Flavour 03/01/2019

03/01/2019 Flavour Classify the kind of molecules make up many flavour and aroma molecules. Investigate the structures, functional groups and names of these molecules.

(Past paper 2008)

The R group is a hydrogen or an alkyl group. Aldehydes (Alkanals) Alkanals are a homologous series of aldehydes. Aldehydes contain the C=O functional group, this is called the CARBONYL group: The R group is a hydrogen or an alkyl group. Ethanal Methanal General Formula  CnH2nO

Naming Branched Aldehydes When naming an Aldehyde there is no need to number the position of the carbonyl group. It is always on carbon number 1. Aldehydes have names ending in -al. 3-methylpentanal

Ketones (Alkanones) Alkanones are a homologous series of ketones. Ketones also contain a CARBONYL functional group but in ketones it is in the middle of a carbon chain. The R groups are alkyl groups. General Formula  CnH2nO Propanone CH3COCH3 Butanone CH3COCH2CH3 The Aldehydes and Ketones are isomers of each other!

Naming Branched Alkanones The C=O carbon is given the lowest possible number in the parent chain. When naming a Ketone it is sometimes necessary to number the position of the carbonyl group in order to distinguish between isomers. Ketones have names ending in -one.

Examples of Aldehydes

Examples of Ketones butanedione Butter flavor heptan -2- one Clove flavor

For each of the following molecules, classify them as either an aldehyde or ketone and name the molecule.

Draw the structural formulas for the following molecules: A Draw the structural formulas for the following molecules: A. 3-Methylpentanal B. 2,3-Dichloropropanal C. 3-Methylbutan-2-one

The chemistry of flavour Can you identify any functional groups in the above molecules?

The chemistry of flavour Molecules responsible for flavour in vegetables are normally trapped inside the cell walls. During cooking the cell walls are damaged for two reasons: • Chemical damage occurs as the cell walls, which are made of cellulose, break down. • Physical damage occurs as water inside the cells boils forming steam and the cell walls break open.

The chemistry of flavour A major issue in cooking is to retain molecules responsible for flavour in the food – overcooking can result in loss of these molecules. One destination for lost flavour molecules is in the cooking water. This will occur if the flavour molecules are water-soluble. If this is the case, many of the flavour molecules will be lost down the drain when the cooking water is poured away.

Naming compounds 1 2 3 4 5 6 7 8 9 propanoic acid? propanone 1 2 3 4 5 6 7 8 9 propanoic acid? propanone methylethanoate? propane propanoic acid propanal? aminopropane? propyne 2-aminopropanoic acid? propanal propene aminopropane propanone? propene? methylethanoate propane? 2-aminopropanic acid Which compound shown is propyne?

Flavour Many flavour and aroma molecules are aldehydes 03/01/2019 Many flavour and aroma molecules are aldehydes Aldehydes and ketones both contain the carbonyl functional group. Aldehydes and ketones can be identified from the ‘-al’ and ‘-one’ name endings. Straight-chain and branched-chain aldehydes and ketones can be named from structural formulae. Given the names of straight-chain or branched-chain aldehydes and ketones, structural formulae can be drawn and molecular formulae written. Oxidation

Oxidation 03/01/2019

03/01/2019 Oxidation Explain what is meant by the term Oxidation when referring to carbon compounds. Compare the oxidation reactions of Primary, Secondary and Tertiary alcohols.

Classification of Alcohols Primary Alcohols (1°) – the carbon atom to which the hydroxyl group is attached to is bonded to no more than one other carbon. The other bonds are to hydrogen atoms. Secondary Alcohols (2°) – the carbon atom to which the hydroxyl group is attached to is bonded to two other carbon atoms. Only one bond is to a hydrogen atom. Tertiary Alcohols (3°) – the carbon atom to which the hydroxyl group is attached to is bonded to three other carbon atoms. There are no bonds to hydrogen atoms.

Oxidation of Alcohols The oxidation of an organic compound causes the oxygen to hydrogen ratio within the molecule to increase. This can be achieved by either removing hydrogen from the molecule or adding oxygen to it. Oxidation is – loss of electrons - loss of hydrogen (H2) - gain of oxygen ( O )

Primary Alcohol  Aldehyde Primary Alcohols Primary alcohols can be oxidised in two stages. The first stage changes the primary alcohol to an aldehyde.   This step involves the loss of hydrogen. Primary Alcohol  Aldehyde Oxidising Agent

Aldehyde  Carboxylic acid In the second stage of oxidation, the aldehyde is further oxidised to produce a carboxylic acid.  This step involves the addition of oxygen. Aldehyde  Carboxylic acid Oxidising Agent

Secondary Alcohol  Ketone Secondary Alcohols Secondary Alcohols can be oxidised in one stage to produce ketones. This involves the addition of oxygen. Secondary Alcohol  Ketone Oxidising Agent

Tertiary Alcohols Tertiary Alcohols cannot be oxidised readily. This is because there is no H directly attached to the Carbon which contains the hydroxyl (OH) group to be removed.

Oxidising Agents In order to oxidise a primary or secondary alcohol an appropriate oxidising agent should be used. Commonly used oxidising agents are listed below: Acidified potassium dichromate solution Benedict’s solution / Fehling's solution Tollen’s solution Acidified potassium permanganate solution Heated solid copper (II) oxide

Oxidation 03/01/2019 When applied to carbon compounds, oxidation results in an increase in the oxygen to hydrogen ratio Primary alcohols are oxidised, first to aldehydes and then to carboxylic acids. Secondary alcohols are oxidised to ketones. Tertiary alcohols cannot be oxidised. Oxidation Reactions

Oxidation Reactions 03/01/2019

Oxidation Reactions 03/01/2019 Explain the oxidation reactions of Aldehydes and Ketones. Familiarise yourself with different oxidising agents that can be used in the lab. Identify the colour changes associated with the use of different oxidising agents.

Which box shows the full structural formula of an alkanal? Which box (or boxes) contain(s) an alkyne? Which box (or boxes) contain(s) an alkene? Which box (or boxes) contain(s) an alkanoic acid? Which box (or boxes) contain(s) a ketone? Which box (or boxes) contain(s) an alkanol?

Procedure 1. Before collecting the carbonyl compounds X and Y set up a water bath. 2. Add sulphuric acid to each of two test tubes to a depth of about 2 cm. Then add potassium dichromate solution to both to give a total depth of about 3 cm in each. 3. To one of these test tubes add about 5 drops of compound X and to the other add about 5 drops of compound Y. 4. Label both test tubes, place both test tubes in the water bath and observe and record any changes. Add Benedict's solution to each of two test tubes to a depth of about 3 cm. Repeat steps 3 and 4. Add Tollens' reagent to each of two very clean test tubes to a depth of about 3 cm. Repeat steps 3 and 4 and immediately after, wash the contents of the test tubes down the drain with large amounts of water. Record your observations.

Hazards Flammable, vapours irritate the eyes, skin and lungs, toxic by skin absorption and by swallowing. Potassium dichromate is toxic if swallowed. It is carcinogenic and very toxic by inhalation. It is also a skin sensitiser and is very toxic to the aquatic environment. Sulphuric acid irritates the eyes. Benedict's solution contains copper salts and so is harmful if swallowed. Tollens' reagent contains diluted sodium hydroxide which irritates the skin and eyes. Care Wear eye protection and immediately wash off any chemical spillages on the skin. When working with Tollens' reagent and compounds X and Y wear gloves.

Oxidation Primary Alcohol Secondary Alcohol Tertiary Alcohol Aldehyde Ketone No Reaction Carboxylic acid No Reaction

Oxidising Agents Colour Change

Acidified potassium dichromate Acidified potassium dichromate solution is used as an oxidising agent. The alcohol is added to the orange solution. On warming the solution, the orange dichromate ions are reduced to green Cr3+ ions. The ion–electron equation shows that this reaction will only occur in the presence of H+ions. This explains why acidified dichromate must be used.

Benedict's solution Benedict's solution can be used as an oxidising agent When an aldehyde is heated with Benedict's solution for a few minutes in a hot water bath, the blue solution slowly produces a red-orange precipitate of copper(I) oxide. Cu2+ ions are reduced to Cu+ ions.

Tollens' reagent Tollens' reagent can be used as an oxidising agent When an aldehyde is heated with Tollens' reagent for a few minutes in a hot water bath, the colourless solution slowly produces a silver mirror on the inside of the test tube. Ag+ ions are reduced to metallic silver.

Copper(II) oxide Copper(II) oxide is used as an oxidising agent The copper(II) oxide is heated strongly and the alcohol vapour is passed over it. When the alcohol is oxidised, the black copper(II) oxide is reduced to pinkish brown copper.

Cr2O72-(aq) ions reduced to Cr3+

Specific Tests for Aldehydes Acidified Dichromate will oxidise primary and secondary alcohols. It cannot be used as the specific test for aldehydes. Benedict’s/ Fehling’s Solutions and Tollen’s Reagent Oxidise aldehydes to carboxylic acids. Will NOT oxidise an alcohol

Oxidation of Alcohols Oxidising agent Colour Change Reaction Acidified permanganate Purple  Colourless MnO4-  Mn2+ Hot copper(II) oxide Black copper oxide  brown copper metal Cu2+ + 2e  Cu(s) 03/01/2019

Oxidation of Aldehydes Oxidising agent Colour Change Reaction Acidified potassium dichromate H+ / Cr2O72- Orange  Blue/Green Cr2O72-  Cr3+ Fehling's / Benedict's Solution Blue  orange / red Cu2+ + 2e  Cu(s) Tollen’s Reagent Colourless  Silver Ag+ + e  Ag(s)

1. Primary alcohols may be oxidised to carboxylic acids in two stages 1. Primary alcohols may be oxidised to carboxylic acids in two stages. a) Draw the full structural formula for each product obtained by the oxidation of the following compound. b) Name each of the products. c) What colour change is observed when the compound is oxidised by acidified potassium dichromate solution?

Oxidation Reactions 03/01/2019 In the laboratory, hot copper(II) oxide or acidified dichromate(VI) solutions can be used to oxidise primary and secondary alcohols. Aldehydes, but not ketones, can be oxidised to carboxylic acids. Fehling’s solution, Tollens’ reagent and acidified dichromate solution can be used to differentiate between an aldehyde and a ketone Antioxidants

Antioxidants 03/01/2019

03/01/2019 Antioxidants Describe the result of the reaction of oxygen with edible oils. Explain what is meant by antioxidants. Write ion-electron equations for the oxidation of antioxidants.

Oxidation of Food Oxidation of food can occur when food is exposed to oxygen in the air. Foods which contain fats and oils are at a particularly high risk of oxidation. The oxidation of unsaturated oils and fats primarily takes place via a free-radical-mediated process and can lead to rancidity. Antioxidants are molecules that reduce the rate of oxidation reactions involving the transfer of electron(s) to an oxidising agent. Antioxidants are often added to foodstuffs to minimise oxidative damage.

Oxidation of food When fats react with oxygen they are broken down, causing: deterioration of flavour (rancidity) loss of colour loss of nutritional value a health risk from toxic oxidation products. As the fat decomposes and reacts with oxygen, chemicals called peroxides are produced. These change into the substances characteristic of the smell and soapy flavour of a rancid fat.

Oxidation of food Antioxidants prevent the formation of peroxides and so slow the process of the food 'going off'. Some antioxidants react with oxygen itself and so prevent the formation of peroxides. Air-tight packaging, using inert gases like nitrogen, vacuum packing and refrigeration can all be used to delay the oxidation process. However, these can still be inefficient and adding antioxidants can be an effective way of extending the shelf life of a product.

Antioxidants in action The apple is protected when dipped in orange juice containing the antioxidant vitamin C Oxidation occurs when the apple is left exposed to air

Vitamin C (ascorbic acid) The antioxidant vitamin C can act as a reducing agent (electron donor), preventing oxidation (electron loss) from the foodstuff. C6H8O6   C6H6O6  +  2H+  +  2e- Dehydroascorbic acid Ascorbic acid

We will look at free radical reactions in more detail later. Oxidative damage Oxidation reactions can produce free radicals. A free radical is a highly reactive species containing an unpaired electron. Free radicals can damage food by removal of an electron. Antioxidant molecules ‘mop up’ free radicals to protect the foodstuff. The antioxidant molecule donates an electron to the potentially damaging free radical. A stable electron pair is formed, stabilising the free radical. The antioxidant itself becomes oxidised (loses an electron). We will look at free radical reactions in more detail later.

How does an antioxidant cancel out a free radical? Radical now in a stable pair Damaging free radical Neutralised free radical Electron transferred Antioxidant Antioxidant converted to a stable free radical

typical antioxidants: E-number Typical foods Ascorbic acid (vitamin C) E300 Beers, cut fruits, jams, dried potato. Helps to prevent cut and pulped foods from going brown by preventing oxidation reactions that cause the discolouration. Can be added to foods, such as potato, to replace vitamin C lost in processing. Tocopherols E306 Oils, meat pies. Obtained from soya beans and maize. Reduces oxidation of fatty acids and some vitamins. Butylated hydroxyanisole (BHA) E320 Oils, margarine, cheese, crisps. Helps to prevent the reactions that break down fats and cause the food to go rancid . Citric acid E330 Jam, tinned fruit, biscuits, alcoholic drinks, cheese, dried soup. Naturally-occuring in citrus fruits like lemons. Helps to increase the anti-oxidant effects of other substances. Helps to reduce the reactions that can discolour fruits. May also be used to regulate pH in jams and jellies. http://www.understandingfoodadditives.org

Antioxidants and health benefits There may be health benefits from the use of antioxidants. Oxidation reactions in the body could be linked to the build-up of fatty deposits that cause blockages in arteries that can cause heart attacks. Antioxidants may be important in preventing this and there could also be a link with the prevention of certain cancers, arthritis and other conditions. The picture is not yet clear and a great deal of research needs to be undertaken. Studies involving 230,000 men and women across the UK have shown that there is no convincing proof that antioxidants have any effect on how long people can live. However 40% of women and 30% of men are reportedly taking these supplements and spending over £333 million on them per year. http://www.understandingfoodadditives.org

Free radicals in living cells Free radicals are present in all living cell and are a part of the cell processes. However excessive free radicals in our cells can attack the cell membranes (the outer coat of the cell). This attack causes cell and tissue damage. Radicals can also break strands of DNA (the genetic material in the cell). Some of the chemicals known to cause cancer, do so by forming free radicals. The imbalance between free radicals and antioxidants can lead to disease and ill health. The 4 main non-enzymatic antioxidants metalonin, α-tocopherol (Vitamin E), ascorbic acid (Vitamin C) and β-carotene (precursor for Vitamin A) can be found in a range of foods in our diet. However medical opinions are divided as regards the impact these antioxidants have our on general health.

Melatonin This is a hormone which helps to regulate sleep in our bodies. This compound can be termed as a terminal antioxidant as once it has removed the free radicals it has to be replaced.

α-tocopherol This is a form of vitamin E and can be found in vegetable oil, nuts and seeds. It has been suggested that it is good for the skin.

Ascorbic Acid This is also known as Vitamin C and is commonly found in fruits and vegetables. It is one of the essential vitamins and the human body is unable to synthesize it. It can be easily oxidised and acts as a hydroxyl or superoxide anion radical scavenger.

β-carotene This is a precursor to vitamin A. It is a highly red-orange pigment found in plants and fruits. In particular it gives carrots their orange colour. It helps human cells to absorb vitamin A.

03/01/2019 Antioxidants Oxygen reacts with edible oils giving the food a rancid flavour. Antioxidants are molecules which will prevent these oxidation reactions taking place. Ion-electron equations can be written for the oxidation of antioxidants.