Alcohols, Phenols and EthersFunc�onal Group- OHSuffix to be used - olHomologous series- Methanol (CH3OH) Ethanol (C2H5OH) Propanol (C3H7OH) Butanol (C4H9OH) Pentanol (C5H11OH) and so on

Markownikoff addi�on1. Boiling Point- * Higher than other organic compounds having equal molecular masses* The boiling point decreases with an increase in branching in alipha�c carbon chains

The rela�ve ease of dehydra�on of alcohols follows the following order: Ter�ary > Secondary > Primary

* Methanol is a colourless liquid and boils at 337 K* It is highly poisonous in nature

* Ethanol is a colourless liquid with boiling point 351 K* It is used as a solvent in paint industry and in the prepara�on of a number of carbon compounds

2. Solubility- * The hydroxyl group in alcohol is involved in the forma�on of intermolecular hydrogen bonding* The solubility of alcohol in water decreases with the increase in the size of the alkyl group

Preparatory Methods Physical Proper�es

R-OH

Chemical Proper�es

Reac�ons involving cleavage of O-H bond

Some Commercially Important Alcohols

Methanol

Ethanol

Reac�on with Metals

Reac�on with phosphorus trihalides

Dehydra�on

Acidity of Alcohols

Acidity of Alcohols

Esterifica�on

Oxida�on

Dehydrogena�on

Reac�on with hydrogen halides

Alcohols: Weaker acids than water

Esterifica�on

Reac�ons involving cleavage of C–O bond

R-CH=CH2 H2O/H⁺H2O2

B2H6H2O2/H2O

N2/H2Na + C2H5OHH2/PdLiAlH4i) LiAlH4ii) H2O

i) RMgXii) H2O/H⁺

An� markownikoff addi�onR-CH=CH2

R-C-Cl

RCHO

R-COOHR-COO-R’

For the prepara�on of - 10 alcohol – HCHO 20 alcohol – RCHO 30 alcohol –

Structure

Methanol

Cyclohexanol 2-MethylcyclopentanolDihydric alcohols

Monohydric alcoholsC2H5OH

Part - 1

CH2OHCH2OH

Compounds containing Csp3 -OH bond

Compounds containing Csp2 -OH bond

NomenclatureClassifica�on

* Primary, secondary and ter�ary alcohols* Allylic alcohols* Benzylic alcohols

* Vinylic alcohol

Trihydric alcohols

CH2OHCHOHCH2OH

Alcohol

O

R-C-RO

Prepara�on

Proper�es

Prepara�on

Proper�es

H

H

142 pm 96 pm

108.90C

:O:

HH

OHOH

CH3

CH3 - CH2 - CH2 - O:

:

HH

H H

HO

O

O

H H

2R-O-H + 2Na 2R-O-Na+H2Sodiumalkoxide

6 CH3-C-OH + 2Al 2 CH3-C-O Al+3H2Aluminiumtert-butoxide

tert-Butyl alcohol

CH3

CH3

CH3

CH3( )3

SecondaryPrimary Ter�ary

R CH2OH > CHOH >> R C- OHR

RR

R

R-O: + H-O:-H R-O-H + :OH

::

::

::

Acid Conjugateacid

Conjugatebase

Base

R-C-OH + H-O-R R-C-O-R’ + H-O-HAcid Alcohol Ester

O OH⁺⥮

ROH + HX → R-X + H2O

RCH2OH RCHOCu573K

R-CH-R’ R-C-R’Cu573K

OH O

R-C-OH CH3-C=CH2Cu573K

CH3

CH3 CH3

RCH2OH R-C=O R-C=OOxida�on

Aldehyde

RCH2OH RCHOCrO3

CH3-CH=CH-CH2OH CH3-CH=CH-CHOPCC

H OH

Carboxylicacid

R-CH-R’ R-C-R’CrO3OH

Sec- alcohol KetoneO

3CH3-CH2-CH2-OH + PCl3 → 3CH3-CH2-CH2-Cl + H3PO3

C2H5OH CH2=CH2+H2O443KH2SO4

CH3CHCH3 CH3-CH=CH2+H2O440K

85%H3PO4OH

CH3

CH3CH3-C-OH CH3-C-CH3+H2O

358K20%H3PO4 CH2

CO + 2H2 CH3OH200-300 atm

573-673 K

ZnO-Cr2O3

C12H22O11 + H2O C6H12O6 + C6H12O6Invertase

C6H12O6 2C2H5OH + 2CO2Zymase

Glucose Fructose

Compound

CH3-OH

Common name IUPAC name

Methyl alcohol Methanol

CH3-CH2-CH2-OH

CH3-CH2-CH2-CH2-OH

HO-H2C-CH2-OH

CH3-CH2-CH2-CH2-OH

n-Propyl alcohol Propan-1-ol

Isopropyl alcohol Propan-2-ol

n-Butyl alcohol Butan-1-ol

sec-Butyl alcohol Butan-2-ol

Isobutyl alcohol 2-Methylpropan-1-ol

tert-Butyl alcohol 2-Methylpropan-2-ol

CH3-CH-CH3OH

CH2-CH-CH2OHOH OH

CH3-CH-CH2-OHCH3

Ethylene glycol

Glycerol

Ethane-1,2-diol

Propane -1,2,3-triol

CH3-C-OHCH3

CH3

Chemical Proper�es

It is a white crystalline compound that has a dis�nc�ve odour

Alcohols, Phenols and EthersStructure

Monohydric Phenol

Part - 2

NomenclatureClassifica�on

Dihydric Phenol

Trihydric Phenol

Electrophilic aroma�c subs�tu�on Reimer-Tiemann Reac�on

Oxida�on

Reac�on of Phenol with zinc dust

Kolbe’s reac�on

Phenols

1) Nitra�on

2) Halogena�on

OH OH

136 pm

1090

::

OH OHCH3

OHOH

OH

OHOH

OHOH

CH3

OHOH

OH

CH3

OH

OH

OH

CH3

OH

OH

PhenolPhenol

CatecholBenzene-1,2-diol

Hydroquinone or quinolBenzene-1,4-diol

o-Cresol2-Methylphenol

m-Cresol3-Methylphenol

p-Cresol4-Methylphenol

Prepara�on

From Haloarenes

From Benzenesul-phonic acid

From Diazonium salts

From Cumene

OH O-Na+ OH

+NaOH

+N2+HCl

623 K300 atm

HCl

NH2-+

N2Cl OHNaNO2+HCl Warm

H2O

O-Na+ OHOleum (i) NaOH

(ii) H⁺

+CH3COCH3

CH3-CHCH3

CH3-C-O-O-HCH3

OHO2

H2OH⁺

1. Boiling Point- * Phenols have higher boiling points in comparison to other organic compounds having equal molecular masses

2. Solubility- * The hydroxyl groups are responsible for the solubility of phenol in water * The solubility of phenol decreases with the increase in the size of the aryl group

Physical Proper�es

H - O - H - O - H - O -

R - O - H - O - H - O - H - O -H H

R

R

R

O OHH

ORH O

R

OHNO2

OH

NO2

OHDilute HNO3

o-Nitrophenol

+

p-Nitrophenol

OHBr

OH

Br

OHBr2 in CS2

Minor

+

Major

273 K

OH ONa OHCOOHNaOH

2-Hydroxybenzoic acid(salicylic acid)

(i) CO2(iI) H⁺

OHCHCl2

O Na⁺CHCl3 + aq NaOH

Intermediate

benzoquinne

Salicylaldehyde

NaOH CHOO Na⁺

H⁺ CHOOH

OH

OH

+ Zn

H2SO4Na2Cr2O7

+ ZnO

O

O

Phenol

Benzene diazonium chloride

Aniline

Cumene hydroperoxide

Cumene

Chemical Proper�es

Cleavage of C–O bond in ethers

Nitra�on

Friedel-Cra�s reac�on

Halogena�on

Electrophilic subs�tu�on

Alcohols, Phenols and EthersStructure

Symmetrical Ethers

Part - 3

NomenclatureClassifica�on

Unsymmetrical Ethers

1. Miscibility Miscibility with water resembles those of alcohols of the same molecular mass

1. By dehydra�on of alcohol

2. Williamson synthesis

2. Boiling Points * Lower than alcohols * This is due to the presence of hydrogen bonding in alcohols which is absent in ethers

Prepara�on Physical Proper�es

Methoxymethane

H

H HH

H141 pm

sp3 hybridised

111.70C

:O:

CH

CH3 CH2 - O - CH2 CH3diethyl ether tetrahydrofuran

methyl phenyl ether

O

O CH3

CH3CH2OH

CH2=CH2

C2H5OC2H5

H2SO4443 K

H2SO4413 K

R-X+R’-ONa⁺::

R-O-R’+Na X::

:OH

:

:O Na

:

:O-R

:

+ NaOH R - X

+-

R:O:

RH O H:

:

R-OH+HX → R-X + H2O

+H-X

R-O-R + HX → RX + R-OH

O-R OH

+R-X

OCH3NO2

OCH3

NO2

OCH3H2SO4

2- Nitroanisole(Minor)

4- Nitroanisole(Major)

+HNO3

OCH3CH3

OCH3

CH3

OCH3

+CH3Cl

2- methoxy-toluene(Minor)

Methyl chloride

4- methoxy-toluene(Major)

+CS2

Anhyd. AlCl3

OCH3COCH3

OCH3

COCH3

OCH3

+CH3COCl

2- methoxy-acetophenone

(Minor)

Ethanoylchloride

4- methoxy-acetophenone

(Major)

+Anhyd. AlCl3

OCH3Br

OCH3

Br

OCH3

Br2 in

p - Bromoanisole(major)

+Ethanoic acid

o - Bromoanisole(minor)

:OR

:

+OR

:

↔-

+OR

:

↔-

OR

:

↔-

OR

:

↔

+

Compound

CH3OCH3

Common name IUPAC name

Dimethyl ether Methoxymethane

C2H5OC2H5 Diethyl ether Ethoxyethane

CH3OCH2CH2CH3 Methyl n-propyl ether 1-Methoxypropane

C6H5OCH3 Methyl phenyl ether(Anisole)

Methoxybenzene(Anisole)

C6H5OCH2CH3 Ethyl phenyl ether(Phenetole)

Ehoxybenzene

C6H5O(CH2)6-CH3

CH3-O-CH2-CH2-OCH3

Heptyl phenyl ether 1-Phenoxyheptane

Methyl isopropyl ether 2-MethoxypropaneCH3O-CH-CH3CH3

Phenyl isopentyl ether 3-Methylbutoxybenzene

1,2-Dimethoxyethane

2-Ethoxy--1,1-dimethylcyclohexane

C6H5-O-CH2-CH2-CH-CH3CH3

H3C CH3OC2H5

Ether