Chirality A chiral center which is a carbon atom with four different groups bonded around it, so there is no line of symmetry to the molecule. (Indicate using *)
Optical Isomers Optical isomerism is a type of stereoisomerism where molecules have the same molecular formula but different spatial arrangement of atoms.
The presence of a chiral center leads to two possible isomers – these are mirror images of each other.
These two different isomers are called enantiomers and are unique due to their effect on plane polarized light. Each enantiomer causes the rotation of plane polarized light by 90deg in opposite directions.
Racemic Mixtures A racemate is formed when optical isomers are produced as a pair of enantiomers in a 1:1 ratio. The optical rotational effect on polarized light is caused by each enantiomer causes the overall effect to be zero, as the opposite directions of rotation cancel out.
The mixture produced is optically inactive.
Equal quantities of the two isomers are produced: nucleophilic addition reaction OR nucleophilic substitution in SN1 mechanism
Nucleophilic Substitution SN1 reactions proceed via a planar carbocation intermediate, meaning the incoming nucleophile can attack via either face of the compound. This means the product is a racemic mixture.
Conversely, SN2 reaction mechanisms occur in a single step, since the nucleophile attacks while simultaneously the leaving group is removed. This means that there is only one possible direction of attack from the nucleophile. Therefore, SN2 reactions produce a single enantiomer.
Nucleophilic Addition
In nucleophilic addition reactions, nucleophiles are able to attack a molecule with a
carbonyl group from above or below the planar carbon-oxygen double bond. This means that the two possible products of the reaction are mirror images, and are therefore optical isomers. This mechanism, therefore, gives evidence for how optical activity arises in molecules. Carbonyl Compounds
Carbonyl Group:
Most common carbonyl compounds are aldehydes and ketones.
These molecules do not contain hydrogen bonds; however, they do have permeant dipole – dipole forces. The only type of intermolecular force which exist between their molecules are Van der Waals Forces. O atom is far more electronegative than the carbon atom – therefore the C=O bond is polarized.
The smaller carbonyl compounds can form hydrogen bonds with water molecules, as the long pair of electrons on the polarized oxygen atom attracts the hydrogen atoms in the water molecule. They are soluble in water.
Topic: Aldehydes Aldehydes have the carbonyl functional group at the end of the molecule.
Suffix: “al”
Structural and Skeletal Diagrams
i. Methanal ii. Propanal
Q. Draw the structural and skeletal diagram for the above:
Topic: Ketones Ketones have the carbonyl functional group in the middle of the molecule.
Suffix: “one”
The first ketone in the homologues series is therefore:
Preparation of Aldehydes & Ketones
Oxidation Reactions
The oxidising agent used for all of the oxidation reactions be acidified potassium dichromate: K2Cr2O7 with sulfuric acid, H2SO4.
Ketones are resistant to further oxidation, so no further oxidation will take
place with secondary alcohols. This is because ketones do not have a readily available hydrogen atom, in the same way that aldehydes (or alcohols) do. An extremely strong oxidizing agent would be needed for oxidation of a ketone to take place - The oxidation will likely oxidise a ketone in a destructive way, breaking a C-C bond.
If the goal is to prepare aldehydes
Then the apparatus must be set up to distill off the aldehydes as it is produced. Reactions of Aldehydes & Ketones 1. Further oxidation of primary alcohol
To oxidize a primary alcohol straight to a carboxylic acid, you would heat the reaction mixture under reflux. The aldehyde would still be produced, but as it evaporates it would condense and drop back into the reaction mixture, to be further oxidized to the carboxylic acid.
Tests to Determine if its an Aldehyde or Ketones
1. Acidified Potassium Dichromate
Potassium dichromate (VI) is used as an oxidizing agent in the oxidation of alcohols.
As the alcohol is oxidized, potassium dichromate (VI) is reduced. This reduction is observed as a color change from orange to green, which indicates the alcohol has undergone oxidation.
2. Using Tollens Reagent (a.k.a The Silver Mirror)
Tollens' reagent contains the silver(I) complex ion [Ag(NH3)2 ]+
When Tollens reagent is reduced it becomes solid metallic silver, Ag.
Positive Result: Aldehyde
Negative Result: Ketone
3. Using Fehling’s Solution
Fehling’s solution is a blue alkaline solution containing copper(II) ions which act as the oxidising agent.
The blue Cu2+ ions are reduced to Cu+ ions and a brick red precipitate is formed.
Positive Result: Aldehyde
Negative Result: Ketone
Reduction All the oxidation reactions involved in the production of carbonyl compounds can be reversed visa reduction reactions.
LiAlH4 is a very reactive compound and will react violently with water and alcohols, so the reaction is carried out in a solvent of dry ether.
Reaction is an example of nucleophilic addition.
Nucleophile: 𝐻:−
First a salt is formed, and then a dilute acid is added to release the alcohol from the salt. The reducing agent can be represented by [H] in the chemical equation.
Nucleophilic Addition – To form Hydroxynitriles
Nucleophile: : 𝐶𝑁 −
This is used in chemical synthesis as it causes the carbon chain to be extended by
one carbon atom. The product of the reaction is a hydroxynitrile.
Common reagent: KCN (Potassium Cyanide)
Why is KCN preferred of HCN as a reagent?
HCN is hard to store and is a toxic gas which reacts to produce dangerous byproducts. All three compounds can form hydrogen bonds to water molecules.
c.) Test: Benedicts Solution | Results: Blue to red
Test: Acidified Potassium/ Sodium Dichromate (VI) | Result: Orange to Green
Test: Potassium Mangante (VII): Result: Purple to coloruless
(iii.) C=O carbonyl bond stretch would be different for propanal and propanone. COOH is not present – Not a carboxylic acid C=O at the end of the molecule are not present – Not an aldehyde
This compound is ketone.
The test to show carvone is a carbonyl compound 2,4 DNP test (M1) which gives orange/red/yellow precipitate (M2)
Test: Warm ammonical silver nitrate | Result: No silver mirror
Test: Fehling’s solution, Benedicts | Result: Stays blue
Carboxylic acids can be prepared by the hydrolysis of nitrile compounds.
Properties ❖ The COOH functional group allows carboxylic acid molecules to form hydrogen bonds between each other. - They can form hydrogen bonds with water, meaning they are soluble in water. As the chain length increases, their solubility decreases since the CH2 groups do not form hydrogen bonds. ❖ Since carboxylic acids have both the C=O and O-H groups they can form hydrogen bonds between molecules. Therefore, melting and boiling points are very high.
Reaction Condition: Reaction is carried out in solvent of dry ether (CH3OCH3).
Used to produce primary alcohols from carboxylic acids.
Type of Reaction: Nucleophilic Addition
Nucleophile: H:-
The aldehydes produced in the reduction reaction can not be isolated because it is more reactive than carboxylic acids, so immediately reduced further to primary alcohols.
Acylation Carboxylic acid has derivative molecules where the -OH group is replaced by another group. Acyl Chlorides are one such derivative that reacts violently due to the very polar – COCl group.
Reagent: Phosphorus Pentachloride, 𝑷𝑪𝒍𝟓
𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝑃𝐶𝑙5 → 𝐶𝐻3 𝐶𝑂𝐶𝑙 + 𝐻𝐶𝑙 + 𝑃𝑂𝐶𝑙3
Esterification Carboxylic acids react with alcohols in the presence of a strong acid catalyst to form esters.
Functional group: COO
Catalyst: Conc. sulfuric acid
Reaction Method: Is carried out under reflux
Remove the – OH from the acid, and the hydrogen from the alcohol – to make water.
They are named after the alcohol and the carboxylic acid from which they are formed.
Esters are sweet-smelling compounds used in food flavorings and perfumes. They have low boiling points and make good solvents for polar molecules.
React via nucleophilic addition – elimination reactions.
Hydrolysis of Esters Ester hydrolysis is the reverse reaction to esterification, converting esters back into alcohols and carboxylic acids.
This process is done by adding water (other conditions would produce other products)
Alkaline Conditions
Acidic Conditions
Condensation Polymers Condensation polymers form a water molecule is removed. Polyesters are formed in this way from the reaction between a dicarboxylic acid and a diol.
Forms an ester linkage – COO-
Can be broken down through hydrolysis due to the polarity within the polymer molecules – They are biodegradable and can be easily broken down by nature, naturally occurring water or moisture. Spectroscopy & Chromatography What is spectroscopy? (03 marks)
Spectroscopy is used to identify the element and compound of atoms and
molecules. They are measured by examining the absorbed or emitted radiant energy based on their physical phenomenon is known as a spectrometer.
What is chromatography? (03 marks)
Chromatography is a separation method where the analyte is combined with a
liquid or gaseous mobile phase, which s pumped through a stationary phase. The components of the analyte interacts different with these two phases.
High Resolution Mass Spectrometry
- More sensitive form of mass spectrometry - Allows the Mr of a substance to be determined to be several decimal places. - Precise atomic masses been given out, which we use to calculate the molecular formula of the compound being tested.
Nuclear Magnetic Resonance (NMR)
Is an analytical technique that allows the structure of a molecule to be determined by analyzing the energy of each bond environment.
Different bond environments within a molecule absorb different amount of energy, so
they are displayed as different peaks on a spectra print out.
The bond environment peaks are measured against a standard molecule,
tetramethylsilane (Si(CH3)4) known as TMS. This is the standard molecule, because it contains four identical carbon and hydrogen environments.
It can easily be identified as it is seen as a peak at δ = 0 ppm on the x-axis.
𝐶 13 NMR Analyses the different carbon environment in a molecule.
- Carbon environments that are near to oxygen atoms have δ values that are shifted to the right. - This is because oxygen is very electronegative and changes the bond environment and affects how it absorbs energy.
Molecule Symmetry
Molecules that have symmetry may display fewer δ peaks than the no. of carbon atoms per molecule. Therefore in these cases, it is important to look at the given molecular formula of a compound in order to decipher its displayed structure.
𝐻1 NMR (Proton NMR)
The different hydrogen environments in a molecule is analyzed and displayed as peaks on a spectra.
- The samples being analyzed must be dissolved in a non-hydrogen contain
solvent, so that the solvent does not produce any peaks on the spectrum. CCl4 is the most common solvent, used along with deuterated solvents containing deuterium, an isotope of hydrogen. This is more complex than C13 spectra as the height of the peaks show the relative intensity of each δ value. The relative intensities correspond to the no. of hydrogens in that certain environment within a molecule, shown as a number above the peak.
Splitting Patterns The peaks of H1 NMR spectra also inform where each environment is positioned within the molecule.
Peaks are split into a smaller cluster, with smaller peaks indicating how many hydrogens are on the adjacent carbon atom within the molecule. These smaller peaks have a splitting pattern and follow a “n+1 rule” where n is no. of hydrogen on the adjacent carbon.
0H on adjacent carbon = Singlet
1H on adjacent carbon = Doublet
2H on adjacent carbon = Triplet
3H on adjacent carbon = Quartet
Your marking scheme does not need you to verify between the 3 and 4 peaks.
