FENOL

Nomenclature.
Phenols are usually named as substituted phenols. The methylphenols are
given the special name, cresols. Some other phenols are named as hydroxy
compounds.

OH OH CH3 OH
OH COOH

Br

phenol m-bromophenol o-cresol salicylicacid

OH OH COOH
OH
OH

OH
OH OH

catechol resorcinol hydroquinone p-hydroxybenzoicacid

physical properties
phenols are polar and can hydrogen bond
phenols are water insoluble
phenols are stronger acids than water and
will dissolve in 5% NaOH
phenols are weaker acids than carbonic acid and
do not dissolve in 5% NaHCO3
Intramolecular hydrogen bonding is possible in some ortho-substituted
phenols. This intramolecular hydrogen bonding reduces water
solubility and increases volatility. Thus, o-nitrophenol is steam
distillable while the isomeric p-nitrophenol is not.

OH
O
H
O
N
O NO2

o-nitrophenol p-nitrophenol
bp100oCat 100mm bpdecomposes
0.2g/ 100mLwater 1.69g/ 100mLwater
volatilewithsteam non-volatilewithsteam
 OH

• Fenol adalah alkohol aromatik

• Khasiat: antiseptik
• Fenol bersifat asam karena fenol terdisosiasi
menjadi ion fenoksida dengan melepaskan H+.
Fenol memp keasaman lebih kuat daripada
alkohol (pKa=10), karena adanya resonansi
dari ion fenoksida, sedang alkoksida tidak ada
stabilisasi
O O O O
 Tabel Keasaman derivat fenol
Senyawa pKa Senyawa pKa
2,4,6 –trinitrofenol 0,38 P-hidroksifenol 9,70
P-nitrofenol 7,15 P-aminofenol 9,70
O-nitrofenol 7,17 Fenol 9,89
P-florofenol 9,96
M-nitrofenol 8,28
P-metilfenol 10,17
P-klorofenol 9,20 Etanol 16,00
P-iodofenol 9,20
P-bromofenol 9,25
• Mengapa substitusi nitro meningkatkan
keasaman fenol, sedangkan substitusi metil
menurunkan keasaman?
• pKa p-nitrofenol adalah 7. Gunakan struktur
resonansi untuk menjelaskan senyawa ini
lebih asam daripada fenol.
• Mengapa pengaruh posisi meta pada
substitusi nitro lebih kecil drpd orto dan para
pada peningkatan keasaman fenol?
Phenols, reactions:
1. as acids
2. ester formation
3. ether formation
4. EAS
a) nitration f) nitrosation
b) sulfonation g) coupling with diaz. salts
c) halogenation h) Kolbe
d) Friedel-Crafts alkylation i) Reimer-Tiemann
e) Friedel-Crafts acylation
as acids:
with active metals:

OH ONa
Na
+ H2(g)
with bases:
CH4 < NH3 < HCCH < ROH < Hsodium
2O < phenols < H2CO3 < RCOOH
phenoxide
< HF

OH ONa

+ NaOH + H2O

SA SB WB WA
CH4 < NH3 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF

OH ONa

+ NaOH + H2O

SA SB WB WA
water insoluble water soluble

OH

+ NaHCO3 NR phenol <H2CO3

CH4 < NH3 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF

water 5% NaOH 5% NaHCO3

phenols insoluble soluble insoluble

carboxylic
acids
insoluble soluble soluble
We use the ionization of acids in water to measure acid strength (Ka):
HBase + H2O H3O+ + Base-

Ka = [H3O+ ][ Base ] / [ HBase]

ROH Ka ~ 10-16 - 10-18

ArOH Ka ~ 10-10

Why are phenols more acidic than alcohols?

ROH + H2O H3O+ + RO-

ArOH + H2O H3O+ + ArO-

O
H O
H O O O O O

Resonance stabilization of the phenoxide ion, lowers

the PE of the products of the ionization, decreases
the ΔH, shifts the equil farther to the right, makes
phenol more acidic than an alcohol
effect of substituent groups on acid strength?

O
H O

G+H
O
2 G+H
O
3

Electron withdrawing groups will decrease the negative charge in the

phenoxide, lowering the PE, decreasing the ΔH, shifting the equil farther
to the right, stronger acid.
Electron donating groups will increase the negative charge in the
phenoxide, increasing the PE, increasing the ΔH, shifting the equilibrium
to the left, weaker acid.
Number the following acids in decreasing order of acid strength (let # 1 =
most acidic, etc.)

O
H O
H O
H O
H O
H

N
O2 C
H3 B
r

3 5 1 4 2
S
O3H C
OOH O
H C
H2OH

1 2 3 4
2. ester formation (similar to alcohols)

OH
CH3 O H+ O
+ CH3CH2C CH3CH2C + H2O
OH O

H3C

O
OH H3C C
COOH O
+ (CH3CO)2O COOH

salicyclicacid aspirin
 O
analgesic
H 3C C anti-inflam atory
O
antipyrretic
CO O H anticoagulant

Reye's syndrom e
aspirin not to be used by children
with high fevers!

OH

aspirin substitute
Tylenol

H 3 C C NH Kidney dam age!

O

acetam inophen
3. ether formation (Williamson Synthesis)
Ar-O-Na+ + R-X  Ar-O-R + NaX
note: R-X must be 1o or CH3
Because phenols are more acidic than water, it is possible to generate
the phenoxide in situ using NaOH.

O
H O
CH
2C
H3

+CH
C
3HB
2r
,Na
OH

C
H3 C
H3
4. Electrophilic Aromatic Substitution
The –OH group is a powerful activating group in EAS and an
ortho/para director.
a) nitration

OH OH
HNO3 O2N NO2
polynitration!
NO2

OH OH OH
diluteHNO NO2
3
+

NO2
b) halogenation

OH OH
Br2(a
q .) B
r Br n
ocatalystrequired
u
sepolarsolvent

Br
polyhalogenation!
OH OH OH
Br2,CCl4 Br
+
non-polars
o lvent
B
r
c) sulfonation

OH OH
H2SO4, 15-20oC SO3H

OH

H2SO4, 100oC

SO3H

At low temperature the reaction is non-reversible and the lower Eact

ortho-product is formed (rate control).
At high temperature the reaction is reversible and the more stable
para-product is formed (kinetic control).
d) Friedel-Crafts alkylation.

O
H O
H
C
H 3 A
lC
l3
+H
3CCC H3
C
l
H
3CCCH3
CH
3
e) Friedel-Crafts acylation

OH OH
O AlCl3
+ CH3CH2CH2C
Cl

Do not confuse FCacylation with esterification:

OH
O
O
+ CH3CH2CH2C O
Cl
Fries rearrangement of phenolic esters.

OH
O
O
+ CH3CH2CH2C O
Cl

AlCl3

OH

O
f) nitrosation

OH OH
HONO
p-nitrosophenol

NO

EAS with very weak electrophile NO+

OH OH
CH3 CH3
NaNO2, HCl

NO
g) coupling with diazonium salts
(EAS with the weak electrophile diazonium)

OH N2 Cl OH
CH3 CH3
+

benzenediazonium N
chloride N

anazodye
h) Kolbe reaction (carbonation)

ONa OH
COONa
125oC, 4-7 atm.
+ CO2

sodium salicylate

EAS by the weakly H+

electrophilic CO2

O C O OH
COOH

salicylic acid
i) Reimer-Tiemann reaction

O
H O
H
C
HCl3,a
q.N
aO +
H H C
HO

7
0oC

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Amina dan Arilamin
 NH2
Anilina
amoinobenzen

• Arilamin bersifat basa, karena adanya lonepair

electron dari nitrogen yang dapat membentuk
ikatan dengan asam Lewis.
• Sifat basa dari arilamin secara umum lebih
rendah dibanding amin alifatis karena lonepair
electron dari nitrogen terdelokalisasi ke dalam
cincin sehingga lebih susah membentuk
ikatan.
relative base strength
RNH2 > NH3 > ArNH2
Kb ionization of the base in water
:Base + H2O H:Base+ + OH-
Kb = [ H:Base+ ] [ OH- ] / [ :Base ]

Kb
aliphatic amines 10-3 – 10-4
ammonia 1.8 x 10-5
anilines 10-9 or less
Why are aliphatic amines more basic than ammonia?

NH3 + H2O  NH4+ + OH-

R-NH2 + H2O  R-NH3+ + OH-

The alkyl group, -R, is an electron donating group. The donation of

electrons helps to stabilize the ammonium ion by decreasing the positive
charge, lowering the ΔH, shifting the ionization farther to the right and
increasing the basicity.
Why are aromatic amines less basic than aliphatic amines?
R-NH2 + H2O  R-NH3+ + OH-

NH2 NH3

+ H2O + OH

NH2 NH2 NH3 NH3

NH2 NH2 NH2 resonance stabilization of the free base,

increases the ΔH, shifts the ionization to
the left, decreasing base strength.
Effect of substituent groups on base strength:

N
H2 N
H3

+H
2O +O
H

G G

Electron donating groups will stabilize the anilinium ion, decreasing the ΔH,
shifting the ionization farther to the right and making the compound a stronger
base.
Electron withdrawing groups destabilize the anilinium ion, increasing the ΔH,
shifting the ionization towards the reactants, making the compound a weaker
base.
Common substituent groups:

-NH2, -NHR, -NR2

-OH
-OR
-NHCOCH3 electron donating
-C6H5 groups
-R
-H
-X
-CHO, -COR
-SO3H electron withdrawing
-COOH, -COOR groups
-CN
-NR3+
-NO2
Number the following in decreasing order of base strength (let #1 = most
basic, etc.

N
H2 N
H2 N
H2 N
H2

N
H3

N
O2 O
CH3

4 1 5 3 2
 NH2 NH2 NH2 NH2

Delokalisasi lonepair electron ke dalam cincin

menyebabkan arilamin lbh susah menerima H+
dibandingkan amin alifatis, sehingga kebasaan arilamin
lbh rendah dibanding amin alifatis

R NH2
Substitusi pada arilamin mengubah sifat basanya

Substituen EDG pKb Substituen EWG pKb

NH2 7,85 Cl 10,02
OCH3 8,66 Br 10,14
CH3 8,92 CN 12,26
NO2 13,0
H 9,37

Secara umum, gugus EDG meningkatkan kebasaan anilin,

sedangkan deaktivator menurunkan kebasaan anilin. Hal ini
karena substituen EDG mendonasikan elektron ke dalam
cincin sehingga atom N lebih kaya elektron, sebaliknya
substituen EWG menarik elektron dari cincin dan dari atom N,
atom N kekurangan elektron, sehingga kebasaan turun
Pembuatan Anilin
Arilamin dibuat melalui nitrasi cincin aromatik diikuti
reduksi gugus nitro
O O-
+
N NH2

H2/Pt

etanol

p-tert-butil-nitrobenzen

SnCl2, H2O
NaOH, H2O
O O
O2N H2N
m-nitrobenzaldehid m-amino benzaldehid

CH3 CH3
Fe, HCl
NaOH, H2O

O2N NO2 H2N NH2

2,4-dinitrotoluene 2,4-diaminotoluene
Reaksi-reaksi Arilamin

• Substitusi Elektrofilik Aromatik

Substitusi amino (-NH2) adalah aktivator kuat
(pengarah orto, para). Adanya substituen amin
(NH2) pada benzen menyebabkan reaksi
substitusi Br sangat cepat sehingga dihasilkan
polisubstitusi.
Penambahan gugus asetil pada NH2 (NHCOCH3)
mengurangi reaktivitas dan kebasaan. Sehingga
pada amida aromatis, produk substitusi mono-
bromo bisa terjadi. Dan dengan hidrolisis akan
diperoleh bromoamin.
 NH2
NH2
Br Br
Br2

H2O

Br

O O
NH2 HN HN NH2
CH3 CH3 Br
Br