Unit 5 Organic Chemistry Reactions

Benzene
Combustion
In excess air, benzene burns to form carbon dioxide and water.

In limited air, it burns with a smoky flame forming carbon and water.

Free-Radical Addition
Chlorine bubble chlorine into boiling benzene in the presence of ultraviolet light, and addition takes place. The chlorine radicals add on, one at a time to the benzene ring until all the -bonds have been broken. (Bromine acts similarly)

Hydrogen when heated with a Nickel catalyst, hydrogen adds on and cyclohexane is formed.

Electrophilic Substitution
Mechanism given that and electrophile E+ adds on to a carbon atom on the benzene ring:

Nitration - when concentrated nitric acid, and a catalyst of concentrated sulphuric acid are warmed together at 60 degrees under reflux, nitrobenzene and water are formed. The electrophile is the NO2 group, which is formed by a protonated nitric acid molecule. (below 55 degrees, the reaction is too slow, above 65 degrees, a second nitrogen dioxide group Is substituted onto the ring.)

Halogens with a catalyst of anhydrous iron halide, chlorine and bromine react rapidly with benzene, if the reagents are dry. For the bromination of benzene, the catalyst is made in situ by adding iron filings to a mixture of benzene and liquid bromine:

This can then react with more bromine to form the electrophile:

Friedel-Crafts, Alkylation benzene reacts with a halogenoalkane in the presence of a catalyst anhydrous aluminium chloride, in dry conditions to form a hydrocarbon and gaseous hydrogen halide:

Friedel-Crafts, Acylation benzene reacts with an acid chloride with the catalyst anhydrous aluminium chloride, which produces the electrophile CH3C+=O:

Sulfonation benzene reacts with fuming sulphuric acid at 40 degrees under reflux. The electrophile is the SO3. The products are benzesulphonic acid and water:

Alkenes benzene adds onto alkenes to form a branched chain alkane substituted into the benzene ring (except with ethene, as it has too few carbons) Detergents add a long chain alkene and benzene, then sulphonate the product, then neutralise with sodium hydroxide to form a detergent. It makes an excellent detergent as its calcium salt is soluble, so no scum if formed in hard water.

Phenol
Electrophilic Aromatic Substitution reactions
Bromine bromine water and phenol and water react, going from the red-brown bromine colour, and forming a white antiseptic smelling precipitate of 2,4,6-tribomophenol

The electrophile is the + bromine atom in an HOBr molecule, formed form the reaction of bromine and water

Nitration reacts with dilute nitric acid to form 2-nitrophenol and 4-nitrophenol plus water

Reacts with concentrated nitric acid, more nitro groups substitute to give 2,4,6trinitrophenol

Phenol as an acid
Water forms the phenate ion:

Sodium hydroxide reacts in a neutralisation reaction to form the salt sodium phenate and water

Sodium- reacts with metallic sodium to form hydrogen and the salt sodium phenate

Sodium hydrogencarbonate/ sodium carbonate phenol is a weaker acid than carbonic acid, so it does not liberate carbon dioxide from either sodium hydrogen carbonate or sodium carbonate.

Phenol as an alcohol
Acid chlorides, aliphatic reacts slowly to form an ester and fumes of hydrogen chloride. The oxygen atom in phenol acts as a nucleophile and attacks the + carbon atom on the acid chloride. Acid chlorides, aromatic reacts in aqueous solution to create C6H5O- ions, which are a stronger nucleophile than phenol molecules.

Benzoic Acid
When warmed with concentrated nitric and sulphuric acids, 3-nitrobenzoic acid and water are formed.

2-methlynitrobenzene
Preparation
Add the nitrating mixture, consisting of concentrated nitric and sulphuric acids, and mix with benzene, then heat in a water bath at 50 degrees. After refluxing, the mixture is cooled and water added to dilute the acids. The mixture is then poured into a separating funnel and the bottom layer, which contains the methylnitrobenzenes is run off. This impure mixture is washed with sodium carbonate solution, to remove residual acid, then with water to remove any residiual sodium carbonate in a separating funnel. It is dried by adding lumps of anhydrous calcium chloride and leaving for several hours It is then decanted into a flask and distilled. The fraction that boils between 218 and 222 degrees is collected. This is 2-methlybenzene.

Amines
Preparation
Reaction of ammonia with a halogenoalkane. If a halogenoalkane is mixed with excess concentrated ammonia in aqueous ethanolic solution, a primary amine is obtained.

An excess of the halogenoalkane will yield the secondary amine.

Reduction of a nitrile/amide reduced by LiAlH4 in dry ether, then hydrolysis of the adduct with dilute acid

As a Base

Water they react reversibly, forming OH- ions Acids when reacted with an acid, a salt is formed.

With Acid Chlorides

A lone pair of electrons on the nitrogen in the amine acts as a nucleophile and attacks the + carbon in the in acid chloride in an addition-elimination reaction

With Halogenoalkanes
A primary amine reacts with a halogenoalkane to produce a mixture of the salts of secondary and tertiary amines. The reagents are heated in ethanolic solution in a sealed tube

If the free amine is required, a strong base is added to the solution and any unreacted primary amine, and secondary and tertiary amines are formed

With d-block metal ions

Amines can act as ligands; the lone pair of electrons on the amine group can form a bond with the empty orbital of some d-block metal ions. The reaction is similar to the formation of ammines with excess ammonia. (see transition metals for more details)

Phenylamine
Preparation
Nitrobenzene and tin mixed in a round bottomed flask with a reflux condenser. Concentrated hydrochloric acid is carefully added, and after the rapid evolution of hydrogen has ceased, the mixture is heated to 100 degrees in a bath of boiling water for 30 minutes. This is the half equation for the reduction of the phenylamine and the phenylammonium ion is formed. The lone pair on the phenylamine picks up a hydrogen ion from the acid:

The tin (Sn) acts as a catalyst. It is oxidised to provides the electrons used to reduce the nitrobenzene in the presence of the acid.

To remove the extra hydrogen from the NH3 group, sodium hydroxide solution is added in excess:

Finally, the mixture is steam distilled by blowing steam onto the mixture and condensing the phenylamine, which is then placed in a separating funnel with sodium chloride to reduce the solubility and the phenylamine layer is run off and dried with potassium carbonate to remove water. It is then distilled using an air condenser. A summary reaction can be represented as:

Electrophilic substitution Reactions

Bromination phenylamine and bromine water form a white precipitatie of 2,4,6tribromophenylamine and hydrogen bromide:

Reactions of the NH 2 group

It acts a weak base, so reacts reversibly with water. It is a weaker base than aliphatic amines. Acid chloride - Reacts with, like an aliphatic primary amine, an acid chloride to form a secondary amine. The phenylamine acts as a nucleophile

Nitrous acid nitrous acid is unstable, and has to be made is situ by mixing a solution of sodium nitrate, NaNO2 with excess dilute hydrochloric acid.

This reacts with the phenylamine to form benzenediazonium chloride in an exothermic reaction. The temperature must be maintained between 0 and 10 degrees. The ionic equation is:

Benzenediazonium Compounds
Preparation
Nitrous acid and phenylamine between 0 and 10 degrees.

Coupling reactions
Phenol phenol mixed with sodium hydroxide, to give the phenate ion:

This is then attacked by a diazonium ion by electrophilic substitution to form a yellow precipitate of 4-hydroxyazobenzene:

2-napthol napthols are compounds with two fused benzene rings and an OH group on one of the rings. It couples with diazonium ions to form a red precipitate, under the same conditions as phenol, dissolved in sodium hydroxide:

Phenylamine with vigorous shaking, a yellow precipitate is formed:

Amides
Preparation
Ammonia and an acid chloride

Hydrolysis
When boiled under reflux with either aqueous acid or alkali, amides are hydrolysed. E.g. ethanamide hydrolysed with dilute acid:

Polyamides
Condensation polymerisation formed from two different monomers, each with two identical functional groups, or in some cases, a single monomer that has two different functional groups:

e.g. Kevlar:

e.g. Nylon: Addition Polymerisation a polymer formed from monomers containing a C=C group. The bond in the monomer breaks, and a new bond forms with another monomer. As a bond is weaker than a bond, and as all bond making is exothermic, such polymerisation is exothermic.

E.g. poly(propenamide)

E.g poly(ethanol) the monomer does not exist. The polymer is manufactured by reacting the polymer polyvinylacetate with methanol in a transesterification reaction.