Reactions of Alcohols and Phenols

OBJECTIVES


Understand the properties and reactions of alcohol and phenol Enumerate and give the processes involving alcohol and phenol Compare and contrast aldehydes and ketones in terms of their structures and properties

Alcohols and Phenols



Alcohol is a compound that has a hydroxyl group (-OH) bonded to a saturated, sp3-hybridized carbon atom. It can be classified as primary, secondary, and tertiary according to the number of alkyl groups directly bonded to the alcohol carbon. Phenol, on the other hand, has a hydroxyl group bonded to an aromatic ring. Its IUPAC name is benzenol.

Solubility in Water
COMPOUND Ethyl alcohol n-butyl alcohol sec-butyl alcohol tert-butyl alcohol Benzyl alcohol Glycerol Phenol SOLUBILITY
SOLUBLE SOLUBLE SOLUBLE SOLUBLE INSOLUBLE SOLUBLE INSOLUBLE

Solubility in Water
 

Increases with of increasing number hydroxyl groups. Solubility of monohydric alcohols decreases with increasing molecular weight. Branched isomers are more soluble than unbranched isomers.

Solubility in Water
Since alcohols can form hydrogen bond with water, low-molecular weight alcohols are water-soluble. However, as the molecular weight of an alcohol increases, the proportion of it that is hydrocarbon increases . The alcohol becomes more like an alkane , less like water, and
less soluble in water.

Test for Alcohols and Phenols (Acidity and Basicity) Basicity)

Compound Ethyl alcohol Phenol Reaction w/ litmus paper
Blue to red Blue to red

Reaction w/ pH paper
6 5

Phenols are more acidic than alcohols because phenoxide the anion is resonance-stabilized by the aromatic ring.

Test for Alcohols and Phenols (Acidity and Basicity) Basicity)

Sharing the negative charge over the ring increases the stability of the phenoxide anion and thus increases the tendency of the corresponding phenol to dissociate. The characteristic property that differentiates phenols from alcohols is acidity. Phenols are weakly acidic and can be neutralized by sodium hydroxide. Alcohols are less acidic than phenols and are not neutralized by sodium hydroxide.

Reaction with Sodium

n-butyl alcohol sec-butyl alcohol Tert-butyl alcohol Phenol 1st 2nd 3rd 4th

Alcohols react with sodium metal to yield alkoxide salts that are themselves strong bases.
2ROH + 2Na 2RONa + H2o

Reaction with Acetyl Chloride



Ester formed when acetyl chloride reacts with alcohol and phenol evident via formation of a top layer, which usually accompanied by the evolution of heat. ROH + CH3COCl ArOH + CH3COCl CH3COOR + HCl CH3COOAr + HCl

Lucas Test
 

 

Lucas reagent is a mixture of concentrated HCl and anhydrous zinc chloride. Test for relative rates of alkyl halide formation Test to deduce structure of alcohols Formation of a chloride from alcohol is indicated by the cloudiness that appears when the separates from the chloride solution.

Lucas Test
Reactivity is measured by the time required for the cloudiness to appear
Tertiary alcohol reacts readily at
room temperature

Secondary alcohol reacts within five minutes Primary alcohol does not react appreciably at room temperature

Lucas Test
Although the alcohols are soluble in the Lucas reagent, the alkyl halide formed is not. As tiny droplets of the alkyl halide form, the solution becomes cloudy, thus providing a visual way to the reaction s progress. Tertiary alcohols react almost instantaneously at room temperature, and secondary alcohols react in 5 to 15 minutes when heated. Primary alcohols are the slowest, requiring several hours of reaction time, even with heat.

Oxidation
One of the most valuable reactions of alcohols is their oxidation to yield carbonyl compounds by a formal loss of H2 from the carbon to which the oxygen is attached: CH3CH2-OH CH3 -HC=O Common oxidizing agents:
Chromic acid (H2CrO4) KMnO4 in acid or basic medium K2Cr2O7

Oxidation
Primary alcohols yield aldehydes or
carboxylic acids

Secondary alcohols yield ketones Tertiary alcohols do not normally react with oxidizing agents.

Iodoform Test
Test for the presence of methyl group attached to a functional carbon. Reagent: NaOH + I2 NaOI Structure of alcohol:
R CH3 C H OH
(sodium hypoiodite)

Positive result: yellow precipitate of iodoform (CHI3).

Bromine Water Test

The bromine in water test is a qualitative test for the presence of phenol.

FeCl3 Test
 

The positive test result is evident by the formation of blue, green, purple, red-brown, or intense red complexes. This is an excellent test for differentiating alcohol from phenols. This is also a test for the presence of an enol group. This test is best carried out in the presence of pyridine for greater accuracy of result.

FeCl3 Test
3
OH

+3

FeCl3

Fe(OAr)3
colored complex

NH Cl-

phenol

Reactions of Aldehydes and Ketones

Aldehydes and Ketones

General formula for Aldehydes: General formula for Ketones:

O R C H
R

O C R

Aldehydes and Ketones



Aldehydes and ketones are structurally very similar; both have a carbon-oxygen double bond called a carbonyl group. They differ in that aldehydes have at least one hydrogen atom bonded to the carbonyl group, whereas in ketones the carbonyl is bonded to two carbon atoms.

Aldehydes and Ketones



Characteristic reactions of aldehydes and ketones:

   

Addition reactions across the double bond Reduction Condensation Haloform reaction

Oxidation Reaction (Benedict s Test)



Preparation: Heat a solution of 17.3 g sodium citrate and 10 g anhydrous sodium carbonate ion 80 mL of distilled water until the salts dissolved. Dissolve 1.73 g of hydrated copper sulfate in 10 mL of water and add this solution to the solution of sodium citrate and sodium carbonate slowly with stirring. Dilute the solution to 100 mL by adding distilled water.

Oxidation Reaction (Benedict s Test)



Benedict s test is one the classical tests employed in the determination of the presence of aldehyde. Benedict solution can oxidize a variety of compounds and precipitation of the cuprous oxide is a positive indication. Aliphatic aldehydes usually produced yellow to orange (yellow, yellowish green, red) precipitate or suspension, sometime greenish in blue solution is observed.

Oxidation Reaction (Benedict s Test)

This test is negative for most ketones and aromatic aldehydes.
O O

+
R H
aldehyde

2Cu+2

4OHR OH

+
carboxylic acid

Cu2O(s)

2H2O

Oxidation Reaction (Chromic Anhydride Test)

Preparation  Dissolve 25 g chromic anhydride in 25 mL concentrated sulfuric acid.  Pour this suspension slowly with stirring to 75 mL of distilled water.  Cool the solution at room temperature before using.

Oxidation Reaction (Chromic Anhydride Test)



The basis of this test is the reduction of chromium (IV), which is orange in color, to chromium (III), which green in color. The positive result for aldehyde is evident by the formation of an opaque blue green or an intense blue to green suspension at a slower rate. If the unknown is an aliphatic aldehyde, initial cloudiness after 5 seconds is observed and the blue green suspension forms after 30 seconds.

Oxidation Reaction (Chromic Anhydride Test)

 

Aromatic aldehydes took longer time to react, about 30 90 seconds. Ketones give a negative test and thus, for this reason this is one of the tests used to distinguish aldehydes from ketones.
O O C H

3 R

+ 2 CrO3 +
ora g - r

3H2SO4

3 R

C OH

3 H2O

Cr2(SO4)3

al

arboxyli a i

opaqu blu - gr or i t r s blu to gr

Oxidation Reaction (Tollen s (Silver Mirror) Test)

Preparation  Clean a container with 10% NaOH and place 2 mL of AgNO3 and add a drop of 10% NaOH.  Add 2% ammonia, drop by drop, with constant shaking, until the precipitate of silver oxide just dissolves.  In order to obtain a sensitive reagent, it is necessary to avoid excessive addition of ammonia.

Oxidation Reaction (Tollen s (Silver Mirror) Test)



This test is used to distinguish aldehydes from ketones. Also known as silver mirror test because of its positive test result is evident by the formation of metallic silver on the surface of the test tube. In some cases, formation of granular gray or black precipitate is observed as a positive test result.

Oxidation Reaction (Tollen s (Silver Mirror) Test)



Ketones result.
+
H

usually

give

negative
H H N
+

test

O C R 2Ag(NH3)2OH Ag(NH
silver nitrate in ammoni m h droxide

O 2Ag(s)

C O

H2 O

NH3

aldeh de

silver mirror

ammoni m salt of car ox lic acid

Oxidation Reaction (Fehling s Test for Aldehydes) Aldehydes)

Preparation  Mix 2.5 mL of each of the following solutions:


Fehling s A. Dissolve 17.32g of hydrated copper sulfate crystals in 200mL of water and dilute to 250mL. Fehling s B. Dissolve 86.5g of sodium potassium tartrate (Rochelle s salt) and 35g of sodium hydroxide in 100 mL of water and dilute to 250mL.

Oxidation Reaction (Fehling s Test for Aldehydes) Aldehydes)



The basis of this test is the reduction of copper (II) to copper (I). For aliphatic aldehydes, formation of brick red, yellow or yellowish green color of precipitate of Cu2O indicates the positive test results. In the course of the reaction, the Fehling s reagent reduced the deep blue copper (II) ion complex to brick red copper (I) oxide.

Oxidation Reaction (Fehling s Test for Aldehydes) Aldehydes)



Aromatic aldehydes give a negative test result. For ketones, this test give a negative test result.
O O C H

2 Cu

+2

C OH

Cu2O(s)
bri k r , y llow or y llowis gr

al

blu

arboxyli a i

Reaction of the Carbonyl Group (Condensation Reaction)

2,4


Dinitrophenylhydrazine

The positive test results for most aldehydes and ketones are evident by the formation of insoluble solid of dinitrophenylhydrazones. The color of the precipitate formed may also indicate the structure of the aldehydes and ketones.

Reaction of the Carbonyl Group (Condensation Reaction)

Aromatic aldehydes and ketones (highly conjugated) tend to form orange to red precipitate while aliphatic and unconjugated aldehydes and ketones tend to form yellow precipitate. The precipitate formed is sometimes oily which become crystalline after some time. Formation of oily precipitate of dinitrophenylhydrazones is characteristic of numerous ketones.

Reaction of the Carbonyl Group (Condensation Reaction)

This maybe use to differentiate aldehydes from ketones. In some cases, mild heating is required in order for the reaction to be visible, but avoid overheating because it may cause oxidation and in effect give false positive test result.
R' NH O C R R' NH2 NH N O
-

C R

+ -

+ -

ldehyde or ketone

2,4-dinitrophenylhydr zine

2,4-dinitrophenylhydr zone

Reaction of the Carbonyl Group (Addition Reaction)

Sodium bisulfite addition


Bisulfate ions react with aldehyde and ketone to form crystalline addition products. Formation of solid product is an evidence of positive test result.

Reaction of the Carbonyl Group (Addition Reaction)

Compounds having active carbonyl carbons do give also a positive test result. Among those compounds are methyl ketones, and low molecular weight cyclic ketones of up to eight- membered cyclic ketone.
O R C R
aldehyde or ketone

H OH R OH SO3 Na
+

Na

S O

sodium bisulfite addition complex

Reaction of the Carbonyl Group (Haloform Rxn / Iodoform Test)



This is to test the presence of the methyl group. Compounds containing the carbonyl group will react with halogen in the presence of a base by a substitution type of reaction.

Reaction of the Carbonyl Group (Haloform Rxn / Iodoform Test)



An alpha halo ketone is formed and when NaOH and iodine are used, a yellow precipitate of iodoform is produced. Positive test result is evident by the formation of yellow precipitate of iodoform with a medicinal odor or foulsmell.

Reaction of the Carbonyl Group (Haloform Rxn / Iodoform Test)

The following give a positive test result:
Acetaldehyde Conjugated aldehydes such as acrolein and furfural Dihydoxy compounds Methyl ketone Secondary alcohol with methyl group adjacent to the carbon bearing the hydroxyl group

Reaction of the Carbonyl Group (Haloform Rxn / Iodoform Test)

OH CH H3C CH3
a tone

CH3

4I2

6NaOH

Na O O

CHI 3

5NaI

+ 5H2O

Iodofor (yellow solid)