Alcohols contain an

1

Chapter 5- Alcohols, Phenols, Ethers, Their
Analogies
Alcohols contain an ____________________________
___________________________________ Phenols
contain an _____________________________________
_________________________ Ethers contain an
________________________________________________
_______________
2

Alcohols, phenols, and ethers can be thought of
as ____________________________________
3

4

The _____ atom in alcohols, phenols, and ethers
is sp3 hybridized. Two of the sp3 orbitals are
involved _________________________, and the
remaining two ____________________________________
_.
In water, the H-O-C bond angle is 104.5 due to
_________________________________________________
_ In alcohols, phenols, and ethers the
corresponding bond angles are closer to the
expected tetrahedral 109.5 due to the
_________________________________________________
__________________________________.
5

Constitutional isomerism in alcohols can arise
from _____________________________ ______________
_______________________________________
6

No isomers are possible for ___________________
__________, CH3OH, and ___________, CH3CH2OH.
Two isomers are possible for C3H8O
For alcohols having the formula C4H10O, two
different carbon skeletons are possible
The OH group can be placed in two unique
positions on each carbon skeleton
7

An alcohol can be viewed as an alkane,
cycloalkane, or alkene ___________________________
_______________________________________________ A
s a result, the molecular formula of an alcohol
still indicates _________________________________
If the CH ratio is the same as for an alkane,
CnH2n2, _______________________________. If the
CH ratio is the same as for a cycloalkane or
alkene, CnH2n, __________________________________
__________________________
8

Alcohols are classified as ______________________
__________________________
9

10

11

12

13

Simple alcohols are usually referred to by their
___________which consist of __________________
followed by a space and the word alcohol.
14

Alcohols are characterized by ___________
______________________forces and are
characterized by ________________________________
than those of hydrocarbons ____________________
_______
15

The strong secondary forces between alcohol
molecules arise _______________________
Although not shown in the above illustration,
each alcohol molecule is ________________________
________________________________________ The
____________and __________ temperatures of
alcohols compared to the corresponding
hydrocarbons is a direct result of
_________________________________________________
____
16

17

The difference in boiling points between
hydrocarbons and the corresponding alcohols
_________________________________________________
_____________ London forces are directly related
to ____________and the proportion of the total
molecular force due to __________________________
_________________________________________________
_______
18

Diols and triols have especially
_________compared to alkanes of similar size due
_________________________ HOCH2CH2OH BP
198C CH3CH2CH2OH BP 97C Alcohols containing 3
or fewer carbons are ____________________________
________________________
Alcohols containing 4 carbons are __________, 5
carbons ______________, and more than 5 carbons
are _____________________________ An alcohol
containing 5 or more carbons is soluble only if
it _______________________________
19

Alcohols are usually considered to be
_____________. Water solutions of alcohols have
a pH of _, the same __________________. Alcohols
resemble water in the fact that they
_________________________________________________
______________________
20

An alcohol can accept a_______(act as a ___) from
____ __________ such as sulfuric acid (H2SO4)
The equilibrium lies far to the left only about
0.1 of the alcohol molecules become protonated,
however, this small concentration is important in
the dehydration reactions of alcohols. The
acidity of alcohols is _________________in
reactions with NaOH or most other strong
bases. The acidity of alcohols is sufficient,
however, to allow them to ________________________
_________________________________________________
_
21

Alcohols can be dehydrated when
_________________________________. The reaction
is called an _____________________. An
___________ is lost from one carbon and an
_________from an adjacent carbon
22

All alcohols can be dehydrated if they contain
_________________________________________________
___ Methanol, for instance, cannot be dehydrated.
It contains _____________________________.
23

The dehydration of alcohols is the reverse of the
______________________________. LeChateliers
principle allows ________________________________
_________________________________________________
________________ When hydration is desired, a
large __________________________________________
When dehydration is desired, the reaction is run
at ______________________________________________
__________________________________________________
________________
24

Dehydration of secondary and tertiary alcohols
may follow a more complicated course than that
for primary alcohols. If the alcohol is
asymmetric, ______________________
In this case, 2-butene is the major product. The
more stable the alkene, _________________________
____________________________________
25

In the dehydration of 2-butanol previously shown,
the predominate 2-butene product formed is a
mixture of cis and trans isomers. The trans
isomer predominates because ______________________
_____________ Dehydration reactions occur during
physiological processes such as
____________________________.
26

The products from the oxidation of alcohols
depend upon reaction conditions Combustion
_________________________________________________
______(CO2). Selective (mild) oxidation
_________________________________________________
____.
27

The weakest bonds in an alcohol are ________and
the ___________________. These bonds only are
oxidized during _________________________________
_ Typical selective oxidizing agents are MnO4-
and Cr2O7-. Primary, secondary, and tertiary
alcohols respond differently to selective
oxidation Primary alcohols are oxidized in two
stages Stage 1 Simultaneous loss of
__________________ ________________from the OH
group and the adjacent C-H carbon producing a
____________and a resulting compound called
____________________________. Stage 2
___________attached to the carbonyl group of the
aldehyde to ____, producing a _____________.
28

The reaction does not stop at the aldehyde when
permanganate or dichromate are used as the
oxidizing agent. Aldehydes can be produced using
milder oxidizing agents. Secondary alcohols
Oxidation cannot proceed beyond the
_____________. These alcohols are oxidized to
__________________________
Tertiary alcohols Oxidation of the OH cannot
occur because ___________________________________
_________________________________.
29

30

Permanganate and dichromate can be used for
_________________________________________________
_________. Permanganate oxidation MnO4-
(_________ solution) is converted
________________________________ Dichromate
oxidation Cr2O72- (__________ solution) is
converted ______________________________ Uses and
limitations Primary and secondary alcohols are
distinguished from tertiary alcohols
_________________________________________________
_______________ Primary and secondary alcohols
are distinguished from ___________________________
__________, which do not undergo permanganate or
dichromate oxidations. Positive permanganate or
dichromate tests do not distinguish primary and
secondary alcohols from _________________________
_______, which are also oxidized by these
reagents.
31

32

Phenols contain an ______ bonded to one of the
sp2 carbon atoms of _______. The phenol family
includes the parent compound, _________, as well
as a wide variety ________________________________
_________________________________________.
33

34

Enols consist of an _____________________________
_________________________________.
Enols are usually ____________________ and are
encountered in __________________________.
35

The O-H bond in phenols is more polar than that
in alcohols because ______________________________
_________________________________________________
_______.
The greater polarity of this bond results in
stronger ________ bonding and correspondingly
higher __________________________________________
____________________________ Phenols are ______
acids but much more ________________.
The pH value of a 0.1 M aqueous solution of
phenol is about 5.
36

Phenol reacts completely with ________________
The equilibrium lies completely to the right. The
extent of the same reaction with an alcohol is
much less than 0.1. The higher _____ of phenols
compared to alcohols is due to the
electron-withdrawing effect of ___________________
_________________________________________________
______
The negative charge on the oxygen atom is
dispersed around the benzene ring rather than
________________, _____________________ as in the
alcohol system. This effect is called
____________________________.
37

Phenols do not undergo ______, because that would
form a ______within the benzene ring destroying
__ _______________________. The oxidation of
phenols is the basis of many _____________________
_________________________________________________
____________
38

Ethers contain an ____________bonded to two
________________. The carbon atoms can be either
________________________________. The common
nomenclature system uses the names of the groups
attached to _______, in __________________________
___________. For ethers containing
__________________, the IUPAC system is used. In
this case the ether is named as a member of some
other family, with the more complex group
determining the base name. The simpler group and
the ether oxygen to which it is attached are
treated as an alkoxy (RO) or aryloxy(ArO) group.
39

40

_____________________are used for cyclic ethers
Any ether is a constitutional isomer of
______________________________. For instance,
C2H6O
41

The boiling point of dimethyl ether is higher
than that of the corresponding alkane, propane,
because _________________________________________
______ This effect falls off rapidly with
________ alkane chain length. Diethyl ether has
the same boiling point as its corresponding
alkane, pentane. Ethers as a class have much ____
boiling points than alcohols due to
_________________________________________________
________ Ethers are _________ towards acids,
bases, and oxidizing agents and are often used
_________________________________________________
_______ Ethers, like alkanes, participate in
___________ and ____________________ reactions
only.
42

When a primary alcohol is dehydrated, it produces
an ___________________________
43

Intramolecular dehydration to form an alkene
competes with _________________ to form an
______________ ___________ is the major product
at 180 C ____________is the major product at
140 C ___________________do not form ethers when
heated with an acid catalyst. The attached
substituents prevent two molecules from
_____________________________________________ Thi
s effect is called ____________________.
44

Thiols, or mercaptans, are ______________________
______________________________________ The SH
group is called the mercapto, or sulfhydryl,
group. The IUPAC nomenclature system adds the
ending _______________ to the name of
_____________, but without dropping the final
e. Thiols have _________________________________
______________________________________
45

Thiols differ from alcohols
Thiols have considerably ___________than those
of alcohols, even though thiols have higher
molecular masses, because thiols
_________________________________________________
_________________ Thiols are ______but much
stronger than alcohols, because the ___ bond is
weaker than the ___ bond, a consequence of the
_______of sulfur compared with oxygen. However,
thiols are weaker acids than _____________.
Thiols are easily oxidized to _______________ by
many oxidizing agents Disulfides are named by
naming the R groups ______________________________
__________________________________________
46

Disulfides are easily reduced back to thiols by
many ________________ In the preceding
equations, the abbreviations (O) and (H)
indicate general conditions for
_______________and __________________,
respectively, without specification of the exact
oxidizing or reducing agent. Thiols react with
_________________________________________________
______________
47

The reactions to form disulfides and insoluble
heavy metal salts are of physiological
importance. Many ______ contain thiol groups and
disulfides critical to ___________________________
________________________________________________
Lead and mercury salts react with thiol groups,
altering ________________________________________
________ A common source of lead is from
_____________________________________________.
The use of _________ ______________also
introduces lead into the environment, however,
its use has been phased out. Mercury from
___________ and other sources enters the food
chain through fish from contaminated rivers,
lakes, and streams. Mercury has a physiological
effect _________________________________________
The aromas and flavors of garlic and onions are
due _____________________________________-
48

Chapter 13 Summary
Structural Relations of Alcohols, Phenols, and
Ethers Alcohols contain an ____________________
_______________________________________________
Phenols contain an ____________________________
______________________________________ Ethers,
like alcohols and phenols, contain an oxygen that
_________________________________________________
_______________________________ The oxygen of
an ether has _______ bonds to ___________________
____________________________
49

Chapter 13 Summary
Constitutional Isomerism in Alcohols
Constitutional isomerism in alcohols is due not
only to different carbon skeletons but also to
_________________________________________________
_______. The CH ratio for an alcohol is the
same as _________________________________________
_________________________________________________
_________
50

Chapter 13 Summary
Classifying and Naming Alcohols Alcohols are
1, 2, or 3 alcohols, depending on whether
_________________________________________________
In the IUPAC system, alcohols are named by
using the ________________________________________
_________ The base name is preceded by a
number indicating the position of ______________,
and the ending of the name is changed
________________________. Prefixes with
numbers are then added at the front to indicate
_________________________________________
Common names for simple alcohols are formed by
using the ________________________________________
_________________________________________________
_____
51

Chapter 13 Summary
Physical Properties of Alcohols Alcohols
participate in hydrogen bonding, which results in
_________________________________________________
_______________
Acidity and Basicity of Alcohols Alcohols are
very weak ___________________
52

Chapter 13 Summary
Dehydration of Alcohols to Alkenes
Intramolecular dehydration of an alcohol in the
presence of an acid catalyst produces
__________. When more than one alkene is
possible, the major product is ___________________
________ A competing reaction for
__________________, but not secondary and
tertiary alcohols, is intermolecular dehydration
to an ether. At 180C, the major product is
________ formed by intramolecular dehydration at
140C, the major product is ___________ formed by
intermolecular dehydration.
53

Chapter 13 Summary
Oxidation of Alcohols Primary and secondary
alcohols undergo ________ __________ by
permanganate (MnO4-) and dichromate (Cr2O72-)
ions. Primary alcohols are oxidized to
________, which are subsequently oxidized to
_____________________. Secondary alcohols are
oxidized to ___________with ______________________
__________ Tertiary alcohols are
______________________. Permanganate and
dichromate form the basis of simple chemical
diagnostic tests for ____________________________
___________________
54

Chapter 13 Summary
Phenols Substituted phenols are named by the
IUPAC system as derivatives of the parent
compound phenol. Phenols are _____________than
alcohols and have ________________________________
___ in water. Phenols are weak ________ but
much stronger than ___________________________.
Phenols undergo oxidation but ________________
55

Chapter 13 Summary
Ethers Ethers are isomeric with________________
. The names of ethers containing simple groups
consist of the names of __________________________
_______________________________________________
Ethers have considerably lower _________than
those of alcohols but are almost ___________as
alcohols in water. Ethers are unreactive
toward __________________________________________
_______
56

Chapter 13 Summary
Thiols Thiols contain the _____________________
_. They have lower _____________than those of
alcohols. Thiols are stronger ______ than
alcohols (but ________ than phenols), form
______________with heavy metal ions, and are
_______________ to disulfides. Disulfides can
be reduced _________________
57

Chapter 13 Summary Of Reactions
58

Chapter 13 Summary Of Reactions-cont.
59

Chapter 13 Summary Of Reactions-cont.