Introduction To Organic Chemistry

16
Introduction to Organic Chemistry

2 ed William H. Brown
16-1
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
16
Carbohydrates
Chapter 16
16-2
16 Carbohydrates
Carbohydrate a polyhydroxyaldehyde or Carbohydrate:
polyhydroxyketone, or a substance that gives these compounds on hydrolysis Monosaccharide a carbohydrate that cannot be hydrolyzed Monosaccharide: to a simpler carbohydrate
monosaccharides have the general formula CnH2nOn, where n varies from 3 to 8 aldose a monosaccharide containing an aldehyde group aldose: ketose a monosaccharide containing a ketone group ketose:
16-3
16 Monosaccharides
monosaccharides are classified by their number of carbon atoms
Name triose tetrose pentose hexose heptose octose
Formula C 3 H 6 O3 C 4 H 8 O4 C 5 H 10 O5 C 6 H 12 O6 C 7 H 14 O7 C 8 H 16 O8 16-4
16 Monosaccharides
There are only two trioses
CHO CHOH CH 2 OH Glyceraldehyde (an aldotriose) CH 2 OH C=O CH 2 OH D ihydroxyacetone (a ketotriose)
often aldo- and keto- are omitted and these compounds are referred to simply as trioses although this designation does not tell the nature of the carbonyl group, it at least tells the number of carbons 16-5
16 Monosaccharides
Glyceraldehyde contains a stereocenter and exists as a pair
of enantiomers
16-6
16 Fischer Projections
Fischer projection a two dimensional representation for projection:
showing the configuration of tetrahedral stereocenters

horizontal lines represent bonds projecting forward vertical lines represent bonds projecting to the rear
CHO H C OH
convert to a Fischer projection
CHO H OH CH 2 OH
CH 2 OH (R)-Glyceraldehyde
(R)-Glyceraldehyde 16-7
16 D,L Monosaccharides
In 1891, Emil Fischer made the arbitrary assignments of D-
and L- to the enantiomers of glyceraldehyde

CHO H OH CH 2 OH D-Glyceraldehyde
25 [E]D = +13.5
CHO HO H CH 2 OH L-Glyceraldehyde
25 [E]D = -13.5
16-8
According to the conventions proposed by Fischer
D-monosaccharide: a monosaccharide that, when written as a monosaccharide Fischer projection, has the -OH on its penultimate carbon on the right L-monosaccharide: a monosaccharide that, when written as a monosaccharide Fischer projection, has the -OH on its penultimate carbon on the left
16-9
Following are
the two most common D-aldotetroses and the two most common D-aldopentoses
CHO CHO HO H H OH H OH H OH CH2 OH CH2 OH D-Erythrose D-Threose
CHO H OH H OH H OH CH2 OH D-Ribose
CHO H H H OH H OH CH2 OH 2-Deoxy-Dribose 16-10
and the three most common D-aldohexoses
H HO H H
CHO OH H OH OH CH 2 OH
H HO HO H
CHO OH H H OH CH2 OH
H HO HO H
CHO NH 2 H H OH CH 2 OH
D-Glucose
D-Galactose
D-Glucosamine
16-11
16 Cyclic Structure
Monosaccharides have hydroxyl and carbonyl groups in the
same molecule and exist almost entirely as five- and sixmembered cyclic hemiacetals
anomeric carbon the new stereocenter resulting from cyclic carbon: hemiacetal formation anomers carbohydrates that differ in configuration at their anomers: anomeric carbons
16-12
16 Haworth Projections
Haworth projections
five- and six-membered hemiacetals are represented as planar pentagons or hexagons, as the case may be, viewed through the edge most commonly written with the anomeric carbon on the right and the hemiacetal oxygen to the back right the designation F- means that -OH on the anomeric carbon is cis to the terminal -CH2OH; E- means that it is trans
16-13
16 H
CHO OH HO H H OH 5 H OH CH2 OH D-Glucose
CH2 OH OH H5 O H OH H C H HO H OH anomeric carbon CH 2 OH 5 O H H H + OH H HO OH( E) OH H E-D-Glucopyranose (E-D-Glucose)
CH 2 OH O H5 OH( F) H OH H HO H OH H F-D-Glucopyranose (F-D-Glucose)
16-14
16 Haworth Projections
six-membered hemiacetal rings are shown by the infix -pyran pyran five-membered hemiacetal rings are shown by the infix -furan furan-
O Furan
O Pyran
16-15
16 Conformational Formulas
five-membered rings are close to being planar so that Haworth projections are adequate to represent furanoses
HOCH 2 H
OH( F) H
HOCH2 H
H H
H H HO OH F-D-Ribofuranose (F-D-Ribose)
H OH( E) HO OH E-D-Ribofuranose (E-D-Ribose)
16-16
for pyranoses, the six-membered ring is more accurately represented as a strain-free chair conformation
HO HO
CH 2 OH O OH OH (F)
F- D-Glucopyranose (chair conformation)
16-17
compare the orientations of groups on carbons 1-5 in the Haworth and chair representations of F-D-glucopyranose in each case they are up-down-up-down-up
CH 2 OH O OH ( F) H H OH H HO H H OH F-D-Glucopyranose (Haworth projection)

HO HO
CH2 OH O OH OH ( F)
F-D-Glucopyranose (chair conformation)
16-18
16 Mutarotation
Mutarotation the change in specific rotation that occurs Mutarotation:
when the E or F forms of a carbohydrate are converted to an equilibrium mixture of the two
[E] after Mutarotation [E] (degrees) (degrees ) +112.0 +18.7 +150.7 +52.8 +52.7 +52.7 +80.2 +80.2 % Present at Equilibrium 36 64 28 72
Monosaccharide E-D-glucose F-D-glucose E-D-galactose F-D-galactose
16-19
16
HO
4
HO
CH2 OH OH O
OHC H D-Galactose HO
4
HO CH2 OH O OH ( F)
4
HO
HO
CH2 OH O
OH F- D-Galactopyranose ( F - D-Galactose)
25 [E]D = +52.8
OH OH ( E) E- D-Galactopyranose ( E - D-Galactose)
25 [E]D = +150.7 16-20
16 Physical Properties
monosaccharides are colorless crystalline solids, very soluble in water, but only slightly soluble in ethanol following are relative sweetnesses (table sugar = 100 is the reference sweetness)
Monosaccharide & Disaccharides D-fructose 174 D-glucose 74 D-galactose 0.22 sucrose (table sugar) 100 lactose (milk sugar)
Other Carbohydrate Sweetening Agent honey 97 molasses 74 corn syrup 74
0.16
16-21
16 Formation of Glycosides
Glycoside a carbohydrate in which the -OH of the anomeric Glycoside:
carbon is replaced by -OR

CH 2 OH H HO H OH H O OCH 3 ( F) H HO HO CH 2 OH O OCH 3 ( F)
H OH Haworth projection
OH Chair conformation
Methyl F-D-glucopyranoside (methyl F-D-glucoside) 16-22

16 Glycosides
Glycoside bond the bond from the anomeric carbon of the bond:
glycoside to an -OR group Glycosides are named by listing the name of the alkyl or aryl group attached to oxygen followed by the name of the e ide carbohydrate with the ending -e replaced by -ide
methyl F-D-glucopyranoside methyl E-D-ribofuranoside
16-23
16 N-Glycosides
The anomeric carbon of a cyclic hemiacetal undergoes
reaction with the N-H group of an amine to form an Nglycoside

N-glycosides of the following purine and pyrimidine bases are structural units of nucleic acids O O NH 2 CH 3 HN HN N
N H Thymine
H Uracil
H Cytosine
16-24
16 N-Glycosides
O HN H 2N N N N H Guanine O HOCH 2 O H H HO OH H H anomeric carbon 16-25 N N a F-N-glycoside bond NH2
NH 2 N N Adenine N N H
16 Reduction to Alditols
The carbonyl group of a monosaccharide can be reduced to
an hydroxyl group by a variety of reducing agents, including NaBH4 and H2/M

H HO H H CHO OH H OH + H2 OH CH2 OH H HO H H CH 2 OH OH H OH OH CH 2 OH
Ni
D-Glucose
D-Glucitol (D-Sorbitol)
16-26
16 Oxidation to Aldonic Acids

Oxidation of the -CHO group of an aldose to a
-CO2H group can be carried out using Tollens, Benedicts, or Fehlings solutions
O
+ + NH3 , H2 O RCO NH4 A g( NH 3 ) 2
RCH +
Tollens' solution O RCH + Cu

citrate or 2 + tartrate buffer
+ Ag Precipitates as a silver mirror
O
RCO + Cu 2 O Precipitates as a red solid
16-27
16 Oxidation to Aldonic Acids

2-Ketoses are also oxidized by these reagents because,
under the conditions of the oxidation, 2-ketoses equilibrate with isomeric aldoses
CH 2 OH C=O (CH OH) n CH 2 OH A 2-ketose CHOH C-OH (CH OH) n CH2 OH An enediol CHO CHOH (CH OH) n CH 2 OH An aldose
16-28
16 Glucose Assay
The analytical procedure most often performed in the clinical
chemistry laboratory is the determination of glucose in blood, urine, or other biological fluid this need arises because of the high incidence of diabetes in the population
16-29
16 Glucose Assay
The glucose oxidase method is completely specific for D-
glucose
HO HO CH2 OH O OH glucose + O2 + H 2 O oxidase H HO H H CO2 H OH H OH OH CH 2 OH
OH F - D-Glucopyranose
H 2 O2 Hydrogen peroxide
D-Gluconic acid 16-30

16 Glucose Assay
O2 is reduced to hydrogen peroxide H2O2 the concentration of H2O2 is proportional to the concentration of glucose in the sample in one procedure, hydrogen peroxide is used to oxidize o-toluidine to a colored product, whose concentration is determined spectrophotometrically
o-toluidine
H2 O2
peroxidase
colored product
H2 O
16-31
16 Ascorbic Acid (Vitamin C)

L-Ascorbic acid (vitamin C) is synthesized both
biochemically and industrially from D-glucose

H HO H H CHO OH H OH OH CH 2 OH both biochemial and industrial syntheses CH2 OH H OH O H HO OH
D-Glucose
L-Ascorbic acid (Vitamin C) 16-32
16 Ascorbic Acid (Vitamin C)

L-ascorbic acid is very easily oxidized to L-dehydroascorbic acid. both compounds are physiologically active and are found in most body fluids
CH 2 OH H OH O O H HO OH oxidation reduction H
CH 2 OH OH O O H O O L-Dehydroascorbic acid 16-33
L-Ascorbic acid (Vitamin C)

16 Maltose
From malt, the juice of sprouted barley and other cereal
grains
CH 2 OH HO HO O
E-1,4-glycoside bond F-maltose because this -OH is beta O OH OH
OH O HO
CH 2 OH
16-34
16 F-Maltose
16-35
16 Lactose
The principle sugar present in milk
about 5% - 8% in human milk, 4% - 5% in cows milk
F-1,4-glycoside bond OH CH 2 OH HO OH D-galactose unit O O HO D-glucose unit 16-36

CH 2 OH
F-lactose because this -OH is beta O OH
OH
16 F-Lactose
16-37
16 Sucrose
Table sugar, from the juice of sugar cane and sugar beet
CH 2 OH HO HO FD-glucopyranose unit F-2,1-glycoside bond E-1,2-glycoside O bond FD-fructopyranose 1 unit OH H O OH CH 2 OH H HO 2 O H CH 2 OH
1
16-38
16 Blood Group Substances

Membranes of animal plasma cells have large numbers of
relatively small carbohydrates bound to them

these membrane-bound carbohydrates are part of the mechanism by which cell types recognize each other; they act as antigenic determinants among the first discovered of these antigenic determinants are the blood group substances
16-39
16 ABO Blood Classification

In the ABO system, individuals are classified according to
four blood types: A, B, AB, and O

at the cellular level, the biochemical basis for this classification is a group of relatively small membrane-bound carbohydrates
16-40
16 ABO Blood Classification

D-galactose in type B blood NAGal E-1,4-) Gal F-1,3-) NAGlu F-1-) Cell membrane of erythrocyte
E-1,2-) Fuc NAGal = N-acetyl-D-galactosamine missing in type O blood Gal = D-galactose NAGlu = N-acetyl-D-glucosamine Fuc = L-fucose
16-41
16 L-Fucose
L-fucose is synthesized biochemically from D-glucose (see
Problem 24.32)
An L-monosaccharide because this -OH is on the left in the Fischer projection Carbon 6 is -CH 3 rather than -CH 2OH CHO HO H H OH H OH HO H CH 3 L-Fucose
16-42
16 Starch
Starch is used for energy storage in plants
it can be separated into two fractions; amylose and amylopectin. Each on complete hydrolysis gives only D-glucose amylose is composed of continuous, unbranched chains of up to 4000 D-glucose units joined by E-1,4-glycoside bonds amylopectin is a highly branched polymer of D-glucose. Chains consist of 24-30 units of D-glucose joined by E-1,4-glycoside bonds and branches created by E-1,6-glycoside bonds
16-43
16 Glycogen
The reserve carbohydrate for animals
a nonlinear polymer of D-glucose units joined by E-1,4- and E-1,6glycoside bonds bonds the total amount of glycogen in the body of a well-nourished adult is about 350 g (about 3/4 of a pound) divided almost equally between liver and muscle
16-44
16 Cellulose
Cellulose is a linear polymer of D-glucose units joined by F-
1,4-glycoside bonds
it has an average molecular weight of 400,000, corresponding to approximately 2800 D-glucose units per molecule
Both rayon and acetate rayon are made from chemically
modified cellulose
16-45
16
Carbohydrates
End Chapter 16
16-46

Introduction To Organic Chemistry

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16

Introduction to Organic Chemistry

Name triose tetrose pentose hexose heptose octose

showing the configuration of tetrahedral stereocenters

convert to a Fischer projection

and L- to the enantiomers of glyceraldehyde

CHO CHO HO H H OH H OH H OH CH2 OH CH2 OH D-Erythrose D-Threose

CHO H OH H OH H OH CH2 OH D-Ribose

CHO H H H OH H OH CH2 OH 2-Deoxy-Dribose 16-10

CHO OH HO H H OH 5 H OH CH2 OH D-Glucose

CH2 OH OH H5 O H OH H C H HO H OH anomeric carbon CH 2 OH 5 O H H H + OH H HO OH( E) OH H E-D-Glucopyranose (E-D-Glucose)

CH 2 OH O H5 OH( F) H OH H HO H OH H F-D-Glucopyranose (F-D-Glucose)

H OH( E) HO OH E-D-Ribofuranose (E-D-Ribose)

F- D-Glucopyranose (chair conformation)

CH 2 OH O OH ( F) H H OH H HO H H OH F-D-Glucopyranose (Haworth projection)

F-D-Glucopyranose (chair conformation)

Monosaccharide E-D-glucose F-D-glucose E-D-galactose F-D-galactose

Other Carbohydrate Sweetening Agent honey 97 molasses 74 corn syrup 74

carbon is replaced by -OR

Methyl F-D-glucopyranoside (methyl F-D-glucoside) 16-22

reaction with the N-H group of an amine to form an Nglycoside

an hydroxyl group by a variety of reducing agents, including NaBH4 and H2/M

16 Oxidation to Aldonic Acids

Tollens' solution O RCH + Cu

+ Ag Precipitates as a silver mirror

16 Oxidation to Aldonic Acids

D-Gluconic acid 16-30

16 Ascorbic Acid (Vitamin C)

biochemically and industrially from D-glucose

L-Ascorbic acid (Vitamin C) 16-32

16 Ascorbic Acid (Vitamin C)

CH 2 OH OH O O H O O L-Dehydroascorbic acid 16-33

L-Ascorbic acid (Vitamin C)

E-1,4-glycoside bond F-maltose because this -OH is beta O OH OH

F-1,4-glycoside bond OH CH 2 OH HO OH D-galactose unit O O HO D-glucose unit 16-36

F-lactose because this -OH is beta O OH

16 Blood Group Substances

relatively small carbohydrates bound to them

16 ABO Blood Classification

four blood types: A, B, AB, and O

16 ABO Blood Classification

Both rayon and acetate rayon are made from chemically

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