Chapter 3: Insecticidal activity of quinoline derivatives
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CHAPTER 3
INSECTICIDAL ACTIVITY OF QUINOLINE DERIVATIVES
3.1 Introduction
Some people are concerned about the use of pesticides. Like all other
chemicals, pesticides should be treated with respect and not injured, but the
risks associated with pesticide use are often exaggerated out of all section,
especially when compared with those of the many domestic products and foods
we use or consume. Broad tests are performed throughout the development
stages of pesticides to minimize hazard to humans, animals and the
environment. Legislation covering development as well as the marketing,
selling, storage and use of pesticides are very strict and wide-ranging.
Many household refining agents are strong irritants. Alcohol may cause
birth defects. Many fruits and vegetables enclose toxins which are far more
potent than garden chemicals. Our body has evolved so that it can cope with a
certain amount of natural and man-made toxins and, provided we eat a
balanced and reasonable diet, there is no need to be excessively concerned
about what we eat. These comparisons should demonstrate that pesticides, used
sensibly, should not give rise to unnecessary concern.
The public are often concerned about the use of pesticides and not
always presented with a balanced view. It is important to be able to provide
reassurance about research and safety aspects (covered later) and to remind
ourselves of the need to keep pests under control. If left to their own devices,
weeds, pests and diseases will damage the health or appearance of cultivated
plants, to a greater or lesser amount. The situation tends to be made poorer by
the way in which we grow plants as gardeners by crowding a mixture of plants
into a small plot, or farmers by raising a large area of the same crop.
Insects are distinguished from other arthropods by having segmented
bodies, jointed legs, and external skeletons (exoskeletons), their body is
divided into three major regions:
1. The head, which having the parts of mouth, eyes, and a pair of antennae.
Chapter 3: Insecticidal activity of quinoline derivatives
90
2. The three-segmented thorax, which usually has three pairs of legs (hence
“Hexapoda”) in adults and usually one or two pairs of wings.
3. The many-segmented abdomen, which enclose the digestive, excretory,
and reproductive structure.
Humans consider certain insects as pests, and attempt to control using
insecticides and a host of other techniques. Some insects injure crops by
feeding on cell sap, leaves or fruits. The few bite humans and livestock to feed
on blood and some are capable of transmitting diseases to humans, pets and
livestock. The insects play a great role in pollination of flowering plants as a
many organisms rely on flowering plants. The insects are considered
ecologically beneficial as predators and a few provide direct economic benefit.
The silkworms and bees have been used widely by humans for the production
silk and honey respectively.
Problems likely to be come across by growers if pests are uncontrolled
include the following:
1. Reduced yields. Pest attack can severely reduce the yields of vegetable,
fruit and flower crops; sometimes the entire crop is obliterated. Along
with feeding on the plants, pests can, throughout spoilage, reduce yields
considerably and spread virus diseases.
2. Reduced quality. Even a minor reduction in quality can make all the
difference to commercial growers. To the gardener, quality aspects may
not be so important but it is still soul destroying to spend time and
money growing plants and then have your efforts ruined.
3. Competition. Weeds will deprive cultivated plants of water, space, light
and nutrients. They will also spoil the overall appearance of the garden.
4. Public health. Pesticides are used extensively throughout the world
against insects bearing potentially life-threatening diseases.
In this country they protect public health by controlling rodents which
can spread disease as well as spoil stored food. They are also used against flies.
Pests such as wasps and lice can spread diseases, and nuisance. Pesticides are
Chapter 3: Insecticidal activity of quinoline derivatives
91
not the only solution to these problems. However, combined with good
growing conditions, attention to hygiene and other cultural practices, they are
an effective and labor saving tool in the war against pests.
The present chapter divided into two sections:
� Section I: Insecticidal activity against stored product pest.
� Section II: Insecticidal activity against mosquitoes and aphids.
Chapter 3: Insecticidal activity of quinoline derivatives
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Section I
INSECTICIDAL ACTIVITY AGAINST
STORED PRODUCT PEST
3. I.1 Introduction
The pulses are staple food throughout the world. The Cow pea Vigna
unguiculata (L.) crop is major source of protein for peoples in the Asia region.
The limiting factor in the production of pulses is qualitative and quantitative
losses caused by insect pest in field and storage [1]. Among them widest spread
and destructive primary pest of stored food product in India is Callosobruchus
chinensis [2].
The bruchids are most destructive pest having genus Callosobruchus,
family Bruchidae, and order Coleoptera. The Pulse beetle attack on pulses and
damage to seed is so serious that grubs destroy endosperm completely and
leaving only seed coat with empty cavities [3]. They are also responsible for
increasing heat through their respiratory and metabolic functions. The Pulse
beetles contaminate the rest food with undesirable odor. Alternatively, pest
infested food also causes major health hazards to human being [4]. The C.
chinensis breeds rapidly on different varieties of pulses having short life span
with great reproductive potential. The warm season and high moisture content
of the grain increases the rapid multiplication of the pest.
3. I.2 Review of Literature
The control of this insect pest is mainly depending on continued use of
organophosphorus, pyrethroid insecticides, fumigant methyl bromide and
phosphine [5]. These are still effective, but their constant use results in the
development of resistance [6-7]. They have very harmful effect on non-target
organisms and accountable for health and environmental problems. The use of
methyl bromide causes ozone deflection with high toxicity [8]. Therefore there
are alternatives to organophosphorus compounds for the control of storage
mites [9]. The cow pea seeds are generally used for family consumption,
therefore fumigant application is not suitable. There are some of the additional
Chapter 3: Insecticidal activity of quinoline derivatives
93
possibilities such as storage in plastic or steel containers, gamma irradiation, or
freezing to protect the pulses. However, most of these methods require high
inputs. Sometimes they are unaffordable for poor farmers and are often
unavailable [10]. An insecticidal compounds having oviposition and adult
deterrent activity exhibited a good control for insect pest in today’s agriculture
economy [11]. There is effect of some essential oils on the oviposition and
emergence of callosobruchus species [12].
Insecticidal and antifeedant activities of medicinal plant extracts against
Attagenus unicolor japonicas were also reported [13]. Also the insecticidal and
antifeedant effects of Junellia aspera, triterpenes and derivatives on Sitophilus
oryzae show good results [14]. The chemical pesticides are valuable in
controlling insect population both in field and storage. Insecticidal effect of
spinosad dust against four stored product insect species in different grain
commodities is observed [15-16]. The majority of agricultural products are
protected by using different heterocyclic compounds. Among them one of the
important heterocycle is quinoline [17-18]. Quinoline has diverse biological
active potential such as antibacterial [19], antituberculosis [20], anticancer [21],
antimalarial [22]. Some diphenyl quinolines and isoquinolines showed good
biological activities [23]. The 8-Hydroxyquinoline derivatives were proving to
be effective against plant hopper species [24]. The aminoquinoline Derivatives
are good against cockroaches [25]. There are some other examples for
quinoline acts as pesticides [26-28]. Therefore they have become the synthetic
targets of many organic and agricultural chemistry groups. The synthesis of 2,
3, 4-trisubstituted quinoline derivatives [29] through trans-esterfication were
done. Most of the reported compounds are new entities in heterocycles library
and interpretated on the basis of their spectroscopic data. With continuation our
previous success in bioscience [30] and above result in synthesis of new
quinoline derivatives motivated us to check the insecticidal activity of the said
compounds. With this vision, the details of the insecticidal, oviposition asnd
deterrent activities of new quinoline derivatives against pulse beetle on cow
pea seeds are given.
Chapter 3: Insecticidal activity of quinoline derivatives
94
3. I.3 Materials and Methods
The tri-substituted quinoline derivatives were synthesized by previously
reported method [29]. The following synthesized compounds have been
selected for insecticidal activities against Callosobruchus chinensis are shown
in the (Fig. 3. 1).
(Fig. 3.1) Structures of compounds The different structures of the tri-
substituted quinoline derivatives preliminary tested for insecticidal activity
against Callosobruchus chinensis.
These entire compounds preliminary tested for their insecticidal activity
against stored product pest. It has been observed that only dimethyl 6-chloro-4-
phenylquinoline-2,3-dicarboxylate (DCPQD-1) has shown excellent results.
Therefore only DDPQD-1 is selected for further investigation.
Chapter 3: Insecticidal activity of quinoline derivatives
95
3. I.4 Biological Assay
The biological assay was performed against a representative test
organism reared under the laboratory conditions.
3. I.4.1 Mass Rearing of Callosobruchus chinensis
Nucleus cultures of Callosobruchus were obtained from the Entomology
department of College of Agriculture, Pune and subsequent generations was
reared in humidity and temperature controlled laboratory conditions. Insect
rearing was carried out in 65 ± 5% relative humidity, 28 ± 2oC temperature and
10 hrs. Light: 14 hrs. dark. To obtain newly emerged pulse beetles of same
generation, 25 insects were released in a plastic container having 250 g of
cowpea seeds covered by a muslin cloth. After 24 hrs all the adults were
removed and egg laid seeds was maintained at required temperature and
humidity. The insects emerged after four weeks was used for entire
experiments. Insect eggs were counted by using hand lens.
3. I.4.2 Insecticidal Activity against Callosobruchus chinensis
3. I.4.2.1 Film Residue Method
Controlling adult is also another important step to protect post harvest
production. Film residue method [31] was used to test the mortality of C.
chinensis. To obtain test dosages individual quinoline compounds at dose 50
and 200 µg/mL was dissolved in acetone in vials of size 5 x 7.5 cm (W/L).
These were kept open to evaporate all solvent for 1 hr. The test solutions were
coated on inner surface of vials and freshly emerged (one day old) 20 adult
brucids were gently placed in vials. With each experiment, a set of control
sample containing only acetone solution (Qualigens) was run for comparison.
Each treatment was prepared in triplicate. Treated adults were held for 24 hrs
similar to the conditions used for maintaining the C. chinensis in the laboratory.
Mortalities were recorded after 24 hrs exposure, during which no food was
given to the adults. A simple microscope was used to verify each beetle by
tracing natural movement of its organs. Adults incapable of rising to the
surface or not showing the characteristic movement were considered moribund
Chapter 3: Insecticidal activity of quinoline derivatives
96
and added to the dead adult for calculating percentage of mortality. After the
preliminary screening, (DCPQD-1) is subjected to dose response bioassay to
determine lethal concentrations.
3. I.4.2.2 Dose -response Bioassay
Twenty Callosobruchus brucids at dose 25 to 400 µg/mL were used for
all the treatments. Commonly used insecticide Malathion® 50EC, India was
treated standard tested at 0.05% as positive control. Acetone is used as control.
The test is replicated thrice for each treatment and control. The results of
experiment with mortality percentage are given in the (Fig. 3.2).
(Fig. 3.2) Mortality data The percentage mortality of compound (DCPQD-1)
against Callosobruchus chinensis at different concentrations (µg/ml) showing
mortality rate increases with increase in concentration at 24, 48 and 72 hrs after
treatments.
3. I.4.2.3 Probit Analysis
The probit analysis was done on the probit program (Version 1.5) by
ecological monitoring division, environmental monitoring system laboratory,
U.S., environmental protection agency, Cincinnati, Ohio 45268. The regression
Chapter 3: Insecticidal activity of quinoline derivatives
97
equation for the compound (DCPQD-1) at 72 hrs after treatment is shown in
the (Fig. 3.3).
(Fig. 3.3) Regression equation The dose response relationship of toxicity data
of (DCPQD-1) against Callosobruchus chinensis showing regression equation
of probit mortality verses log of concentration.
3. I.4.3 Oviposition and Adult Deterrency
The 10 gm Vigna unguiculata (Cow pea) seeds treated separately with
each treatment of quinoline compounds at dose 25 to 100 µg/mL. These were
kept separately in small plastic containers of size 8.5 x 10 cm (W/L) covered
with muslin cloth. The seeds will be allowed to evaporate acetone for 1 hr and
used for the further experiment. Five pairs of adult bruchids of either sex were
released in each container. All the adults were removed after 5 days of release
and number of eggs laid was recorded. The oviposition deterrence activity (%
reduction in oviposition) was calculated using formula [32]. Total number of
adults emerged in each treatment was counted after 28 days of their release. A
control set was also maintained without any treatment of test solution well as
Chapter 3: Insecticidal activity of quinoline derivatives
98
with standard Neemarch® 50EC treatment with 100 µg/mL concentrations. The
percent adult emergence was calculated by reported formula [33].
3. I.4.4 Formulae
Oviposition deterrence = No. of eggs laid in control – No. of eggs laid in
treatment / No. of eggs laid in control x 100
Percent emergence = 100 x adult emergence / No. of eggs lay down.
Percent deterrence = 100 - Percent emergence
3. I.5. Results
3. I.5.1 Insecticidal Activity against C. chinensis (Complete Randomized
Block Design)
The efficacy of the compounds tested against Pulse beetle indicated that
all the treatments exhibited significantly superior over untreated solvent
control. When the observations recorded after 72 hrs after treatments
(DCPQD-1) shows 81.67% excellent mortality indicated superiority among the
other concentrations. The significant difference did not exist among the
concentration tested at 100 and 50µg/mL concentrations. The insecticidal
activity against C. chinensis were arranged in complete randomized block
design is listed in (Table 3.1).
(Table 3.1) Insecticidal Activity The insecticidal activity of synthesized
compound (DCPQD-1) at different concentrations against Callosobruchus
chinensis adults was shown in complete randomized block design. The Mean
percentage SE mortality was shown at 24, 48, and 72 hrs after treatments.
Sr.
No.
Treatments
(µg/ml)
Mortality (%) hrs after treatment
24* 48* 72*
1 25 0.00
(0.00)
0.00
(0.00)
21.67
(27.71)
2 50 5.00
(6.15)
8.33
(16.6)
36.67
(37.26)
Chapter 3: Insecticidal activity of quinoline derivatives
99
3 100 11.67
(19.89)
23.33
(25.30)
41.67
(40.20)
4 200 26.67
(31.07)
43.33
(41.16)
71.67
(57.86)
5 400 36.67
(37.26)
63.33
(52.74)
81.67
(64.70)
6 Malathion (0.05%) 51.67
(45.95)
71.67
(58.93)
91.67
(73.40)
7 Control (Solvent) 0.00
(0.00)
0.00
(0.00)
0.00
(0.00)
8 SE ± 1.16 1.54 1.75
9 CD @ 5% 3.96 5.22 5.96
* Mean of three replications
**Figures in parenthesis are Arcsin transformation
3. I.5.2 Probit Analysis
The (DCPQD-1) has shown 96.47 µg/mL LC50 value at 72 hrs after
treatments against the C. chinensis by probit analysis technique as shown in the
(Table 3.2).
(Table 3.2) Dose response study Probit analysis results of (DCPQD-1)
compound against Callosobruchus chinensis showing the LC50 value, upper
fugicidal limit, lower fugicidal limit and chi-square value.
Sr. No. HAT* Conc. (µg/ml) Regression
equation χ
2 LC 50 LFL UFL
1 24 556.08 417.14 903.81 Y=1.41x+2.21 2.84
2 48 250.91 213.53 305.05 Y=1.89x+0.45 3.08
3 72 96.47 79.40 116.95 Y=1.48x+0.87 4.65
* Hours after treatments
Chapter 3: Insecticidal activity of quinoline derivatives
100
3. I.5.3 Oviposition Deterrence
The results indicate that oviposition activity decreases with increase in
concentration as shown in (Fig. 3.4).
(Fig. 3.4) Oviposition deterrence The oviposition deterrent activity of
synthetic (DCPQD-1) against Callosobruchus chinensis at different
concentrations
Among the four concentrations, the 100µg/ml concentration shows the
significant oviposition deterrency is 80.00% as evidence from lowest number
of eggs laid by the female. The detail results have been given in (Table 3.3).
(Table 3.3) Oviposition deterrence The oviposition deterrent activity of
(DCPQD-1) against Callosobruchus chinensis at different concentrations
Sr. No. Concentration (µg/mL) Oviposition deterrence* (%)
1 25 32.21±3.51
2 50 51.28±5.13
3 75 64.10±4.04
4 100 80.00±3.21
5 Neemarch® EC 50 (100) 87.17±4.93
*±SD. Mean of the three replications
Chapter 3: Insecticidal activity of quinoline derivatives
101
3. I.5.4 Adult Deterrence
The adult deterrency shown by (DCPQD-1) at concentration of
100µg/ml is 64.63%. At the concentration of 75µg/ml, it shows 44.33% adult
deterrency. For the concentrations 50 and 25µg/ml the value for adult
deterrency is 28.70 and 27.30 respectively as shown in the (Table 3.4) and
(Fig. 3.5).
(Table 3.4) Adult deterrence The percentage of adult deterrence is against
Callosobruchus chinensis, for compound (DCPQD-1).
Sr. No. Concentration (µg/mL) Adult deterrence* (%)
1 25 27.34±3.79
2 50 38.70±2.51
3 75 44.33±4.04
4 100 64.63±2.52
5 Neemarch® EC 50 (100) 76.00±4.04
*±SD. Mean of the three replications
(Fig. 3.5) Adult deterrence The adult deterrent activity of the (DCPQD-1)
against Callosobruchus chinensis is at different concentrations showing the
increase in activity with increase in the concentration.
Chapter 3: Insecticidal activity of quinoline derivatives
102
The arrangement of experiment is shown in as shown in the (Fig. 3.6)
below.
(Fig. 3.6) Experimental set for activity against stored product pest
Callosobruchus chinensis.
3. I.6 Conclusions
We have reported the insecticidal activity of new quinoline derivatives.
The different concentration of (DCPQD-1) is found to be significantly effective
against Pulse beetle as compared to untreated control. It responded 81.67%
excellent mortality at 72 hrs after treatment. According to Probit analysis, LC50
value for the compound (DCPQD-1) is 96.47µg/ml. Along with insecticidal
activity, it also showed the 80.00% oviposition deterrent and 64.63% adult
deterrent activity at low concentrations is the main finding of this research
communication for future.
Chapter 3: Insecticidal activity of quinoline derivatives
103
Section II
INSECTICIDAL ACTIVITY AGAINST
MOSQUITO (Anopheles stephensi)
AND APHID (Myzus persicae)
3. II.1 Introduction
Insects have been major pests of humankind at least since the
beginning of recorded history. For this there are continuous efforts on structural
modification of pesticides useful for non target organisms but exhibiting good
pesticidal activities to target organism. To this day insects continue to cause
problems in domestic, agricultural, and health situations. It no wonders that
people have continually sought new solutions to controlling insect pests. Even
when new control methods are discovered and established, insects evolve into
resistance species so that the method is only of real value for a few brief years.
Modern science and technology are now enabling scientists to find
physiological and biochemical events critical to insects. Armed with this new
knowledge, researchers should be able to develop novel control strategies that
focus on key events such that they can be altered, influenced, disrupted, and/or
inhibited the biological process.
In the 21th century, pesticide must have the characteristics of high
efficiency, low toxicity, economy and friendly environmental profile.
Medicament and pesticide researchers pay greatly attention to amide
compounds because of their high-efficiency, low toxicity and safety to
environment, in recent years, amide compounds have become the mainstream
in new pesticide discovery. Amide compounds also have broad biological
activities such as insecticide, acaricide, fungicide and herbicide, and amide
substructure is often used as pharmacophore in new pesticide discovery.
The evolvement of discovery, varieties, action mechanism and structure-
activity relationship of amide compounds were introduced in detail. And
phenoxy acetamide has the role of inhibition of cell division, and to some
Chapter 3: Insecticidal activity of quinoline derivatives
104
extent to enhance the role of antineoplastic agents, and has a good fungicidal
activity. Oxygen and nitrogen containing heterocycles are getting immense
importance in the area of pharmaceuticals and agrochemicals. Pesticides belong
to agrochemical area, which includes insecticides, fungicides, rodenticides,
herbicides and fumigants. Among pesticides, insecticides are widely used
chemicals by Indian farmers to control various diseases caused by different
insects. Indiscriminate usage of pesticides in the fields is causing resistance
development by insects resulting lower yields of the crops. Ultimately the
farmer is at receiving end with enormous financial loss.
To overcome this problem an intense research is currently in progress to
develop pyrethroids, nicotinoids where the usage of chemical is at gross level;
however, the insect based diseases are well controlled. This is the emerging
area with a lot of potential and there is a need to synthesize a new class of
pyrethroids, nicotinoids and subjected to bio-evaluation in order to find a
promising candidate. In addition, quinolines as a very important class of
nitrogen -containing heterocyclic compounds, are widely used in health care
and plant protection.
Man knows that he will die some day, still his desire to live as long as
possible. Diseases are our main enemies because they prevent us not only from
enjoying happy and healthy life but also cut short our stay on this earth. The
race has been going on between the diseases and scientific investigations. The
majority of pharmaceutical products that mimic natural products with
biological activity are heterocycles. Among them one of the important
heterocycle is quinoline. Quinoline has diverse biological activities such as
antibacterial [34], antituberculosis [35], anticancer [36], antimalarial [37],
antifungal [38] and antimicrobial [39]. Due to their enormous importance they
have become the synthetic targets of many organic and medicinal chemistry
groups [40]. The structural diversity of quinolines has been based on the
various conventional name reactions [41].
Chapter 3: Insecticidal activity of quinoline derivatives
105
When we say undesirable organisms, we are referring to organisms
(plants, animals, insects, etc.) that are harmful to us. The pests eat our crops,
while others spread diseases. Weeds can be considered a pest for just growing
in the wrong places (our yards). The chemicals which used for controlling pests
are calls pesticides. In addition to applications in agriculture, pesticides have
uses. Many pests transmit diseases which are very dangerous to us. For
example, in the past, malaria was once a serious disease that killed millions of
people worldwide. To overcome this problem, we used DDT, to kill the
mosquitoes. It was victorious, and the number of people who died from malaria
minimize drastically.
3. II.2 Review of Literature
The identification of novel larvicidal and insecticidal compounds
requires the bioassay tests. Malaria is one of the most common vector-borne
diseases extensive in tropical and subtropical regions, including America, Asia,
and Africa [42]. It is a complex disease caused by plasmodial species and is
vectored by female anopheline mosquitoes in which Anopheles stephensi is
responsible in urban areas [43]. Vector mosquitoes control is an essential and
effective part for reducing transmission of vector-borne diseases [44].
Successful method of reducing mosquito densities to an appreciable level for
which malaria epidemics can be controlled is by attacking the larval breeding
places by the use of larvicides [45-46]. In many parts of the world chemical
insecticides have continued to be used for controlling mosquitoes. However,
control of malaria and other mosquito borne diseases becoming more difficult
because the development of resistance in mosquitoes against currently used
synthetic insecticides [47-49].
Aphid is a polyphagus pest and is one of the most serious pests
due to their high population reduces the yield and quality of crop due to sap
sucking and transmission of the numerous viruses of plant [50-51]. Potato leaf
roll virus (PLRV) is transmitted by few aphid species in which M. persicae is
the most efficient and persistent [52]. Control of the spread of PLRV relies
Chapter 3: Insecticidal activity of quinoline derivatives
106
mainly on planting healthy seed potatoes and on the timely application of
insecticides to suppress aphid populations [53]. However, insecticides rapidly
select for insecticide resistant M. persicae and other aphid species [54-57]. This
has been possible through the continued discovery and commercialization of
new insecticide chemistries. Therefore, it is critically necessary to discover new
insecticidal candidates with different chemistries and with varying modes of
action [58].
4. II.3 Materials and Methods
The synthetic approach of 2, 3, 4-trisubstituted quinolines by previously
reported method [59] were done through trans-esterification are as selected for
insecticidal activities are shown in the (Fig. 3. 1).
(Fig. 3.1) Structures of compounds The selected compounds of the tri-
substituted quinoline derivatives tested for insecticidal activity against
mosquitoes and aphids.
Most of the reported compounds were new entities in heterocycle library
and interpretated on the basis of their spectroscopic data. With continuation
our previous success in bioactive compounds [60] and above result in the
synthesis of new quinoline derivatives moved us to check an insecticidal
activity of the said quinoline derivatives. The following compounds have been
selected to investigate an insecticidal activity against mosquito and aphids on
the basis of their structure and primary test.
Chapter 3: Insecticidal activity of quinoline derivatives
107
3. II.3.1 Biological Assay
All bioassays were performed on representative test organisms. The
bioassay was repeated at 27 ± 2°C according to statistical requirements.
Assessments were made on a dead or alive basis. The mortality rates were
corrected using Abbott’s formula. Evaluations are based on a percentage scale
of 0-100 in which 0 % no activity and 100 % total kill.
3. II.3.2 Larvicidal activity against mosquito, Anopheles stephensi (Liston)
3. II.3.2.1 Solution preparation
The specific derivatives of quinoline, 250 mg was placed in a standard
measuring flask and dissolved in 0.9 ml of acetone and 0.1 ml of Tween 80 was
added as an emulsifier. This mixture was diluted to 250 ml using tap water to
prepare the stock solution, which was as a stock solution (1000 µg/ml). From
stock solution, 100 ml was diluted with water up to 250 ml to prepare 400
µg/ml test solution.
This sequential method was used to prepare 200, 100, 50 and 25 µg/ml
solutions. A mixture of 0.9 ml of acetone and 0.1 ml of Tween 80 was made up
to 250 ml in a standard measuring flask by adding tap water to serve as the
control solution. An insecticidal activity was determined according to the
guidelines of WHO and Yankanchi et al and Patil et al, [61-62]. Bioassays
were conducted for 24 hrs in glass beakers of 250 ml of test solutions with
three replicates [Fig. 3.8a and 3.8b].
(Fig. 3.8a) The Experimental Set for Larvicidal activity against mosquitoes,
Anopheles stephensi
Chapter 3: Insecticidal activity of quinoline derivatives
108
(Fig. 3.8b) Larvicidal activity against mosquitoes, Anopheles stephensi at two
concentrations 100(µg/ml) and 200(µg/ml) of 1a
Twenty-five third instar larvae of Anopheles stephensi were introduced
into each test solution with the appropriate control solution. The results were
observed after 24 hrs and the percentage mortality was corrected by using
Abbott’s formula [63]. The LC50 values are calculated using the computation
program of probit analysis [64]. The mortality data were recorded in the (Table
3.5) as follows.
(Table 3.5) Insecticidal activity of quinoline derivatives 1a-d against mosquito
Sr. No.
Conc. (µg/ml)
Percentage mortality 1a 1b 1c 1d
1 25 23 20 17 23
2 50 37 37 27 30
3 100 47 50 43 33
4 200 53 73 67 53
5 400 67 87 87 70
Chapter 3: Insecticidal activity of quinoline derivatives
109
3. II.3.3 Insecticidal activity against Green peach Aphid, Myzus persicae
(Sulzer)
The insecticidal activities of the tri-substituted quinolines (1a-d) were
evaluated using a previously reported procedure [65-66]. The insecticidal
activity was tested against aphid, Myzus persicae by leaf-dip method [Fig 3.9a]
(Fig. 3.9a) Insecticidal activity against Green peach Aphids, Myzus persicae
Tobacco (Nicotiana tabacum) leaves of 5 cm area were dipped in 1ml of
test solution and allowed to dry. The leaves were placed on moistened pieces of
filter paper in petri dishes. The dishes were infested with 25 aphid adults with
three replicates [Fig. 3.9b]. The controls used acetone instead of insecticide
solution.
(Fig. 3.9b) Insecticidal activity against Green peach Aphids, Myzus persicae at
concentration 100(µg/ml) of 1b
Chapter 3: Insecticidal activity of quinoline derivatives
110
Percentage mortalities were evaluated 24 hrs after treatment [Fig.
3.9c]. The aphids which are dead and which are not moves after touch by
painting brush are considered as dead.
(Fig. 3.9c) Dead Green peach Aphids, Myzus persicae after application of 1b
The data were corrected and subjected to probit analysis and LD50
values were determined. The mortality data are summarized in (Table 3.6).
(Table 3.6) Insecticidal activity of quinoline derivatives (1a-d) against Aphid
Sr. No.
Conc. (µg/ml)
Percentage mortality 1a 1b 1c 1d
1 25 27 43 36 33
2 50 47 50 50 47
3 100 63 67 63 50
4 200 70 77 73 63
5 400 83 90 87 77
3. II.4 Results and Discussion
All the tested compounds have been prepared according to our reported
procedure. The percentage mortality of mosquito (Anopheles stephensi) and
green peach aphid, (Myzus persicae) of the target compounds are summarized
in the (Table 3.5) and (Table 3.6). Compound 1b found to be high larvicidal
Chapter 3: Insecticidal activity of quinoline derivatives
111
activity against mosquito with an LC50 value of 85.74µg/ml as shown in the
(Table 3.7).
(Table 3.7) The 24 hrs LC50 values (ppm) and their 95 % fiducidal (upper and
lower) limits, regression equation and Chi-square (χ2) values of quinoline
derivatives for the late 3rd instar larvae of Anopheles stephensi.
Sr.
No. Comp.
Conc. (µg/ml) Regression equation χ
2* LC 50 LFL UFL
1 1a 137.03 102.95 192.62 Y = 2.9813 + 0.9433 X 1.02 2 1b 85.74 71.74 101.73 Y = 1.8607 + 1.6267 X 1.00
3 1c 107.20 91.18 126.52 Y = 0.6800 + 2.0900 X 2.74
4 1d 164.14 126.99 226.46 Y = 2.7000 + 1.0400 X 4.27
*at (0.05) significance level
The compound 1b revealed high insecticidal activity against aphids with
LD50 value of 83.58µg/ml as shown in the (Table 3.8).
(Table 3.8) The 24 hrs LD50 values (ppm) and their 95 % fiducidal (upper and
lower) limits, regression equation and Chi-square (χ2) values of quinoline
derivatives for the adult of Myzus persicae.
Sr.
No. Compds.
Conc. (µg/ml) Regression equation χ
2* LC 50 LFL UFL
1 1a 130.75 101.12 162.63 Y = 1.7807 + 1.4667 X 1.81
2 1b 83.58 58.96 108.07 Y = 2.6500 + 1.2200 X 1.74
3 1c 102.93 75.51 130.97 Y = 2.3957 + 1.0967 X 0.64
4 1d 151.90 108.78 202.28 Y = 2.9863 + 0.9233 X 1.77
*at p= (0.05) significance level
Our results are coinciding with the previous results [67] that the
introduction of a hydrophilic factor, such as the use of heterocyclic rings
including oxygen and/or nitrogen might benefit the bioactivity of compounds.
The increase of electronegative atoms in the molecule that is application of an
electronegative atom (i.e., chlorine, fluorine) encouraged better bioactivity as
shown in the (Fig. 3.10).
Chapter 3: Insecticidal activity of quinoline derivatives
112
(Fig. 3.10) Insecticidal efficacy (LC50) against Mosquitoes and (LD50)
against Aphids.
3. II.5 Conclusions
In conclusion, the different 2, 3, 4-trisubstituted quinoline derivatives
have been tested for their insecticidal activities against mosquitoes and aphids.
Among the tested compounds, diethyl-4-phenyl-6-chloroquinoline-2,3-
dicarboxylate 1b is found to be potential insecticide for protection of animals
and plants with lowest LC50 and LD50 from mosquito and aphid respectively.
Chapter 3: Insecticidal activity of quinoline derivatives
113
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