Carbonyl Compounds - Thomas Tallis Science

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Transcript Carbonyl Compounds - Thomas Tallis Science

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The carbonyl group

The

carbonyl group

(>C=O) is the functional group found in compounds such as

aldehydes

ketones

, and

carboxylic acids

 In

aldehydes

the carbonyl group is at the end of the carbon chain and so has at least one hydrogen attached to it.

 In

ketones

the carbonyl group is in the middle of a carbon chain and so has two

alkyl groups

attached to it.

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Representing aldehydes and ketones

Aldehydes and ketones cannot be distinguished by their molecular formula because they have the same functional group.

What is the molecular formula of the aldehyde and ketone below?

an aldehyde

Both have the molecular formula

C 3 H 6 O a ketone

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Representing aldehydes and ketones

Aldehydes and ketones are therefore represented either using

displayed

structural formulae

CH 3 CHO CH 3 CH 2 CH 2 CHO

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CH 3 COCH 2 CH 3 CH 3 CH 2 COCH 2 CH 3

Naming aldehydes

Aldehydes are named using the suffix –

, and follow the same conventions as for naming alkanes.

ethanal propanal

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2-methylbutanal

Naming ketones

Ketones are named using the suffix –

one

propanone hexan-3-one

Like alkenes, ketones with four or more carbon atoms display

positional isomerism

because the carbonyl group may appear between different carbon atoms. In these cases, a number is used before the –

one

to indicate the first carbon involved.

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Naming aldehydes and ketones activity

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Synthesis of aldehydes and ketones

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Properties of aldehydes and ketones

The carbonyl group is polar due to the greater electronegativity of oxygen (3.4) than carbon (2.6). This influences the properties of aldehydes and ketones, such as solubility.

Small aldehydes and ketones are soluble in water due to hydrogen bonding between a lone pair on the oxygen of the carbonyl group and the hydrogen of the water.

As size increases, solubility decreases due to interference in hydrogen bonding by the hydrocarbon ‘tails’ of the aldehydes/ketones.

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δ+ δ-

Boiling points: a comparison

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Boiling points and intermolecular forces

The general increase in boiling points from alkanes to aldehydes/ketones and alcohols is due to the intermolecular forces between each type of molecule.



Alkanes

are only held together by van der Waals forces. These forces increase with the size/length of a molecule.

 The polar carbonyl group in

aldehydes

and

ketones

means that as well as van der Waals forces, these molecules are also held together by dipole –dipole interactions.



Alcohols

are held together by van der Waals forces and dipole –dipole interactions. In addition, these molecules can form hydrogen bonds with each other, due to the slightly positive hydrogen atom of the hydroxyl group.

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Reactivity of the carbonyl group

Although double bonds require more energy to break than single bonds, compounds with double bonds tend to be more reactive as addition reactions are possible. Some of the chemical properties of aldehydes and ketones result from the polar nature of the C=O bond.

δ+ δ-

 The positive charge on the carbon atom makes it open to attack by

nucleophiles

.  Aldehydes and ketones can be

reduced

, forming primary and secondary alcohols respectively.

 Aldehydes may also be

oxidized

to carboxylic acids. © Boardworks Ltd 2010 14 of 38

Nucleophilic addition using cyanide

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Dangers of HCN

Hydrogen cyanide (HCN) is highly volatile liquid (boiling point 26 °C), which has a faint bitter almond smell. In solution, hydrogen cyanide partially dissociates:

HCN (aq) H + (aq) + CN (aq)

Hydrogen cyanide is highly toxic because it inhibits a mitochondrial enzyme that is essential for respiration. Being so volatile and flammable, it is difficult to handle safely. A safer alternative is potassium cyanide, which is a solid at room temperature and is therefore easier to handle. An acidified solution contains both the H + and CN ions. © Boardworks Ltd 2010 16 of 38

Reduction of aldehydes and ketones

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Distinguishing aldehydes & ketones

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Detecting a carbonyl group

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Reactions of aldehydes and ketones

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Aldehydes and ketones: true or false?

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Carboxylic acids Carboxylic acids

have a

carboxyl group

(-COOH) consisting of a carbonyl group and a hydroxyl group attached to the terminal carbonyl carbon.

Carboxylic acids are named using the suffix –

oic acid

. Methanoic acid is the simplest carboxylic acid and is found in bee and ant stings. Ethanoic acid is the acid that gives vinegar its sharp taste and smell. It is also important in the chemical industry and about 6.5 million tonnes are used worldwide each year © Boardworks Ltd 2010 23 of 38

Naming carboxylic acids

Boiling points of carboxylic acids

Synthesis of carboxylic acids

Oxidation of 1 ° alcohols and aldehydes

Carboxylic acids can be created by the oxidation of aldehydes by oxidizing agents such as potassium dichromate(VI).

They can also be created by the oxidation of primary alcohols, again using potassium dichromate(VI).

Hydrolysis of nitriles

Carboxylic acids can also be prepared by the hydrolysis of

nitriles

The nitrile is refluxed with water and hydrochloric acid. The carboxylic acid can then be distilled from the reaction mixture. 28 of 38 © Boardworks Ltd 2010

Reactivity of carboxylic acids

The reactivity of carboxylic acids results, in part, from the polarization of its bonds.

δ+ δ δ δ+

The reactions of carboxylic acids include: 

neutralisation

– the carboxylic acid loses a proton to form a carboxylate salt 

nucleophilic substitution

– the positively-charged carbon is attacked by a nucleophile, resulting in substitution of the OH group 

esterification

– reaction with an alcohol to form an ester.

Forming the carboxylate ion

Carboxylic acids are weak acids and partially dissociate in aqueous solution:

carboxylate ion

The negative charge is delocalized across the carboxylate group, resulting in a more stable ion. The delocalization is represented by adding a second dotted line to the carbon oxygen bonds, which are both equivalent. 31 of 38 © Boardworks Ltd 2010

Reactions with carbonates

Carboxylic acids are the only organic compounds that are strong enough acids to react with either sodium carbonate or sodium hydrogencarbonate.

Reaction of ethanoic acid and sodium carbonate:

2CH 3 COOH + Na 2 CO 3 → 2CH 3 COONa + CO 2 + H 2 O sodium ethanoate

Reaction of methanoic acid and sodium hydrogencarbonate:

HCOOH + NaHCO 3 → HCOONa + CO 2 sodium methanoate + H 2 O

The formation of bubbles of carbon dioxide gas makes these reactions useful as a test for carboxylic acids. © Boardworks Ltd 2010 32 of 38

Reactions with alkalis

Carboxylic acids will react with alkalis, such as sodium hydroxide, in a neutralization reaction:

RCOOH + NaOH → RCOONa + H 2 O

Reaction of propanoic acid and sodium hydroxide:

CH 3 CH 2 COOH + NaOH → CH 3 CH 2 COONa + H 2 O sodium propanoate

Reaction of butanoic acid and potassium hydroxide:

CH 3 CH 2 CH 2 COOH + KOH → CH 3 CH 2 CH 2 COOK + H 2 O potassium butanoate

Carboxylic acids: a summary

Glossary

What’s the keyword?

Multiple-choice quiz