H2O
CH3–CH2– C–CH3   CH3–CH2– C–CH3    CH3–CH2– C–CH3

NH2 OH
(6) Hydroxylation : Forms vicinal diols (glycols)

Converting an alkene to a glycol requires adding a hydroxy group to each end of the double bond. This
addition is called hydroxylation of the double bond.
(a) Syn hydroxylation, using KMnO4 / NaOH or using OsO4/H2O2
General reaction :
OsO4,H2O2
C=C –C=C–
or KMnO4,OH
(cold, dilute) HO OH
H CH2CH3
CH2CH3
C
KMnO4 H OH
e.g.   
C cold
( dilute) H OH
H CH2CH3 CH2CH3
cis-3-hexene
H
OH
OsO4 / H2O2
   

OH
Cyclopentene H
cis-Cyclopentane-1, 2-diol
(b) Anti hydroxylation, using per acids
H

OH
RCOOH, H
  
H2O
Cyclopentene H
OH
trans-Cyclopentane-1, 2-diol
Chemical reactions of alcohols

1. Reaction with hydrogen halides
General reaction :
R – OH + HX R – X + H2O (R may rearrange)
Reactivity of HX : Hl > HBr > HCl
Reactivity of ROH: allyl, benzyl > 3o > 2o > 1o
  
Mechanism H
R – OH   R–
– OH2 X R–X
–X
R
cons. HBr
e.g. CH3CHCH3 CH3CHCH3
or NaBr,H2SO4
OH reflux Br
Isopropyl alcohol Isopropyl bromide
HCl, (anhydrous) ZnCl2

Lucas reagent
e.g. CH3CH2CH2CH2CH2OH CH3CH2CH2CH2CH2Cl
heat n-Pentyl chloride
n-Pentyl alcohol
CH3 CH3
conc. HCl
e.g. CH3–C–CH3    CH3–C–CH3
room temp.
OH Cl
tert- Butyl alcohol tert-Butyl chloride
2. Reaction with Phosphorus trihalides

(1) Several phosphorus halides are useful for converting alcohols to alkyl halides. PBr3, PCl3, & PCl5
work well and are commercially available.
(2) Phosphorus halides produce good yields of most primary and secondary alkyl halides, but none
works well with ter. alcohols. The two phosphorus halides used most often are PBr3 and the
P4 / I2 combination.
General reaction :
(PX3  PCl3 , PBr3 , Pl3 )
3R – OH + PX3       3R – X + H3PO3
Mechanism
The mechanism for the reaction involves attach of the alcohol group on the phosphorus atom, displacing
a bromide ion and forming a protonated alkyl dibromophosphite (see following reaction).

•• •• •• 
••
••
RCH2OH + X – P –X 
 R–CH 2O–PX2 + X
••
••
X H
Protonated
alkyl dibromophosphite
In second step a bromide ion acts as nucleophile to displace HOPBr2, a good leaving group due to the
electronegative atoms bonded to the phosphorus.

••
••
X + RCH2 – OPX2 
 RCH2X + HOPX2
A good leaving group
CH3 CH 3
PBr3
e.g. CH3CH2CH CH2OH   CH3CH 2CH CH2Br
2–Methyl–1–butanol 2–Methyl–1–bromobutane
P  I2
CH 3CH2OH    CH3CH2I
Ethyl alcohol Ethyl iodide
3. Reaction with thionyl chloride

O
Heat
R–OH+Cl–S–Cl   R–Cl+SO2+HCl
4. Dehydration of alcohols
acid
– C – C –   – C = C – + H2O (Rearrangement may occur)
H OH
Mechanism
CH3 H CH3 H
••   ••
••
••
Step 1 : CH3– C – O –H+H–O CH3– C – O – H + H – O

••
CH3 H CH3 H
Protonated alcohol
or alkyloxonium ion
CH3 H CH3
 C H
Step 2 : CH3– C – O –H +
••
••
CH3 CH3 O–H

CH3 ••
A carbocation
H CH2
H–C–H H C H

••
Step 3 : C + O–H CH3 CH3 + H –O – H

•• ••
CH3 CH3 2-Methylpropene
Reactivity of ROH : 3º > 2º > 1º
5. Reaction with metals


RO–H+M RO M + ½H2 M=Na, K, Mg, Al, etc
o o o
Reactivity order of ROH: CH3OH > 1 > 2 > 3
Na 
e.g. CH 3CH2OH  CH3CH2O M + ½H2
Ethyl alcohol Sodium ethoxide
CH3 CH3
Al
3
CH3–C–OH  (CH3–C–O)3Al + H2 
2
H H
Isoporpyl alcohol Aluminium Isopropoxide
CH3 CH3

CH3–C–OH CH3–C–O K
K


CH3 CH3
tert–Butyl alcohol Potassium tert-butoxide
6. Ester formation
General reaction
O  O
R–C R'OH H R–C
+ + H2O
OH Alcohol OR'
Acid Ester
O 
O
H
e.g. CH3CH2O – H + CH 3C   CH3C + H2O
OH OC2H5
Acetic acid Ethyl acetate
O H2SO4 O
CH2–CH2–CH2–C + C2H5OH CH2–CH2–CH2–C +H2O
OH reflux OC2H5
Ethyl alcohol
-Phenyl butyric acid (8 moles) Ethyl -phenyl butyrate
(1 mole) (85-88% yield)
7. Oxidation reactions
(a) oxidation of primary alcohols
Oxidation of a primary alcohol initially forms an aldehyde. obtaining the aldehyde is often difficult, since
most oxidizing agents are strong enough to oxidize the adehydes formed. CrO3 acid generally oxidizes a
primary alcohol all the way upto the carboxylic acid
(b) oxidation of secondary aldohols
Sec. alcohols are easily oxidized to give excellent yields of ketones. The chromic acid reagent is often
best for laboratory oxidations of secondary alcohols. The active species in the mixture is probably
chromic acid,

H2CrO4, or the acid chromate ion, HCrO4
(c) Resistance of tertiary alcohols to oxidation

Oxidation of ter-alcohol is not an important reaction is organic chemistry. Ter-alcohols have hydrogen
atoms on the carbinol carbon atom, so oxidation must take place by breaking C–C bonds. These
oxidations require severe conditions and result in mixtures of products.
H
 
C2H5NH CrO3Cl
R–C=O
Primary R–CH2OH An aldehyde
KMnO4
R–COOH
A carboxylic acid
R R

K Cr O7 or CrO3 / H
Secondary R–CHOH 22      R–C = O
A ketone
R
KMnO4
Tertiary R–C–OH     no reaction
H
C5H5NHCrO3Cl
e.g. CH3CH 2CH2OH      CH3CH2C=O
n-Propyl alcohol Propionaldehyde
(1º)
CH3 CH3
KMnO4
CH3CH2CHCH2OH    CH3CH2CHCOOH
2-Methyl-1-butanol 2-Methylbutanoic acid
(1º)

CrO3 / H
CH3CH2CHCH2CH3    CH3CH2CCH2CH3
OH O
3-Pentanol 3-Pentanone
(2º)
OH
CrO3
Ex.   A
H2SO4
acetone
Identify A
OH O
CrO3
Ans.  
H2SO4
acetone
ETHER
Structure of ether
Compound Hybridization Bond angle
O
µ µ µ H H sp3 104.5º
O O O water
H H
O
C 110º C H 104.5º H (CH3)3C 132º C(CH 3)3 R H sp3 108.5º
H Water Di-ter.butyl ether Alcohol
H
H H O
R R
dimethyl ether sp3 111.7º
Ether
Classificaion of Acyclic ethers

S.No. Type Example Name
CH3–O–CH3 Methoxy methane
1 Simple ether
CH3–CH2–O–CH2–CH3 Ethoxy ethane
2 Mixed ether CH3–O–CH2–CH3 Methoxy ethane
IUPAC Nomenclature of ether “Alkoxy Alkane”

S.N. Compound IUPAC Name
1. CH3–CH–O–CH3 2-Methoxy propane
CH3
2. Cl–CH2–O–CH3 Chloromethoxy methane
OCH3
3. Methoxy benzene (Anisole)
CH3 CH3
4. 3-Ethoxy-1, 1-dimethyl cyclohexane

H
OCH2–CH3
Cl
5. H trans-1-Chloro-2-methoxy cyclobutane
OCH3
H
CH2–OH
6. 2-Ethoxy ethan-1-ol
CH2–O–CH2–CH3
Method of Preparation of Ether

(1) Williamson synthesis
General reaction
RX + R – OR’
n–Pr Br
e.g. (i) n-PrOH   CH3CH2CH2O– CH2CH2CH3
Di-n-propyl ether
Na
(ii) MeOH  PhCH2Br
 Me O    CH2–O–CH3
Benzylmethyl ether
Na
(iii) t-BuOH   t-Bu O  EtBr
 t-Butyl ethyl ether
(This reaction produces a poor yield of ether because of the bulkiness of t-BuO–)
2. Williamson’s Continuous Etherification process or by Dehydration of Alcohols

 
(i) ROH + H RO H2
••  S2
 
N
ROH + R – OH2   R2OH + H 2O ROR + H3O
••
  
(ii) ROH + H ROH2 R .... S1N
••  
ROH + R ROR ROR
••
H2SO 4
o CH2=CH2
180 C Ethene
e.g. CH3CH2OH
H2SO 4
o CH3CH2OCH2CH3
140 C Diethyl ethene
Mechanism
H
•• 
Step-1: CH3CH2–O– H + H — OSO3H CH3CH2–O– H + —OSO3H
•• ••
This is an acid-base reaction in which the alcohol accepts a proton from the sulfuric acid
H
•• 
Step-2 : CH 3CH 2–O– H + CH 3CH 2 –O–H
•• ••
Another molecule of the alcohol acts as a nucleophile and attacks the protonated alcohol in an SN2
reaction.
H H H
 ••
••
Step-3 : CH3CH2–O– CH2CH3 + O–H CH3CH2–O–CH2CH3 +H–O–H


•• •• •• ••
Another acid-base reaction converts the protonated ether to an ether by transferring a proton to a
molecule of water (or to another molecule of the alcohol).
Only one combination of alkythalide and alkoxide is appropriate for the preparation of each of the
following ethers by Willianson ether synthesis. What is the correct combination in each case ?
3. Form alkenes
(a) By addition of alcohols in alkenes
When alcohol is added to alkenes in presence of acid, we get ethers.
General reaction
H2SO4
(I) C=C   carbocation
(II) Carbocation + alcohol ether

 
e.g. (I) Me2C = CH2 + H (H2SO4) Me3 C
 
 –H
(II) Me3 C + EtOH Me3C–O–Et   Me3COEt
H
(b) Alkoxymercuration - demercuration
Hg(OAc )2 NaBH4
C=C    –C–C–   – C – C –
ROH
••
AcOHg O –H H OR
••
mercurial ether
e.g.
(i) Hg(OCOCF3 )2
(i) RCH=CH2+R’OH      RCH(OR’)CH3
(ii) NaBH 4
CH3 CH3
(i) Hg(OCOCF3 )2
(ii) CH2=CHCH3+CH3CH(OH)CH3      CH 3–CH–O–CH–CH3
(ii) NaBH 4
CH3 CH3
(i) Hg(OCOCF3 )2
(iii) CH3CH=CHCH3+CH3CH(OH)CH2CH3      CH3–CH2–CH–O–CH–CH2–CH3
(ii) NaBH 4
Reactions of ethers
1. With HX
General reaction

X H H
••   HX
••
R–O–R'
••
+HX R – O – R X–R + O–R'
••
X–R + X–R’
–R’
••
alkyl halide
HBr
e.g. (i) CH3CH2CH2CH3 2CH3–CH2Br
2. Reaction with sulphuric acid

Ethers dissolve in concentrated solutions of strong inorganic acids to from oxonium salts, i.e. ether
behave as bronsted Lowry bases.
conc.H2SO4  

R2O + H2SO4 (R – O – R)HSO4 
  R–OH + R–O–SO 2 OH
alkyl hydrogen
H sulphate
When heated with dilute H2SO4

R2O + H2SO4 
  2ROH
 H O
e.g. C2H5OC2H5 + H2SO4 
  C2H5OH + C2H5OHSO4 2 C2H5OH + H2SO4

3. Autoxidation of ethers :
When ethers are stored in the presence of atmospheric oxygen, they slowly oxidize to produce
hydroperoxides and dialkyl peroxides, both of which are explosive. Such a spontaneous oxidation by
atmospheric oxygen is called an autoxidation.
General reaction
OOH
excess O2
R–O–CH2–R'    R–O–CH–R' + R–O–O–CH2–R'
(Slow)
ether Hydroperoxide dialkl peroxide
OOH
H3C CH3 H3C H3C CH3
excess O2
Ex. (i) C=C    CH–O–C–CH3 + CH–O–O–CH
( weeks or months )
H3C CH3 H3C H3C CH3
CH3 Diisopropyl peroxide
Hydroperoxide
OOH
h
(ii) CH3CH2–O–CH2CH3  CH3–CH–O–CH2CH 3
Diethyl ether 1-Ethoxyethyl hydroperoxide
4. Reaction with acid chlorides and anhydrides

Reagent : ZnCl2, AlCl3 etc.
AlCl3
General reaction (i) R–O–R + R–CO–Cl    R–Cl + RCOOR
Mech.
RCOCl + AlCl3 RCO+ + AlCl4
+  AlCl
R'–O + RCO+ R'–O – COR RCOOR’ + R"  4 R”Cl + AlCl3
R" R"
Anhydous
ZnCl
e.g. C2H5OC2H5 + CH3COCl  2  C2H5Cl + CH3COOC2H5
ZnCl2
(ii) R2O + (CH3CO) 2O   2CH3COOR
acid anhydride
anhydrous
AlCl3
e.g. C2H5OC2H5 + (CH3CO)2O     2CH3COOC2H5
5. Reaction with carbon monoxide :

Ether react with CO at 125-180oC and at a pressure of 500 atm, in the presence of BF3 plus a little
water.
BF3
500 atm
R2O + CO    
 RCOOR
125 180 C
6. Reaction with halogens :

When treated with chlorine or Br, ether undergo substitution, the extent of which depends on the
conditions.
Cl2 Cl2
CH3CH2OCH2CH3 
hv
 CH3CHClOCH2CH3 
hv
 CH3CHClOCHClCH3
in presence of light
Cl2
(C2H5)2O 
hv
 (C2Cl5)2O
Perchloro
diethyl ether
Mech.
The reaction proceeds by a free–radical mechanism, and –substitution occurs readily because of
resonance stabilization of the intermediate radical
•• Cl  •• ••
Cl2
R'O–CH 2R"  R'O–CHR" R'O=CHR   R'O–CHClR" + Cl , etc.

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ALCOHOLS & ETHERS Page # 3

(b) By Oxymercuration - demercuration process :

R–C— C–H + OH + NaBH4 R–C— C–H + Hg + CH3–C–O

Ex. Give the major product of the following reaction

(a) dil H2SO4

CH3–CH–CH=CH2 (b) (i) Hg(OCOCH 3)2 / H 2O

(2) From alkyl halides : By nucleophilic substitution reactions

(3) From Grignard reagents

(a) From air

(b) From ethylene oxide

(i) Addition of formaldehyde gives a primary alcohol

(ii) Addition to an aldehyde (other than formaldehyde) gives a secondary alcohol

(iv) Addition to an acid halide or an ester gives a tertiary alcohol

(4) By reduction of carbonyl compounds

(b) Lithium aluminium hydride reduction of aldehydes and ketones

C 2H5–C–Cl + 4H C2H5CH2OH + HCl

benzaidehyde benzyl alcohol

(ii) Reduction of a ketone gives a secondary alcohol

Ex. Identify (X) in the following reaction

Ex. What are the product A, B, C, D and E in the following reactions?

(5) By reaction of nitrous acid on aliphatic primary amines

e.g. (i) C2H5NH2 + HNO2 C2H5OH + N2 + H2O

(6) Hydroxylation : Forms vicinal diols (glycols)

(b) Anti hydroxylation, using per acids

Chemical reactions of alcohols

HCl, (anhydrous) ZnCl2

2. Reaction with Phosphorus trihalides

A good leaving group

3. Reaction with thionyl chloride

Step 1 : CH3– C – O –H+H–O CH3– C – O – H + H – O

CH3 CH3 O–H

Step 3 : C + O–H CH3 CH3 + H –O – H

5. Reaction with metals

(c) Resistance of tertiary alcohols to oxidation

Compound Hybridization Bond angle

Classificaion of Acyclic ethers

IUPAC Nomenclature of ether “Alkoxy Alkane”

1. CH3–CH–O–CH3 2-Methoxy propane

2. Cl–CH2–O–CH3 Chloromethoxy methane

4. 3-Ethoxy-1, 1-dimethyl cyclohexane

Method of Preparation of Ether

2. Williamson’s Continuous Etherification process or by Dehydration of Alcohols

Step-3 : CH3CH2–O– CH2CH3 + O–H CH3CH2–O–CH2CH3 +H–O–H

(II) Carbocation + alcohol ether

2. Reaction with sulphuric acid

4. Reaction with acid chlorides and anhydrides

5. Reaction with carbon monoxide :

6. Reaction with halogens :

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