Beruflich Dokumente
Kultur Dokumente
CHEM 2353
Fundamentals of Organic Chemistry
Aldehydes and
Chapter
Chapter
4 Ketones
2
Chapter 4 Notes
C C
R H R R'
3
aldehyde ketone
C C
R R' R H
ketone aldehyde
O O O O
C H C R' C C
R O R O R O R'
carboxylic acid ester acid anhydride
C H
R N
amide
H 4
Chapter 4 Notes
Nomenclature of
Aldehydes and Ketones
C C C
H H CH3 CH3 CH3 H
Methanal 2-Propanone Ethanal
(Formaldehyde) (Acetone) (Acetaldehyde)
Gas at room temperature; 1 billion pounds used annually Product of oxidation of ethanol in
35-40% solution in water, called in U.S.; good solvent for most the liver; consuming large quantities
formalin, used to preserve organic compounds, and is of ethanol causes acetaldehyde to
biological specimens, sterilize also soluble in water; solvent build up in bloodstream faster than
instruments, and embalm for coatings such as fingernail it can be consumed in the liver to
cadavers; present in wood smoke, polish and enamel paints, etc. make other products, leading to
and helps to preserve smoked nausea, sweating, reduced blood
meats by killing bacteria. pressure, etc.
O
C
O
H
C
CH3 CH2CH3
2-Butanone
Benzaldehyde (Methyl ethyl ketone, MEK)
Causes the odor of almonds Common industrial solvent
and cherries, and is also found 6
in apricots and peaches.
Chapter 4 Notes
Nomenclature of Aldehydes
• Select the longest carbon chain containing the
carbonyl carbon.
• The -e ending of the parent alkane name is replaced
by the suffix -al.
• The carbonyl carbon is always numbered “1.” (It is
not necessary to include the number in the name.)
• Name the substituents attached to the chain in the
usual way.
O
O
C H
CH3CH2CH2 C H
CH3 CH2 CH CH2 CH3
7
Nomenclature of Ketones
• Select the longest carbon chain containing the
carbonyl carbon.
• The -e ending of the parent alkane name is replaced
by the suffix -one.
• Number the chain starting with the end closest to the
ketone group (i.e., the carbonyl carbon should have
the lowest possible number).
• Name the substituents attached to the chain in the
usual way.
O
O C CH3
Br O O CH3
CH3
CH3 O O
CH3 CH2CH3
10
Chapter 4 Notes
O O
CH3 O O
CH3 C C CH3
O O
C CH3 C
H H
Br CH3
11
– 2,4,6-trimethylheptanal
– 3-ethylcyclopentanone
– 4-chloro-2-phenylpentanal
– para-nitrobenzaldehyde
Physical Properties of
Aldehydes and Ketones
13
C
δ+
δ+ δ− δ+ δ− δ+ δ−
C O C O C O
14
Chapter 4 Notes
+ δ− +
δ O δ
H H
δ−O Oδ
−
C C+
R δ+ R' R δ R'
16
Chapter 4 Notes
18
Chapter 4 Notes
Some Important
Aldehydes and Ketones
19
H C OH C O
HO C H HO C H
H C OH H C OH
H C OH H C OH
CH2OH CH2OH
Glucose Fructose
One of the most important of the Another important carbohydrate; a
carbohydrates, which are polyhydroxy major component of corn syrup; found
aldehydes and ketones; the metabolism in honey, syrups, and preserves; in
of glucose is a major source of energy combination with glucose it forms the
for living organisms disaccharide sucrose.
20
Chapter 4 Notes
Dihydroxyacetone
2-Heptanone
Active ingredient in "bronzers" that
Found in oil of clove; also present in
provide fake suntan coloration; reacts
the odor of many fruits and dairy
with dead, outer skin cells to produce
products, and is also responsible for
a darker color; fades as the dead skin
the odor of blue cheese.
cells slough off.
O
O
CH3
CH3O
H
HO Zingerone
HO The pungent, hot component of ginger
Vanillin
flavoring in Vanilla beans
21
CH3 CH3
CH3
Acetophenone
CH3 Used in perfurmery, and as an organic
O solvent; also used in the synthesis of
some pharmeceuticals
Camphor
Isolated by steam distillation from the camphor tree CH3
of China and Japan. Camphor is a counter-irritant
(produces a superficial inflammation to reduce deeper
inflammation) and antipruritic (anti-itching)
medication; it appears to selectively stimulate cold
sensors. It also stimulates the respiratory systems and
inspires deep breathing, but can cause convulsions
and respiratory collapse in larger doses. O
CH3CHCH3
Menthone 22
Chapter 4 Notes
O
O
H
H
Hyacinthin
Cinnamaldehyde
Found in hyacinth
The flavoring in oil of cinnamon; obtained by
steam distillation from the bark of the
cinnamon tree; has a carminative action
(releases hydrogen sulfide, methane, and
hydrogen from the intestine) CH3
2-Methylundecanal
H One of the first of the synthetic H
perfumes, introduced by Coco
Chanel in 1921 as Chanel No. 5
O
Citronellal
Found in citronella oil;
23
used as an insect repellant
HO
H
O Acrolein
3-(para-Hydroxyphenyl)- Produced from the breakdown of
2-butanone triglycerides in meat during cooking; the
Responsible for the odor acrid smell of this compound is obvious
of ripe raspberries. during barbeques. It also contributes to
the taste of caramel, where it is produced
by decomposing sucrose
O Vitamin K1
A fat soluble vitamin btained from green leafy vegetables, cabbage, cauliflower, kale,
spinach, pork liver; also made by intestinal bacteria. Essential for blood clotting. 24
Chapter 4 Notes
O
O O
Ionone
Responsible for the odor of
Butanedione
freshly picked raspberries, A volatile yellow liquid compound
violets (and the extract, oil of
with the odor of cheese; gives butter
violets), and sun-dried hay.
its characteristic flavor. It also
contributes to the odor of armpits and
O O unwashed feet by the action of bacteria
OH which ferment the compounds in
perspiration.
Humulone
HO OH A component of hop resin, a
viscous yellow material
obtained from the blossoms
of the female hop plant
(Humulus lupulus); it adds to
the bitter taste of some beers.
25
CH3
Steroid nucleus
O
Testosterone
O A male sex hormone
CH3 H
C OH C
CH3 CH3 C
CH3
O O
Progesterone Norethynodrel
A female sex hormone Active ingredient in birth-control pills 26
Chapter 4 Notes
Reactions of
Aldehydes and Ketones
27
C
H [O]
CH3 O
[O]
CH3CHCH2 C H
O
[O]
CH3 C CH3
29
CH3 OH
[O]
CH3CHCH2 CH CH3
OH
[O]
30
Chapter 4 Notes
R C R + 2 Ag(NH3)2(OH)2 NR
ketone Tollen's reagent 31
C
H Tollen's
reagent
Tollen's
Unknown reagent silver ppt 32
Chapter 4 Notes
O OH
Pt
R C R' + H2 R C R'
a ketone
H
a secondary alcohol 33
O
Pt
CH3 C CH3 + H2
Pt
+ H2
34
Chapter 4 Notes
O OH OCH3
+ +
H H
CH3 C H CH3 C H CH3 C H
CH3OH CH3OH
OCH3 OCH3
35
O OCH3
OH OCH3
hemiacetal carbon acetal carbon
CH3 C H CH3 C H
OCH3 OCH3
a hemiacetal an acetal
OH OCH3
hemiketal carbon ketal carbon
OCH3 OCH3
a hemiketal a ketal
37
CH3
CH3O OCH3
OH
O O
OCH3
38
Chapter 4 Notes
OH OCH3 O OCH3
O O
CH3 CH2CH3 H
O H O OCH3 O CH2CH3
OH CH2CH2CH3 CH2CH2CH3
39
CH3 O
H+
CH3 CH C CH3 + CH3CH2OH
40
Chapter 4 Notes
H2C CH2
C
H2
H OH H OCH3
O H+ O
+ CH3OH + H2O
41
O H
C1
6CH2OH
H C2 OH C5 O
H OH
H C3 OH H+ H
C4 OH H C1
HO C4 H
HO C3 C2 H
H C5 OH
H OH
6 CH2OH β-D-glucose
D-glucose
42
Chapter 4 Notes
OCH3
OCH2CH3
H+
CH3 C CH2CH2CH3 + H2O
OCH2CH3
O OH
H+
+ H2O
CH3 44
Chapter 4 Notes
R C H H+ R C H H+ R C H
aldehyde ROH ROH
OR OR
hemiacetal acetal
6. Addition of an Alcohol to a Ketone to form a Ketal
O OH OR
+ +
R C R H R C R H R C R
ketone ROH ROH
OR OR
hemiketal ketal
7. Hydrolysis of an Acetal to give an Aldehyde
OR O
+
H
R C H + H2O R C H + 2 ROH
aldehyde alcohol
OR
acetal
8. Hydrolysis of a Ketal to give a Ketone
OR O
+
H
R C R + H2O R C R + 2 ROH
ketone alcohol
OR
ketal 46