SEC ASSIGNMENT (PESTICIDE

CHEMISTRY)

NAME-ADVAITA
CLASS-B. Sc(H) CHEMISTRY (IInd YEAR)
ROLL NO.-1518097
 PAPER-1 (DECEMBER-2017)

Q.1

(i) A pesticide is a chemical or other substance used to kill unwanted insects or weeds.
e.g. fungicides, insecticides, herbicides etc.
(ii) C15H21N3O2
(iii)A leaving group is a charged or uncharged atom or group that gets detached from the atom that is
considered to be residual or main part of substrate in a specific reaction.
e.g. C6H5CH2Br + 4 CH3COOH C6H5CH2(CH3COO) + HBr
here Br is the leaving group.
(iv C6H6Cl6
(v) C10H19O7PS

Q.2

(i) Fungicides are chemical compounds or biological organisms used to kill parasitic fungi or their
spores.
e.g. thiocarbamates

(ii) Systemic fungicides are those that are absorbed into the plant. Locally systemic fungicides move
within the plant but not far from the site of penetration. Some locally systemic fungicides can have a
translaminar mode of action and move through the leaf from one side of the leaf to the other. Systemic
fungicides require the plant to be actively growing in order to circulate through the plant to control
disease. New leaf growth is protected for a short period. Unlike contact fungicides, systemic
fungicides can sometimes be used to supress a disease after it has infected a plant

(iii) Pre-emergent herbicides prevent the germination of seeds by inhibiting a key enzyme. In some
areas of the world, they are used to prevent crabgrass from appearing in lawns. Preemergent
herbicides are applied to lawns in the spring and fall, to prevent the germination of weed seeds.

(iv)Glyphosate is a soil acting herbicide with structural formula C 3H8NO5P.

Q.3
(i) C14H9Cl5

(ii) C10H14O5PS

(iii) C14H20ClNO2

(iv) Insecticides are substances used to kill insects. They include ovicides and larvicides used against
insect eggs and larvae, respectively.
e.g. organophosphates, pyrethroids and carbamates

Q.4
(i)Both organochlorine and organophosphorus have similar mode of action. Organochlorines affect
gamma amino butyric acid (GABA) channel while organophosphorus targets the acetylchlonestese
ultimately both results in paralysis and death of insects.Organophosphorous can be quite lethal to
other organisms as well as it causes acute poisoning which can lead to death while organochlorine
degrades easily and get accumulated in biosphere and are less lethal.Therefore, organochlorines are
more preferable insecticides in comparison to organophosphorus.

(ii)It is prepared by heating a mixture of chloral and chlorobenzene in molar ration (1:2) in presence
of conc. H2SO4.
(iii) Parathion is synthesized from diethyl dithiophosphoric acid (C2H5O)2PS2H by chlorination to
generate diethylthiophosphoryl chloride ((C2H5O)2P(S)Cl), and then the chloride is treated with
sodium 4-nitrophenolate
2 (C2H5O)2P(S)SH + 3 Cl2 → 2 (C2H5O)2P(S)Cl + S2Cl2 + 2 HCl
(C2H5O)2P(S)Cl + NaOC6H4NO2 → (C2H5O)2P(S)OC6H4NO2 + NaCl

(iv) C12H11NO2

Q.5

(i)
(a)p p (b)o o (c)o m (d)m m
Order: (a)>(b)>(d)>(c)

(ii)HCH (Hexachlorocyclohexane) upon hydrolysis with alc. NaOH gives trichlorobenzene.

C6H6Cl6 + alc. NaOH C6H3Cl3
(iii) Parathion is reduced readily to the nontoxic O,O-diethyl O-4-aminophenyl phosphorthioate.
(C2H5O)2P(S)OC6H4NO2 + 6 H → (C2H5O)2P(S)OC6H4NH2 + 2 H2O

(iv) C6Cl4O2

Q.6
(i) The two main groups of organochlorine insecticides are the DDT-type compounds and the
chlorinated alicyclics. Their mechanism of action differs slightly.
The DDT like compounds work on the peripheral nervous system. At the axon's sodium channel, they
prevent gate closure after activation and membrane depolarization. Sodium ions leak through the
nerve membrane and create a destabilizing negative "afterpotential" with hyperexcitability of the
nerve. This leakage causes repeated discharges in the neuron either spontaneously or after a single
stimulus. DDT has a negative temperature correlation-the lower the surrounding temperature the more
toxic it becomes to insects.

(ii) (1) Carbamates inhibit cholinesterase (ChE) as OPs do, and they behave in almost identical
manner in biological systems, but with two main differences. Some carbamates are potent inhibitors
of aliesterase (miscellaneous aliphatic esterase whose exact functions are not known), and their
selectivity is sometimes more pronounced against the ChE of different species.

(2) ChE inhibition by carbamates is reversible. When ChE is inhibited by a carbamate, it is said to be
carbamylated, as when an OP results in the enzyme being phosphorylated. In insects, the effects of
OPs and carbamates are primarily those of poisoning of the central nervous system, since the insect
neuromuscular junction is not cholinergic, as in mammals.

(3) The only cholinergic synapses known in insects are in the central nervous system. (The chemical
neuromuscular junction transmitter in insects is thought to be glutamic acid, but that has not been
proved.)

Q.7

(i) C7NH16O2+1
(ii) C10H19O6PS2

(b)

(1) The Organophosphorus work by tying up or inhibiting certain important enzymes of the nervous
system, namely cholinesterase (ChE). The enzyme is said to be phosphorylated when it becomes
attached to the phosphorous moiety of the insecticide, a binding that is irreversible.

(2) This inhibition results in the accumulation of acetylcholine (ACh) at the neuron/neuron and
neuron/muscle (neuromuscular) junctions or synapses, causing rapid twitching of voluntary muscles
and finally paralysis.
 PAPER-2(2018)
Q.1
(a) done in paper-1 Q.5 (iii) part
(b)DDT, Methyl Parathion

(c) Biomagnification refers to the tendency of the substance to concentrate as they move from one
trophic level to the next. For example DDT, it gets into the fat stores of animals where it can remain
for years as metabolic pathways cannot break it. Since large organisms like humans consume using
small organisms which already have DDT in small amount the concentration in large organisms
increases then it was in smaller organisms.
(d)Malathion, Parathion
(e) Insecticides are pesticides that are formulated to kill, harm, repel or mitigate one or more species
of insect.
e.g. DDT, carbamates
(f) A herbicide is a pesticide used to kill unwanted plants.
e.g. Trifluralin, atrazine
(g)Structure in paper-1 Q.7(a) (i) part
Role- Acetylcholine is an organic chemical that functions in the brain and body of many types of
animals as a neurotransmitter. It causes muscles to contract, activates pain responses and regulates
endocrine and REM sleep functions.

Q.2
(b) 1. Pesticides can reach surface water through runoff from treated plants and soil.
2. Groundwater pollution due to pesticides is a worldwide problem. According to the USGS, at
least 143 different pesticides and 21 transformation products have been found in ground water,
including pesticides from every major chemical class.
3. Heavy treatment of soil with pesticides can cause populations of beneficial soil microorganisms
to decline which causes decrease in soil fertility in future.
 4. Pesticide sprays can directly hit non-target vegetation, or can drift or volatilize from the treated
area and contaminate air, soil, and non-target plants Many ester-formulation herbicides have been
shown to volatilise off treated plants with vapours sufficient to cause severe damage to other plants.
(c) (i)Done in Q.7(a) (i)
Malathion is an insecticide.
(ii) Done in Q.5 (iv) part
Chloranil is a fungicide.

Q.3
(a)DDT is available in form of various isomers in which p,p isomer is more effective to kill insects
.Other isomers of DDT are also known oo,mm,om but all these have different toxicity towards target.
Mode of action:
 It destroys the delicate balance of sodium and potassium ions within the axons of the neuron in a
way that prevents normal transmission of nerve impulses, both in insect and mammals.
 It apparently acts on the sodium channel to cause "leakage" of sodium ions. Eventually the neurons
fire impulses spontaneously, causing the muscles to twitch- "DDT jitters" followed by convulsions
and death.
 DDT has a negative temperature correlation-the lower the surrounding temperature the more toxic
it becomes to insects.
(b) 1. DDT persist in the environment for long time which causes its bio-accumulation and bio-
magnification in living organisms.
2. It causes thinning of egg-shell of birds.
3. It causes causes significant anatomical, behavioral abnormalities and physiological in humans
and also wildlife.
4. It is carcinogenic in nature.
(c) 1.Natural pesticides are usually less toxic then conventional pesticides.
2.They only affect the target organisms and related organisms unlike broad spectrum conventional
pesticides which affect organisms like birds which are not related to the process of harming crops.
3.They are effective even when applied in small amounts and gets decomposed easily hence
reducing pollution.
4.They do not pollute soil or kill useful microorganisms hence soil fertility is not affected.

Q.4
(a) Upon entering the body—through ingestion, inhalation, or contact with skin—organophosphorus
inhibit cholinesterase, an enzyme in the human nervous system that breaks down acetylcholine, a
neurotransmitter that carries signals between nerves and muscles.As a result excess acetylcholine
(Ach) gets collected at different nerves and receptors in the body because acetylcholinesterase is
blocked.
(b) A systemic fungicide may be defined as a fungicidal compound which is readily translocated as
such in the plant, rendering the tissues penetrated toxic to fungi. These are taken up and redistributed
through the xylem vessels.
e.g. Benlate and thiobendazol
(c) The anilides represent a class of organic compounds that are formally "derived from aromatic
amines by conversion of an active hydrogen of –NH groups into – C(=O)–R groups with any
necessary substitution.
Synthesis of Alachlor:
 PAPER-3(MAY 2017)
Q.1
(a) Done in paper-1 Q.1 (i)
(b)
(i)Carbofuran- insecticide

(ii)Parathion-insecticide

(iii)Done in Q.5 (iv)

(iv)Done in Q.3 (iii)
(c) Neem oil spray.
Source-Neem tree
(d) DDT is a non-polar compound and hence is fat-loving and is also called lipo-philic (fat-loving)
(e) Gammexane or lindane is the stereoisomer which has insecticidal property.
(h) Hydrogen cyanide
(i)IUPAC name-1,2,3,4,5,6-hexachlorocyclohexane

(j) Broad-spectrum insecticides are chemicals that are designed to kill or manage a wide variety of
insects. Broad-spectrum insecticides are used when many different species of insects are causing harm
or when the specific insect causing harm is unknown.
Q.2
(a)Done in Paper-2 Q.2 (b)
(b) 1. Pesticides protects the crops from harmful organisms.
2.They increase the productivity per hectare hence allowing farmers to grom more crops on less
land.
3. They decrease exposure to food contaminated with harmful micro-organisms and naturally
occurring toxins, preventing food-related illnesses.
4. Pesticides like fungicide applied to control plant disease may also control those fungi that may
have been preventing economic losses by controlling insect pests.
(c) Malathion is produced by the addition of dimethyl dithiophosphoric acid to diethyl maleate or
diethyl fumarate. The compound is chiral but is used as a racemate.
Uses-Malathion is a pesticide that is widely used in agriculture, residential landscaping, public
recreation areas, and in public health pest control programs such as mosquito eradication.
Q.3
(a)Done in paper-2 Q.3 (b)
(b)Pesticides are classified on the basis of target organism into following category:
1. Insecticides-eg. endosulfan, malathion
2. Rodenticides
3. Nematicides
4. Fungicides-eg. Copper oxychloride, mancozeb
5. Herbicides-eg. 2,4-D, butachlor
(c)-CONH- group belongs to anilides group.
Mode of action- Its mode of action is elongase inhibition, and inhibition of geranylgeranyl
pyrophosphate (GGPP) cyclisation enzymes, part of the gibberellin pathway. Stated more simply, it
works by interfering with a plant's ability to produce protein and by interfering with root growth.

Q.4
(a)Done in paper-2 Q.3 (c)
(b) Carbaryl is often inexpensively produced by direct reaction of methyl isocyanate with 1-naphthol.
C10H7OH + CH3NCO → C10H7OC(O)NHCH3
Alternatively, 1-naphthol can be treated with excess phosgene to produce 1-naphthylchloroformate,
which is then converted to carbaryl by reaction with methylamine.
Merits: 1.It can be used to control large variety of pests like rats, mosquitoes.
2.It can be used on fruits,lawns,vegetables and even buildings.
 3.Product with carbaryl can be formulated into no. of formulations like dust, wettable
powders
Demerits: 1. It kills both beneficial and targeted organisms.(e.g. honey bees)
2.It can also be methyl isocyanate (MIC) as an intermediate. MIC is highly poisonous
chemical. Leak of this chemical during production caused Bhopal gas tragedy, the most lethal
industrial tragedy.
(c) Organic pesticides are naturally occurring or contains less chemicals which when added to soil
doesn’t detiorate it’s quality. They are less toxic and hence, are environment friendly. They are not
water soluble like inorganic pesticides so doesn’t cause water pollution.
(d) 1. Fungicides target fungi and their spores, and herbicides control weeds.
2.Herbicides are like acetanilide while fungicides include thiocarbamates, cupric salts.
 PAPER-4
Q.1
(a) 1,1'-(2,2,2-Trichloroethane-1,1-diyl) bis(4-chlorobenzene)

(b)(i) DDT

(ii)Malathion

(iii)Carbaryl

(iv)Alachlor

(v)Chloranil
(c) Carbamates are not very stable under aquatic conditions, and so do not persist long in the
environment.
(d)Organophosphates affect not only target organism but also other animals like birds,amphibians and
mammaals.
(e) γ-isomer of BHC or lindane is toxic because of following reasons: The EPA and WHO both
classify lindane as "moderately" acutely toxic. Most of the adverse human health effects reported for
lindane have been related to agricultural uses and chronic, occupational exposure of seed-treatment
workers. Exposure to large amounts of lindane can harm the nervous system, producing a range of
symptoms from headache and dizziness to seizures, convulsions, and more rarely, death.
(f) Carbaryl
(g)Neem spray
Source-Neem tree
(h) When a pesticide is first used, a small proportion of the pest population may survive exposure to
the material due to their distinct genetic makeup. These individuals pass along the genes for resistance
to the next generation.
(i)Methoxychlor is known to be less persistent then DDT and hence is preferred over it.
Q.2
(a)Done in paper-2 Q.2 (b)
(b)Although pesticides are very harmful for environment and living beings but due to their several
advantages we still use them.
1.Pesticides help in increasing the growth per hectare and hence helping grow more on less area.
2.Pesticides protects the crops from harmful organisms.
3. They decrease exposure to food contaminated with harmful micro-organisms and naturally
occurring toxins, preventing food-related illnesses.
4. Pesticides like fungicide applied to control plant disease may also control those fungi that may
have been preventing economic losses by controlling insect pests.
(c) Done in paper-1 Q.4 (ii)
Uses- DDT was a commonly-used pesticide for insect control.It was also used initially by the military
in WW II to control malaria, typhus, body lice, and bubonic plague.
Q.3
(a)
 (i) The OPs work by tying up or inhibiting certain important enzymes of the nervous system, namely
cholinesterase (ChE). The enzyme is said to be phosphorylated when it becomes attached to the
phosphorous moiety of the insecticide, a binding that is irreversible.
 This inhibition results in the accumulation of acetylcholine (ACh) at the neuron/neuron and
neuron/muscle (neuromuscular) junctions or synapses, causing rapid twitching of voluntary muscle
and finally paralysis.
(ii)Done in paper-2 Q.3 (b)
(iii)Carbamates are preferred over organochlorines due to several advantages like enhanced
insecticidal activity, less toxicity and greater photostability.
(b)Following chemical reaction shows the procedure of manufacturing of lindane

Q.4
(a)Done in paper-2 Q.3 (c)
(b)Preparation done in paper-1 Q.4 (iii)
Demerits- Parathion exposure can lead to lowered concentration, slower information processing time,
memory and speech impairment, depression and anxiety.
Merits-It is a broad spectrum pesticide and hence can be used for killing large range of insects and
mites.
(c) Degradation involves both biotic and abiotic transformation processes. Biotic transformation is
mediated by microorganisms, while abiotic transformation involves processes such as chemical and
photochemical reactions.
Biodegradation is generally recognized as biggest contributor to degradation. Whereas plants, animals
and fungi (Eukaryota) typically transform pesticides for detoxification through metabolism by broad-
spectrum enzymes, bacteria (Prokaryota) more commonly metabolize them.
In surface waters, phototransformation can substantially contribute to degradation. In “direct”
phototransformation, photons are absorbed by the contaminant, while in “indirect”
phototransformation, reactive species are formed through photon absorption by other substances.
Pesticide electronic absorption spectra typically show little overlap with sunlight, such that only a few
(e.g., trifluralin) are affected by direct phototransformation.[3] Various photochemically active light
absorbers are present in surface waters, enhancing indirect phototransformation.
(d) 1. Natural pesticides are naturally occurring while synthetic pesticides are man-made.
 2. Natural pesticides contain very low amount of chemicals while synthetic pesticides are totally
chemical based.
3.Natural pesticides are environment friendly while synthetic pesticides are non-environment friendly.