Chemistry 1102

Charlie Bond
MCS Rm 4.16/4.27
Charles.Bond@uwa.edu.au
What is Organic Chemistry?
Organic Reactions I II
Alkanes (Ch 21)
Conformational Analysis (Ch 21)
Stereochemistry I II III (Ch 22)
Alkyl Halides I II (Ch 24)
Alcohols and Ether I II (Ch 24)

Oxidation of alcohols
Primary alcohols can be oxidised to aldehydes or carboxylic acids
[O] = 1 oxidising equivalent, a generic way of describing an oxidant

[O]

Secondary alcohols can be oxidised to ketones:

[O]

[O]

Tertiary alcohols cannot be simply oxidised:

Oxidation of Alcohols
Oxidation of a 1 alcohol gives an aldehyde or a
carboxylic acid, depending on the oxidizing agent and
experimental conditions
the most common oxidizing agent is chromic acid
CrO3
+ H2O
Chromium(VI)
oxide

H2SO4

H2CrO4

Chromicacid

Eg chromic acid oxidation of 1-octanol gives octanoic

acid
CH3(CH2)6CH2OH
1Octanol

CrO3
H2SO4 , H2O

O
CH3(CH2)6CH
Octanal
(notisolated)

O
CH3(CH2)6COH
Octanoicacid
3

Oxidation of Alcohols
to oxidize a 1 alcohol to an aldehyde, use PCC
CrO3 + HCl +

Pyridine

CrO3Cl-

N+
H
Pyridiniumchlorochromate
(PCC)

PCC oxidation of geraniol gives geranial

Geraniol

PCC
OH CH Cl
2 2

Geranial

Tertiary alcohols are not oxidized by either of these

reagents; they are resistant to oxidation

O
H

Demonstrations

Ethers - Structure
The functional group of an ether is an
oxygen atom bonded to two carbon atoms
oxygen is sp3 hybridized with bond angles of
approximately 109.5
in dimethyl ether, the C-O-C bond angle is
110.3
H
H

C
H

H
6

Ethers - Nomenclature
IUPAC
the longest carbon chain is the parent alkane
name the -OR group as an alkoxy substituent
Common names:
name the groups bonded to oxygen followed by the
word ether
O
Et2O
Ethoxyethane
(Diethylether)
CH3
CH3OCCH3
CH3

2Methoxy2methylpropane
(methyltertbutylether,MTBE)

OH
OEt

trans2Ethoxycyclohexanol
7

Ethers - Physical Properties

Ethers are polar molecules
each C-O bond is polar covalent
however, only weak attractive forces exist
between ether molecules

Ethers - Physical Properties

boiling points are lower than those of alcohols
Boiling
Molecular Point
Weight
(C)
46
78
24
46

StructuralFormula
CH3CH2 OH
CH3OCH3

Name
ethanol
dimethylether

CH3CH2 CH2CH2OH

1butanol

74

117

CH3CH2 OCH2CH3

diethylether

74

35

88
90
88
90

138
230
71
84

CH3CH2 CH2CH2CH2OH 1pentanol

HOCH2CH2CH2CH2 OH 1,4butanediol
CH3CH2 CH2CH2OCH3 butylmethylether
CH3OCH2CH2OCH3
ethyleneglycol
dimethylether

Solubility
inWater
infinite
7.8g/100g
7.4g/100g
8g/100g
2.3g/100g
infinite
slight
infinite
9

Ethers - Physical Properties

ethers are hydrogen bond acceptors
How many H-bonds can they accept?

10

Reactions of Ethers
Ethers resemble hydrocarbons in their resistance to
chemical reaction
they do not react with strong oxidizing agents such as
chromic acid, H2CrO4
they are not affected by most acids and bases at
moderate temperatures
Because of their good solvent properties and general
inertness to chemical reaction, ethers are excellent
solvents in which to carry out organic reactions

11

Williamson Synthesis of Ethers

This method of synthesising ethers brings together two parts of alkyl
halide and alcohol chemistry:
the first step is the formation of an alkoxide from an alcohol:

the second step involves nucleophilic substitution on an alky

halide where the alkoxide acts as the nucleophile:

12

Thiols - Structure

The functional group of a thiol is an -SH

(sulfhydryl) group bonded to a tetrahedral
carbon

13

Thiols - Nomenclature
IUPAC names:
the parent chain is the longest chain containing the
-SH group
add -thiol to the name of the parent chain
Common names:
name the alkyl group bonded to sulfur followed by the
word mercaptan
alternatively, indicate the -SH by the prefix mercapto
SH

SH

Ethanethiol
2Methyl1propanethiol
(Ethylmercaptan)
(Isobutylmercaptan)

OH
HS
2Mercaptoethanol
14

Thiols - Physical Properties

Low-molecular-weight thiols have a
STENCH
Presentinthe
scentofskunks:

CH3CH=CHCH2 SH
2Butene1thiol

CH3
CH3CHCH2CH2SH
3Methyl1butanethiol
(Isobutylmercaptan)

CH3
SH
Naturalgas
CH3 -C-SH
CH3 -CH-CH3
odorants:
CH3
2Methyl2propanethiol
2Propanethiol
(tertButylmercaptan) (Isopropylmercaptan)
15

Thiols - Physical Properties

The difference in electronegativity
between S and H is 2.5 - 2.1 = 0.4
Because of their low polarity, thiols
show little association by hydrogen bonding
have lower boiling points and are less soluble
in water than alcohols of comparable MW
Thiol

BoilingPoint
(C)

BoilingPoint
Alcohol
(C)

methanethiol

methanol

65

ethanethiol
1butanethiol

35
98

ethanol
1butanol

78
117

16

Acidity of Thiols
Thiols are stronger acids than alcohols
-

CH3CH2OH + H2 O

CH3CH2O + H3 O

pKa =15.9

CH3CH2SH + H2 O

+
CH3CH2S + H3 O

pKa =8.5

Thiols react with strong bases to form

salts
+

CH3CH2SH + Na OH
pKa8.5
Stronger
Stronger
acid
base

CH3CH2S Na
Weaker
base

+ H2O
pKa 15.7
Weaker
acid

17

Oxidation of Thiols
thiols are oxidized by a variety of oxidizing
agents, including O2, to disulfides
disulfides, in turn, are easily reduced to
thiols by several reagents
2HOCH2 CH2 SH
Athiol

oxidation
reduction

HOCH2 CH2S-SCH2 CH2 OH

Adisulfide

this easy interconversion between thiols and

disulfides is very important in protein
chemistry

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