Announcements & Agenda (04/04/07)
Will start with quiz today
Review session today @ 3pm (same place)
Today
 Amides (13.5)
 Sugars! Section 14.1-14.3
Carbohydrates
Monosaccharides
Cyclic Monosaccharides (?)
1
Last Time: Hydrolysis of Esters
• an ester reacts with water to produce a
carboxylic acid and an alcohol.
• an acid catalyst is required.
O

H+
H—C—O—CH2—CH3 + H2O
O

H—C—OH
+ H—O—CH2—CH3
Base Hydroylsis forms an alcohol plus the salt of a
carboxylic acid!
2
What acid and alcohol make the
following ester?
O
H 3C
0%
1.
2.
3.
4.
0%
0%
0%
1
C
2
3
4
O
C
H2
C
H2
CH3
Ethanol (2C) and acetic acid (2C)
Propanol (3C) & acetic acid (2C)
Ethanol (2C) & propionic acid (3C)
Methanol (1C) & propionic acid (3C)
5
3
Last Time: Base Hydrolysis of
Triglycerides Make Soaps
4
Last Time: Amines (Derivatives of NH3)
Typically 3 kinds:
• primary (1°) amines: 1 carbon group is bonded to N
• secondary (2°) amines: 2 carbon groups bonded to N
• tertiary (3°) amines: 3 carbon groups bonded to N.
Can H-bond like alcohols, although N is not as polar
• decent BPs & solubility in water
Act as weak bases:
CH3—NH2 + H2O
CH3—NH3+ + OH–
Useful properties of amine salts:
• solids at RT, very soluble in body fluids (ideal for drug
molecules, and salts don’t stink 
5
Last Time: Alkaloids
• physiologically active nitrogen-containing
compounds.
• often addictive.
N
CH 3
nicotine
6
Morphine and Codeine
• alkaloids.
• obtained from the
oriental poppy plant.
• used as painkillers.
• modified to make
heroin.
7
Chocolate
Chocolate is found in
cocoa beans
O
H
CH3
N
N
O
N
N
CH3
8
Last Time: Amides (13.5) made from…
Amine + Carboxylic Acid
Amides are produced
• by reacting a carboxylic acid with ammonia
or an amine (1° or 2°).
• using heat.
O

Heat
CH3—C—OH + NH3
O

CH3—C—NH2 + H2O
O
O

Heat

CH3—C—OH + CH3—NH2
CH3—C—NH—CH3 + H2O
9
Some Amides in Health and Medicine
10
Physical Properties of Amides
SIMILAR TO AMINES…
• primary (−NH2) or secondary (−NH−) amides
form hydrogen bonds.
• primary have higher mp’s than secondary.
•
tertiary (no H on N) do not form hydrogen bonds &
have lower melting points.
• all form hydrogen bonds with water.
• with 1-5 carbon atoms are soluble in water.
11
Hydrolysis of Amides
IMPORTANT TO KNOW
Amides undergo
• Acid hydrolysis to produce a carboxylic
acid and an ammonium salt.
• Base hydrolysis to produce the salt of a
carboxylic acid and an amine or ammonia.
• REACTIONS LOOK SIMILAR TO THOSE
OF ESTERS!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!
12
Hydrolysis Reactions
acid hydrolysis
O
||
CH3—C—NH2
O
||
CH3—C—OH + NH4+Cl–
HCl + H2O
NaOH
O
||
CH3—C—O– Na+ + NH3
base hydrolysis
13
Ch 14 Carbohydrates
• a major source of
energy from our diet
• composed of C, H, & O
• also known as
saccharides, which
means “sugars.”
14
Practice Problems (Ch 14)
14.05, 14.07, 14.09, 14.13, 14.15,
14.19, 14.21, 14.23, 14.25, 14.27,
14.29, 14.31, 14.33, 14.35, 14.37,
14.39, 14.41, 14.47, 14.49, 14.51,
14.53, 14.57, 14.59
15
Carbohydrates
• produced by
photosynthesis in plants
• Example: glucose
synthesized in plants
from CO2, H2O, and
energy from the sun.
• are oxidized in living
cells to produce CO2,
H2O, and energy.
16
Types of Carbohydrates
• Monosaccharides: simplest carbohydrates.
• Disaccharides: consist of two monosaccharides.
• Polysaccharides: contain many monosaccharides.
17
Monosaccharides
• typically 3-6 carbon atoms
• have a C=O group (aldehyde or ketone)
•
•
aldoses
ketoses
• several hydroxyl groups
18
Aldoses
• monosaccharides with an
aldehyde group…
• …and many hydroxyl
groups.
triose
(3C atoms)
tetrose (4C atoms)
pentose (5C atoms)
hexose (6C atoms)
O
║
C─H aldose
│
H─ C─OH
│
H─ C─OH
│
CH2OH
Erythose
19
Ketoses
CH2OH
• monosaccharides with a
│
ketone group…
C=O
ketose
• …and many hydroxyl
│
groups.
H─ C─OH
│
H─ C─OH
│
H─C─OH
│
Fructose, a ketohexose
CH2OH
20
Fischer Projections
• also used to represent carbohydrates.
• places the most oxidized group at the top.
• shows chiral carbons as the intersection of
vertical and horizontal lines.
21
D & L Notations: Know This Now…
In a Fischer projection, the −OH group on the
• chiral carbon farthest from the carbonyl group
determines an L or D isomer.
• left = L for the L-form.
• right = D for the D-form. (MOST COMMON IN
NATURE!)
22
Learning Check
Identify each as the D or L isomer.
A.
B.
C.
CH2OH
O
C H
HO
H
HO
H
H
HO
H
HO
CH2OH
L
__-Ribose
O
O
C H
HO
H
OH
H
OH
H
H
OH
CH2OH
L Threose
__-
CH2OH
D Fructose
__23
D-Glucose
• found in fruits, corn
syrup, and honey
• an aldohexose with
the formula C6H12O6
• known as blood
sugar in the body
• the monosaccharide
in polymers of
starch, cellulose,
and glycogen
24
Blood Glucose Level
In the body,
• normal blood: [glucose] = 70-90 mg/dL.
• a glucose tolerance test measures blood
glucose for several hours after ingesting
glucose.
25
D-Fructose
• is a ketohexose
C6H12O6
• is the sweetest
carbohydrate
• found in fruit
juices and honey
• converts to
glucose in the
body
CH2OH
C O
HO C H
H C OH
H C OH
CH2OH
D-Fructose
26
D-Galactose
• is an aldohexose
C6H12O6.
• not found free in nature.
• is obtained from lactose,
a disaccharide.
• has a similar structure to
glucose except for the
–OH on C4
Which C is C4???
O
C H
H C OH
HO C H
HO C H
H C OH
CH2OH
D-Galactose
27
Cyclic Structures (14.3)
• prevalent form of monosaccharides with 5
or 6 carbon atoms
O
O
• form when the hydroxyl group on C-5
reacts with the aldehyde group or ketone
group
•
Orgo-Chem reaction not previously mentioned:
“C=O” + ROH → hemiacetal
28
Drawing Cyclic Structures: Practice!
Example: Glucose
STEP 1 Number the carbon chain and turn
clockwise to form a linear open chain.
H O
C
1
H 2 C OH
HO 3 C H
H 4 C OH
H
5C
OH
H
H OH H
O
HOCH2 C C C C C
6
5
4
3
2
1
H
OH OH H OH
6 CH OH
2
29
Cyclic Structure for Glucose
STEP 2 Fold into a hexagon.
• Bond the C5 –O– to C1.
• Place the C6 group above
the ring.
• Write the –OH groups on C2
& C4 below the ring (These
are the C atoms that pointed
down from Step 1).
• Write the –OH group on C3
above the ring.
• Write a new –OH on C1.
CH2OH
6
5
O
4
OH
1
OH
3
2
OH
OH
30
Cyclic Structure for Glucose
STEP 3 Write the new –OH on C1
• down for the  form.
• up for the  form.
CH2OH
O
OH
OH
O
OH
OH
-D-Glucose

CH2OH

OH
OH
OH
OH
-D-Glucose
31
Summary of the Formation of
Cyclic Glucose
32
Mutarotation
• cyclic structures open and close.
• -D-glucose converts to β-D-glucose & vice versa.
• at any time, only a small amount of open chain forms.
CH2OH
CH2OH
O
OH
H
O
OH
OH
OH
OH
-D-glucose
(36%)
CH2OH
O
O
C
OH
H
OH
D-glucose (open)
(trace)
OH
OH
OH
OH
β-D-glucose
(64%) 33
Cyclic Structure of Fructose
• is a ketohexose.
• reacts the -OH on C-5 with the C=O on C-2
CH2OH
C O
CH2OH
HO C H
CH2OH
OH
H C OH
H C OH
CH2OH
O
O
OH
OH
OH
CH2OH
OH
OH
α-D-fructose
-D-fructose
CH2OH
D-fructose
34