ALCOHOLS AND PHENOLS
ALCOHOLS AND PHENOLS
Alcohols contain an OH group connected to a a saturated C
(sp3)
They are important solvents and synthesis intermediates
Phenols contain an OH group connected to a carbon in a
benzene ring
Methanol, CH3OH, called methyl alcohol, is a common
solvent, a fuel additive, produced in large quantities
Ethanol, CH3CH2OH, called ethyl alcohol, is a solvent, fuel,
beverage
Phenol, C6H5OH (“phenyl alcohol”) has diverse uses - it
gives its name to the general class of compounds
OH groups bonded to vinylic, sp2-hybridized carbons are
called enols
WHY THIS CHAPTER?
To begin to study oxygen-containing functional
groups
These groups lie at the heart of biological
chemistry
2.1 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),
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
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
2.2 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
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+
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-
ALCOHOLS, PHENOLS AND ETHERS,
Alcohols, Phenols, and Thiols
Ethers
Reactions of Alcohols
COMPOUNDS WITH OXYGEN
ATOMS
Alcohols -OH hydroxyl
CH3-OH , CH3CH2-OH
Phenols
Ethers -O- CH3-O-CH3
LEARNING CHECK AL1
Classify each as an alcohol (1), phenol (2),
or an ether (3):
A. __ CH3CH2-O-CH3 C. ___ CH3CH2OH
B. _____
NAMING ALCOHOLS
A carbon compound that contain -OH (hydroxyl)
group
In IUPAC name, the -e in alkane name is
replaced with -ol.
CH4 methane
CH3OH methanol (methyl alcohol)
CH3CH3 ethane
CH3CH2OH ethanol (ethyl alcohol)
ETHANOL CH3CH2OH
Acts as a depressant
Kills or disables more people than any other
drug
12-15 mg/dL ethanol metabolized by a social
drinkers in one hour
30 mg/dL ethanol metabolized by an alcoholic
in one hour.
MORE NAMES OF ALCOHOLS
IUPAC names for longer chains number the chain
from the end nearest the -OH group.
CH3CH2CH2OH 1-propanol
CH3CHOHCH3
2-propanol
CH3CCH3HCH2CH2COHHCH3
5-methyl-2-hexanol
SOME TYPICAL ALCOHOLS
OH
“rubbing alcohol” CH3CHCH3
2-propanol (isopropyl alcohol)
antifreeze HO-CH2-CH2-OH
1,2-ethanediol (ethylene glycol)
OH
glycerol HO-CH2-CH-CH2OH
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
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
NITRO-PHENOLS
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
REVIEW: PREPARATION OF ALCOHOLS BY
REGIOSPECIFIC HYDRATION OF ALKENES
Hydroboration/oxidation: syn, non-Markovnikov
hydration
Oxymercuration/reduction: Markovnikov
hydration
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
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
REDUCTION OF ALDEHYDES AND KETONES
Aldehydes gives primary alcohols
Ketones gives secondary alcohols
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-”
MECHANISM OF REDUCTION
The reagent adds the equivalent of hydride to
the carbon of C=O and polarizes the group as
well
REDUCTION OF CARBOXYLIC ACIDS AND ESTERS
Carboxylic acids and esters are reduced to give
primary alcohols
LiAlH4 is used because NaBH4 is not effective
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
REACTIONS OF GRIGNARD REAGENTS WITH
CARBONYL COMPOUNDS
REACTIONS OF ESTERS AND GRIGNARD
REAGENTS
Yields tertiary alcohols in which two of the substituents carbon
come from the Grignard reagent
Grignard reagents do not add to carboxylic acids – they
undergo an acid-base reaction, generating the hydrocarbon of
the Grignard reagent
GRIGNARD REAGENTS AND OTHER
FUNCTIONAL GROUPS IN THE SAME
MOLECULE
Can't be prepared if there are reactive
functional groups in the same molecule,
including proton donors
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
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
SOCl2 or PBr3 via SN2 mechanism
CONVERSION OF ALCOHOLS INTO TOSYLATES
Reaction with p-toluenesulfonyl chloride (tosyl chloride, p-TosCl)
in pyridine yields alkyl tosylates, ROTos
Formation of the tosylate does not involve the C–O bond so
configuration at a chirality center is maintained
Alkyl tosylates react like alkyl halides
STEREOCHEMICAL USES OF TOSYLATES
The SN2 reaction of an alcohol via a tosylate, produces
inversion at the chirality center
The SN2 reaction of an alcohol via an alkyl halide proceeds
with two inversions, giving product with same arrangement as
starting alcohol
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
Tikrit University
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
DEHYDRATION WITH POCL3
Phosphorus oxychloride in the amine solvent pyridine
can lead to dehydration of secondary and tertiary
alcohols at low temperatures
An E2 via an intermediate ester of POCl2
CONVERSION OF ALCOHOLS INTO ESTERS
OXIDATION OF ALCOHOLS
Can be accomplished by inorganic reagents, such as KMnO4,
CrO3, and Na2Cr2O7 or by more selective, expensive reagents
OXIDATION OF PRIMARY ALCOHOLS
To aldehyde: pyridinium chlorochromate (PCC,
C5H6NCrO3Cl) in dichloromethane
Other reagents produce carboxylic acids
OXIDATION OF SECONDARY ALCOHOLS
Effective with inexpensive reagents such as
Na2Cr2O7 in acetic acid
PCC is used for sensitive alcohols at lower
temperatures
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
