LECTURE - 12
Structure And Mode Of Action Of Oxadiazines & Phenyl Pyrazoles
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OXADIAZINES
INDOXACARB: C22H17 ClF3 N3O7
(S)-methyl7-chloro-2, 5-dihydro-2- [[(methoxycarbonyl) [4 -
(trifluoromethoxy) phenyl] amino] carbonyl] indeno[1,2-e][1,3,4]
oxadiazine-4a(3H)-carboxylate
Indoxacarb, an oxadiazine manufactured by DuPont, acts
as a sodium channel blocker. This relatively new pesticide was
registered in California, January 2001.
Mode of action
Indoxacarb is a non-systemic, used to control sucking insects. Indoxacarb affects insects
from direct exposure and through ingestion of treated foliage/fruit. Once indoxacarb is absorbed or
ingested, feeding cessation occurs almost immediately. It kills by binding to a site on sodium
channels and blocking the flow of sodium ions into nerve cells. The result is impaired nerve
function, feeding cessation, paralysis, and death (Brugger, 1997). It may take days for insects to die.
Indoxacarb is used on a range of crops, which include fruits (apples, pears, and tomatoes),
vegetables (broccoli, Brussels sprouts, cabbage, cauliflower, eggplant, potato, and lettuce),
soybeans, alfalfa and peanuts.
Trade names: Avaunt and Steward.
Biological activity of Indoxacarb:
Bheemanna and Patil, 1999 reported that indoxacard @75 ga.i/ha gave good control of boll
worms on cotton. Papa et al., 1999 reported that indoxacarb alone and in combination with
methomyl and lufenuron gave 83and 92 per cent control of Spodoptera litura (Fab.), respectively
Suhas et al, 1999 showed that indoxacarb @ 50g a.i/ha had lowered the incidence of
Helicoverpa armigera (Hub.) on pigeon pea. Indoxacarb (0.024%) had showed 86.66 % ovicidal
property against Spodoptera litura eggs followed by spinosad (0.015%) up to an extent of 73.33 per
cent (Ahmed et al., 2001)
Indoxacarb @ 1ml/l was found to be highly effective in controlling H. armigera in cotton by
giving 100% mortality (Rao et al., 2001). Tong et al., 2002 reported that indoxacarb @ 0.072g a.i/ha
was effective against Trichoplusia ni (Hub.) on cabbage.
Bargavi, 2002 reported that indoxacarb @ 0.0145 % was effective in reducing the larval
population of H. armigera (53.67%) on chick pea and increased the pod yield of chick pea. Soujanya
et al., 2004 reported that novaluron 0.005% + indoxacarb 0.00725% and indoxacarb 0.0145% were
found to be the most effective among all the treatments in controlling Plutella xylostella (Linn.) on
cabbage and recorded increased yields.
Effect on other organisms and plants
Indoxacarb has no reported adverse effect on non-target terrestrial plants. It had no
phytotoxic effect at application rates approximately equivalent to its intended field use rate of 0.065
lbs active ingredient per acre in vegetables. It is moderately toxic to avian species. In bees,
indoxacarb is considered highly toxic by contact moderately to very highly toxic to freshwater and
estuarine/marine fish on an acute basis with LC50s ranging from 0.024 to >1.3 mg/L.
PHENYLPYRAZOLES
FIPRONIL
Fipronil (C12H4Cl2F6N4OS), a phenylpyrazole insecticide, was discovered by Rhone-Poulenc
Agro in 1987, introduced in 1993, and registered as a
pesticide in the U.S in 1996 (Bobe et al. 1998)
Fipronil exhibits neurotoxic activity by blocking
the GABA- regulated chloride channels of neurons. It is
useful for the control of roaches, ants, termites, fleas
and ticks. It is often formulated as insect bait, sprays for
pets, and as a granular turf product to control mole
crickets.
Mode of action
Fipronil affects target species by blocking the chloride channels of neurons; therefore the
resting membrane potential cannot be re-established, the result is excessive neuronal activity.
Fipronil is readily transformed into its desulfinyl photodegradate when exposed to sunlight. This
photoproduct has a high affinity for insect GABA regulated chloride channels. Consequently, the
photoproduct is neurotoxic towards insects. This neurotoxic photoproduct is not a metabolite in
mammals.
Fipronil disrupts normal nerve function by targeting the γ-aminobutyric acid type A (GABA)
receptor system of insects (Kidd and James 1991). Fipronil represents the second generation of
insecticides that act on the GABA receptor system as a noncompetitive blocker. Fipronil’s
mechanism of action is to block the voltage gated chloride channels of neurons. The effect is to
remove normal inhibition, resulting in excessive neuronal activity (Kidd and James, 1991).
It was determined that fipronil interferes with the passage of chloride ions through the
GABA channel. At sufficient doses, fipronil causes excessive neural excitation, severe paralysis and
insect death (Bobe et al., 1998). Fipronil also demonstrates a selective toxicity towards insects by
having a tighter binding affinity toward the insect GABA-regulated chloride channels compared to
mammalian GABA receptors (Hainzl et al., 1998).
Biological activity of Fipronil:
It is used on a variety of foliar and soil insects including corn rootworm, Colorado potato
beetle, and rice weevil that attack a variety of crops, mostly corn and rice (University of Minnesota,
2001). Fipronil is also effective for locust and termite control, against insects in both larval and adult
stages, as well as insects resistant to pyrethroid, organophosphate, and carbamate insecticides
(Kidd and James 1991; University of Minnesota 2001; Bobe et al., 1997). Effective against soil insects,
foliage feeders, Diamond back moth, Heliothis group. Not effective against aphids and
[Link] et al., 1998 reported that fipronil @ 0.01% was highly effective against Thrips tabaci
(Lind.) infesting [Link] treatment with imidacloprid @ 8g/kg and soil application of fipronil
granules @ 20 kg/ha at sowing time were found effective against Chilli thrips up to 50 days after
sowing (ANGRAU, 2001). Rupal et al., 2003 reported that treatment with fipronil 0.3 G @ 60 g/bed
followed by sprayings with fipronil @ 2.4 ml/l had resulted in maximum yield per hectare and also
less average number of thrips per six leaves on [Link] et al., 2003 reported that
treatment with fipronil 5% SC @ 50-75 g a.i/ha was effective in lowering the populations of thrips,
aphids and jassids infesting cotton.
Mammalian toxicity: Fipronil has a relatively low vapor pressure, does not readily volatilize.
Fipronil is toxic to mammals via ingestion. The oral LD50 for rats is 97mg/kg. and dermal LD50 of
greater than 2000 mg/kg in [Link] names: Chipco, Choice, Frontline, Topspot, Combat,
Maxforce, Regent