Bicyclo[2.2.1]hepta-2,5-diene or norbornadiene (NBD) is a bicyclic hydrocarbon molecule used in many fields of chemistry since its first synthesis in 1950. NBD is the precursor of Aldrin, an agrochemical that was commonly used as an insecticide until the end of the XX century. Norbornadiene is capable of interconverting into its isomer, quadricyclane (QC), by the incidence of ultraviolet light. After that, the QC can release heat to return to the initial stage of NBD. To increase the energy efficiency and to enable the reaction to occur at the solar light, chemists have synthesized a wide variety of NBD derivatives. Papers in more than seventy years have studied and reported the physical and chemical properties of those compounds and their applications as rocket fuel, solar energy cell, homogeneous catalysis, and agrochemicals published between 1950 and 2021. Even computational chemistry has been used to investigate the NBD derivatives synthetic routes, elucidation, and application. In addition, this review describes other applications of norbornadiene.

Nematode is a major problem in agriculture, the effective way to control this pest is through chemical control, but the efficient molecules present in the market have great toxicity to mammals and birds. Thus, there is a constant demand for the development of new nematicide molecules. This study describes the synthesis of 21 novel esters derived from norbornadiene and evaluation of their potential activity against Meloidogyne javanica. The esters 5-25 presented 50% mortality of the nematodes. The acid 3 and the ester 4 caused 96 and 93% mortality of the nematodes, respectively. The lethal concentration to kill 50% of the nematodes (LD50) were determined as being 11.8 µg mL-1 for the acid 3 and 99.4 µg mL-1 for the ester 4. According to the results obtained it is believed that polarity seems to be a key factor for the higher activity of compound 3 compared to structurally similar ester derivatives.

ABSTRACT: The demand for effective insecticides in pest control with low toxicity to the non-target organisms, such as natural enemies and pollinators, is increasing steadily. A good alternative for synthetic insecticides is natural compounds, including essential oils (EO). This work assessed toxicity of essential oils extracted from Artemisia annua, A. absinthium, A. camphorata, A. dracunculus and A. vulgaris against the melonworm Diaphania hyalinata (Linnaeus, 1758) (Lepidoptera: Crambidae) larvae, a pest of Cucurbitaceae, and their selectivity for fire ant Solenopsis saevissima (Smith) (Hymenoptera: Formicidae) and jataí bee Tetragonisca angustula (Latreille) (Meliponinae). The plants were grown in a greenhouse with mineral fertilization and were used for EO extraction. The insects in the bioassay belonged to the second instar of D. hyalinata and adult forms of S. saevissima and T. angustula. Essential oil from A. annua induced a high mortality rate in D. hyalinata (96 %) over a 48 h period. The same essential oil was selective for predator S. saevissima (42 % mortality) and pollinator T. angustula (74 % mortality), while causing high mortality in D. hyalinata. The insecticidal activity of A. annua oil was attributed to the synergism of its constituents viz., camphor and 1,8-cineole. Therefore, this essential oil contains constituents that are promising for effective use as insecticide due to its high toxicity and rapid action against D. hyalinata as well as low toxicity for predator and pollinator.

The demand for new insecticides is increasing due to the appearance of insect populations that are resistant to currently used products. New insecticides should be efficient in controlling pests and present low toxicity to non-target organisms. Ascia monuste (Lepidoptera: Pieridae) is a destructive pest of cole vegetables, and the fire ant Solenopsis saevissima (Hymenoptera: Formicidae) is an important predator of these caterpillars in brassica crops. Tetragonisca angustula (Hymenoptera: Apidae) is very important in pollinating many plants and providing honey. Therefore, this study evaluated the toxicity of synthetic amides to A. monuste and its selectivity in favor of S. saevissima and T. angustula. The amides (2E,4E)-N-propylhexa-2,4-dienamide (3) and (2E, 4E)-N-butylhexa-2,4-dienamide (4) caused high (96 and 93%, respectively) and fast (48 h) mortality of A. monuste. The amides 3 and 4 were not harmful to the predator (mortality of 5.7% for amide 3 and 7.14% for amide 4) and were slightly harmful to the pollinator (mortality of 38.57% for amide 3 and 28.12% for amide 4). The amides 3 and 4 are promising, as insecticides, due to the high and rapid mortality of A. monuste with low and moderate toxicity to S. saevissima and T. angustula, respectively.

Ten 4,7-methanoisobenzofuran-1(3H)-ones were synthesized and their insecticidal activities against the insect pest Diaphania hyalinata were evaluated. The most active substances have been selected from the initial screening to find the dose to kill 50 (LD50) and 90% (LD90) of the melonworm. Time-mortality curves of the three selected formulations at the LD90 concentration have been made against D. hyalinata. From the time-mortality curves we found that the formulation (3aR,4R,5S,6S,7S,7aS)- and (3aS,4S,5R,6R,7R,7aR)-5,6-dichlorohexahydro-4,7-methanoisobenzofuran-1(3H)-one + (3aR,4R,5R,6R,7S,7aS)- and (3aS,4S,5S,6S,7R,7aR)-5,6-dichlorohexahydro-4,7-methanoisobenzofuran-1(3H)-one has killed 50% of the melonworm after 2 h, presenting the best knockdown effect. Bioassays against Solenopsis saevissima and Tetragonisca angustula were carried out for the lactones selected in the initial screening against D. hyalinata. The formulation (3aS,4R,5S,6S,7S,7aR)- and (3aR,4S,5R,6R,7R,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one + (3aS,4R,5R,6R,7S,7aR)- and (3aR,4S,5S,6S,7R,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one has killed 31.25 and 68.30% of the pest natural enemy and the pollinator bee, respectively. At the same concentration this formulation killed 90% of D. hyalinata. The selectivity in favor of the non-target organisms has rendered this formulation a position as a promising agrochemical.

O adsorvente quitosana-Fe(III)-reticulado (Ch-FeCL) foi desenvolvido usando Fe(III) imobilizado em esferas de quitosana. Após o processo de secagem, as esferas apresentam um diâmetro de cerca de 1 mm e são estáveis ao ar. O comportamento de adsorção do As(III) e As(V) na Ch-FeCL foi avaliado em pH 7 por estudos realizados em batelada e em coluna. As máximas capacidades de adsorção estimadas pelo modelo de adsorção de Langmuir foram 21,24 e 27,59 mg g-1 para As(III) e As(V), respectivamente. A cinética de adsorção é descrita pela equação cinética de pseudo-segunda ordem. Os resultados de adsorção em coluna indicaram que o arsênio não foi encontrado na solução efluente atécerca de 60 e 759 volumes de leito para As(III) e As(V), respectivamente. Os resultados foram satisfatórios quando se empregou o adsorvente na remoção de As(III) e As(V) de amostras de águas subterrâneas, torneira e rio.

The crosslinked chitosan-Fe(III) (Ch-FeCL) adsorbent was developed using Fe(III) immobilized on chitosan beads. After drying, the beads presented a diameter of approximately 1 mm and are stable in air. The adsorption behavior of As(III) and As(V) on the Ch-FeCL was evaluated at pH 7 by studies conducted in batch and in columns. Maximum adsorption capacities estimated by the Langmuir adsorption model were 21.24 and 27.59 mg g-1 for As(III) and As(V), respectively. Adsorption kinetics is described by the pseudo second order kinetic equation. The results of column adsorption indicated that arsenic was not found in the effluent solution from roughly 60 and 759 bed volumes for As(III) and As(V), respectively. Results were satisfactory when employing the adsorbent for removal of As(III) and As(V) from groundwater, tap water and river water samples.

Neste trabalho relatamos uma síntese versátil de quatorze γ-lactonas análogas, dentre as quais nove são inéditas, a partir do furfural prontamente disponível. A atividade fitotóxica dos compostos sintetizados foi avaliada in vitro pela influência no crescimento de coleóptilos de trigo. A maior parte das porcentagens de inibição foi pequena e não diferenciou do controle após a terceira diluição (100 µmol L-1). Em geral, as lactonas α,β-insaturadas apresentaram melhor atividade que as saturadas. Os compostos mais ativos a 1000 µmol L-1 apresentaram inibições de 51, 68 e 76%. Os resultados indicam que, independentemente da saturação, a presença do anel γ-lactonônico é importante para a bioatividade, mas a sua presença não implica necessariamente boa potência.

In this work we report a versatile synthesis of fourteen γ-lactones all structurally related, nine of which are novel compounds, accomplished from the readily available furfural. The phytotoxic activity of the synthesized compounds was evaluated in vitro by the influence on the growth of wheat coleoptiles. The percentages of inhibition were mostly small and not statistically different from control after the third dilution (100 µmol L-1). In general, α,β-unsaturated lactones presented better activities than the saturated ones. The most active compounds presented 51, 68 and 76% of inhibition in 1000 µmol L-1. The results indicate that regardless of saturation, the presence of the γ-lactone moiety is important for the bioactivity, but their presence has no implications with potency.

Mixtures of α-Santonin and various solvents were irradiated by either high or low pressure mercury lamps. The photochemical reactions afforded lumisantonin (11) (76% in acetonitrile), (3S,3aS,9bS)-3,6,6-trimethyl-3,3a,4,5-tetrahydronafto[1,2-b]furan-2,7(6H,9bH)dione (12) (100% in acetonitrile), 10α-acetoxy-3-oxo-1,7αH,6,11βH-guaia-4-en-6,12-olide (8) (26% in acetic acid), 10α-hydroxy-3-oxo-1,7αH,6,11βH-guaia-4-en-6,12-olide (10) (32%) and (E)-3-((3S,3aS,7aS)-3-methyl-2-oxo-6-(propan-2-ylidene)hexahydrobenzofuran-7-(7aH)-ylidene)propanoic acid (9) (44%) (in water/ acetic acid 1:1, v/v). Lactone 12 was also prepared by irradiation of lumisantonin in diethyl ether. Lactones 8 and 10 were converted, respectively, into the 10α-acetoxy-3β-hydroxy-1,7αH,6,11βH-guaia-4-en-6,12-olide (13) (87%) and 3β,10α-dihydroxy-1,7αH,6,11βH-guaia-4-en-6,12-olide (14) (75%) by sodium borohydride reduction. The effects of the compounds on the development of radicle of Sorghum bicolor and Cucumis sativus were evaluated.