Beruflich Dokumente
Kultur Dokumente
OBJECTIVES:
1. Reaction of Alcohols
Inference: Alcohols are capable of being converted to metal salts, alkyl halides, esters,
aldehydes, ketones, and carboxylic acids. Alcohols are only slightly weaker acids than water,
with a K a value of approximately 1 × 10 −16. The reaction of ethanol with sodium metal (a base)
produces sodium ethoxide and hydrogen gas.This reaction is identical to the reaction of sodium
metal with water. However, the latter reaction occurs faster because of the increased acidity of
water (K a value of 1 × 10 −15). Likewise, similar reactions occur with potassium metal.
The acidity of alcohols decreases while going from primary to secondary to tertiary. This
decrease in acidity is due to two factors: an increase of electron density on the oxygen atom of
the more highly‐substituted alcohol, and steric hindrance (because of the alkyl groups, which
inhibit solvation of the resulting alkoxide ion). Both of these situations increase the activation
energy for proton removal.
The basicity of alkoxide ions increases while going from primary to tertiary. This increase in
basicity occurs because the conjugate base of a weak acid is strong. The weaker the acid, the
stronger the conjugate base.
B. Lucas Test
Structure/
Formula of
Test Samples Time Time when Minutes Visible results Compound
Started the reaction elapsed Responsible
observed for the
visible
results.
The solution
remains
colourless
n-butyl alcohol 11:26 11:26 6 minutes unless it is ZnCl2
subjected to
heat. The
solution forms
an oily layer
when heated.
The solution
turns turbid and
sec-butyl alcohol 11:39 11:40 1 minute forms an oily ZnCl2
layer in three to
five minutes
(varies based on
the solubility
The solution
1 minute turns turbid and ZnCl2
tert-butyl alcohol 11:39 11:36 forms an oily
layer
immediately.
Inference: Primary, Secondary and Tertiary Alcohols are classified based on their reactivity
with the Lucas reagent. The reaction that occurs in the Lucas test can be seen as a nucleophilic
substitution reaction. In this reaction, the Chloride in the zinc-chloride bond is replaced with a
hydroxyl group originating from the given alcohol.
The reaction displays the difference in reactivity of the different types of alcohol as well as the
difference in the ease at which corresponding carbocations of the alcohols are formed. For
example, primary alcohols do not react readily at room temperature with the added Lucas reagent
whereas tertiary alcohols react immediately.
The observation of a change where the clear and colourless characteristic of the solution changes
to a turbid, cloudy, and hazy one implies that a chloroalkane has formed. This observation is a
positive indication for the Lucas test.
Primary, Secondary, and Tertiary alcohols react with the lucas reagent to form the chloroalkane
at different rates. Tertiary alcohols react the fastest due to the fact the organic chloride has
relatively low solubility in the aqueous mixture.
Structure/ Formula of
Types of Alcohol Visible Result Compound Responsible for
the visible results.
n-butyl Alcohol Greenish color and form 2 Butanoic Acid
immediate layer
sec-butyl Alcohol Same result in n-butyl 2-butanoic
tert-butyl Alcohol Orange color
Inference: The oxidation of alcohols using acidified sodium or potassium dichromate solution.
This reaction is used to make aldehydes, ketones and carboxylic acids, and as a way of
distinguishing between primary, secondary and tertiary alcohols. The oxidising agent used in
these reactions is normally a solution of sodium or potassium dichromate acidified with dilute
sulphuric acid. If oxidation occurs, the orange solution containing the dichromateions is reduced
to a green solution containing chromium ions.
D. Iodoform Reaction
Structure/ Formula of
Test Samples Visible Result Compound Responsible for
the visible results.
n-butyl Alcohol Cloudy yellow with light CHI3
yellow precipitate Iodoform
sec-butyl Alcohol Same result in n-butyl CHI3
Iodoform
tert-butyl Alcohol Light yellow mixture without
precipitation
3. Darw and name 8 isomeric alcohols with formula C6H12O. Which of these alcohols would
react with aqueous acidic CrO3? Show the products you would expect from each other reaction.
Answer: Alcohols are easily synthesized and easily transformed into other compounds, they
serve as important intermediates in organic synthesis. A multistep synthesis may use Grignard-
like reactions to form an alcohol with the desired carbon structure, followed by reactions to
convert the hydroxyl group of the alcohol to the desired functionality. The most common
reactions of alcohols can be classified as oxidation, dehydration, substitution, esterification, and
reactions of alkoxides. Phenols are rather easily oxidized despite the absence of a hydrogen atom
on the hydroxyl bearing carbon. Among the colored products from the oxidation of phenol by
chromic acid is the dicarbonyl compound para-benzoquinone (also known as 1,4-benzoquinone
or simply quinone); an ortho isomer is also known. These compounds are easily reduced to their
dihydroxybenzene analogs, and it is from these compounds that quinones are best prepared. Note
that meta-quinones having similar structures do not exist. The redox equilibria between the
dihydroxybenzenes hydroquinone and catechol and their quinone oxidation states are so facile
that milder oxidants than chromate (Jones reagent) are generally preferred.