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CAPE CHEMISTRY UNIT II MODULE I

Alcohols and phenol and Alkenes Worksheet and Re!s!on "#!de


1. First part of homework - Due October 3, 2008
(a) Describe the reaction of butan-2-o with io!ine in so!ium h"!ro#i!e.
(b) Describe the reaction between pheno an! so!ium h"!ro#i!e
2. $asswork (websites for a!!itiona notes incu!e! with each section)
(a) The structure of alcohols
%k" &roup- ' -O(
O#"&en more eectrone&ati)e than carbon an! h"!ro&en
$ is ', ( is ' an! O is -
*ote + bent structure aroun! O which ha)e 2 one pairs
(b) Classes of alcohol
http,--www.chem&ui!e.co.uk-or&anicprops-acohos-back&roun!.htm.top
/he carbon bearin& the +O( &roup,
0rimar" - has one 1 &roup an! two h"!ro&ens
2econ!ar" - has two 1 &roups an! one h"!ro&ens
/ertiar" - has three 1 &roups
(c) Two types reaction of alcohols
Fission of the 1O-( bon!
Fission of the 1-O( bon!
%cohos has ten!enc" for (
'
to !issociate in presence of a base
%cohos act ike aci!s 3weaker aci! than water4
(d) Fission of RO-H bond
http,--www.chem&ui!e.co.uk-or&anicprops-acohos-so!ium.htm.top
(i) reaction with so!ium (
2
(&) an! *a ako#i!e
ethano ' *a (
2
(&) ' *a etho#i!e
propano ' *a (
2
(&) ' *a propo#i!e
(ii) reaction with carbo#"ic aci! (esterifcation)
http,--www.chem&ui!e.co.uk-or&anicprops-acohos-esterification.htm.top
propano an! butanoic aci! prop" butanoate ' water
butano an! propanoic aci! but" propanoate ' water
$ata"st + ($ or conc. (
2
2O
5
(e) Fission of the R-OH bond
(i) (ao&enation usin&, ($, (6r, (7, 06r
3
, 0$
8
$%907O* :. 9%12(%;; $%0< $(<9 =2 91 O1>%*7$ + %;$O(O;2 ? 0(<*O; 0%>< 1 OF @
3mention on"4
(ii) Deh"!ration + reaction with conc. (
2
2O
5
(as cata"st)
http,--www.chem&ui!e.co.uk-or&anicprops-acohos-!eh"!ration.htm.top
% primar" acoho reacts with co! concentrate! suphuric aci! to form ak" h"!ro&ensuphate ,
<thano ' conc. suphuric aci! <th" h"!ro&ensuphate ' Aater
If the alcohol is in excess an! the reaction mi#ture is warme! to 150
o
$, an ether is forme!
<th" h"!ro&ensuphate ' ethano (e#cess) Dieth" ether (etho#"ethane) 'suphuric aci!
If the concentrated sulphuric is in excess an! the temperature is raise! to 1B0
o
$, water is eiminate!,
with the formation of an akene,
eth" h"!ro&ensuphate ' conc. suphuric aci! (e#cess) ethene ' suphuric aci!
Deh"!ration + main" 3
o
acoho + carbocation stabiiCe! b" ak" &roups
(iii) o#i!ation
$ombustion of 1
o
, 2
o
an! 3
o
+ !e&ra!ation of $ skeeton $O
2
, (
2
O
1eaction with o#i!ants - maintain $ skeeton
1eactions with, D9nO5 - ('E D2$r2OB - (' Or *a2$r2OB- ('
http,--www.chem&ui!e.co.uk-or&anicprops-acohos-o#i!ation.htm.top
D9nO5-(' is a stron&er o#i!iCin& a&ent than D2$r2OB
O#i!ation pro!uct !epen!s on the cass of acoho
Aith D2$r2OB - (' or *a2$r2OB - ('
1
o
+ o#i!iCe! to a!eh"!es an! further o#i!ation to carbo#"ic aci! if temperature is raise! or if a!eh"!e
is not !istie! off
2
o
- o#i!iCe! to ketones
3
o
+ resistant to o#i!ation
Aith D9nO5-('
1
o
+ o#i!iCe! !irect" to carbo#"ic aci!
2
o
- o#i!iCe! to ketones
0rimar" acoho
0rimar" acoho, -O( on $ with 2 h"!ro&ens attache! 3-O( on $ attache! to 1 other $4
Durin& o#i!ation, 3-2(4 one from +O( an! one other
1esut + a!eh"!e
%!eh"!e, 1 ( attache! to the carbon" $
$%907O* :. 9%12(%;; $%0< $(<9 =2 91 O1>%*7$ + %;$O(O;2 ? 0(<*O; 0%>< 2 OF @
Further o#i!ation to the carbo#"ic aci!
/o obtain the a!eh"!e + !isti off as it is forme!
%!eh"!e has ower b.p. than acoho + no h"!ro&en bon!s.
0rimar" acoho a!eh"!e carbo#"ic aci!
e.&. propan-1-o, propana!eh"!e, propanoic aci!
2econ!ar" acoho
Aith D9nO5-(', D2$r2OB - (' or *a2$r2OB - ('
2econ!ar" acoho, -O( on $ with 1 h"!ro&en attache!
3-O( on $ attache! to 2 other $4
Durin& o#i!ation, 3-2(4 one from +O( an! one other
1esut + ketone
/he carbon" carbon in a ketone !oes not ha)e a h"!ro&en- no further o#i!ation (ketones resist o#i!ation)
/ertiar" acoho
/ertiar" acoho, -O( on $ with 0 h"!ro&en attache!
3-O( on $ attache! to 3 other $4
*o o#i!ation e#cept un!er e#treme con!itions
7o!oform reaction - (to be !one a&ain in a!eh"!es an! ketones)
http,--www.chem&ui!e.co.uk-or&anicprops-acohos-io!oform.htm.top
%cohos with the formua $(
3
$((O()1 3ethano if 1 F (4 are o#i!iCe! b" so!ium io!ate (7) to
$(3$O1 an! therefore &i)e a positi)e io!oform test.
7n the formua $(
3
$((O()1, /he apha carbon is $(
3.
/he apha carbon is one carbon awa" from the
carbon with the functiona &roup.
7o!oform is $(7
3
,

/ri-io!omethane (fine "eow cr"stas with characteristic sme)
2ta&e 1, acoho is o#i!iCe! to a carbon" compoun!
<#ampe, <thano in the presence of 7
2
- *aO( <thana
2ta&e 2, /he 3 h"!ro&ens on the apha carbon are repace! with io!ine
<#ampe, ethana in the presence of 7
2
- *aO( /ri-io!o-ethana
2ta&e 3, /he e#cess base h"!ro"ses the moecue an! causes the $-$ bon! to break, reeasin&
triio!omethane 3$(7
3
4.
<#ampe, /ri-io!o-ethana in the presence of O(
-
/ri-io!omethane ' the metho#i!e anion
$%907O* :. 9%12(%;; $%0< $(<9 =2 91 O1>%*7$ + %;$O(O;2 ? 0(<*O; 0%>< 3 OF @
From $hem&ui!e,
2ummar" of the reactions !urin& the triio!omethane (io!oform) reaction
We will take the reagents as being iodine and sodium hydroxide solution.
(e)
(f) The structure of phenol
http,--www.chem&ui!e.co.uk-or&anicprops-pheno-back&roun!.htm.top
0heno wi be ook at a&ain after the topic 6<*G<*<
From $hem&ui!e,
The structure of phenol
The simplest way to draw the structure of phenol is:
$%907O* :. 9%12(%;; $%0< $(<9 =2 91 O1>%*7$ + %;$O(O;2 ? 0(<*O; 0%>< 5 OF @
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.
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.
$%907O* :. 9%12(%;; $%0< $(<9 =2 91 O1>%*7$ + %;$O(O;2 ? 0(<*O; 0%>< 8 OF @
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.
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.
$%907O* :. 9%12(%;; $%0< $(<9 =2 91 O1>%*7$ + %;$O(O;2 ? 0(<*O; 0%>< H OF @
Making esters from phenol using an acyl chloride
A typical acyl chloride is ethanoyl chloride, CH
3
COCl.
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 C
6
H
5
COCl. 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.
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, (CH
3
CO)
2
O.
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.
$%907O* :. 9%12(%;; $%0< $(<9 =2 91 O1>%*7$ + %;$O(O;2 ? 0(<*O; 0%>< B OF @
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.
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.
$%907O* :. 9%12(%;; $%0< $(<9 =2 91 O1>%*7$ + %;$O(O;2 ? 0(<*O; 0%>< 8 OF @
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).
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.
$%907O* :. 9%12(%;; $%0< $(<9 =2 91 O1>%*7$ + %;$O(O;2 ? 0(<*O; 0%>< @ OF @