UNIT V

Important Reagents
Aluminium chloride (AlCl3) Preparation 1. Aluminium dissolves rapidly in HCl. The reaction leads to the formation of aluminium chloride with the liberation of hydrogen.

2. By passing dry chlorine gas over heated aluminium powder.

Applications 1. Aluminium chloride is used a catalyst in Friedel Crafts alkylation and acylation.

2. In Gatterman Koch synthesis of benzaldehyde, AlCl3 is used with a small amount of cuprous chloride.

3. Isomerisation:- When n-butane is heated in the presence of aluminium chloride, isobutene is formed on isomerization.

4. Phthalic anhydride reacts with benzene in the presence of AlCl3 to form o-benzylbenzoic acid.

5. It is also used as a catalyst in the preparation of malachite green and crystal violet dyes.

Boron trifluoride (BF3) Preparation 1. It is prepared by heating together a mixture of boron trioxide, sodium fluoride and concentrated sulphuric acid.

2. By passing fluorine gas over hot boron.

Applications 1. Furan reacts with acetic anhydride in the presence of BF3 to form acetylfuran.

2. BF3 acts as a catalyst in Friedel-Crafts reactions

3. BF3 acts as a catalyst in the preparation of carboxylic acids from alcohols.

4. Esters can be prepared from various compounds using BF3 as catalyst.

5. BF3 acts as a catalyst in nitration reaction.

6. BF3 acts as a catalyst in Beckmann rearrangement reactions.

Lithium aluminium hydride (LiAlH4) Preparation 1. By the direct synthesis from elements.

2. By the direct combination of lithium hydride and aluminium chloride in ether solution.

Applications 1. It is a strong reducing agent and reduces certain halides of group III, IV and V.

2. It reduces aldehydes, ketones and carboxylic acids.

3. Hydrolysis:- It is hydrolysed by water evolving hydrogen.

Some other Reactions

Sodium borohydride (NaBH4) Preparation 1. Methyl borate dissolved in tetrahydrofuran reacts with sodium hydroxide to form sodium borohydride.

2. Sodium hydride reacts with diborane to form sodium borohydride.

Applications 1. It is used to prepare diborane.

2. It is used to prepare lithium borohydride.

3. It is used as a reducing agent in organic chemistry.

Phosphorous pentachloride (PCl5) Preparation 1. Phosphorous trichloride reacts with sulphuryl chloride and forms PCl 5.

2. By passing chlorine gas over PCl3 gives PCl5.

Applications 1. It is used in organic reactions for the replacement of hydroxyl group by chlorine atom.

2. It converts alcohols into alkyl chlorides.

3. It converts amides into nitriles.

4. It converts esters into acid chlorides.

5. It converts carbonyl group (CO) into CCl2.

Phosphorous pentaoxide (P2O5) Preparation When phosphorous is burnt with oxygen, P2O5 is formed.

Applications 1. On heating with P2O5 malonic acid gives carbon suboxide.

2. Acetamide when heated with P2O5 gives acetonitrile.

3. It dehydrates carboxylic acids into anhydrides.

4. It dehydrates alcohols into alkenes.

5. Reacting with ethers it forms alkenes and alcohols.

Sodium / Ethanol (Na / C2H5OH) Applications 1. On reduction with sodium amalgam and ethanol, thiophene is converted into tetrahydro thiophene.

2. Pyridine undergoes reduction with Na/C2H5OH to form piperidine.

3. Sodium reacts with alcohol to produce sodium ethoxide and hydrogen. Hence, it acts as a reducing agent.

4. It reduces alkyl cyanide to primary amines.

5. It reduces aldehydes and ketones to primary alcohols and secondary alcohols.

Alcoholic KOH Applications 1. With alcoholic KOH, 1-chloro-1-phenylethane undergoes dehydrohalogenation forms styrene.

2. Ethyl iodide is heated with alcoholic KOH to form ethylene.

H2 / Ni Applications 1. Ethylene adds hydrogen under pressure and in the presence of Ni catalyst to produce ethane.

2. Benzene reacts with hydrogen in the presence of nickel catalyst at 150 0C under pressure to form cyclohexane.

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3. By passing hydrogen gas over nickel at very high temperature, it reduces C=C and CC bonds. Hence, unsaturated hydrocarbons, aldehydes, ketones, nitriles, nitro compounds can be reduced using this reagent. This reaction is called hydrogenation.

H2/Pd BaSO4 Applications 1. Benzoyl chloride reacts with hydrogen in the presence of palladium catalyst with barium sulphate to form benzaldehyde.

2. When reduced with hydrogen in the presence of palladium catalyst with barium sulphate, acetyl chloride forms acetaldehyde.

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Zn/Hg HCl Applications 1. Cyclopentanone on reduction with Zn/Hg HCl forms cyclopentane. (Clemmensen reduction)

2. Acetophenone reacts with Zn/Hg HCl to form ethylbenzene. (Clemmensen reduction)

NH2-NH2 / C2H5ONa Applications 1. Wolff-Kishner Reduction:- Both aldehydes and ketones are reduced to parent alkanes by treatment with NH2-NH2 / C2H5ONa.

Silver oxide (Ag2O) Preparation It is prepared by combining aqueous solutions of silver nitrate and an alkali hydroxide.

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Applications 1. Diazoketone is decomposed by water in the presence of silver oxide to yield a carboxylic acid with one more carbon atom.

2. It is used in Arndt-Einstein reaction to ascend the acid series.

3. (+)-Chlorosuccinic acid is hydrolysed to (+)-malic acid by Ag2O.

Periodic acid (HIO4) Applications

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Lead tetraacetate (Pb(OAc)4 Preparation It is prepared by the gradual addition of red lead to a mixture of acetic acid and acetic anhydride at 55 80 0C. On cooling the reaction products, lead tetraacetate separates out.

Applications 1. Oxidation of hydroquinones:- Lead tetraacetate oxidises hydroquinones to quinones.

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2. Oxidation of vicinal alcohols:- 1,2-Glycols are oxidized at room temperature by lead tetraacetate to aldehydes, ketones or both according to the structure of the glycol.

3. Oxidation of alcohols:- Lead tetraacetate in refluxing benzene, hexane or chloroform is a good reagent for the oxidation of primary and secondary alcohols to the corresponding aldehyde or ketone.

4. Acetoxylation of active methylene group:-

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5. Acetoxylation of aromatic hydrocarbons:-

6. As methylating agent:-

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Osmium tetroxide (OsO4) Preparation Osmium tetroxide is formed slowly when osmium powder reacts with oxygen.

Applications 1. Formation of oxofluorides:-

2. Oxidation of alkenes:-

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