Академический Документы
Профессиональный Документы
Культура Документы
Chapter 5
5.1 Structure and Bonding
5.2 Naming Aldehydes and Ketones
5.3 Some Important Aldehydes and
Ketones
5.4 Physical Properties of Aldehydes and
Ketones
5.5 Chiral Molecules
5.6 Oxation and Reduction
5.7 Addition Reactions
Introduction
o carbonyl compounds : compounds with
C
carbonyl group
O
aldehyde ketone
Ester
Aldehyde
Ketone Amide
Carboxylic Acid
Aldehydes and Ketones
Only differ by location of carbonyl
Aldehydes RCHO
Ketones RC(=O)R’
A carbonyl group
• In an aldehyde
is attached to
at least one H
atom.
• In a ketone is
attached to
two carbon
groups.
5
Structure
• The functional group of an aldehyde is a
carbonyl group bonded to a hydrogen atom
– in methanal, the simplest aldehyde, the
carbonyl group is bonded to two hydrogens
– in other aldehydes, it is bonded to one
hydrogen and one carbon
• The functional group of a ketone is a carbonyl
group bonded to two carbons
O O O
HCH CH3 CH CH3 CCH3
Meth anal Ethanal Prop anone
(Formaldehyde) (Acetaldeh yd e) (Aceton e)
Naming Aldehydes and Ketones
Naming Aldehydes
9
Example
Aldehydes in Flavorings
• Several naturally occurring
aldehydes are used as flavorings for
O
foods and fragrances.
C H
Benzaldehyde
(almonds)
O
Copyright © 2007 by Pearson Education, Inc.
CH=CH C H Publishing as Benjamin Cummings
Cinnamaldehyde (cinnamon)
12
Ketones in Common Use
Butter
flavoring
16
Table 8.1: IUPAC nomenclature and common names for aldehyde and ketone compounds.
nomenclature
Aldehyde HCHO Methanal Formaldehyde
18
Solution
19
20
Solution
21
Learning Check
22
Solution
23
Learning Check
Name the following compounds.
O
|| O
A. CH3—CH2—CH2—C—CH3 B.
CH3 O
| ||
C. CH3—C—CH2—C—H
| 24
CH3
Solution
25
Learning Check
26
Solution
CH3 O
│ ║
A. 4-methylpentanal CH3─CH─CH2─CH2─C─H
Cl O
│ ║
B. 2,3-dichloropropanal Cl─CH2─CH─C─H
CH3 O
│ ║
C. 3-methyl-2-butanone CH3─CH─C─CH3
27
Physical Properties
30
Boiling Points
Aldehydes and ketones have
• Polar carbonyl groups (C=O).
+ -
C=O
• Attractions between polar groups.
+ - + -
C=O C=O
• Higher boiling points than alkanes and ethers of
similar mass.
• Lower boiling points than alcohols of similar mass.
31
Comparison of Boiling Points
58
C. CH3—CH2—OH or CH3—O—CH3
33
Solution
A. CH3—CH2—OH
O
B.
C. CH3—CH2—OH
34
Solubility in Water
The electronegative O atom of the
carbonyl group in aldehydes and
ketones forms hydrogen bonds
with water.
35
Learning Check
Indicate if each is soluble or insoluble in water.
A. CH3—CH2—CH3
B. CH3—CH2—OH
O
||
C. CH3—CH2—CH2—C—H
O
||
D. CH3—C—CH3
36
Solution
A. CH3—CH2—CH3 insoluble
B. CH3—CH2—OH soluble
O
||
C. CH3—CH2—CH2—C—H soluble
O
||
D. CH3—C—CH3 soluble
37
Synthesis of Aldehydes and
ketones
Preparation of Aldehydes
Oxidation of primary alcohol
Hydration of alkynes
ALDEHYDES
Ozonolysis of alkenes
Example : H
H
PCC H3 C C O
H3 C C OH [O]
H ethanal
ethanol
ii) Hydration of Alkynes
General equation :
H2SO4 H OH enol
R C C R' + H2O R C C R'
HgSO4
alkyne
tautomerism
O
R CH2 C R'
aldehyde
Keto- Enol Tautomerism
O OH
|| |
CH3-C-CH3 CH3-C = CH2
acetone acetone
(keto form) (enol form)
iii) Ozonolysis of Alkenes
General equation :
H H H H
i) O3
R C C R' R C O + O C R'
ii) Zn/H3O+
alkene aldehyde
Example 1 :
H H H
i) O3
H3C C C CH2 CH3 H3 C C O +
ii) Zn/
2-pentene H 3 O+ ethanal H propanal
O C CH2 CH3
iii) Ozonolysis of Alkenes
Example 2 :
CH3
i) O3 O O
C CH2 CH CH2 C
ii) Zn/ H
H 3 O+ CH3 H
4-methylcyclopentene 3-methylpentandial
iv) Hydrolysis of Gem Halides
To produce aromatic aldehyde
Example :
H
X X H O
CH3 C C
hv or H 2O
+ 2X2
hv or H 2O
+ 2Cl2
Br Gem halides
Br Br
4-bromotoulene
4-bromobenzaldehyde
Preparation of Ketones
Oxidation of secondary alcohol
Hydration of alkynes
KETONES
Ozonolysis of alkenes
Friedel-Crafts acylation
i) Oxidation of 20 Alcohol
General equation :
OH O
K2Cr2O7
R C R' [O] R C R'
H+
H ketone
20 alcohol
•Secondary alcohols are oxidised to ketones using oxidation agent such as PCC,
chromic acid or potassium dichromate and sulfuric acid.
Example :
OH O
K2Cr2O7
H3C C CH3 [O] H3 C C CH3
H+
H propanone
propanol
ii) Hydration of Alkynes
Example :
OH H
H2SO4
H3C C C H + H2O H3C C C H enol
HgSO4
propyne
tautomerism
O H
H3 C C C H
H
propanone
iii) Ozonolysis of Alkenes
Example :
CH2 CH3 O
i) O3
H3C C C CH2 CH3 H3C C CH2 CH3
ii) Zn/
H H 3 O+ 2-butanone
3-methyl-3-hexene
+
O C CH2 CH3
H
propanal
iv) Friedel-Crafts Acylation
To produce aromatic ketone
Example :
O
H3 C C
O
AlCl3
+ H3C C Cl
Chloroethane
Benzene Aromatic
Ketone
Reaction of Aldehydes and
Ketones
K2Cr2O7
H2SO4, H2O
Oxidation
• Example
O O
|| ||
CH3(CH2)4 - C-H + K2Cr2O7 H+ CH3(CH2)4 – C - OH
hexanal hexanoic acid
Reduction
H H
| H+ |
R- C=O R- C-OH
aldehyde alcohol 10
R’ R’
| H+ |
R- C=O R-C-OH
ketone alcohol 20
• Example
H
| LiAlH4
CH3- C=O CH3CH2OH
ethanal H+ ethanol
(alcohol 1o)
• Tollens’ reagent,
which contains Ag+,
oxidizes aldehydes,
but not ketones.
• Ag+ is reduced to
metallic Ag, which
appears as a
“mirror” in the test
tube. Copyright © 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings
58
Benedict’s Test
59
Learning Check
Write the structure and name of the oxidized product when each is mixed with Tollens’
reagent.
1. butanal
2. acetaldehyde
60
Solution
61
Addition Reactions
| + - + - |
—C=O + X—Y —C—O—X
|
Y
62
Acetal Formation
• Alcohols add to the carbonyl group of aldehydes and ketones.
• The addition of two alcohols forms acetals.
63
Hemiacetal Formation
• The addition of one alcohol to an aldehyde or ketone forms an
intermediate called a hemiacetal.
• Usually, hemiacetals are unstable and difficult to isolate.
64
Cyclic Hemiacetals
A stable cyclic hemiacetal forms when the C=O group and the —
OH are both part of a five- or six-atom carbon compound.
65
Learning Check
Identify each as a 1) hemiacetal or 2) acetal.
O—CH3
|
A. CH3—CH2—C—H
|
OH
O—CH2CH3
|
B. CH3—CH2—C—CH2—CH3
|
O—CH2CH3
66
Solution
O—CH3
|
A. CH3—CH2—C—H 1) hemiacetal
|
OH
O—CH2CH3
|
B. CH3—CH2—C—CH2—CH3 2) acetal
|
O—CH2CH3
67
Learning Check
Draw the structure of the acetal formed by
adding CH3OH to butanal.
68
Solution
69
Chiral Molecules
72
Chiral Compounds
Chiral compounds
• Have the same number of atoms
arranged differently in space.
• Have one or more chiral carbon
atoms bonded to four different
groups.
• Are mirror images like your
hands. Try to superimpose your
thumbs, palms, back of hands,
and little fingers. Copyright © 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings
73
Mirror Images
The mirror images of
• Chiral compounds cannot be superimposed.
• Two compounds of bromochloroiodomethane can align the H and I
atoms, which places the Cl and Br atoms on opposite sides.
76
Enantiomers
Have same
• mp,
• bp,
• same chemistry
– Except: reaction with other chiral
molecules
77
Smell:
R-(-)-carvone S-(+)-carvone
Spearmint Caraway
(Dill)
(Manderine Orange Peel)
78
Learning Check
Identify each as a chiral or achiral
compound.
Cl Cl Cl
CH2CH3 H Br
A B C
79
Solution
Identify each as a chiral or achiral
compound.
Cl Cl Cl
CH2CH3 H Br
A B C
80
Fischer Projections
A Fischer projection
• Is a 2-dimensional representation of a 3-dimensional molecule.
• Places the most oxidized group at the top.
• Uses vertical lines in place of dashes for bonds that go back.
• Uses horizontal lines in place of wedges for bonds that come
forward.
81
Drawing Fischer Projections
82
D and L Notations
• By convention, the letter L is assigned to
the structure with the —OH on the left.
• The letter D is assigned to the structure
with the —OH on the right.
CH2OH CH2OH
Br Br
Cl Cl
B. H C CH3 and CH3 C H
H H
84
Solution
Indicate whether each pair is a mirror image that
cannot be superimposed
Br Br
Cl Cl
No
B. H C CH3 and CH3 C H
H H
85