9/29/2013

CHEMISTRY OF AMINES & BENZENES

Keane Campbell MSc; BSc; ASc September 29, 2013

Describe the Chemical Reactions of Primary Amines (RNH2) with Dilute Acids; Obj. 2.14
Amines are organic derivatives of ammonia. They are classified as primary (10), secondary (20) or tertiary (30) amines according to number of alkyl or aryl (ring groups) attached to the nitrogen atom. Examples are

The IUPAC system names amine functions as substituents on the largest alkyl group. The simple NH2 substituent found in 10 amines is called an amino group, note the compound above. For 20 and 30 amines a compound prefix (e.g. dimethylamino)

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Reactions of Amines
Due to the unshared electron pair, amines can act as both as a BronstedLowry base (when it accepts a proton from a Bronsted-Lowry acid) or a nucleophile. For example, a primary amine such as ethylamine reacts with hydrochloric acid to form a substituted ammonium salt. The amine group is protonated:

Describe selected chemical reactions of Benzene, Methylbenzene and Nitrobenzene; Obj. 2.15
Reactions of Benzene Bromination Bromination does not react with bromine unless a Lewis acid is present in the mixture. When the Lewis acid (FeBr3) is present, however, benzene reacts readily with bromine, and the reactions give bromobenzene.

Nitration Benzene reacts slowly with hot concentrated nitric acid to yield nitrobenzene. The reaction is much faster if it carried out by heating benzene with a mixture of concentrated nitric acid and concentrated sulphuric acid.

Concentrated H2SO4 increases the rate of the reaction by increasing the concentration of the electrophile, the nitronium ion (NO2+)

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Reactions of Methylbenzene (Toluene)

When substituted benzenes undergo electrophilic attack, groups already on the ring affect both the rate of the reaction and the site of attack. We say, therefore, that substituent groups affect both reactivity and orientation in electrophilic aromatic substitutions. Toluene reacts about 25 times faster than benzene under the same conditions. We say that toluene is activated toward the electrophilic aromatic substitution and that the methyl group is an activating group. Activating groups are substituents that cause the ring to be more reactive than benzene. They are ortho-para directors because they tend to direct the incoming group into the ortho and para positions.

Note, students, activating groups e.g. CH3 are electron-donating hence they cause the ring to become more electron-rich i.e. have a higher electron cloud density.

Reactions of Methylbenzene (Toluene)

Bromination of Toluene A mixture of 1, 2 and 1, 4 substituted methylbenzenes is obtained i.e. ortho and para

Nitration of Toluene A mixture of 1, 2 and 1, 4 substituted methylbenzenes is obtained.

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Reaction of Nitrobenzene
Nitrobenzene reacts with tin and hydrochloric acid to produce phenylamine.

Sulphuric acid reacts with nitric acid to form the nitronium ion (NO2+), a powerful electrophile. The type of mechanism is electrophilic aromatic substitution. Step 1: Nitric acid accepts a proton from a stronger acid, H2SO4.

Mechanism of Selected Chemical Reactions; Obj. 2.16

Step 2: Now that it is protonated nitric acid can dissociate to form a nitronium ion.

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Mechanism of Selected Chemical Reactions

Step 3: The nitronium ion is the actual electrophile in nitration, it reacts with benzene to form a resonance-stabilized arenium ion.

Step 4: The arenium ion then loses a proton to a Lewis base and becomes nitrobenzene.

Selected Chemical Reactions of Phenols; Obj. 2.17

Bromination The hydroxyl group is a powerful activating group, and an ortho-para director in electrophilic substitution. Phenol itself reacts with bromine in aqueous solution to yield 2, 4, 6-tribromophenol. Note that a Lewis acid is not required for the bromination of this highly activated ring:

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Selected Chemical Reactions of Phenols

Esterification Phenols react with acyl chloride to form an ester:

Sodium Phenoxide formation

Phenol is converted to sodium phenoxide by dissolving it in sodium hydroxide solution.

Formation of an Azo Compound; Obj. 2.18

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Formation of an Azo Compound

Aniline yellow, is the first azo-dye to be made

State Uses of Azo Compound; Obj. 2.19

The main uses of azo compounds are as dyes, food colourings and chemical indicators e.g. methyl orange. Azo compounds are used in industry as dyes for many different textile types. These types include silk, leather, wool and cotton which are namely intended for clothing and decoration. Azo compounds are also used as intermediates in organic synthesis.