Lecture 5 Alkohol

C 2004 Barry Linkletter, UPEI
LECTURE 5
2
Introduction
Nomenclature
Properties :-
Physical
Chemical
Reactions:-
Hydration of alkene
Reduction of carbonyl
Carbonyl + Grignard reagents
Dehydration
Conversion to R-X
Oxidation
Alcohols contain an OH group connected to a a saturated C
(sp
3
)
They are important solvents and synthesis intermediates
Methanol, CH
3
OH, called methyl alcohol, is a common solvent,
a fuel additive, produced in large quantities
Ethanol, CH
3
CH
2
OH, called ethyl alcohol, is a solvent, fuel,
beverage
Phenols contain an OH group connected to a carbon in a
benzene ring
Phenol, C
6
H
5
OH (phenyl
alcohol) has diverse uses - it
gives its name to the general
class of compounds
Some Common Alcohols

Some Important Alcohols

Some Important Phenols

Step 1. Name the longest chain to which the hydroxyl (OH)
group is attached. The name for this chain is obtained by
dropping the final -e from the name of the hydrocarbon
parent name and adding the ending -ol.
Step 2. Number the longest chain to give the lowest possible
number to the carbon bearing the hydroxyl group.
Step 3. Locate the position of the hydroxyl group by the number of
the C to which it is attached.
Step 4. Locate and name any other substituents.
Step 5. Combine the name and location for other groups, the
hydroxyl group location, and the longest chain into the
final name.
Give the IUPAC name for each of the following compounds:
2,5-heptadiol
3-methyl-1-butanol
4-ethyl-3-hexanol
3-bromo-2-pentanol
a)
b)
c) d)
Give the IUPAC name for each of the following compounds:
4-ethyl-2-heptanol
2-methyl-1-butanol
3-methyl-3-hexanol
Classification of alcohol
Hydrogen Bonding
The structure around O of the alcohol or phenol is similar to
that in water, sp
3
hybridized
The oxygen-hydrogen bond is an especially polar bond
because oxygen is much more electronegative than hydrogen
is.
The OH bond is therefore a polar bond, and any molecule
which contains an OH bond (like an alcohol) is a polar
molecule.

Hydrogen Bonding
A positively polarized hydrogen atom from one molecule is
attracted to a lone pair of electrons on a negatively polarized
oxygen atom of another molecule
This produces a force that holds the two molecules together

These intermolecular
attractions are present
in solution but not in
the gas phase, thus
elevating the boiling
point of the solution
Boiling Points
Because alcohols hydrogen bond to each other, they have much
higher boiling points than similar alkanes and alkyl halides.
The boiling point of alcohols increases as the molecules become
larger.

Solubility of alcohols
The general rule in solubility is like dissolves like.
Since the OH group makes alcohols polar, they will mix with
polar solvents like water as long as the carbon chain is
fairly short.
The longer the carbon chain, the less soluble the alcohol is.

Solubility of alcohols
Alcohols with higher molar masses are less soluble in water
because the increasing size of the nonpolar chain disrupts
the hydrogen bonding network.
There is a solubility limit on the carbon chain length for
alcohols.
In general, a single OH group will make alcohols containing
three to four carbon atoms soluble in water.
As the number of carbons in the alcohol increases, the
solubility decreases.

Alcohols are weak Brnsted bases
Protonated by strong acids to yield oxonium ions, ROH
2
+

Alcohol and Phenol Acid-Base Properties

Alcohols and phenols also are weak Brnsted acids
Can transfer a proton to water to a very small extent
Produces H
3
O
+
and an alkoxide ion, RO
, or a phenoxide
ion, ArO

Alcohol and Phenol Acid-Base Properties

Brnsted acidity measurements
The acidity constant, K
a
, measure the extent to which a
Brnsted acid transfers a proton to water

and pK
a
= log K
a

Relative acidities are more conveniently presented on a
logarithmic scale, pK
a
, which is directly proportional to the
free energy of the equilibrium
Differences in pK
a
correspond to differences in free energy

Generating Alkoxides from Alcohols
Alcohols are weak acids requires a strong base to form
an alkoxide such as NaH, sodium amide (NaNH
2
), and
Grignard reagents (RMgX)
Alkoxides are bases used as reagents in organic chemistry
Phenol Acidity
Phenols (pK
a
~10) are much more acidic than alcohols (pK
a
~
16) due to resonance stabilization of the phenoxide ion
Phenols react with NaOH solutions (but alcohols do not),
forming soluble salts that are soluble in dilute aqueous
A phenolic component can be separated from an organic
solution by extraction into basic aqueous solution and is
isolated after acid is added to the solution
Alcohols are derived from many types of compounds
The alcohol hydroxyl can be converted to many other
functional groups
This makes alcohols useful in synthesis
REVIEW: PREPARATION OF ALCOHOLS BY
REGIOSPECIFIC HYDRATION OF ALKENES
Hydroboration/oxidation: syn, non-Markovnikov hydration
Oxymercuration/reduction: Markovnikov hydration
Reduction of a carbonyl compound in general gives an
alcohol
Note that organic reduction reactions add the equivalent
of H
2
to a molecule
Aldehydes gives primary alcohols
Ketones gives secondary alcohols
Sodium borohydride, NaBH
4
is not sensitive to moisture and it
does not reduce other common functional groups
Lithium aluminum hydride (LiAlH
4
) is more powerful, less
specific, and very reactive with water
Both add the equivalent of H

The reagent adds the equivalent of hydride to the carbon of
C=O and polarizes the group as well
Carboxylic acids and esters are reduced to give primary alcohols
LiAlH
4
is used because NaBH
4
is not effective
Alkyl, aryl, and vinylic halides react with magnesium in ether or
tetrahydrofuran to generate Grignard reagents, RMgX
Grignard reagents react with carbonyl compounds to yield
alcohols
Grignard reagents act as nucleophilic carbon anions
(carbanions, : R) in adding to a carbonyl group
The intermediate alkoxide is then protonated to produce the
alcohol
Two general classes of reaction
At the carbon of the CO bond
At the proton of the OH bond
DEHYDRATION OF ALCOHOLS TO YIELD
ALKENES
Alcohols undergo dehydration (loss of water) when they are
heated in the presence of a strong acid catalyst.
The OH and an H are removed from adjacent carbon atoms
to yield an alkene.
Example

The dehydration of alcohols is the reverse of the hydration of
alkenes
ALKENES
If there is more than one possible product of a dehydration
reaction, the major product can be predicted from Zaitsevs
Rule:
Zaitsevs Rule when an alkene is produced in an elimination
reaction, the major product is the one with the more highly
substituted double bond.

Tertiary alcohols are readily dehydrated with acid
Secondary alcohols require severe conditions (75% H
2
SO
4
,
100C) - sensitive molecules don't survive
Primary alcohols require very harsh conditions impractical
ALKENES
The first step in this reaction is protonation of the hydroxyl
group, converting it into a good leaving group (H
2
O) .
Then, a C-O bond is converse into alkyl halides when treated
with hydrochloric/bromic acids (HCl or HBr).
Tertiary alcohols then ionize to the 3 carbocation which
undergoes an S
N
1 reaction with X-.
Primary alcohols react by an S
N
2 displacement of water from
the substrate by Cl-.
Secondary alcohols may react by either an S
N
1 or S
N
2
mechanism depending on the structure of the 2 alcohol.
Tertiary alcohols react reasonably rapidly with concentrated
HCl or HBr at low temperature
A tertiary alcohol reacts if it is shaken with concentrated
hydrochloric acid at room temperature. A tertiary
halogenoalkane (haloalkane or alkyl halide) is formed.
1 and 2 alcohols are resistant to acid use SOCl
2
(Thionyl
chloride) or PBr
3
(Phosphorus tribromide) by an S
N
2
mechanism
Can be accomplished by inorganic reagents, such as
KMnO
4
, CrO
3
, and Na
2
Cr
2
O
7
or by more selective, expensive
reagents
Alcohol forms a chromate ester followed by elimination with
electron transfer to give ketone.
The mechanism was determined by observing the effects of
isotopes on rates
Primary alcohols are oxidized first to aldehydes, but the
aldehydes are then usually oxidized into carboxylic acids
(using pyridinium chlorochromate (PCC, C
5
H
6
NCrO
3
Cl) in
dichloromethane).
Secondary alcohols are oxidized to ketones, which cannot be
oxidized any further:
Effective with
inexpensive reagents
such as Na
2
Cr
2
O
7
in
acetic acid (PCC is
used for sensitive
alcohols at lower
temperatures).

Lecture 5 Alkohol

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C 2004 Barry Linkletter, UPEI

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