UNIT-2: ORGANIC

CHEISTRY

CHAPTER-1 Carbohydrates

PART-A SHORT QUESTIONS AND ANSWERS

Q1. What is mutarotation?
Answer : Model
Paper-4,Q
Mutarotation is a phenomenon exhibited bythe aqieous solution of sugars in which the
change
rotation occurs with

of
time. specife

Figure illustrates the crystallisation of glucose, where glucose is crystallized from its
concentrated
solution into twoforms i.e, a and ß D(+) Glucose. After crystallization if each them is separately aqueous

of
water andallowed to stand, their specific rotation changes + 52.7° dissolved i
gradually until a constant value, is reacb
Thus, mutarotation can be defined as the spontaneous change in the specific rotation of an
optically
compound. active

Concentrated aqueous
solution of D(+) Glucose

Recrystallisation by
Crystallisation at 30°C evaporation of water
above 98°C

Glucose B(D)+ Glucose

AnOyD)=+ [a] 1120 [a] =+19°C
= M.P. 146°C M.P. = 150°C
Glucose
[a], =52.7
Figure :Mutarotation of Glucose
Q2. Draw the Haworth formulaof
() a-D-(+)glucopyranose (ii) a - D-( fructo furanose
(iüi) B-D-(+) gluco pyranose
Answer :
6 March-12, Q8(b)
CH,OH 6
(i) (ii) 1 (iii) CH,OH
HOH CH,OH
H OH

2 H
OH H OH 4

OH 2 H 4 3/ ÖH OH H
HO H
3 2
H ÖH H
OH
H OH
a-D-(+)Glucopyranose a-D-()Fructofuranose
B-D-(+)Glucopyranose
Q3. What are epimersand anomers? Give examples.
(KU)Sep./Oct.-21, Q10()
OR
What is Epimers? Give Examples?
(MGU) July/Aug.-22,Q2
(Refer Only Epimers)

OR
What areepimersand anomers, give one example each? Q
(OU)Sep./Oct.-20,
Answer :
Epimers
They differ in the arrangement of- H and-OH groups or at a-carbon at second carbon atom of sugars.

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50 Chapter-1: Carbohyydrates
Example:Glucose and Mannoseand epimers of cach other.

CHO CHO
H-C-OH| OH--H
OH–C-H HO-CH
(CHOH), (CHOH),
CH,OH CH,OH
Glucose Mannose

Anomers

Stereoisomers of sugars with different at first carbon atom are called

configuration as Anomers.

Example:a-D Glucose and B-D Glucose.

OH H
OH

H-C-OH H-C--OH
HO–C-H HO–C-H
H-C-OH H-C-OH
H-C H-
D CH, OH CH, OH
a-D(+)-Glucose B-D(+)-Glucose

Q4. Give Lobry de Bruyn Van Ekenstein rearrangement.

Answer : [ModelPaper-2, Q4 |(OU) MaylJune-19,Q3]

When D-glucose heated with a strong alkali solution, it results in the formation of brown resinous product.
is
When dilute alkali used, D-glucose undergoes reversible isomerization to yield a mixture containing
is

D-mannose, D-glucose and D-fructose. When mannoseand fructose are treated with dilute alkali, the same
mixture is formed. This reaction is called Lobry de Bruyn van Ekenstein rearrangement.

CHO CHO ÇH,OH

H--OH HO-H
(CHOH)3 (CHOH)3 (CHOH)3

H,OH H,OH CH,OH

D-fructose
D-glucose Epirs D-mannose
Q5. Explain the Kiliani-Fisher method for the synthesisof D-mannose.

Answer : SepJOct.-15, Q18(b)

Kiliani-FischerSynthesis

It is a method of converting one aldose into another with one extra carbon atom. It is also referred as
lengthening of carbon chain of aldose or stepping up the sugar.

Example

D-Arabinose is converted toD-glucose when reacted with HCN to give diastereomeric cyanohydrins. On
hydrolysis they give corresponding aldonic acids and then reduced via lactones to give D-glucose and D-Mannose.

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CN CO,H CHO
CHO HO4-H HO Na-Hg HO
HO HO -H
HO HCN HO H H,0 HO- H
H- HO -H Co,
H- -OH H-OH -OH

H H+OH
H-OH H -OH
HOH
HOH CH,OH CH,OH HOH
CH,OH CH,OH
CH,OH

D-Arabinose Cyanohydrin oAldonicacid D-mannose

Aldonolactonod
and Epimerisation. IModel Paper-3, Q4 |(KU) PP-22,
Q6. Write about Mutarotation O

Answer :
Mutarotation

Changein specific rotation of sugar with time is called as Mutarotation". There are 2 crystalline forms of
D-glucose which were isolated. They are

1. a-D Glucose-crystallises in concentrated aqueous solution with specific rotation +112".

2. B-D Glucose-crystallisesfrom hot glacial acetic acid with specific rotation +19°.

When they are dissolved in water and allowed to stand, the specific rotation changes gradually.The specifc

rotation of a-form decreases and that of B-rises to attain equilibrium with a value of +52.5°. This is called as

mutarotation.

HOH H HOH
HOH H -OH H- -OH
HO-H HO- -H
HO- -H
HOH H-OH/ H- -OH
H H+OH H
CH,OH CH,OH H,OH
a-D(+)-glucose Open-chain form B-D-(+)-glucose

[a]'s = 112°
=
19°

Epimerization

The process of inversion of configuration of one asymmetric centre of a compound with two or more
asymmetric centre is called as Epimerization. The compoundsthat are getting converted are called epimers.
CHO CHO
HOH |HO -H|
HO H HO -H
H OH H- OH
H OH HoH
CH,OH H,OH
D-glucose D-mannose

It is achieved by enzymes or by chemical methods.

52
Chapter-1: Carbohydrates
PART-B
ESSAY OUESTIONS AND
ANSWERS
1.1 INTRODUCTION:
Writenote on
a
CLASSIFICATION AND NOMENCLATURE
Q7.

Answer : carbohydrates.

Carbohydrates are the most

abundant organic
they contain hydrogen and molecules in They literally means
Cbecause

or C,(H,0),
oxygen in the same ratio as
nature.
in water)
"hydrates
thus correspondsto the
oa
formula C(H,oy
Example: CH,0,-Glucose
But there are several non carbohydrate
compounds which appear as
hydrates of carbon.

OH
ds
CH,COOH CH- COOHait ovi Saoisonecao
Acetic acid
CH, –
nW
Lactic acid
Atthe same time there are some carbohydrates that do not satisfy
Example
the general
formula.tso
CH,0, CH,0,,
Deoxyribose Sucrose
Therefore, carbohydrates can be
defined as, optically
active polyhydroxy aldehydes
compounds which produce these or ketones and the
compounds on hydrolysis. Most of the
are soluble in water and sweet to carbohydratesare similar to sugar as they
taste, hence they are also
referred as Saccharides in Greek saccharam means
sugars).

Q8. Give the nomenclatureand

classification of carbohydrates.
Answer :
Nomenclature

Naming carbohydrates is not easy due to their complexity. So

theyare generally identified with their common
names. Carbohydrates without cyclic
structure are named based on three specific
characters. They are,
(1) Number of carbon atoms present
(ii) Presence of aldehyde or ketone group

)
functional

(iii) D or L configuration
According to the Number of Carbons Present

Carbohydrates containing three carbons are named as trioses, four carbons as tetroses, five
carbons as pentoses
and six as hexoses. The suffix -ose is common for them.
(ii Presence of Aldehyde or Ketone
0Ifthe carbohydrates containaldehyde functional group, they are called as aldoses. If the functional group is
ketone they are called as ketoses.

(ii) D or L Configuration
The hydroxylgroup present on the last carbon of the carbohydratechain determines D or L configuration.
If- OH group is on the right, then it is as a D-Aldose or D-ketose. If-
called OH group is onthe left side
of the last carbon,then it is called as L-Aldose or L-Ketose.

Classification

Carbohydrates are broadly divided into two types: sugars and non-sugars based on their taste. If they are
SWeet to taste, they are called as sugar or saccharides. If not they are called as non-sugars.

These are further classified into three types,

(a) Monosaccharides (b)Oligosaccharides (c) Polysaccharides

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 UNIT-2: ORGANIC CHEMISTRY
(a) Monosaccharides
Saccharides which cannot be hydrolysed further are called as Monosaccharides (or) simple sugars, (e
formula Monosaccharides is, C,H,0,(n =2 to 6).

of
Example: Erythrose, Ribose, Glucose, Fructose etc.
(b) Oligosaccharides
Saccharides which give 2-10 units of monosaccharideson hydrolysis are called as Oligosaccharides

Example: Disaccharides -2 monosaccharides, Trisaccharides- 3 monosaccharides.

(c) Polysaccharides

Saccharides which give more than 10 units of monosaccharides on hydrolysis are called polysacchanid
(or)Non-sugars. These are powder like substances and are also insoluble in water or form suspensions
Example: Starch, Cellulose, Glycogen.
1.2 MONOSACCHARIDES:ALL DISCUSSIONS TO BE CONFINED TO (+)GLUCOSE
AS AN EXAMPLE OF ALDOHEXOSES AND (-) FRUCTOSE AS AN EXAMPLE OE
KETOHEXOSES
Q9. Nhat are monosaccharides? Give the classification of monosaccharides with suitable
examples.
Answer :
Monosaccharides

For answer refer Unit-2,Chapter-1, Page No. 52, Q.No. 8, Topic: (a) Monosaccharides.
Monosaccharides are divided into two main classes. They are,

(i) Aldoses
These monosaccharides contain an aldehyde group (-CHO)and can be represented as,
CHO

(CHOH),

H,OH
Aldoses

(ii) Ketoses

These monosaccharides'contain a keto group

Land can be represented as,
CH,OH

(ÇHOH),

H,0H
Ketoses

The aldoses
and ketoses are further
subdivided based on the number
pentoses etc. Hence for
tetroses, of carbon atoms present
naming a monosaccharide, it is such as triose
group as well as the necessary to indicate both the
number of carbon atoms. For type of carbony
atoms. Table below example, aldohexOses contain
illustrates the aldehydic group and
subclassification of ca
monosaccharides.
No. of Carbon Atoms Generic
Name AldoOse Series
Example Ketose Series
Diose Example
Aldodiose
3 Trioses
Glycoaldehyde
Aldotriose
Glyceraldehyde Ketotriose
Dihydroxyacetone
4 (Glycerose)
Tetroses Aldotetrose
Erythrose Ketotetrose
Pentose Erythrulose
Aldopentose Ribose
6 Hexoses Ketopentose Ribulose
AldohexOse Glucose
KetohexOse Fructose (Levulose)
Table: Subclassification
of
Monosaccharides

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54
Both glucose and fructose Chapter-1:Carbohydrates
are samein molecular
formula but differ with their structural formula.
Glucose is called as an aldose sugar or
aldehyde group in its structure. It's
aldohexose because the presence of six carbon atoms and an
chemical

of
formula Is
CH,,0, and its structure is given as,

H- -OH

HO
H -OH

H- -OH

H,OH

D-Glucose (Aldohexose)
Fructose is calledas a ketosugaror keto hexose
because of the presenceof six carbon
in its atoms and keto group
structure. It's chemical formula is CH,,0,and
its structure is given as,

CH,OH

HO- --H
H-- -OH

H -OH

H,OH

D-Fructose (Keto hexose)

1.3 CHEMICAL PROPERTIES ANDSTRUCTURAL ELUCIDATION: EVIDENCES FOR

STRAIGHT CHAIN PENTAHYDROXY ALDEHYDESTRUCTURE
Q19. Discussthe various chemical propertiès of glucose.

Answer :
Model paper-1, Q144a)

Chemical Properties of Glucose

(i) Oxidation

(a) With Br, Water (Weak Oxidizing Agent)

Glucose is oxidized with bromine water, a weak oxidizing agent to give D-gluconic acid. In this reac
tion, CHOgroup is converted to (a monocarboxylic acid) COOH group.

CHO |COOH
H C- OH H–C OH
|
H –C- H Oxidation
HO –C- H
+Br, water
[O]
H-C- OH H–C OH
-
H-C- OH H-0- OH
CH,OH CH,OH

D-glucose D-gluconic acid (Hexonic acid)

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UNIT-2: ORGANIC CHEMISTRY
(b) With HNO, (Strong Oxidizing Agent)
agent) to give
Glucose is oxidized with concentrated nitric acid(a strong oxidizing
D-glucaric aci

CH,OH groups are oxidized to

(D-gluco saccharic Inthis reaction, both CHO and
acid). COOH
groups.
CHO çooH
H-C- OH H-C OH

HOC- H +HNO,
Oxidation
H C-H
HC- OH Nitric acid
3[0]
HC OH

H-- OH HC OH

COOH
CH,0H
D-glucose D-glucaric acid

(ii) Reduction

(a) With HI and Red Phosphorous

Glucose undergocs®complete reduction with hydrogen iodide (HI) and red phosphorous at 100°c
to form n-hexane.

CHO

H-C-OH
Reduction
HO– C- H +HI+ Red P
CH, – (CH,), – CH,
100°C
H-C- OH n-hexane

H-C-0H
CH,0H
D-glucose
hDIAST
(b) With NaBH, or HPd
Glucoseundergoesmild reduction with sodium borohydride (NaBH,) or
undergoes catalytic reduction
with H/Pd to form D-glucitol (D-sorbitol). In this reaction, CHO group
is converted into CH,OH.

CHO
H-C- OH
CH,OH
HO –C-H +NaBH, or H,/Pd
Reduction

Sodium (CHOH),
2[H]
H-C- OH borohydride CHOH
H-C-OH D-glucitol
(D-sorbitol)
CH,OH
D-glucose

-CHO Reduction
CH, –OHJ
(iii) Acetylation of Glucose

D-glucose upon acetylation i.e., eitherupon heating with sodium acetate or by treatment with acetic
in the presence of pyridine, anhydrtu
results
in the formation of two anomeric penta-acetates,
that, D-glucose solution contains both The reason for hs
and B-glucose formsin equilibrium,
0.
with
which separately react
the acetate to give rise to two anomeric acetates.

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56 TChapter-1:Carbohydrates
CH,OH
CH,OAC
H
H H
Pyridine H
OH 5AC,O
H + 5CH,COOH
OHN OH OAC H
ACO OAC
H
H. OAC
a- D-glucose a-D-pentaacetate

CH,OH
CH,OAC
H OH H
Pyridine OAC
H +,5AC,0
OH 5CH,COOH
OAC
ÖH
ACO
H ÒAC
B-D-glucose B- D-glucoe pentaacetate

(iv) Reaction with Hydrogen Cyanide

Glucose when reacted with hydrogen cyanide (HCN),forms two isomers of cyanohydrin., D-gluconitrile
and D-mannonitrile. In this reaction, HCN gets added at CHO group which results in the fomation of an
asymmetric carbon atom.

H CN CN
H "C- OH HO-CH
H-C- OH H-C- OH H-C- OH
HO C-H + H-CN HO-C- H HO–C H
H-C- OH H-COH H-C OH
H-C- OH H–C- OH H-C-OH
CH,OH CHOH CH OH
D-glucose D-gluconitrile D-mannonitrile

(v) Reaction with Hydroxylamine

Condensation of glucose with hydroxylamine (NH,OH)gives D-glucose oxime.

HC =N- OH
He0
H–C OH H-C-OH
HO–C- H +NH,OH -H HO-CH
H-C- OH H– -OH
H-COH H-C- OH
CH,OH CH,OH
D-glucose D-glucose oxime

Q11. Explain the evidencefor straight chain pentahydroxyaldehyde structure.

OR
Explain the evidences for straight chain pentahydroxyaldehydeof glucose.
(OU)JunelJuly-22, Q14(a)

OR

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 UNIT-2: ORGANIC CHEMISTRY
51
Explain the open chain structure of Glucose. (KU)
Sep.Jt21,Qt
OR
Discuss the structural elucidation of glucose.
MarchlApril-18, Qa
OR
How is the straight chain structure of glucose established?
March-14, Q2
Answer :
Open Chain Structure of GIucose

It involves elucidation of the following,

1. Molecular Formula of Glucose

It is determined by elemental analysis and molecular weight. The determined molecular formula is CH n
2. Acetylation of Glucose

Glucose molecule on reaction with acetic anhydride in the presence ofpyridine|gives a glucose pent

acetate mnolecule, hence this reaction suggest that the glucose molecule has 5 OH groups.

H-(-OH H-c-o--CHs

HO--H CH-c0--CH H3C--0-G H o +5CH3COOH

Acetic aid
Anhydrous pyridine H----CH3
H--oH
acete andufoido
HC-OH H-¢-0--CH3
CH2-OH
CH-0--CH3

Glucose Glucose Pentaacetate

3. Reaction with Hydroxylamine

Glucose reacts with the hydroxylamine (NH, OH) to give oxime product and reaction with the HCN
to give cyanohydrin product. Hence this reaction suggest that the glucose molecule having one aldehyde
functional group present at C, carbon atom.

-H HC=N-OH
H--OH H---OH
NHl -OH
HO--H HO-H
Hydroxylamine
H--OH -Hz0 H--OH
H-C-OH H--OH
CHz-OH H2-OH
Glucose
Glucoxime product

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58
Reaction with HCN Chapter-1: Carbohydrates

OH
-H
H--CN
H--oH
HCN H-C-OH
HO-H
Nucleophilic HO-H
H--OH Addition
H-C-OH
H--OH
H--OH
CH OH
CH,-OH
Glucose
Note: Aldehydes and Gluco cyanohydrin
ketones undergo Nucleophilic
Addition reactions.
4. Reduction to n-hexane

Glucose on reduction with HI (or)Red

phosphorous vields n-hexane.It indicates
that all the six carbon atoms
in glucose molecule linked linearly or it has unbranched six-carbon
chain or straight (open) chain structure.
H
Glucose n-hexane
(or) Redp
5. Reduction

(i) Glucose reduces Tollen's reagent to metallic silver and Fehling's reagent to red precipitate of Cu,0. It
also reduces Br, water to HBr. In these reactions glucose is oxidised to gluconic acid. These reactions
indicates that glucose molecule contain an aldo group.
Br,/H,0
CoOH
Gluconic acid

Glucose
(CHO –COOH)
Silver mirror
Tollen's
(Glucose + Ag,O >Silver mirror)
Reagent

AgNO, + NH,OH 2AgOH +NH,NO,

Ag,0 +H,o
6.
Oxidation

Glucose on oxidation with strong oxidising agent, such as concentrated nitric acid (HNO) gives saccharie

acid. This reaction suggest that glucosehas a primary alcoholic group (i.e., CH, OH group). –
Conc. HNO,
Glucose Dicarboxylic acid/Saccharic acid / Gluconic acid
(CHO COOH; CH,OH COOH)
Based on all the above reactions, the structure of Glucose is,

CHO
ÇooH
CHOH
CHOH
Cu,ott
CHOH
CHOH
H,OH

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59
1.4 NUMBER OF OPTICALLY ACTIVE ISOMERS POSSIBLE FOR THE STRUCTI
cONFIGURATION OF GLUCOSE BASEDON D-GLYCERALDEHYDE AS PRIMA
STANDARD (NO PROOF FOR CONFIGURATION IS REQUIRED)
Q12. Determine the number of optical isomersproducedby aldosesand ketoses.
Answer :
Determination of Number of Optical Isomers Produced by Monosaccharides

The maximum number of optical isomers of monosaccharides (i.e., aldoses and ketoses) depends on h.
number of asymmetric carbon atoms (n) present in the molecule.The formula
given for the number of optically
active isomers for different aldoses and ketoses is 2", where n = number of asymmetric carbon atoms. This is
ac.
cording tothe Le Bel-van't Hoff rule. Since glucosehas 4 asymmetric carbon
atoms, it can exist in 16 isomerie 2=
forms. Similarly, glyceraldehyde with one chiral carbon has 2' =2 stereoisomers.

Optical Isomers of Aldoses

(i) Aldotrioses

These consist of asingle asymmetric carbon atom. Thus Aldotrioses exist as two optical isomers (2=2l)
or one pair of enantiomers.
CHO CHO
H-C OH
!
HO -C-H
CH,OH CH,OH

D-Glyceraldehyde L-Glyceraldehyde

Where, * is the asymmetric carbon.

(iü) Aldotetroses

These consist oftwo asymmetric carbon atoms.Thus, aldotetroses exist as four (2)optical isomers or two
pairs of enantiomers.

CHO CHO CHO CHO

H--OH HOC-H HO-C H HC- oH
HC- OH HO-*C-- H HC-OH HO-*CH
CH,OH CH,OH CH,OH CH,OH
D()Erythrose L()Erythrose DThreose L(+)Threose
(ii) Aldopentoses
These consist of three asymmetric carbon atoms.Thus,
isomers.
aldopentose exist as eight (2)or fourpairs of optical

CHO CHO CHO CHOitst

H-OH -H
HO-Ho
HO C-H HO H-OH
H(-OH -OH
H
HO c-H
H¢-OH HO-H alcr H -OH HO -H
H,OH CH,OH
CH,OH CH,OH
D Ribose L+)Ribose D( Arabinose
L(+) Arabinoses
CHO
CHO CHO
H-oH HO
HO-H
CHO

HO(-H H-OH
H-OH HO¢-H H-OH
H--OH HO-H
H,OH
H-OH HO -H
CHOH H,OH
CHOH
D(+) Xylose
ML Xylose D)Lyxose L(+) Lyxose

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60
AldohexOses Chapter-1: Carbohydrates
(iv)

These consist of four

asymmetric carbon
atoms (n = Thus,
pairs of optical isomers. as sixteen (2') or eight

4),.
Aldohexoses exist
CHO
CHO
CHO
HC- OH "HO-C– H
CHO
HOCH H-C-OH
UGHC- OH HOC- H HC- OH HO-C– H
H"C- OH uo-C-H
H-C-OH HO-C-H
eHC–OH HOC-H H-C-OH H-C-H
CH,OH CH,OH
CH,OH CH,OH,
D(+)-Allose LO Allose D+) -Altrose LO- AItrose
CHO CHO CHO CHO
HC- OH HO-C–H HOCH H-C- OH
HO"C– H H-C- OH HO-"C-H H -C- OH
H-C OH HO-C– H H-C- OH HO–C- H
HC- OH HO–"C-H HC OH HO–"C– H
CH,OH CH,OH CH,OH CH,OH
D(+)-Glucose L() Glucose D(+) -Mannose L Mannose
CHO CHO CHO CHO

H-C-oH H HO-C–H H-C-OH

H-C- OH HO C-H H-C- OH HO–C-H

HO–C-H H - 0H HO–-C–H H-C-OH

HC-oH HOC– H H-C-OH HO–-C– H

CH,OH CH,OH CH,OH

CH,OH
D() Gulose L(+)Gulose D() Idose L(+) ldose

CHO CHO CHO CHO

HCOH H-C– H HO°CH HC- OH

HOC- H HC- OH HO-CH H-C- OH

HOC– H OH HOCH H-c-OH
HC-0H HOC- H HO-C-H
CH,0H CH,OH CH,OH CH,OH

D(+)Galactose L()Galactose D() Talose LO Talose

Among these 8 pairs, glucose, galactose and mannose are important.

Note: D-glucose is the naturally occurring aldose monosaceharide (aldohexose).

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Optical Isomers of Ketoses 1.5 EVIDENCE FOR CYCLIC

STRUC.
TURE OF GLUCOSE
Ketoses possess a keto group (C=0)on the C-2
(PYRANOSE
They as ketotriose, ketotet
STRUCTURE, ANOMERIG
position of the molecule. exist

roses, ketopentoses, ketohexoses and ketoheptoses etc. AND ANOMERS). PROOF CARBON
FOR THE
RING SIZE (METHYLATION.
Examples HY
DROLYSIS AND OXIDATION D
1. Ketotrioses ACTIONS). HAWORTH
FORMULA
AND CHAIR
Example: Dihydroxyacetone the starting
CONFORMATIONAL
rial for all other ketoses.
is mate
FORMULA
Q13. Discussthe evidence for cyclic structus
'CH,0H of glucose.

OR
Give the evidences for cyclic structure
3
CH,OH of glucose. (OU)Sep./Oct.-21,Q4

Dihydroxyacetone OR

2.
Explain mutarotation of glucose.
Ketotetroses:Example: D-Erythrulose
(ReferOnly Mutarotation) Oct.-13,Q8(b)
CH,OH
Answer :
C=0
carbon The chemical properties of D(+)Glucose are

HCoAsymmetric given as a pentahydroxy aldehyde with an open chain

structure. But there are some reactions which cannot be

CH,OH explainedby the open chain structure of D(+)-Glucose.

Evidences to prove Cyclic Structure of D(+)-Glucose

3. Ketopentoses 4. Ketohexoses
(i) Reaction with NaHSO, and NH,
Example: D-Ribulose Example: D-Fructose Glucose does not react with NaHSO, and NH,
due to its ring structure.
CH,OH
CH,OH
C=0 (i) a and ß Varieties

C=0 The carbon present in the aldehyde functional

HO"C-H
HC- OH group of glucose becomes
and can form a
andß varieties of glucose.The a
chiral in the ring structure

H"C-OH and

HC-oH forms differ in arrangenent around the 1 carbon.

HC-0H
CH,OH H OH HOH
CH,OH
HOH H+OH
5. Ketoheptoses HOH HO H

H-OH H+OH
Example: D-Sedoheptulose
H H
CH,OH CH,OH H,OH
C=0 a-D-(+)-glucose B-D-(+)-glucose

HC OH
These a-D(+)-Glucose and B-D(+)-Glucose
knownas anomers.
are

HOC-H (iii) Mutarotation

Ordinary glucose exists as 37% a and 63% 5

uo-OH variety. In aqueous solution, a andB varieties show
increase and decrease in specific rotation till equilibrium
H -C-OH is attained. This is knownas mutarotation. MutarotatiOl

CH,0H is explained by the opening and closing of hemiaceta

ring.

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62
Chapter-1:Carbohydrates
H OH

H -OH HSo HO H
HO -H HOH H -OH
H -OH HO H
HO- -H
H HOH H -OH
H,OH H+ÖH H
CH,0H H,OH
a-D-(+)-glucose
B-D-(+)-glucose
[a], =112° Open-chain form

[a]'s =190
(iv)
Characteristic Reaction ofAldehydes

The concentration of aldehydic form

in equilibrium causes the reactions with hydroxyl amine.
amount of aldehydic form remains after As ittie
reaction with hydroxvlamine. it does not
react with sodium bisulphite and
reagent.
schiff's

(V) Formation of Glucosides

Glucose reacts with methanoltoform a and B methyl-D-Glucosides.They are hydrolysed

and methanol only in acidic back to giucose
solution. Hence there is no mutarotation of glucosides.

H OMe MeOH
HOH H- OH
HO -H o HO- -H
H -OH H+OH
H H
CH,OH CH,OH
Methyl a-D-glucoside Methyl B-D-glucoside
Q14. Establish the cyclic structure of glucose.

OR
[Model Paper-2, Q14(a) |MarchlApril-17, Q2(c)]

Describe the cyclic structure of glucoseand explain how it can be established. Oct.-16, Q2(c)

OR
Discuss in brief how the cyclic structure of glucosecan be established. March/April-15, Q8(a)

OR
Describe the steps involved in the establishment of cyclic structure of glucose.Oct-14, Q2(c)
OR
How do youdeterminethe ring size of Glucose structure? March-13, 2(b)

OR
Discussthe determination of the ring structure of glucose. Oct.-12, a9(a)

Answer : Rdehaye alcoleniacedald

Cyclic or Ring Structure

Hemiacetals are unstablecompounds formed by the reaction of aldehyde with alcohols. As glucose contains
an aldehydic 5- OH groups, possible that there occurs
and it is intramolecularinteraction between the aldehydic
group and any one OH group to result in the formation of cyclic hemiacetal. The basic question that arises is that

Which -OH group undergoes intramolecular interaction according to Baeyer's strain theory, 5 and 6-membered
ings are relatively more stable than compounds containing 3, 4 or 7 atoms. Based on this observation, it can be

predicted that C-4 and C-5 OH groups are more favoured for the formation of cyclic hemiacetal. Among them, OH
Broup at C-5is more favoured because the bond angle strain experienced by 6-membered ring systems is relatively
less than
5-membered ring.

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 UNIT-2: ORGANIC CHEMISTRY
Pyranose Rings of a and ß Glucose
H--OH
H
H-c-OH HO1-H
C-OH H-2¢-OH

C-H HO H H~2 -OH H-c-OH

H-C-OH
HO-H HO H
-fox
-H H-c-oH H-c-OH
5
H-c H-
CH2-OH
CH,OH 6

CH,OH CH,OH
In the above
structure, -OH group of C-5 reacts
with the aldehydic group due to which the C-1(known -D(+)-glucose B-D(+)-glucose
as hemiacetal carbon) Becomes chiral or asymmetric.
Pyranose is a six membered ring
structure
Anomers generally written for hexoses. a and ß varieties ar

called as anomers of D(+)-glucose because they difem

Addition of hydrogen atom of C-5 -OH to the
aldehydic carbon atom, results in the formation of a in configuration around the 1"carbon ofthe ring ony

OH group. This group can be found either on the right Q16. Determine the ring structure of monosac.
side or on the left side, which gives rise to two isomers.
charides glucoseand fructose.
When the hydroxyl group is present on the right of C-1,

the isomer is called a-D-glucose and when it is on left, Answer :

the isomer is named B-D-glucose.
Determination of Ring Structure

H--cOH HO1H The ring structure of monosaccharides is deter

H-cOH H--c2OH mined by the following reactions,

HO-H HO--H 1
Methylation

H-OH H-c-OH 2 Hydrolysis

H- 5 3. Oxidation

CH,OH CH,0H Initially glucose is reacted with CH, –OH n the

presence of HCI, forms two types of methyl glucoside.

a-D(+)-glucose B-D(+)-glucose
namely methyla-D-glucoside and B-D-glucoside the
It can be noticed that both a- and B-D-glucose glucoside do not show the presence of aldehydic group
have sameconfigurations at C-2, C-3, C-4 and C-5, but and mutarotation.
have different configuration at C-1. Hence a-and B-D
glucose are diastereomers. Such isomers which differ From the above reaction it is confirmed that al
among themselves with respect to the configuration dehydic group is not free it might have associated wth
at asymmetric carbon are called anomers and this one of the other groups. In order to account these facts

asymmetric carbon atom is known as anomeric carbon

it is proposed that the -CHO group might be reaçting
atom. This anomeric carbon atom can be easily identified one of the
from others as it is linked to two oxygen atoms.
with
OH groups to form the equilibrium

mixture two cyclic hemiacetalforms. This proposal

of
Q15. Discusson pyranosering structure and was based onfactthat aldehyde reacts with alcohol to

anomers of D-glucose. form unstable hemiacetal.

Answer :
Then, Tollens proposed 5-membered ring (Fu
Haworth introduced projection formulae, for ranose) to glucose, but a 6 membered ring exhibits less

better representation of the cyclic structure of glucose. bond strain than 5 membered ring. Latter Haworth, Hist
He suggested pyranose structures and chair
their and their coworkers have shownthat glucose exisls us
conformations for a and B varieties of
D(+)-glucose. six membered ring based on the following,

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64
Chapter-1:Carbohydrates
a-D(+) Glucose
CH,0H/dryHCI
(CH),SO,
Methyl
a-D(+) Gucoside NaOH
(Methylation)
Methyl 2, 3, 4, 6
dil HCI
tetra-o-methyl 2,3, 4, 6 tetra-o-methyl
g-D(+)Glucoside a-D()
(Reflux Glucose

(Hydrolyis)

Br,/H0
2,3, 4, trimethoxy (Oxidation)
xylo glutaric
acid
Conc.HNO, Tetra-o-methyl gluconolactone

[Oj (Lactone)
Hence glucose by acetal formation,
methylation, hydrolysis of acetal followed by
and HNO, forms 2, ,4 trimethoxy xylo The acid formed contains twoacid
glutaric acid.
oxidation with Brho
aight havebeen produced irom greups (-COOH) which
-CHO and-CHOH roups which are inyolved in cyclic
Based on these reactions glucose had hemiacetal formation.
Pyranose structure.
If possess furanose ring then
it
dimethoxy succinic acid would have
47 been produced at the end.
Explain the Haworth

Answer : projections of pyranose

structures.

The glucose rings can be represented as derivatives of pyran. The following points
should be taken into
consideration while writing the formula ofglucose in
pyranöse form.
Initially, the 6-memberedpyranose ring
(containing 5 carbons and 1 oxygen) is drawn. It is assumed
the lower thickened edge that
of the ring is nearest to the observer.
2. The next step is to draw the carbon atoms
starting from C-1 to C-5 in the
clockwise direction.
3. To make the structure simpler, ring
carbons are not written.
H OH

2 CH,OH
H--OH
3
HOC-H 1

4 OH H
H-OH 2 OH

H OH

a-D(+)-glucose a-D(+)-glucopyranose
4
H and OH groups are indicatedby dråwing lines perpendicularto the plane of the ring. Any line that projects

upwards, lies above the plane and any line that is projected downwards, lies below the plane.

Those -OH groups which lie on the right in the open chain form are projected downwards, while the H atoms
are projected upwards. An exception to this is C-5, where the H atom at C-5 in the open-chain ring is at the

right which is projected downwardsin the pyran ring.

6.
Similarly, -OH groups that are present on the left side of the ring carbon are projected upwards in the py

ranose form..

CH,OH
CH,OH
H H OH
H
Anomeric OH Anomeric
OH atom carbon atom
carbon
OH OH
OH
3
ÒH OH
H
B-D(+)-glucopyranose
a-D(+)-glucopyranose

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 UNIT-2: ORGANIC CHEMISTRY
Q18. Explain the chair and boat form of the glucose.

Answer :

From careful observation of the structure of ß-form of glucose (B-D-glucopyranose) it can be

the far right carbon in B-glucose has one -OH up, the next -OH ddown, the next -OH up, the next -OH noticedtha
down
finally the CH,OH group up.
This kind of arrangement of OH (and CH,OH)groups aboveand below andthe
the
plane
the ring keeps these groups out of each others way. As a result of this, the B-glucose becomes the
most
the hexoses.Inthe o-glucose, the far right carbon has -OH group below the plane of the ring,
thereby
stable

lacking
optimal Therefore, a-form of glucose
staggering. is not much stable. The ring forms ofsugars are not
planar,
can assumeboat or chair forms as shown below.
by

H H(a)
OH
OH
OH (e) OH
OH CH,OH
i
CH,OH H

HO H

OH

OH fOH
H
OH.

H
H

OH
-H
OH

Boat form Chair form A H{ Chair form B

OH OH

The boat form is less stable than the chair form. The two chair forms A and B can interchange by interconversiu
of axial and equatorial groups. In the case of glucose, the chair form A presents all the OH groups in the eqatorial
plane. So,in this conformation, the stèric crowding is reduced and the OH groups are readily accessible.

1.6 STRUCTURE OF FRUCTOSE:EVIDENCE OF 2-KETOHEXOSE STRUCTURESAME

OSAZONE FORMATION FROM GLUCOSE AND FRUCTOSE, HYDROGEN BONDING
IN OSAZONES

Q19, Explain how 2-ketohexoses are considered as ketoses (fructose). Model Paper-3, Q14a)

OR

Give the evidence for 2-ketohexosestructure. (OU)June/July-22, Q4

Answer :

Structure of Fructose

Fructose is the most general form of ketose, which is available widely in fruits and common table suga

(sucrose).It is an example of ketoses and also most important among them. The structural determinationof iructos
is as follows:

(a) The molecular formula of fructose is CH,,0,.

(b) It forms penta O-acetyl derivative same as glucose indicating the presence of five -OH groups

(c) It gives cyanohydrins suggesting the presence of carbonyl group.

(d) Fructose reduces reagents of Tollens andFehling'stests similar to glucose. It gives a mixture of carboxylie

acids but with decreasedcarbons on reaction with nitric acid. This showsthat frùctose is a ketone.

by
(e) The keto group in cyanohydrin, followed
position of fructose is known by reaction with HCN to give
hydrolysis and the Hence,fructose
reduction with HI/P(red) )forming 2-methyl hexanoic acid as final product.

is a 2-ketohexose.

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 66
CH,OH Carbohydrates
Chapter-1:
CH,OH
CH,OH CH,
cøCN) CHCOOH
CHOH çOHCOOH
HCN CHOH
CHOH
H,O HVA ÇH,
CHOH P(red)
HOH CHOH
CHOH CH,
CHOH
CHOH
CH,
CH,OH
CH,0H
CH,OH CH,
Fructose
Cyanohydrin
Hydroxy acid a-Methyl-Caproic acid (or)
2-methyl hexanoic acid

The above sequence of

(2-Carboxy-n-hexane) 2-motin-han
reaction givesan idea of fructose
A0 Explain the formation of
structure with ketose group.
glucosazoneand fructosazone.
OR
Discuss the Osazone formation from glucose and the importanceof hydrogen bonaing
involved in
it.
March/April-15, Q9(a)

OR
Explain the glucosazoneformation.
March-13, Q7(b)
(ReferOnly Glucosazone Formation)

Answer :
Reaction with Phenylhydrazine (Osazone Formation)

Reaction of glucose with phenylhydrazine gives rise to D-glucose phenylhydrazone.

However, treatment
with excess (3 moles) reagent results the formation
in of a D-glucosazone by reaction with 2
molecules.
phenylhydrazine

(a) Glucose when treated with CHNH.NH,, gives glucose phenylhydrazone.

HÇ 0
HC=NNHC,H,
H-C- OH H-C OH
H –C- H +C,H,NH.NH HO-C– H
- H,0
H-C- OH Phenylhydrazine
H-C-OH
H -COH H-C- OH
CH,OH
CH,OH
D-glucose lD-glucose phenylhy drazone

(b)
However in the presence of excess reagent, the glucose phenylhydrazone so formed undergoes oxidation
with second phenylhydrazine molecule to form a carbonyl group (C=0)on second carbon atom.

= NNHC
HC H, HC =N.NHC H,

H––H HO-C-H + CHNH, +NH

H-(-0H
+ CH,NH.N,H, H-C-OH
H–C-OH H-C-OH
CH,OH CH,OH

(c)
Finally,the carbonyl group of phenylhydrazone reacts with third phenylhydrazine molecule to give
D-glucosazone obtained as needle shaped crystals. These osazones are used for identifying the sugars.

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 UNIT-2: ORGANIC CHEMISTRY
HC=NNHC H,
HC=NNHC H,

C0 C=NNHC

H.
HO -C- H
+CH,NH NH, -H0 HO-C -H
H-C- OH H-C- OH
H-C- OH H-C- OH
CH,OH CH,OH
Cyclic intermediate D-glucosazone yellow
(Needie shaped crystals)

(Yellow ppt)

Note: Glucose and mannosealso form the same osazone when treated with phenylhydrazine as glucose and man.

nose are C, epimers (i.e., they differ only in configuration aC).

(i) Formation of Fructosazone

Similar to glucose, fructose also forms fructosazone which is similar to glucosazone (formed by glucose).

CH2OH
CsHsNHNH2 HTHOH CHH
=O
NNHCotts
A-NHCstts
-H20
¢HOH)S (ÇHOH)3 (CHOH3
H20H bHOH

Fructose Fructose phenyl hydrazóne -CstisNH2)

CH=NNHCsH5 CH=O

-NNHC|Hs CstsNHNH2
-NH3
H2OH
Fructosazone

It should be noted that the fructosazone formed with fructoseis same as glucosazone obtained from glucose.

This implies that glucose and fructose differ among themseives only in the configurationofC-l and C-2.

bonding involved osazone formation due to chelated ring by two carbon

Inter molecular hydrogen is in

atoms.

Importanceof Hydrogen Bonding

The hydrogen atoms present in the osazones are bonded by internal hydrogen bonds. These hydrogen bonds
stabilize the osazones as soon as the formation ofosazone takes place. Thus, no other carbon atoms(Exeept
C, and C,) can further participate in osazone formation.

1.7 cYCLICSTRUCTURE FOR FRUCTOSE (FURANOSE STRUCTURE, HAWORTH

FORMULA)
a21. Explain the concept of cyclic structure of fructoseand furanose structure with Hawortn
projections.

Answer :

Cyclie Strucure of Fructose

The cyclic structure of fructose can be explained with the help of six membered hemi ketal ring sruetu
D-fructose also exhibits mutarotation similar to D-glucose under equilibrium conditions. a, B forms of D-rucos
in the open chain form are
represented as,
68 Chapter- 1:Carbohydrates
HOH,C OH CH,OH HO CH,OH

HO – C-H
HO –C=H
HO-CH
H-C-OH
H-C-0H H-C-OH
HO–C-OH
HO–C-OH HO-C-OH
CH, CH,- 0-H CH
a-Dfructose
D -fructose
B-D frctose
(Openchain)

Haworth Projections
Alcohols react with the carbonyl group of aldehvdes and ketones to form
hemiacetals and hemiketais.
chain is long and
flexible it Wraps aroundto
the carbon form cyclic hemiketal l or hemiacetal to give five membered
six membered rings.
or

The carbonyl group C, reacts

of fructose at with the hydroxvi group at C.to form 2 types of cyclic hemiketa
h 5 membered rings called a and B-D-Fructofuranose.

8.F
HOH,COH
HO H CH,OHo CH,OH
H+OH KH HO
HOH,C H OH
H
ÖH
a-D-()-Fructofuranose

HOCH,OH
HOH CH,OHo
HO
OH
H+OH H CH,OH
HOH,C H
OH H
B-D-(-)-Fructofuranose

Fischer projection Haworth projection

Q22. Comparethe Haworth structure of glucoseand fructose.

Answer : MarchlApril-16. Q8(a)

Haworth Structure of Glucose

6 6
CH,OH CH,0H

H H OH
H H
4 4

OH H OH
OH OH HO
2 3

H OH H
a-D(+)Glucopyranose B-D+)Glucopyranose
(0)
The Haworth structure of glucose consists of two Pyranose structures (a and B).

(i1)
These pyranose structures are in hexagonal shape.
(iiy
These structures of glucose consists of 4-OH, 1-CH,OH groups and 5 hydrogen bonds.
(iv) of six membered cyclie structure.
The pyranose structure of glucose consists

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 UNIT-2: ORGANIC CHEMISTRY
Haworth Structure of Fructose

HO -H,C OH
CH,- OH HO-H,C

H H
H OH/
OH H
4 CH,- OH
4 3

OH H H
OH
a-D(-)Fructo Furanose B-D(-) Fructo Furanose
(i) The Haworth structure of fructose of two anomers of
consists furanose (aand B).

(1) These anomers are pentagonal in

shape.

(ii) These anomers of fructose consists of 3 -OH. 2 -CH.OH groups and 3

hydrogen atoms each.
(iv) This structure consists ofa 5 membered ring called furanose.
1.8 INTERCONVERSION OF MONOSACCHARIDES
1.8.1 Arabinose to D-Glucose, D-Mannose (Kiliani -Fisher Method)
Q23. Explain the Kiliani-Fisher method for
conversion of arabinose to glucoseand mannose.
OR
Write aboutthe Killiani-Fischersynthesis.
(MGU) JulylAug.-22, Q9
Answer :

Kiliani-Fisher Synthesis (Conversion of Aldopentose to

Aldohexose)
The conversion ofa lower aldose to higher
analogue (i.e., aldopentOse to aldohexose) is
series of reactions. This synthesis is carried out bya
known as Kiliani Fisher synthesis. It
dehydration reactions, followedby reduction
involves, addition of HCN, hydrolysis,
of lactone in the presence of Na-Hg
is represented as follows, yields the product. The synthesis

CN COOH
CHO
H-C-OH H-C-OH
HO-–H H,0 H--0H
HO–-H Heat H-C-0H
H--OH
Hydrodysis

H-C-0H -HO Na-Hg/H0*

HO-C-H
HO-C-H Reduction
H-C-OH
CHO
H--OH H

HO-¢-H CH, OH
H-c-OH
CH, OH
H--OH CH,OH
HCN Cyanohydrin Gluconic acid H,OH
H--OH derivative (Aldonicacid)
CH, OH
a D-gluconolactone (AldohexOse)

COOH D-glucose

(D- arabinose) H-C-H HO-C-H CHO

Aldopentose HO-C-H H,0" HO -¢-H HO–-H

H-C--OH H-C-0H
Heat HO -(-H
Hydrolysis Na-Hg / H,0"
HC-H
H,0
HO-CH Reduction
H-(-OH H-C-OH H-C-OH
CH, OH
H-e
CH, OH H-C-OH
H-e-OH
D-mannono CH,OH
D-mannonic H,OH
nitrile
acid D-mannose
a-D-mannono
lactone
(AldohexOse)
D(+) glucose and D(+)
mannose are optically
Further if twodiastereomers butnot mirror active
differ in the images, Hence they are
configuration at about single diastereomes
Therefore D(+) glucose and carbon atom, they are
D() mannose differ at C, called epimes
one epimer into another epimer is carbon atom, hence they are epimers,
called epimerisation. The conversion e
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 Carbohydrates
Chapter-1:
70 Epimerisation-Lobry De Bruyn Van Ekenstein Rearrangement
Epimers,
1.8.2 about epimerization.
Explain
Q24. OR Q2(c)
Oct.-12,
epimers? How

Answer
:
What are
is D(+) Glucose converted into its epimer.

Epimer answer refer Unit-2, Chapter-1, Page No. 49, or

Q.No.
two

3.
For
is in which one asymmetric carbon atom which contains
a process in a compound
Epimerization
carbon atoms, undergoes a change in its configuration.
carbon
more
asymmetric
formulae of epimers is depicted in figure. It may be 1 noted that the group on second OH
The structural Hence glucose
left side.
is onthe right side the Fischer projection whereas in mannose, it is towards to carbon
of
with respect
in glucose are considered to be epimers. Similarly, D-glucose and D-galactose are epimers
mannose the left side.
is on
and
The OH
group on 4C in glucose onthe right and in galactose,

it
epimers).
is
atom 4 (C, CHO CHO 1CHO

H–2C-OH
C-H
H– 3C-H
HO– 4C -H
H– SC-OH
H– 3C-H
H–C-
T
OH

H–5C–OH
| HO –

H–4C– OH
H–5C–OH
óCH,OH 6CH,OH 6CH,0H
D-galactose D-glucose
D-mannose

Figure: Structural Formulae of C,and C, Epimers

Epimerization can be accomplished either by using enzymes or by chemical means.

Example:
1. Conversion of galactose to glucose in liver by the enzyme epimeraše.
2. Conversion of glucose to mannose.

Glucose and mannose are epimers which differ only in their C-2 configuration.The conversion of glucose
steps.
into mannose is carried out in three
CHO CHO
H-C-OH HO-C- H
HO -(-H HO- C-H
H-C-OH H-Ç-OH
H-C-OH H-Ç-OH
CH,OH CH,OH

D-glucose 3D-mannose
Step 1: Oxidation of Glucose

Glucose is oxidized with bromine water to form gluconic acid.

CHO COOH
H--OH H-C- OH
H -C-H Oxidation
HO- C-H
+ Br, water
HC-0H (0)

H-ç-OH
H-OH H-C- OH
CH,0H CH,OH

D-glucose D-Gluconic acid

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 UNIT-2:ORGANIC CHEMISTRY
Step 2: Heating of Gluconic Acid

Gluconic acid when heated in the presence of pyridine (CH,N), results in the formation
of a
containing gluconic acid and its epimer (epimeric gluconic acid). Both these aldonic acids are
a

mioxtba
epimers
difer in the configuration of OH group about C-2. The mixture containing these epimeric aldonic acids
further to obtain lactones.

COOH COOH C=0

HC-OH HO C-H HO –C–H H-C-OH
HO-C-H Pyridinc(C,H,N) HO-C-H H – C-H Ot HO– C-H
H-C-OH Heat H-C H-C
H-C-OH
H-C-OH H-C-OH H-C-OH
H-¢-OH
CH,OH CH,OH CH,OH CH,OH
Guconic acid
Epimeric gluconic acid y-D-Mannonolactone
y-D-Gluconolactong
(D-Ghucose acid) (D-Mannonic acid)

Step 3:Reduction of Lactone

Lactone undergoes reduction with sodium amalgam (Na-Hg) to give D-mannose. Thus, this proces hel
in the conversion of glucoseto mannose (its epimer).

'CHO
21
HO-C-H
HO-C-H HO--H
HO-H Reduction
H-t-OH
Na-Hg/H
H

HC-OH
(amalgam)
HC-0H
bH,OH
6CH,OH
D-Mannonolactone D-Mannose

Q25. Explain about Lobry debruynVan Ekenstein rearrangement.

Answer :

Action of Alkalí (Lobry de Bruyn-van Ekenstein Rearrangement)

Mechanism

1
Initial

1on.
step involves the rémoval of . hydrogen atom of D-glucose by the base to yield D-glucose enoldi

2 Proton can be added to this enolate anion. The type of product formed (D-glucose or
D-mannose) upo
protonation isdependent upon the direction from which the proton attacks the enolate
anion. If the pro
attacks from above, then forms D-mannose and ifthe attack is made from below
then D-glucose is Tom
it
3. This enolate anion is resonance stabilized. Hence
Oxygen ofC-1Ito
it is also 1 yield
possible to protonate the
an enediol.

4 Deprotonation from C-2 OHgroup results in the formation of an enolate anion,which is also resonai
stabilized. Hence it is possible to protonate it at C-1 to yield D-fructose.

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72
HCo Chapter-1:Carbohydrates
H
HO H
-OH
dil. alkali
Ho HO
CHO
H
-OH
H OH HO HO
-H
HOH H -OH
H -OH
H,OH HOH H-OH
D-Glucose CH,OH CH,OH
D-Mannose

CH,OH

HOH
HOH
HOH
CH,OH
D-Fructose
1.8.3 D-Glucose to D-Arabinose
by
Ketohexose (-) Fructose and Ruff's Degradation -
AldohexOse
Ketohexose (-) Fructose to
()Glucose to
Aldohexose (+)Giucose
026. Explain the following
conversions with equations
() D-Glucose to D-Arabinose
(ii) D-Glucose to D-Fructose
(OU)Sep.Oct.-20, Q12 |March-12, Q2(c)]

OR
Discuss the conversionof glucose
to arabinose and glucoseto
fructose. March/April-15, Q2(c)

)
Answer :

D-Glucose to D-Arabinose

Ruff's degradation is a chemicalreaction

/ Ruff's Method

which H
CO0

OH
(Ca2t) HC =0
eliminate the one carbon in the aldose chain. It means
that hexoses are transformed into pentosesand pentoses
HO HO H
are transformed H OH
into, tetroses etc. In Ruff's reaction. fH,0, H
OH +CO,
calcium D-gluconate (calcium salt of aldonic acid) H -OH Fe+
H OH
is oxidized with H,0, in the presence of ferric ion
as catalyst the reaction. In this reaction, the bond
in CH,0Ca CH,OH
between C,and C,carbons are broken to form CO, and
Calcium D-gluconate D-arabinose
aldehyde. The chemical reaction can be illustrated as,

Calcium salt of aldonic acid is formed by oxidizing the glucose with aqueous solution of bromine. Ca(OH),
is then added to the resultant compound i.e.,

HC =0 COO COO (Ca 2)

H OH H OH H OH '-H
HO H HO H OH–
Br, Ca(OH),/CaCO,
Heat
H,O,|Fe? HOCH
OH +H,0 H OH H OH
H
Fentons reagent
H OH
(Weak
H OH H OH H-C-OH
oxiding

CH,OH agent)
CH,OH CH,OH H--OH
CHOH
Ca[C,H,0,:
Calcium-D-gluconate Arabinose
D-(+)glucose D-(+)gluconic acid

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UNIT-2: ORGANIC CHEMISTRY
(ii) D-Glucose to D-Fructose

The conversion of D-gucose to D-fructose involves three steps. They are,

) Osazone formation

(i1) Hydrolysis of osazone

(iii) Reduction of ozone.

Initially, D-glucose is combined with phenylehy drazine which results in the formation of osazone.

In the second step, the hydrolysis of osazone gives an "osone". This step is again carried out in dil. HCI

In the final step, the reduction of ozone to ketone in the presence of zinc and acetic acid produces fructoes

H-C=0 HC- N.NHC H,

Phenyle
CHOH C=N.NHC H,
hydrazine

(CHOH), 3C,H,NHNH, (CHOH),

CH,OH H,OH
D-glucose Glucosazone

Hydrolysis
2H,0
2NH, - NH-C,H,

CH,0H CHO
C=0 C=0
Zn/CH,COOH
(CHOH), (CHOH),
-(CH,OH) CH,OH
D-fructose Glucosone
Q27. Convert Arabinose to D-glucose and Glucoseto Fructose.
Answer :
(MGU) July/Aug.-21, Q3
Arabinose to D-Glucose

For answer refer Unit-2, Chapter-1,Page No. 69, Q.No.23.

Glucose to Fructose

For answer refer Unit-2, Chapter-1,Page No. 72,Q.No.26, Topic (ii).

Q28. Write the conversion of ketohexose to aldohexose.

OR
Describe the interconversions of,

(i)
(OU)Sep/Oct.-21, Q15
D-glucose to D-arabinose and
(ii) Fructose to glucose.
Answer :
D-Glucose to Arabinose

For answer refer Unit-2, Chapter-1, Page No. 72,

Q.No. 26,Topic ().
(ii) Fructose to Glucose
The conversion of ketohexose
i.e., D-fructose to aldohexose
series of i.e., D-glucose or D-mannose
reactions. They are represented as follows, involves a

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74 Chapter-1:Carbohydrates
CH,OH

H--OH COOH
HC-0H
HO–C-H Conc.HNO, H--OH
(Oxidation)
HOP-H
H-Ç-OH HO-(-H
fractional
H-¢-OH H--OH
distillation H-¢-OH
CH,OH H--OH CH,OH
D-glucitol CH,OH
CH,OH
D-gluconic acid 1-D-gluconolactone

+NaHg
HO-C-H (Reduction)
-¢-OH
(or)
H-¢-OH NiH,
CHOH CH,OH
=0
COOH
HO--H -H
D-fructose HO--H HO
HO-C-H
cetlirbs Conc.HNO. HO--H H,0* HO PC-H
H-Ç-OH
(Oxidation)
H-¢-OH H
H-¢-OH
CH,OH
H-¢-OH H-¢-OH
CH,OH CH,OH
D-mannital
D-mannonoic acid y-D-mannolactone

The lactones formed are in mixture. Thus they are separated by fractional crystallisation and after sepration

the y-D-gluconolactone and y-D-mannonolactone are reduced to D-glucose and D-mannose respectively by either

LAIH, or Na-Hg/H,0*

CHO
H--OH
HO --H
NaHg/H,0*
y-D-gluconolactone H--0H
(or) LiAIH,
H--OH
H,OH
D-Glucose

CHO
HO –-H
NaHg/H,0 HO -C-H
y-D-mannonolactone
(or) LiAIH, H--OH
H-C-OH
CH,OH
D-Mannose

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