Pesticides

BRIEF HISTORY OF PEST CONTROL

2500 B.C. -Sumerians began using sulfur as an insecticide.
800 B.C. -Chinese and Egyptians used herbs and oils to control
insect pests.
300 B.C. -Chinese monitored pest emergence and regulated
planting dates.
1100-1600 A.D. -Chinese used soaps, tobacco and arsenic to
control pests.
1800's -Countries regulated and quarantined goods for
inspection before unloading.
1899–The first major biological control success: cottony cushion
scale in California. The cottony cushion scale insect almost
destroyed the citrus industry in California during the late 1800's.
Albert Kebele was sent to Australia and found Vidalia beetles
feeding on it. He brought back a population and released the
beetles in California.
1939-"Insecticide Era,” synthetic insecticides were
developed. The importance of this event was quickly
manifest with the outbreak of WWII.

• Mode of entry
1. Contact
2. Ingestion
3. Systemic
4. Inhalent

• Modes of action
• Acetylcholinesterase (Ach. E.) Inhibition
• Nerve poison
• Hormone disruptor
An ideal pesticide
1. Kills target pest
2. Non-persistent, short lived
3. No adverse effects on other organisms.
4. No genetic resistance
5. Less costly than economic losses

Types of Pesticides
6. Insecticides
7. Herbicides
8. Fungicides
9. Bactericides
10. Rodenticides
11. Biopesticides
 First Generation Pesticides (i.e. pre 1940s)
•Natural substances
•Sulphur, lead, arsenic, mercury
•Plant extracts: nicotine, pyrethrum
•Degradable

Second Generation Pesticides

•Synthetic organic compounds-630 biologically-active
compounds, 35,000 pesticide products
i,e. DDT – Dr. Mueller, Nobel Prize in 1948. It was cheap, easy
to produce, persistent, insoluble in water.

Third Generation Pesticides (1985+)

•Genetically engineered predators
•Genetically engineered plants
•Round-up ready corn, wheat, rice.
Pesticide Ingredients
Pesticide products contain both "active" and "inert" ingredients.

INSECTICIDE LABELS
•Common name - specific name given to the active ingredient; similar
to the scientific name of an insect.

•Chemical name - describes the chemical compound structure.

•Trade name - (Such as "Merit 0.5 G“) the commercial name given by
the company producing the insecticide.
INSECTICIDE TOXICITY
Toxicity is defined as the dose that will kill 50 percent of the test
animals it was administered to. The dose is expressed as
milligrams of insecticide per kilogram of lab animal body weight.

It is referred to as the LD50.

Lower LD50 = greater toxicity

Pesticide law in the U.S. requires that labels be placed on all

products, and must include words like "Danger-Poison,"
"Warning," and, "Caution" along with the LD50 for oral and
dermal toxicity.
(Toxicity Oral/dermal LD50 Signal Words Insecticide
category) (mg/kg body (required on examples
weight) label)
Highly toxic <50 oral and/or Danger-Poison Parathion,
<200 dermal nicotine,
Moderately toxic 50-500 oral and/or Warning Rotenone,
200-2000 dermal diazinon
Slightly toxic 500-5000 oral Caution Malathion,
and/or 2000-20000 carbaryl
dermal
Low toxicity >5000 oral and/or Caution Permethrin
>20,000 dermal
Types of Pesticides
•Inorganics - usually obtained by mining; do not contain organic
compounds (those that contain carbon).

• Botanicals - obtained from flowers or plants. Ex-

Pyrethrum, nicotine, rotenones, and neem extracts.

• Synthetic organics - man-made. Ex-

Organochlorines, organophosphates, carbamates, pyrethroids, and
chloronicotinyls.

•Insect growth regulators (IGR’s) - kill insects by affecting insect growth

•Microbials - include fungus, bacteria, and viruses.

Natural insecticides
Synthetic insecticides
 Mechanism of action/Disturbance of chemical signal system
1. Enzyme inhibition
2. Mimicking of true signal substances/Agonists- Nicotine; 2,4-D,etc
3. Blocking the receptor/Antagonists-Succinylcholin
4. Generating reactive molecules destroy cellular components
5. Toxicants that dissolve in lipophilic membrane and disturb physical
structure
6. Weak organic base or acids degrade pH gradient across membrane
7. Toxicants that disturb electrolytic or osmotic balance or pH
8. Strong electrophiles, alkalis, acids, oxidants or reductants that
destroy tissue, DNA or proteins
9. Na ion channels stay open, resulting in random neuron fire and
death “DDT Jitters”
Enzyme Inhibitions
How Acetyl-cholinesterase Normally Works
Blocking of enzymes by organophosphorus/carbamates
Organochlorine activity
Insecticides: DDT
Physical & Chemical Properties of DDT
• 1,1,1-trichloro-2,2-bis-(p-chlorophenyl) ethane

• Technical grade DDT

– 65–80% was the active ingredient, 4,4’-DDT

– 15–21% of the nearly inactive 2,4’-DDT
– 4% of 4,4’-DDD
– 1.5% of 1-(4-chlorophenyl)-2,2,2-trichloroethanol

• Degrades into 2,4’-DDE, and 2,4’-DDD 4,4’-DDE

 1,1,1-Trichloro-2-(2-chlorophenyl)-2-(4-
chlorophenyl)ethane

1,1,1-Trichloro-2,2-bis(4-chlorophenyl)ethane,

1,1-Dichloro-2,2-bis(4-chlorophenyl)ethene
1,1-Dichloro-2,2-bis(4-chlorophenyl)ethane
Reactions
Raw materials: Monochlorobenzene and chloral
 Cl OH
H Cl
Cl +
Cl O OH Cl H
OH Cl
-
+
Cl C h lo r o b e n z e n e
H O S O
Cl
+ H + O S O
-H S O 4 -
O OH
Cl O

Cl
Cl

H
+ H H H
Cl O Cl O Cl O
Cl
Cl + H Cl H Cl H Cl H
Cl H
Cl Cl Cl
H+
+
-H 2 O

Cl Cl Cl Cl

Cl Cl

+
Cl Cl
H
Cl H Cl H
-H +
Cl Cl

Cl Cl
Biomagnification

DDT and DDE are

readily stored
in fats of
vertebrates
DISPOSAL
Under current federal guidelines, DDT and DDD are potential candidates
for incineration in a rotary kiln at 820–1,600 °C. Destruction efficiency with
this method is reported to be >99.99%. DDT powder may be disposed off
by molten salt combustion at 900 °C. Landfill disposal methods are rarely
used at the present time as half life of DDT is 2-15 years.

Degradation Pathway

DDT

DDE DDD
“Total DDT” refers to the sum of the concentrations of p,p'-DDT, o,p'-DDT,
p,p'-DDE, o,p'-DDE, p,p'-DDD, and o,p'-DDD.
Herbicides

Mode of action
•Lipid biosynthesis inhibitors
•Amino acid biosynthesis inhibitors
•Plant growth regulators formation
•Photosynthesis inhibitors
•Nitrogen-metabolism inhibitors
•Pigment inhibitors
•Cell-membrane disruptors
•Seedling-growth inhibitors
Organic Herbicides
•Oils
Diesel oil, standard solvent, xylene-type, aromatic oils, polycyclic, etc.
•Aliphatics
Acrolein, Glyphosphate methyl bromide.
•Amides
Diphenamide, Naptalam,
•Phenoxy
2,4-D, 2,4,5-T
• Aryl carboxylic acids
2,3,6 TBA, Diacamba, tricamba, chloramben, Fenac.
•Carbamates
Propham, chloropham, barban.
•Triazines
Atrazine, simazine, ametryne , terbuteryne
•Ureas
Monuron, diuron, fenuron
•Uracils
Bromacil, terbacil, lenacil. and many more types
2. Aryl carboxylic acid
3. Triazines
 4. Ureas

3-(4-Chlorophenyl)-1,1-dimethylurea

Thioureas
5. Uracils

Pyrimidine-2,4(1H,3H)-dione
2,4-D
Reactions
2,4-D is manufactured from 2,4-dichlorophenol in a four step process.
•Step 1 - The (acidic) phenol is neurtralised with caustic soda.

•Step 2 - Sodium monochloroacetate is produced in another exothermic

reaction.
•Step 3 - The NaDCP is condensed with NaMCA to produce the sodium salt of
2,4-D.

Unwanted side reactions occur but are kept to a minimum through the
choice of optimum operating conditions. NaMCA and water undergo a
reaction that produces sodium glycollate and hydrochloric acid.
a.
 b. NaMCA also reacts with caustic soda to produce sodium glycollate and
NaCl. For this reason the stoichiometric ratio of MCAA and caustic soda is
strictly controlled to avoid build-up of excess caustic soda.

•Step 4 -An ageing period is required to ensure the phenol content of the Na
2,4-D is below 0.5 w/w %. During the ageing step, caustic soda is slowly
added to the reaction mass to react with any remaining phenol. The addition
rate is controlled so that alkaline conditions are maintained in the reactor.

•Step 5 – HCl is added to convert Na salt of 2,4-D to acid.

Mechanism of herbicide action
2,4-D is a synthetic auxin, which is a class of plant growth regulators. It is
absorbed through the leaves and is translocated to the meristems of the
plant. Uncontrolled, unsustainable growth ensues causing stem curl-over,
leaf withering, and eventual plant death.

ENVIRONMENTAL IMPLICATIONS
The various products containing 2,4-D are used as herbicides. They have
low acute toxicity to animals, but are toxic to fish. There should be no
adverse environmental effect if used in accordance with label
instructions. The problems associated with the related phenoxy
herbicide 2,4,5-T relate to TCDD (2,3,7,8-tetrachlorodibenzo-p-dioxin) -
an impurity that it commonly contains which is absent in 2,4-D.
Parathion (IUPAC name O,O-Diethyl O-(4-nitrophenyl) phosphorothioate)
Reactions
Parathion is synthesized from diethyl dithiophosphoric acid by chlorination
to generate diethylthiophosphoryl chloride. In a salt metathesis(double
displacement) reaction, the chloride treated with sodium 4-nitrophenolate
produce parathion.

2 + 3 Cl2 → 2 + S2Cl2 + 2 HCl

+ → + NaCl

Phosphoric acid
Degradation of parathion leads to more water-soluble products.

1. Hydrolysis
It occurs at the aryl ester bond resulting in diethyl thiophosphate and
4-nitrophenol.

+ H2O → HOC6H4NO2 + (C2H5O)2P(S)OH

2. Reduction
Degradation proceeds differently under anaerobic conditions: the nitro
group on parathion is reduced to the amine.

+ 6 H → (C2H5O)2P(S)OC6H4NH2 + 2 H2O
Mode of action
Parathion acts on the enzyme acetylcholinesterase indirectly. After an
insect (or a human) ingests parathion, an oxidase replaces the double
bonded sulfur with oxygen to give paraoxon.

(C2H5O)2P(S)OC6H4NO2 + 1/2 O2 → (C2H5O)2P(O)OC6H4NO2 + S

The phosphate ester is more reactive in organisms than the

phosphorothiolate ester, as the phosphorus atoms become much more
electropositive.
Parathion was used as a chemical warfare agent, most notably by an
element of the British South Africa Police (BSAP) attached to the Selous
Scouts during the Rhodesian Bush War. They used it to poison clothing
that was then supplied to anti-government guerrillas. When the enemy
soldiers put on the clothes, they were poisoned by absorption through
the skin. It is known as "Folidol", is an organophosphate insecticide. It
was originally developed in the 1940s. It is highly toxic to non-target
organisms, including humans, so its use has been banned or restricted
in most countries.
Biopesticide from Chrysanthemum flower