Terpenes

Introduction
o In natural habitats plants are surrounded by number
of enemies such as bacteria, viruses, fungi
nematodes, insects and herbivores animals.

o Plants can not avoid these enemies by moving away.

o Instead; they protect themselves in other ways,

e.g. - Cuticle (waxy outer layer)
& - Periderm (secondary protective tissue)

which provide barrier to bacterial and fungal activities

.
o Plants also defend themselves against herbivores and
pathogenic microbes by producing some defensive
chemical compounds called Secondary compounds.

o These Secondary compounds may serve other

important functions such as;
• Structural support (lignin)
or • Pigments (anthocyanins)
 Metabolites
o Primary metabolites: Are produced in all plants and
have direct role in growth and development
e.g. amino acids, nucleotides and sugars etc.

o Secondary metabolites : A diverse array of organic

compounds have no direct function in growth and
development and have restricted distribution in plant
kingdom
e.g. Terpenes, Phenloics and Nitrogen-containing
compounds.
 What are TERPENES?
o Are the largest and most diverse group of plant
secondary compounds
o Are unsaturated organic compounds, produced by a
variety of plants, particularly conifers

o They are often strong-smelling

o They may protect the plants that produce

them by repelling insects.
 What are TERPENES?

• Terpenes are unsaturated hydrocarbons formed

by joining together isoprene units.

• Terpenes and its derivatives are constituents of

Essential oils of a wide variety of fruits and floral
flavors and are responsible for the distinctive
aroma of spices.
• All Terpenes are built up from units of
isoprene.
• The name ‘terpene’ is derived from the
Greek word ‘terebinth’.

• Terebinth is a type of pine tree from

which terpene-containing resins are
obtained.
• Natural organic compounds.

• Used in perfumes, essential oils and

medicines.
 Essential oils contain terpenes

• Lavender – used to relieve tension.

• Ylang-ylang – used to treat anxiety.

• Lemon oil – aids good circulation.

• Essential oils often contain a mixture of

terpenes.
 Spices contain terpenes

• Terpenes in plants can be oxidised to produce

the compounds responsible for the distinctive
aroma of spices.

• Terpenes containing oxygen or other functional

groups are known as ‘terpenoids’.

• Common spices containing terpenes include

cloves, cinnamon and ginger.
 Terpenes are a large and varied class of
hydrocarbons that typically contain either ten or
fifteen carbon atoms built from a five-carbon
building block called isoprene .
 Acyclic Monoterpenes
Myrcene
Structure determination:
1- Elemental analysis & molecular weight determination show that the
molecular formula is C10H16
Catalytic Hydrogenation
2- Myrcene H2/Pt Saturated compound
C10H16 C10H22

So, Myrcene contains three double bonds

C10H22 CnH2n+2 General formula of paraffin

So, Myrcene is an open-chain compound

3- Myrcene forms an adduct with maleic anhydride

O O

1:4- addition
O O Diels-Alder reaction

O O
Maleic anhydride 1:4- adduct

So, two of the three double bonds are conjugated

4- Ozonolysis of Myrcene produces:

O3
Myrcene

O O
+ 2 + C5H6O3
H3C CH3 H H
Acetone Formaldehyde Ketodialdehyde
Structure of the Keto-dialdehyde C5H6O3
Oxidation of Keto-dialdehyde produces:
COOH
O
Keto-dialdehyde + CO2
CrO3/AcOH
COOH
Succinic acid
Formation of succinic acid shows that the keto-dialdehyde contains two
adjacent methylene groups

H 2C
and since the compound contains also a ketonic and two
H 2C O
aldehydic groups
CHO

So, It’s structure must be

CHO
Now the equation of Ozonolysis can be written as follows: O
O O
CHO
O3 + 2 +
Myrcene H3C CH3 H H
CHO
Acetone Formaldehyde Ketodialdehyde
Considering the products from Ozonolysis:
 The formation of acetone indicates the presence of

Isopropylidene grouping A

 The loss of 2 carbons as formaldehyde indicates the presence of

2 terminal methylene groups CH2

B
2

 The formation of keto-dialdehyde indicates the presence of

the structural unit

C
Combining the structural units A , B ,and C

We get the following three propabilities for the structure of Mycene

or or

(I) (II) (III)

5- Hydration of Myrcene in presence of dil.H2SO4 followed by oxidation of the
resulting alcohol gives Citral (terpene aldehyde of known structure)

Hydration mild
Myrcene alcohol
dil.H2SO4 oxidation CHO

Citral

So, the carbon skeleton of Myrcene should be :

 Then Myrcene should have Structure (I)

On the basis of this structure the last equation can be represented as follows:

CH3 CH3

Hydration H-O-H
dil.H2SO4 CH2 CH2 -OH2

CH3

-H mild
CH2 -OH oxidation CHO

Citral
The structure was supported by the following fact:
 Myrcene has U.V absorption at λmax 224 nm (ϵ 14,600)

Calculated value is :
214 ………………………………….for Heteroannular (and acyclic ) dienes
+ 5 …………………….…....…Increment for each c-substituent
= 219 nm
 Citral
Structure determination:
1- Elemental analysis & molecular weight determination show that the
molecular formula is C10H16O
NH2-OH
2- Oxime C Carbonyl gp. is present
Hydroxylamine O

Reduces Fehling solution

3- Citral
On reduction it gives primary alc.

On oxidation it gives an acid with the same no of carbon atom

Carbonyl gp. is in the form of aldehydic gp. C

H O
4- Catalytic Hydrogenation of Citral
It consumes 3 moles of H2 to produce saturated alc.

H2/Ni
Citral Saturated alc.
C10H16O C10H22O CnH2n+1OH

We deduce that:
Since one mole of H2 is consumed for aldehydic gp.;
So , a. there are 2 C=C bonds
b. The parent saturated hydrocarbon will be CnH2n+2 = C10H22
Citral is an Open-Chain compound
5- Heating Citral with pot.hyd.sulfate yields p-cymene

This reaction establishes the relative positions of methyl- and isopropyl- gps.
And since Citral has the following skeleton structure

+ 2 C=C + -CHO
6- Position of the double bonds:
A) Ozonolysis of Citral gives the following:
CH3

O O H

H
+
O3 H O
O
Laevulinic ald. Glyoxal
+
O

Acetone

The structure of Citral is

CHO

(I)
B) Oxidation of Citral gives the following:
CH3

O O OH

OH
+
HO O
O
O
i.KMNO4 Laevulinic acid Oxalic acid
ii.K2Cr2O7
+
O

Acetone
This also shows that Citral should have structure (I)
C) Structure (I) was also supported by the following reaction:

NaOH,
Citral Unsaturated ketone CH3CHO
C10 . . . C8. . . C2 . . .
2 C=C One C=C

• Since the ketone produced from this reaction contains only one double bond
• Then, Citral undergo cleavage at one of the double bonds
• This reaction is similar to the cleavage of α,β-unsaturated aldehydes by
alkaline reagents
• So, It can be deduced that one of the double bonds of Citral must be in the
α,β-position with respect to –CHO gp.

NaOH,
C CH CHO C O CH3-CHO
Structure of unsaturated ketone can be established by ozonolysis:
CH3

O3 O
unsaturated ketone
H
C8 . . .
Laevulinic ald.
O
+
O

Acetone

O
The structure of unsaturated ketone is

The cleavage of Citral by alkali is shown below:

O
Citral NaOH CH3-CHO
C10.. C2..

C8..
This to indicates the two carbon atoms of the double bond that had been broken by alkali
The Structure of Citral was confirmed by its synthesis from isoprene:
H2C Br H2C Br H2C
CH HBr CH CH2
HBr
C 1,4-addition C Marconikof,s C
H2C CH3 H3C CH3 Br
rule H3C
O CH3
Isoprene
Na O
H2
Br )C
CH2 O NaOH O
Sodioacetylacetone
O
C
Br Br
H3C CH3

Reformatski i)Zn/ICH2CO2Et
reaction ii) H+
OH
Red. OH- Ac2O
CHO COOH COOEt -H2O COOEt

Citral
Isomerism in Citral:

CHO H

H Two geometrical CHO

isomers are possible

Citral (a) Citral (b)

geranial neral
trans- (or E-) form cis- (or Z-) form

Na/Hg H H Na/Hg

CH2OH H
dil. H2SO4 dil. H2SO4
H CH2OH
Cyclize
faster
OH

geraniol α - terpineol nerol

 Monocyclic Monoterpenes

Limonene
Limonene is an optically active compound
(+) form in Lemon & Orange oil
(-) form in Peppermint oil
(±) modification in Turpentine oil
Structure determination:
1- Elemental analysis & molecular weight determination show that the
molecular formula is C10H16
Br2
2- Limonene C10H16Br4 contain 2 C=C
add 2 moles of Br2

So, It’s parent saturated hydrocarbon has a M.F. C10H20 Ξ CnH2n

then, Limonene is a Monocyclic compound
3- Limonene Se ,
dehydrogenation

p-cymene
C10H14
Limonene has the p-menthane skeleton
in which 2 C==C must be inserted

4- Position of double bonds

Dehydration of (+) α-terpineol gives (+) limonene

- One of the double bonds

should be in 1:2- position
KHSO4 ,
(or)
-H2O
- The position of the other
OH double bond remains uscertain

I Limonene
II
Proof of the 8:9 - position for the second double bond
7
 Structure (I) contains a chiral centre at C4 hence can exhibit
1
optical activity , But (II) is symmetric and so can not be optically 6 2
active. Then, (I) must be the correct structure of Limonene
5 3
 Chemical proof for the position of second double bond is the *
4
conversion of limonene to carvone (of known structure)
8
Cl 10 9
Cl
N=O
N OH
Cl N O
H isomerisation
Nitrosyl chloride

nitroso compound iso-nitroso compound

-HCl alc. KOH

N OH
O
hydrolysis
NH2OH +
hydroxylamine

carvone carvone oxime

Synthesis of (±) Limonene (dipentene)
O
EtOOC COOEt HOOC COOH
2 OEt
I
Ethyliodopropionate C H O-Na+
2 5 hydrolysis
+
C C
NC COOEt COOEt HOOC COOH
NC
ethylcyanoacetate
-2 CO2
(CH3CO)2O ,
-H2O

CH3 CH3
Br OH O O
C C C C
HBr CH3MgX estrification

COOEt COOEt COOEt COOH

pyridine -HBr

CH3

C KHSO4 ,
2mole CH3MgX

COOEt OH

(±) - Limonene
dipentene