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Organometallic

Chemistry
B R Thorat
Department of Chemistry,
Govt of Maharashtra,

Ismail Yusuf Arts, Science and Commerce


College, Jogeshwari (E), Mumbai 60

Organometallic Chemistry

Class of compounds (R-M) that


contain a covalent bond
between carbon and metal

Also known as organoinorganics, metallo-organics

organopalladium

chlorophyll

Gilman reagent

Tetracarbonyl
nickel

ferrocene

Organo zinc

Organo
chromium
boron, silicon, arsenic, and selenium

Grignard
reagent

hemoglobin and
myoglobin

Vit B12

Chemical Reactivity
of Organometallic
compounds

Carbon attached to non-metal such as O, N, S, halogen


etc carries partial positive charge and are the source of
electrophile.

The carbon attached to metal (electropositive) carries partial


negative charge. Their use is based on the polarity of R-M bond.
The C-M bond is not 100% ionic but it increases with
electropositivity of metal (M). The order of polarity is K > Na > Li
> Mg > Zn > Hg > Cu.
In synthesis, they act as nucleophiles that can bond with relatively
positive carbon atoms in compounds such as alkyl halides,
aldehydes, and ketones.
For example, the Grignard reagent, RMgX (where X equals Br, Cl,
or I)

The First Organometallic Reagents

Grignard Reagents
Discovered by Victor Grignard in
1900
Key factors are ethereal solvent and
water-free conditions

Awarded Nobel Prize in 1912


Victor Grignard
Grignard, Victor , 18711935, French chemist. He shared the 1912 Nobel Prize in
Chemistry for his work in organic synthesis based on his discovery (1900) of the
Grignard Reagent. He taught at the Univ. of Nancy (190919) and at the Univ. of
Lyons (from 1919 until the end of his career).

Organomagnesium Compounds
Grignards Reagent:
The organometallic compounds with the general molecular formula RMgX are
called as Grignards reagents [Nobel Prize winner 1912 in Chemistry]. This
reagent is highly reactive and widely used for the organic synthesis.
Synthesis
It can be obtained by carrying out the reaction of organic halide with magnesium in
dry ether.
+

R-X

dry ether

Mg

R-MgX

R is alkyl, allyl, vinyl or aryl group and X is Cl. Br, or I.


The following solvents are most commonly used for the synthesis as- diethyl ether
(b.p. 34.60C), diethylene glycol, diglyme (b.p. 1600C), tetrahydrofuran (b.p. 660C).
Initially small amount of iodide or ethylene bromide is added to initiate the reaction.
1.

(CH3)2CH-Br

Cl
2.

3.

CH2=CH-CH2I

Mg

Mg

dry ether

MgCl

THF

Mg

(CH3)2CH-MgX

dry ether

CH2=CH-CH2-MgI

Organomagnesium Compounds
Grignards Reagent:
The R group should not contain a group bearing active hydrogen atom such as
COOH, -CCH, -OH, -NH2, etc.
The reactivity of alkyl halide is RI > RBr > RCl > RF whereas organomagnesium
fluoride are not known yet.
The Grignard reagent was exist in dimeric form which is in equilibrium with dialkyl
magnesium compound and magnesium dihalide.
The X-ray diffraction studies shows that the two ether molecules are also tightly
bonded to magnesium in RMgX.
OEt2
R

Mg
OEt2

Organomagnesium Compounds
Grignards Reagent: Reactivity
The RMgX is colorless and unstable solid hence it is freshly prepared when
required and used in ethereal solution. The C-Mg bond is highly polar in which
carbon bearing partial negative charge and magnesium bearing partial positive
charge because of large electronegativity difference between them. The Grignard
reagents are strong bases and are also used as powerful nucleophiles.
Reaction with water and alcohol:Grignard reagent behaves as a strong base and hence react with weak acids such as
water or alcohol forming corresponding hydrocarbon.
R-MgX +

H2O

R-H

R-MgX +

R'OH

R-H

MgX(OH)
MgX(OR')

The reagent similarly reacts with phenols and acids. These reaction is used for the
synthesis of deuterium containing hydrocarbons. E.g.
H3C
CH2MgX
H3C

dry ether

H3C

D2O

CH2-D
H3C

MgX(OD)

Organomagnesium Compounds
Grignards Reagent: Reactivity
Reaction with carbonyl compound and ethylene oxide:Grignard reagents are behaves as carbanion or nucleophile and they are added to
carbonyl group of various carbonyl compounds.
R-MgX

OMgX

R
alkoxide

OH2
or H3O+

OH
R
alcohol

Mechanism:By using appropriate carbonyl compounds, the reaction is useful for the preparation
of alcohols.
+

MgX
O

O Mg
X
Mg

Mg
X

-MgX2

X
OH2
OH

OMgX

O Mg
X
Mg
X

O Mg
MgX2

Organomagnesium Compounds
Grignards Reagent: Reactivity
By using appropriate carbonyl compounds, the reaction is useful for the preparation
of alcohols.
Primary alcohol:- Grignard reagent reacts with formaldehyde or ethylene epoxide
with subsequent hydrolysis.
H

H
R-MgX

OMgX

R-MgX

RCH2-CH2-OMgX

OH

or H3O+

H R

OH2

H R

OH2

R-CH2-CH2-OH

or H3O+

Secondary alcohol:- Grignard reagent reacts with aldehydes other than


formaldehyde followed by acid catalyzed hydrolysis gives secondary alcohol.
R'
R-MgX +

Ether

R'
OMgX

OH

or H3O+

H R

R'

OH2

H R

Tertiary alcohol:- Grignard reagent reacts with ketone (symmetrical and


asymmetrical), esters, acyl chloride, carboxylic acid, etc forming tertiary alcohol
R'
R'
after hydrolysis. R-MgX R'
OH
Ether
+

OMgX

R''

R''

R'
2 R-MgX +

O
HO

Ether

R'
OMgX
R R

or H3O+

OH2
or H3O+

OH

R''

R'
OH
R R

Organomagnesium Compounds
Grignards Reagent: Reactivity
Nature of the product depends on the nature of starting carbonyl compound. If R, R
and R are bulkier groups and atleast one group of this containing -hydrogen atom,
then tertiary alcohol undergoes dehydration forming alkene.
R'
R-MgX +

Ether

R-MgX +

O
X

R'

OMgX
R OR''

R''O

R'

R'

Ether

R-MgX

O
R

R'

R-MgX

R X

OMgX
R R

R'
OMgX

R'

R'
OMgX
R R

R'

OH2

or H3O+

OH2

OH
R R

R'

or H3O+

OH
R R

The above reaction shows that, each mole of ester or acyl chloride can be reacted
with two moles of Grignard reagent. They are converted into tertiary alcohol through
ketone intermediate. The Grignard reagent is more reactive towards ketone than
ester and acyl chloride.
Reaction with cyanide or nitriles:It is useful synthesis for the ketones. Grignard reagents add to a nitrile group
followed by the hydrolysis of the resulting complex.
R
R-MgX + R'-CN

NMgX
R'
imine salt

OH2
or H3O+

R
NH

R'

R'
imine

2+
+
O + NH4 + Mg

Organomagnesium Compounds
Grignards Reagent: Reactivity
Acetylenic exchange:An acetylenic hydrogen atom is acidic in nature. Grignard reagent act as base and
reacts with it to give hydrocarbon and an alkynyl Grignard reagent. The resulting
reagent reacts with other organic compounds such as ketone forming alkynyl
alcohol.
R'
HC CH

+ R-MgX

HC CMgX +

R'

1. O
R-H

R''

R''
OH

+
OH2 or H3O

Carbonation:Carboxylic acid can be synthesized by carbonation of the Grignard reagent followed


by hydrolysis. A solid carbon dioxide (dry ice) is used for this reaction. The carbon
dioxide is solidified under pressure at -780C. The Grignard reaction shows
nucleophilic addition to the carbonyl group of carbon dioxide.
O
R-MgX

CO2

OH2

R
OMgX

+ MgX(OH)
OH

Grignard reagent shows same reaction with sulfur dioxide forming corresponding
sulfinic acids asO

R-MgX

SO2

R S

OH2

R S
OMgX

+ MgX(OH)
OH

Organomagnesium Compounds

Grignards Reagent: Reactivity


Conjugate addition:,-Unsaturated carbonyl compounds have two reaction sites, therefore nucleophilic
addition of Grignard reagent can be occurs either at the acyl carbon (1,2-addition) or at
the alkenyl carbon atom (1,4-addition).
R''
R'-MgX

R'''

+
R'''

R''

OMgX

R'' R'
R
(1,4- addition)

R'''

OMgX

R'
(1,2- addition)

The composition of the product can be varied with sterric bulk of R in the Grignard
reagent and R group in the carbonyl compound. As size of R- group increases, the
amount of 1,4-addition product increases, but ,-unsaturated aldehydes gives only 1,2addition product. Also as size of R- group of the Grignard reagent increases, the amount
of 1,4-addition product increases. The 1,4-addition of the Grignard reagent was proceeds
though six membered transition state, whereas the 1,2-addition reaction proceeds through
four membered transition state. In four membered transition state, the sterric hindrance
between RR increases the energy of intermediate than in six membered transition
state. Also as size of R and R increases the magnitude of RR or and RR
interaction also increases in the six membered transition state, and therefore decreases the
yield of 1,4-additon. The removal of byproduct MgX2 (Lewis acid) increases the yield of
1,4-addition product.
Also if electron withdrawing group attached to alkene moiety, increases the yield of 1,4addition product.

Organomagnesium Compounds
Grignards Reagent: Reactivity
X
R''
R'-MgX

R'

+
R'''

R''
R'''

Mg
R
O

H3O+

R'''
R'' R'

O
R

The cuprous salts (Cu2X2) was added to the Grignards reagents forming less
reactive product such as [R2MgCu or RCu) containing copper (I) which forming coordinate bond strongly with carbonyl oxygen atom in six membered transition state.
Grignard reagent shows 1,4-addition reaction with carbonyl compound except ,unsaturated aldehyde.

Organo-lithium compound (R-Li)


The bond between carbon and lithium atom was 43% ionic while CMg bond was is about 36% in nature, therefore organo-lithium
compounds shows all reactions that shows by Grignard reagent.

It is very reactive with oxygen and moisture, hence stored and reacts
in dry solvent.
Reactions with carbonyl compounds
HCOH

RLi

H2CR-OLi

aq. acid

R-CH2-OH

aq. acid
R'CHO

+ RLi

R'2CO

+ RLi

R-CHR'-OH

RCHR'-OLi
aq. acid
R'2CR-OLi

R'2CR-OH

Organo-lithium compound (R-Li)


Reaction with epoxide
RLi +

H3C

SN2

OLi

aq. acid

OH

H3C

H3C

Wittig reaction

The ether undergoes rearrangement reaction in presence of strong base such as n-BuLi to
form alcohol. The ether must contain -hydrogen atom with respect to oxygen.

R-CH2-O-R'

Synthesis of Ketone
RLi

R'

R'

n-BuLi

R'

aq. acid

R'
R
OH

: From cyanide or nitrile compounds


ether

R
N-Li
R'

aq. acid

RLi excess
O

R'

aq. acid

R R
OH
R'

Organo-lithium compound (R-Li)


Synthesis of Ketone

: From carboxylic acid

R'Li

R-COOH

R-COOLi

R'

R'Li

aq. acid

OLi
OLi

Reaction with methoxyl amine


CH3O-NH2

RLi

CH3Li

R-NH2

- 78 C

Synthesis of carboxylic acid


RLi

CO2

ether

R-COOLi

aq. acid

R-COOH

R-CO-R'

Organo-lithium compound (R-Li)


Reaction with isocyanide

RLi

+ R'

+
N

ether

R'

+
N

Li

Li
N

R'

Isocyanide

Acyl anion equivalent

RCO-COOH

CO2

aq. acid

R''COCl

Li
R'

O
aq. acid

aq. acid
aq. acid

R''2CO aq. acid

R''CO-COR

R''X

R''-CO-R
R'' R''
COR
HO

Lithium organo-cuprate reagents (R2CuLi)


The organo cuprate reagents are Cu(I) reagents which are less stable and more
reactive. E.g. RCu.
The lithium organo cuprates are prepared by using two equivalent of lithium
compound with one equivalent of cuprous iodide in ether.
These reagents are more stable and more reactive than the well known Cu(I)
reagents.
The aryl, alkenyl and primary alkyl cuprates are prepared by this route or procedure
but secondary and tertiary cuprates are readily obtained from corresponding lithium
derivative and ether soluble derivative of copper (I) iodide such as the complex with
tributylphosphine or dimethyl sulphide.

CH3Li

2 (CH3)3CLi

CuI

ether

CuI.Ph3P

CH3Cu
ether

CH3Li

Li(CH3)2Cu

Li[(CH3)3C]2Cu.PPh3

Lithium organo-cuprate reagents (R2CuLi)


Reaction with organic halide and other homologues reactants
It replaces bromine or iodine from organic halide by alkyl or alkenyl or aryl groups at or
below room temperature to gives substituted products.
It also reacts with primary alkyl tosylates and with carbonyl group of ketone slowly
therefore the reaction in presence of unprotected ketonic group is also possible while aldehydic
group shows addition reaction below -90oC.
The secondary alkyl halide are not gives product to high yield by using ordinary organo
cuprates such as R2CuLi, these difficulty can be overcome by using higher order cuprates
such as Li2R2Cu(CN) which is prepared from two equivalent of organo lithium compound and
one equivalent of cuprous cyanide. It also reacts very fastly with primary alkyl bromide.

1. n-C6H13-OTs
OH
H3C
H
2.
Br

H
Br

(C4H9)2CuLi

C10H22

ether, -75 C
H3C

3.

Li(CH3)2Cu
o
ether, -15 C
H3C

(sec-C4H9)2Cu(cn)Li2
o

THF, -78 C

I
4.

H
CH3

Cl

Br

OH
H

) Cu(CN)Li
2 o
2
THF, O C

Cl

Lithium organo-cuprate reagents (R2CuLi)


The important feature of this reagent was that they react with secondary alkyl halide by SN2
mechanism therefore if the starting alkyl halide is optically active then product obtained is
having inversion in configuration.
C2H5
Br

(C4H9)2CuLi

CH3

C2H5

CH3

C6H5

ether-THF, reflux

But corresponding iodide gives a racemic product on reaction with lithium diphenylcuprate
which indicates that the reaction of cuprates with iodides at any rates takes place by a one
electron transfer and not by SN2 reaction.
Alkenyl halide reacts with organocuprates with retensation in configuration of the double
bond to give substituted alkene.

(C2H5)2CuLi

C6H5

Br

Li(CH3)2Cu
ether, 0oC

2 HC CH
C2H5

)2 CuLi

C6H5
H

H
CH3

I
HMPA
-30 to 25 oC

C2H5
(63%; 95% Z)

Lithium organo-cuprate reagents (R2CuLi)


Reaction with acid halide and epoxide
Organocuprates are reacts radialy with acid chloride to give ketone and with epoxide to gives
alcohol by the attack at less substituted carbon.

O
Cl

Li(CH3)2Cu
ether, 0 oC

CH3

R
C3H7

OH

(C3H7)2Cu(CN)Li2
o

THF, O C
86%

Li(CH3)2Cu
OH

ether, -10 C
CH3

Lithium organo-cuprate reagents (R2CuLi)


Reaction with ,-unsaturated ketones
The R2CuLi react with ,-unsaturated ketones to forming -substituted saturated ketone
which is not react further with reagent at the given reaction conditions.
The steric hindrance also affects the yield of reaction which is increased by using Lewis
acid catalyst such as boron trifluoride etherate.
CH3
OMe

OMe

Li(CH3)2Cu
o

ether, -10 C
O

O
(

) Cu(CN)Li
2
2
o

ether, -50 C

n-C4H9
(n-Bu)2CuLi, BF3
Diethyl ether, -70oC
O

O
53%

Reformatsky reaction (C-Zn bond)


The reaction between carbonyl compounds such as aldehydes or ketones and ester of bromoacids in presence of zinc metal to form -hydroxy ester after hydrolysis
R

R''
O

+ Zn

R'
A carbonyl
compound

Dry C6H6

COOEt
Br
2-bromo ester

BrZnO
R
R'

R''
COOEt

OH2

HO

R''

R
R'

COOEt

3-hydroxy ester

In absence of benzene, resulting intermediate zinc bromide is hydrolyzed by using dilute


sulfuric acid or dilute alkali gives -hydroxy acid which can be radially dehydrated to form
mainly ,-unsaturated acid.
The -bromo ester does not forming Grignard reagent, whereas -iodo compound is rearly
observed and -chloro ester either reacts slowly or fail to react unless they are activated by
using Cu-bronze.
Drawback:
A serious drawback of the Reformatsky reaction is the formation of -keto ester as a side
product by the self condensation of the -bromo ester.

Reformatsky reaction (C-Zn bond): Applications


1

Synthesis of -hydroxy ester and unsaturated ester.


1.

Ph-CHO +

Zn

Ph

BrCH2COOEt

Ph

OH2

CH2COOEt

CH2COOEt

BrZnO

HO
H3O +
PhCH

COOEt

1. Zn, Ether

+ BrCH2COOEt

2.
COOEt

OH
COOH

+
2. H3O

COOH

1. Zn, Ether

3.
S

HOOCCH2

CHCOOEt

CHO + BrCH2COOEt

+
2. H3O

CH=CH-COOEt

The Reformatsky reaction is useful for the synthesis of various natural products such
as- geranic ester, citral, camphoronic acid, fenchane, cadalene (terpenoid), vitamin A, etc.

BrCH2COOEt

COOEt

COOEt

Zn, Ether

Ac2O

HO

1. H3O +
2. Distil Ca-salt

CHO

Natural
Products

Natural products

Chemical compounds produced by the living organism


(animal, plants, microorganisms, etc) those usually has a
pharmacological or biological activities

There are number of metabolism occurred in organisms for the synthesis of various natural
products, intermediates, etc. The intermediates and products formed by metabolism are
called as metabolites.

Terpenes

Primary
Metabolite

Alkaloids

Vitamins

Metabolite

Harmones

Steroids

Secondary
Metabolite

Primary
Metabolite

The primary metabolite is directly involved in normal


growth, development and reproduction of organism.
E.g. PABA (p-aminobenzoic acid) is the primary and
essential metabolite

The secondary metabolite is not directly involved in


growth, development and reproduction but usually has an
important ecological function. E.g. Pigments

Secondary
Metabolite

Terpenes
The term terpene was given to the compounds isolated from terpentine, a volatile liquid
isolated from pine trees.

Terpenoids are the hydrocarbons of plant origin of the general formula (C5H8)n as well as
their oxygenated, hydrogenated and dehydrogenated derivatives are also found.

Terpenoids also form a group of naturally occurring compounds majority of which


occur in plants widely in the leaves and fruits of higher plants and are volatile
substances which give plants and flowers their fragrance.

Terpenes
Classification: Most natural terpenoid hydrocarbon have the general formula (C5H8)n. They can
be classified on the basis of value of n or number of carbon atoms present in the structure.
Sr. No.

Number of carbon atoms

Value of n

Class

Example

10

Monoterpenoids(C10H16)

Citral

15

Sesquiterpenoinds(C15H24)

Farnesol

20

Diterpenoids(C20H32)

Retinol

25

Sesterpenoids(C25H40)

Geranyl farnesol

30

Triterpenoids(C30H48)

Squalene

40

Tetraterpenoids (C40H64)

Carotene

>40

>8

Polyterpenoids(C5H8)n

Rubber

Each class can be further subdivided into subclasses according to the number of rings present
in the structure.
i) Acyclic Terpenoids: They contain open structure.
ii) Monocyclic Terpenoids: They contain one ring in the structure.

iii) Bicyclic Terpenoids: They contain two rings in the structure.


iv) Tricyclic Terpenoids: They contain three rings in the structure.
v) Tetracyclic Terpenoids: They contain four rings in the structure.

Terpenes

The simpler mono and sesqui terpenes are chief constituent of the
essential oils obtained from sap and tissues of certain plant and trees
The di and tri terpenoids are not steam volatile. They are obtained from
plant and tree gums and resins

Tertraterpenoids form a separate group of compounds called Carotenoids

Terpenes
(Isoprene rule)
All terpenes on distillation gives isoprene as one of the product
(may be in some cases by thermal decomposition of terpene).
CH2 (Isoprene unit) Otto Wallach (1887) pointed out that carbon skeleton of terpenoids
H2C
can be built up from isoprene unit.
2-methylbuta-1,3-diene
Isoprene rule stats that the terpenoid molecules are constructed from
two or more isoprene unit.
CH3

Further Ingold suggested that isoprene units are joined in the terpenoid via head to tail
fashion. Special isoprene rule states that the terpenoid molecule are constructed of two or
more isoprene units joined in a head to tail fashion.
H3C

Head

Head

H2C
CH2
(Isoprene unit)

Tail

C
Tail

C
Head

Tail
C C

But this rule can only be used as guiding principle (for the skeleton of carbon) and not as a
fixed rule.
For example carotenoids are joined tail to tail at their central and there are also some
terpenoids whose carbon content is not a multiple of five

Terpenes (Examples)

Terpeniol: It is present in various essential


oils like cardamom oil. The -terpeniol
possesses an odour of lilac and used as
flavoring agent in perfumes and cosmetics

CH3

2-(4-methylcyclohex-3-en-1-yl)propan-2-ol
Terpeniol
OH
H3C

CH3

CH3

(2Z)-3,7-dimethylocta-2,6-dienal
CHO

H3C

Citral

Citral: It is chief constituent of lemon grass oil.


Citral is used as flavouring agent for soap, cosmetics
and perfumes

CH3

Cmphor: It occurs in camphor tree. Camphor is


used as plasticizer for the production of celluloid
and photographic films. It is used as disinfectant
and pain reliever
CH3

2,6,6-trimethylbicyclo[3.1.1]hept-2-ene
CH3
H3C

Pinene

CH3
O
H3C

CH3

1,7,7-trimethylbicyclo[2.2.1]heptan-2-one
Camphor

Pinene: It is bicyclic monoterpenoid occurs in


turpentine oil. Pinene is used in the synthesis
of wide variety of other terpenes. It is also used as
paint thinner

Alkaloids
Originally the name alkaloid was given to all organic bases isolated from plants.
Konigs (1880) suggested, alkaloids are naturally occurring organic bases which contain
pyridine ring.
Further Ladenburg modified this definition and said alkaloids have atleast one nitrogen
atom in heterocyclic ring.
Generally, alkaloids have basic properties, physiological action and are of plant origin.
Classification: Alkaloids are classified on the basis of nature of the chemical nucleus
containing nitrogen (pyridine, pyrrol, quinoline, tropane, etc) present in the molecule
Sr. No.

Group of alkaloids occurring to nucleus

Example

Purrolidine group

Hygrine

Pyridine group

Recinine

Pyrrolidine-pyridine group

Nicotine

Quinoline group

Quinine

Isoquinoline group

Papaverine

Phenanthrene group

Morphine

Tropane group

Atropine

Alkaloids (Examples)
Nicotine: Contains pyrrolidine-pyridine rings. It
is also called as tobacco alkaloid as it is isolated
from tobacco leaf.
It is toxic and addictive component of a tobacco.
It is a substance of abuse.
It is used in insecticide and in the synthesis of
nicotinic acid.

3-(1-methylpyrrolidin-2-yl)pyridine
N

Nicotine

CH3
N

Atropine: It is from tropane group of alkaloid.


It occurs in deadly night shade (atropa bella
donna).
It is also found in many members of solanaceae
family.
Atropine is used to reduce saliva and fluid in
the respiratory tract.
It is used as anticholinergic drug.
N CH3

8-methyl-8-azabicyclo[3.2.1]oct-3-yl
3-hydroxy-2-phenylpropanoate

C 6H 5

CH 2OH

Atropine

Vitamins
Vitamins are the substances that are required for the proper growth, maintenance and well
being of all animals organism. E.g. vit. A, vit. B, vit. K, vit. D, etc.
They are required in very minute quantities.
Vitamins are not produced by the body (with exception of vit. D and vit. K) and hence
must be taken from daily foods.
There are about thirteen essential vitamins, broadly classified into fat soluble and water
soluble vitamins.

Fat soluble vitamins: Fat soluble vitamins


are A, D, E, and K. These are soluble in fat
and also absorbed by body from intestinal
tract. Human body has to use bile acid to
absorb fat soluble vitamins. These vitamins
are stored in body fat.

Water soluble vitamins: Vitamin B


complex group and vitamin C are water
soluble. They cannot be stored in body
therefore provided by food every day.

HOH2C
H3C

CH3

CH3

CH3

Vitamin A
CH 2OH

Retinol

Vitamin C
Ascorbic acid

HO
HO

OH

CH3

Vitamin A is referred to be the vitamin for growth


and body repair. Deficiency of vitamin A causes
night blindness.

Vit. C is important in the formation of collagen, a protein


that holds together the connective tissues of skin, muscle
and blood vessels. Deficiency of vitamin C causes scurvy.

Hormones
Harmones are secreted by ductless endocrine glands of animal body. Only minute
amount of harmones are necessary to carried out various physiological reactions in the
body.
Harmones are classified as
Non-steroidal Harmones

Steroidal Harmones

Non-steroidal harmones are further classified based on their physiological activity as


thyroid harmones, pituitary harmones and pancreatic harmones
I

OH

OH
HO

Thyroxine

Adrenaline
I

NH
HO

COOH

CH3
H

Secreted by the adrenal gland. It


raises the blood pressure and heart
rate and dilates lung passage

NH2

Secreted by thyroid glands. Deficiency or excess


of this harmone results the grave complications.

Structure determination of natural products: Terpenoids

Molecular formula
Nature of oxygen atom present

Unsaturation
Dehydrogenation
Oxidative degradation

Number of the rings present


Spectroscopic studies
X-ray analysis

Ozonolysis in terpenoids
Hofmann exhaustive methylation and degradation in alkaloids
Synthesis

Structure determination of natural products: Terpenoids

Molecular formula

Molecular formula is determined by usual quantitative analysis.


Mol. wt determination methods or by means of mass
spectrometry.
If terpenoid is optically active, its specific rotation can be
measured

Nature of oxygen
atom present

If oxygen is present in terpenoids its functional nature is


generally as alcohol aledhyde, ketone or carboxylic groups

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