Natural Products

1. Write the structure of menthol and give its two uses.

Menthol is used i) in perfumes ii) as a flavoring agent. iii) in liquors iv) in candles, chewing
gums and certain brands of cigarettes v) as antiseptic in ointments, inhalers (vicks inhaler),
nasal sprays and gargles.vi) in tooth pastes, shaving creams, face creams etc.

2. What is glycosidic bond? Give an example.

The linkage between monosaccharide units through oxygen in oligo and polysaccharides is
called glycosidic bond.
Eg. In maltose, the two glucose units are linked through 1-4 glycosidic bond
3. Sucrose is a non-reducing sugar. Give reason.
For a sugar to act as reducing agent, it should have free aldehyde or ketone group or should have
free anomeric carbon. In sucrose the anomeric carbons of both glucose (C1) and fructose (C2)
are involved in glycosidic bond (1-2) formation. Hence sucrose is non-reducing.
4. Mention any two medicinal uses of i) Morphine ii) Cocaine
Morphine is used: i) as an hypnotic (sleep producing drug) ii) as an analgesic
Cocaine is used as local anesthetic in surgery and dentistry
5. State isoprene rule.
The skeleton structure of all terpenoids is built up of isoprene units joined head to tail. This is
called isoprene rule.

6. Name the monosaccharides obtained when i) Sucrose ii) Lactose are hydrolyzed
Sucrose on hydrolysis gives α-D-glucose and β-D-fructose
Lactose on hydrolysis gives β-D-galactose and α-D-glucose
7. How is the presence of 5 hydroxyl groups in glucose established?
When glucose is treated with acetic anhydride in presence of pyridine, glucose penta-acetate is
formed. This shows the presence of 5-OH groups in glucose.

8. What are anomers? Give an example.

The isomers which differ in the spatial orientation of groups on anomeric carbon (the newly
formed chiral carbon due to cyclisation in sugars) are called anomersEg. α-D-glucose and β-D-
glucose are anomers
9. What are epimers? Give an example.
Epimers are the isomers which differ in the orientation of groups on a specific chiral carbon
Eg. Glucose and galactose are C4 epimers; Glucose and mannose are C-2 epimers
10. How is the presence of N-CH3 group indicated in nicotine?
When nicotine hydroiodide is treated with methyl iodide yields nicotine isomethiodide which on
oxidation with potassium ferricyanide followed by dichromate oxidation yields N-methyl
proline. This reaction shows the presence of N-CH3 group indicated in nicotine
K3Fe(CN)6
C10H14N2 HI CH3I C10H14N2 CH3I C10H13N2O CH3
CrO3

N-methyl proline
11. Write the structure of menthol and indicate the isoprene units.

12. Write the structure of nicotine and name the heterocyclic rings present in it.

The heterocyclic rings present are pyridine and pyrolidine

13. Give any two uses of the following terpenoids: i) Vitamin A ii) Limonene iii) α-Terpineol
iv) Menthol v) β-Carotene vi) Camphor (2m each)
i) Vitamin A: used i) in the treatment of night blindness ii) to cure xerophthalmia
ii) Limonene: used i) as a flavor in food, beverages and pharmaceutical preparations ii) in the
manufacture of p-cymene etc. iii) as a fragrance in perfumes
iii) α-Terpineol: is used i)in perfumes and cosmetics. ii) as a flavoring agent iii) as a potential
anticancer agent
iv) Menthol: used i) in perfumes ii) as a flavoring agent. iii) in liquors iv) in candles, chewing
gums v) as antiseptic in ointments, inhalers (Vicks inhaler), nasal sprays and gargles vi) in tooth
pastes, shaving creams, face creams etc
v) β-Carotene: used i) in pharmaceuticals ( usually as a source of vit A and potential anticancer
agent) ii) as a food and feed additive. iii) for coloring butter and margarine (artificial butter).
vi) Camphor: used i)as a moth repellant ii) as an incense ( in religious offerings) iii) in
pharmaceutical preparations due to its analgesic, antiseptic and stimulating effects iii) as a
preservative in cosmetics
14. Give any two uses of the following alkaloids: i) Ephedrine ii) Caffeine iii) Cocaine
iv) Atropine v) Quinine vi) Morphine (2m each)
i) Ephedrine: Used as used in the treatment of asthma and fever, ii) used to prevent low blood
pressure during spinal anesthesia
ii) Caffeine: used i) as a mild stimulant to the central nervous system, the heart and respiratory
system.ii) in sleep preventing pills iii) in beverages (coffee and tea)
iii) Cocaine: used i) as a Rodenticide ii) as local anaesthetic in surgery and dentistry
iv) Atropine: used i) to dilate (enlarge) the pupil of the eye during eye surgery and
ophthalmology ii) as an antispasmodic ( contraction of muscles)
v)Quinine: used i) as a potential antimalarial ii) as an antiseptic iii) as a flavoring agent in
carbonated drinks
vi) Morphine: i) as an hypnotic (sleep producing drug) ii) as an analgesic ( pain reliever)
15. What is mutarotation? Give the mechanism.
The phenomenon of change in specific rotation of a solution of an optically active compound
with time is called mutarotation
Eg. A freshly prepared solution of α ,D-glucose has the specific rotation of 112 0 and gradually
decreases to 52.70 on keeping. Similarly, freshly prepared solution of β-D-glucose has the
specific rotation of 18.70 which gradually increases to 52.70. Thus, specific rotation of both forms
of glucose changes to a constant value of 52.70
Mechanism of mutarotation: The mechanism of mutarotation involves a concerted attack by acid
and base (water is amphiprotic i,e it acts as an acid as well as a base) to produce the open chain
structure and then it recylises to the other anomeric form.

16. How do you show the presence of -CHO group in citral?

Citral forms an oxime with hydroxyl amine and gives an adduct with NaHSO3. These reactions
indicate the presence of a carbonyl group in citral. Citral on reduction with sodium amalgam and
alcohol gives a primary alcohol, geraniol and on oxidation with moist silver oxide gives geranic
acid. These reactions indicate the presence of an aldehyde group in citral.

17. How do you show that citral contains two carbon carbon double bonds?
When citral is treated with bromine in methylene chloride dibromo derivative is obtained by
consuming two molecules of bromine which indicates citral contains two carbon carbon double
bonds. C10H16O +Br2 C10 H12 Br4O
18. How is fructose converted to glucose? (4m)
 Conversion of fructose to glucose involves the following steps.
i)Fructose on reduction with hydrogen in presence of nickel catalyst gives a mixture of sorbitol
and mannitol.
ii) Sorbitol is separated from the mixture and then oxidized with H2O2 in presence of
ferrous sulphate (Fenton’s reagent) forms glucose

19. How is glucose converted to fructose? (4m)

Conversion of glucose to fructose involves the following steps.
i) When glucose is treated with excess of phenyl hydrazine, glucosazone is formed
ii) Glucosazone on hydrolysis with dil. HCl gives glucosone
iii) Glucosone on reduction with zinc and acetic acid forms fructose

20. What are alkaloids? How are alkaloids classified? Give an example for each.(4m)
Alkaloids are the class of naturally occurring organic nitrogen-containing bases. Alkaloids
have diverse and important physiological effects on humans and other animals, According to the
nature of hetero cyclic ring present, alkaloids are classified as follows.
1. Pyrolidine alkaloids Eg. Hygrine
2. Piperidine alkaloids. Eg.piperine
3. Pyridine-pyrolidine alkaloids.Eg. Nicotine
4. Pyridine-piperidine alkaloids.Eg .Anabasine
5. Quinoline alkaloids. Eg. quinine
6. Isoquinoline alkaloids.Eg. Morphine
7. Indole alkaloids.Eg. Reserpine
21. Write any four general characteristics of alkaloids. (4m)
General characteristics of alkaloids
1. State: Generally alkaloids are colorless crystalline solids( coniine and nicotine are liquids.)
2. Solubility: Generally, alkaloids are insoluble/sparingly soluble in water but soluble in organic
solvents like alcohol, ether, benzene etc. However, liquid alkaloids are soluble in water.
3. Optical activity: They show optical activity, most of them are laevorotatory. It is useful in
resolving (separating) racemic mixture.
4. Basic nature: They are strongly basic and form salts with mineral acids such as HCl, HNO 3etc.
They are readily soluble in water.
5. Precipitation: Certain substances known as ‘alkaloidal reagents’ such as tannic acid , picric
acid, phosphomlybdic acid etc. can precipitate alkaloids from aqueous or acid solution. Many of
these have charactestic colors and definite crystalline shapes. Hence, they are used in the
identification of alkaloids.6. Physiological action: Generally, alkaloids are intensely bitter to
taste and often have pronounced physiological action when administered to humans and other
animals. Some are poisonous. Many are used in trace quantities for medicinal purpose.
22. How terpenoids classified based on number of isoprene unit? Give an example for each (4m)
Terpenoids are classified on the basis of no. of isoprene units present in them. One terrene unit is
taken as equivalent to two isoprene units.
Class No. of isoprene units M.F Examples
Monoterpenes 2 C10H16 Citral
Sesquiterpenes 3 C15H24 Zingiberene
Diterpenes 4 C20H32 Vitamin A
Triterpenes 6 C30H48 Lanosterol
Tetraterpenes 8 C40H64 β-Carotene
Polyterpenes n (C5H8)n Natural rubber
23. How terpenoids classified based on structure? Give an example for each. (4m)
Each class of terpenoids is further classified on the basis of their structure into two types.
They are 1) Acyclic terpenoids. Eg. Acyclic monoterpenoid-citral
2) Cyclic terpenoids. Cyclic terpenoids are further classified as monocyclic, bicyclic or
tricyclic according to the no. of rings they contain.
 Monocyclic mono terpenoid-menthol,
 Bicyclic mono terpenoid-camphor
 Monocyclic sesqui-terpenoid-zingiberene
24. How do you prove the presence of three double bonds in zingiberene? Give equation.
Zingiberene adds on three moles of hydrogen in presence of platinum catalyst to form
hexahydrozingiberene, C15H30. This indicates the presence of three double bonds in zingiberene.
C15H24 + 3H2 C15H30
25. How do you prove the presence of isopropylidine group in zingiberene?
Ozonolysis followed by reduction of zingiberene yields acetone, levulinic acid and succinic acid.
Formation of acetone as one of the products reveals the presence of isopropylidene group.

26. Write the Haworth structures of i) Maltose ii) Sucrose iii) Lactose iv) Glucose v) Galactose
vi) Mannose vii) Fructose
i) Maltose ii) Sucrose
 iii) Lactose iv) Glucose

v) Galactose vi) Mannose

vii) Fructose

27. Write the structural formula of the following: i) Citral ii) Zingiberene iii) Menthol
iv) Vitamin A v) Limonene vi) α-Terpineol vii) Nicotine viii) Camphor
(each 2m)
i) Citral ii) Zingiberene iii) Menthol

iv) Vitamin A v) Limonene

vi) α-Terpineol vii) Nicotine

ix) Camphor
28. Write the structural formula of the following alkaloids: i) Ephedrine ii) Caffeine
iii) Cocaine iv) Atropine (each 2m)

i) Ephedrine ii) Caffeine

iii) Cocaine iv) Atropine

29. How do you establish the presence and position of double bonds in citral? Give equations.
Presence of two double bonds: It adds on two molecules of hydrogen or bromine which
indicates the presence of two double bonds in citral.

Position of double bonds: a) Citral on oxidation with alkaline KMnO4, followed by chromic
acid yields acetone, oxalic acid and levulinic acid (4-oxopentanoic acid). The formation of these
products confirms the above structure of citral.

This reaction clearly indicates the position of two double bonds.

The position of two double bonds is further confirmed by ozonolysis. Citral on ozonolysis yields
levulinic aldehyde, acetone and glyoxal
30. Name and write the structure of products formed when citral is treated with potassium
permanganate followed by chromic acid.
Citral on oxidation with alkaline KMnO4, followed by chromic acid yields acetone, oxalic acid
and levulinic acid (4-oxopentanoic acid).

31. Describe the synthesis of citral from methyl heptenone.

32. Outline the synthesis of nicotine from succimide(4m)

Succinimide is reduced and treated with dimethyl sulphate to get N-methyl Pyrrolidone which is
condensed with ethyl nicotinate

succinimide N-methyl Pyrrolidone

33. Elucidate the open chain structure of glucose.
The open chain structure of glucose can be deduced from the following experimental
observations.
1. Molecular formula: From elemental analysis and molecular mass determination, the molecular
formula of glucose is C6H12O6.
2. Presence of straight chain of 6 carbon atoms: When glucose is reduced with hydriodic acid in
presence of red phosphorus, n-hexane is formed. This shows that all the 6 carbon atoms in
glucose are in a straight chain.

3. Presence of 5 –OH groups: When glucose is treated with acetic anhydride in presence of
pyridine, glucose pentaacetate is formed. This shows the presence of 5-OH groups in glucose.

4. Presence of carbonyl group: Glucose reacts with hydroxyl amine to form glucose oxime which
indicates the presence of carbonyl group.

Similarly, it reacts with HCN to form cyanohydrins, which also indicates the presence of
carbonyl group.
5. Presence of aldehyde group: Glucose on oxidation with mild oxidizing agent like bromine
water gives gluconic acid which shows presence aldehyde group because mild oxidizing agents
oxidize only aldehyde group.
6. Presence of primary alcoholic group: oxidation with strong oxidizing agent like nitric acid
gives glucaric acid, a dicarboxylic acid.

Formation glucaric acid indicates the presence of primary alcoholic group (-CH 2OH).Based on
the above evidences, Emil Fischer gave the following open chain structure to glucose.

34. Write a note on elucidation of structure of citral.

1. Molecular formula: From analytical data and molecular weight determination, the molecular
formula of citral is C10H16O.
2. Presence of two double bonds: It adds on two molecules of hydrogen or bromine which
indicates the presence of two double bonds in citral.

3. Presence of carbonyl group: Citral forms an oxime with hydroxyl amine and gives an adduct
with NaHSO3. These reactions indicate the presence of a carbonyl group in citral.
4. Presence of an aldehyde group: Citral on reduction with sodium amalgam and alcohol gives a
primary alcohol, geraniol and on oxidation with moist silver oxide gives geranic acid. These
reactions indicate the presence of an aldehyde group in citral.
5. Carbon skeleton: When citral is heated with potassium hydrogen sulphate, it gives para-
cymene, a cyclic compound of known structure.

This reaction reveals the relative positions of methyl and isopropyl groups in citral.
6. Position of –CHO group: On hydrolysis with aqueous potassium carbonate solution, citral
gives 6-methyl-5-hepten-2-one and acetaldehyde. This indicates the position of –CHO group in
citral.

Based on the reactions 5 & 6, citral may be represented by the following structure.

Following evidences further confirm the structure of citral.

7. Position of double bonds: a) Citral on oxidation with alkaline KMnO4, followed by chromic
acid yields acetone, oxalic acid and levulinic acid (4-oxopentanoic acid). The formation of these
products confirms the above structure of citral.

This reaction clearly indicates the position of two double bonds.

b) The position of two double bonds are further confirmed by ozonolysis. Citral on ozonolysis
yields levulinic aldehyde, acetone and glyoxal

35. How do you prove the presence of six membered ring in glucose by
i) Periodic acid oxidation method ii) nitric acid oxidation method (methylation method)
i) HIO4 (periodic acid) oxidation method
Methyl - β-D-glucoside is obtained by treating glucose with methanol in the presence of dry HCl.
This on treatment with periodic acid, consumes two equivalents of periodic acid to form a
dialdehyde and equivalent of formic acid. These products are formed by oxidation of groups at
(C-2,C-4) and C-3 respectively. The dialdehyde thus formed when treated with bromine water
followed by acid hydrolysis yields glyceric acid, an optically active compound. This confirms
the presence of 6m ring in glucose. Equation:

If glucose were to have 5membered ring, the product formed is optically inactive.
ii) HNO3 oxidation method: β-D-glucoside on methylation with methanol in the presence of dry
HCl is gives to methyl- β-D-glucoside. This on treatment with dimethyl sulphate and NaOH to
form penta methyl derivative. When it is hydrolysed with dil. HCl, it gives a tetra methyl
derivative which is in equilibrium with the open chain form. This contains an aldehyde group,
4 –OCH3 groups and a free –OH group. The above product is subjected to oxidation with nitric
acid to give trimethoxy glutaric acid (5C atom chain). This means that the –OH group at C-5 is
involved in ring formation and hence the glucose ring must be a 6 membered one. On the other
hand if glucose had 5membered ring, 2, 3-dihydroxysuccinic acid (4C atom chain) would have
been formed.
Glucose CH3OH/HCl Methyl glucoside (CH3)2SO4/NaOH tetra methyl glucoside

H2O/HCl

Tetra methyl glucose

HNO3

Trimethoxy glutaric acid and dimethoxy succinic acid

36. What happens when glucose is treated with excess of phenyl hydrazine? Give equation.
When glucose is treated with excess of phenyl hydrazine, glucosazone is formed

37. Give a test to show the presence of i)—CHO group ii) –CH2OH group in glucose.
i) Presence of carbonyl group: Glucose reacts with hydroxyl amine to form glucose oxime which
indicates the presence of carbonyl group.

Similarly, it reacts with HCN to form cyanohydrins, which also indicates the presence of
carbonyl group.
Presence of aldehyde group:
Glucose on oxidation with mild oxidizing agent like bromine water gives gluconic acid which
shows presence aldehyde group because mild oxidizing agents oxidize only aldehyde group.

ii) Presence of primary alcoholic group: oxidation with strong oxidizing agent like nitric acid
gives glucaric acid, a dicarboxylic acid.

Formation glucaric acid indicates the presence of primary alcoholic group (-CH2OH).
38. Write a note on elucidation of structure of zingiberene.
1. Molecular formula: From elemental analysis and molecular mass determination, the
molecular formula of zingiberene is C15H24.
2. Presence of 3 double bonds: Zingiberne adds on three moles of hydrogen in presence of
platinum catalyst to form hexahydrozingiberene, C15H30. This indicates the presence of three
double bonds in zingiberene. C15H24 + 3H2 C15H30
3. Presence of conjugated double bonds: When zingiberene is reduced with sodium and alcohol,
it yields dihydrozingiberene, C15H26. This shows that two of the double bonds are conjugated.
C15H24+ 2 [H] C15H26
4. Carbon skeleton: When zingiberene is heated with sulphur, it undergoes dehydrogenation to
form cadalene which is 1,6- dimethyl -4-isopropyl naphthalene.

This reaction indicates that cadalene like carbon skeleton must be present in zingiberene.
5. Presence of isopropylidene group (ozonolysis): Ozonolysis of zingiberene yields acetone,
levulinic acid and succinic acid. Formation of acetone as one of the products reveals the presence
of isopropylidene group as one of the double bonds (=).
6. Position of double bonds: Oxidation of dihydrozingiberene with alkaline KMnO 4 yields a
ketodicarboxylic acid. This on oxidation with NaOBr yields a tricarboxylic acid along with
bromoform. This suggests the presence of a methyl keto group in keto carboxylic acid. These
reactions indicate the position of double bonds in zingiberene.
Based on the above observations, zingiberene can be represented by the following structure

39. How do you prove the presence of three double bonds in zingiberene? Give equation.
Zingiberne adds on three moles of hydrogen in presence of platinum catalyst to form
hexahydrozingiberene, C15H30. This indicates the presence of three double bonds in zingiberene.
C15H24 + 3H2 → C15H30
40. Describe the synthesis of zingiberene from methyl heptenone.
41. How do you prove the presence of isopropylidine group in zingiberene?
Ozonolysis followed by reduction of zingiberene yields acetone, levulinic acid and succinic acid.
Formation of acetone as one of the products reveals the presence of isopropylidene group.

42. What happens when glucose is oxidized with nitric acid?

Glucose gets oxidized to Glucaric acid when treated with nitric acid

43. How would you prove that α-terpineol contains one double bond?
When α-terpineol is treated with bromine or heated with hydrogen gas in presence of
platinum catalyst, it consumes one molecule of bromine or hydrogen which indicates the
presence of one double bond.
C10H18OBr2(dibromo-α-terpineol)<---------C10H18O(α-terpineol-------- C10H20O(dihydro-α-
terpineol)