Alcohols, Phenols & Ethers

ALCOHOLS, ETHERES AND PHENOLS

ALCOHOLS
(i) Functional group = -OH
(ii) Nomenclature
(a) Common system:- Alkyl alcohol
(b) Derived system: - CH3OH is called carbinol. All other alcohol members are considered its
alkyl derivatives ex: - CH3CH2OH – Methyl carbinols.
(c) IUPAC system:- Alkanols or (secondary suffix is ol)
(iii) Hybridization of oxygen & carbon in Alcohol is sp3 & tetrahedral geometry
(iv) General formula is CnH2n+2O
(v) In these compounds C−O bond length is 1.42 Å.
(a) Monohydric Alcohol:-Which contains only one alcoholic -OH group?
Ex. R-OH, C2H5OH CH3–OH OH
Ethanol methanol
Phenol
(1) Primary alcohol:- the hydroxyl group is attached with primary (10) carbon atom.
Ex. CH3CH2OH
(2) Secondary alcohol:- the hydroxyl group is attached with secondary (20) carbon atom.
Ex. CH3
CHOH Iso propyl alcohol
CH3
(3) Tertiary alcohol:- the hydroxyl group is attached with tertiary (30) carbon atom.
Ex. CH3
│
CH3 — C— OH (Ter. Butyl alcohol)
│
CH3
(b) Di hydric Alcohol:- Which contains two –OH groups?
Ex. Glycol CH2 – CH2
│ │
OH OH
(c) Trihydric Alcohol:- Which contains three –OH groups?
Ex. Glycerol CH2–CH−CH2
│ │ │
OH OH OH

(d) Polyhydric Alcohols:- Which contains more than three -OH groups?
Ex. Sorbitol, Manitol. CH2-OH
│
(CHOH)4
│
CH2OH.

PREPARATIONS OF ALCOHOLS:-
1. From Alkyl halides: -Alcohols can be prepared by treating Alkyl halides with aq. KOH, AgOH,
Ag2O (moist)

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
R-X + aq KOH R-OH + KX
Alkylhalide Alcohol

Ex. C2H5Br + aq. KOH C2H5-OH + KBr
Ethyl bromide Ethanol

(ii) CH3CH2CH2-Cl + AgOH CH3-CH2-CH2-OH + AgCl
Propylchloride Propanol

(iii) CH3CH2I + aq. KOH CH3-CH2-OH + KI

Ethylidoide Ethanol
(iv) 2C2H5Br + Ag2O (moist) 2CH3CH2OH + 2AgBr
Ethyl bromide Ethanol

2. From Alkenes → Alcohols can be prepared by hydration of alkenes with the help of dilute acid.
This reaction is occurs through Electrophillic Addition Reaction.
Dil. H2SO4
C=C + HO H dil HCl or H+
-
C —C
│ │
OH H Alcohol
dil. H2SO4
Ex. H2C= CH2 + HOH H2C – CH2
Ethene │ │
OH H Ethanol
dil. H2SO4
(ii) CH3 – CH = CH2 + HOH CH3-CH-CH3
Propene │
OH propan–2–Ol
CH3 CH3 CH3
| dil H2SO4 | |
(vi) CH3-CH-CH=CH2 + HOH CH3-C – CH2-CH3 + CH3-CH-CH-CH3
│ │
This is due to hydride shift OH [80%] OH(20%)
3˚Carbocation formed

3 From Aldehydes Ketones or carbonyl comp:-

Alcohols can be prepared by catalytic reduction or by using reducing reagent such as LiAlH4, LiAlH
NaBH4 etc from aldehydes and Ketones as.
H+
R-CHO + LiAlH4 R-CH2–OH
Aldehyde Alcohols

O OH
+
║ H │
Ex. (i) R-C-R + NaBH4 R-CH-R
Ketone Alcohol

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H+
(ii) CH3-CHO + LiAlH CH3-CH2-OH
Acetaldehyde Alcohol
O OH
+
║ H │
(iii) CH3-C-CH3 + NaBH4 CH3-CH-CH3
Acetone Propan-2-Ol
Ni or Pt
(iv) CH3-CHO + H2 CH3-CH2-OH
n
Red Ethanol
Aldehyde 1˚Alcohol
Redn
Ketone 2˚ Alcohol
4 From Carboxylic Acid:- Alcohols can be prepared by catalytic reduction or by using reducing
reagent such as LiAlH4 of carboxylic acid as.
H+
R-COOH + LiAlH4 R-CH2-OH + H2O
Carboxylic acid Alcohol
H+
Ex. (i) CH3COOH + LiAlH CH3-CH2-OH
Acetic acid Ethanol
H+
(ii) C2H5-COOH + LiAlH4 C2H5-CH2OH
Propanoic acid Propanol
5 From Grignard Reagent :-With the help of Grignard reagent we can prepared 1˚, 2˚,3˚ Alcohols.

1˚ Alcohol 2˚ Alcohol 3˚ Alcohol

HCHO CH3CHO O
║
CH3-C-CH3
CH2—CH2 HCOOC2H5 + CH3COOC2H5 +
O 2 molecules of G.R. 2 moles. of G.R.

H H
│ │ H2O/H+ OH
Ex. H—C ═ O + CH3-MgBr H−C−OMgBr CH3CH2OH + Mg
│ 1˚ alcohol Br
CH3

H CH3
+
│ H2O/H │ OH
(ii) CH3–CH=O + CH3-MgBr CH3−C−OMgBr CH3−CH−OH + Mg
│ 2˚ Alcohol Br
CH3

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CH3 CH3 CH3
│ │ H2O/H+ │
(iii) CH3-C=O + CH3-MgBr CH3-C-OMgBr CH3-C-OH
│ │
CH3 CH3
(iv) CH2-CH2 + CH3-MgBr CH3CH2CH2-OMgBr H2O/H+ CH3CH2CH2OH + Mg(Br)OH
O 1˚Alcohol

O OMgBr CH3
║ │ +CH3MgBr │ OC2H5
(v) H-C-OC2H5 + CH3-MgBr H-C-OC2H5 CH3-CH-OH + Mg
−Mg(Br)OH
│ 2˚ Alcohol Br
CH3

O OMgBr CH3
║ │ +CH3MgBr │ OC2H5
(vi) CH3-C-OC2H5 + CH3-MgBr CH3-C-OC2H5 HOH CH3-C-OH + Mg
│ │ Br
CH3 CH3 3˚Alcohol

6 From Hydroboration Oxidation:-

B2H6 H2O2/OH-
Alkene (Alkyl)3B Alcohol (But acc. to the
Anti-Markownikoff)
B2H6or BH3 H2O2/OH-
Ex. 3.CH3-CH=CH2 (CH3-CH2-CH2)3B CH3-CH2-CH2-OH

7 By Hydrolysis of Ether:- Ether on hydrolysis in presence of dil. mineral Acid gives

alcohols as. dil H2SO4
Ex. C2H5-O-C2H5 + HOH 2C2H5OH
Ethylethanoate Ethanol

8 By Hydrolysis of Ester:-The ester on treatment with water in presence of dil. mineral

Acid gives the alcohols as.
O
║ dil H2SO4
Ex. CH3-C-O-C2H5 + HOH C2H5OH + CH3COOH
Ethylethanoate Ethanol Acetic acid.

9 From Primary Amines: - Primary amines on treatment with HNO2 give alcohols as.

Ex. C2H5-NH2 + HONO C2H5-OH + N2 + H2O

Ethanamene Ethanol
In this reaction if we take ethyl amine then main product will be ethanol while if we take methyl
amine then main product will be dimethyl ether.

10 By Oxymercuration demercuration Reaction: - Alkenes on treating with

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mercuric acetate [Hg (CH3COO)2] followed by reduction give the Alcohols as.
HOH
Ex. >C═C< + Hg(CH3COO)2 >C−C< >C−C<
│ │ │ │
H OHg(CH3COO) H OH
11 Preparation of Ethanol by Fermentation Process.
(i) Molasses:- waste product in sugar industry is called molasses. It is a mixture of sugar 30%)
and invert sugar (32−40%).
(ii) Invert sugar:- combine form of glucose and fructose is called as invert sugar.
(iii) Starch solution is technically called `Mesh`
(iv) Crushed germinated barley solution is called `Malt`
(v) Distillation of wash is done in special apparatus `Coffee`s still`, which is based on computer
current method. From this distillation yield of alcohol is 90%, which is called Raw spirit.

Invertase Xymase
(i) C12H22O11 + H2O C6 H12 O6 + C6 H12O6 C2H5OH + CO2
Glucose Fructose Ethylalcohol
This process is called fermentation process or in presence of microbes like Yeast break down of
complex organic compounds into simple compounds is called fermentation (proposed by Lebeig)

(i) Diastase (ii) maltase (iii) Xymase

(ii) Starch Maltose Glucose Ethanol + CO2
maltase Xymase
(iii) Maltose Glucose ethanol + CO2
+
Fructose

PHYSICAL PROPERTIES OF ALCOHOL’S.

(i) Lower members of alcohol (up to 12 C) are colourless liquids having characteristic smell and
burning taste while higher members are colourless, waxy solids & odorless.
(ii) Boling Point:—the B.Pt. of alcohol is much higher than that of corresponding aliphatic
hydrocarbon’s and alkyl halides.
This is due to intermolecular hydrogen bond present in between alcohol molecules as..
Hydrogen bond

---H—O---H—O---H—O---
│ │ │
R R R
(b) B.Pt. is inversely proportional to branching present in hydrocarbon chain.
Eg. Primary > Secondary > Tertiary alcohols
(c) B.Pt α Molecular wt
Eg. CH3OH < C2H5OH < C3H7OH < C4H9OH
(iii) Viscous nature of alcohol is directly proportional to H—bonding or number of –OH groups. That is
why we can say alcohol is less viscous than glycerol & manitol is more viscous than glycerol.
(iv) Ethanol is liquid while glucose is solid. It is due to more H−bonding is glucose.
(v) Alcohols are toxic in nature also. Toxic nature increases with increment in molecular weight or
branching. Ethanol is exception, which is less toxic in nature. It is most useful organic solvent.
(vi) Methanol causes blindness.

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(vii) Isopropyl is called as rubbing alcohol.
(viii) Cholesterol is also an example of complex alcohol which is called notorious alcohol because it
causes heart attack
(ix) Solubility: → these are highly soluble in water due to formation of intermolecular hydrogen
bonding with water.
* Solubility directly proportional to branching present in hydrocarbon chain.
Ex. Primary < Secondary < Tertiary Alcohols.

* Solubility inversely proportional to the molecular wt of hydrocarbon chain.

Ex.CH3OH > C2H5OH > C3H7OH > C4 H9OH

1. Rxn with Conc H2SO4

Con. H2SO4 CH2 ═ CH2 + H2O
[165- 170˚C] Alkene

,,
CH3-CH2-OH CH3 – CH2SO4H
Ethanol 100˚C
,,
Excess CH3CH2–O−CH2CH3 + H2O
140˚C Ether
Mechanism

Protonated ether
Mechanism

2. Rxn with Al2O3 Al2O3

CH2 ═ CH2 + H2O
[350-500˚C] Alkene

CH3-CH2-OH
Ethanol Al2O3 CH3-CH2-O-CH2-CH3 + H2O
[180-250˚C Ether

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3. Chemical properties:- 2Na
2C2H5ONa + 1/2 H2
PCl3
3C2H5Cl + P(OH)3
PCl5
C2H5Cl + HCl + POCl3
SOCl2
C2H5Cl + SO2(g) + HCl(g)
HCl+ZnCl2
C2H5Cl + H2O
NaOCl
CHCl3 + HCOONa
C2H5OH CaOCl2
Ethanol CHCl3 + (HCOO)2Ca
NaOH+Cl2
CHCl3 + HCOONa
NaOI
CHI3 + HCOONa
NaOH+I2
CHI3 + HCOONa
P+I2 or PI3
3C2H5I + P(OH)3
HI/ZnCl2
C2H5I + H2O

4. Dehydrogenation by Cu/ 300˚C:- This reaction also used for identification or test for 1˚, 2˚ and 3˚
alcohols
300˚C
Ex. CH3–CH2–OH + Cu CH3-CHO + H2
Ethanol (1˚ alcohol) Acetaldehyde

CH3 O
│ 300˚C ║
(ii) CH3−CH−OH + Cu CH3−C−CH3 + H2
Isoporopylalcohol Acetone (Ketone)
(2˚ alcohol)
CH3 CH3
│ 300˚C │
(iii) CH3−C−OH + Cu CH3−C ═ CH2 + H2O
│ 2- Methylpropene (alkene)
CH3
Tertiary butyl alcohol [3˚ Alcohol]

Thus (i) 1˚ alcohols gives aldehydes on dehydrogenation with Cu/300˚C

(ii) 2˚ alcohols give ketones on dehydrogenation with Cu/300˚C
(iii) While 3˚ alcohols gives alkenes on the dehydrogenation with Cu/300˚C

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5. Oxidation by K2Cr2O7:- On oxidation by K2Cr2 O7 the 1˚ alcohol gives the acid of same carbon no. the
2˚ alcohol gives the acid of one carbonless while 3˚ alcohol under goes oxidation to gives acid of two
carbons less than of the parent alcohol.
Oxidation [O]
1. CH3CH2OH + K2Cr2O7 CH3-CHO CH3COOH or CH3COOK
[Ethanol] 1˚ acetaldehyde Acetic acid
CH3
│ [O] [O]
2. CH3-CH-OH + K2Cr2O7 CH3-C - CH3 CH3COOH + HCOOH or CH3COOK + CO2 + H2O
Isopropyl alcohol ║ Acetic acid
O acetone
CH3 O
│ [O] ║ [O]
3. CH3−C−OH + K2Cr2O7 CH3 –C−CH3 CH3COOH + CO2 + H2O
│ Acetone acetic acid
CH3 [3˚ Alcohol]

This Rxn also be used for identification of primary, secondary and tertiary alcohol.
(i) For oxidation of 10 alcohol, acidic KMnO4 is used as oxidant while for 20 alcohol acidic
K2Cr2O7(more strong than KMnO4) is used.
(ii) For both (10 and 20 alcohol) we can use common oxidizing agent also, like chromic acid in dilute
H2SO4. Colour of this solution is orange and it turns into green colour due to Cr+3.

6. Lucas Test. → It is used for identification of 1˚, 2˚ & 3˚ alcohols.

Function:- Addition of Cl by nucleophilic substitution.
Lucas Reagent - Cone HCl + Anhyd . ZnCl2

Function: - of ZnCl2 is formation of carbocation

Lucas Reagent.

Tertiary Secondary Primary

Alcohol Alcohol Alcohol gave ppt
Gave ppt. in few Gave ppt. in few minutes in many hours or days
Second. Rxn Rxn Rxn
CH3 CH3 CH3−CH2−OH + HCl
│ │
CH3−C−OH + HCl CH3-CH-OH + HCl ZnCl2
│
CH3 ZnCl2 ZnCl2
CH3
│ CH3−CH−Cl + H2O CH3−CH2−Cl + H2O
CH3−C−Cl │
│ + H2O CH3
CH3

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7. Oxidation through Fenton`s Reagent:- Higher and branched alcohols are converted into diols through
Fenton’s reagent. (FeSO4 + H2O2) is Fenton`s reagent.

Fe+2 + H2O2 Fe+3 + OH¯ + OH

8. Self condensation: - when alcohol is heated with sodium ethoxide then by self condensation they
convert into higher alcohol.
R R
│ │
R−CH2−CH2− OH + H− CH− CH2 −OH R− CH2 −CH2 −CH −CH2 −OH
−H O higher alcohol
2
The above reaction is called as Guerbet`s Reaction

9. Victor Mayer test.

It is used for identification of 1˚, 2˚ & 3˚ alcohols.
R. B. W.
Red Blue white/ (colourless)
Primary Alcohol secondary Alcohols Tirtary Alcohols

CH3−CH2−OH (CH3)2 CH−OH CH3

│
Ethanol St.-i PI3 CH3−C−OH
│
CH3
St.−i P+I2 or PI3 (CH3)2CH−I
St. i PI3 or P+I2
CH3−CH2−I St. ii Ag NO2
Ethyl Iodide CH3
St.−ii AgNO2 │
(CH3)2CH−NO2 CH3−C –I
│
CH3−CH2−NO2 CH3
Nitroethane St. iii HONO
St.iii -H2O St.− ii AgNO2
-H2O HONO (CH3)2 −C−NO2
║ CH3
CH5−C−NO2 NO │
║ Pseudo Nitrolic Acid CH3 − C−NO2
N-OH │
Nitrolic Acid St. iv NaOH CH3
St. (iv) NaOH St. – iii HONO
–H2O No Salt Formation
CH3−C−NO2 Blue Colour no reaction
║ White Colour or Colourless
N−ONa
Sodium Salt of Nitrolic Acid (Red Colour)

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10. ESTERIFICATION:- When alcohol is treated with carboxylic acid in presence of either acid or base
as a catalyze then the ester is formed. This is called Estrification.
H+
Ex. R−OH + R'–COOH R'–COOR + H2O
Alcohol carboxylic acid Ester.
H+
Ex. CH3CH2−OH + CH3COOH CH3COOCH2CH3 + H2O
Ethanol acetic Acid Ethyl ethanoate

MECHAISM OF ESTRIFICATION.

O OH OH
║ │ HOR │
CH3−C + H+ CH3 – C+ CH3−C −O-R CH3COOR + H2O
│ │ │
OH OH alcohol OH unstable
Acetic acid
* In this reaction Rxn alcohol acts as base or nucleophile because it provides lone pair of Electrons.
* In this Rxn OH- removed from carboxylic acid.
* Reactivity order of alcohol is 1˚ > 2˚ > 3˚
CH3 CH3
│ │
* Reactivity order of acid CH3COOH>CH3CH2 COOH>CH3−CH-COOH> CH3−C−COOH
│
or acidic strength CH3
* Acidic strength α - Inductive effect (ie.-I effect)
Acidic strength α1/+I effect

Ex. C−C−COOH> C−C−COOH> C−C−COOH

│ │ │
Cl Br I

FEW GENERAL POINTS.

(i) Absolute Alcohol. The 100% pure ethyl alcohol is called absolute alcohol.

(ii) Rectified Sprit. Absolute alcohol 95.5% + 4.5 % water is k/as Rectified sprit.
(iii)Methylated Sprit. Rectified Sprit + 0.5% Methanol is k/as methylated sprit
(iv) Power Alcohol. Petrol (or Gasoline) + 20% Ethyl alcohol + Benzene is k/as power Alcohol.
(v) Denatured spirit:- (rectified spirit + pyridine and caoutchoucine)
(vi) Wash :- ( 10 % to 15 % alcohol)
(vii) Grain spirit:- (ethyl alcohol) – 90% alcohol
(viii) Wood spirit:- (methanol)
(ix) Alcoholic beverages:
Drink % of alcohol Drink % of alcohol
Brandy 40-50 Whisky 40-50
Rum 45-55 Beer 3-6
Gin 40-45 Champaign 8-10

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(v) Acidic Strength of Alcohol.
CH3 CH3
│ │
CH3−OH > CH3−CH2−OH > CH3−CH –OH > CH3 −C – OH
│
1˚ 2˚ 3˚ CH3
(vii) Acidic Strength of Carboxylic Acid.
CH3 CH3
│ │
CH3COOH > CH3CH2COOH> CH3-CH-COOH > CH3- C-COOH
│
CH3
+ I effect Increases and-hence Acidic strength decreases.
We know that
Acidic strength α - I effect
Acidic strength α 1/+ I effect

ETHER’S
(1) Functional gp. = O or R-O-R1. It is a dialkyl of water or alkoxy derivatives of alkane or
anhydride of alcohols.
(2) IUPAC Name = alkoxy alkane
(3) Hybridization of oxygen is sp3 & bond angle is 1100 due to counter balance repulsion of alkyl
groups. and carbon oxygen bond length is 1.42 Å.
(4) General formula is CnH2n + 2O.
(5) Cylic ether

Oxirane 1,4-Dioxane
(6) Aromatic ether OCH3 OC2H5 O

Anisole Phenitole Diphenylether

PREPARATIONS

1. Williamson’s Synthesis:- When alkyl halid is treated with a particular sodiumalkoxide then the
ether’s are formed. This Rxn is called William Son’s Synthesis as.
R-X + NaOR' R−O− R' + NaX
Akylhalide Sodium alkoxide (Ether) alkoxyalkane

Ex. i) CH3-CH2-Br + NaOCH3 CH3-CH2-O-CH3 + NaBr

Ethylbromide Sodiummethoxide Methoxy ethane

(ii) CH3-CH2-Br + NaOCH2CH3 CH3-CH2 −O−CH2CH3 + NaBr

Sodium Ethoxide Ethoxy ethane
n 2
Limitations: -This Rx is occurs through the SN reaction mechanism. So only primary akylhalides with
sodium alkoxide give ethers.

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2. By using Ag2O. Alkyl halide on treatment with Ag2O gives ether and silver halide as.
2R-X + Ag2O R-O-R + 2AgX
Ex. CH3-CH2 –Br + Ag2O CH3CH2-O-CH2-CH3 + 2AgBr

3. From Alcohols. (a)Alcohols on treatment with cone H2SO4 at 140˚C temperature gives ether as.
140˚C
Ex. CH3CH2–OH (excess) + Conc. H2SO4 CH3-CH2–O-CH2-CH3 + H2O
Ethanol Ethoxyethane
(a) Alcohols on treatment with Al2O3 at 180˚ – 250˚C temperature gives ether as.
180˚- 250˚C
Ex . CH3CH2-OH (excess) + Al2O3 CH3-CH2-O–CH2–CH3 + H2O

4. By Using Grignard Reagent.

Br
CH3- MgBr + Cl–CH2-O-CH2–CH3 CH3-CH2-O-CH2-CH3+Mg
G.R. Chloromethoxyethane Ethoxy Ethane Cl

PHYSICAL PROPERTIES.
(1) 1st two members are gasses while other member’s are colourless. Liquids with ethereal smell.
(2) Solubility: - Ether are highly soluble in organic solvents such as benzene ethanol CCl4, chloroform
etc. But also soluble in water due to formation of intermolecular hydrogen bonding with water as.
R-O---H O R
│ │ │
R H--- O R
(3) Boling Point: - Ether has low boiling point then the isomeric alcohol. This is due to weak
intermolecular forces present b/w ether molecules while strong inter molecular hydrogen bonding
b/w alcohol So B.Pt of ethers lower than alcohols. Ex. B.P of diethyl ether is 307.6 K.
(4) These are highly volatile liquid due to low boiling point.

(5) POLAR NATURE:- Ether’s are polar molecules due to their angular structure and have definite
dipole moment.

CHEMICAL PROPERTIES:-
1 .formation of oxonium salt: - Ethers on treatment with conc. acid forms Oxanium salt as.

C2H5 C2H5
O + BF3 O: → BF3
C2H5 C2H5

C2H5 +
C2H5 OC2 H5 + conc. HCl O:→H Cl-
Ethoxy ethane C2H5
Oxonium salt

. C2H5 +
C2H5OC2H5 +Conc H2SO4 O:→H HSO4-
C2H5

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2. dil H2 SO4
CH3CH2-OH + CH3CH2-OH
Eathanol eathanol
PCl3 2CH3CH2Cl + POCl3
Ethylchloride
PCl5
C2H5-O-C2H5 2 CH3CH2–Cl + POCl3
Ether SOCl2
2CH3CH2–Cl + SO2
CH3COCl
CH3COOCH2CH3 + CH3CH2Cl
(CH3CO)2O
2CH3COOCH2CH3

3. Al2O3
 2CH2 = CH2 + H2O
Ethane
Cl2 (C2Cl5)2O ( pentachloroether ) or perchloro ether
Light
C2H5OC2H5 Cl2/dark
Ethoxyethane CH3 – CH – O – CH – CH3 [α-α'dichloro Ether]
20˚C Cl Cl
Air CH3 – CH2 –O − CH –CH3 [Ether hydrogen peroxide]
O-OH [Highly explosive]
O3 /Ozone CH3 – CH2
O → O [Ether peroxide]
CH3 – CH2
♣ The reactivity order of halogen in halogenations is – F2 > Cl2 > Br2 > I2
♣ Test for peroxide in the ether:-
[Ether + freshly prepared FeSO4 solution + Few drops of KCN] – Red colour [Fe (CNS)3]
Appearance of red colour confirms the presence of peroxide
Combustion: Fe+2 Peroxide
Fe+3 KCNS
Red colour [Fe (CNS)3]
Note:- when ether is oxidized with acidic K2Cr2O7 then it forms aldehyde.

5. Reaction with HI or (halogen acids)

Cold
HI CH3CH2–OH +C2H5I
Ethanol Ethyliodide
CH3–CH2–O–C2H5
ethoxy rthane
2HI 2CH3CH2I + H2O
Ethyliodide

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 In unsymmetrical ether, the alkyl halide (alkyl iodide) formed of smallest alkyl group compound.
HI
EX. CH3CH2 –O − CH3 CH3 –CH2 – OH + CH3I
Methoxy ethane cold ethanol methyl Iodide
CH3 CH3
│ HI │
EX. CH3 –CH – O − CH3 CH3 – CH – OH + CH3I ,
Cold

In tertiary alkoxyalkane it is reversed as

CH3 CH3
│ │
CH3 – C – O CH3 + HI CH3 − C I + CH3OH
│ │
CH3 CH3
This is due to the formation of 3˚ carbonium ions.
Note:- The above reaction is called Ziesel`s Method of Alkoxy group estimation. If we take
unsymmetrical ether with hot H —X then we get two different types of alkyl halide and by the test of
both alkyl halide we can confirm alkoxy group of ether.
Uses:-
1. Wurtz reaction
2. Alcohol + ether Natelite (used in place of petrol)
3. Ether is also called as inert solvent of aliphatic chemistry, due to inertness of oxygen.
4. Due to inertness of oxygen, it is best solvent for preparation of highly reactive compounds such as
G.R.
5. It is used as an anesthetic. Other compounds such as ethrane and isoflurane also used as an
anesthetic.
F
Cl │
CH−C−O−CHF2 CF3−CH−O−CHF2
F │ │
F Cl
Ehrane isoflurane

6. Anethole, Eugenol, Vanillin, Thymol used as flavourings and in perfumed because of their pleasant
odour.

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PHENOL,S
1. Functional group = -OH
2. IUPAC name = -ol
3. Hybridization of oxygen = sp3
OH OH OH OCH3
CH3

Phenol o-Cresol Anisole

CH3
p-Cresol
CH2OH OH OH OH
OH

OH
Benzyl alcohol catechol Resorsinol OH
Quinol
Preparations: -
1. from Chlorobenzene ( Dow;s process)
Chlorobenzene on alkaline hydrolysis i.e. heated with 10% NaOH (aq NaOH) at 623 K temp and
at high pressure in presence of copper salt; formed phenol. This process is k/as Dow’s process as.
Cl ONa
623 K and
+ 2NaOH (10%) + NaCl + H2O
High pressure
Chlorobenzene sodium phenoxide
OH
HCl (dilute)
+ NaCl

Phenol
2. From salicylic acid / sodium salicylate:- Soda lime salicylate or Salicylic acid on the reaction with
soda lime gives phenols as.
EX. OH OH
COONa
+ Soda lime + Na2CO3

Sodium salicylate phenol

EX. OH OH
COOH 2NaOH
+ CaO + Na2CO3

Salicylic acid phenol

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 Alcohols, Phenols & Ethers
3. From Grignard reagent: - On hydrolysis of oxygen derivatives of corresponding Grignard reagent;
Phenol can be prepared as.
EX.
MgBr OMgBr OH
Hydrolysis OH
+.1/2 O2 + H2O + Mg
Br
Phenol

4. From Benzene: - Benzene on oxidation in the presence of V2O5 {vanadium pentaoxide} at 300˚ C
temperature then the phenol is formed as.
OH
300˚C
+ V2O5

Benzene phenol
5. from benzene diazonium chloride salt:-
Benzene diazonium chloride salt on treatment with water in acidic medium gives phenols.
N2+Cl- OH
+
H
+ H2O + N2 + HCl
Or H3O+
Pheno
6. from cumene: - Oxidation of cumene with oxygen in the presence of catalyst gives cumene hydro
peroxide which on rearrangement in presence of dilute H2SO4 gives phenols as.
CH3
│
H CH3 –CH
AlCl3 Catalytic
+ CH3 –CH = CH2
propane oxidation
Benzene isopropyl benzene(cumene)
CH3
│
CH3-C-O-OH OH O
║
Dil. H2SO4 + CH3-C-CH3
Acetone
Cumene Hydroperoxi Phenol
7. By Rasching process: Benzene on treatment with hydrochloric acid HCl and air in the presence of
cupric chloride [CuCl2] or ferric chloride at 500 k. then the phenol is formed as.
H OH

CuCl2/FeCl3
+2HCl +O2 + H2O
500 K
Benzene phenol

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PHYSICAL PROPERTIES
1. Pure phenols are colourless, crystalline solids or liquids. But get coloured due to atmospheric oxidation.

2. Boiling point:- Phenols have higher boiling pt. then the aromatic hydrocarbons and halo arens of
comparable molecular masses. This is due to presence of intermolecular hydrogen bonding as shown
below.
Inter molecular hydrogen bonding
H O -------- H O -------- H O

3. Solubility:- phenols are less (or sparingly) soluble in water although it form inter- molecular hydrogen
bonding with water. this is due to presence of larger hydrocarbon in the molecule
NOTE Phenols containing substituent group such as –HO, -NO2, etc. can also from intra molecular
hydrogen bonding. This is called chelation or ortho- effect also called Intra molecular hyd. bonding
H O H O
O ║ O ║
N C−H
O

O-nitro Phenol Salisaldehyde

CHEMICAL PROPERTIES

1. Acidic nature or acidic character:- phenols are acidic in nature because phenoxide ions is more
resonance stabilized then the phenols .This is due to in resonance structure of phenoxide ion the negative
charge present on most electronegative element i.e . At oxygen. While in phenol, oxygen has positive
charge in resonating structures. The phenoxide ions are better stabilized then phenol and there fore
phenol has greater tendency to donate or release a proton and behaves as an acid.
Phenol:

Phenoxide ion:

2. Reaction due to O –H bond of phenol:-

ONa OCH3
Ex.1
CH3Br + NaBr

Sodium phynoxide Anisole

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 Alcohols, Phenols & Ethers
ONa OC2H5
Ex.2 C2H5Br
+ NaBr

ONa Phenitole
Na
+ H2

OCOCH3
CH3COCl
+ HCl
Phenyl acetate

O-H OCOCH3
+
(CH3CO)2O + CH3COOH
Phenyl acetate
OCOC6H5

C6H5COCl + HCl
Phenyl benzoate
OSO2C6H5

C6H5SO2Cl + HCl
Phenyl benzene sulphonate

3. reaction due to -OH group

Zn dust
Distillation + ZnO

OH Benzene
NH2
NH3
Anhyd ZnCl2 + H2O
Phenol
Aniline
Cl
2. PCl5
573K + POCl3 + HCl

PCl5 Chlorobenzene
(excess) (C6H5)3 PO4 + C6H5Cl
Triphenyl phosphate
4. Electrophillic substitution Reactions of phenol:- -OH group in phenols is strong ortho -& para-
directing in nature. In resonating structure we obtained electron density is higher at the ortho- and para-
position so electron deficient species attack on ortho and para position.

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 Alcohols, Phenols & Ethers
OH OH
dil NO2
OH +
HNO3
Nitration NO2
o-nitrophenol p-nitrophenol
OH
Phenol Conc.HNO3 O2N NO2
H2SO4

NO2
Picric acid (2, 4, 6-Trinyto phenol or TNT)

5. Friedel Craft reaction:- Phenol when treated with alkyl halide in presence of anhydrous
aluminium chloride AlCl3 (halogen carrier) then ortho- or para- cresol are formed.
This is known as Friedel Craft reaction.
OH OH OH
Anhydrus CH3
+ CH3Cl +
AlCl3

Phenol o-Cresol CH3

p-Cresol
OH
Br2/ water Br Br
Halogen- Bromine water
ation
tri-Bromophenol
Br
OH
Br
Br2/CS2 or CCl4
OH
o-Bromophenol

OH
SO3H
Phenol
25˚C o-phenolsulphonic acid
Sulphona-
tion OH

100˚C
p-phenolsulphonic acid

SO3H

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6. ADDITION OF –CHO GROUP

Remer Timen Reaction:- when phenol is treated with chloroform in presence of alkali at high
temperature the major product is 2-hydropxy benzenaldehyde [i.e. Salisaldehyde]

OH OH
CHCl3 + KOH CHO

675 K
Phenol Salisaldehyde
OH OH OH
aq KOH C–OH CHO
+ CCl2 OH

Salisaldehyde
7. Coupling Reaction:- phenol couples with diazonium salt in alkaline solution to form 4- hydroxyazo
benzene. This is known as coupling reaction. It is used in azo-dyes as.
Alkaline medium
+ -
N2 Cl + H OH
pH=9-10 -HCl
Benzendiazonium salt Phenol

N=N OH

4-hydroxyazo benzene

8. Kolbes Reaction → when sodium phenoxide is heated with CO2 at 400.K, then the salicylic acid is
formed . This is known as Kolbe’s Smith Reaction or Kolbe`s Reaction.
ONa OH OH
COONa COOH
+
+ CO2 400.K H / H2 O
6-7atm
Sodium phenoxide sodium salicylate Salicylic acid

9. REACTION WITH PTHALIC ANHYDRIDE:-

OH OH

OH
CO Conc H2SO4
O +
CO - H2O C
O

C
║
O
Phenolphthalein

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10. Liberman’s nitroso reaction:- This reaction is used as test for phenol.
OH OH
+
H
+HNO2 conc H2O
-H2O Green colour Red colour
H2SO4 alkaline
Phenol N=O
p-nitrosophenol blue colour

11. REACTION WITH FORMALDEHYDE:- Phenols condenses with formaldehyde in presence of acid
or alkali to from p – hydroxyl benzyl alcohol. And a small amount of o- isomer. These under further
condensation with other phenol molecules . To gave bakelite or Formaldehyde resin as.

OH OH OH
CH2OH
+
+ HCHO H + nHCHO Bakelite or
Formaldehyde Phenol Formaldehyde resin

Phenol CH2OH

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