Agrochemicals and Pesticides

Pesticides

Syllabus: Pesticides and their classification, preparation of some common organochlorinated and
organophosphorous insecticides: BHC, DDT, parathion, methyl parathion, paraoxon and
malathion. Herbicides: trichlorophenoxy compounds, properties , uses and mode of action.

Insects: Insects are a class of invertebrates with a

three-part body (head, thorax and abdomen),
three pairs of jointed legs, two compound eyes
and one pair of antennae. Insects usually have
wings.

Insects
 Agrochemicals and Pesticides
Pests and Pesticides

Pest: An insect or small animal that is

harmful or that damages plants, food, and
other crops.
Pesticides: In general, a pesticide is a
chemical or biological agent (such as a virus,
bacterium or disinfectant) that deters
(Discourage), incapacitates (injuries), or kills
the pests. The term pesticide includes
herbicide, insecticide, nematicide,
molluscicide, avicide, rodenticide,
bactericide, fungicide, growth regulator etc. Crop pests
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Classification of Pesticides

Pesticides can be classified from various view points. Such as Classified by:
(i) Target organism: Examples: herbicides, insecticides, rodenticides, pediculicides etc.
(ii) Chemical structure: Examples: organic, inorganic, synthetic.
(iii) Physical state: Examples: gaseous.
(iv) Plant - derived pesticides: Examples: pyrethroids, rotenoids, nicotinoids.
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Organochlorinated Pesticides

Organochlorine pesticides are

chlorinated hydrocarbons that are used
in agriculture and mosquito control.
Methoxychlor
Representative compounds in this
group include DDT, methoxychlor,
dieldrin, chlordane, toxaphene, mirex,
kepone, lindane, and benzene
hexachloride. Chlordane
Dieldrin
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Action Mechanism of Organochlorinated Pesticides

Their toxic action is not fully understood, but they are known to
disrupt the nervous system. The two main groups
of organochlorine insecticides are the DDT-type compounds and
the chlorinated alicyclics. The mechanism of action is
the insecticide binding at the GABAA site in the gamma-
aminobutyric acid (GABA) chloride ionophore complex, which
inhibits chloride flow into the nerve.
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Pesticides and Insecticides Spraying
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Organophosphorous Pesticides

Organophosphorous pesticides are the pesticides that

are organoderivatives of phosphoric acid and whose
fundamental structure is as follows:
Dichlorvos Dimethoate Malathion

O or S
R1
P X
R2
Where Methamidophos Methylparathion Chlorpyrifos
R1 and R2 may be alkoxy (methoxy, ethoxy, etc.)
X may be amino, p-nitrophenoxy group, etc.

Glyphosate Gluphosinate
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Organophosphorous Pesticides: Mechanism of Action : Acetylcholine

Acetylcholine, an ester of choline and acetic

acid that serves as a transmitter substance of nerve
impulses within the central and peripheral nervous
systems. Acetylcholine is the chief neurotransmitter
of the parasympathetic nervous system, the part of
the automatic nervous system (a branch of the
peripheral nervous system) that contracts smooth
muscles, dilates blood vessels, increases bodily
secretions, and slows heart rate. Acetylcholine can
stimulate a response or block a response and thus can
have excitatory or inhibitory effects.
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Organophosphorous Pesticides: Mechanism of Action

Acetylcholinesterase (AChE) is a cholinergic enzyme primarily found at

postsynaptic neuromuscular junctions, especially in muscles and
nerves. It immediately breaks down or hydrolyzes acetylcholine (ACh),
a naturally occurring neurotransmitter, into acetic acid and choline.
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Organophosphorous Pesticides: Mechanism of Action

When Organophosphorous pesticides are sprayed on pests , they

uptake it, the hydroxyl group present in enzyme starts reacting with -
OX group of the pesticides and form an inactive enzyme-pesticide
complex. As a result the enzyme () loses its enzymatic activity and
ultimately the pests die.

Choline

Representation of biochemical interaction organophosphate and acetylcholinesterase

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Insecticides: BHC
BHC (Benzene hexachloride): BHC is an important insecticide. The commercial BHC possesses 5
isomers. These are alpha (55-70%), beta(5-14%), gamma(10-13%), delta(6-8%) and epsilon(3-4%).
The gamma BHC is usually known as Gammexane or Lindane.
Preparation: BHC is prepared by the chlorination of benzene in presence of sunlight. Chlorine gas
is passed into liquid benzene in the presence of sunlight.

Uses: The insects that are not killed by DDT are killed by Gammexane. Gammexane has
successfully applied against the common diseases carrying insects, household stock,
horticulture, stored food and agriculture pests.
Side Effect: It has no contact action on human system and so it is safe insecticide for
domestic use.
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Insecticides: DDT
DDT: DDT is manufactured by exothermic condensation of chlorobenzene with chloral at about 300C
in presence of oleum or 99% sulphuric acid.

Side effect of DDT: DDT is transmitted to human body when people eat the meat of birds and
fishes that are injured by eating DDT affected insecticides. Thus the DDT dissolved in fat harms
human body. However the pests that were controlled / killed using DDT, now a days they have
developed their resistance against DDT. It was proved in 1962. Since then the use of DDT has
been limited.
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Insecticides: Parathion

Parathion (Properties): It is soluble in many organic solvents. It is highly toxic to warm-blooded

animals and can be absorbed through the skin, lungs and digestive tract. It is effective generally
against aphids, spider mites, and certain other insect pests. It acts rapidly mainly as contact
insecticide.

Uses: It is cheap, effective and powerful in small concentration. It is a very powerful insecticide. It
kills mites and ticks and is mainly used on vegetables and citrus crops. Its serious disadvantages is its
extremely poisonous nature which makes its preparation, handling and use most hazardous.

Preparation: Parathion is prepared by treating diethylchlorothiophosphate with sodium p-

nitrophenate. Ther reaction is carried out in chlorobenzene or in aqueous medium in the presence of
emulsifier.
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Insecticides: Parathion
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Insecticides: Methyl Parathion
Preparation: Methyl parathion is prepared by treating dimethylchlorothiophosphate with sodium p-
nitrophenate. The reaction is carried out in organic solvents like chlorobenzene, xylene, or aliphatic
ketones.
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Insecticides: Methyl Parathion

Properties:
1. Colour: White crystalline substance.
2. Melting point: 35 to 360C.
3. Solubility: About 55 mg/L water.
4. Hydrolysis rate: > parathion, in 175 days at 200C at pH 1 to 5.

Uses: Methyl parathion is used for protecting cotton fields. It controls numerous insects by
contact and stomach action. It is generally applied as a spray, mainly from an emulsifiable
concentrate formulation.
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Insecticides: Paraoxon

Preparation: Paraoxon is prepared by treating sodium-p-nitrophenoxide with

diethylchlorophosphate using xylene as solvent.
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Insecticides: Paraoxon

Properties:
1. Form: Oil
2. Colour: Yellow
3. Solubility: Water soluble (3.627g/L at 20°C)
4. Boiling point: 169-170°C

Uses: It is used as the most potent acetylcholinesterase-inhibiting insecticide

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Insecticides: Malathion
Preparation: Malathion is prepared by the addition of dimethyldithiophosphoric acid to maleic
acid ester in the presence of basic catalysts in various organic solvents

Malathion
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Insecticides: Malathion

Properties: Malathion is one of the safest organophosphorus compounds now

marketed in the form of emulsion concentrate. It is also possible to use malathion in
the form of dusts or suspensions prepared form a wettable powder.
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Herbicides: Definition

Herbicides: The chemicals that are widely used in the agricultural fields to control the growth of
herbs, weeds and bushes which are are called herbicides. Examples: 2, 4- D (2,4-dichlorophenoxy
acetic acid), 2,4,5-T (2,4,5-trichlorophenoxy acetic acid) etc.

Herbs
Weeds
Bushes
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Herbicides: Classification
Classification: Herbicides can be classified based on
1. Mode of action
2. Mode of application
3. Chemical family.

1. Mode of action: According to the mode of action herbicides are of three

types. Such as
(a) Plant sex cell killer
(b) Growth inhibitor
(c) Plant growth regulator cum weed killers
(a) Plant sex cell killer: These types of herbicides make the unwanted plants
sexually sterile and check its pollination during flowering season. Bis chloro-
isobutyrate is an example of such herbicide. Bis-chloroisobutyrate
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Herbicides: Classification

(b) Growth inhibitor: When these types of herbicides are sprayed over a plant, cause Ca(CN)2
the leaves to whiter (dry up/ fade) and ultimately drop out. As a result the plants are
deprived off their food maker and slowly face extinction (death). Calcium cyanide,
magnesium silicate etc.
(c) Plant growth regulator cum weed killers: When these types of herbicides are
sprayed over in small concentration, bring about certain changes in plants and in
higher doses act as weed killers. The dwarfing/weed killers in agriculture are generally
known as plant tranquillizers and they cut stem growth above certain height and in
this manner do not allow an unwanted species to attain its natural growth. 2,4-D and
2, 4, 5-T are the most important growth regulators cum weed killers.
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Herbicides: Classification
2. Mode of application: According to the mode of application herbicides of two types. Such as:
a. Selective herbicides and
b. Non-selective herbicides
a. Selective herbicides: The herbicides that kill only one unwanted plant but not other are called
selective herbicides. 2,4-D is an example of selective herbicide.
b. Non-selective herbicides: The herbicides that are used to kill more than one unwanted plants
are called non-selective herbicides. Sodium chlorate, sodium arsenate etc. are common examples
of non-selective herbicides.
3. According to chemical family:
a. Organic and
b. Inorganic
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Herbicides: Trichlorophenoxy compounds (2, 4, 5-T)
2,4,5-trichlorophenoxy acetic acid: 2,4,5 – trichlorophenoxy acetic acid is manufactured by
chlorinating 1,2,4-trichloro benzene in presence of aluminium-mercury amalgam. 1,2,4,5-tetrachloro
benzene thus formed is treated with NaOH in methanol to form a mixture of 2,4,5-trichlorophenol
and 2,4,5-trichloromethoxy benzene. 2,4,5-trichloromethoxy benzene is separated from the mixture
by solvent extraction method. The left 2,4,5-trichlorophenol is neutralized with caustic soda to
produce 2,4,5-trichloro sodium phenate. Then the product is reacted with sodium mono chloroacetic
acid to form sodium salt of 2,4,5-trichlorophenoxy acetic acid. Acidification and crystallization of
the mother liquid is carried out to furnish
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Herbicides: Trichlorophenoxy compounds (2, 4, 5-T)

Preparation reactions of 2, 4, 5-T