• Hydroxyl (OH) functional group ( ROH )

• Oxygen is sp3 hybridized

• Polar molecule why…….?
== > (Oxygen have 2 lone pairs)
1.Primary alcohol:
Carbon with –OH is bonded to one other carbon.

H H
H C– C– OH or CH3CH2 OH or R CH2 OH
H H
2.Secondary alcohol:
Carbon with –OH is bonded to two other carbons.
H H
H C–--- C– OH or CH3 C H OH or R – CH OH
H HCH
3. Tertiary alcohol:
Carbon with –OH is bonded to three other
carbons.
H CH3 R
H HCH
H C------ C– OH or CH3 C --- OH or R – C -- OH
H HCH
H CH3 R

4. Aromatic (phenol): -OH is bonded to a

benzene ring. OH
CH3CH2CH2OH
CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3

Primary (1o) Secondary (2o)

CH3 OH
CH3 C OH
CH3

Tertiary (3o) Aromatic (phenol)

 OH
CH2 CHCH2CHCH3

pent-4-ene-2-ol
(1997 revision of IUPAC rules)

4-penten-2-ol (old)
1.Find the longest carbon chain containing
the carbon with the -OH group.
2. Drop the -e from the alkane name, add -ol.
3. Number the chain, starting from the end
closest to the -OH group.
4.Number and name all substituents.
 CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3

2-methyl-1-propanol
2-butanol
CH3 OH
CH3 C OH
CH3
Br CH3
2-methyl-2-propanol
3-bromo-3-methylcyclohexanol
 Naming Priority
• Acids • Alkenes
• Esters • Alkynes
• Aldehydes • Alkanes
• Ketones • Ethers
• Alcohols • Halides
• Amines
• When -OH is part of a higher priority class of
compound, it is named as hydroxy.
• Example:

OH
CH2CH2CH2COOH
4-hydroxybutanoic acid
• Alcohol can be named as alkyl alcohol.
• Useful only for small alkyl groups.
• Examples:

CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3

isobutyl alcohol sec-butyl alcohol

 Naming Diols
• Two numbers are needed to locate the two
-OH groups.
• Use -diol as suffix instead of -ol.

HO OH

1,6-hexanediol
 Glycols
• 1, 2 diols (vicinal diols) are called glycols.
• Common names for glycols use the name of the
alkene from which they were made.

CH2CH2 CH2CH2CH3
OH OH OH OH
1,2-ethanediol 1,2-propanediol
ethylene glycol propylene glycol
• -OH group is assumed to be on carbon 1.
• For common names of disubstituted phenols,
use ortho- for 1,2; meta- for 1,3; and para- for
1,4.
• Methyl phenols are cresols. OH
OH

H3C

Cl
4-methylphenol
3-chlorophenol para-cresol
meta-chlorophenol
1. Boiling point of alcohol
2. Solubility of alcohol
3. Acidity of alcohol
i) Higher compared to corresponding alkane..
Why?
ii) Unusually high boiling points due to hydrogen
bonding between molecules
 alcohol M.p B.p Density
• Methanol -97 65 0.792
• Ethanol -114 78 0.789
• Propan-1-ol - 126 97 0.804
• Propan-2-ol - 88 82 0.786
• Butan-1-ol - 90 118 0.810
• 2-methylpropan-1-ol -118 108 0.802
• Butan-2-ol -114 100 0.808
• 2,2-dimethylethanol 25 83 0.789
• Pentan-1-ol - 79 138 0.817
• Hexan-1-ol - 52 158 0.819
Small alcohols are miscible in water,
but solubility decreases as the size of
the alkyl group increases
Solubility decreases as the size
of the alkyl group increases.
• pKa range: 15.5-18.0 (water: 15.7)
• pKa … ?
• Acidity decreases as alkyl group
increases.
• Halogens increase the acidity.
• Phenol is 100 million times more acidic
than cyclohexanol!
 Table of Ka Values

CH3 OH
 React methanol and ethanol with sodium
metal (redox reaction).

CH3CH2OH + Na CH3CH2O Na + 1/2 H2

React less acidic alcohols with more

reactive potassium.
1
(CH3)3C OH + K (CH3)3CO K + /2 H2
1. Manufactured preparation of alcohol
2. Lab preparation of alcohol
i) Grignard reagents
ii ) Reduction of aldehyde/ketones
iii) Hydrolysis of alkyl halide
iv) Hydration of alkenes
Preparation of Methanol :
By passing (execess) hydrogen and carbon
monoxide over chromium (III) oxide/Zinc
Oxide as catalyst at 350- 400o C
Cr2O3/ZnO cat

2H2 + CO ============ > CH3OH

350-400 oC high preesure
• Preparation of Ethanol :
• By direct hydrolysis of ethylene.
• Mixture of C2H4 and water vapour
passed over phosphoric acid 300oC 68-
70 atm pressure
phosphoric acid
• C2H4 + H2O ======== > CH3CH2OH
• 300 oC 68-70 atm
• Fermentation:
• Diastase

• 2(C6H10 O5)n + nH2O == > n C12 H22 O11

• 60oC
maltose
• Maltase

• C12 H22 O11 + H2O === > C6H12 O6

Glucose
Zymase

• C6H12 O6 === > 2CH3CH2OH + 2CO2

• ethanol
1. Grignard Reaction (RMgX)
H ether H H2O H
C=O + RMgMX == > H C–OMgX ==> H C OH + MgXOH
H R dil acid
R
Formaldehyde 1o alcohol

R1 ether H H
C=O + RMgMX == > R1 C–OMgX ==> R1 C OH + MgXOH
H R R
Acetaldehyde 2o Aocohol
 Grignard + formaldehyde yields a primary
alcohol with one additional carbon.

CH3 H H CH3 H
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H
H H H

CH3 H
HOH
CH3 CH CH2 CH2 C O H
H
 Grignard + aldehyde yields a secondary alcohol.

CH3 H H3C CH3 CH3

H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H
H H H

CH3 CH3
HOH
CH3 CH CH2 CH2 C O H
H
Grignard Reaction (RMgX)

R2 ether R2 R2
C=O + RMgMX == > R1 C–OMgX ==> R1 C OH + MgXOH
R1 R R
Acetone 3o Aocohol
 Grignard + ketone yields a tertiary alcohol.
CH3 H H3C CH3 CH3
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H3C
H H CH3

CH3 CH3
HOH
CH3 CH CH2 CH2 C O H
CH3
Some Grignard Reagents
Br
ether MgBr
+ Mg

Cl MgCl
ether
CH3CHCH2CH3 + Mg CH3CHCH2CH3

CH3C CH2
ether
Br + Mg CH3C CH2
MgBr
R1 LiAlH4
Since LiALH4 is
C=O == == > R1 CH2OH strong reduction
H Ether agent, other
Acetaldehyde 1o Aocohol reduction agent
such as:

R1 LiAlH4
LiBH4 ( in Ether )
C=O == == > R1 CHOH NaBH4(In
R Ether
R Ethanol/H2O)
Aacetone 2o Aocohol
Also can be used.
 Comparison of
Reducing Agents
• LiAlH4 is stronger.
• LiAlH4 reduces more
stable compounds
which are resistant
to reduction.
1. Hydrolysis (substitution) of OH- on alkyl
halide

CH3CH2X + HOH ===>CH3CH2OH + HX

• 2.Hydration of alkenes

H2C=CH2 + H2O == > CH3CH2OH

1. Dehydration to alkene
2. Oxidation to aldehyde, ketone
3. Substitution to form alkyl halide
4. Reduction to alkane
5. Esterification
6. Williamson synthesis of ether
1. Conc. H2SO4 produces alkene
2. Carbocation intermediate
3. Saytzeff product
4. Bimolecular dehydration produces ether
5. Reaction condition:
Low temp, 140°C and below, favors ether
High temp, 180°C and above, favors alkene
 H
OH OH
H2SO4
CH3CHCH3 CH3CHCH3
CH3CHCH3
alcohol
H2O
CH2 CHCH3
+
H3O
CH3OH CH3 OH2 CH3 O CH3
H
CH3OH CH3OCH3
H2O
 • 1° alcohol to aldehyde to carboxylic acid
• Difficult to stop at aldehyde
• Use pyridinium chlorochromate (PCC) to limit the
oxidation.
• PCC can also be used to oxidize 2° alcohols to
ketones.

OH N H CrO3Cl O
CH3CH2CH2CH2 CH3CH2CH2CH
1. 2° alcohol becomes a ketone
2. Reagent is Na2Cr2O7/H2SO4
3. Active reagent probably H2CrO4
4. Color change: orange to greenish-blue

Example

OH O
Na2Cr2O 7 / H2SO 4
CH3CHCH2CH3 CH3CCH2CH3

=>
• Cannot lose 2 H’s
• Basis for chromic acid test

=>
• Collins reagent: Cr2O3 in pyridine
• Jones reagent: chromic acid in acetone
• KMnO4 (strong oxidizer)
• Con. Nitric acid (strong oxidizer)
• CuO, 300°C (industrial dehydrogenation).
=>
 • Dehydrate with conc. H2SO4, then add H2
• Tosylate, then reduce with LiAlH4
OH
H2SO4 H2
CH3CHCH3 CH2 CHCH3 CH3CH2CH3
Pt
alcohol alkene alkane

OH OTs
TsCl LiAlH4
CH3CHCH3 CH3CHCH3 CH3CH2CH3 =>
alcohol tosylate alkane
 • -OH of alcohol is protonated
• -OH2+ is good leaving group
• 3° and 2° alcohols react with Br- via SN1
• 1° alcohols react via SN2

+ H -
H3O Br
R O H R O H R Br =>
• Chloride is a weaker nucleophile than
bromide.
• Add ZnCl2, which bonds strongly with
-OH, to promote the reaction.
• The chloride product is insoluble.
• Lucas test: ZnCl2 in conc. HCl
– 1° alcohols react slowly or not at all.
– 2° alcohols react in 1-5 minutes.
– 3° alcohols react in less than 1 minute.
• HI does not react
• Poor yields of 1° and 2° chlorides
• May get alkene instead of alkyl halide
• Carbocation intermediate may rearrange.
• Good yields with 1° and 2° alcohols
• PCl3 for alkyl chloride (but SOCl2 better)
• PBr3 for alkyl bromide
• P and I2 for alkyl iodide (PI3 not stable)

=>
• P bonds to -OH as Br- leaves
• Br- attacks backside (SN2)
• HOPBr2 leaves
• Produces alkyl chloride, SO2, HCl
• S bonds to -OH, Cl- leaves
• Cl- abstracts H+ from OH
• C-O bond breaks as Cl- transferred to C
Can be carried out by following methods

• Fischer: alcohol + carboxylic acid

• Tosylate esters
• Sulfate esters
• Nitrate esters
• Phosphate esters
 • Acid + Alcohol yields Ester + Water
• Sulfuric acid is a catalyst.
• Each step is reversible.
O CH3 + O CH3
H
CH3 C OH + H O CH2CH2CHCH3 CH3C OCH2CH2CHCH3

+ HOH
 Sulfate Esters
Alcohol + Sulfuric Acid

O +
O
H
HO S OH + H O CH2CH3 HO S OCH2CH3
O O

O + O
H
CH3CH2O H + HO S OCH2CH3 CH3CH2O S OCH2CH3
O O
 Nitrate Esters
O +
H O
N OH + H O CH2CH3 N OCH2CH3
O O

CH2 O H CH2 O NO2

CH2 O H + 3 HO NO2 CH2 O NO2
CH2 O H CH2 O NO2

glycerine nitroglycerine =>

 Phosphate Esters
O O O
CH3OH CH3OH
HO P OH CH3O P OH CH3O P OCH3
OH OH OH

CH3OH
O
CH3O P OCH3
=>
OCH3
 • ROH + Na (or NaH) yields sodium alkoxide
• RO- + 1° alkyl halide yields ether (Williamson
ether synthesis)

CH3
CH3CH2CHCH3 + CH3CH2 Br CH2CH2CH O CH2CH3
O
=>
 Acid Catalyst

CH3-CH2 OH == > CH2=CH2+ H2O

Acid Catalyst

• CH3CH –CH2 == > CH3CH2=CH2 + H2O

H OH
1. Solvent
2. Sources of other materials
=>
Preparation Substitution Reaction
Starh, Sugar,
R-COOC2H5 C2H5NH2 C2H5Cl
Cellulose
He
(hy at w

)
n
i
RC droly th K

tio
HN
H

ta
OO sis OH KO

en
) Cl

O2
H so ith

rm
H
Es ln il w r

Fe
ter Bo l 5o

t(
C
C2H4 ific ,P

as
at i l2

Ye
on SO
Heat 170oC – H2O

Vapour + Air (A
g at 600 o C) (O
C2H5OH xid )
c H2SO4

em
p) Zn +Acid / LiAlH (re
duction) CH3CHO
w t 4

(lo
SO
4
H 2 O
c hH
2 Ex Li
wit Al
n
ce H
Iodo 2 CO3 sol

dil a
ss
C2H5HSO4 arm 4 (re
test

W ac

- H2O
du

cids
id
l+

Na
K ct
ho

io
C

form

C
o
co

2
r2 O n)
40

a
Al
Heat with C2H5OH

I2 +N
4 1
ss

7 (O
SO
ce

xi
da
Ex

2
H

tio
n

n)
co

C2H5ONa CH3COOH
CHI3
C2H5OC2H5
 Methanol
• “Wood alcohol”
• Industrial production from synthesis gas
• Common industrial solvent
• Fuel at Indianapolis 500
– Fire can be extinguished with water
– High octane rating
– Low emissions
– But, lower energy content
– Invisible flame =>
 Ethanol
• Fermentation of sugar and starches in grains
• 12-15% alcohol, then yeast cells die.
• Distillation produces “hard” liquors
• Azeotrope: 95% ethanol, constant boiling
• Denatured alcohol used as solvent
• Gasahol: 10% ethanol in gasoline
• Toxic dose: 200 mL ethanol, 100 mL methanol

=>
 2-Propanol
• “Rubbing alcohol”
• Catalytic hydration of propene

100-300 atm, 300°C

CH2 CH CH2 + H2O CH3 CH CH3
catalyst
OH

=>
Formation of Phenoxide
Ion
Phenol reacts with hydroxide ions to form
phenoxide ions - no redox is necessary.

O H O
+ OH
+ HOH
pKa = 15.7
pKa = 10

=>
 Glycols (Review)
• Syn hydroxylation of alkenes
– osmium tetroxide, hydrogen peroxide
– cold, dilute, basic potassium permanganate
• Anti hydroxylation of alkenes
– peroxyacids, hydrolysis
 Organometallic Reagents

• Carbon is bonded to a metal (Mg or Li).

• Carbon is nucleophilic (partially
negative).
• It will attack a partially positive carbon.
–C-X
–C=O
• A new carbon-carbon bond forms.
=>
 Organolithium Reagents
• Formula R-Li (reacts like R:- +Li)
• Can be produced from alkyl, vinyl, or aryl
halides, just like Grignard reagents.
• Ether not necessary, wide variety of
solvents can be used.

=>
 Reaction with Carbonyl
• R:- attacks the partially positive carbon in the
carbonyl.
• The intermediate is an alkoxide ion.
• Addition of water or dilute acid protonates the
alkoxide to produce an alcohol.

R
C O R C O R C OH
HOH
OH
=>
 How would you
synthesize…
OH CH2OH
CH3CH2CHCH2CH2CH3

OH OH
C CH3
CH3 =>
CH2CH3
 Grignard and Ester (1)
• Grignard attacks the carbonyl.
• Alkoxide ion leaves! ? !

H3C CH3
R MgBr C O R C O MgBr
CH3O
OCH3

CH3 CH3
R C O MgBr R C + MgBrOCH3
O
OCH3
Ketone intermediate =>
 Second step of reaction
• Second mole of Grignard reacts with the
ketone intermediate to form an alkoxide ion.
• Alkoxide ion is protonated with dilute acid.
CH3 CH3
R MgBr + R C R C O MgBr
O
R
HOH
CH3
R C OH
R =>
 How would you
synthesize...
Using an acid chloride or ester.

OH
CH3
CH3CH2CCH3 C
CH3 OH

OH
CH3CH2CHCH2CH3 =>
 Grignard Reagent +
Ethylene Oxide
• Epoxides are unusually reactive ethers.
• Product is a 1º alcohol with 2 additional
carbons.
O O MgBr

MgBr + CH2CH2
CH2 CH2

HOH
O H
CH2CH2
=>
 Limitations of Grignard
• No water or other acidic protons like
O-H, N-H, S-H, or -C—C-H. Grignard
reagent is destroyed, becomes an alkane.
• No other electrophilic multiple bonds, like
C=N, C—N, S=O, or N=O.

=>
 Reduction of Carbonyl
• Reduction of aldehyde yields 1º alcohol.
• Reduction of ketone yields 2º alcohol.
• Reagents:
– Sodium borohydride, NaBH4
– Lithium aluminum hydride, LiAlH4
– Raney nickel

=>
 Sodium Borohydride
• Hydride ion, H-, attacks the carbonyl
carbon, forming an alkoxide ion.
• Then the alkoxide ion is protonated by
dilute acid.
• Only reacts with carbonyl of aldehyde or
ketone, not with carbonyls of esters or
carboxylic acids.
O H O H O H
C C + C
H H3O
H H H
=>
 Lithium Aluminum
Hydride
• Stronger reducing agent than sodium
borohydride, but dangerous to work with.
• Converts esters and acids to 1º alcohols.
O H O H
C C
OCH3 LAH H3O+
H
=>
 Catalytic Hydrogenation
• Add H2 with Raney nickel catalyst.
• Also reduces any C=C bonds.

OH O OH

NaBH4 H2, Raney Ni

=>
 Thiols (Mercaptans)
• Sulfur analogues of alcohols, -SH.
• Named by adding -thiol to alkane name.
• The -SH group is called mercapto.
• Complex with heavy metals: Hg, As, Au.
• More acidic than alcohols, react with
NaOH to form thiolate ion.
• Stinks! =>
 Thiol Synthesis
Use a large excess of sodium hydrosulfide
with unhindered alkyl halide to prevent
dialkylation to R-S-R.

_ _
H S R X R SH + X

=>
 Thiol Oxidation
• Easily oxidized to disulfides, an
important feature of protein structure.
Br2
R SH + HS R R S S R + 2 HBr
Zn, HCl

•Vigorous oxidation with KMnO4,

HNO3, or NaOCl, produces sulfonic acids.
O
HNO3
SH S OH
boil
O =>
 Biological Oxidation
• Catalyzed by ADH, alcohol dehydrogenase.
• Oxidizing agent is NAD+, nicotinamide
adenine dinucleotide.
• Ethanol oxidizes to acetaldehyde, then acetic
acid, a normal metabolite.
• Methanol oxidizes to formaldehyde, then
formic acid, more toxic than methanol.
• Ethylene glycol oxidizes to oxalic acid, toxic.
• Treatment for poisoning is excess ethanol.
=>
 Unique Reactions of Diols
• Pinacol rearrangement
• Periodic acid cleavage

=>
 Pinacol Rearrangement
• Pinacol: 2,3-dimethyl-2,3-butanediol
• Dehydration with sulfuric acid
CH3 CH3 CH3 CH3 CH3
+
H CH3
CH3 C C CH3 CH3 C C CH3 CH3 C C
CH3
OH OH OH OH OH
H
CH3 CH3 CH3
CH3
CH3 C C CH3 C C CH3 CH3 C C CH3
CH3
OH OH CH3 OH CH3

CH3
CH3 C C CH3 =>
O CH3
pinacolone
 Periodic Cleavage
of Glycols
Same products formed as from
ozonolysis of the corresponding alkene.
H CH3 CH3
HIO4 H
CH3 C C CH3 CH3 C C CH3
+
OH OH O O

OsO4 O3
H2O2 (CH3)2S

H CH3
C C =>
H3C CH3
 Oxidation States
• Reagents used:
CrO42- reduced to Cr2O3
KMnO4 reduced to MnO2
• Oxidation: loss of H2, gain of O, O2, or X2
• Reduction: gain of H2 or H-, loss of O, O2,
or X2
• Neither: gain or loss of H+, H2O, HX
=>