Chapter Scopes

Introduction

CHAPTER 7

Carbonyl Compounds

IUPAC nomenclature / naming of carbonyl compounds Physical properties Aldehydes nucleophilic addition, condensation, oxidation, reduction Ketones nucleophilic addition, condensation, reduction Mechanism: carbonyl condensation and addition Characteristic tests to differentiate aldehydes and ketones

Organic carbonyl compounds contain C=O, carbonyl group of atoms. Molecular formula equals to an alkene plus an oxygen atom, CnH2nO. H 2 types: Aldehydes, RCHO or R C O R R Ketones, CO or C O R R

Examples of Aldehydes & Ketones

Nomenclature
Naming aldehydes : 1. Named by replacing the terminal e of the corresponding alkane name with al.

Examples of aldehydes :

Aldehyde: Ethanal O or CH3 C H Ketone: Propanone O CH3 C CH3 or

Ethanal

O CH3CH

CH3 CHO

Propanal

O CH3CH2CH

CH3 CO CH3

2. The parent chain must contain the CHO group & the CHO chain group is numbered as carbon 1.

2-Ethyl-4-methylpentanal CH3 O CH3CHCH2CHCH CH2CH3

Nomenclature
Naming Ketones : 1. Named by replacing the terminal e of the corresponding alkane name with one. 2. The parent chain is the longest one that contains the ketone group & the numbering begins at the end nearer the carbonyl carbon.

Examples of ketone :

Exercises:
Write the structural formula for: (i) but-2-enal (ii) pentan-2-one

3-Hexanone CH3CH2CCH2CH2CH3 O 4-Hexen-2-one CH3CH=CHCH2CCH3 O 2,4-Hexanedione CH3CH2CCH2CCH3 O O

(iii) pentane-2,4-dione
(iv) 3-methylhexanedial

Exercise :
Name the following compounds: (i) CH3CH2CH2CHO (ii) CH2=CHCOCH3 (iii) C2H5COC2H5 (iv) (CH3)2CHCHO

Physical Properties Polar Compound

Aldehydes & ketones are polar compounds due to polarity of carbonyl group. CO bond is polar as O atom is more electronegative than C, causing e density on O higher

Physical Properties Solubility in H2O

Aldehydes & ketones are soluble in H2O by forming hydrogen bonds with water molecules. R + + C O H O R H + hydrogen bonding The solubility decreases when the length of the C chain increases.

Electrophilic carbon reacts with bases and nucleophiles

Nucleophilic oxygen reacts with acids and electrophiles

Physical Properties Boiling Point

Physical Properties Boiling Point

Aldehydes & ketones have lower bp than corresponding alcohols & carboxylic acids. They cant form hydrogen bonds with each other.

Preparation of Carbonyl Compounds:

Oxidation of Alcohols Alcohol is refluxed with a dilute acidified potassium dichromate (VI), K2Cr2O7 OR potassium manganate (VII), KMnO4 Oxidation of 1 Alcohols Aldehydes RCH2OH + [O] RCH + H2O O e.g: CH3CH2OH + [O] CH3CHO + H2O

Aldehydes & ketones have higher b.p than non-polar compounds of comparable molecular weight. Due to permanent dipolepermanent dipole interaction

Preparation of Carbonyl Compounds:

Oxidation of 2 Alcohols Ketones RCHR + [O] RCR + H2O OH

Chemical Reaction of Aldehydes & Ketones

The chemical reactions of aldehydes & ketones are very similar. Can be classified into: a) oxidation b) nucleophilic addition c) carbonyl condensation The main difference is in oxidation. Aldehydes can be oxidised easily but not ketones.

(A) Oxidation of Aldehydes

Oxidation aldehydes are oxidized to carboxylic acids oxidizing agent: a mixture of H2SO4 & K2Cr2O7 / acidified KMnO4 R-C-H + [O] R-C-OH O O

e.g: CH3CHCH3 + O CH3CCH3 + H2O

OH O

Exercises : Oxidation

(B) Nucleophilic Addition

Both aldehydes & ketones undergo nucleophilic addition. In C=O group, the electrophilic C atom has a partial positive charge is susceptible towards nucleophilic attack

(1)

(2)

(3)

1. CH3-C-H + O ??? O Ethanal 2. H C O + O ???

Important class of reactions that allow the interconversion of C=O into a range of important functional groups.

benzaldehyde

1) Formation of the new bond between the nucleophile, Nu to the C of the C=O group 2) Formation of an intermediate alkoxide 3) Protonation of the intermediate alkoxide (work-up with dilute acid) to give an alcohol derivative

Examples of Nucleophilic Addition

Nucleophilic Addition: Reduction

Nucleophilic Addition of Water: Hydration

Reduction

Hydration
Reaction with hydrogen cyanide (HCN) Reaction with Grignard Reagent (RMgX) (refer to Chapter 5)

Aldehydes & ketones can be reduced to alcohol by reducing agent, NaBH4 or LiAlH4 in ether.

Aldehyde / ketone reacts with water to yield geminal diol. The nucleophilic addition of H2O is catalyzed by both acid & base. The reaction is reversible & diol product can eliminate H2O to regenerate ketone / aldehyde

H
RCR O ketone [H] RCR OH 2 alcohol

Mechanism of Base-catalyzed Hydration

O C

Reaction with Hydrogen Cyanide (HCN)

1. Reaction of aldehydes with HCN reacts with HCN forms cyanohydrin (consists of cyanide & OH group) an important method of increasing the no. of C atoms in a molecule. O OH CH3CH + HCN CH3CCN H cyanohydrin

Reaction with Hydrogen Cyanide (HCN)

2. Reaction of ketones with HCN To form cyanohydrin Example: CH3 C O Phenylethanone CH3 + HCN C CN OH cyanohydrin

O C

Alkoxide ion intermediate OH HOH

OH OH gem diol C + OH OH

Reaction with Hydrogen Cyanide (HCN)

Mechanism:

(C) Carbonyl Condensation Reaction

Carbonyl Condensation Reaction

Also called aldol condensation. Displacement at alpha carbon. Alpha Carbon:

Carbon beside carbonyl carbon

CH3CH2CH

Exercise : Aldol Condensation

What is the structure of the aldol product from propanal ? O CH3
ALDOL = aldehyde-alcohol

CH3CH2CH + CH2CH NaOH

Characteristic Test for Aldehydes & Ketones

Characteristic Test for Aldehydes only

a) Silver mirror test: Few drops of aldehyde are added to Tollens reagent (which contains diamminesilver(I) ion, [Ag(NH3)2]+), and the mixture is heated The colourless solution produces a GREY precipitate of silver (Ag) (or silver mirror on the test tube)

Characteristic Test for Aldehydes only

b) Fehlings test: Aldehyde is added to Fehlings solution (which contains Cu2+ ions) & mixture is boiled. Cu2+ (dark blue) is reduced to a reddish-brown precipitate of copper (I) oxide, Cu2O c) Dichromate (VI) test: when boiled with a little K2Cr2O7 & dilute H2SO4 CHO is oxidized into COOH Orange dichromate, Cr6+ reduced to green Cr3+

2,4-dinitrophenylhydrazine test Solution of 2,4-DNP in mixture of methanol & conc. H2SO4 = Bradys Reagent Bradys reagent is added to the aldehydes & ketones at room T, giving yellow / orange crystalline precipitates of 2,4-dinitrophenylhydrazone.
34

O RCH

Tollens reagent

AgNO3 NH4OH

O RCOH + Ag
Silver mirror

Upon learning this chapter, you should be able to:

Use IUPAC nomenclature to name and draw correct structure of simple organic compounds with different functional groups. Select reagents to accomplish appropriate functional group transformations. Draw/write the products of organic chemical reactions. Describe elementary mechanism of a particular organic reaction and write the reaction equation. Explain the physical properties of organic compounds. Suggest chemical tests to differentiate the organic compounds.