BR102013032724A2 - formulation and use of insecticidal activity amides - Google Patents

Abstract

formulation and use of amides with insecticidal activity. The present patent application discloses furnaces based on 1- (pyrrolidin-1-yl) hexan-1-ont and n-pentylexanamide amides. These amides have pronounced insecticidal activity against the green caterpillar pest caterpillar and also have low insecticidal activity against solenopsis saevissima, the natural enemy of cuta absolute, and can therefore be used in the field as selective insecticides.

Description

FORMULATION AND USE OF INSETICIDED ACTIVITY

FIELD OF THE INVENTION [1] This invention describes the use of saturated carbon chain amides as a selective insecticide against the Tuta absolute vegetable pest, and formulations containing such compounds may be used by insecticide industries to combat this insect.

TECHNICAL PA STATE [2] Brazil ranks 8th in the world ranking of tomato production (Picanço, MC, Guedes, RN, Milk, GLD, Fontes, PCR and Silva, EA (1995). Incidence of absolute Scrobipalpuloides in tomato under different tutoring and chemical control systems (Hortic. Bras. 13, 180-183). Crop is often damaged by pests, and one way to minimize this damage is by using chemical control and natural predators. [3] The tomato pest larva Tutaabsol is the main problem faced by tomato growers around the world and can cause losses of up to 70% in production. The difficulty of controlling this pest is linked to its resistance to insecticides used in its control which leads to the need for up to 85 applications / crop. [4] Solenopsis saevissima is a group that includes ecologically important ants, widely distributed in Brazil. They are among the most variable and best adapted species of ant fauna, occupying in addition to natural environments, those modified by anthropic action. Among the functions performed by ants within the arthropod community, their activity as predators stands out. Thus, it is desirable that insecticides not be toxic to ant Solenopsis saevissima, a natural enemy of Tuta absolute. [5] The main tool employed in pest control is the use of insecticides which are efficient, inexpensive and easy to use. The development of new molecules that model natural insecticides and have the same degree of pest toxicity as commercial products, but without insect resistance to commercially used compounds, may be a way to solve the problem of agricultural pests. One model that can be used in these syntheses is the amides found in plants of the Piperaceae family, especially those found in black pepper (Piper nigrum L.) (NAVICKIENE, D. Η. M .; MIRANDA, JE; BORTOLI, SA; KATO , MJ; BOLZANI, VS Toxicity of extracts and isobutyl amides from Piper tuberculatum: Potent compounds with potential for control of the velvet bean Caterpillar; Pest. Manag Sci, v.63, pp. 399-403, 2007). [6] The most commonly used insecticides for Tuta Absolute control are classified by chemical group. They are: pyrethroids, organophosphates, dithiocarbamates, diacylhydrazine, urea derivatives, benoylurea, avermectin, aryl propyl benzyl ether and acylurea. (Anvisa, 2013. Available at <portal.anvisa.gov.br>). [7] The present invention has the advantage that they are amides which are known to improve stability and provide the possibility of establishing intermolecular hydrogen bonds with biological targets, in addition to having significant biological activity against insect pests at concentrations those presented by the Ministry of Agriculture, 2013 (available at <www.agricultura.gov.br>). The selectivity of these amides over a natural enemy demonstrates another important feature in the context of integrated pest management. [8] There is a difference between the repellent action and insecticidal activity of a substance. The repellents have the objective of inhibiting the action of insects interfering in their behavior before the preservation situation. Insecticides act to eliminate insects at different stages of their life cycle. [9] Patent application PI 0705674-5 describes the use of ten new esters (pyrethroids) which have shown insecticidal activity on some common pest caterpillars in Brazil, (Tuta absolut, Diaphania hyalinata and Ascia monuste orseis). The insecticidal activity against the natural enemy predatory wasp (Protonectarina sylveirae) and honey-producing pollinating wasp (Tetragonica angustula) was evaluated and the new esters showed low toxicity against these two wasps. [10] Patent application WO1987001935 discloses the use of azepine, pyrrolidine and piperidine derived amides. The use of 1- (pyrro) idin-1-yl) exan-1-one has been found to provide a useful composition for topically administering physiologically active agents through the skin and mucous membranes of humans and animals. [11] ATKINS et al. (1975) described the use of 143 compounds to determine the repellent potential of bee (Apis mellifera) under laboratory conditions (ATKINS, EL; MACDONALD, RL; GREYWOOD-HALE, EA. Repellent Additives to Reduce Pesticide Hazards to Honeybees: Laboratory Testing Journal of Apicultural Research Vol 14 (2): 85-87 (1975) and in the field (ATKINS, EL; MACDONALD, RL; GREYWOOD-HALE, EA Repellent Additives to Reduce Pesticide Hazards to Honeybees: Field Test Environmentai Entomology, Volume 4, Number 2, April 1975, pp. 207-210) In laboratory and field use of 1- (pyrrolidin-1-yl) hexan-1-one has reached a moderate repellency level. highly repellent for bees (Apis mellifera). [12] Studies by Mc Govern et al. (McGovern TP; Gillenwater HB; McDonald LL Repellents for adults [the confused beetle] Tribolium confusum: amides of three heterocyclic amines. Journal of the Georgia Entomological Society USA, April 1979.V. 14 (2) p. 166-174) report the use of amides synthesized from three heterocyclic amines as repellents for adult Tribolium confusum. The use of 1- (pyrrolidin-1-yl) hexan-1-one showed low activity as repellent for the adult Tribolium confusum, however, Alexander and Beroza (Alexander, B.; Hand M. Beroza, 1963. Aliphatic amides of cyclic amines and tolyl maleimides mosquito repellents J. Econ. Entomol 56 (1): 58-60) reported that 1- (pyrrolidin-1-yl) hexan-1-one is a promising repellent for the Aedes aegypti mosquito. [13] Studies by Gavryushina et al. (Gavryushina, VM; Naumov, Yu. A; Adelfinskaya, LK Synthesis and repellent properties of N-alkylamides and N-alkydiacylimides of carboxylic acids. Khimicheskie Sredstva Zashchity Rastenni, Volume 5, pages 82-86, Journal, 1975) describe the synthesis and repellent properties of 54 compounds (N-alkylamides and N-alkylhydiacylamides of carboxylic acids). Among these compounds N-pentylexanamide achieved a significant level of flea repellency (Xenopsylla cheopis).

DESCRIPTION PE FIGURES [14] Figure 1: Dose-mortality graph of 1- (pyrrolidin-1-yl) hexan-1-one and N-pentylexanamide for Tuta absolute third instar caterpillars.

DESCRIPTION OF THE INVENTION [15] The present invention reports a formulation and insecticidal activity of saturated amides in the fight against Tuta absolute agricultural pest, in addition to the selectivity of these compounds in favor of non-target organisms known as natural enemy (Solenopsis saevissima). [16] 1- (Pyrrolidin-1-yl) exan-1-one (I) and A / - (pentyl) exanamide (II) amides have the following structures: Synthesis and characterization of amides [17] To a tritubulated balloon hexanoic anhydride (commercially available) starting material (0.4 g, 1.87 mmol) dissolved in anhydrous CH2 Cl2 (10.0 mL) was added, then for each reaction, the corresponding amines 1- ( pyrrolidin-1-yl) exan-1-one and N- (pentyl) exanamide (1.87 mmol). The solution was kept under stirring and inert atmosphere for four hours at 0 ° C. After this time the reaction mixture was added to NaHCO3 solution to neutralize the acid formed in the reaction. The organic and aqueous phases were separated with the aid of a separatory funnel. The organic phase was added anhydrous magnesium sulfate (MgSO4) to remove residual water. Magnesium sulfate was removed by simple filtration and the filtrate concentrated on a rotary evaporator to remove excess amine and dichloromethane. The residue obtained was purified by silica gel column and characterized by infrared spectroscopy, nuclear magnetic resonance (1 H and 13 C NMR) and mass spectrometry.

Formulation [18] For the preparation of the final product, the amides described in this patent application should be formulated using surfactants, dispersants, antioxidants, preservatives, stabilizers, polymers, among other substances acceptable in the manufacture of insecticides. In the process of preparing the final product only one of the ingredients alone or a combination thereof may be employed.

Biological Assay [19] For the bioassay, the toxicity of the compounds of the present invention on the tomato caterpillar Tuta absolu (Meyrick) (Lepidoptera: Meyrick) as a pest and the foot ant Solenopsis saevissima (Smíth) (Hymenoptera: Formicidae) was determined. as a natural enemy.

Experiment [20] The insects were weighed and treated with solutions containing the insecticide amides diluted in acetone. The initial dose used was 30 pg of each substance per mg body mass of the insect. To the thorax of each insect was applied 0.5 µl of the solution using a 10 µl microsyrene. For the control, the insects were treated with 0.5 pL of acetone. After application of the treatments the insects were kept in petri dishes (9 cm diameter x 2 cm high) containing food. The foods used were: tomato leaflets for Tuta absolute, and candi (85% sugar and 15% honey) and water for the natural enemy Solenopsis saevissima. Candi and water were offered in plastic containers (1.5 cm in diameter x 1.0 cm in height). [21] Mortality of Tuta absolute and Solenopsis saevissima was assessed at 1, 6, 12, 24, 48, 72 hours after treatment application. In the evaluations the insects were considered dead when they lost the motor coordination. [22] Mortality values were corrected by the ABBOTT formula (1925) in relation to the control, and then subjected to a propitite analysis (Finney 1971) to obtain dose-mortality curves. These curves estimated lethal doses (DLs) that caused 50, 80 and 95% mortality. [23] Insect mortality data 48 hours after treatment application were subjected to analysis of variance and treatment averages were compared by the Scott-Knott test at p <0.05. [24] The results of the evaluation of the biological activity of amides I and II are shown in Tables 1,2 and 3. [25] Table 1. Mean mortality at 30 mg compound concentration per mg Tuta absolute after 48 hours of application.

Average mortality percentage (%) ± Treatment standard deviation ________________ (compounds) Absolute tuta______________ ______________________________________________48h______________________ Amide I 100 ± 0.00 A

Amide II________________________100 ± 0.00 A__________________ [26] Table 2. Doses required to cause 50% (DL5o). 80% (DL8o) and 95% (DL95) mortality of Tuta absolute (Lepidoptera: Gelechiidae) after 48 h of exposure.

Amide dL50 (95% DÜT (95% DL95 (95% p5 j? P ~ _____________ IC) b lC) b ___________ IC ^ ___________________________ I 3.65 6.84 12.43 3.08 0.511 0.78 II _______ 6.05 9.06 _________ 13.31 4.79 1,549 0.54 b DL: Dose lethal in pg amide / mg of insect; CI: 95% confidence interval c Curve slope [27] Table 3. Mortality of natural enemy Solenopsis saevissima 48 hours after DL 80 application of both amides to Tuta absolut . ______Amide__________________ Mortality (%) ____________ I 8.00 ± 5.83 _________Jl______________________ 4.00 í 2.45 ____________ CONCLUSION [28] The commercial potential of an insecticide depends on some factors such as: cost of synthesis, compound activity, stability. and selectivity in favor of a natural enemy.Therefore, according to the results obtained, these amides have good industrial applicability because they are effective in controlling Tuta absolute, selectivity in preserving the predatory species Solenopsis saevi and low cost synthesis.

Claims (2)

1) Formulation comprising 1- (pyrrolidin-1-yl) exan-1-one and / or A / - (pentyl) exanamide amides associated with one or more acceptable ingredients for the preparation of insecticides, more specifically surfactants, dispersants , antioxidants, preservatives, stabilizers and polymers. 2) Use of 1- (pyrrolidin-1-yl) exan-1-one or A / - (pentyl) exanamide amides, which are for the control of Tuta absolut.