Hydroxy compounds

Introduction Alcohols are compounds whose molecules have a hydroxyl group (-OH) bonded to a carbon atom. When the hydroxyl group is attached directly to an aromatic ring, it is called a phenol. There are primary, secondary and tertiary alcohols. Saturated aliphatic alcohols have the general formula CnH2n+1OH, where n equals the number of carbon atoms. Naming the alcohol: Isomerism: Alcohols exhibit both structural and optical isomerisms. Physical properties of alcohols: Boiling point of alcohol is much higher than that of similar alkane, due to intermolecular hydrogen bonding. (Branching, no. Of carbon atoms, isomeric alcohols affect boiling point) Alcohols are more soluble in water compared to their corresponding alkanes due to their ability to form hydrogen bonds with water molecules. Alcohols are good polar solvents. Preparation of alcohols: From alkenes: Reagent: steam Condition : phosphoric acid catalyst , 65 atm, 300oC Equation : C2H4 + H2O C2H5OH From alkyl halides: Alkyl halides undergo alkaline hydrolysis (mechanism : __________________) to yield the alcohols. Reagent : aq. NaOH
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Condition : Reflux Equation : R X + OH- R-OH + X-

From carboxylic acids, aldehydes and ketones (Reduction) Carboxylic acids and aldehydes are reduced to their primary alcohols. Ketones are reduced to their secondary alcohols. Equations :

Reagent : LiAlH4 in dry ether, water Tertiary alcohols cannot be formed in this method.

Reactions of alcohols:
Combustion: C2H5OH + 3O2 2CO2 + 3H2O Oxidation to aldehydes, ketones and carboxylic acids:

Equation :

Oxidising agents : acidified potassium dichromate (VI) or potassium manganate(VII). Primary alcohols are oxidised to aldehydes under distillation. Further oxidation yields carboxylic acids. Secondary alcohols are oxidised to ketones.

Tertiary alcohols are not oxidised.

Distinguishing test for different types of alcohol Reagent : potassium dichromate Heat Colour of dichromate changes from orange to green if alcohol is primary or secondary. If no colour change, it is tertiary. Use 2,4-DNPH, we are able to differentiate between the carboxylic acid from the ketones. If orange ppt with DNPH, it is a secondary alcohol.

Reaction with sodium: Alcohols react with reactive metals such as sodium to form alkoxides and hydrogen gas. Alcohols are close to neutral. They are very slightly acidic.

Williamson synthesis (in the chapter of halogenoalkanes):

What is the name of mechanism? Halogenation: Use HCl/ZnCl2, reflux , HBr (from NaBr, conc sulfuric acid). Alcohol and water are formed. Equation :

PCl5 reacts vigorously with ethanol at r.t. to form chloroethane, POCl3 and HCl. PCl3 reacts similarly. H3PO3 and the chloroalkane are formed.
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Alcohol is refluxed with thionyl chloride (sulfur oxide dichloride) SOCl2 to form SO2, HCl and the halogenoalkane.

Dehydration of alcohol to alkene: Reagent : excess conc. H2SO4 Condition : 170oC.

Esterification :
Important : ****** Alcohols react with carboxylic acids to form esters, condition: 60oC with reflux. Catalyst : concentrated sulfuric acid

Esterification also takes place when alcohols react with acid chlorides:

Iodoform formation:
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Quite important too! Reagent : aqueous iodine in NaOH (aq) Condition : warm Observation : yellow crystals of tri-iodomethane (iodoform) formed.

Overall equation : CH3CH2OH + 4I2 + 6OH- HCOO- + CHI3 + 5I- + 5H2O

This reaction can only take place for an alcohol containing this group:

Phenols:
The presence of hydrogen bonds makes the melting point of phenols higher than those of comparable hydrocarbons. All reactions involve breaking of the O-H bond in phenol. However, it is difficult to break the C-O bond of a phenol. Reaction with sodium :

Reaction with bases . Phenol is acidic and can react with bases to give salt and water.

Phenol + NaOH sodium phenoxide + H2O

Phenol is not acidic enough to liberate carbon dioxide from carbonates. There is no reaction between phenol and sodium carbonate. This can be a distinguishing test between phenol and carboxylic acids. Oxidation : Phenol is not oxidised. Halogenation of benzene ring: Important * : Phenol reacts with aq. Bromine to produce tri-substd product.

Observations : white ppt forms, reddish brown solution decolourises. Important. The hydroxyl group is strongly activating. Reactions occur at room temperature. Why? Under reaction with liquid bromine, 2-bromophenol and 4 bromophenol are formed. Nitration of benzene ring: Phenol reacts with conc HNO3 at r.t. without H2SO4 to form a tri-substd product.

When dil. HNO3 is used, only mono-substd nitro compound is formed.

Reaction with neutral FeCl3(aq) Phenol reacts with aq. Neutral iron(III) chloride to form a violet complex. Used as a test for the presence of phenol.

Acidity of ethanol and phenol: The ethoxide ion is not stabilised wrt. Ethanol due to ___________. In the phenoxide ion, a p-orbital of the oxygen overlaps with the pi-electron cloud of the benzene ring. The negative charge of the phenoxide ion can be spread around the ring, thus the anion is resonance stabilised.
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Phenol is more acidic than water. Alcohol is a weaker acid than water. It does not react with alkalis. Presence of electron-withdrawing groups in the ring: 2,4,6-trichlorophenol is a stronger acid than phenol. Which of these, trichlorophenol or phenol has a lower pKa value? Presence of electron-releasing groups: On acidity of aliphatic alcohols: Electron-withdrawing groups attached to the carbon containing hydroxyl group stabilises the alkoxide ions when formed. This makes the alcohol more acidic. How about electron-donating groups are attached?
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Some notes were adapted from www.chemguide.co.uk