CCC6 In mass spectroscopy electrons samples are bombarded with electrons.

These electrons can knock of electrons of the samples and they can also break the sample compound forming other species. After that they are detected and the data of the mass/charge ratio is plotted against abundance. From this data it is possible to determine what compounds were present in the sample depending on the mass/ charge ratio. And usually the charges on the ions are +1 so the sample can be determined just by comparing the result with the molecular mass of the compound. H-NMR data of a given sample can be used to find out how many different environments the hydrogen atoms in a given sample are in. This is represented by peaks on the data. From the mass spectroscopy data of the starting material a peak at 329.790769 is observed. This is the molecular weight of 2, 4, 6-tribromoaniline. This peak could correspond to the molecular ion of 2,4,6-tribomoaniline. Also from the H-NMR data for the starting material two peaks are observed which corresponds that the hydrogen atoms in the compounds must be into two different environments within the same compound. And in 2,4,6-tribomoaniline the hydrogen atoms are in two different environments once when it is attached with nitrogen and when it is attached with carbon. Therefore 2, 4, 6-tribromoaniline must be present in the starting material. Similarly from the mass spectroscopic data of the reaction products a peak at 314.7798 is observed. And the molecular mass of 1, 3, 5-tribromoaniline is 314.76 g/mol. And also in the H-NMR data of the product only one peak is observed and thus it can be inferred that the hydrogen atom which is present in the compound are all in a similar environment. And indeed in of 1, 3, 5-tribromoaniline all the hydrogen atoms are in similar environment i.e. attached to carbon atoms. Thus proving the existence of 1, 3, 5-tribromoaniline in the product. Electrophilic Aromatic Substitution Reaction An electrophilic aromatic substitution reaction is the attack of an electrophile on an aromatic ring substituting for a proton. This reaction allows for the introduction of other functional groups onto the aromatic ring. The electrophile attacks the aromatic ring at the aliphatic position removing two electrons destabilizing the aromatic ring, but creating a resonancestabilized carbocation called a sigma complex (arenium ion). Then the aliphatic proton is lost to give the substitution product. The reaction rate with the aromatic ring depends on its substituents. Groups that increase the reaction rate with benzene are called activators, while ones that decrease the reaction rate are called deactivators. Activators stabilize the arenium ion by increasing the electron density on the aromatic ring by adding two electrons via resonance or through hyperconjugation, the overlap of neighboring sigma bond with the aromatic pi system. Deactivators decrease the electron density by removing two electrons via resonance or induction, resulting in the destabilization of the arenium ion.

The following reaction shows the general mechanism-

Electrophilic aromatic substitution reaction can also be used to remove an amino group from aromatic compounds. This is exactly what happened in the experiment that was conducted. Here one of the oxygen atoms is protonated which is removed as water. Then the nitrogen of the amino group attacks the positive nitrogen on the nitrogen oxygen double bond. Then one molecule of water is removed and nitrogen nitrogen triple bond forms, with a positive charge on the nitrogen attached to the benzene ring. This charge is neutralised by pushing electron from the benzene ring. The following reaction illustrates this-

Preparation of 2,4,6-tribomoaniline Aniline was dissolved in glacial acetic acid and water and the solution turned brown. The solution was placed in an ice bath and then on top of a magnetic stirrer. A stirrer bar was put into the solution. After that a mixture of bromine and glacial acetic acid was added to slowly to the solution by using a dropping funnel, This caused the formation of a white precipitate. The bromine was added until the solution turned yellow. After that water was added to the mixture to precipitate the remaining solid. The precipitate was 2,4,6,-tribromoaniline. The white precipitate formed was filtered out by suction filtration and was then washed with water and then it was dried between two filter papers. Its mass was measured and then a small amount of 2,4,6,-tribromoaniline was kept for measuring its melting point. The mass of this product was 6.6908g. Preparation of 1,3,5-tribromobenzene The 2,4,6-tribomoaniline from the previous part of the experiment was dissolved in toluene and ethanol. Then the mixture was warmed in a water bath to dissolve the 2,4,6tribomoaniline completely. The solution was then put under reflux and sulphuric acid was added to the solution. The solution was then heated to boiling and then sodium nitrite was added to the solution which caused the solution to turn orangish purple. The solution was kept under reflux for 45 minutes. Then mixture was then removed and cooled in an ice bath. The mixture was then filtered under suction filtration and washed with a small quantity of cold ethanol and with water. The orange precipitate then was washed thoroughly with water. This was a crude product of 1,3,5-tribromobenzene. Recrystallisation The orange salt obtained was then recrystallised in minimum quantity of hot ethanol. After the salt dissolved charcoal was added to it and the mixture turned black. The charcoal was then removed by hot filtration through a fluted paper. Then the solution was placed in an ice bath to recrystalise and a white salt formed which was filtered under suction and dried. The crystals were of 1,3,5-tribromobenzene. The mass of the product obtained was measured and small amount of itwas taken in order to measure its meting point. The amount of product obtained was 0.98g. Melting point

The amino group activates ortho and para positions. When these positions are attacked the lone pairs on the amino group can delocalise into the pi system giving it stability. For this reason when aniline is nitrated with nitric acid and sulphuric acid the product is 3nitroaniline. But when 2,4,6-tribomoaniline is nitrated with sodium nitrite the +NO species directly attacks the amino group which at the lone pair eventually removing it. It cannot attack the ortho or para position because of the bromine atoms attached to the benzene ring which is a strong electron withdrawing groups and any electrons delocalized into the pi system will be removed and no stability is obtained.