<<Alcohols>>

P H Y S I C A L P R O P E RT I E S ~ ~

1) Melting points, boiling points: Relatively high due to intramolecular Hbonds.

2) Solubility in water: -OH group form H-bond with water molecules, so
miscible with water in all proportions. For members with >6 carbons,
degree of significance of -OH group decrease, so less or not soluble.
3) Highly inflammable for short-chained members.
4) Characteristic deep, broadband between 3300 cm-1 to 3600 cm-1 in IR
spectrum due to presence of -OH group.
5) Relatively neutral.

C H E M I C A L P R O P E RT I E S ~ ~

Reactions involving breakage of C-O bond:

1) Dehydration of alcohols:
(a) Intramolecular dehydration (alkenes formation):
-alcohol heat with excess conc. sulphuric acid.
-heat with pumice stone ,Al2O3.
ease : 3>2>1
(b) Intermolecular dehydration (ether formation ):
-Excess alcohols heat with conc. H2SO4. (Reversible)
2) Halide formation:
(a) With hydrogen halide:
- R-OH + HX ---> R-X + H2O
-Lucas Reagent ,ZnCl/HCl --- rate of cloudiness exist:3>2>1.
(b) With phosphorus halide:
- 3 R-OH + PX3 ---> 3 R-X + H3PO3
- R-OH + PX5 ---> R-X + POX3 + HX

Reactions involving breakage of O-H bond:

1) Reaction with active alkali metals (alkoxide formation):
- R->-OH <----> R->-O- + H+
- the alkoxide ion formed is destablised by the +ve inductive conferred
by the electron donating alkyl group, equilibrium position shift to the
left.

2) Esterification:
- Formed by refluxing with carboxylic acids, acyl chlorides, acid
anhydrides under catalyst of conc. H2SO4.
3) Oxidation:
- oxidizing agents commonly used:
KMnO4/H+ (aq), (violet to colorless)
K2Cr2O7/H+ (aq). (orange to green)
- 1alcohol ---> aldehyde ---> carboxylic acid
- 2alcohol ---> ketone
- 3alcohol ---> no reaction.
- Green colour changes from orange forms the basis of the
breathalyser.
4) Triiodomethane formation (Iodoform test):
- alcohols with -C(CH3)H-OH group + I2/NaOH (aq)
---> R-COO-Na+ + CHI3.

<<Phenols>>
P H Y S I C A L P R O P E RT I E S ~ ~

Solubility in water: slightly dissolved.

Relatively acidic.
The lone pair of O is partially overlap with the ring system, this multiple
bond character confers it a strong C-O bond.

C H E M I C A L P R O P E RT I E S ~ ~

1) Alkoxide formation:
- The negative charge is dispersed throughout the phenoxide
ion(conjugate base) by conjugation with the - e- of the ring, so it's
well stabilized and more acidic.
- Due to the acidity, it react with NaOH(aq) but alcohols do not, reaction
with NaOH(aq) can be used to distinguish between them.
2) Other reactions of the -OH group:
- Halide formation: slow/no reaction.
- Oxidation: complex polymers formed.
- Elimination: product is not stable due to high angle strain.

- Esterification: slow reaction. Can be modified by using acyl chlorides

instead of acids and converting phenol into phenoxide ion.
- Reaction with NaHCO3: no reaction but carboxylic acids do, a means
for distinguishing the two.
- Reaction with neutral Iron() chloride: Violet coloration. (Identification
of phenols.)

Topic: Hydroxy Compounds

LSC

1.1 General properties of Hydrox Compounds

Alcohol:

The hydroxyl group(OH) is attached to a

sp3 C

atom

CH3

CH3 C CH3 tertiary(3) ROH 3C attached to the C containing OH

OH
2-methylpropan-2-ol
CH3CH2 CH
OH

CH3 secondary(2)ROH 2C attached to the C containingOH

butan-2-ol

CH3CH2CH2 OH primary (1) ROH 1 C attached to the C containing OH

propan-1-ol
Phenol: OH is directly attached to a sp2 C atom in an aromatic ring.
OH
OH

phenol

OH
benzene-1,4-diol
In alcohols R-O-H, the O is sp3 hybridized (similar to H 2O)
In phenols Ar-O-H, the O is mainly sp2 hybridized because the lone pair of
O has to overlap with the p orbitals of the benzene ring so that the C-O
bond has some double bond character. Therefore, It is more difficult to
break.
Due to the presence of the polar O-H group & the ability to from hydrogen
bond with water, alcohols with 1 to 6 C atoms are very soluble in water.
Phenols are slightly soluble in water.

Hydrogen bonding:
alcohol & phenol molecules can form intermolecular H-bonds. Then, It
has usually higher melting point & boiling point than other carbon
compounds with the same no. of carbon atoms(except RCOOH).

1.2Preparation of ROH:
A. Hydrolysis of RX

KOH(aq), reflux
(1/ 2)R-X(l) + OH (aq)------------------------> (1/2)ROH (aq) + X (aq)
AgNO3(aq)/ethanol, warming
(3) R-X(l) + H2O(aq)---------------------------------> (3)ROH(aq) + HX(aq)

{3RX undergo elimination easily if heating under reflux with KOH(aq)

in
addition to substitution . It is better to warm with AgNO 3(aq)
+ ethanol mixture.}

B. reduction of ketone , aldehyde & carboxylic compound

(NOT for 3ROH)
O
LiAIH4/dry ether ,H 2O
OH
ketone R-C-R`------------------------------------- R-CH-R`

aldehyde, RCOOH, RCOOR`----------------------- 1ROH

LiAIH 4 is a very powerful reducing agent.
> heating is usually not required because the reaction is already
vigorous(especially for aldehydes)
O
LiAIH 4 can also reduce RCOOH,RCOOR`,R-C-CI
LiAIH 4 does not react with C=C bonds
NaBH4 only react reduces aldehyde & ketone

C. Hydration of alkene:
H2SO/cold
OSO3H
H 2O
OH
R-C=C-R` ----------- R- C-CH2R --------- R-C-CH2R`

H H

D. From 1 aliphatic amine:

RCH2NH2 +NaNO2/HCI-- RCH2OH +N2(effervescence)

1.3 Test for Phenol & ROH:

ROH & Phenols react with Na but NOT Mg
(RCOOH react vigorously with both Na and Mg)
ROH do not decolorize cold Br 2/CCI4 or Br2(aq) in the absence of light
but >phenols decolorize Br 2(aq) with the formation of a white ppt. at
room temperature (Note that phenylamine also react with Br 2(aq) to give
a white ppt.)
>Phenol can form a coloured( usually violet )complex with neutral
FeCI3(aq).
Water soluble ROH (1 to 6C) can be distinguished by the Lucas test(by
mixture with saturated ZnCl 3 + conc. HCI)
~~3 turn cloudy at once.
~~2 turn cloudy at about 5 minutes (not precipitation)
~~1 does not change( only dissolves in the acid, due to the formation of
ROH2 positive ion).
> ROH (RCOOH ,NOT phenols) react immediately with PCI 5 to give HCI(g)
which fumes with NH3(g)

CH3
O
>-CH-OH group(& -C-CH 3 too ) can be identified by the iodoform
test(I2/NaOH) BECAUSE OF formation of yellow ppt.of CHI 3.
>Further reaction for ROH & phenol:
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~

Method
|
+acidified K2Cr2O7

ROH
|
phenol
|
| no observable change | acidified K 2Cr2O7
from orange to green
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~
+NaOH+
|
|
|
BENZENEDIZONIUM
| orange ppt
| no observable change |
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~

1.4 Preparation of Phenols

FROM diazonium salt ( an important intermediate in synthesis )
The diazonium ion will begin to breakdown with the resulting formation
of phenol and effervescence of nitrogen at above 278K.
N2
-------
OH
dil H positive
above 5.`C

1.5 reaction phenol

phenol reacts with NaOH .Therefore, phenol is a much stronger than
alcohol.
OH
O Na +
+ Na OH ------
+H 2O
alcohols do not react with NaOH, 1to 5 Carbon alkanols are only miscible
NaOH(aq).
The fact that phenol is soluble in Naoh(aq) can be used in isolation of
phenol from other organic compounds(except RCOOH).

1.6 Acidity of Alcohols & Phenols

A CI D I T Y :

B A S I C S T R E N GT H :

OH

> H - O - H > R- OH

O < H- O

< R- O

H2O is more acidic than ROH because RO is less stable than OH .

Phenol is more acidic than ROH because a phenoxide ion is more stable
than an alkoxide ion due to the delocalization of e while the e donating
alkyl group in ROH destabilizes the alkoxide ion.

1.6 ESTERIFICATION
alcohol react with mineral acid or organic acid (with H 2SO4(l) or dry
HCIas catalyst ) to give ester& water
Ester can be found when alcohol reacts with acid chloride or acid
anhydride.
[no catalyst].
~ LEE SUN CHUN 7B 23~