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AnnouncementsAnnouncements & Agenda& Agenda (04/04/07)(04/04/07)

Will start with quiz todayWill start with quiz today

Review session today @ 3pm (same place)Review session today @ 3pm (same place)

TodayToday Amides (13.5)Amides (13.5) Sugars! Section 14.1-14.3Sugars! Section 14.1-14.3

CarbohydratesCarbohydrates

MonosaccharidesMonosaccharides

Cyclic Monosaccharides (?)Cyclic Monosaccharides (?)

22

• an ester reacts with water to produce a an ester reacts with water to produce a carboxylic acid and an alcohol.carboxylic acid and an alcohol.

• an acid catalyst is required. an acid catalyst is required. OO

HH++

HH——CC——OO——CHCH22——CHCH3 3 ++ HH22OO

OO HH——CC——OHOH + + HH——OO——CHCH22——CHCH33

Last Time: Last Time: HydrolysisHydrolysis of Esters of Esters

Base Hydroylsis forms an alcohol plus the salt of a Base Hydroylsis forms an alcohol plus the salt of a carboxylic acid!carboxylic acid!

33

What acid and alcohol make the What acid and alcohol make the following ester?following ester?

H3C C

O

O CH2

CH2

CH3

11 22 33 44 55

0%

0%

0%

0% 1.1. Ethanol (2C) and acetic acid (2C)Ethanol (2C) and acetic acid (2C)

2.2. Propanol (3C) & acetic acid (2C)Propanol (3C) & acetic acid (2C)

3.3. Ethanol (2C) & propionic acid (3C)Ethanol (2C) & propionic acid (3C)

4.4. Methanol (1C) & propionic acid (3C)Methanol (1C) & propionic acid (3C)

44

Last Time: Base Last Time: Base HydrolysisHydrolysis of of Triglycerides Make SoapsTriglycerides Make Soaps

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Last Time: Amines (Derivatives of NHLast Time: Amines (Derivatives of NH33))

Typically 3 kinds:Typically 3 kinds:• primary (1°) amines:primary (1°) amines: 1 carbon group is bonded to N 1 carbon group is bonded to N• secondary (2°) amines:secondary (2°) amines: 2 carbon groups bonded to N 2 carbon groups bonded to N• tertiary (3°) amines:tertiary (3°) amines: 3 carbon groups bonded to N. 3 carbon groups bonded to N.

Can H-bond like alcohols, although N is not as polarCan H-bond like alcohols, although N is not as polar• decent BPs & solubility in waterdecent BPs & solubility in water

Act as weak bases:Act as weak bases:

CHCH33——NHNH22 + H + H22OO CH CH33——NHNH33++ + OH + OH––

Useful properties of amine salts:Useful properties of amine salts:• solids at RT, very soluble in body fluids (ideal for solids at RT, very soluble in body fluids (ideal for drug molecules, and salts don’t stink drug molecules, and salts don’t stink

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Last Time: AlkaloidsLast Time: Alkaloids

• physiologically active nitrogen-containing physiologically active nitrogen-containing compounds.compounds.

• often addictive. often addictive.

N

CH3

nicotine

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Morphine and CodeineMorphine and Codeine

• alkaloids.alkaloids.• obtained from the obtained from the

oriental poppy plant.oriental poppy plant.• used as painkillers. used as painkillers. • modified to make modified to make

heroin.heroin.

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ChocolateChocolate

Chocolate is found in Chocolate is found in cocoa beanscocoa beans

N

NN

N

O

O

CH3

CH3

H

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Last Time: Amides (13.5) made from… Last Time: Amides (13.5) made from… Amine + Carboxylic AcidAmine + Carboxylic Acid

Amides are producedAmides are produced• by reacting a carboxylic acid with ammonia by reacting a carboxylic acid with ammonia

or an amine (1or an amine (1° or 2°).° or 2°).• using heat.using heat. OO O O HeatHeat CHCH33——CC——OH +OH + NHNH33 CH CH33—C—C——NHNH22 + H+ H22OO

OO O O Heat Heat CHCH33——CC——OH + OH + CHCH33——NHNH22 CH CH33—C——C—NH—CHNH—CH33 + H+ H22OO

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Some Amides in Health and MedicineSome Amides in Health and Medicine

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Physical Properties of AmidesPhysical Properties of Amides

SIMILAR TO AMINES…SIMILAR TO AMINES…• primary (primary (−−NHNH22) or secondary () or secondary (−−NHNH−−) amides ) amides

form hydrogen bonds.form hydrogen bonds.• primary have higher mp’s than secondary.primary have higher mp’s than secondary.

• tertiary (no H on N) do not form hydrogen bonds & tertiary (no H on N) do not form hydrogen bonds & have lower melting points.have lower melting points.

• all form hydrogen bonds with water.all form hydrogen bonds with water.• with 1-5 carbon atoms are soluble in water.with 1-5 carbon atoms are soluble in water.

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Amides undergoAmides undergo• Acid hydrolysisAcid hydrolysis to produce a carboxylic to produce a carboxylic

acid and an ammonium salt.acid and an ammonium salt.

• Base hydrolysisBase hydrolysis to produce the salt of a to produce the salt of a carboxylic acid and an amine or ammonia.carboxylic acid and an amine or ammonia.

• REACTIONS LOOK SIMILAR TO THOSE REACTIONS LOOK SIMILAR TO THOSE OF ESTERS!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!OF ESTERS!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!

Hydrolysis of AmidesHydrolysis of AmidesIMPORTANT TO KNOWIMPORTANT TO KNOW

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acid hydrolysisacid hydrolysis OO

|||| OO CH CH33——CC——OH + NHOH + NH44

++ClCl––

|||| HClHCl + H+ H22O O CHCH33——CC—NH—NH22

NaOHNaOH OO ||||

CHCH33——CC——OO– – NaNa++ + NH + NH33

base hydrolysisbase hydrolysis

Hydrolysis ReactionsHydrolysis Reactions

1414

Ch 14 CarbohydratesCh 14 Carbohydrates

• a major source of a major source of energy from our diet energy from our diet

• composed of C, H, & Ocomposed of C, H, & O

• also known as also known as saccharides, which saccharides, which means “sugars.”means “sugars.”

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Practice Problems (Ch 14)Practice Problems (Ch 14)

11 22 33 44 55

14.05, 14.07, 14.09, 14.13, 14.15, 14.05, 14.07, 14.09, 14.13, 14.15, 14.19, 14.21, 14.23, 14.25, 14.27, 14.19, 14.21, 14.23, 14.25, 14.27, 14.29, 14.31, 14.33, 14.35, 14.37,14.29, 14.31, 14.33, 14.35, 14.37,

14.39, 14.41, 14.47, 14.49, 14.51,14.39, 14.41, 14.47, 14.49, 14.51,

14.53, 14.57, 14.59 14.53, 14.57, 14.59

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CarbohydratesCarbohydrates

• produced by produced by photosynthesis in plants photosynthesis in plants

• Example: glucose Example: glucose synthesized in plants synthesized in plants from COfrom CO22, H, H22O, and O, and

energy from the sun.energy from the sun.• are oxidized in living are oxidized in living

cells to produce COcells to produce CO22, ,

HH22O, and energy.O, and energy.

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Types of CarbohydratesTypes of Carbohydrates

• Monosaccharides:Monosaccharides: simplest carbohydrates. simplest carbohydrates. • Disaccharides:Disaccharides: consist of two monosaccharides. consist of two monosaccharides.• Polysaccharides:Polysaccharides: contain many monosaccharides. contain many monosaccharides.

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MonosaccharidesMonosaccharides

• typically 3-6 carbon atomstypically 3-6 carbon atoms

• have a C=O group (aldehyde or ketone)have a C=O group (aldehyde or ketone)• aldosesaldoses• ketosesketoses

• several hydroxyl groupsseveral hydroxyl groups

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AldosesAldoses

• monosaccharides with an monosaccharides with an aldehyde group… aldehyde group…

• ……and many hydroxyl and many hydroxyl groups.groups.

triose triose (3C atoms)(3C atoms)

tetrose tetrose (4C atoms)(4C atoms)

pentosepentose (5C atoms) (5C atoms)

hexose hexose (6C atoms)(6C atoms)

OO ║║

CC─H aldose─H aldose ││ HH── C C─OH─OH │ │ HH── C C─OH─OH │ │

CHCH22OHOH

ErythoseErythose

2020

KetosesKetoses

• monosaccharides with a monosaccharides with a ketone group…ketone group…

• ……and many hydroxyl and many hydroxyl groups.groups.

CCHH22OH OH

│ │ C=C=O ketoseO ketose │ │ HH── C C─OH─OH ││ HH── C C─OH─OH │ │

HH──CC─OH─OH ││

CHCH22OHOH

Fructose, a ketohexose

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Fischer ProjectionsFischer Projections

• also used to represent carbohydrates.also used to represent carbohydrates.• places the most oxidized group at the top.places the most oxidized group at the top.• shows chiral carbons as the intersection of shows chiral carbons as the intersection of

vertical and horizontal lines.vertical and horizontal lines.

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D & L Notations: Know This Now…D & L Notations: Know This Now…In a Fischer projection, the In a Fischer projection, the −OH group on the−OH group on the• chiral carbon chiral carbon farthest from the carbonyl groupfarthest from the carbonyl group

determines an L or D isomer. determines an L or D isomer. • left = left = LL for the L-formfor the L-form..• right = right = DD for the D-formfor the D-form. (MOST COMMON IN . (MOST COMMON IN

NATURE!)NATURE!)

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Learning CheckLearning Check

Identify each as the D or L isomer.Identify each as the D or L isomer.

A.A. B.B. C. C.

__-Ribose __-Ribose __- Threose __- Fructose __- Threose __- Fructose

CH2OH

HO H

HO H

HHO

O

C H

CH2OH

HO H

OHH

O

C H

CH2OH

H OH

H OH

HO H

O

CH2OH

L L D

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D-GlucoseD-Glucose

• found in fruits, corn found in fruits, corn syrup, and honeysyrup, and honey

• an an aldoaldohexose with hexose with the formula Cthe formula C66HH1212OO66

• known as known as blood blood sugarsugar in the body in the body

• the monosaccharide the monosaccharide in polymers of in polymers of starch, cellulose, starch, cellulose, and glycogenand glycogen

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Blood Glucose LevelBlood Glucose LevelIn the body, In the body, • normal blood: [glucose] = 70-90 mg/dL.normal blood: [glucose] = 70-90 mg/dL.• a glucose tolerance test measures blood a glucose tolerance test measures blood

glucose for several hours after ingesting glucose for several hours after ingesting glucose.glucose.

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D-FructoseD-Fructose

• is a is a ketoketohexose hexose CC66HH1212OO66

• is the is the sweetest sweetest carbohydratecarbohydrate

• found in fruit juices found in fruit juices and honeyand honey

• converts to converts to glucose in the glucose in the bodybody

H OH

CH2OH

C

HO

H OH

H

C

O

C

C

CH2OH

D-Fructose

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D-GalactoseD-Galactose

• is an is an aldoaldohexose hexose CC66HH1212OO66..

• notnot found free in nature. found free in nature.• is obtained from lactose, is obtained from lactose,

a disaccharide.a disaccharide.• has a similar structure to has a similar structure to

glucose except for the glucose except for the

– –OH on C4OH on C4

Which C is C4???Which C is C4???

H

H

H OH

CH2OH

C

HO

HO HC

OH

C

C

O

C H

D-Galactose

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Cyclic Structures (14.3)Cyclic Structures (14.3)

• prevalent form of monosaccharides with 5 or 6 prevalent form of monosaccharides with 5 or 6 carbon atomscarbon atoms

• form when the hydroxyl group on C-5 reacts form when the hydroxyl group on C-5 reacts with the aldehyde group or ketone groupwith the aldehyde group or ketone group• Orgo-Chem reaction not previously mentioned: Orgo-Chem reaction not previously mentioned:

“C=O” + ROH “C=O” + ROH → hemiacetal→ hemiacetal

O O

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Drawing Cyclic Structures: Practice! Drawing Cyclic Structures: Practice! Example: GlucoseExample: Glucose

STEP 1STEP 1 Number the carbon chain and turn Number the carbon chain and turn clockwise to form a linear open chain. clockwise to form a linear open chain.

HHO

H

CH2OH

OHC

H

H

OH

OH

C

C

C

OH

C1

2

3

4

5

6

6 5 4 3 2 1

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OH

OH

OHOH

CH2OH

O

Cyclic Structure for GlucoseCyclic Structure for GlucoseSTEP 2STEP 2 Fold into a hexagon. Fold into a hexagon. • Bond the C5 –O– to C1. Bond the C5 –O– to C1. • Place the C6 group above the Place the C6 group above the

ring. ring. • Write the –OH groups on C2 Write the –OH groups on C2

& C4 below the ring (These & C4 below the ring (These are the C atoms that pointed are the C atoms that pointed down from Step 1). down from Step 1).

• Write the –OH group on C3 Write the –OH group on C3 above the ring. above the ring.

• Write a new –OH on C1.Write a new –OH on C1.

6 5

4 1

3 2

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Cyclic Structure for GlucoseCyclic Structure for Glucose

OH

OH

OHOH

CH2OH

O

-D-Glucose -D-Glucose

OH

OH

OHOH

CH2OH

O

STEP 3 Write the new –OH on C1 • down for the form.• up for the form.

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Summary of the Formation of Summary of the Formation of Cyclic GlucoseCyclic Glucose

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MutarotationMutarotation

• cyclic structures open and close. cyclic structures open and close. -D-glucose converts to -D-glucose converts to ββ-D-glucose & vice versa.-D-glucose & vice versa.• at any time, only aat any time, only a small amount of open chain forms. small amount of open chain forms.

-D-glucose D-glucose (open) -D-glucose D-glucose (open) ββ-D-glucose-D-glucose

(36%) (trace)(36%) (trace) (64%) (64%)

OH

CH2OH

OH

OC

H

OH

OHOH

OH

OHOH

CH2OH

OOH

OH

OHOH

CH2OH

O

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D-fructoseD-fructose -D-fructose-D-fructoseαα-D-fructose-D-fructose

O CH2OH

OOHH

OH

OH

CH2OH

O OOHH

CH2OH

OH

OH

CH2OH

H OH

H OH

HHO

O

CH2OH

C

C

C

C

CH2OH

Cyclic Structure of FructoseCyclic Structure of Fructose

• is a ketohexose.is a ketohexose.• reacts the reacts the --OH on C-5 with the C=O on C-2OH on C-5 with the C=O on C-2