PHENOL CONTENTS Prior knowledge Synthesis from benzene Reactions of the OH group Reactions of the ring Benzene diazonium chloride - preparation Benzene diazonium chloride - reactions

Before you start it would be helpful to… PHENOL Before you start it would be helpful to… know the functional groups found in organic chemistry know the arrangement of bonds around atoms recall and explain electrophilic substitution of aromatic rings

PHENOL Structure phenol is an aromatic alcohol with formula C6H5OH the OH group is attached directly to the benzene ring it is an almost colourless crystalline solid

PHENOL Structure phenol is an aromatic alcohol with formula C6H5OH the OH group is attached directly to the benzene ring it is an almost colourless crystalline solid Preparation You cannot put an OH group directly onto a benzene ring by electrophilic substitution, so phenol has to be synthesised in a multi-stage process

PHENOL 1 Structure phenol is an aromatic alcohol with formula C6H5OH the OH group is attached directly to the benzene ring it is an almost colourless crystalline solid Preparation You cannot put an OH group directly onto a benzene ring by electrophilic substitution, so phenol has to be synthesised in a multi-stage process 1 Step 1 - Nitration of benzene reagents conc. nitric acid and conc. sulphuric acid (catalyst) conditions reflux at 55°C equation C6H6 + HNO3 ——> C6H5NO2 + H2O mechanism electrophilic substitution

PHENOL 2 Structure phenol is an aromatic alcohol with formula C6H5OH the OH group is attached directly to the benzene ring it is an almost colourless crystalline solid Preparation You cannot put an OH group directly onto a benzene ring by electrophilic substitution, so phenol has to be synthesised in a multi-stage process 2 Step 2 - Reduction of nitrobenzene reagents tin and conc. hydrochloric acid conditions reflux equation C6H5NO2 + 6 [H] ——> C6H5NH2 + 2H2O mechanism reduction

PHENOL 3 Structure phenol is an aromatic alcohol with formula C6H5OH the OH group is attached directly to the benzene ring it is an almost colourless crystalline solid Preparation You cannot put an OH group directly onto a benzene ring by electrophilic substitution, so phenol has to be synthesised in a multi-stage process 3 Step 3 - Diazotisation of phenylamine reagents nitrous acid and hydrochloric acid (use sodium nitrite) conditions keep below 10°C equation C6H5NH2 + HNO2 + HCl ——> C6H5N2+ Cl¯ + 2H2O reaction type diazotisation

PHENOL 4 Structure phenol is an aromatic alcohol with formula C6H5OH the OH group is attached directly to the benzene ring it is an almost colourless crystalline solid Preparation You cannot put an OH group directly onto a benzene ring by electrophilic substitution, so phenol has to be synthesised in a multi-stage process 4 Step 4 - Substitution of diazo group by OH reagents water conditions warm above 10°C equation C6H5N2+ Cl¯ + H2O ——> C6H5OH + N2 + HCl reaction type hydrolysis / substitution

PHENOL - REACTIONS OF THE OH GROUP Water phenol is a weak acid it dissolves very slightly in water to form a weak acidic solution it is a stronger acid than aliphatic alcohols the ring helps weaken the O-H bond and stabilises the resulting anion C6H5OH(aq) C6H5O¯(aq) + H+(aq)

PHENOL - REACTIONS OF THE OH GROUP Water phenol is a weak acid it dissolves very slightly in water to form a weak acidic solution it is a stronger acid than aliphatic alcohols the ring helps weaken the O-H bond and stabilises the resulting anion C6H5OH(aq) C6H5O¯(aq) + H+(aq) NaOH phenol reacts with sodium hydroxide to form a salt - sodium phenoxide it is ionic and water soluble C6H5OH(aq) + NaOH(aq) ——> C6H5O¯ Na+(aq) + H2O(l)

PHENOL - REACTIONS OF THE OH GROUP Water phenol is a weak acid it dissolves very slightly in water to form a weak acidic solution it is a stronger acid than aliphatic alcohols the ring helps weaken the O-H bond and stabilises the resulting anion C6H5OH(aq) C6H5O¯(aq) + H+(aq) NaOH phenol reacts with sodium hydroxide to form a salt - sodium phenoxide it is ionic and water soluble C6H5OH(aq) + NaOH(aq) ——> C6H5O¯ Na+(aq) + H2O(l) Sodium phenol reacts with sodium to form an ionic salt - sodium phenoxide hydrogen is also produced this reaction is similar to that with aliphatic alcohols such as ethanol 2C6H5OH(s) + 2Na(s) ——> 2C6H5O¯ Na+(s) + H2(g)

PHENOL - REACTIONS OF THE AROMATIC RING ELECTROPHILIC SUBSTITUTION Ease the OH group is electron releasing it increases the electron density of the delocalised system it makes substitution much easier compared to benzene a p orbital on the oxygen overlaps with the p orbitals in benzene the p orbital on the O overlaps with the p orbitals in the ring p orbitals in the system

PHENOL - REACTIONS OF THE AROMATIC RING ELECTROPHILIC SUBSTITUTION Bromine the OH group is electron releasing it increases the electron density of the delocalised system it makes substitution much easier compared to benzene the electron density is greatest at the 2,4 and 6 positions substitution takes place at the 2,4 and 6 positions phenol reacts readily with bromine water WITHOUT A CATALYST it is so easy that multiple substitution takes place other electrophiles such as NO2+ react in a similar way

BENZENE DIAZONIUM CHLORIDE Structure has the formula C6H5N2+ Cl¯ a diazonium group is attached to the ring the aromatic ring helps stabilise the ion

BENZENE DIAZONIUM CHLORIDE Structure has the formula C6H5N2+ Cl¯ a diazonium group is attached to the ring the aromatic ring helps stabilise the ion PREPARATION reagents phenylamine, nitrous acid and hydrochloric acid conditions keep BELOW 10°C equation C6H5NH2 + HNO2 + HCl ——> C6H5N2+ Cl¯ + 2H2O notes nitrous acid is unstable and is made in situ from sodium nitrite C6H5NH2 + NaNO2 + 2HCl ——> C6H5N2+ Cl¯ + NaCl + 2H2O the solution is kept cold to slow down decomposition of the diazonium salt C6H5N2+ Cl¯ + H2O ——> C6H5OH + HCl + N2

DIAZONIUM SALTS - REACTIONS Benzene diazonium chloride undergoes two main types of reaction SUBSTITUTION OF THE DIAZONIUM GROUP nitrogen (N2) expelled COUPLING REACTIONS nitrogen atoms are retained

DIAZONIUM SALTS - SUBSTITUTION OH reagents water (HYDROLYSIS) conditions warm above 10°C equation C6H5N2+ Cl¯ + H2O ——> C6H5OH + HCl + N2 use the only reasonably simple way to substitute OH phenol is an antiseptic and is used to make polymers

DIAZONIUM SALTS - SUBSTITUTION OH reagents water (HYDROLYSIS) conditions warm above 10°C equation C6H5N2+ Cl¯ + H2O ——> C6H5OH + HCl + N2 use the only reasonably simple way to substitute OH phenol is an antiseptic and is used to make polymers I reagents potassium iodide solution conditions warm equation C6H5N2+ Cl¯ + KI ——> C6H5I + KCl + N2

DIAZONIUM SALTS - COUPLING reagents phenol and sodium hydroxide conditions alkaline solution below 10°C equation C6H5N2+Cl¯ + C6H5OH + NaOH ——> C6H5-N=N-C6H4OH + NaCl + H2O (4-hydroxyphenol)azobenzene YELLOW use making azo dyes THE AZO GROUP

SOME AZO DYES (4-hydroxyphenol)azobenzene YELLOW 4-phenylazophenylamine YELLOW The first azo dye to be made methyl orange YELLOW IN ALKALI RED IN ACID