Raffles Institution (Junior College)

H2 Chemistry 2010/11
Tutorial 15 Hydroxy and Phenol
Compounds
Prepared by: Mr Chen Yongchang, Joseph

Question 1
(a)
Draw the full structural formulae for all the alcohols with the molecular formula
C4H10O and classify each as a primary, secondary or tertiary.
(b)

Compare and contrast the behaviour of these alcohols with oxidising agents such as
acidified, aqueous potassium manganate(VII).

(c)

One of these alcohols is found to have the following properties.

It exists as a pair of optical isomers.

On warming with iodine and aq NaOH a pale yellow precipitate is obtained.

On heating with an excess of concentrated sulphuric acid at 180oC a mixture

of three alkenes is obtained.
Identify the alcohol, explaining your reasoning. Also, give the full structural formulae
of the three alkenes.

Answer:
(a)

(b)

All primary and secondary alcohols are oxidised by acidified, aqueous potassium
manganate(VII). Tertiary alcohols are not oxidised.
Observation: Purple KMnO4 turns colourless.
Products: Primary alcohols to give carboxylic acids. Secondary alcohols to give
ketones.

(c)

Butan-2-ol

It possesses a chiral carbon. And it does not have a plane of symmetry. Thus,
it exists as a pair of optical isomers.
It possess a CH3CH(OH)- group. Hence the alcohol gives a positive iodoform
test (yellow CHI3 ppt).
CH3CH2CH(OH)CH3 + 4I2 + 6NaOH CHI3 + CH3CH2COO- + 5NaI + 5H2O

Butan-2-ol undergoes dehydration to give three alkenes.

Question 2
How, and under what conditions would you expect a compound with the formula given below
to react, if at all, with the following reagents? Draw the structural formula of the organic
product(s) formed (if any) for reagents from (a) to (j).
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(j)

sodium
sodium hydroxide
sodium carbonate
phosphorus(V) chloride
hydrogen bromide
ethanoic acid
ethanoyl chloride
aqueous bromine
bromine in CCl4
potassium manganate(VII)

OH

CH CHCH2OH

Answer:
(a)

Phenolic and alcoholic OH react with sodium to form the respective phenoxide and
alkoxide ion.
Condition: Room temperature

(b)

Phenolic but not alcoholic OH reacts with sodium hydroxide.

Condition: Room temperature

(c)

Both phenolic and alcoholic OH do not react with sodium carbonate which is a weak
base.

(d)

Only the alcoholic OH gets substituted with Cl.

Condition: Room temperature

(e)

Alcoholic OH gets substituted with Br and the electrophilic addition of HBr across
the C=C bond.
Condition: Room temperature

(f)

Alcoholic OH (but not phenolic OH) reacts with ethanoic acid to give an ester.
Condition: Reflux, conc H2SO4 catalyst

(g)

Both Alcoholic and phenolic OH react with ethanoyl chloride to form esters.
Condition: Room temperature

(h)

Both ring substitution (at 2-, 4- and 6-) and addition across the C=C bond occur.
Condition: Room temperature

(i)

Both ring substitution and addition across the double bond occurs.
Condition: Room temperature

(j)

Diol formation.
Condition: Cold, dilute, alkaline KMnO4
Oxidative cleavage of the double bond.
Condition: Concentrated, acidified KMnO4, reflux

Question 3
Alcohol B, with the molecular formula of C5H12O, forms esters which are responsible for the
flavours of various fruits. Reaction of B with acidified potassium dichromate(VI) produces a
compound C, C5H10O2. Heating B over Al2O3 produces D, C5H10. Vigorous oxidation of D
forms 2-methylpropanoic acid as one of the products.
Suggest structures for B, C and D and explain the reactions involved.
Answer:

Compound

Structural Formula

H3C CH

CH2

CH2OH

CH2

COOH

CH

CH2

CH3

H3C CH
CH3

H3C CH
CH3

B being an alcohol undergoes dehydration when heated with Al2O3 to give an alkene D.
Oxidation of D forms 2-methlypropanoic acid, which suggest that D is a terminal alkene.
Therefore, the suggestion for D is a 3-methylbut-1-ene.

Product D
H3C CH CH

[O]

CH2

2-methlypropanoic acid
H3C CH

CH3

CH2

COOH

CO2

H2O

CH3

Oxidation of B to C gives an additional oxygen in product C, which suggests C is a

carboxylic acid. Therefore, B must be a primary alcohol in order to oxidize into a carboxylic
acid.

Product B
H3C CH
CH3

CH2

[O]

CH2OH

Product C
H3C CH CH2

COOH

CH3

Question 4
Arrange the following in order of increasing acidity:
phenol, 2-nitrophenol, ethanol, methylpropan-2-ol, water, methanol, 2-methylphenol.
Explain your answer.
Answer:
methylpropan-2-ol < ethanol < methanol < water < 2-methylphenol < phenol < 2-nitrophenol

In general, acidity: alcohol < water < phenol.

The relative acid strength depends on the relative stability of the respective conjugate bases,
namely the phenoxide, the hydroxide and the ethoxide ions. The more stable the conjugate
base, the more acidic the compound.
Alcohols

contain alkyl groups which are electron donating, intensify electron density on O
atom

destabilise the alkoxide ions (compared to hydroxide ions)

acidity decreases as number of alkyl group increases.

Phenols

phenoxide ions are stabilised by delocalisation of the negative charge on the oxygen
into the ring.
Phenol containing an electron-releasing substituent (e.g. methyl group)

less acidic than an unsubstituted phenol

delocalisation of negative charge into the ring is hindered

Phenol containing an electron-withdrawing substituent (e.g. nitro group)

more acidic than an unsubstituted phenol

delocalisation of negative charge into the ring is enhanced.

Question 5
CH3CH(OH)CH2CH3
A

(CH3)3COH
B

Alcohols A and B are isomers.

(a) Draw the structural formula of one other alcohol isomeric with A and
B.
(b) What reagent would you use to dehydrate A and B to alkenes? Draw
the structural formulae of the three alkenes that are obtained by
dehydrating A.
(c) Describe a reaction (reagent and observation) by which A could be
distinguished from B.
(d) Name the class of compound formed when A reacts with ethanoyl
chloride, and draw its structural formula.
(e) Draw diagrams to illustrate how A gives rise to optical isomerism.

[1]

[3]

[2]
[2]
[2]

N92/I/9
(a)

CH3(CH2)3OH

(b)

Conc. H2SO4 and 170oC

(c)

Tri-iodomethane test. When iodine and sodium hydroxide is warmed with A,

yellow crystals of tri-iodomethane are formed. There is no precipitate
observed with B.

(d)

Ester Group
(e)