Alcohol, Phenols, Thiol & Ether Res 2

Alcohols, Thiols, Ethers,
Aldehydes and Ketones
In this unit we continue surveying some of the families of

organic molecules that play important roles in biochemistry;
looking both at their physical and chemical properties. The
Group VIA elements, oxygen and sulfur, typically form two
covalent bonds to attain a filled valence shell. The families that
include oxygen and sulfur with two single bonds include
alcohols C-O-H, ethers C-O-C, thiols C-S-H, sulfides C-S-C
and disulfides C-S-S-C. We will also look at two more
important carbonyl containing functional groups, aldehydes
and ketones.
Introduction
The organic groups covered in this Unit all have important biological
roles
• Alcohols
• Triglycerides
• Amino acids and proteins
• Ethers
• Biologically active molecules
• Thiols
• Odorants
• Sulfides
• Ketones
• Carbohydrates and metabolic intermediates
• Aldehydes
• Carbohydrates and metabolic intermediates
2
Introduction
Alcohols were first encountered back in Unit 2
• Alcohols comprise a hydroxyl group (-OH) attached to an
alkane-type carbon atom.
C O H
3
Introduction
Ethers
• Ethers have an oxygen attached to two alkane-type carbon
atoms.
C O C
4
Introduction
Sulfur containing functional groups
• Sulfur, like oxygen, is a Group VIA element
• Sulfur forms functional groups which are analogous to
some of the groups formed by oxygen.
5
Introduction
Thiol
• Thiols look similar to alcohols and comprise a sulfhydryl
(also called mercaptan) group (-SH) bonded to an alkane-
type carbon.
C S H
6
Introduction
Sulfides
• Sulfides look similar to ethers and contain a sulfur atom
that is bonded to two alkane-type carbon atoms.
C S C
7
Introduction
Disulfides
• Disulfides look similar to a sulfide, but contain two sulfur
atoms that are bonded to each other and to two alkane-
type carbon atoms.
C S S C
8
Introduction
Ketones
• Ketones are a carbonyl containing functional group in
which the carbonyl carbon is bonded to two other carbon
atoms.
C C C
9
Introduction
Ketones in the news; Diacetyl
• http://www.usatoday.com/news/health/2007-10-27-
diacetyl_N.htm
10
Introduction
Aldehydes
• Aldehydes are a carbonyl containing functional group in
which the carbonyl carbon is bonded to at least one
hydrogen atom.
C C H
11
Question
Circle and label the functional groups found in the following
compounds.
alkene
alcohol
alcohol alkene ether

ether
ketone amine
ether
12
Question
compounds.
alkene
thiol
sulfide
ammonium carboxylate
ion ion disulfide
thiol
sulfide
13
Question
compounds.
alcohol
ketone
aldehyde
aldehyde ketone
ether
phenol
14
Alcohols, Ethers, Thiols, Sulfides and
Disulfides
The IUPAC rules for naming alcohols
• Find the longest carbon chain containing the carbon to
which the hydroxyl group is attached.
• Remove the “-e” ending and replace with “-ol”
• Number the carbon chain from the end closest to the
hydroxyl group.
• Identify, name and locate any substituent groups
If the hydroxyl group is being treated as a substituent group,
refer to it as a “hydroxyl” group.
15
Disulfides
Examples of alcohol names
16
Disulfides
The IUPAC rules for naming thiols
which the sulfhydryl group is attached.
• Add the ending “-thiol”, without removing the “-e”
• Number the carbon chain from the end closest to the
sulfhydryl group.
17
Disulfides
Examples of thiol names
(Common names are shown in parentheses)
18
Disulfides
We will not use the IUPAC rules for naming the ethers,
sulfides and disulfides.
• Instead of using an ending, the substituents attached to the
oxygen or sulfur will be listed in front fo the family name.
19
Disulfides
Examples of ether, sulfide and disulfide names
20
Question
Name the following structures.
A) CH3 OH 2-Methyl Butanol.
CH3 CH CH CH3
CH3
CH3 S CH CH3
B) CH3
C) \ CH3 CH SH
S CH2 CH3
SH5 S
21
Disulfides
Alcohols are also labeled according to the number of carbons
that are attached to the carbon that the hydroxyl group is
attached to.
• This will be important for predicting the products of
oxidation reactions involving alcohols.
OH OH OH
CH3 C H CH3 C CH3 CH3 C CH3
H H CH3
primary (1°) secondary (2°) tertiary (3°)
22
Disulfides
The hydroxyl groups of alcohols are good hydrogen bonding
donors and acceptors
23
Disulfides
The other functional groups are not as good at forming
hydrogen bonds.
• Ethers can only accept hydrogen bonds.
• Sulfur has about the same electronegativity as carbon, and
therefore, is non-polar.
This is reflected in the boiling points and solubilities of these

molecules.
24
25
Preparations of Alcohols, Ethers, Thiols and
Sulfides
• In this unit we will be learn many new reactions.
• Pages 346 and 347 in Raymond contains a nice summary

of all of the reactions that will will cover in this unit.
26
Sulfides
Alcohols, Ethers, Thiols and Sulfides can be prepared from
alkyl halides using nucleophilic substitution reactions.
• A nucleophile is an electron rich atom or group or atoms.
• The halogen atom make a good leaving group.
• The nucleophile “attacks” that atom to which the halogen is
attached and the halogen leaves.
• This results in the the nucleophile substituting for the
leaving group.
27
Sulfides
Using nucleophilic substitution to prepare alcohols from alkyl
halides:
The OH- attacks The Cl- leaves
The OH- attacks The Br- leaves
The OH- attacks The I- leaves
28
Sulfides
Using nucleophilic substitution to prepare ethers, thiols and
sulfides from alkyl halides:
29
Sulfides
Another way to produce alcohols is the hydration of alkenes
• We saw this reaction back in Unit 2
OH H
H+
C C + H2O C C
alkene alcohol
30
Reactions Involving Water (Unit 4)
Hydration
• In the hydration reaction water is also split, but instead of
being used to split another molecule, it is added to another
molecule to produce a single product.
• The water it is added to either an alkene or alkyne:

• H OH
The hydration of an alkene produces an alcohol.
H C C H + H OH H C C H
acid
catalyst
H H H H
ethene ethanol
(an alkene) (an alcohol)
31
Hydration
• This can also be written in shorthand as:
• The H+ below the reaction arrow is used to indicate that this is an acid-catalyzed
reaction.
• The shorthand is used to emphasize what happens H toOHthe key reactant.
H2O
H C C H H C C H
H+
H H H H
ethene ethanol
32
Hydration example
• On an earlier slide a reaction from the Citric Acid Cycle
was shown, which involved the dehydrogenation of
succinic acid to produce fumaric acid.
• The sequent reaction in the Citric Acid Cycle is an example
of a hydration reaction:
O O H2O O H OH O
HO C C C C OH HO C C C C OH
H H H H
fumaric acid malic acid
33
Sulfides
Another way to produce
alcohols is the
hydration of alkenes
• When we looked at
hydration reactions
back in Unit 2 we
conveniently picked
reactants that would
only produce one
product.
• It is possible to have
multiple products in
hydration reactions.
34
Sulfides
Multiple products occur whenever there are a different
number of hydrogen atoms attached to the two carbons
double-bonded carbons in the alkene.
• Markovnikov’s Rule can be used to predict which of the
two products is predicted to be the major product.
-The hydrogen from the water in a hydration reaction is added to the
double-bonded carbon atom that originally carried the most hydrogen
atoms.
• If you consider hydrogens as a source of wealth, this can

be more simply stated as
-“The rich get richer!”
35
Preparations of
Alcohols ...
More examples of
hydration reactions:
36
Reactions of Alcohols and Thiols
Back in Unit 4 we developed several definitions for Oxidation-
Reduction Reactions.
37
Oxidation and Reduction (Unit 4)
Ways of recognizing oxidation/reduction reactions:
• Oxidation and reductions always occur together
Oxidation Reduction
An atom loses An atom gains

electrons electrons
An atom gains a An atom loses a

bond to oxygen bond to oxygen
An atom loses a An atom gains a

bond to hydrogen bond to hydrogen
38
Back in Unit 7 we saw how the definition “loses hydrogens”
could be applied to the oxidation of hydroquinones to produce
quinones
39
Carboxylic Acids & Phenols, Other Reactions
(Unit 7)
The oxidation of
hydroquinones is also
an important biological
reaction.
• A chemical oxidation
of hydroquinones
can be carried out
the oxidizing agent
K2Cr2O7 (potassium
dichromate)
• The K2Cr2O7 is not
acting as a base to
remove 2 H+ ions,
instead it is removing
40
2 H• atoms.
This same definition can also be applied to the oxidation of
alcohols by potassium dichromate (K2Cr2O7).
The oxidation
requires that
there are
hydrogens to be
removed on the
carbon to which
the hydroxyl is
bound
41
Application: Breathalyzer(http://science.howstuffworks.com/breathalyzer3.htm
1. The sulfuric acid
removes the alcohol
from the air into a
liquid solution.
2. The alcohol reacts
with potassium
dichromate to
produce:
1. * chromium sulfate
2. * potassium sulfate
3. * acetic acid
4. * water
The silver nitrate is a
42
catalyst ,
• The oxidation of primary (1°) alcohols is a way for
preparing aldehydes and carboxylic acids.
• The oxidation of secondary (2°) alcohols is a way for

preparing ketones.
• The oxidation of tertiary (3°) alcohols does not occur

because there are not hydrogens attached to the carbon to
to which the hydroxyl is attached
43
44
45
In biological reactions the
coenzyme NAD+ is often used as
the oxidizing agent.
• The NAD+ takes the electrons
away from alcohols to produce
aldehydes, carboxylic acids and
ketones.
46
Example
• The oxidation of malate to oxaloacetate that occurs in the
citric acid cycle:
O O O O
C C
NAD+ NADH + H+
HO C H O C
CH2 CH2
C C
O O O O
L-malate oxaloacetate
47
Thiols can be oxidized to form disulfides using I2 as oxidizing
agent
• We will see this oxidation reaction when we discuss
proteins in Unit 10
48
Sulfides
Another reaction that we saw back in Unit 2 was the
dehydration of alcohols to produce alkenes.
• We saw this reaction back in Unit 2
OH H
H+ +
C C C C H2O
heat
alcohol alkene
49
Sulfides
Like the complement hydration reaction, dehydration can also
produce multiple products.
50
Sulfides
Multiple products occur whenever there are a different
number of hydrogen atoms attached to the two carbons that
are on either side of the carbon to which the hydroxyl is
attached.
• There is a rule that can be used to predict which of the two
products is predicted to be the major product.
-In a dehydration of an alcohol, the hydrogen will be removed from the

neighboring carbon atom that carries the fewest hydrogen atoms.
• If you consider hydrogens as a source of wealth, and since

we are removing wealth, this can be more simply stated as
-“The poor get poor!”

51
Sulfides
Examples of dehydration
of alcohols
52
Aldehydes and ketones are carbonyl containing functional
group.
O O
C C H C C C
aldehyde ketone
• They have an array of important roles to play in biological

chemistry.
• We just saw how they can be prepared from the oxidation
of primary and secondary alcohols.
• Back in Unit 7, we also saw how they can be prepared
from the decarboxylation of α-keto acids and β-keto acids.
53
Carboxylic Acids & Phenols, Other Reactions
(Unit 7)
The decarboxylation of β-keto acids produces ketones
The decarboxylation of α-keto acids produces aldehydes
(Raymond’s answers to problems 10.27b and 10.31 are wrong)
54
The IUPAC rules for naming aldehydes
• Remove the “-e” ending and replace with “-al”
• Number the carbon chain from the carbonyl carbon.
Some of the smaller aldehydes have common names which
are more often used than the IUPAC names.
55
The IUPAC rules for naming ketones
• Remove the “-e” ending and replace with “-one”
• Number the carbon chain from end of the chain closest tothe
carbonyl carbon.
Common names are also used ketones
• The names of the two substituent groups connected to the
carbonyl carbon are listed and followed by the family name
ketone.
56
Examples of names for aldehydes and ketones
57
Aldehydes and ketones can serve has hydrogen bond
acceptors, but not donors.
• This means that they cannot hydrogen bond to themselves,

and so have much lower boiling points than alcohols
• However, they can hydrogen bond to water, so small

aldehydes and ketones are soluble in water.
58
Question
Draw structures for the following molecules:
A) 3-Methylheptanal
B) 3-Methy-2-pentanone
C) Methyl s-butyl ketone
60
Oxidation of Aldehydes
We have already seen how aldehydes and alcohols can be
oxidized to carboxylic acids with K2Cr2O7
61
Aldehydes can also be oxidized with the copper(II) ion (Cu2+)
• This reaction oxidizes aldehydes, but not alcohols.
• The Cu2+ ion forms a clear blue solution
• The Cu+ that is produced in the reaction forms an orange/red
precipitate.
62
Aldehydes can also be
oxidized with the copper(II)
ion (Cu2+)
• The reaction is called the
Benedict’s reaction, and
has been used for years
in a clinical setting to test
for the presence
O
C
H
of
glucoseH inC the
OH
urine.
HO C H
H C OH
H C OH
CH2 OH
glucose
Cu2+ Cu2+ + Cu+ Cu+
63
Reduction of Aldehydes and Ketones
In Unit 4 we saw how H2 could be used to reduce alkenes to
alkanes in the hydrogenation reaction.
• Because this reaction involves adding hydrogens to a
molelcule, it is a reduction reaction.
64
Hydrogenation
• Another type of oxidation/reduction reaction is the
hydrogenation reaction:
• In this example, an alkene is reduced to an alkane. H H
H H
‣ This isCconsidered
C reduction,
+ because the hydrogenHis bringing
H2 C in
C additional
H
electrons to the molecule. platinum
H H catalyst
H H
• The alkane that is produced in this reaction is considered “saturated” because it
can no longer absorb any more hydrogen atoms.
unsaturated saturated
65
Often chemist use a shorthand method of writing equations
like these:
• The equation shown on the previous slide can be written
as follows:
H H
H H H2
C C H C C H
Pt
H H
H H
• One of the reactants, H2, is placed above the reaction arrow
‣ Technically, this equation is no longer balanced
• The shorthand method of writing a chemical equation is used to emphasize what

happens to a key component of the reaction
‣ In this case it is the alkene.

66
The same reaction can also be used to reduce aldehydes
and ketones to alcohols:
67
In biochemistry, NADH + H+ is used instead of H2
• The reduction of a ketone containing steroid by the enzyme
Hydroxsteroid dehydrogenase.
68
Reactions of Alcohols with Aldehydes and
Ketones
Aldehydes and ketones
can react with alcohols to
form hemiacetals,
hemiketals, acetals and
ketals. O H
• Theses reactions will C CH2 OH
become in important in H C OH C O
the next unit when we
HO C H HO C H
talk about
H C OH H C OH
carbohydrates.
• This is because H C OH H C OH
carbohydrates are rich CH2 OH CH2 OH

in aldehydes, ketones glucose fructose
and alcohols
69
Ketones
The first reaction, which is similar to the reduction of
aldehydes and ketones, involves adding an alcohol across
the carbonyl to form a hemiacetal (from aldehydes) or a
hemiketal (from ketones).
O H O H
H3C CH2 C + O CH2 CH3 H3C CH2 C O CH2 CH3
H H
Propanal Ethanol
(Aldehyde) (Hemiacetal)
(Alcohol)
O H O H
CH3 C + O CH2 CH3 CH3 C O CH2 CH3
CH3 CH3
Propanone Ethanol
(Ketone) (Alcohol) (Hemiketal)
70
Ketones
Hemiacetal and hemiketal formation is catalyzed by acids.
71
Ketones
As we will see with the carbohydrates, the carbonyl group
and the alchohol that react can come from the same
molecule.
• This will produce a ring molecule.
72
Ketones
A hemiacetal or hemiketal can react with a second alcohol to
form an acetal or ketal.
• This is a substitution reaction and produces an water
molecule:
O H + H O CH2 CH3 O CH2 CH3
H3C CH2 C O CH2 CH3 H3C CH2 C O CH2 CH3 + H O H

H H
Ethanol
(Hemiacetal) (Alcohol) (Acetal)
O H + H O CH2 CH3 O CH2 CH3
CH3 C O CH2 CH3 CH3 C O CH2 CH3 + H O H

CH3 CH3
Ethanol (Ketal)
(Hemiketal)
(Alcohol)
73
Ketones
Sometimes the two
reactions are
combined into a single
reaction equation:
74
Question
Complete the following reaction:
CH3 CH2 C H + 2 CH3 CH2 OH
75
Question
Draw the structure of the hemiacetal that can form from this
molecule:
OH O
CH3 CH CH2 CH2 CH2 C H
76
The End

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Alcohol, Phenols, Thiol &amp; Ether Res 2

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Alcohols, Thiols, Ethers,

Aldehydes and Ketones

In this unit we continue surveying some of the families of

alcohol alkene ether

(Common names are shown in parentheses)

CH3 C H CH3 C CH3 CH3 C CH3

This is reflected in the boiling points and solubilities of these

• Pages 346 and 347 in Raymond contains a nice summary

The OH- attacks The Br- leaves

The OH- attacks The I- leaves

• The water it is added to either an alkene or alkyne:

• If you consider hydrogens as a source of wealth, this can

An atom loses An atom gains

An atom gains a An atom loses a

An atom loses a An atom gains a

• The oxidation of secondary (2°) alcohols is a way for

• The oxidation of tertiary (3°) alcohols does not occur

-In a dehydration of an alcohol, the hydrogen will be removed from the

• If you consider hydrogens as a source of wealth, and since

-“The poor get poor!”

• They have an array of important roles to play in biological

(Raymond’s answers to problems 10.27b and 10.31 are wrong)

• This means that they cannot hydrogen bond to themselves,

• However, they can hydrogen bond to water, so small

• One of the reactants, H2, is placed above the reaction arrow

‣ Technically, this equation is no longer balanced

• The shorthand method of writing a chemical equation is used to emphasize what

‣ In this case it is the alkene.

carbohydrates are rich CH2 OH CH2 OH

H3C CH2 C O CH2 CH3 H3C CH2 C O CH2 CH3 + H O H

O H + H O CH2 CH3 O CH2 CH3

CH3 C O CH2 CH3 CH3 C O CH2 CH3 + H O H

CH3 CH2 C H + 2 CH3 CH2 OH

CH3 CH CH2 CH2 CH2 C H

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Alcohol, Phenols, Thiol & Ether Res 2

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