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Organic Chemistry Solomon Periodic Acid
Organic Chemistry Solomon Periodic Acid
CHAPTER 22
CARBOHYDRATES
H
CH2OH
C
Cu2 (complex)
(H
OH)n
or
(H
CH2OH
OH)n
oxidation products
Cu2O
CH2OH
Benedicts
solution
(blue)
Aldose
Ketose
(brick-red
reduction
product)
Sugars that give positive tests with Tollens or Benedicts solutions are known
as reducing sugars, and all carbohydrates that contain a hemiacetal group give
positive tests.
In aqueous solution the hemiacetal form of sugars exists in equilibrium with relatively
small, but not insignificant, concentrations of noncyclic aldehydes or a-hydroxy ketones.
It is the latter two that undergo the oxidation, perturbing the equilibrium to produce
more aldehyde or a-hydroxy ketone, which then undergoes oxidation until one reactant
is exhausted.
L
Carbohydrates that contain only acetal groups do not give positive tests with
Benedicts or Tollens solutions, and they are called nonreducing sugars.
Acetals do not exist in equilibrium with aldehydes or a-hydroxy ketones in the basic
aqueous media of the test reagents.
Reducing Sugar
Nonreducing Sugar
Alkyl group or
another sugar
C
C
C
R
Hemiacetal (RH
orCH2OH)
(gives positive
Tollens or
Benedicts test)
R
Acetal (RH
orCH2OH)
(does not give a
positive Tollens or
Benedicts test)
995
sss
How might you distinguish between a-d-glucopyranose (i.e., d-glucose) and methyl
a-d-glucopyranoside?
Although Benedicts and Tollens reagents have some use as diagnostic tools [Benedicts
solution can be used in quantitative determinations of reducing sugars (reported as glucose)
in blood or urine], neither of these reagents is useful as a preparative reagent in carbohydrate
oxidations. Oxidations with both reagents take place in alkaline solution, and in alkaline
solutions sugars undergo a complex series of reactions that lead to isomerizations (Section 22.5A).
Bromine water is a general reagent that selectively oxidizes the J CHO group to a
J CO2H group, thus converting an aldose to an aldonic acid:
CHO
(H
CO2H
Br2
OH)n
(H
H2O
OH)n
CH2OH
CH2OH
Aldose
Aldonic acid
Experiments with aldopyranoses have shown that the actual course of the reaction is
somewhat more complex than we have indicated. Bromine water specifically oxidizes the
b anomer, and the initial product that forms is a d-aldonolactone. This compound may
then hydrolyze to an aldonic acid, and the aldonic acid may undergo a subsequent ring
closure to form a g-aldonolactone:
OH
HO
HO
OH
O
OH
Br2
HO
HO
H2O
HO
H2O
HO
-D-Glucopyranose
H2O
D-Glucono-d-
lactone
HO
OH
HO
OH
HO
H2O
OH
H2O
OH
H
O
H
OH
OH
OH
D-Gluconic
D-Gluconic-g-
acid
lactone
Dilute nitric acida stronger oxidizing agent than bromine wateroxidizes both
the J CHO group and the terminal J CH2OH group of an aldose to J CO2H
groups, forming dicarboxylic acids are known as aldaric acids:
CHO
(H
OH)n
CH2OH
Aldose
CO2H
HNO3
(H
OH)n
CO2H
Aldaric acid
996
CHAPTER 22
CARBOHYDRATES
C
C OH
OH
O
H C
C
HO
OH
OH
OH
OH
OH
H2O
C
O
OH
H
H
or
H
OH O
OH
C
C
OH
H
OH
OH
Aldaric acid
(from an aldohexose)
OH
OH
H
HO
HO
OH
O
HO
OH
HO
H
HNO3
HO
OH
OH
OH
OH
OH
sss
OH
D-Glucose
OH
D-Glucaric
acid
OH
OH
CH2OH
D-Erythrose
it is subjected to nitric acid oxidation. Write Fischer projection formulas for d-threose
and its nitric acid oxidation product.
(g) What are the names of the aldaric acids obtained from d-erythrose and d-threose?
sss
PRACTICE PROBLEM 22.8 d-Glucaric acid undergoes lactonization to yield two different g-lactones. What are their
structures?
*Older terms for an aldaric acid are a glycaric acid or a saccharic acid.
of Polyhydroxy Compounds
L
OH
HIO4
HIO3
H2O
OH
Since the reaction usually takes place in quantitative yield, valuable information can often
be gained by measuring the number of molar equivalents of periodic acid consumed in
the reaction as well as by identifying the carbonyl products.
Periodate oxidations are thought to take place through a cyclic intermediate:
C
C
OH
(H2O)
IO4
OH
O
O
I
C
O
O
O
IO3
as formic acid. Periodate oxidation of glycerol, for example, gives two molar equivalents of formaldehyde and one molar equivalent of formic acid:
O
C
H
H
H
OH
OH
(formaldehyde)
H
O
2 IO4
C
H
OH
(formic acid)
OH
O
H
Glycerol
(formaldehyde)
C
H
2. Oxidative cleavage also takes place when an J OH group is adjacent to the carbonyl
997
998
CHAPTER 22
CARBOHYDRATES
while dihydroxyacetone gives two molar equivalents of formaldehyde and one molar
equivalent of carbon dioxide:
O
C
H
O
O
C
H
OH
(formic acid)
OH
2 IO4
C
H
(formic acid)
OH
OH
O
H
Glyceraldehyde
(formaldehyde)
H
O
H
C
C
H
OH
OH
2 IO4
(formaldehyde)
(carbon dioxide)
H
Dihydroxyacetone
(formaldehyde)
3. Periodic acid does not cleave compounds in which the hydroxyl groups are separated
by an intervening J CH2 J group, nor those in which a hydroxyl group is adjacent
CH2OCH3
CH2
IO4
no cleavage
CH2OH
OH
IO4
no cleavage
CH2R
sss
PRACTICE PROBLEM 22.9 What products would you expect to be formed when each of the following compounds
is treated with an appropriate amount of periodic acid? How many molar equivalents of
HIO4 would be consumed in each case?
(a) 2,3-Butanediol
(b) 1,2,3-Butanetriol
(c)
OCH
HO
(d)
(e)
HO
OH
OH
(f) cis-1,2-Cyclopentanediol
(g) HO
OH
(h) d-Erythrose
OCH3
OH
sss
PRACTICE PROBLEM 22.10 Show how periodic acid could be used to distinguish between an aldohexose and
a ketohexose. What products would you obtain from each, and how many molar
equivalents of HIO4 would be consumed?
999
Aldoses (and ketoses) can be reduced with sodium borohydride to give compounds
called alditols:
CH2OH
CHO
(H
OH)n
NaBH4
(H
or
H2, Pt
CH2OH
OH)n
CH2OH
Alditol
Aldose
O
OH
HO
H
HO
H
H
OH
H
OH
OH
OH
NaBH4
H
HO
H
H
OH
OH
H
OH
OH
OH
D-Glucitol
(or D-sorbitol)
sss
(a) Would you expect d-glucitol to be optically active? (b) Write Fischer projection
formulas for all of the d-aldohexoses that would yield optically inactive alditols.
OH
(H
OH)n 3 C6H5NHNH2
CH2OH
(H
NNHC6H5
NNHC6H5
CH2OH
Aldose
Phenylosazone
1000
CHAPTER 22
CARBOHYDRATES
C
C
H
N
A
NHC6H5
OH
H
tautomerization
Phenylosazone Formation
C6H5
(C6H5NH2)
A
(formed from
the aldose)
H
C
C
NH
O
(2 C6H5NHNH2)
NNHC6H5
Osazone formation results in a loss of the chirality center at C2 but does not affect
other chirality centers; d-glucose and d-mannose, for example, yield the same phenylosazone:
H
H
HO
O
OH
H
C6H5NHNH2
NNHC6H5
NNHC6H5
HO
C6H5NHNH2
HO
HO
OH
OH
OH
OH
OH
OH
OH
D-Glucose
sss
OH
Same phenylosazone
OH
D-Mannose
This experiment, first done by Emil Fischer, established that d-glucose and d-mannose
have the same configurations about C3, C4, and C5. Diastereomeric aldoses that differ
in configuration at only one carbon (such as d-glucose and d-mannose) are called
epimers. In general, any pair of diastereomers that differ in configuration at only a single
tetrahedral chirality center can be called epimers.
PRACTICE PROBLEM 22.12 Although d-fructose is not an epimer of d-glucose or d-mannose (d-fructose is a ketohexose), all three yield the same phenylosazone. (a) Using Fischer projection formulas,
write an equation for the reaction of fructose with phenylhydrazine. (b) What information about the stereochemistry of d-fructose does this experiment yield?