CAPE CHEMISTRY UNIT II MODULE I

Alcohols and phenol and Alkenes Worksheet and Revision guide

1. First part of homework - Due October 3, 2008

(a) Describe the reaction of butan-2-ol with iodine in sodium hydroxide.

(b) Describe the reaction between phenol and sodium hydroxide

2. Classwork (websites for additional notes included with each section)

(a) The structure of alcohols

 Alkyl group- + -OH
 Oxygen more electronegative than carbon and hydrogen
 C is +, H is + and O is -
 Note – bent structure around O which have 2 lone pairs

(b) Classes of alcohol

http://www.chemguide.co.uk/organicprops/alcohols/background.html#top
The carbon bearing the –OH group:
 Primary - has one R group and two hydrogens
 Secondary - has two R groups and one hydrogens
 Tertiary - has three R groups

(c) Two types reaction of alcohols

 Fission of the RO-H bond
 Fission of the R-OH bond
 Alcohols has tendency for H+ to dissociate in presence of a base
 Alcohols act like acids [weaker acid than water]

(d) Fission of RO-H bond

http://www.chemguide.co.uk/organicprops/alcohols/sodium.html#top
(i) reaction with sodium  H2(g) and Na alkoxide
ethanol + Na  H2(g) + Na ethoxide
propanol + Na  H2(g) + Na propoxide

(ii) reaction with carboxylic acid (esterifcation)

http://www.chemguide.co.uk/organicprops/alcohols/esterification.html#top
propanol and butanoic acid  propyl butanoate + water
butanol and propanoic acid  butyl propanoate + water

Catalyst – HCl or conc. H2SO4

(e) Fission of the R-OH bond

(i) Halogenation using: HCl, HBr, HI, PBr3, PCl5
[mention only]

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(ii) Dehydration – reaction with conc. H2SO4 (as catalyst)
http://www.chemguide.co.uk/organicprops/alcohols/dehydration.html#top

A primary alcohol reacts with cold concentrated sulphuric acid to form alkyl hydrogensulphate :

Ethanol + conc. sulphuric acid  Ethyl hydrogensulphate + Water

If the alcohol is in excess and the reaction mixture is warmed to 140oC, an ether is formed

Ethyl hydrogensulphate + ethanol (excess)  Diethyl ether (ethoxyethane) +sulphuric acid

If the concentrated sulphuric is in excess and the temperature is raised to 170oC, water is eliminated,
with the formation of an alkene:
ethyl hydrogensulphate + conc. sulphuric acid (excess)  ethene + sulphuric acid

Dehydration – mainly 3o alcohol – carbocation stabilized by alkyl groups

(iii) oxidation
 Combustion of 1o, 2o and 3o– degradation of C skeleton  CO2, H2O
 Reaction with oxidants - maintain C skeleton

Reactions with: KMnO4 / H+; K2Cr2O7 / H+ Or Na2Cr2O7/ H+

http://www.chemguide.co.uk/organicprops/alcohols/oxidation.html#top

 KMnO4/H+ is a stronger oxidizing agent than K2Cr2O7

 Oxidation product depends on the class of alcohol

 With K2Cr2O7 / H+ or Na2Cr2O7 / H+

o
1 – oxidized to aldehydes and further oxidation to carboxylic acid if temperature is raised or if aldehyde
is not distilled off
2o - oxidized to ketones
3o – resistant to oxidation

 With KMnO4/H+
o
1 – oxidized directly to carboxylic acid
2o - oxidized to ketones

Primary alcohol
Primary alcohol: -OH on C with 2 hydrogens attached [-OH on C attached to 1 other C]
During oxidation: [-2H] one from –OH and one other
Result – aldehyde

Aldehyde: 1 H attached to the carbonyl C

Further oxidation to the carboxylic acid

To obtain the aldehyde – distill off as it is formed

Aldehyde has lower b.p. than alcohol – no hydrogen bonds.
CAMPION J. MARSHALL CAPE CHEM U2 M1 ORGANIC – ALCOHOLS & PHENOL PAGE 2 OF 10
Primary alcohol  aldehyde  carboxylic acid
e.g. propan-1-ol, propanaldehyde, propanoic acid

Secondary alcohol
With KMnO4/H+, K2Cr2O7 / H+ or Na2Cr2O7 / H+

Secondary alcohol: -OH on C with 1 hydrogen attached

[-OH on C attached to 2 other C]

During oxidation: [-2H] one from –OH and one other

Result – ketone

The carbonyl carbon in a ketone does not have a hydrogen- no further oxidation (ketones resist oxidation)

Tertiary alcohol

Tertiary alcohol: -OH on C with 0 hydrogen attached

[-OH on C attached to 3 other C]

No oxidation except under extreme conditions

Iodoform reaction - (to be done again in aldehydes and ketones)

http://www.chemguide.co.uk/organicprops/alcohols/iodoform.html#top
Alcohols with the formula CH3CH(OH)R [ethanol if R = H] are oxidized by sodium iodate (I) to
CH3COR and therefore give a positive iodoform test.

In the formula CH3CH(OH)R: The alpha carbon is CH3. The alpha carbon is one carbon away from the
carbon with the functional group.

Iodoform is CHI3: Tri-iodomethane (fine yellow crystals with characteristic smell)

Stage 1: alcohol is oxidized to a carbonyl compound

Example: Ethanol in the presence of I2 / NaOH  Ethanal

Stage 2: The 3 hydrogens on the alpha carbon are replaced with iodine
Example: ethanal in the presence of I2 / NaOH  Tri-iodo-ethanal

Stage 3: The excess base hydrolyses the molecule and causes the C-C bond to break, releasing
triiodomethane [CHI3].
Example: Tri-iodo-ethanal in the presence of OH-  Tri-iodomethane + the methoxide anion

CAMPION J. MARSHALL CAPE CHEM U2 M1 ORGANIC – ALCOHOLS & PHENOL PAGE 3 OF 10

From Chemguide:
Summary of the reactions during the triiodomethane (iodoform) reaction

We will take the reagents as being iodine and sodium hydroxide solution.

(e)
(f) The structure of phenol
http://www.chemguide.co.uk/organicprops/phenol/background.html#top

Phenol will be look at again after the topic BENZENE

From Chemguide:

The structure of phenol

The simplest way to draw the structure of phenol is:

CAMPION J. MARSHALL CAPE CHEM U2 M1 ORGANIC – ALCOHOLS & PHENOL PAGE 4 OF 10

There is an interaction between the delocalised electrons in the benzene ring
and one of the lone pairs on the oxygen atom. This has an important effect on
both the properties of the ring and of the -OH group.

One of the lone pairs on the oxygen overlaps with the delocalised ring
electron system . . .

. . . giving a structure rather like this:

The donation of the oxygen's lone pair into the ring system increases the
electron density around the ring. That makes the ring much more reactive
than it is in benzene itself.

It also helps to make the -OH group's hydrogen a lot more acidic than it is in
alcohols.

The -OH group attached to the benzene ring in phenol has the effect of
making the ring much more reactive than it would otherwise be.

For example, as you will find below, phenol will react with a solution of
bromine in water (bromine water) in the cold and in the absence of any
catalyst. It also reacts with dilute nitric acid, whereas benzene itself needs a
nitrating mixture of concentrated nitric acid and concentrated sulphuric
acid.

CAMPION J. MARSHALL CAPE CHEM U2 M1 ORGANIC – ALCOHOLS & PHENOL PAGE 5 OF 10

Reaction with bromine water

http://www.chemguide.co.uk/organicprops/phenol/ring.html#top

If bromine water is added to a solution of phenol in water, the bromine water

is decolourised and a white precipitate is formed which smells of antiseptic.

The precipitate is 2,4,6-tribromophenol.

Notice the multiple substitution around the ring - into all the activated
positions. (The 6- position is, of course, just the same as the 2- position. Both
are next door to the -OH group.)

Note: Bromine water is normally used as a test for a C=C double bond. The important
difference with phenol is the formation of a white precipitate as well as the bromine water
being decolourised.

If you choose to follow this link, use the BACK button on your browser to return to this page.

Combustion of phenol

http://www.chemguide.co.uk/organicprops/phenol/other.html#top

Phenol burns in a plentiful supply of oxygen to give carbon dioxide and water.

However, for compounds containing benzene rings, combustion is hardly ever

complete, especially if they are burnt in air. The high proportion of carbon in
phenol means that you need a very high proportion of oxygen to phenol to get
complete combustion. Look at the equation.

As a general rule, the hydrogen in a molecule tends to get what oxygen is

available first, leaving the carbon to form carbon itself, or carbon monoxide, if
there isn't enough oxygen to go round.

Phenol tends to burn in air with an extremely smoky flame - full of carbon
particles.

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Esterification of phenol

http://www.chemguide.co.uk/organicprops/phenol/other.html#top

You will probably remember that you can make esters from alcohols by
reacting them with carboxylic acids. You might expect phenol to be similar.

However, unlike alcohols, phenol reacts so slowly with carboxylic acids that
you normally react it with acyl chlorides (acid chlorides) or acid anhydrides
instead.

Making esters from phenol using an acyl chloride

A typical acyl chloride is ethanoyl chloride, CH3COCl.

Phenol reacts with ethanoyl chloride at room temperature, although the

reaction isn't as fast as the one between ethanoyl chloride and an alcohol.
Phenyl ethanoate is formed together with hydrogen chloride gas.

Sometimes it is necessary to modify the phenol first to make the reaction

faster.

For example, benzoyl chloride has the formula C6H5COCl. The -COCl group is
attached directly to a benzene ring. It is much less reactive than simple acyl
chlorides like ethanoyl chloride.

In order to get a reasonably quick reaction with benzoyl chloride, the phenol
is first converted into sodium phenoxide by dissolving it in sodium hydroxide
solution.

CAMPION J. MARSHALL CAPE CHEM U2 M1 ORGANIC – ALCOHOLS & PHENOL PAGE 7 OF 10

The phenoxide ion reacts more rapidly with benzoyl chloride than the original
phenol does, but even so you have to shake it with benzoyl chloride for about
15 minutes. Solid phenyl benzoate is formed.

Making esters from phenol using an acid anhydride

A typical acid anhydride is ethanoic anhydride, (CH3CO)2O.

The reactions of acid anhydrides are slower than the corresponding reactions
with acyl chlorides, and you usually need to warm the mixture.

Again, you can react the phenol with sodium hydroxide solution first,
producing the more reactive phenoxide ion.

If you simply use phenol and ethanoic anhydride, phenyl ethanoate is formed
together with ethanoic acid.

This reaction isn't important itself, but a very similar reaction is involved in
the manufacture of aspirin (covered in detail on another page - link below).

If the phenol is first converted into sodium phenoxide by adding sodium

hydroxide solution, the reaction is faster. Phenyl ethanoate is again formed,
but this time the other product is sodium ethanoate rather than ethanoic
acid.

CAMPION J. MARSHALL CAPE CHEM U2 M1 ORGANIC – ALCOHOLS & PHENOL PAGE 8 OF 10

Properties of phenol as an acid

http://www.chemguide.co.uk/organicprops/phenol/acidity.html#top

With indicators

The pH of a typical dilute solution of phenol in water is likely to be around 5 -

6 (depending on its concentration). That means that a very dilute solution
isn't really acidic enough to turn litmus paper fully red. Litmus paper is blue
at pH 8 and red at pH 5. Anything in between is going to show as some shade
of "neutral".

With sodium hydroxide solution

Phenol reacts with sodium hydroxide solution to give a colourless solution

containing sodium phenoxide.

In this reaction, the hydrogen ion has been removed by the strongly basic
hydroxide ion in the sodium hydroxide solution.

With sodium carbonate or sodium hydrogencarbonate

Phenol isn't acidic enough to react with either of these. Or, looked at another
way, the carbonate and hydrogencarbonate ions aren't strong enough bases
to take a hydrogen ion from the phenol.

Unlike the majority of acids, phenol doesn't give carbon dioxide when you mix
it with one of these.

This lack of reaction is actually useful. You can recognise phenol because:

 It is fairly insoluble in water.

 It reacts with sodium hydroxide solution to give a colourless solution
(and therefore must be acidic).

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  It doesn't react with sodium carbonate or hydrogencarbonate solutions
(and so must be only very weakly acidic).

With metallic sodium

Acids react with the more reactive metals to give hydrogen gas. Phenol is no
exception - the only difference is the slow reaction because phenol is such a
weak acid.

Phenol is warmed in a dry tube until it is molten, and a small piece of sodium
added. There is some fizzing as hydrogen gas is given off. The mixture left in
the tube will contain sodium phenoxide.

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