organic chemistry 3 Flashcards
what is the formula for benzene
C₆H₆
what are the two ways of representing benzene
kekule model delocalised model
What was Friedrich August Kekulé’s proposal about the structure of benzene?
Kekulé proposed that benzene was made up of a planar (flat) ring of carbon atoms with alternating single and double bonds between them.
What additional atoms did Kekulé propose were bonded to each carbon atom in benzene?
In Kekulé’s model, each carbon atom is also bonded to one hydrogen atom.
How did Kekulé adapt his model of the benzene molecule?
He later adapted the model to propose that the benzene molecule was constantly flipping between two forms (isomers) by switching over the double and single bonds.
What would you expect the bond lengths to be in benzene according to the Kekulé model?
According to the Kekulé model, you’d expect benzene to have three bonds with the length of a C–C bond (154 pm) and three bonds with the length of a C=C bond (134 pm).
What have X-ray diffraction studies revealed about the carbon-carbon bonds in benzene?
X-ray diffraction studies have shown that all the carbon-carbon bonds in benzene have the same length of 140 pm, which is between the length of a single bond and a double bond.
What does the consistency in bond lengths observed in benzene indicate about the Kekulé model?
The consistent bond length of 140 pm observed in benzene suggests that the Kekulé structure cannot be entirely accurate.
What does the delocalised model propose about the bonding in benzene?
The delocalised model proposes that benzene’s bonding involves delocalised pi-bonds formed by the overlapping of p-orbitals on carbon atoms.
How are sigma-bonds formed in the delocalised model of benzene?
In the delocalised model, each carbon atom forms three s-bonds—one to a hydrogen atom and one to each of its neighboring carbon atoms—due to head-on overlap of their atomic orbitals.
What happens to the remaining p-orbital on each carbon atom in the delocalised model of benzene?
Each carbon atom has one remaining p-orbital containing one electron, which overlaps sideways with the p-orbitals of neighboring carbon atoms to form a ring of delocalised p-bonds.
How are the electrons in the delocalised model of benzene represented, and why?
The electrons in the delocalised model are represented as a circle inside the ring of carbons rather than as double or single bonds because they are delocalised and do not belong to a specific carbon atom.
What happens when you react an alkene with hydrogen gas?
Two atoms of hydrogen add across the double bond, a process known as hydrogenation, and the enthalpy change of the reaction is called the enthalpy change of hydrogenation.
What is the expected enthalpy change of hydrogenation for benzene based on the Kekulé structure?
If benzene had three double bonds (as in the Kekulé structure), the expected enthalpy change of hydrogenation would be (3 × 120 =) –360 kJ mol–1.
when cyclohexane is hydrogenated what is the enthalpy change of hydrogenation
-120 kj mol⁻¹
What is the experimental enthalpy change of hydrogenation for benzene, and how does it compare to the expected value?
The experimental enthalpy change of hydrogenation for benzene is –208 kJ mol–1, which is far less exothermic than the expected value.
What conclusion can be drawn from the discrepancy between the expected and experimental enthalpy changes of hydrogenation for benzene?
The discrepancy suggests that more energy must have been put in to break the bonds in benzene than would be needed to break the bonds in the Kekulé structure.
What does the discrepancy between the expected and experimental enthalpy changes of hydrogenation for benzene indicate about its stability?
The difference indicates that benzene is more stable than the Kekulé structure would be.
what does the difference in in energy indicate about benzene and the kekule model
This difference indicates that benzene is more stable than the Kekulé structure would be.
What is thought to be the reason for benzene’s extra stability compared to the Kekulé structure?
The extra stability of benzene is thought to be due to the delocalised ring of electrons.
How do alkenes react with bromine water at room temperature, and what is the result?
Alkenes react easily with bromine water at room temperature, decolorizing the brown bromine water. This reaction is an electrophilic addition reaction, where the bromine atoms are added across the double bond of the alkene.
What is the expected reaction between benzene and bromine based on the Kekulé structure, and what are the actual conditions required for this reaction?
Based on the Kekulé structure, one would expect a similar reaction between benzene and bromine. However, to make it happen, you need hot benzene and ultraviolet light, and it remains difficult.
How is the difference in reactivity between benzene and other alkenes explained?
The difference is explained by the presence of delocalized p-bonds in benzene, which spread out the negative charge and make the benzene ring very stable. Therefore, benzene is reluctant to undergo addition reactions that would destroy the stable ring.
what type of reaction does benzene prefer to undergo, and why?
Benzene prefers to undergo electrophilic substitution reactions instead of addition reactions. This is because in alkenes, the p-bond in the C=C double bond attracts electrophiles strongly due to its localized high electron density. In benzene, however, this attraction is reduced due to the negative charge being spread out.
What happens when benzene is burned in oxygen?
When benzene is burned in oxygen, it produces carbon dioxide and water.
What occurs if benzene is burned in air?
2C₆H₆ + 15O₂ ⟶ 12CO₂ + 6H₂O
If benzene is burned in air, a very smoky flame is produced due to insufficient oxygen for complete combustion. Many carbon atoms remain unburned and form particles of soot in the hot gas, resulting in a smoky flame.
what happens when you burn benzene in air
If you burn benzene in air, you get a very smoky flame — there’s too little oxygen to burn the benzene completely. A lot of the carbon atoms stay as carbon and form particles of soot in the hot gas — making the flame smoke.
What are compounds containing a benzene ring commonly called?
arenes or ‘aromatic compounds’
Why doesn’t benzene undergo electrophilic addition reactions like alkenes?
Benzene doesn’t undergo electrophilic addition reactions like alkenes because addition reactions would break the very stable ring of delocalised pi-bonds.
Describe the process of electrophilic substitution reactions in benzene.
In electrophilic substitution reactions, a hydrogen atom in benzene is substituted by an electrophile.
What are the two steps involved in the mechanism of electrophilic substitution reactions in benzene?
The mechanism involves two steps: addition of the electrophile to form a positively charged intermediate, followed by loss of H+ from the carbon atom attached to the electrophile, reforming the delocalised ring.
Why does an electrophile need to have a strong positive charge to attack the benzene ring?
The delocalised p-bonds in benzene spread out the charge density across the ring, requiring an electrophile with a strong positive charge to effectively attack the benzene ring.
How can some compounds be made into stronger electrophiles for attacking the benzene ring?
Some compounds can be made into stronger electrophiles using a catalyst called a halogen carrier.
What role does a halogen carrier play in making compounds stronger electrophiles?
a halogen carrier polarises halogens such as br2 and cl2 the positive part of the halogen acts as the electrophile
Name some examples of halogen carriers.
Halogen carriers include aluminium halides, iron halides, and iron.
What are Friedel-Crafts reactions used for in organic synthesis?
Friedel-Crafts reactions are used for forming C–C bonds in organic synthesis.
What are the two types of Friedel-Crafts reactions?
The two types are Friedel-Crafts alkylation and Friedel-Crafts acylation.
Describe Friedel-Crafts alkylation.
Friedel-Crafts alkylation puts any alkyl group onto a benzene ring using a halogenoalkane and a halogen carrier.
Describe Friedel-Crafts acylation.
Friedel-Crafts acylation substitutes an acyl group for a hydrogen atom on benzene, typically using an acyl chloride instead of a halogenoalkane.
What conditions are required for Friedel-Crafts reactions to occur?
The reactants need to be heated under reflux in a non-aqueous solvent (like dry ether) for Friedel-Crafts reactions to occur.
What happens when benzene is warmed with concentrated nitric acid and concentrated sulfuric acid?
When benzene is warmed with concentrated nitric acid and concentrated sulfuric acid, a nitration reaction occurs, and nitrobenzene is formed.
What role does sulfuric acid play in the nitration reaction of benzene?
Sulfuric acid acts as a catalyst in the nitration reaction of benzene, facilitating the formation of the nitronium ion (NO2+), which is the electrophile.
what is the formula for phenol
C₆H₅OH
What property of phenol makes it more likely to undergo electrophilic substitution than benzene?
The presence of the -OH group makes phenol more likely to undergo electrophilic substitution than benzene.
How does the lone pair of electrons from the oxygen atom in the -OH group of phenol contribute to its reactivity?
One of the lone pairs of electrons in a p-orbital of the oxygen atom overlaps with the delocalised p-bonds in the benzene ring, causing the lone pair of electrons from the oxygen atom to be partially delocalised into the p-system.
How does the partial delocalization of the lone pair of electrons from the oxygen atom affect the reactivity of phenol?
This increases the electron density of the ring, making it more likely to be attacked by electrophiles.
How does phenol react with orange bromine water?
Phenol reacts with orange bromine water, causing it to decolorize.
Why does substitution occur more than once when phenol reacts with electrophiles?
The -OH group in phenol makes the ring highly attractive to electrophiles, leading to multiple substitution reactions.
What is the product formed when phenol reacts with orange bromine water, and what are its properties?
The product formed is 2,4,6-tribromophenol, which is insoluble in water and precipitates out of the mixture. It has a characteristic antiseptic smell.
How can aspirin be synthesized using phenol?
Aspirin can be synthesized through an esterification reaction of salicylic acid, which is a derivative of phenol.
What steps are involved in the synthesis of aspirin from salicylic acid?
- Add ethanoic anhydride and a few drops of phosphoric acid to salicylic acid in a test tube.
- Warm the reaction mixture to 50 °C and leave it for about 15 minutes.
- Add cold water to the reaction mixture, then cool it on ice to allow aspirin crystals to form.
- Filter the crystals under reduced pressure.
- Recrystallize the aspirin in a mixture of water and ethanol.
What is an amine?
An amine is a compound derived from ammonia (NH3) where one or more of the hydrogens is replaced with an organic group.