Dr.

Anil Kumar Ojha, Assistant Professor, Department of

Chemistry
B.Sc Part -1 ( Honour’s and Subsidiary)

Halogen derivatives
Compounds derived from hydrocarbon by the replacement of one or more hydrogen atom (s) by the halogen atom
(s) are known as halogen derivatives. The halogen derivatives of alkanes, alkenes, alkynes and arenes are known
as alkyl halides (haloalkanes), alkenyl halides (haloalkenes), alkynyl halides (haloalkynes) and aryl halides
(halobenzenes) respectively. Halogen derivatives may be classified as follows :

Organic Compounds Containing Halogen (S)

Alkyl halide Aryl halide

Mono haloalkanes Poly haloalkanes

Primary alkyl halide Secondary alkyl halide Tertiary alkyl halide

Alkyl Halides.
(1) Monohaloalkanes : These are halogen-substituted alkanes. The general formula is C n H 2 n +1 X , where X is any
halogen. Alkyl halides have been further classified, on the basis of nature of the carbon atom to which halogen is
attached into following categories :
(i) Primary alkyl halide : The halogen is attached to primary carbon atom, i.e. RCH 2 X .
R
(ii) Secondary alkyl halide : The halogen is attached to secondary carbon atom, i.e. CHX .
R
R
(iii) Tertiary alkyl halide : The halogen is attached to tertiary carbon atom, i.e. R C X.
R
Preparation of alkyl halides : (1) By free radical halogenation of alkanes, e.g.
CH 4 + X 2 ⎯⎯ ⎯⎯→ CH 3 X + HX (where, X = Cl, Br only)
UV light

Excess

Note: ❑ The formation of di, tri, tetra-halides etc. (as side products) also takes place.
❑ Iodination of alkanes is a reversible process, therefore, formation of iodoalkanes is possible only in the presence
of oxidising agents such as HIO 3 , conc. HNO 3 etc., which oxidises the HI produced. Iodination with methane does
not take place at all.
❑ Fluorination of alkanes takes place with rupture of C – C bonds in higher alkanes. Therefore alkyl fluorides are
generally prepared by halide exchange reactions. Alkyl fluorides are, therefore, prepared indirectly by heating alkyl
chlorides with inorganic fluorides e.g. AsF3 , SbF 3 , AgF , Hg 2 F2 etc. (Swarts reaction)
 2 CH 3 CH 2 Cl + Hg 2 F2 → 2 CH 3 CH 2 F + Hg 2 Cl 2
(2) By reaction of halogen acids (HX) to alkenes, e.g. RCH = CH + HX → R C H − CH
2 3
|
X

(3) By reaction of PCl 5 or PCl 3 or SOCl 2 with alcohol :

RCH 2 OH + PCl 5 → RCH 2 Cl + POCl 3 + HCl ; 3 RCH 2 OH + PCl 3 → 3 RCH 2 Cl + H 3 PO 3

RCH 2 OH + SOCl 2 ⎯⎯ ⎯ ⎯→ RCH 2 Cl + HCl + SO 2

Pydrine

(4) By reaction of alcohols with halogen acids: RCH 2 OH + HX ⎯⎯ ⎯ → RCH 2 X + H 2 O

2 ZnCl

(5) By Hunsdiecker reaction: RCOOAg + X 2 → RX + AgX + CO 2

Note: ❑ This reaction proceeds through free radical mechanism.

❑ The yield of alkyl halide is 1 o  2 o  3 o .

❑ This reaction is used to reduce the length of carbon chain.
❑ Only bromides are obtained in good yield in this reaction. The chlorides can also be obtained by this reaction
but the yield is very low. Iodides however cannot be obtained because these form esters with silver salts.
(Birnbaurn Simonini reaction). 2 RCO 2 Ag + I 2 → RCO 2 R + CO 2 + 2 AgI

Properties :
Physical properties: (1) Lower members like CH 3 Cl, CH 3 Br , C 2 H 5 Cl are colourless gas while some of the
higher members are colourless sweet smelling liquids. Higher homologues are odourless solids.
(2) The boiling point and density is in the order R − F  R − Cl  R − Br  R − I
Example CH 3 F CH 3 Cl CH 3 Br CH 3 I

B.P. ( o C ) –78.4 – 23.8 3.6 42.5

Density (gm ml
−1
) 0.84 0.92 1.73 2.28

(3) They have very low solubilities in water but miscible with non-polar solvents.
(4) These have a cumulative toxicity and are carcinogenic.
Chemical properties : (1) Alkyl halides undergo nucleophilic substitution reaction :
In general, RCH 2 − X + Y  → RCH 2 − Y + X 

Where, Y  = Cl  , Br  , OH  , RO  , RS  , CH 3 COO  , CN  , R  , NH 2  , N 3  , NO 2 

Similarly alkyl halide reacts with compound with general formula ‘HY’ as below
RX + HY → RY + HX , Where, HY = H 2 O, ROH, RCOOH, NH 3
The general reactions are as follows :

R – OH (Alcohol)

R – OR' (Ether)

R – SH (Thiol)

R – CN (NItrile)
R–X
, Pri or Sec) R – SR' (Thioether)
(X = Cl, Br or I)
(Alkyne)

(Ester)

(quaternary ammonium halide)

Note: ❑ Reactivity of halides towards SN 1 –mechanism is 3 o  2 o  1 o and SN 2 –mechanism is
1o  2 o  3 o .

❑ Polar solvents favour SN 1

while non polar solvents favour SN 2
mechanism.
❑ High concentration of nucleophiles favour SN 2
while low concentration SN 1
mechanism.

❑ Rate of reaction in SN 1
mechanism do not depend upon the nature of the attacking nucleophile. However,
in SN , rate depend on the strength of the attacking nucleophile.
2

(2) Alkyl halides undergo dehydrohalogenation which is a -elimination reaction in which halogen is lost
from -carbon atom while H is lost from -carbon atom. This reaction is governed by Saytzeff’s rule.
Note: ❑ Ease of dehydrohalogenation among halides : 3 o  2 o  1o .

Br CH 3
(3) Isomerization : CH CH CH CH Br ⎯⎯
 / anhy. AlCl
⎯⎯⎯
| |
⎯→ CH 3 CH 2 − CH − CH 3 + CH 3 − C − Br
3
3 2 2 2
|
CH 3

(2) Dihaloalkanes : These have been classified in two categories namely Gem-dihalide in which the two
halogens are attached to same carbon atom and vic-dihalide in which the two halogens are attached to
Cl CH 2 Cl
adjacent carbon atom, e.g. CH 3 CH ; |
Cl
Ethylidene chloride (gem - dihalide) CH 2 Cl
Ethylene chloride (vic- dihalide)

The vic-dihalides are prepared by reaction of halogens to alkene where as gem-dihalide are prepared by
CH 2 Cl
reaction of PCl 5 to aldehyde. CH 2 = CH 2 + Cl 2 → |
; CH 3 CH = O + PCl 5 → CH 3 CHCl 2 + POCl 3 + HCl
CH 2 Cl

The gem and vic-dihalides can be distinguished by reaction with aq. KOH :
CH 2 Cl CH 2 OH
| + aq. KOH → | ;
CH 2 Cl CH 2 OH
diol

OH − H 2 O
CH 3 CHCl 2 + aq. KOH → CH 3 CH ⎯⎯ ⎯→ CH 3 CHO
OH
(3) Trihaloalkanes
(i) Chloroform (CHCl 3 ) : It can be prepared by reaction of acetone or ethyl alcohol with bleaching powder.
2 CH 3 CH 2 OH + 8 Cl 2 + Ca(OH ) 2 → 2 CHCl 3 + (HCOO ) 2 Ca + 10 HCl
The important properties of CHCl 3 (sweet smelling liquid) are as follows :

(a) On oxidation it yields phosgene gas which is very poisonous: CHCl 3 + [O] ⎯⎯ ⎯⎯→ COCl 2 + HCl
sun light
air Phosgene

For medical purpose, the chloroform is filled in coloured bottles and kept in dark to avoid sunlight. Further
the bottles are filled upto neck to avoid oxygen (air) and 1% C 2 H 5 OH is added to convert phosgene into
harmless ethyl carbonate.
 (b) Upon alkaline hydrolysis with KOH, chloroform gives potassium formate.
OH
CHCl 3 + 3 KOH → CH OH → HCOOH ⎯⎯ ⎯→ HCOOK + H 2 O
KOH

OH

(c) With acetone it forms chloretone which is used as a hypnotic.

(d) When chloroform is warmed with a primary amine and alc. KOH, it forms isocyanide. The reaction is
called carbylamine reaction, RNH 2 + CHCl 3 + 3 KOH → RNC + 3 KCl + 3 H 2 O (R = alkyl or aryl)
The carbene is the reaction intermediate.
(e) When CHCl 3 is treated with phenol in the presence of NaOH, salicyladehyde is formed. The reaction is
called Reimer Tiemann reaction.
OH OH OH
CHO
+ CHCl 3 + 3 NaOH ⎯⎯→ + 3 NaCl +
Major product
CHO
 O 
(ii) Iodoform : When methyl ketones  − C|| − CH  or alcohols having following structure reacts with I 2 and
 3 
 
 

alkali (aq. NaOH or aq. Na 2 CO 3 ), a yellow solid of melting point 119 o C is obtained. The solid is called
H
iodoform and the reaction is called Iodoformic. |
R − C − CH 3
(Where, R = H, alkyl, aryl)
|
OH

As a rule all methyl ketones and alkanol-2 give +ve iodoform test, e.g.
Alcohols and ketones which gives +ve iodoform test –ve Iodoform test (due to absence of − CH 3 gp.)
CH 3 CH 2 OH H
|
H − C − OH
|
H

CH 3 − CH − CH 3 H
| |
OH CH 3 CH 2 C − OH
|
H
C 6 H 5 COC 6 H 5 , C 6 H 5 COC 6 H 11

The reaction is as follows : C 2 H 5 OH + 4 I2 + 6 NaOH → CHI 3 + HCOONa + 5 NaI + H 2 O

H
|
The mechanism is as follows : R − C − CH 3 + NaOI → R
C = O + NaI + H 2 O
| CH 3
OH

R R
C = O + 3 NaOI → I R C = O + 3 NaOH ; C = O + NaOH → CHI 3 + RCOONa
CH 3 3C I3 C Yellow ppt.

(4) Tetrahaloalkanes
(i) Freons is trade name of fluorochloromethanes having general formula CFX Cl y , where (x + y = 4 ) .
(ii) The prefix per means that all H atoms of the hydrocarbons are replaced by fluorine atoms, e.g.
perfluorooctane CF3 (CF2 )6 CF3 . These are chemically inert due to electrostatic force of attraction between
 + on C and  − on F.
(iii) When CCl 4 instead of CHCl 3 is used in Reimer Tiemann reaction the product is salicylic acid.

OH OH OH
+ CCl 4 + 4 NaOH ⎯⎯→
COOH +

Salicylic acid
(Major product)
Aryl Halides. COOH

These are organic compounds in which halogen is directly attached to benzene ring, e.g.
Cl
These can be prepared by reaction of halogen to aromatic hydrocarbon.
Cl

+ + HCl chlorobenzene

(2) By Sandmeyer’s reaction : When acid solution of diazonium salt is added to a solution of cuprous halide
dissolved in corresponding halogen acid, aryl halides are obtained, e.g.

Cl I

⎯⎯ ⎯⎯→
Cu 2 Cl 2
+ N2; + KI ⎯⎯→ + N 2 + KCl
HCl

Br

+ HBr ⎯⎯ ⎯⎯→
Cu 2 Br2
+ HCl + N 2
OH Cl

(3) By reaction of phenol with PCl 5 , ⎯⎯⎯→

PCl 5
+ POCl 3 + HCl

Properties
Physical properties : Aryl halides are generally colourless liquid or crystalline solid. They are soluble in
organic solvents but insoluble in water. The boiling points and melting points are in the following order :
Aryl iodides > Bromides > Chlorides > Fluorides

Chemical properties : The properties can be discussed under two categories :

(1) Properties due to benzene ring : As halogen (s) are ortho para directing, the reactions are as follows :
Cl Cl Cl

⎯⎯ ⎯⎯ ⎯→
Cl 2 / FeCl 3 Cl +

o-dichloro benzene
Cl
p-dichloro benzene

Cl Cl Cl Cl

+
 + +

(2) Properties due to halogen atom : Unlike alkyl halide, the aryl halides do not easily undergo nucleophile
substitution reaction since halogen atom is tightly attached to benzene ring, e.g.
Cl OH

o
⎯ ⎯⎯ ⎯⎯
2 Na , CH 3 I
⎯⎯ ⎯⎯⎯ ⎯→
NaOH , 300 C
+ NaCl
Wurtz- Fittig's 200 atm
reaction Phenol

CN

⎯ ⎯⎯o⎯ ⎯⎯ ⎯ ⎯ ⎯→
Cu 2 (CN )2 NH 3 , Cu 2 O

Pyridine, 200 C

When chlorobenzene is heated with chloral in the persence of conc. H 2 SO 4 , D.D.T. is formed. it is non
biodegradable. It slowly changes to another compound, DDE by loss of a HCl molecule.

Cl Cl
Cl
CCl 3 CH = O + ⎯⎯ ⎯⎯→ CCl 3 CH
H 2 SO 4
⎯⎯ ⎯→ CCl 2 = C
− HCl
− H 2O
Cl Cl Cl
p, p-dichlorodiphenyl (D.D.E)
trichlloroethane
(D.D.T)(insecticide)

Alcohols.
Alcohols are compounds of the general formula ROH, where R is alkyl or substituted alkyl group. The
group may be open chain or cyclic, it may contains double bond, a halogen atom, an aromatic ring or
additional hydroxyl groups, e.g.
OH

CH 3 CH 2 CH 2 CH 2 OH ; ; ; ;
Butanol -1
Benzyl alcohol Cyclohexanol (1-cyclo hexene) methanol Cinnamyl alcohol

Alcohols can be classified as, ALCOHOLS

Monohydric alcohols Dihydric alcohols Trihydric alcohols

contain (1-OH group) contains (2-OH groups) contains (3-OH groups)

e.g.Glycol
e.g. Glycerol

Primary Secondary Tertiary

 (1) Monohydric alcohols
Preparation : (i) By oxymercuration - demercuration reaction of alkene :
 
  NaBH / OH − −
CH 3 − CH = CH 2 + (CH 3 COO )2 Hg + H 2 O ⎯⎯⎯→CH 3 − CH − CH 2
THF
 ⎯⎯ ⎯4⎯ ⎯→ CH 3 − CH − CH 3 + Hg + CH 3 COO
−1 / 2 B 2 H 6
CH 3 COOH
 | |  |

 OH HgOCOCH  OH
3 2 - propanol

Note: ❑ It is fast and convenient. The addition of water to an alkene is anti-Markownikoff and free from
rearrangement.
(ii) Hydroboration of alkene :
1
3 CH 3 − CH = CH 2 + B 2 H 6 → (CH 3 − CH 2 − CH 2 )3 B ⎯⎯ ⎯ ⎯→ 3 CH 3 − CH 2 − CH 2 − OH + H 3 BO 3
3 H 2O2
−
Propene 2 Tripropyl boron OH / H 2O 1- propanol
Diborane

Note: ❑ In this reaction addition of water to an alkene is syn, anti-Markownikoff and free from
rearrangement.

(iii) Hydrolysis of ethers : C 2 H 5 − O − C 2 H 5 + H 2 O ⎯⎯ ⎯⎯ ⎯→ 2 C 2 H 5 OH

dil. H 2 SO 4


(iv) By reaction of Grignard reagent with formaldehyde/ other aldehydes/ ketones

(a) When Grignard reagent reacts with HCHO, it forms primary alcohol.
R R
| | X
H − C = O + RMgX → H − C − OMgX → H − C − OH + Mg
| | | OH
H H H
(b) Oxirane on reaction with Grignard reagent also forms primary alcohol.
O X
+ RMgX → RCH 2 CH 2 OMgX → RCH 2 CH 2 OH + Mg
OH
(c) Any aldehyde except formaldehyde when treated with Grignard reagent forms secondary alcohol.
R R
| | X
R  − C = O + RMgX → R  − C − OMgX → R  − C − OH + Mg
| | | OH
H H H
(d) When 2-alkyl oxirane reacts with Grignard reagent, secondary alcohol is formed. The ring is opened
from least hindered site.

1 CH 3 CH 3
O | | X
+ RMgX → RCH 2 − CH − OMgX → RCH 2 − C − OH + Mg
| OH
3 2 H
(e) When ketone reacts with Grignard reagent, it forms tertiary alcohol.
R R
R R | R | X
C = O + RMgX → C − OMgX → C − OH + Mg
R  R  R  OH
(f) When 2, 2-dialkyl oxirane reacts with Grignard reagent, it forms tertiary alcohol.
 O R1 R1
R1 | | X
+ RMgX → RCH 2 − C − OMgX → RCH 2 − C − OH + Mg
R2 | | OH
R2 R2

OH
(v) By reduction of carbonyl compounds : C = O + 2H → C
H
The reduction can be carried out by using H 2 /catalyst like Ni, Pt, Pd, LiAlH 4 , NaBH 4 , NaH, LiH. When the
reduction is carried out by using metal/solvent combination it is known as Bouveault blanc recduction. The
 
 
intermediates are : R − C − OEt ; R − CH − OEt ; R − CH . In case of metal hydride the reaction intermediate
| | |
O O O
  

is R 2 − C − O
|
H
(vi) By hydrolysis of ester : R1 COOR 2 + KOH → R1 COOK + R 2 OH
(vii) By reaction of alkyl boride with CO :
O
|| OH 
R 3 B + CO → R 2 − B − C − R ⎯⎯ ⎯
⎯→ R 2 BCH
LiBH 4
⎯⎯
OH
⎯→ RCH 2 OH
R H 2O

(viii) By reaction of primary amines with nitrous acid : RNH 2 + HNO 2 → ROH + N 2 + H 2 O
(ix) From glucose : C 6 H 12 O 6 ⎯⎯ ⎯ ⎯→ 2CH 3 CH 2 OH + 2CO 2
Zymase

(ix) Industrial method for methanol and ethanol are as follows :

ZnO + CrO 3
CH 4 + H 2 O ⎯⎯ ⎯→ CO + 3H 2 ; CO + 2 H 2 ⎯⎯
Heat
o
⎯⎯ ⎯→ CH 3 OH
400 C , 200 atm

for ethanol we take ethylene obtained from petroleum : CH 2 = CH 2 + H 2 O(steam) ⎯⎯ ⎯⎯

H 3 PO 4
o
→ CH 3 CH 2 OH
300 - 350 C

It is an Oxo process.
Physical properties: Alcohols are liquid with high boiling point due to intermolecular hydrogen bonding.
Methanol, ethanol, both propyl alcohols and tert-butyl alcohol are completely miscible with water.
Chemical properties : Chemical properties of alcohols can be discussed under three categories :
(1) Reactions involving RCH2 OH cleavage : The reactivity order : Allyl > benzyl > Tert > Sec > Pri
(i) RCH 2 OH + HX → RCH 2 X + H 2 O ; R may rearrange, Reactivity : HI > HBr > HCl
(ii) RCH 2 OH + PX 3 → RCH 2 X + H 3 PO 3 (iii) RCH 2 OH + PCl 5 → RCH 2 Cl + HCl + POCl 3
(iv) RCH 2 OH + SOCl 2 → RCH 2 Cl + SO 2 + HCl (v) 3 RCH 2 OH + PCl 3 → 3 RCH 2 Cl + H 3 PO 3
(2) Reactions involving RCH2 – O H cleavege : The order of reactivity :
CH 3 OH > Primary > Secondary > Tertiary
(i) Alcohols react with metals like Na to form alkoxide and evolve H 2 . This reaction shows acidic nature of
1  
alcohols : RCH 2 − O − H + M → R O M + H 2 Where, M = Na , K, Al, Mg, Zn
2
The relative acidity is : H 2 O  ROH  RC  CH  H 2  NH 3  RH
     
The relative basicity is : R  N H 2  H  RC  C  R O  O H


(ii) Ester formation : ROH + R COOH ⎯⎯→

H
RCOOR + H 2 O
(3) Miscellaneous : (i) Oxidation : (a) Oxidation of alcohols : Number of -H atoms  Oxidation rate of alcohol
 Product yield e.g. R − CH 2 − OH ⎯⎯⎯→ RCHO + H 2 O
[O ]

(Primary alcohol
or
Alcohol with 2 - H )
 R
R R
CHOH ⎯⎯
⎯→ [O ]
C = O + H 2O ; R C OH ⎯⎯⎯→
[O ]
No oxidation under
R R
Secondary alcohol R
or Tertiary alcohol
Alcohol with 1 - H or
alcohol wi th no  - H atom

ordinary conditions
(ii) Iodoform test : Alcohols having following structure gives positive iodoform test.
H
|
R − C − CH 3 i.e. As a rule all alkanol-2 gives positive iodoform test.
|
OH
(iii) Reaction with Lucas reagent (anhydrous ZnCl 2 and conc. HCl) : Lucas reagent has been used to
distinguish primary, secondary and tertiary alcohols :
(a) Allyl alcohol or tertiary alcohol ⎯⎯ ⎯⎯⎯ ⎯→ White turbidity at once
Lucas Reagent

The alkyl halide so formed is insoluble in the medium hence turbidity appears.
(b) Secondary alcohol + Lucas reagent → Turbidity after 5 minutes
(c) primary alcohol + Lucas reagent → No turbidity
(iv) Dehydrogenation : RCH 2 OH ⎯⎯
⎯
Cu
o
→ RCHO + H 2
300 C

R R CH 3
CHOH ⎯⎯
⎯
Cu
→ C = O + H 2 ; CH 3 − C − OH ⎯⎯
⎯
Cu
→ C = CHCH 3
R o
300 C R o
300 C CH 3
CH 3 C2 H 5

(v) When ethanol is heated with Al 2 O 3 , it forms different depending upon temperature, e.g.

CH 3 CH 2 OH ⎯⎯ ⎯
Al 2 O 3
o
→ CH 2 = CH 2 + H 2 O ; CH 3 CH 2 OH ⎯⎯ ⎯
Al 2 O 3
o
→ CH 3 CH 2 OCH 2 CH 3 + H 2 O
350 C 200 C Diethyl ether

(vi) Primary, Secondary and Tertiary alcohols can be distinguished by Victor Meyer’s Method :
(a) RCH 2 OH ⎯⎯→
⎯ RCH 2 I ⎯⎯
HI
⎯⎯→ RCH 2 NO 2 ⎯⎯
AgNO 2
⎯⎯→ R − C − NO 2 ⎯⎯
OHNO
⎯⎯→ R − C − NO 2
NaOH

Primary alcohol || ||
NOH NONa
Nitrolic acid Red sodium salt or nitrolic acid

R R R R
(b) CHOH ⎯⎯→
⎯
HI
CHI ⎯⎯ ⎯⎯→
AgNO 2
CH − NO 2 ⎯⎯ ⎯⎯→
OHNO
C − NO 2 ⎯⎯ ⎯⎯→ Blue colour
NaOH
R R R R |
Secondary alcohol NO
Pseudo nitrolic acid

R R
(c) R C OH ⎯⎯→
⎯ R HI
C I ⎯⎯ ⎯
⎯→ No reaction
HNO 2

R R
(2) Dihydric alcohol Chemical Properties
Glycol (Ethane – 1, 2- di-ol) CH 2 − ONa CH 2ONa
| |
Preparation Na Na
⎯⎯⎯→
CHOH CH − OH
Lab. Method | |
3CH 2 = CH 2 + 2KMnO 4 + 4H 2O → CH 2 − OH CH 2 − ONa
Mono sodium Disod. glycerolate
CH 2 − OH glycerolate
3| + 2MnO 2 + 2KOH HCl gas
CH 2 − Cl CH 2 − OH
CH 2 − OH limited | |
(Glycol) CHOH + CHCl
| |
Chemical Properties CH 2OH CH 2 − OH
HCl gas
CH 2ONa CH 2 − Cl CH 2 − Cl
Na 323K excess | |
|
433 K CH 2ONa CH − Cl + CH − OH
Disodium glycolate | |
CH 2 − OH CH 2 − Cl
HI
CH 2 − Cl CH 2 − I CH 2 CH 3
HCl 433K | || |
| HI
473 K CH 2 − Cl CH − I → CH ⎯⎯⎯→ CH − I
| | |
Ethylene chloride
CH 2 − I CH 2 − I CH 2 − I
CH 3 CH 3
 (Glycerol)

Phenols.
Phenols are the organic compounds in which − OH group is directly linked to aromatic ring system. The
simplest formula of such compound is phenol (C 6 H 5 OH ) . Structure of some common phenols is as follows :
OH OH OH
OH

; ; ;

Phenol o-Cresol m-Cresol

p-Cresol
OH OH
OH
OH
Catechol OH
Resorcinol OH
Quinol

Preparation : (1) Phenols can be prepared by reaction of benzene sulphonic acid with NaOH.

OH
 + NaOH ⎯⎯→ + H 2 O ⎯⎯ ⎯⎯→
(i) NaOH
+ Na 2 SO 3
(ii) HCl

(2) Phenols can also be obtained by warming diazonium salt solution with hot dilute acid solution.

OH

+ HX + N2

Cl OH
o
(3) Phenols can be prepared from aryl halides, + NaOH ⎯⎯ ⎯
⎯→
300 C
+ NaCl
200 atm

OH OH
(4) By reaction of phenolic acid with soda lime. + NaOH (CaO ) → + Na2CO
COOH

Physical properties : (1) Phenols are colourless liquid or crystaline solids. They turn pink due to oxidation.
(2) Phenols are weak acid and have high boiling point due to intermolecular hydrogen bonding.
Chemical properties :
Due to benzene ring
similar to alcohols
Chemical Due to – OH group
different from alcohols
Miscellaneous

(1) Properties due to benzene ring : We have already discussed that − OH group is o-p directing. The
reactions due to benzene ring are briefly as follows :

OH OH
NO2
dil. H2SO4, 200 C
+
HNO3
p- notrophenol
o- notrophenol
NO2

OH

O2N NO2
conc. NHO3
H2SO4, 

NO2 2, 4, 6 – trinitrophenol (Picric acid)

OH OH

SO3H
H2SO4
+
20oC

o- phenol sulphonic acid (major product) SO3H

OH OH

H2SO4 SO3H
+
100 C
o

OH SO3H
major product
Note: ❑ It is important to note that Br2 in water yields tri-bromo derivative but in CCl 4 only
monobromoderivative. It is because of greater ionisation of Br2 in water in comparison to that of CCl 4 in
which the ionisation is very small.
(2) Reactions due to – OH groups which are similar to alcohols
(i) Reactions with acids : Ester formation occurs.
OH OOCR

+RCOOH +H2O
OH OOC. C6H5

Esterification can also be carried out with acid chloride. +C6H5COCl

Benzoyl chloride
Phenyl benzoate
The reaction is known as Schotten-Baumann reaction.
Further, when phenyl esters are treated with anhyd. AlCl 3 they undergo Fries rearrangement which
involves migration of acyl group to o– or –p– positions of the ring with respect to − OH group, to form
phenolic ketones.

OOC.CH3 OH OH
COCH3
+

Steam volatile COCH3

o & p – hydroxy acetophenone
 OH Cl OH NH2

(ii) +HCl + POCl3 (iii) + H2 O

Chlorobenzene OH AnilineOR

(iv) Phenols with alkyl halide forms ether. +HX

(3) Reactions in which phenol differs from alcohols

(i) Phenols gives colour with FeCl 3 due to formation of the complex, the exact nature of which is not known,
but iron is hexavalent. The colours are as follows :
Phenol, Resorcinol, Salicylicacid : Violet colour
p-Hydroxy benzoic acid
Catechol, o-cresol : Green
m-cresol, p-cresol : Blue or blue-violet
Quinol : Red
OH
(ii) Phenols are acidic in nature.
(iii) When phenol is distillet with Zn, − OH group is removed. + ZnO

Reimer Tiemann Reaction : When phenol is refluxed with chloroform and NaOH, it forms salicylic aldehyde
as major product. OH OH OH
CHO
+
Salicylic acid (Major product)
CHO
However, if CCl 4 / NaOH is used the major product is salicylic acid.
OH OH OH
COOH
+
Salicylic aldehyde (Major Product)
COOH

The reaction intermediates are as follows :

⊝ ⊝ ⊝
O O O O
H CHCl2
; CCl2 ; ;
⊝

CHCl2
Salicylic acid is of great importance since it has been used to prepare some compounds.

OH OH OCOCH3
COOCH3 COOH
Methyl salicylate (Oil of winter green) Acetyl salicylic acid
(aspirin)
(used as analgesic)
Kolbe reaction or Kolbe-Schmidt reaction : When sodium phenoxide reacts with CO 2 at 120 o C under

5-7 atmosphere followed by acidification with H , it forms salicylic acid.

ONa OH OH

o
COONa ⎯⎯→ COOH
+ CO 2 ⎯⎯ ⎯
⎯→
120 C H
5 − 7 atm

Salilylic acid

The reaction intermediate (s) are :

⊝ ⊝
O O OH
⊝ ⊝
COO COO
; ;

Phthalein reaction : OH OH OH OH

O
||C
C
O O
C
C
||O
||O
Phenolphthalein
Phthalic anhydrolic
note that H para to OH is removed.
Ledrer-Manasse reaction : When phenol reacts with formaldehyde in the presence of acid or alkali, it forms
bakelite, a thermostat polymer.
OH
OH OH OH

–H2O

CH2OH CH2 OH

+ CH2
Bakelite

OH
Liebermann’s nitroso reaction

Phenol ⎯⎯ ⎯⎯⎯⎯⎯ ⎯→ deep green or blue colour ⎯⎯

NaNO 2 / conc. H 2 SO 4
⎯→ Red ⎯⎯
H 2O
⎯⎯→ green or blue colour
NaOH

The reactions are as follows :

OH OH O

NO NOH
p-nitrosophenol quinone monoxime

; H2SO4

OH
O
⊕
OH
O

N– OH
N– OH
 OH OH


Nitrosation : + HNO 2 ⎯⎯
H
⎯
o
→
10 C

NO
p-nitrosophenol

OH OH

Hydrogenation : + 3H2 ⎯⎯→

⎯
Ni
150 − 200 o C

Cyclohexanol

Oxidation : Phenols turn pink or red or brown when exposed to air and light due to slow oxidation. The exact
nature of these oxidation product is not known; but probable products are quinones and phenoquinones.

OH O O ………..

O O ………..
quinone Phenoquinone

When phenols is oxidised with potassium persulphate in alkaline solution, it forms quinol and the reaction
is known as Elbs persulphate oxidation.
OH OH

O
quinol

Some important Points.

Halogen derivatives
(1) Many of alkyl halides burn with green edged flame.
(2) C 2 H 5 Cl is used as a local anaesthetic.

(3) C 2 H 5 SH (Ethyl mercaptan) is added to LPG (household cooking gas) to detect leakage. The compound
has a typical smell.
(4) CCl 4 is used to extinguish fire under the name pyrene.

(5) CCl 4 resist hydrolysis with boiling water due to non availability of d-orbitals in C.
 (6) CCl 4 is an antihelminthic medicine against hookworm.

(7) C 2 Cl6 is a solid and is known as artificial camphor.

(8) Freon-14 is CF4 , Freon-13 is CF3 Cl , Freon-12 is CF2 Cl 2 and Freon-11 is CFCl 3 . All of these are used
as refrigerant.
(9) Lindane or Gammaxane or 666 is an isomer of BHC (C 6 H 6 Cl 6 ) and is used as insecticide against
termites. It is obtained by reaction of Cl 2 / hv with benzene.
Cl
Cl Cl
+ 3Cl 2 ⎯⎯→hv

Cl Cl
Cl
BHC

(10) Westron (acetylene tetrachloride) is used as a good industrial solvent for oil, fats,, paints ansd varnishes
etc.
(11) Iodoform has antiseptic properties because on coming in contact with organic matter of skin it
decomposes to give free iodine which is an antiseptic.
(12) Chloretone is a sleep inducing medicine (hypnotic). Phosgene is harmful poisonous gas used in warfare.
Chloropicrin is a tear gas and insecticide.
Alcohols
(1) Wood spirit : Methyl alcohol (CH 3 OH ) is called wood spirit. It is obtained by distructive distillation of
wood. Drinking of methanol causes blindness.
(2) Grain alcohol. Ethyl alcohol (C 2 H 5 OH ) is called grain alcohol. It is used in preparation of various
beverages, by using different percentages.
(3) Proof, over proof and under proof spirit. An alcohol-water mixture containing 57.1% alcohol by volume or
49.3% by weight is called proof spirit. A sample having higher percentage of ethyl alcohol in comparison to
proof spirit is called over proof spirit (O.P.) and the one having lower percentage is called under proof spirit
(U.P.).
e.g., 10 O.P. means 100 ml of given sample contains alcohol as 110 ml of proof spirit. 10 U.P. means 100 ml of
given sample contains as much alcohol as present in 90 ml of proof spirit.
(4) Methylated spirit of denatured spirit. Ethyl alcohol containing 5 to 10% methyl alcohol is called methylated
spirit. It is unfit for drinking purposes. Widespread deaths due to liquor poisoning occur mainly due to the presence
of methyl alcohol. It is also called denatured spirit. Denaturing can also be done by adding 0.5% pyridine, petroleum
naptha, rubber distillate (caoutchoucine) or CuSO 4 .
(5) Power alcohol. A mixture of 80% petrol, 20% ethyl alcohol with co-solvent benzene is called power
alcohol. It is used to run automobiles.
(6) Absolute alcohol. 100% ethanol is called absolute alcohol. It is generally prepared by azeotropic
distillation.
(7) Rectified spirit. Ethyl alcohol (95.87%) + water (4.13%) mixture is known as rectified spirit.
(8) Pyroligneous acid contains acetic acid (10%), methyl alcohol (2.5%) and acetone (0.5%).
(9) Fusel oil is mixture of n-propyl alcohol, n-butyl alcohol, n-amyl alcohol and isoamyl alcohol.
(10) Argol is potassium hydrogen tartarate. It is used to manufacture tartaric acid.
(11) Tincture of iodine is 2-3% alcoholic solution of iodine.
(12) In the oxidation of alcohol by acidified K 2 Cr2 O 7 , its colour changes from orange to green due to the
formation of Cr2 (SO 4 )3 .
 (13) 3 o alcohols are resistant to oxidation due to lack of -hydrogen.
(14) 1 o alcohols on dehydrogenation with red hot copper form aldehydes, 2 o alcohols form ketones and 3 o
alcohols form alkenes by dehydration.
(15) Fischer-Speier esterification, CH 3 COOH + HOC 2 H 5 ⎯⎯ ⎯⎯→ CH 3 COOC 2 H 5 + H 2 O
dry HCl

Acetic acid Ethyl alcohol Ethyl acetate

(16) The rates of esterification of three types of alcohols (R O − H ) are quite different and can be employed
in their distinction. The percentages of esters obtained by 1 o , 2 o and 3 o alcohols with acetic acid are 45.7%, 5.4%
and 1.4% respectively (because reactivity order is 1 o  2 o  3 o ).
(17) In the esterification reaction, the water formed is removed by Dean and Stark apparatus. It should be
noted that, bulkier the acid or alcohol, slower is the rate (due to stearic hinderance), Decreasing order of rate of
reaction of differnet alcohols and acids is, CH 3 OH  C 2 H 5 OH  (CH 3 ) 2 CHOH  (CH 3 )3 C − OH
HCOOH  CH 3 COOH  (CH 3 ) 2 CH − COOH  (CH 3 )3 C − COOH
(18) Alcohols cannot be dehydrated using anhydrous CaCl 2 because it forms an addition compound,
CaCl 2 . 4 CH 3 OH .
(19) The name fermentation has been derived from Latin word ferver meaning to boil, as during this process
there is lot of frothing due to evolution of CO 2 and this gives the appearance of boiling liquid. Favourable conditions
for fermentation are (i) Optimum temperature (25 − 30 o C ) , (ii) A low concentration of solution, (iii) Presence of
certain inorganic compounds (like ( NH 4 ) 2 SO 4 , phosphate etc.) which acts as food for the ferment cells.
(20) Pinacol-Pinacolone rearrangement. The reaction involves dehydration of diols through the formation of
carbocation intermediate which rearranges to more stable compound.
OH OH CH 3
| | |
H+
CH 3 − C − C − CH 3 ⎯⎯
⎯→ CH 3 − C − C − CH 3
| | − H 2O || |
CH 3 CH 3 O CH 3
Pinacol Pinacolone

(21) Order of acidity : H 2 O  ROH (1 )  ROH (2 )  ROH (3 )  RC  CH  RCH 3

o o o

(22) Hydroxylation of alkene can be carried out either by cold alkaline KMnO 4 or peroxy formic acid
(HCO 2 OH ) . Hydroxylation by either reagent is stereoselective and stereospecific. Cold alkaline KMnO 4 gives syn
addition and peroxy acid gives anti addition.
(23) The reaction of glycol with ketone is used in the protection of keto group in the reactions where it is to
be protected.
(24) Oxidation of glycol with lead tetracetate give formaldehyde.
CH 2 OH
| + (CH 3 COO )4 Pb → 2 HCHO + 2 CH 3 COOH + (CH 3 COO ) 2 Pb
CH 2 OH
(25) Glycol is used as an antifreeze for automobile radiators and as a coolant for aeroplane aviation petrol
under the name prestone.
(26) Glyceryl trinitrate is an inorganic ester.
(27) Glyceryl trinitrate is colourless, oily liquid insoluble in water and is called Nobel’s oil.
(28) On detonating it explodes violently giving CO 2 , N 2 , O 2 as gaseous products.
4 C 3 H 5 (ONO 2 ) 3 12 CO 2 + 10 H 2 O + 6 N 2 + O 2
(29) It is a safer explosive when absorbed on keiselguhr and is known as dynamite.
(30) Its mixture with cellulose nitrate is known as blasting galetin or geilgnite.
(31) Its mixture with cellulose nitrate (gun cotton) and vaseline is called cordite. It is a smokeless powder.
(32) Nobel’s oil is also used in the treatment of angina pectoris and asthma.
 (33) Dunstan’s test for glycerol. A drop of phenolphthalein is added to approx. 5 ml. of borax solution. The
pink colour appears. On adding 2-3 drops of glycerol, the pink colour disppears. The pink colour reappears on
heating and disappears on cooling again.
Phenols
(1) Aqeous solution of phenol is also called carbolic acid.
(2) 2, 4, 6-Trinitrophenol is called picric acid.
(3) Phenol is stronger acid as compared to ethanol but weaker acid as compared to acetic acid.
(4) Groups with +M effect and +I effect decrease the acid strength.
(5) Groups with +M effect and –I effect decrease the acidity at p-position, but at m-position, the acidity is
increased due to –I effect.
(6) Benzene-1, 3, 5-triol is also called phloroglucinol.
(7) In general, acid strength increases as
Cresols << Phenol << p-Chlorophenol << m-Nitrophenol << o-Nitrophenol < p-Nitrophenol << Picric acid
(8) Ph-O bond acquires double bond character due to resonance and is less susceptible to cleavage.
O
(9) Fries rearrangement : ||
O – C – CH3 OH OH

COCH3
+
Phenyl acetate o-Hydroxyacetophone
COCH3
p-Hydroxyacetophone
The p-isomer is formed predominantly at low temperature while high temperature favours the formation of
o
(10) Phenol on condensation with resorcinol in the presence of conc. H 2 SO 4 give fluorescein.
(11) In the Reimer-Tiemann reaction, the electriophile used is : CCl 2 (dichloromethylene).
NO2
(12)NO2 OH is also called as 2, 4, 6-trinitroresorcinol or styphinic acid.
OH NO2

(13) The solubilities of o, m and p-nitrophenol in water increases in the order o  m  p . In fact o-
nitrophenol contains intramolecular H-bonds.
(14) Phenols cannot be converted into esters by direct reaction with carboxylic acids whereas alcohols can
be. This is due to the fact that the esterification reaction is exothermic for alcohols but slightly endothermic for
phenols.
(15) In Elb’s persulphate oxidation the second − OH group is mainly introduced at the p-position but if this
position is occupied than at o-positions.