1. Introduction
Several organic compounds have not been approved as applied pesticides showed some useful actions against different pests. They may be considered as cores of new pesticides. Some compounds were prepared and assessed for their pesticidal activities. They showed persuasive effects as fungicides, herbicides (phytocidal effects), nematicides, molluscicides, insecticides as well as rodenticides comparing with commercial pesticides.
2. Materials and methods
2.1. Tested chemicals
Both indol-3-acetic acid GRG, El-Gomhouria Drug Company; indole-3-butyric acid, Sisco Research Laboratories, Mumbai, India, and other chemicals and solvents were purchased from El-Gomhouria Drug Company, Egypt. Standards of used herbicide, metribuzin (sencor), (4-amino-6-tert.butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one) and used fungicide metalaxyl, N-(2,6-dimethylphenyl-N-methoxyacetyl)-DL-alaninemethylester were donated by Kafr El-Zayat Company for pesticides, Egypt. Based on [1-2] with modification, some benzotriazole, benzylidine, coumarin, imidazolidine, indole, oxazolone and pyrazole, derivatives were prepared and identified [3-7].
2.2. Instruments
Structural confirmation was carried out by determination of melting points on kofler block; elemental micro analysis (C, H, N, X); IR, UV, NMR and Mass spectroscopy measurements in Microanalytical Center, Cairo University, Giza, Egypt. NMR spectra were recorded on Varian Mercury-VX-300 NMR Spectrometer using tetramethylsilane (TMS) as a standard. Mass spectra were recorded on a Schimadzu MS5988-mass spectrometer at 70 ev. Determination of soluble sugars, chlorophyll contents and total soluble phenols (TSP) were done on Unico-1200 Spectrophotometer. Both enzymatic activity and nucleic acids contents were measured using Nicolet 100 UV-VIS Spectrophotometer, Thermo Electron Corporation.
2.3. Tested fungi
Wood decay fungi,
2.4. Tested animals
Albino norway rats strain (
Through these studies,
Seed treatment was carried out according to [18]. Toxic effects on the seedling stage (after germination) of both root and shoot systems using the plain agar was done according to [19]. In dried wheat seedlings, total soluble sugars (T.S.S), reducing sugars (R.S) and non-reducing sugars (non-R.S) expressed as g/g dried plant were determined [20]. Chlorophyll (a and b) contents were calculated in µg/g tissue fresh weight [21]. Total soluble phenolics were determined as mg gallic acid equivalent (mg GAE)/g fresh weight [22-23]. Mortality test was carried out on Albino norway rats strain (
3. Results and discussion
3.1. Fungicidal activity of some indole derivatives [7]
In the vast heterocyclic structural space, the indole nucleus occupies a position of major importance as antimicrobial agents. Combination of IAA (at 100 µg/ml) with
1-Acetylindole-3-butyric acid affected both RNA and DNA contents differently according to the tested fungus and concentration. It reduced them in
2.19 | 4.75 | 0.6 0.005 | 420 (222 – 823) | Indole-3-acetic acid | |
2.72 | 7.04 | 0.87 0.011 | 523 (322 – 859) | 1-Benzoyl indole-3-acetic acid | |
3.00 | 2.78 | 1.28 0.025 | 576 (388 – 858) | Indole-3-butyric acid | |
0.14 | 4.54 | 1.41 0.01 | 26.6 (21.3 –33.3) | 1-Acetyl indole-3-butyric acid | |
2.67 | 1.29 | 1.03 0.015 | 513 (335 – 793) | 1-Benzoyl indole-3-butyric acid | |
0.35 | 8.57 | 1.11 0.008 | 67.4 (53.0- 85.8) | 2-Phenylindole | |
0.45 | 5.33 | 0.98 0.007 | 86.7 (66.4 – 113) | 1-Acetyl-2-phenylindole | |
0.52 | 0.63 | 1.02 0.008 | 99.9 (77 – 129.9) | 1-Benzoyl-2-phenylindole | |
1.0 | 3.6 | 0.69 0.006 | 192 (126 – 296) | Metalaxyl | |
4.66 | 2.83 | 0.81 0.011 | 807 (440 – 1514) | Indole-3-acetic acid | |
3.30 | 2.99 | 0.97 0.014 | 572 (359 – 923) | 1-Benzoyl indole-3-acetic acid | |
4.03 | 1.28 | 1.38 0.003 | 699 (458 – 1073) | Indole-3-butyric acid | |
0.34 | 3.87 | 1.21 0.009 | 59.0 (47.0 – 74) | 1-Acetyl indole-3-butyric acid | |
2.59 | 2.62 | 1.38 0.026 | 448 (325 – 622) | 1-Benzoyl indole-3-butyric acid | |
0.55 | 8.1 | 1.06 0.008 | 96 (74.6- 123.4) | 2-Phenylindole | |
0.54 | 7.78 | 1.03 0.008 | 93 (71.7 – 120.0) | 1-Acetyl-2-phenylindole | |
2.05 | 2.18 | 1.02 0.001 | 355 (247 – 514) | 1-Benzoyl-2-phenylindole | |
1.00 | 4.78 | 0.93 0.008 | 173 (127 –237.6) | Metalaxyl | |
1.43 | 3.76 | 0.93 0.001 | 301 (207.9- 438) | Indole-3-acetic acid | |
0.81 | 3.96 | 0.91 0.008 | 171 (125 – 236) | 1-Benzoyl indole-3-acetic acid | |
1.18 | 9.33 | 0.98 0.001 | 249 (179 – 349) | Indole-3-butyric acid | |
0.09 | 1.72 | 1.1 0.006 | 19 (14.4 – 24.8) | 1-Acetyl indole-3-butyric acid | |
2.31 | 0.46 | 1.0 0.14 | 488.4 (319 –753) | 1-Benzoyl indole-3-butyric acid | |
0.08 | 0.48 | 0.67 0..004 | 17.7 (11.8 –26.4) | 2-Phenylindole | |
0.07 | 2.15 | 0.61 0.004 | 15.0 (9.5 – 23.2) | 1-Acetyl-2-phenylindole | |
0.38 | 3.99 | 0.73 0.005 | 81 (57.2 – 115) | 1-Benzoyl-2-phenylindole | |
1.00 | 1.03 | 0.80 0.007 | 211 (145 – 310) | Metalaxyl | |
4.36 | 4.42 | 0.94 0.016 | 1009 (539–1923) | Indole-3-acetic acid | |
5.38 | 9.08 | 0.71 0.008 | 1244 (633–2515) | 1-Benzoyl indole-3-acetic acid | |
2.78 | 2.38 | 0.79 0.01 | 644 (368 – 1151) | Indole-3-butyric acid | |
0.51 | 6.1 | 1.57 0.018 | 117 (97.6 – 141) | 1-Acetyl indole-3-butyric acid | |
2.87 | 2.64 | 0.79 0.01 | 663 (377 – 1192) | 1-Benzoyl indole-3-butyric acid | |
0.15 | 7.14 | 0.81 0.005 | 34.6 (25.1 –47.5) | 2-Phenylindole | |
0.16 | 1.79 | 0.85 0.005 | 37.5 (27.6 –50.7) | 1-Acetyl-2-phenylindole | |
0.53 | 3.31 | 1.0 0.008 | 122.2 (93 –161) | 1-Benzoyl-2-phenylindole | |
1.00 | 3.21 | 0.98 0.01 | 231 (167.7 –321) | Metalaxyl |
It could be concluded that 2-phenylindole and 1-acetylindole-3-butyric acid affected both RNA and DNA contents in the tested fungi, which may develop deformed and dead cells. These effects of indole acetic acid and some derivatives are due to formation of 3-methylene-2-oxindole, which may conjugate with DNA bases and protein thiols [34]. There were highly effective against polyphenoloxidase and peroxidase activities that means disturbance in the cell physiology as [28] revealed that IAA alone or with
3.2. Insecticidal activity of the prepared indole derivatives [36]
The Egyptian cotton leaf-worm,
Lethal effects
The tested compounds were more effective against the 4th larval instar than the 6th instar after 5 days except 1-acetylindole-3-butyric acid (3) and 1-acetyl-2-phenylindole (7). The effect was increased after nine days in all cases. 1-Benzoyl-2-phenylindole (8) was less effective on the 6th instar. 2-Phenyl indole (6) and its 1-acetyl derivative (7) were more effective on the 6th instar. Lethal effects were increased in all tested compounds against 6th instar except for compounds 2 and 5. It was also found that substitution of compound 3 raised the toxicity on the 6th instar. The increase due to its acetylation was greater than benzoylation. Substitution of 2-phenyl moiety on the indole ring in stead of side aliphatic carboxylic group increased the larval mortality in case of compound 6 more than in indole-3-acetic acid (1). Substitution with 1-acetyl on 2-phenylindole multiplied the lethality against the two tested larval instars, while substitution with 1-benzoyl in compound 8 enhanced the toxicity only against the 4th larval instar. The most effective compound was indole-3-butyric acid (2) with 70.9 and 39.7 g/gm LC50 values on the 4th instar after 9 and 13 days, while 1-acetylindole-3-butyric acid (3) and 1-acetyl-2-phenylindole (7) were more effective with 151.4 and 80.6 g/gm LC50 values against the 6th instar. So, compounds 2, 3 and 7 were chosen for egg treatment.
Sub-lethal effects (Fresh body weight)
The larval weight of the 4th instar (after 7 days) was differently affected with the applied derivatives. Benzoylation of indole-3-acetic acid in compound 4 affected the larval weight in non systematic arrangement with concentrations. Acetylation of indole-3-butyric acid in compound 3 reduced the larval weight at 50 and 100 µg/gm, followed by an increase at higher concentrations. On the contrary, its benzoyl derivative (compound 5) increased the larval weight at lower concentration, followed by reduction at the two higher concentrations. Light reduction occurred at low concentrations, followed by gradual activation with increasing the concentration, which was exhibited by compound 6. Substitution with 1-acetyl moiety in compound 7 increased the larval weight at low concentration followed by inhibition percents ranging from 3.2 to 18.5% of control at 100-1000 µg/gm. Benzoylation of 2-phenylindole in compound 8 decreased the reduction effect more than compound 7. Comparing with the untreated 6th larval weight (0.77 gm) after two days, all the tested compounds reduced the treated larval weight at all concentrations with different degrees and arrested their development to 7 days after treatment. Compounds 1 and 2 showed narrow differences among their concentrations with less reducing effect, followed by compounds 8,6, 5 and 7. Compounds 3 and 4 were the most active derivatives in weight reduction. From these results, the hormonal effect was obviously clear through the activation of larval weight in most cases when applied earlier at the 4th instar more than at the 6th instar (Figure 1).
Development
Untrated 4th instar larvae developed to pupal and adult stages after 6-7 and 9-10 days, respectively. Indole-3-acetic acid (1) at 10 µg/gm delayed this development to 29 and 45 days, respectively. However, the other compounds were less effective causing developing of 50, 10, 75, 92, 13, 63, and 83% of the treated larvae to pupae in case of compounds 2, 3, 4, 5, 6, 7 and 8, respectively after 21 days. While, compounds 5 and 7 caused complete transformation of the treated population to adults, compounds 2, 4, 6 and 8 caused developing of 75, 75, 55 and 67 % of pupae to adults. Compound 3 (1-acetylindole-3-butyric acid) was the most effective structure blocking adult emergence to 25% of the treated population after 45 days. Regarding 6th larval instar, its control completely developed to the pupal and adult stages after 2-3 and 7-8 days, respectively. All compounds arrested the larval development except compounds 3 and 5, which caused 25 and 18% pupation after 13 days. Compound 1 was the most effective inhibiting the adult emergence, followed by compound (4), 1-benzoylindole-3-butyric acid (5), indole-3-butyric acid (2), 2-phenylindole (6), 1-acetylindole-3-butyric acid (3), 1-benzoyl-2-phenylindole (8) and 1-acetyl-2-phenylindole (7). They blocked the adult emergence to 7, 14, 31, 33, 39, 46, 48 and 50% of the treated population after 35 days. From the results, the duration of
Malformations
Comparing with the untreated larvae, compounds 1 and 2 exhibited 14.6% and 16.7% malformation in the intermediates of the treated 4th larval instar at 200 µg/ml, with no effect on 6th larvae. Acetylation of indole-3-butyric acid in compound 3 affected the intermediates at lower concentrations in the 6th larval instar, while its benzoylation increased this effect against the 4th instar only. Acetylation of 2- phenylindole caused 32.6 and 61.1% intermediate malformation at 100 and 200 µg/ml in treated 4th instar larvae. 1-Benzoyl-2-phenylindole affected 4th larvae at 10 µg/ml with 7.6% malformation. However, its effect was as high as 10.1% at the higher concentrations against 6th instar intermediates. These malformation symptoms appeared as larval-pupal intermediates in which the posterior portion of the body only exhibited the pupal shape, while the anterior portion had larval head capsule and thoracic legs (Figure 3). Malformation of the produced pupa (forming abnormal pupa without wings or that failed to shed the larval cuticle) resulted from the 4th larval instar, which was more sensitive than that from 6th larval instar to treatment with compounds 1-3, 2-phenylindole (6) and 1-benzoyl-2-phenylindole (8). The effects of compounds 4 and 5 depended on the applied concentration. Benzoylation of 2-phenylindole increased the pupae malformation. Adult malformation (adult failed to shed the pupal cuticle or adult with dwarf wings) was affected with the tested compounds, concentration and larval instar. Adult emergence from both treated instars was affected. Compounds 1, 2, 3 and 5 blocked the adult emergence to 10.3 - 47.4%, 16.7 - 50%, 20.2 - 50.6% and 10.6 - 55.7% in systematic arrangement, respectively from 4th larval populations comparing with 100% of control. The blocking effect was reduced with increasing the concentration. They blocked adult emergence to 25.9-43.7%, 36.8-57.0%, 31.9-40.9% and 32.5-66.9%, respectively in non systematic arrangement in case of the 6th larval population. Compound 4 caused 9.5-20.8% and 22.9-69.5% adult emergence in case of the treated 4th and 6th larval instars, respectively. Although 2-phenylindole and its 1-acetyl derivative affected the adult emergence from both treated instars in non systematic arrangement, its 1-benzoyl derivative blocked the adult emergence with increasing the concentration. Adult emergence was more inhibited from 4th larval instar treatment indicating that treatment of the lower larval instars gave good results of control (Figure 4).
Effect on eggs
Egg hatchability was inhibited increasingly in systematic arrangement with concentrations. Both 1-acetylindole-3-butyric acid (3) and 1-acetyl-2-phenyl-indole (7) completely stopped hatching when mixed at 100 g/gm with the medium. As the untreated egg mass hatched completely within 24 hours, treated eggs took 48-96 hours and 6-7 days at high concentrations of compound 2 and compounds 3&7, respectively. After 48 hours, only dipping the egg masses in solutions of compound 2 inhibited hatching with IC50 value equaled 29.1 g/ml and killed the produced larvae with LC50 value equaled 26.2 g/ml. Transferring treated eggs to the poisoned medium enhanced the toxicity to IC50 equaled 13.2 g/gm and LC50 equaled 15.2 g/gm. Although acetylation of compound 3 decreased larval mortality in dipping technique with or without transferring the eggs to the poisoned medium, it enhanced egg-hatching inhibition when dipped only in the toxic solutions. Although compound 7 was less effective when egg masses were dipped in it, its mixing with the used medium greatly enhanced the effect with IC50 value equaled 15.3 g/gm on egg-hatching and LC50 value equaled 7.5 g/gm on larval mortality. In conclusion, mortality of 4th instar larvae was increased with increasing the aliphatic side chain. Substitution of N-H of 2-phenylindole raised the toxicity, vice versa in case of indole-3-butyric acid against the same instar. The tested compounds affected larval weight, pupation and adult emergence indicating that treatment induced an effect typical to juvenile hormone excess. These effects varied according to the tested compound. These delayed effects are expressed as developmental abnormalities in the adult stage. These effects may be due to oxidative decarboxylation forming 3-methylene-2-oxindole, which may conjugate with DNA bases and protein thiols [34]. It may be also due to inhibition of cholinesterase [40]. Its effect is associated with cell phenoloxidase (PO) and peroxidase activities [6, 41]. Phenoloxidase (PO) is believed to be a key mediator of immune function in insects.
This notice may clarify the effect of the tested compounds on adult emergence and pupation. N-H and N-substituted indole-2- and 3-carboxamide showed a strong inhibitory (95-100%) effect on superoxide anion (SOD). Substitution on 1-position of the indole ring caused significant differences between the activity results regarding lipid peroxidation inhibition [42] emphasizing the differences in effects due to the derivative structure.
3.3. Pesticidal activities of some pyrazole derivatives [5]
Due to antimicrobial activity of some 3,5-dimethylpyrazole derivatives [43], 3,5-dimethylpyrazole (1), 1-Benzoyl-3,5-dimethylpyrazole (2), 3-methyl-1-phenylpyrazol-5-one (3) and 3-methyl-1-(2,4-dinitrophenyl)-pyrazol-5-one (4) were prepared, structurally confirmed and studied for their effects against
Pyrazole derivatives inhibited the growth of root and shoot systems of wheat and squash seedlings differently. Benzoylation of 3,5-dimethylpyrazole (1) decreased its inhibition on wheat shoot system growth, vice versa against its root system. Introducing the 2,4-dinitro- moiety enhanced the toxicity of 3-methyl-1-phenyl pyrazol-5-one (3) on wheat shoot and root systems. Compounds 1, 2, 3 and 4 inhibited cucumber seedlings root system with 95, 109, 95 and 58 µg/ml and its shoot system with 38, 90, 60 and 78 µg/ml, comparing with 115 and 86 µg/ml of metribuzin, respectively. It gave 81 and 52 µg/ml on wheat shoot and root systems. The standard herbicide was less effective than the tested compounds on quash shoot system. Compound 1 was inactive against
3.4. Pesticidal effects of some imidazolidine and oxazolone derivatives [6]
Actually we were interested to evaluate pesticidal actions of some imidazolidine and oxazolone derivatives as some of them are insecticides, herbicides and fungicides [44]. So three other derivatives of imidazolidine: 5,5-dimethylimidazolidin-2,4-dione, 5,5-diphenylimidazol-idin-2,4-dione and 5,5-diphenylimidazolidin-2-thione-4-one and two oxazolone derivatives: 4-Benzylidine-2-methyloxazol-5-one and 4-Benzylidine-2-phenyl-oxazol-5-one were prepared and checked for their structure. Their fungicidal, phytocidal and insecticidal effects were carried out as in case of pyrazole derivatives.
Fungicidal activity
Imidazolidine derivatives appeared more effective than the oxazol-5-one derivatives on
From the obtained results, fungitoxic activities proved to be a function of both the tested compound and the used fungus. In general, through analysis of variance (ANOVA) of hyphal growth inhibition percents, compound 3, 5,5-diphenylimidazolidin-2-thione-4-one was the most active against the tested fungi with Mean SE of growth inhibition equaled 34.69e. The other tested compounds were arranged as Mean SE was 32.742.53d, 28.672.79c, 25.082.44b and 24.652.29b and 19.932.00a, respectively in case of standard fungicide, compound 5, compounds 1 and 2, compound 4.
Phytocidal activity
The tested compounds inhibited germination and shoot growth of treated
Insecticidal activity
The tested compounds exhibited low mortality on 24 hours treated
The tested compounds exhibited phytocidal and fungicidal activities higher than their insecticidal effects. Differences in these compounds could be referred to chemical structure as in imidazolidine derivatives, presence of the 2-thione in compound 3 increased its fungitoxic effect nearly against all of the tested fungi. Substitution of 5,5-dimethyl moiety in compound 1 increased the toxicity more than 5,5- diphenyl moiety in compound 2 against
3.5. Fungicidal effects of certain benzotriazole and coumarin derivatives [48]
To extend the spectrum of newly discovered antifungal compounds facing continuous fungal infections, six benzotriazole derivatives as well as two coumarin derivatives were synthesized, confirmed for their structure and evaluated on
In vitro fungitoxicity effects
Effect of the tested 1,2,3-triazole and coumarin derivatives on three soil fungi and two foliar fungi based on their structure differences. 5,6- Dichlorobenzotriazole proved to be highly toxic against
Effect on polyphenoloxidase and peroxidase activities
5,6-Dichlorobenzotriazole at 0.1, 0.25, 0.5, 1 and 2 IC50 rates in µg/ml affected both polyphenoloxidase (PPO) and peroxidase (PO) enzymes for each tested fungi. Their activities were in non-systematic response depending on the type of fungus and concentration. The activity of polyphenoloxidase was highly increased in
Effect on DNA and RNA contents
5,6-Dichlorobenzotriazole at several rates of its IC50 values affected DNA and RNA contents in each tested fungus. In
3.6. Rodenticidal activity of certain benzotriazole and coumarin derivatives [53]
The previously explained benzotriazole and coumarin derivatives were studied also for their rodenticidal effects against the white Noway rat. In fact the two coumarin derivatives might be expected in their effects, while the benzotriazole derivatives were tested to stand on their toxicity related to studied coumarin comparing with Coumachlor, 3-(-acetonyl-4-chlorobenzyl)-4-hydroxy-coumarin as standard anticoagulant rodenticide.
During the baiting of the tested rats (
Benzotriazole derivatives weakly affected the haemoglobin and haematocrit of both males and females within the tested doses (10-300 mg/kg) with ED50 of >300 mg/kg. While, dicoumarol and furopyrone were highly and moderately toxic against haemoglobin of male and female rats with ED50 values of 24 & 27 mg/kg and 90 & 130 mg/kg body weight, respectively. Furopyrone and dicoumarol were moderately active on haematocrit of males with ED50 values of 53 and 65 mg/kg but on females with 135 and 195 mg/kg respectively. Red blood cells(RBC’s) of females were found to be more sensitive to coumachlor, dicoumarol, furopyrone, 5,6-dimethylbenzotriazole, benzotria-zole followed by 1-benzoyl-5,6-dimethylbenzotriazole as highly toxic compounds reducing RBC’s of males with ED50 values of 7, 12, 19, 28, 40 and 44 mg/kg, respectively (Loomis, 1976). Coumachlor, dicoumarol, furopyrone and 5,6-dimethylbenzotriazole were also highly toxic against RBC’s of females with ED50 value of 10.5, 25, 32 and 40 mg/kg, respectively. However the other compounds moderately reduced the RBC’s counts of males and females. White blood cells (WBC’s) of males were highly sensitive to 5,6- dichlorobenzotriazole, coumachlor and dicoumarol with ED50 values of 12, 13, and 37 mg/kg, whereas dicoumarol and 5,6-dichlorobenzotriazole were highly toxic in reducing it in females with ED50 values of 32 and 42 mg/kg, respectively. The other compounds proved to be moderately toxic in both males and females except benzotriazole, 1-acetylbenzotriazole and furopyrone. 5,6-Dichlorobenzotriazole was nearly equal to coumachlor in reducing males WBC’s, whereas dicoumarol and 5,6-dichlorobenzotriazole were more effective than coumachlor against female WBC’s.
Benzotriazole derivatives as well as furopyrone weakly affected sALT enzyme in both males and females. 5,6-Dimethylbenzotriazole was more potent reducing sAST enzyme activity in both males and females with ED50 values of 8.8 and 13.5 mg/kg, respectively. Dicoumarol was also highly toxic compound against sAST in males and females with ED50 of 24 and 32 mg/kg, respectively whereas coumachlor was highly toxic against females and moderately against males with 24 and 54 mg/kg ED50 values, respectively. 5,6-Dimethylbenzotriazole was more potent reducing sAST activity in both males and females with ED50 values of 8.8 and 13.5 mg/kg, respectively. Dicoumarol was also categorized as highly toxic against sAST in males and females with ED50 of 24 and 32 mg/kg, respectively whereas coumachlor was highly toxic against females and moderately against males with 24 and 54 mg/kg ED50 values, respectively. 1-Acetylbenzotriazole was moderate reducing sAST activity in males with ED50 equalled 160 mg/kg. The other derivatives and furopyrone weakly affected it in both sexes.
3.7. Pesticidal activity of some benzylidine derivatives [4]
Actually ,- unsaturated ketones were prepared according to Claisen Schmidt reaction (CSR) mechanism for searching their potency controlling some pests based on their biological history [55-56]. These biological activities of chalcone derivatives (as benzylidine derivatives) directed the attention to prepare some chaclone derivatives; dibenzylidineacetone, dibenzylidineacetylacetone and benzylidineacetophenone (chalcone).
Phytocidal effectsBenzylidineacetophenone (chalcone), dibenzylidineacetone and dibenzyli-dineacetylacetone were active against the root system of wheat seedlings (
Comparing with methomyl (Lannate), Dibenzylidineacetone and lannate proved to be highly toxic against the cotton leaf worm (
Generally, the prepared compounds caused moderately phytotoxic effects on both wheat and squash seedlings but they were specific on root system of wheat seedlings. Dibenzylidineacetone caused nearly the same effects as methomyl against cotton leaf worm. So, it could be concluded that dibenzylidineacetone after different biological tests may be safe as an insecticide against cotton leaf worm as it was previously prepared as a sun protection cream [57].
3.8. Evaluation of certain benzylidine and pyrazole derivatives against wood decay fungi [58]
Wood decay fungi are destructive agents of wood industry. They degraded the used fungicides [59,60]. Due to their importance and the activities of benzylidine and pyrazole derivatives, their toxic effects were evaluated on the white rot fungus
IC50g/ml (95%C L) | Slope S.E | IC50 g/ml (95%C L) | Slope S.E | |||
1,5-Diphenylpenta-1,4-dien -3–one | 295.4 c (250-350) | 1.51 0.019 | 5.9 | 976.9 b (796-1198) | 1.17 0.02 | 6.8 |
1,7-Diphenyl hepta-1,6-dien-3,5–dione | 317.1 b (263-383) | 1.35 0.02 | 0.4 | 1995.4 a (1452-2747) | 0.93 0.02 | 6.4 |
1,3-Diphenylpropen-3-one (Chalcone) | 84.5 e (57.1-124.4) | 0.86 0.01 | 4.3 | 103.9 g (66.6-160.8) | 0.73 0.01 | 2.5 |
3,5-Dimethylpyrazole | 867.7 a (759-992) | 1.96 0.026 | 3.0 | 944.8 c (784-1138) | 1.3 0.021 | 2.6 |
3-Methyl-1-phenylpyrazol-5-one | 744.2 b (655-846) | 2.18 0.028 | 0.5 | 632.4 d (549.6-728) | 2.06 0.026 | 3.9 |
3-Methyl-1-(2,4-dinitro- phenyl)-pyrazol-5-one | 19.6 f (16.7-22.9) | 2.16 0.028 | 9.1 | 112.7 f (88.9-142.7) | 1.17 0.01 | 3.9 |
Boric acid | 252.5 d (226-282.3) | 2.38 0.033 | 2.5 | 189.1 e (166.3-215) | 2.0 0.026 | 7.9 |
In vivo antifungal activity
After six weeks exposure to fungal attack, the average mass loss in control was 41.27 and 41.53% for poplar (
Treatment | Conc (IC50 values) | ||||||
Retention Kg/m3 | Mass loss % SE | Retention Kg/m3 | Mass loss % SE | ||||
Un-Leached | Leached | Un-Leached | Leached | ||||
Control | 0.0 | 0.0 | 41.27 g 0.43 | 41.27 e 0.43 | 0.0 | 41.53g 0.42 | 41.53g 0.42 |
1,3-Diphenyl-propen-3-one Chalcone) (3) | 0.5 | 0.022 | 30.43 f 0.77 | 33.03 d 0.37 | 0.021 | 30.83f 0.92 | 34.87f 0.37 |
1.0 | 0.044 | 28.10 e 0.61 | 31.07 c 0.58 | 0.043 | 28.10e 0.35 | 32.30d 0.15 | |
5.0 | 0.194 | 26.23 d 0.55 | 29.33 b 0.26 | 0.210 | 26.4 d 0.49 | 31.10c 0.51 | |
10.0 | 0.447 | 23.87 c 0.61 | 28.10 a 0.42 | 0.463 | 24.80c 0.68 | 29.0 b 0.21 | |
3-Methyl-1-(2,4-dinitro-phenyl)-pyr-azol-5-one (6) | 0.5 | 0.004 | 29.23 f 0.82 | 31.13 c 0.52 | 0.019 | 30.0 f 0.32 | 33.30e 0.38 |
1.0 | 0.009 | 23.40 c 0.67 | 30.13 c 0.55 | 0.039 | 25.57d 0.43 | 31.17c 0.15 | |
5.0 | 0.042 | 18.07 b 0.45 | 29.40 b 0.35 | 0.199 | 20.87b 0.20 | 29.47b 0.55 | |
10.0 | 0.089 | 13.67 a 0.54 | 28.63 b 0.37 | 0.394 | 14.47a 0.34 | 27.5 a 0.58 |
The effect of compound 6 was reduced by leaching samples more than compound 3 ensuring that the former is easily leached due to its hygroscopic nature. Descriptive analysis proved compound 6 more significantly effective with general mean of mass loss ± SE of 25.12% ± 2.58 in comparison to 29.98% ± 1.63 of compound 3 in case of un-leached poplar samples, while no significant differences between them in leached samples were observed. In Scots pine sapwood, significance appeared in both cases as compound 6 achieved general mean of mass loss ± SE of 26.49% ± 2.44 and 32.59% ± 1.31 comparing with 30.33 % ± 1.61 and 33.76 % ± 1.16 of compound 3 in un-leached and leached samples. Differences between the benzylidine derivatives in their fungicidal activity could be referred to the conjugation among carbonyl groups, phenyl rings and double bonds, so compound 2 was less effective due to lack of this conjugation because of CH2 moiety. Compound 3 was more effective than compound 1 may be due to the lipophilicity [61]. The effect of benzylidine derivatives (benzaldhyde derived compounds) was greatly inhibited against
3.9. Phytocidal effects of some azole derivatives [63]
Phytocidal effects of five-memberred heterocyclic derivatives were studied on monocotyledonous (
In seed treatment, wheat seedlings growth was more sensitive to the tested compounds than seed germination. Pyrazole derivatives were less effective than both indole and benzotriazole derivatives against seed germination, while their effects against vegetation depended on the structure. 5,6-Dichlorolbenzotriazole was more potent than the standard herbicide, metribuzin against both seed germination and growth of seedlings. 1-Acetylindole-3-butyric acid caused nearly the same effect of metribuzin on seed germination, whereas its effect on seedling growth was less than it. However, the other benzotriazole, indole and pyrazole derivatives were less effective than it against both seed germination and seedling growth. Screening effects of the tested compounds on root and shoot systems of squash (
Concentrations. in µg/ml
Single post-emergence treatment with both 5,6-dichlorobenzotriazole and 3-methyl-1-(2,4-dinitro-phenyl)pyrazol-5-one affected the total soluble sugars contents in a function of concentration and time after treatment (Figure 7). Both reduced and non-reduced sugars alternatively changed regarding the time after treatment. 100
4. Conclusion
Several prepared organic compounds are tested for their pesticidal actions. Indole derivatives inhibited hyphal growth of several plant pathogenic fungi based on treated fungus and structure affecting sugars, RNA and DNA contents as well as enzymes disturbing cell physiology. They caused lethality, larval weight reduction, inhibition of pupation and adult emergence with inhibiting egg hatchability of
References
- 1.
WL(Benson F. R. Hartizel L. W. Savell W. 1952 Dimethyl benzotriazole and its acyl derivatives. J. Am. Chem. Soc. 74: 4719. - 2.
Vogel A I 1976 A text book of practical organic chemistry 4th edition. BNNO 582443946 Thames Polytechnic London, S.E. 16 6PF 886p. - 3.
Abdel-Aty A S 1996 Rodenticidal activity of certain organic molecules “Chemistry and rodenticidal activity of some benzotriazole and coumarin derivatives”. MSc, Pesticide Chem. Department, Faculty of Agriculture, Alexandria University, Egypt. - 4.
S(Abdel-Aty A. 2004 Pesticidal effects of some benzylidine derivatives. Alex. J. of Agricultural Res.49 1 99 105 - 5.
Abdel-Aty A S 2007 Pesticidal activities of some pyrazole derivatives. J. Adv. Agric. Res.12 4 783 793 - 6.
Abdel-Aty A S 2009 Pesticidal activity of some imidazole and oxazole derivatives. World J. of Agricultural Sci.5 1 105 113 - 7.
Abdel-Aty A S 2010 Fungicidal activity of certain indole derivatives against some plant pathogenic fungi. J. Pestic. Sci. 35 (4), 431-440. - 8.
Torgeson D C 1967 Fungicides.1 Agricltural and industerial applications environmental interactions. Academic Press New York and London - 9.
El Ghaouth E. A. Arul J. Grenier Asselin. A. 1992 Antifungal activity of chitosan on two postharvest pathogens of strawberry fruits. Phytopathol.,82 398 402 - 10.
Topps J. H. Wain R. L. 1957 Investigation on fungicides. III. The fungitoxicity of 1- and 5- alkyl salicylanilide and p-chloroanilines.Ann. Appl. Biol.,45 3 506 511 - 11.
Finney D J 1971 Probit analysis. 3rd edition Cambridge University Press, London 38p. - 12.
Broesch S. 1954 Colorimetric assay of phenol oxidase. Bull. Soc. Chem. Biol.36 711 713 - 13.
Fehrmaun H. Dimond A. E. 1967 Peroxidase activity and phytophthora resistance in different organs of potato plant. Phytopathol.57 69 72 - 14.
Stoev E. A. Makarova V. G. 1989 Laboratory manual in biochemistry. Mir Publishers, Moscow;66 71 - 15.
Lowry OH, Rosebrough NJ, Farr AL, Randall RJ 1951 Protein measurements with folin phenol reagent. J. Biol. Chem.,193 265 275 - 16.
Hegazi E. M. El -Menshawy A. M. Hammad S. M. 1977 Mass rearing of the Egyptian cotton leafworm, Spodopteralittoralis (Boisd.) on semi-artificial diet. Proc.2nd Arab Pesticide Conf., Tanta Univ.61 70 - 17.
Kubo I. Nakanishi K. 1977 In ”Host plant resistance to pests.” Hedin. P. A. Ed., American Chemical Society: Washington, ACS Symp. Ser.62 165 - 18.
Grodzinsky A. M. Grodzinsky D. M. 1973 Short reference in plant physiology. Naukova Domka, Rev, R. U.S.:433 34 - 19.
Zemanek J(1963 The method of testing the effectiveness of herbicides on agar medium Rostle. Vyroba9 621 632 - 20.
Thomas W. Dutcher R. A. 1924 Picric acid method for Carbohydrate. J. Am. Chem. Soc.46 1662 1669 - 21.
Hipkins M. F. Baker N. R. 1986 Photosynthesis energy transduction. Spectroscopy, IRL Press, Oxford, Washington:51 101 - 22.
Mc Cue P. Zhheng Z. Pinkham J. L. Shetty K. 2000 A model for enhanced pea seedling vigour following low pH and salycilic acid treatments. Process Biochem.35 603 613 - 23.
Bioresource Technol.Horii A. Mc Cue P. Shetty K. (200 Seed vigour. studies in. corn soybean. tomato in. response to. fish protein. hydrolysates consequences on. phenolic-linked responses. 98 2170 2177 - 24.
Desheesh M. A. El-doksch H. A. El -Sebaii M. A. Kadous E. A. Abdel-Aty A. S. 1997 Isolation, identification and biological activities of several organic compounds from families Chenobodiaceae and Plumbaginaceae weeds. Alex. Sci. Exch.18 4 439 447 - 25.
Wintrobe MM 1965 Clinical hematology, 4th ed. Lea & Febiger philadelphia. - 26.
Dacie J V, Lewis S M 1991 Practical hematology, 7th ed. 624p. - 27.
Reitman S. Frankel S. 1957 Acoduimetric method for the determination of serum glutamic oxaloacetate and glutamic pyruvate trans aminase. Am. J. Clin Path. 28:56. - 28.
Yu T. Zheng X. D. 2007 Indole-3-acetic acid enhances the biocontrol of Penicillium expansum and Botrytis cinerea on pear fruit by Cryptococcus laurentii. FEMS Yeast Res.7 3 459 64 - 29.
Slininger P. J. Burkhead K. D. Schisler D. A. 2004 Antifungal and sprout regulatory bioactivities of phenylacetic acid, indole-3-acetic acid, and tyrosol isolated from the potato dry rot suppressive bacterium Enterobacter cloacae S11:T:07. J Ind Microbiol Biotechnol.31 11 517 24 - 30.
Wang H X, Ng T B 2002 Demonstration of antifungal and anti-human immunodeficiency virus reverse transcriptase activities of 6-methoxy-2-benzoxazolinone and antibacterial activity of the pineal indole 5-methoxyindole-3-acetic acid. Comp Biochem. Physiol. C Toxicol. Pharmacol.132 2 261 268 - 31.
Ryu C K, Lee J Y, Park R E, Ma M Y, Nho J H 2007 Synthesis and antifungal activity of 1H-indole-4,7-diones. Bioorg. Med. Chem. Lett.17 1 127 131 - 32.
Sharaf E F, Farrag A A 2004 Induced resistance in tomato plants by IAA against Fusarium oxysporumlycopersici. Pol. J. Microbiol.53 2 111 116 - 33.
Kumar V. Kumar A. Kharwar R. N. 2007 Antagonistic potential of fluorescent pseudomonads and control of charcoal rot of chickpea caused by Macrophominaphaseolina. J Environ Biol.28 1 15 20 - 34.
Folkes L. K. wardman P. 2001 Oxidative activation of indole-3-acetic acid to cytotoxic species a potential new role for plant auxins in cancer therapy. Biochem. Pharmacol.61 129 136 - 35.
Kappas A. 1983 Genotoxic activity of plant growth-regulating hormones in Aspergillusnidulans. Carcinogenesis4 11 1409 11 - 36.
Ali S E, Abdel-Aty A S 2010 Insecticidal activity of some indole derivatives. against Spodoptera littoralis (Boisd.). Alex. J. Agric. Res.55 1 1 11 - 37.
Ben Jannet. H. Harzallah-Skhiri F. Mighri Z. Simmonds M. S. Blaney W. M. 2000 Responses of Spodoptera littoralis larvae to Tunisian plant extracts and to neo-clerodane diterpenoids isolated from Ajuga pseudoiva leaves. Fitoterapia71 2 105 112 - 38.
Glazebrook J. 2005 Contrasting mechanisms of defense against biotrophic and necrotrophic pathogens. Annu. Rev. Phytopathol.43 205 227 - 39.
Gigolashvili T. Berger B. Mock H. P. Muller C. Weisshaar B. Flugge U. I. 2007 The transcription factor HIG1/MYB51 regulates indlic glucosinolate biosynthesis in Arabidopis thaliana. Plant J.50 886 901 - 40.
Bodur E. Cokugras A. N. 2005 The effects of indole-3 acetic acid on human and horse serum butyryl cholinesterase. Extended Abstracts/Chemico-Biological Interactions 157-158: 373-377. - 41.
De Melo M. P. Pithon-Curi T. C. Curi R. 2004 Indole-3-acetic acid increases glutamine utilization by high peroxidase activity-presenting leukocytes. Life Sci.75 14 1713 1725 - 42.
Olgen S. Kiliç Z. Ada A. O. Coban T. 2007 Synthesis and evaluation of novel N-H and N-substituted indole-2- and 3-carboxamide derivatives as antioxidants agents. J Enzyme Inhib Med Chem.22 4 457 462 - 43.
Kocyi B. Kayamacio L. Rollas S. 2002 Synthesis, characterization and evaluation of antituberculosis activity of some hydrazones. Farmaco57 7 595 599 - 44.
Fidanza M A, Dernoeden P H 1996 Brown patch in perennial ryegrass as influenced by irrigation, fungicide, and fertilizers. Crop Sci.,36 6 1631 1638 - 45.
Khan K. M. Mughal U. R. Khan M. T. Zia U. Perveen S. Choudhary M. I. 2006 Oxazolones: new tyrosinase inhibitors; synthesis and their structure-activity relationships. Bioorg. and Medicin. Chem.14 17 6027 6033 - 46.
Duarte V. Gasparutto D. Jaquinod M. Cadet J. 2000 In vitro DNA synthesis opposite oxazolone and repair of this DNA damage using modified oligonucleotides. Nucleic Acids Res.28 7 1555 63 - 47.
Bioorg. and Medicin. Chem. Lett.Tandon M. Coffen D. L. Gallant P. Keith D. Ashwell M. A. (200 Potent selective inhibitors. of bacterial. methionyl t. R. N. A. synthetase derived. from an. oxazolone-dipeptide scaffold. 14 8 1909 11 - 48.
Ahmed S M, Abdel-Aty A S, Desheesh M A 2004 Fungicidal effects of certain benzotriazole and coumarin derivatives. Alex. Sci. Exch.25 2 321 330 - 49.
Holla B. S. Poojary K. N. Balakrishna K. Gowda P. V. Kalluraya B. 1996 Synthesis, charaterization and antifungal activity of some N-bridged heterocycles derived from3-(3-bromo-4-methoxyphenyl)-4-amino-5-mercapto1,2,4 triazole. Farmaco Edizione scientifica51 12 793 99 - 50.
Yoo B. R. Suk M. Y. Han J. S. Mu Y. M. Hong S. G. Jung I. 1998 Synthesis and biological evaluation of [1-(1H-1,2,4-triazol-1-yl) alkyl]-1-silacyclopentanes. Pesticide Sci.52 2 138 144 - 51.
Sheng X. L. Jin X. L. Yang F. Zheng G. 1999 Study on the techniques of chemical control on wheat root disease. Acta Phytophylacica Sinica26 1 69 73 - 52.
Loomis T A 1976 Essentials of Toxicology. 2nd ed. Lea & Febiger, Philadelphia. - 53.
albus). Proc. 1st Conf. of the Central Agric. Pesticide Lab. Sep. 2002, I: 295- 305.Desheesh M. A. El -Shazly A. M. Kadous E. A. Abdel-Aty A. S. (200 Biochemical rodenticidal activities. of some. synthesized 1 2 3 -triaz-ole.coumarin derivatives. on albino. rat . Rattus norvgicus. var - 54.
Brooks J E, Rowe F P 1974 Commensal rodent control. WHO/ VBC/79. 726. - 55.
Friis-Moller A. Fuursted C. M. Christensen K. S. B. Kharazmi A. 2002 In vitro antimycobacterial and antigionella activity of licochalcone A from Chinese licorice roots. Planta Med.68 5 416 419 - 56.
Gonzalez J J, Estevez B A 1998 Effect of (E)-chalcone on cyst nematodes (Golobodera pallida and G. rostochinensis). J. Agric. and Food Chemistry46 3 1163 1165 - 57.
An encyclopedia of chemicals, drugs and biologicals. Merck & Co., INC. Rahway, NS., USA: 2977)Conrad D. (193 Organic Syn. 1. 2. In . Windholz M. Budavari S. Blumetti R. Otterbein E. (eds (1983. - 58.
Abdel-Aty A S, Mohareb A S O 2008 Preliminary evaluation of certain benzylidine and pyrazole derivatives against wood decay fungi.Journal of Pest Cont. and Environ. Sci.16 2 111 125 - 59.
Kramer C. Kreisel G. Fahr K. Kässbohrer J. Schlosser D. 2004 Degradation of 2-fluorophenol by the brown-rot fungus Gloeophyllum striatum: evidence for the involvement of extracellular Fenton chemistry.Appl Microbiol Biotechnol.64 3 387 395 - 60.
Mares D. Romagnoli C. Andreotti E. Forlani G. Guccione S. Vicentini C. B. 2006 Emerging antifungal azoles and effects on Magnaporthe grisea. Mycol. Res.110 6 686 96 - 61.
Cheng S. S. Liu J. Y. Hsui Y. R. Chang S. T. 2006 Chemical polymorphism and antifungal activity of essential oils from leaves of different provenances of indigenous cinnamon (Cinnamomum osmophloeum). Bioresour Technol.97 2 306 12 - 62.
Microbiology148 (Pt 6): 1939-46.Kamada F. Abe S. Hiratsuka N. Wariishi H. Tanaka H. (200 Mineralization of. aromatic compounds. by brown-rot. basidiomycetes-mechanisms involved. in initial. attack on. the aromatic. ring - 63.
Abdel-Aty A S 2011 Phytocidal effects of some azole derivatives. J. of Pest Cont. and Environ. Sci.,19 1 15 37 - 64.
Jiang L L,Wang G D,Chen Q, Yang G F (Luo Y. P. Jiang L. L. Wang G. D. Chen Q. Yang G. F. (200 Synthesis herbicidal activities. of novel. triazolinone derivatives. 2008 Synthesis and herbicidal activities of novel triazolinone derivatives. J Agric. Food. Chem.56 6 2118 24 - 65.
Grossmann K. 2003 Mediationof herbicide effects by hormone interactionsJ. Plant Growth Regulat.2 109 122 - 66.
Ruhland C T, Fogal M J, Buyarski C R, Krna M A 2007 Solar ultraviolet-B radiation increases phenolic content and ferric reducing antioxidant power in Avena sativa. Molecules12 6 1220 1232 - 67.
Oncel I. Keleş Y. Ustün A. S. 2000 Interactive effects of temperature and heavy metal stress on the growth and some biochemical compounds in wheat seedlings. Environ Pollut.107 3 315 320 - 68.
Sung N D, Park H J, Park S H, Pyon J Y 1991 Herbicidal activity and molecular design of benzotriazole derivatives. J. Korean Agric. Chem. Soc.34 3 287 294 - 69.
EP 0227284 A1, 1987-01-07.Beek J. R. (198 Plant Growth. Regulating Triazoles. [. P] E. - 70.
Szyszka R. Grankowski N. Felczak K. Shugar D. 1995 Halogenated benzimidazol-es and bezotriazoles as selective inhibitors of protein kinases CKI and CKII from Saccharomyces cerevisiae and other sources. Biochem. and biophys.l Res. Comm.208 1 418 424