Alcohols, Phenols and Ethers

Department of Chemical Engineering, University of the Philippines, Diliman, Quezon

City

Date Performed: February 27, 2015

Date Submitted: March 4, 2015

Answers to Questions

1.) Give the balances equations for all the reactions.

A. Lucas Test
Ethanol + HCl, ZnCl2
CH3CH2OH + HCl no reaction
Isopropyl alcohol + HCl, ZnCl2
(CH3)2CHOH + HCl (CH3)2CHCl + H2O
Tert-butanol + HCl, ZnCl2
(CH3)3COH + HCl (CH3)3CCl + H2O
Benzyl alcohol + HCl, ZnCl2
C6H5CH2OH + HCl no reaction
B. Oxidation of Alcohols
Ethanol + KMnO4
CH3CH2OH + KMnO4 CH3COOH + H2O + MnO2 + K+
Isopropyl alcohol + KMnO4
2 (CH3)2CHOH + KMnO4 2 (CH3)2CO + 2 H2O + MnO2 + K+
Tert-butanol + KMnO4
(CH3)3COH + KMnO4 no reaction
Benzyl alcohol + KMnO4
C6H5CH2OH + KMnO4 C6H5COOH + 2 H2O + MnO2 + K+
Diethyl ether + KMnO4
C6H5CH2OH + KMnO4 no reaction
C. Reaction of Phenols
Phenol + Br2
C6H5OH + 3 Br2 C6H5OHBr3 + 3 HBr (Br in ortho and para
positions)
Phenol + KMnO4
C6H5OH + KMnO4 C6H4O2 + H2O + MnO2 + K+ (oxygen in para
position)
Phenol + FeCl3
6 C6H5OH + FeCl3 [Fe(OC6H5)6]3- + 3 HCl
naphthol + FeCl3
3 C6H5NO3 + FeCl3 Fe(C6H5NO3)3 + 3 HCl
 Nitrophenol + FeCl3
3 BrC6H5OH + FeCl3 Fe(BrC6H5)3 + 3 HCl
Bromophenol + FeCl3
3 C10H7OH + FeCl3 Fe(C10H7O)3 + 3 HCl

2.) Explain why the Lucas test is applicable only to alcohols containing 5 or less
carbons.
It is only applicable to alcohols with 5 or less carbons for these
compounds are soluble in the Lucas reagent because of their ability to form
H-bonds. Compounds with more than 5 carbons are too large to be soluble in
the reagent and therefore will not react with it.

3.) Explain why tertiary alcohols and ethers cannot undergo oxidation upon
reaction with potassium permanganate.
Under strong reaction conditions such as strong oxidizing agents
(KMnO4) and elevated temperatures, cleavage of C-C bonds takes place and a
mixture of carboxylic acids containing lesser number of carbons is formed.

4.) Correlate the structure of the phenolic compounds with the measured pH
values.
The hydroxyl group in phenol is directly attached to the sp 2 hybridized
carbon of benzene ring which act as an electron withdrawing group. Due to
this, the charge distribution in phenol molecule, as depicted in its resonance
structures, causes the oxygen of the hydroxyl group to be positive.
The presence of electron withdrawing groups such as nitro groups
enhances the acidic strength of phenol. The effect is more pronounced when
such a group is present in ortho and para positions due to delocalization of
the negative charge in phenoxide ion.

References

1. Carey FA. 2010. Organic Chemistry 8th ed. McGraw Hill. New York.
2. McMurry, JE. 2007. Organic Chemistry 7th ed. Brooks-Cole, New York.