Professional Documents
Culture Documents
Phenols
2
Why this Chapter?
To begin to study oxygen-containing
functional groups
3
17.1 Naming Alcohols and Phenols
General classifications of alcohols based on
substitution on C to which OH is attached
Methyl (C has 3 H’s), Primary (1°) (C has two
H’s, one R), secondary (2°) (C has one H, two
R’s), tertiary (3°) (C has no H, 3 R’s),
4
IUPAC Rules for Naming Alcohols
Select the longest carbon chain containing the hydroxyl
group, and derive the parent name by replacing the -e
ending of the corresponding alkane with -ol
Number the chain from the end nearer the hydroxyl group
Number substituents according to position on chain, listing
the substituents in alphabetical order
5
Naming Phenols
Use “phenol” (the French name for benzene)
as the parent hydrocarbon name, not
benzene
Name substituents on aromatic ring by their
position from OH
6
17.2 Properties of Alcohols and
Phenols
The structure around O of the alcohol or phenol is similar to that in water, sp3
hybridized
Alcohols and phenols have much higher boiling points than similar alkanes and alkyl
halides
A positively polarized OH 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
7
Properties of Alcohols and
Phenols: Acidity and Basicity
Weakly basic and weakly acidic
Alcohols are weak Brønsted bases
Protonated by strong acids to yield oxonium ions,
ROH2+
8
Alcohols and Phenols are Weak
Brønsted Acids
Can transfer a proton to water to a very small
extent
Produces H3O+ and an alkoxide ion, RO, or
a phenoxide ion, ArO
9
Acidity Measurements
The acidity constant, Ka, measures the extent to
which a Brønsted acid transfers a proton to water
[A] [H3O+]
Ka = ————— and pKa = log Ka
[HA]
Relative acidities are more conveniently presented on
a logarithmic scale, pKa, which is directly proportional
to the free energy of the equilibrium
Differences in pKa correspond to differences in free
energy
Table 17.1 presents a range of acids and their pKa
values
10
pKa Values for Typical OH Compounds
11
Relative Acidities of Alcohols
Simple alcohols are about as acidic as water
Alkyl groups make an alcohol a weaker acid
The more easily the alkoxide ion is solvated by water
the more its formation is energetically favored
Steric effects are important
12
Inductive Effects
Electron-withdrawing groups make an alcohol a
stronger acid by stabilizing the conjugate base
(alkoxide)
13
Generating Alkoxides from Alcohols
Alcohols are weak acids – requires a strong base to
form an alkoxide such as NaH, sodium amide NaNH2,
and Grignard reagents (RMgX)
Alkoxides are bases used as reagents in organic
chemistry
14
Phenol Acidity
Phenols (pKa ~10) are much more acidic than
alcohols (pKa ~ 16) due to resonance stabilization of
the phenoxide ion
Phenols react with NaOH solutions (but alcohols do
not), forming salts that are soluble in dilute aqueous
solution
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
15
Nitro-Phenols
Phenols with nitro groups at the ortho and para
positions are much stronger acids
16
17.3 Preparation of Alcohols: A
Review
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
17
1,2-Diols
Review: Cis-1,2-diols from hydroxylation of an alkene
with OsO4 followed by reduction with NaHSO3
Trans-1,2-diols from acid-catalyzed hydrolysis of
epoxides
18
17.4 Alcohols from Reduction of
Carbonyl Compounds
Reduction of a carbonyl compound in general gives
an alcohol
Note that organic reduction reactions add the
equivalent of H2 to a molecule
19
Reduction of Aldehydes and Ketones
Aldehydes gives primary alcohols
Ketones gives secondary alcohols
20
Reduction Reagent: Sodium
Borohydride
NaBH4 is not sensitive to moisture and it does not
reduce other common functional groups
Lithium aluminum hydride (LiAlH4) is more powerful,
less specific, and very reactive with water
Both add the equivalent of “H-”
21
17.5 Alcohols from Reaction of Carbonyl
Compounds with Grignard Reagents
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
22
Mechanism of the Addition of a
Grignard Reagent
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
23
17.6 Reactions of Alcohols
Conversion of alcohols into alkyl halides:
- 3˚ alcohols react with HCl or HBr by SN1 through carbocation intermediate
- 1˚ and 2˚ alcohols converted into halides by treatment with SOCl 2 or PBr3
via SN2 mechanism
24
25
Dehydration of Alcohols to Yield
Alkenes
The general reaction: forming an alkene from an
alcohol through loss of O-H and H (hence
dehydration) of the neighboring C–H to give bond
Specific reagents are needed
26
Acid- Catalyzed Dehydration
Tertiary alcohols are readily dehydrated with acid
Secondary alcohols require severe conditions (75%
H2SO4, 100°C) - sensitive molecules don't survive
Primary alcohols require very harsh conditions –
impractical
Reactivity is the result of the nature of the
carbocation intermediate
27
Conversion of Alcohols into
Esters
28
17.7 Oxidation of Alcohols
Can be accomplished by inorganic reagents, such as
KMnO4, CrO3, and Na2Cr2O7 or by more selective,
expensive reagents
29
Oxidation of Primary Alcohols
To aldehyde: pyridinium chlorochromate (PCC,
C5H6NCrO3Cl) in dichloromethane
Other reagents produce carboxylic acids
30
Oxidation of Secondary Alcohols
Effective with inexpensive reagents such as Na2Cr2O7
in acetic acid
PCC is used for sensitive alcohols at lower
temperatures
31
17.9 Phenols and Their Uses
Industrial process from readily available cumene
Forms cumene hydroperoxide with oxygen at high
temperature
Converted into phenol and acetone by acid
32
17.10 Reactions of Phenols
The hydroxyl group is a strongly activating, making
phenols substrates for electrophilic halogenation,
nitration, sulfonation, and Friedel–Crafts reactions
Reaction of a phenol with strong oxidizing agents
yields a quinone
Fremy's salt [(KSO3)2NO] works under mild conditions
through a radical mechanism
33
Quinones in Nature
Ubiquinones mediate electron-transfer processes
involved in energy production through their redox
reactions
34
17.11 Spectroscopy of Alcohols
and Phenols
Characteristic O–H stretching absorption at 3300 to
3600 cm1 in the infrared
Sharp absorption near 3600 cm-1 except if H-bonded:
then broad absorption 3300 to 3400 cm1 range
Strong C–O stretching absorption near 1050 cm1
(See Figure 17.11)
Phenol OH absorbs near 3500 cm-1
35
Nuclear Magnetic Resonance
Spectroscopy
C NMR: C bonded to OH absorbs at a lower
13
field, 50 to 80
1H NMR: electron-withdrawing effect of the nearby
oxygen, absorbs at 3.5 to 4 (See Figure 17-13)
Usually no spin-spin coupling between O–H proton and
neighboring protons on C due to exchange reactions
with moisture or acids
Spin–spin splitting is observed between protons on the
oxygen-bearing carbon and other neighbors
Phenol O–H protons absorb at 3 to 8
36