Organic

Chemistry
By

Dr. rer. nat. Zeinab

Mohamed

2020
 Br2/NaOH NH2 Hoffmann
CONH2

Br2/NaOH
COBr3 COONa + CHBr3
COCH3

haloform

N(CH3)2
NaNO2/HCl
HO3S NH2 HO3S N N Cl

HO3S N N N(CH3)2

methyl orange
NH2
N
N Cl N
NaNO2/HCl -HCl
N
NH2
NH2
N
H
Benzotriazole
 Hydroxy compounds -OH

Alcohols Phenols
-OH attached to -OH attached to
aliphatic C Aromatic C

C H 2O H OH

B e n z y l a lc . P henol
Phenols: are organic compounds contains one or more –OH
group attached directly to benzene ring
OH OH OH OH

CH3 OH

OH
p h en o l o -cr e so l c a te ch o l q u in o l

OH OH OH

HO OH

HO OH
OH
R eso r cin o l p y r o g a llo l p h lo r o g lu c in o l
OH
OH

1 -n a p h th o l 2 -n a p h th o l
 -n a p h th o l  -n a p h th o l
Preparation of Phenol
O

Fe
OCOph
3

FeCl3 X
phCOCl Na2CO3
phenylbenzoate NO REACTION

OH
Zn / 

NaOH OC2H5
OCOCH3 ONa
CH3COCl C2H5I

phenetol
phenylacetate phenylethyl ether

Cl NO2

O NO2

p-nitro diphenylether
 O
Reactions of Phenol
F e
O C O p h
3

F e C l3 X
phC O C l N a2C O 3
p h e n y lb e n z o a te N O R E A C T IO N
O H

N aO H O C 2H 5
O C O C H 3 O N a
C H 3C O C l C 2H 5I

p h e n e to l
p h e n y la c e ta te p h e n y le th y l e th e r

C l N O 2

O N O 2

p -n itr o d ip h e n y le th e r
 OH OH
CH3

+ OH
OH OH

CH3Cl/AlCl3 Br Br Br
OH OH CH3
+
NO2 OH
Br2/AlCl3
+
HNO3/H2SO4
Br Br
OH 2,4,6-tribromophenol
oleum OH
NO2
SO3H

(CH3)2SO4 +
OH

NO2 NO2
2-Hydroxy-benzenesulfonic acid
SO3H
OCH3
OCH3 OH

NO2 CH3COCl/AlCl3 AlCl3/CS2

Picric acid

COCH3 COCH3
Reimer Tiemann Reaction
OH OH
CHO
1)OH
2)H+

OH -Cl
CHCl3 CCl3 CCl2
dichloro carbene
OH O O

OH H
CCl2
CCl2

O
CHCl2 O OH
OH
CH CHO
OH OH 1) -H2O
2) H+
 OH OH
Kolb-Schmidt Reaction COOH
1)OH / CO2
2)H+

OH O
O O OH
O H C OH
OH O
C O COOH
C O H
O

Hydroxy-methylation Reaction OH OH
CH2OH
1)OH / HCHO
2)H+

OH
O O OH
O H CH2 OH
OH O
H C H CH2OH
CH2 H
O

OH OH OH OH
CH2OH CH2OH
1)OH / HCHO
+
2)H+

CH2OH CH2OH
4-Hydroxymethyl-phenol 2,4-Bis-hydroxymethyl-phenol
 OH
COUPLING

N N OH
N N Cl

HO
OH

N N

paracetamol CH3
CH3

OH OH OH OH

HNO3 Zn CH3COCl
H2SO4 HCl

NO2 NH2 NHCOCH3

p-acetamol
Phthalein Reaction
OH
COOH

+ 2 1)conc H2SO4 
2) NaOH
COOH

HO OH OH
HO

C OH
O
-H2O
O
O
O
ph.ph in Acid medium
O
colorless
O O Na
HO HO

OH
C C
OH

O Na O Na
O O
ph.ph in Basic medium ph.ph in strong basic medium
pink colorless
Aromatic Alcohols they are aromatic compounds in which -OH
Group is not directly attached to the aromatic ring but to a side-chain
CH2OH

benzyl alcohol
Preparation C H 2C l

b e n z y l c h lo r id e

N aO H

CHO M gBr
C H 2O H C H 2 O M gBr O
Z n /H C l H 2O H C H
re d u c tio n
b e n z a ld e h y d e
b e n z y l a lc o h o l p h e n y l m a g n e s iu m b r o m id e
 C H 2O N a
C H 2O C O C H 3
CH3

(C H 3 C O ) 2 O
H I/P b en zy l a ceta te
Na

C H 2C l COOH
C H 2O H CHO
P C l5 [O ] [O ]

b en zy l a lco h o l b en za ld eh y d e b en zo ic a cid
C H 2C N
KCN C H 2C O O H

h y d ro ly sis

p h en y l a cetic a cid
Carboxylic Acids -COOH
COOH CH CH COOH COOH CH2 COOH

OH
Benzoic acid Cinnamic acid salicylic acid Phenylacetic acid

COOH COOH COOH

COOH
COOH

COOH
NH2
COOH COOH CH3
phthalic acid Anthranilic acid
Isophthalic acid tere-phthalic aci p-Toulic acid o-Amino benzoic acid
Preparation methods
MgBr

O OMgBr
OH
C O
C O hydrolysis C O
+

benzoic acid
CH2MgBr OMgBr
CH2 C O
OH
O
CH2 C O
+ C O hydrolysis

benzyl magnesium bromide

CH2OH phenylacetic acid
CH2Cl CH2CN
CH2COOH
PCl5 KCN hydrolysis

benzyl alc.
CH3 COOH phenylacetic acid
KMnO4

CH3 phthalic acidCOOH

o-Xylene
 Reactions
1. Acidity acids reacts with sod. Carbonate or sod. bi carbonate → evolution of CO2

RCOOH+ Na2CO3 RCOONa + H2O + CO2

2. Reaction with ammonia solution acids reacts with NH4OH→ ammonium salt
(neutral solution)

RCOOH+ NH4OH RCOONH4 + H2O

3. Reaction with NaOH acid reacts with NaOH→ sodium salt of acid

RCOOH+ NaOH RCOONa + H2O

 4. Reaction with FeCl3 Ammonium or sod salt of acid react with
ferric chloride solution forming ferric salt of acid
COONH4 COONH4 CH=CH-COONH4 CH2COONH4 COONH4

COONH4 OH

FeCl3

COO COO CH=CHCOO CH2COO COO

Fe Fe
Fe2 Fe Fe
COO OH
3 3
3 3
3
Buff ppt Buff ppt Buff ppt reddish violet ppt
COOH
Only salicylic acid reacts directly with FeCl3 as phenol
Forming violet color of ferric phenate Fe
O
3
5. Reaction with sodalime (decarboxylation)→
COOH
COONa evolution of CO2
Na2CO3
COOH + CO2 + H
CH2O
COOH CH=CH-COOH 2COOH COOH

sodium Benzoate
COOH OH
COOH COONH4

NH4OH
Soda lime+ H O
NaOH/Ca(OH)2 2

Ammonium Benzoate
CH=CH2 CH3
COOH
COOCH3

CH3OH
OH
6. Esterification in presence of conc sulfuric acid
PhCOOH + ROH methylbenzoate PhCOOR
COOH COOH COOCH3

(CH3CO)2O CH3OH
or CH3COCl
OCOCH3 OH OH
Acetylsalicylic acid Salicylic acid methylsalicylate
Aspirin Vicks odour
Reactions of phthalic acid
Phthalein Reaction
OH
COOH

+ 2 1)conc H2SO4 
2) NaOH
COOH

HO OH OH
HO

C OH
O
-H2O
O
O
O
ph.ph in Acid medium
O
colorless
O O Na
HO HO

OH
C C
OH

O Na O Na
O O
ph.ph in Basic medium ph.ph in strong basic medium
pink colorless
Fluorescence
Flourscene testtest

HO OH HO OH
HO O
OH

O
C C
conc. H2SO4
O O

flourscene in acidic
C C medium
O O colorless

Na O O
O
NaOH

O Na

flourscene in basic medium

C orange/green flourscent colour
O
Cinnamic acid characterized by the presence of C=C group so it
decolorize KMnO4 solution (Bayer test), and bromine solution
as well
Acidity of carboxylic acids is higher than that of phenols so
carboxylic acid react with sod. Carbonate and phenols do not.
Acidic character increase in presence of e-withdrawing groups

2-phenyl-2-propanol

1-phenyl ethanol
 O
NaOH
2 ph C H phCOONa + ph-CH2OH
sod. benzoate benzyl alcohol
Mechanism:

O O
OH
C H C H
OH

O O O O
NaOH
C H + H C C H + C OH
OH H
H Hydride shift

OH O
C H + C O Na
H