Beruflich Dokumente
Kultur Dokumente
(ALCOHOLS)
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1
INTRODUCTION
Alkane with hydroxyl group (–OH)
General formula for aliphatic alcohol,
CnH2n+1OH
Aromatic alcohol – phenol (-OH attached
to the benzene rings)
2
INTRODUCTION
OH CH2-OH
CH3CH2-OH
3
INTRODUCTION
OH OH OH
CH3
Br
4
CLASSIFICATION
Methyl alcohol CH3-OH
10 Alcohols R-CH2-OH
R
20 Alcohols R-CH-OH
R
30 Alcohols R-C-OH
R
5
NOMENCLATURE
Structure General name IUPAC name
CH3-OH methyl alcohol methanol
CH3CH2-OH ethyl alcohol ethanol
CH3CH(OH)CH3 isopropyl alcohol 2-propanol
OH cyclohexyl cyclohexanol
alcohol
6
Naming the alcohol
1. The suffix ‘–e’ in the alkane parent name is
replaced by ‘–ol’
2. The location of the –OH on the longest chain
is given by the smallest possible number
7
IUPAC rules for naming alcohols
1. Determine parent name
2. Give the lowest number to the carbon
bearing the –OH group
3. Identify substituent groups and their position
4. Name the alcohol
8
Naming Alcohols, R-O-H:
CH3 CH3
CH3CHCH2CHCH3 CH3CCH2CH2CH3
OH OH
4-methyl-2-pentanol
2-methyl-2-pentanol
2o 3o
CH3
HO-CHCH2CH3 CH3CH2CH2-OH
10
For phenol, C attach to the –OH group is C 1
OH OH OH
CH3
CH2CH3 Br
11
Alcohol with 2 hydroxy groups
Structure General name IUPAC name
CH2(OH)CH2-OH
ethylene glycol 1,2-ethanediol
CH3CH(OH)CH2-OH
propylene glycol 1,2-propanediol
HO-CH2CH2CH2-OH trimethylene
1,3-propanediol
glycol
OH-CH2CHCH2-OH
glycerol 1,2,3-propanetriol
OH
12
Benzene derivatives with 2 –OH groups are
name as benzenediol
OH OH OH
OH
OH
OH
13
EXCERCISE
(a)
-CH2CH(CH3)CH2-OH
(b)
-OH
NO2
(b)
-OH
Br
14
PHYSICAL PROPERTIES
Most simple alcohols are liquids
MeOH & EtOH are volatile liquids, b.p.
65oC & 78oC respectively
Mr , b.p.
ROH with C > 12 are solids
15
PHYSICAL PROPERTIES
16
PHYSICAL PROPERTIES
(ii) Boiling point
As molecular weight increase, van der Waals
forces increase, boiling point will increase too.
18
PHYSICAL PROPERTIES (Solubility)
δ+
H
δ-
R O
Hydrophilic area
δ- H Hydrogen
O δ+ bonding
H
R OH
H
δ- δ+
R O Hydrophobic area
H
O δ+
H
δ-
19
PHYSICAL PROPERTIES (Solubility)
Phenol is not completely soluble in water below
66oC, but completely soluble above this temp.
Phenol is a colourless crystalline solid which is
hygroscopic
4-nitrophenol is more soluble in water than 2-
nitrophenol because can form H-bonding with
water molecules
20
PHYSICAL PROPERTIES (Solubility)
2-nitrophenol 4-nitrophenol
δ-
δ- O
δ+ O δ+ O H H
H δ- δ+
O N
δ- O
N
δ+
O
O δ+ δ-
δ- H
Intramolecular H-bonding O δ+
H H
Intermolecular H-bonding
21
Acidity of phenol & alcohol
22
Acidity of phenol & alcohol
CH3CH2O- is e- richer than OH-, thus H2O
> acidic than CH3CH2OH
Phenol > acidic than H2O & CH3CH2OH
because phenoxide ion formed is more
stable
The phenoxide ion formed is stabilised
by resonance effect
23
Acidity of phenol & alcohol
O H O -
release proton
+ H+
Phenoxide ion
24
Phenoxide ion stability
O - O O O
- -
Oδ-
δ- δ-
δ-
25
Example:
OH CH2CH2-OH CH2-OH OH
acidity increase
26
Example:
COOH OH
Na2CO3 KOH K, Na
NaHCO3 NaOH NaH
Weak bases Strong bases Very strong bases
27
EXCERCISE
29
PREPARATION OF ALCOHOLS
2.Hydration of Alkenes
follows Markovnikov’s rule
Example:-
30
PREPARATION OF ALCOHOLS
Mechanism
CH3CH-CH3
●
● OH
●●
31
PREPARATION OF ALCOHOLS
3. Hydrolysis of Haloalkanes
CH2Cl CH2OH
+ NaOH(aq)
32
PREPARATION OF ALCOHOLS
4. Addition of Grignard reagent to
carbonyl compounds
33
PREPARATION OF ALCOHOLS
1o Alcohol CH3CH2CH2-OH
+ Mg(OH)Cl
34
PREPARATION OF ALCOHOLS
CH3 CH3
CH3CH2-MgCl + HC=O CH3CH2CH-OMgCl
ethanal
H3O+
CH3
2o Alcohol CH3CH2CH-OH
+ Mg(OH)Cl
35
PREPARATION OF ALCOHOLS
(c) Formation of 3o alcohol (Grignard reagent + ketone)
O O-MgCl
CH3-MgCl + CH3-C-CH3 CH3-C-CH3
propanone CH3
H3O+
O-H
3o Alcohol CH3-C-CH3 + Mg(OH)Cl
CH3
36
EXCERCISE
ii. CH3
H2O / H+
-CH=CH-CH3 B + C
37
ALCOHOL REACTIONS
(a) As an acid
38
ALCOHOL REACTIONS
(a) As a base
●● ●●
CH3CH2-O-H
●●
+ HA CH3CH2O+-H + A-
H
39
ALCOHOL REACTIONS
(1) Esterification
O O
H+,
R-C-OH + R’-OH R-C-OR’ + H-O-H
40
ALCOHOL REACTIONS
(1) Esterification
Example:-
O H+, O
CH3C-OH + CH3-OH CH3C-OCH3 + H-O-H
41
ALCOHOL REACTIONS
(1) Esterification
Alcohol reacts with acyl chloride to form ester
O O
base
CH3C-Cl + CH3-OH CH3C-OCH3 + HCl
42
ALCOHOL REACTIONS
(2) Dehydration of alcohol
•Involve formation of carbocation
•Possible of rearrangement
H2SO4(con.)
CH3CH2CH2OH CH3CH=CH2
180 C 0
propanol propene
43
ALCOHOL REACTIONS
(3) Formation of haloalkane
44
ALCOHOL REACTIONS
Example:-
• ROH + HX RX + H2O
45
ALCOHOL REACTIONS
(3) Formation of haloalkane
•ROH reacts with PX3, PX5 , SOCl2
General reaction:
(i) 3ROH + PX3 3RX + H3PO3
(ii) ROH + PCl5 RCl + POCl3 + HCl
(iii)ROH + SOCl2 RCl + SO2 + HCl
46
ALCOHOL REACTIONS
(4) Oxidation of alcohols
47
ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol
O O
[O] [O]
RCH2OH RC-H RC-OH
48
ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol
Example:-
O O
K2Cr2O7/H
+
K2Cr2O7/H+
CH3CH2OH CH3C-H CH3C-OH + Cr 3+
green
orange
49
ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol
• Sarett-Collins reagent is a special oxidation agent
to change a 1o alcohol to an aldehyde
• CrO3 is added to excess pyridine to form
pyridinium chlorochromate (PCC)
O
CH3CH2CH2OH + PCC CH3CH2C-H
propanol propanal
50
ALCOHOL REACTIONS
(4) Oxidation of 2o alcohol
• form ketone which cannot be oxidised further
under normal conditions
R R
[O]
R’CH-OH R’C=O + H2O
2o alcohol ketone
CH3 CH3
KMnO4/H+
51
ALCOHOL REACTIONS
(4) Oxidation of 3o alcohol
• Does not undergo oxidation under normal
condition
R
[O]
R’-C-OH no reaction
R’’
3o alcohol
52
Chemical test for R-OH
Lucas test
• Lucas reagent : HCl + ZnCl
(con.) 2
53
Example: OBSERVATIONS :
CH2OH
HCl / ZnCl2 Does not turn
cloudy
OH
HCl / ZnCl2 Turn cloudy
within 5 minute
54
OBSERVATIONS :
CH3
OH Turn cloudy
HCl / ZnCl2 immediately
55
Haloform Reaction
Methyl carbinol cleavage to give Carboxylic
acids and Haloform
H
X2 , H+
CH 3 C H HCX 3 + H C OH
OH-
OH O
H
X2 , H+
CH 3 C R HCX 3 + R C OH
OH-
OH O
56
IODOFORM TEST
OH
CH3CH2CCH3 + 3I2 base (OH-)
2-butanol
CH3CH2COO- + CHI3↓
yellow precipitate
(iodoform)
57
PHENOL
Manufacture of phenol by Cumene process
(a) Friedel-Crafts reaction
CH3-CH-CH3
AlCl3
+ CH3CH=CH2
Isopropylbenzene
(cumene)
58
PHENOL
(b) Oxidation of Cumene
O -OH
CH3-CH-CH3
CH3-C-CH3
1200C Cumene
+ O2
hydroperoxide
59
Phenol reactions
1. Reaction at functional group -OH
(a) Reaction with Na
OH O-Na+
+ Na + ½ H2
60
Phenol reactions
1. Reaction at functional group -OH
(b) Reaction with NaOH
OH O-Na+
+ NaOH + H2 O
61
Phenol reactions
2. Electrophilic substitution reactions
(a) Halogenation (Bromination)
-OH is ortho-para director
in Br2, aqueous solution, white precipitate 2,4,6-
tribromophenol will form
OH OH
Br Br
+ 3Br2 / H2O + 3HBr
Br
62
Phenol reactions
2. Electrophilic substitution reactions
(a) Bromination to get monobromination (catalyst:
FeBr3 or CS2)
OH OH OH
Br
CS2
+ Br2 + + HBr
50C
Br
63
Phenol reactions
2. Electrophilic substitution reactions
(b) Nitration
OH OH
Dilute HNO3 NO2
+
Room temp.
OH
NO2
OH
O2N NO2
Concentrated HNO3 Yellow
precipitate
NO2
64
Phenol reactions
3. Esterification
phenol is a weaker nucleophile than alcohol since
the lone pair e- of O atom are delocalised to the
benzene ring
reacts with an acid derivative such as acid chloride
to form an ester
CH3
OH O-C=O
Cl
+ CH3-C=O + Cl-
65
Phenol reactions
4. Identification test for phenols
phenol reacts with aqueous solution of iron (III)
chloride giving a light purple complex
OH OH
+ FeCl3 (aq)
FeCl3
Purple
complex
66
EXERCISE 1
67
EXERCISE 2
68
Common used of alcohol and
phenol
Ethyl alcohol is a poison. LD50 =
~10g/Kg orally in mice.- Nausea,
vomiting, flushing, mental excitement or
depression, drowsiness, impaired
perception, loss of coordination, stupor,
coma, death may occur. (intoxication)
Phenol is an important industrial
chemical. Major use is in phenolic resins
for adhesives and plastics.
69
Phenols in Medicine
Many phenols are used as antiseptics and
disinfectants.
OH OH OH
OH OH
CH2CH2CH2CH2CH2CH3
71