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STONE COLD RATTLESNAKE (113)

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AROMATIC HYDROCARBONS
Aromatic hydrocarbons are those which contain one or more benzene rings. The name of the class come from the fact that many of them have strong, pungent aromas. Symbolic structures of some common aromatic hydrocarbons are shown below. Those hydrocarbons which do not contain a benzene ring are called aliphatic hydrocarbons.













A vast number of aromatic compounds can be produced by substitutions for one or more of the ring hydrogen’s.
Aromatic hydrocarbons have ring structures. Ring systems with double bonds that cannot be localized are called mesomere systems. Aromatic hydrocarbons carrying hydroxyl-groups are called phenols. There exist also ring compound with ring elements other than carbon. Such ring systems are termed heterocyclic rings. Heterocyclic rings are components of nucleotides that have an important role in the cell.
Benzene and its derivatives belong into this group, some of whose members occurring in plants are characterized by a strange, ‘aromatic’ smell. The benzene molecule has a ring-shaped structure with six C-H-groups that are linked alternately with C-C single and C=C double bonds. The structure should thus be written (according to KEKULE):







The electron theory distinguishes between two types of bonds in such a ring system, the sigma-bonds and the pi-bonds that are arranged vertically to each other and are conjugated so that the double bonds of such a system cannot be localized directly. Such a system is also called a mesomere system. There exist consequently six equal ‘aromatic’ bonds. A compound consisting of two benzene rings is naphthalene
Aromatic hydrocarbons with hydroxyl-groups are called phenols. They are able to dissociate in alkaline solutions and to form phenolates.






Structure of Amines

Sp3 (tetrahedral) nitrogen including the lone pair


Tertiary amines usually cannot be isolated as separate enantiomers
Basicity of Amines, Acidity of Ammonium Ions
N lone pair relatively easily protonated










    • water solubility of amines can be easily changed with pH


    • aromatic amines are water-soluble (protonated) below pH 4


    • aliphatic amines are water-soluble (protonated) below pH 9



Basicity Trends
1. Aromatic amines are less basic due to resonance delocalization of the N lone pair



2. Amides are nonbasic due to strong delocalization of the N lone pair



3. Electron withdrawing effects decrease basicity

because the N lone pair is less available for bonding to a proton


Preparations of Amines
1. substitution reactions:

SN2 reaction of ammonia on alkyl halides

but the amine product is still nucleophilic and further substitution often results

primary amines can be made by using a great excess of NH3 to avoid further substitution


2. Reduction reactions:



Reactions of Amines

1. substitution reactions:

SN2 reactions on alkyl halides, but over substitution is a problem, except for making quaternary ammonium ions









    • acyl substitutions to make amides (usually from acid chlorides)



2. Diazonium Salts
Secondary amines react with HNO2 (nitrous acid) to make N-nitrosoamines
Primary amines react with HNO2 to form a diazonium ion (diazotization reaction)







    • aliphatic diazonium ions are unstable, give carbocations


    • possible products include rearrangements, eliminations, nucleophilic substitution



Aryl diazonium ions are relatively stable and can be replaced by many nucleophiles this method provides a good way to attach nucleophiles to aromatic rings
Sandmeyer reactions : CuX as catalyst to convert diazonium ion to ArX

3. Elimination Reactions







    • Hoffmann elimination - from a quaternary ammonium hydroxide


    • Cope elimination - from a tertiary amine oxide



Pyrrole







    • pyrrole is even more reactive than benzene in electrophilic aromatic substitution











    • the porphine ring system is a tetrapyrrole - found in heme, chlorophyll, etc.






Pyridine








    • pyridine is less reactive than benzene in electrophilic aromatic substitution






Alkaloids

Naturally occurring amines, such as morphine. The alkaloid name comes from their basic (alkaline) properties.



ALDEHYDES AND KETONES
What are aldehydes and ketones?
Aldehydes and ketones as carbonyl compounds
Aldehydes and ketones  compounds which contain a carbonyl group ,i.e., a carbon-oxygen double bond. In aldehydes, the carbonyl group has a hydrogen atom attached to it together with either

  • a second hydrogen atom

  • or, more commonly, a hydrocarbon group which might be an alkyl group or one containing a benzene ring.


Simple examples of aldehydes are

It should be noted here that all aldehydes have exactly the same end to the molecule. All that differs is the complexity of the other group attached.
When writing formulae for these, the aldehyde group (the carbonyl group with the hydrogen atom attached) is always written as -CHO - never as COH. Since it is the representation for an alcohol.
What are ketones
In ketones, the carbonyl group has two hydrocarbon groups attached. Again, these can be either alkyl groups or ones containing benzene rings.
Some examples of ketones

Notice that ketones never have a hydrogen atom attached to the carbonyl group.

Propanone is normally written CH3COCH3. Notice the need for numbering in the longer ketones. In pentanone, the carbonyl group could be in the middle of the chain or next to the end - giving either pentan-3-one or pentan-2-one.
Bonding and reactivity
Bonding in the carbonyl group 
Oxygen is far more electronegative than carbon and so has a strong tendency to pull electrons in a carbon-oxygen bond towards itself. As a result one of the two pairs of electrons that make up a carbon-oxygen double bond is even more easily pulled towards the oxygen. That makes the carbon-oxygen double bond very highly polar.
It can be visualised as

Chemical properties
The slightly positive carbon atom in the carbonyl group can be attacked by nucleophiles. (A nucleophile is a negatively charged ion (for example, a cyanide ion, CN-), or a slightly negatively charged part of a molecule (for example, the lone pair on a nitrogen atom in ammonia, NH3)).
During the reaction, the carbon-oxygen double bond gets broken. The net effect of all this is that the carbonyl group undergoes addition reactions, often followed by the loss of a water molecule. This gives a reaction known as addition-elimination or condensation.
Note that both aldehydes and ketones contain a carbonyl group. That means that their reactions are very similar in this respect.
Difference between aldehydes and ketones
An aldehyde differs from a ketone by having a hydrogen atom attached to the carbonyl group. Thus the aldehydes are very easy to oxidise.
For example, ethanal, CH3CHO, is very easily oxidised to either ethanoic acid, CH3COOH, or ethanoate ions, CH3COO-.
Ketones on the other hand do not have that hydrogen atom and are resistant to oxidation. They are only oxidised by powerful oxidising agents which have the ability to break carbon-carbon bonds.
Physical properties
Boiling points
Methanal is a gas (boiling point -21°C), and ethanal has a boiling point of +21°C. That means that ethanal boils at close to room temperature.
The other aldehydes and the ketones are liquids, with boiling points rising as the molecules get bigger.
The size of the boiling point is governed by the strengths of the intermolecular forces.
Explanation


  • Van-der waals forces :These attractions get stronger as the molecules get longer and have more electrons. That increases the sizes of the temporary dipoles that are set up. This is why the boiling points increase as the number of carbon atoms in the chains increases - irrespective of whether you are talking about aldehydes or ketones.


  • van der Waals dipole-dipole attractions Both aldehydes and ketones are polar molecules because of the presence of the carbon-oxygen double bond. As well as the dispersion forces, there will also be attractions between the permanent dipoles on nearby molecules.


That means that the boiling points will be higher than those of similarly sized hydrocarbons - which only have dispersion forces.
a comparison of three similarly sized molecules










molecule type boiling point (°C)


Notice that the aldehyde (with dipole-dipole attractions as well as dispersion forces) has a boiling point higher than the similarly sized alkane which only has dispersion forces. It should be noted that, the aldehyde’s boiling point isn’t as high as that of alcohol’s. In the case of alcohols, there is hydrogen bonding as well as the other two kinds of intermolecular attraction.
Although the aldehydes and ketones are highly polar molecules, they don’t have any hydrogen atoms attached directly to the oxygen, and so they can’t hydrogen bond with each other.
Solubility in water
The smaller aldehydes and ketones are freely soluble in water but solubility falls with chain length. For example, methanal, ethanal and propanone - the common small aldehydes and ketones - are miscible with water in all proportions.
The reason for the solubility is that although aldehydes and ketones can’t hydrogen bond with themselves, they can hydrogen bond with water molecules.
One of the slightly positive hydrogen atoms in a water molecule can be sufficiently attracted to one of the lone pairs on the oxygen atom of an aldehyde or ketone for a hydrogen bond to be formed.
There will also, of course, be dispersion forces and dipole-dipole attractions between the aldehyde or ketone and the water molecules. As a result of  these attractions there is a release of  energy which helps in supplying the energy needed to separate the water molecules and aldehyde or ketone molecules from each other before they can mix together.
As chain lengths increase, the hydrocarbon “tails” of the molecules (all the hydrocarbon bits apart from the carbonyl group) start to get in the way.
By forcing themselves between water molecules, they break the relatively strong hydrogen bonds between water molecules without replacing them by anything as good. This makes the process energetically less profitable, and so solubility decreases







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