Chemistry

Name: ....

Carbonyls Summary
Describe the oxidation of alcohols using Cr2O72-/H+ including the oxidation of primary alcohols to form aldehydes and carboxylic acids; the control of the oxidation product using different reaction conditions (reflux and distillation) and the oxidation of secondary alcohols to form ketones

Partial Oxidation Primary Alcohols forming Aldehydes -

Acidified potassium dichromate and heat with distillation. Colour change orange (Cr +6) green (Cr +3).

Complete Oxidation Primary Alcohols forming Carboxylic Acids -

Acidified potassium dichromate and heat with reflux. Colour change orange (Cr +6) green (Cr +3).

Oxidation of Secondary Alcohols forming Ketones -

Acidified potassium dichromate and heat with reflux. Colour change orange (Cr +6) green (Cr +3).

Tertiary Alcohols - Are inert (do not react) to oxidation.

Oxidation is the loss of hydrogen or the addition of oxygen.

Describe the oxidation of aldehydes using Cr2O72-/H+ to form carboxylic acids

Aldehydes can be oxidised (addition of oxygen) using acidified potassium dichromate to form carboxylic acids with heat under reflux and a colour change of orange green is observed. Remember that ketones cannot be oxidised further (no reactive H).

Describe the reduction of carbonyl compounds using NaBH4 to form alcohols and outline the mechanism for nucleophilic addition reactions of aldehydes and ketones with hydrides

Reagent: Sodium borohydride in the presence of water, NaBH4(aq). Condition: Warm Aldehydes Aldehydes are reduced to primary alcohols.

Ketones Ketones are reduced to secondary alcohols.

Nucleophilic Addition Reaction

Reduction is the Reduction is the addition of hydrogen addition of hydrogen. or the loss of oxygen.

Describe the use of 2,4-dinitrophenylhydrazine to detect the presence of a carbonyl group in an organic compound and identify a carbonyl compound from the melting point of the derivative

2,4-dinitrophenylhydrazine will detect the presence of a carbonyl functional group by forming the 2,4-dinitrophenylhydrazone which is a yellow/ orange precipitate.
Remember that this test is only positive for aldehydes and ketones and will not form a yellow/ orange precipitate with a carboxylic or ester because the functional group is different.

The hydrazone precipitate can be used to identify the compound:

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Purify the hydrazone precipitate by recrystallisation. Measure the melting point of the purified solid. Compare the melting point with data table values.

Describe the use of Tollens reagent (ammoniacal silver nitrate) to detect the presence of an aldehyde group and distinguish between aldehydes and ketones, explained in terms of the oxidation of aldehydes to carboxylic acids with reduction of silver ions to silver

Reagent: Ammoniacal silver nitrate (Tollens Reagent) Conditions: Heat 60oC water bath Carbonyl Compound Aldehyde Ketone Why? The aldehyde undergoes an oxidation reaction and forms a carboxylic acid (the ketone is not able to undergo further oxidation). Observation Silver mirror (precipitate) No visible reaction

The Tollens reagent (the weak oxidising agent) contains Ag+(aq) ions. The Ag+ (aq) ions in the Tollens reagent (ammoniacal silver nitrate) are reduced (gain electrons) to form silver Ag(s) metal - this is the silver mirror/ precipitate.

Ag+(aq) + e- Ag(s)