Synthesis of the minor sex pheromone component of two brazilian soybean stink bugs (Het.: Pentatomidae), and an analogue compound

Article

Synthesis of the Minor Sex Pheromone Component of Two Brazilian Soybean Stink Bugs (Het.: Pentatomidae), and an Analogue Compound

Paulo H. G. Zarbin^a*, Aurélia Reckziegel^b, Ernst Plass^b, Alfredo R. M. de Oliveira^a, Fábio Simonelli^a and Francisco de A. Marques^a

^a Universidade Federal do Paraná, Departamento de Química, CP 19081 - 81531-990 - Curitiba-PR, Brazil

^b Institute of Organic Chemistry ¾ University of Hamburg, Martin-Luther-King-Platz-6, D-20146, Hamburg-Germany

Os percevejos Euschistus heros e Piezodorus guildinii (Heteroptera: Pentatomidae) são importantes pragas da cultura da soja no Brasil. Uma característica marcante nestas espécies é o fato de que ambas se utilizam das mesmas estruturas químicas como feromônios sexuais, ou seja, os ésteres metílicos 2,6,10-trimetildodecanoato de metila (1) (minoritário) e o 2,6,10-trimetiltridecanoato de metila (2). No intuito de se verificar a exata função biológica destas estruturas e melhor entender o sistema de comunicação de cada espécie, realizou-se a síntese do componente minoritário 1 juntamente com um composto análogo, o 2,6,10-trimetiltetradecanoato de metila (3). Tais compostos serão submetidos a testes em laboratório, juntamente com o componente majoritário 2, já previamente sintetizado.

The stink bugs Euschistus heros and Piezodorus guildinii (Heteroptera: Pentatomidae) are economically important soybean pests in Brazil. An intriguing characteristic of these species is the fact that they use the same chemical compounds as sex pheromone, e.g., methyl 2,6,10-trimethyldodecanoate (1) (minor) and methyl 2,6,10-trimethyltridecanoate (2). In order to investigate the specific biological function of these molecules and to increase the knowledge of the communication system of each species, we have synthesized the minor component 1 and an analogue compound, methyl 2,6,10-trimethyltetradecanoate (3). These compounds will be tested on indoor bioassay, in addition with the previously synthesized major component 2.

Keywords: Piezodorus guildinii, Euschistus heros, methyl 2,6,10-trimethyldodecanoate, sex pheromone, synthesis

Introduction

Soybean is damaged by complexes of stink bugs around the world. In Brazil, the species of major importance in practically all soybean growing regions are Nezara viridula (L.), Piezodorus guildinii (Westwood) and Euschistus heros (F.), which attacks has led to the use of more than 4 millions litres of chemical insecticides annually^1,2. Forming part of a system of integrated pest management, the use of pheromones can be an useful alternative tool for the control of these pests.

Although there are some 35,000 species of Heteroptera worldwide, yet sexual pheromones are fully known only for a few species³. The diverse nature of the group itself has hindered progress³. In 1994, Aldrich and his co-workers identified methyl 2,6,10-trimethyldodecanoate (1) and methyl 2,6,10-trimethyltridecanoate (2) as components of the male-produced sex pheromones of E. heros⁴. They also identified 2 as the second major component of the male-specific volatile constituents of the Central America stink bug Euschistus obscurus (Figure 1).

We have recently reported that compounds 1 (minor) and 2 are also male-produced sex pheromones of the stink bug P. guildinii⁵. Although the different species liberate a similar pheromone blend, unique ratios of these compounds might be involved in species isolation, since it was previously observed on indoor bioassay that the activity of pure synthetic isomers of 2, in females E. heros, does not significantly differ from that of the synthetic racemic mixture⁶.

In order to investigate the specific biological function of these compounds and to understand the communication system mechanism of each species, this work is aimed to synthesizing the minor component 1 and an analogue structure, methyl 2,6,10-trimethyltetradecanoate (3) (Figure 1). These compounds and the previously synthesized major component 2⁷ will be tested individually and in different ratios on indoor bioassay and the results will be reported in due course.

Experimental

The IR spectra refer to films and were measured on a Bomem M-102 spectrometer. The ¹H-NMR spectra were recorded with TMS as an internal standard at 400 MHz on a Bruker ARX 400 spectrometer. The ¹³C-NMR spectra were recorded with TMS as an internal standard at 100 MHz on a Bruker ARX 400. GC-EIMS (70 eV) analysis was carried out on a Varian Saturn 2000 GC-MS spectrometer in a split injector mode. A VA-5 capillary column (30 m x 0.25 mm x 0.25 mm) was operated at 70° C for 1 min, increased to 270° C at a rate of 7° C/min and held at this temperature for 10 min. All reagents and solvents used in the syntheses were of highest commercially available standard. Chromatographic purifications were carried out on silica gel 60, Merck, 230-400 mesh.

(3RS)-3,7-Dimethyloct-6-enyl-1-acetate (5): To a mixture of pyridine (50 cm³) and citronellol 4 (15.00 g, 96.15 mmol) cooled at 0 ^oC under nitrogen, acetic anhydride (14.15 cm³, 150 mmol) was added in one portion, and the resulting mixture was stirred for 12 h. The reaction was quenched by addition of hot water (50 cm³) followed by addition of ethyl ether (100 cm³). The aqueous layer was extracted with ethyl ether (3 x 60 cm³) and the organic layer was dried over anhydrous magnesium sulfate and concentrated in vacuo. The product was purified by flash chromatography on silica gel using a mixture of hexane/ethyl acetate (24:1 v/v), yielding citronellyl acetate 5 as a colorless oil (17.00 g, 91.40 mmol, 95%). ¹H-NMR (400 MHz, CDCl₃) d 0.91 (d, ³J 6.6 Hz, 3H); 1.16-1.48 (m, 3H); 1.50-1.59 (m, 1H); 1.60 (s, 3H); 1.61-1.68 (m, 1H); 1.69 (s, 3H); 1.90-2.20 (m, 2H); 2.40 (s, 3H); 4.02-4.15 (m, 2H); 5.09 (t, ³J 7.0 Hz, 1H); ¹³C-NMR (100 MHz, CDCl₃) d 17.65; 19.42; 21.05; 25.40; 25.72; 29.50; 35.44; 36.99; 63.05; 124.58; 131.35; 171.24.

(3RS, 6E)-3,7-Dimethyl-8-oxo-6-octenyl-1-acetate (6): To a mixture of selenium dioxide (5.31 g, 48.0 mmol) in methylene chloride (100 cm³) maintained at 5 ¾ 10°C, tert-butyl hydroperoxide (288 mmol) was added dropwise. After 20 minutes at 10 °C, citronellyl acetate 5 (17.8 g, 95.9 mmol) was added in one portion. The resulting mixture was stirred during 30 minutes at 0 °C and then the cooling bath was removed. The mixture was allowed to warm to room temperature, and the stirring of the resulting solution was continued for 2-3 h. After all starting material had been consumed (~ 4 h, detected by gas chromatography), the mixture was carefully concentrated in vacuo without heating. The residue was diluted in hexane (50 cm³) and treated with 10% aqueous potassium hydroxide solution (40 cm³), yielding an aqueous lemon yellowish solution. The organic layer was treated twice with 10% aqueous potassium hydroxide solution (40 cm³), followed by treatment with brine (80 cm³). The organic layer was dried over anhydrous magnesium sulfate and concentrated in vacuo to afford an oil. Flash chromatography over silica gel using hexane/ethyl acetate (5:1 v/v) as eluent afforded aldehyde 6 (7.6 g, 38 mmol, 40 %) and the corresponding alcohol (7.5 g, 38 %). ¹H-NMR (400 MHz, CDCl₃) d 0.97 (d, ³J 6.1, 3H); 1.32-1.74 (m, 5H); 1.75 (s, 3H); 2.05 (s, 3H); 2.32-2.44 (m, 2H); 4.06-4.18 (m, 2H); 6.48 (t, ³J 7.0 Hz, 1H); 9.40 (s, 1H); ¹³C-NMR (100 MHz, CDCl₃) d 9.20; 19.23; 21.01; 26.47; 29.65; 35.29; 35.37; 62.66; 139.41; 154.57; 171.22; 195.31.

(3RS, 6E)-3,7-Dimethylnona-6,8-dienyl-1-acetate (7): To a mixture of the salt CH₃PPh₃Br (6.25 g, 17.5 mmol) in THF (100 cm³), cooled at ¾25 ^oC under argon, was added dropwise a solution of ⁿBuLi (16.9 mmol, 10.6 cm³, 1.6 mol L^-1 in hexane). After the addition was completed, the mixture turned dark orange. After 10 min the salt was consumed and a solution of aldehyde 6 (3.0 g, 15 mmol) in THF (30 cm³) was added to the mixture. After 5 minutes the cooling bath was removed and the mixture was allowed to warm to room temperature. After all starting material had been consumed (~10 min, detected by gas chromato-graphy) the reaction mixture was quenched with saturated aqueous NaCl solution (20 cm³). The aqueous layer was extracted with petroleum ether (5 x 50 cm³), and the organic phase was dried over anhydrous MgSO₄ and concentrated in vacuo. The residue was purified by flash chromatography over silica gel using a mixture of hexane/ethyl acetate (10:1 v/v), yielding 1.90 g of compound 7 (57 %). ¹H-NMR (400 MHz, CDCl₃) d 0.92 (d, ³J 6.6 Hz, 3H); 1.20-1.73 (m, 5H); 1.74 (s, 3H); 2.04 (s, 3H); 2.09-2.22 (m, 2H); 4.04-4.15 (m, 2H); 4.93 (d, ³J 10.7 Hz, 1H); 5.08 (d, ³J 17.3, 1H); 5.44 (t, ³J 7.1 Hz, 1H); 6.35 (dd, ³J 17.3 and 10.7 Hz, 1H); ¹³C-NMR (100 MHz, CDCl₃) d 11.66; 19.37; 21.04; 25.60; 29.53; 35.39; 36.55; 62.93; 110.49; 133.06; 134.00; 141.56; 171.22.

(3RS, 6E, 8E)- and (3RS, 6E, 8Z)-3,7-Dimethylundeca-6,8-dienyl-1-acetate (7a): As described above, the reaction of compound 6 (3.50 g, 17.5 mmol), and the salt CH₃CH₂CH₂PPH₃ Br (6.49 g, 17.5 mmol) afforded 7a (2.33 g, 65 %). ¹H-NMR (400 MHz, CDCl₃) d [0.92 (d, ³J 6.6 Hz, 3H); 0.93 (d, ³J 6.6 Hz, 3H)]; [0.99 (t, ³J 7.8 Hz, 3H); 1.01 (t, ³J 7.8 Hz, 3H)]; 1.19-1.29 (m, 1H); 1.35-1.50 (m, 2H); 1.51-1.62 (m, 1H); 1.63-1.70 (m, 1H); [1.73 (s, 3H); 1.76 (s, 3H)]; 2.04 (s, 3H); 2.06-2.17 (m, 2H); 2.20-2.29 (m, 2H); 4.04-4.16 (m, 2H); 5.23-5.38 (m, 1H); [5.58 (t, ³J 6.6 Hz, 1H); 5.62 (t, ³J 6.6 Hz, 1H)]; [5.76 (d, ³J 11.7 Hz, 1H); 6.04 (d, ³J 15.3 Hz, 1H)]; ¹³C-NMR (100 MHz, CDCl₃) d 12.44; [13.98; 14.92]; 16.70; 19.40; [21.03; 22.08]; [25.49; 25.86]; [29.51; 29.56]; [35.41; 35.44]; [36.73; 36.77]; 62.96; [129.24; 130.22; 130.24; 131.35; 132.25; 132.72; 133.60; 133.78]; 171.20

(3RS, 6E)-3,7-Dimethylnona-6,8-dien-1-ol (8): To a solution of compound 7 (1.90 g, 9.59 mmol) in methanol (10 cm³) at 0 ^oC, was added a solution of K₂CO₃ (0.5 mol L^-1, 19.2 cm³). The mixture was stirred at room temperature until all starting material had been consumed. This solution was concentrated in vacuo and extracted with ether. The organic layer was treated with saturated NaCl solution, dried over anhydrous MgSO₄ and concentrated in vacuo. The product was purified by flash chromato-graphy over silica gel using a mixture of hexane/ethyl acetate (1:5 v/v), yielding 1.48 g of compound 8 (99 %). ¹H-NMR (400 MHz, CDCl₃) d 0.92 (d, ³J 6.6 Hz, 3H); 1.19-1.31 (m, 1H); 1.35-1.48 (m, 3H); 1.55-1.66 (m, 2H); 1.73 (s, 3H); 2.05-2.25 (m, 2H); 3.64-3.75 (m, 2H); 4.92 (d, ³J 10.7 Hz, 1H); 5.08 (d, ³J 17.3 Hz, 1H); 5.47 (t, ³J 7.1, 1H); 6.35 (dd, ³J 17.3 and 10.7 Hz, 1H); ¹³C-NMR (100 MHz, CDCl₃) d 11.64; 19.47; 25.68; 29.25; 36.80; 39.84; 61.13; 110.43; 133.25; 133.91; 141.59.

(3RS, 6E, 8E)- and (3RS, 6E, 8Z)-3,7-Dimethylundeca-6,8-dien-1-ol (8a): As described above, compound 7a (2.33 g, 11.0 mmol) was converted into alcohol 8a (1.82 g, 98 % yield). ¹H-NMR (400 MHz, CDCl₃) d [0.91 (d, ³J 6.6 Hz, 3H); 0.92 (d, ³J 6.6 Hz, 3H)]; [0.99 (t, ³J 7.1 Hz, 3H); 1.01 (t, ³J 7.1 Hz, 3H)]; 1.19-1.28 (m, 1H); 1.34-1.46 (m, 2H); 1.55-1.68 (m, 2H); [1.72 (s, 3H); 1.76 (s, 3H)]; 1.84 (br, s, 1H); 2.04-2.16 (m, 2H); 2.20-2.28 (m, 2H); 3.63-3.74 (m, 2H); 5.21-5.40 (m, 1H); [5.58 (t, ³J 6.1 Hz, 1H); 5.61 (t, ³J 6.1 Hz, 1H)]; [5.75 (d, ³J 11.7 Hz, 1H); 6.05 (d, ³J 16.0 Hz, 1H)]; ¹³C-NMR (100 MHz, CDCl₃) d 12.43; [13.98; 14.93]; [19.50; 19.54; ]; 22.09; [25.55; 25.86]; [29.22; 29.30]; [36.95; 37.00]; 39.86; [61.16; 61.18]; [129.22; 130.41; 130.48; 131.33; 132.26; 132.65; 133.52; 133.78].

(3RS, 6E)-3,7-Dimethylnona-6,8-dienal (9): To a stirred solution of dimethyl sulfoxide (2.21 g, 28.4 mmol) in methylene chloride (8.50 cm³) cooled at ¾60 ^oC under nitrogen, was added a solution of oxalyl chloride (1.80 g, 14.2 mmol) in methylene chloride (27.4 cm³), and the reaction mixture was stirred for 20 minutes. Alcohol 8 (1.48 g, 9.48 mmol) dissolved in methylene chloride (67.0 cm³) was added. The mixture was stirred for 1 h at ¾60 ^oC and then treated with trimethylamine (7.88 cm³, 57.0 mmol).The cooling bath was removed and the mixture was allowed to warm to room temperature over a period of 30 minutes. After addition of hexane (60 cm³), the mixture was poured into water (25 cm³) and extracted with a solution of hexane/ethyl acetate (2:1 v/v). The organic phase was treated with saturated NaHCO₃ solution and saturated NaCl solution, dried over anhydrous MgSO₄ and concentrated in vacuo to give 1.40 g of crude 9. This unstable aldehyde was directly used for the next step without purification.

(3RS, 6E, 8E)- and (3RS, 6E, 8Z)-3,7-Dimethylundeca-6,8-dienal (9a): As described above, compound 8a (1.82 g, 10.7 mmol) was converted into aldehyde 9a (1.70 g).

2,6,10-Trimethyldodecan-1-ol (11): To a mixture of the salt [HOCH₂CH(CH₃)CH₂PPh ₃]Br (3.88 g, 9.35 mmol), [prepared by reaction of (2RS)-2-methyl-3-hydroxy-1-bromopropane and Ph₃P in benzene⁸, 87 % yield] in THF (80 cm³), cooled at ¾25 ^oC under argon, was added a solution of ⁿBuLi (18.7 mmol, 11.7 cm³, 1.6 mol L^-1 in hexane). After the addition was completed the mixture turned dark orange. In 10 min the salt was consumed and a solution of aldehyde 9 (1.21 g, 7.85 mmol) in THF (10 cm³) was added to the mixture. After 5 minutes the cooling bath was removed and the mixture was allowed to warm to room temperature. After all starting material had been consumed (~20 min, detected by Gas Chromatography) the reaction mixture was quenched with saturated NaCl solution (20 cm³). The aqueous layer was extracted with cold petroleum ether (5 x 50 cm³). The organic phase was dried over anhydrous MgSO₄ and concentrated in vacuo. The residue was diluted in pentane (~ 20 cm³) and kept at -10 ^oC for 24 h. This was filtrated and the solvent was removed in vacuo. The crude product was dissolved in hexane and hydrogenated over Pd/C (100 mg) at room temperature and 25 psi in a Parr^® apparatus for 2 h. The mixture was filtered through Celite^® and the filtrate was evaporated at reduced pressure. The crude product was purified by flash chromatography over silica gel, using a mixture of hexane/ethyl acetate (7:1 v/v), to afford 1.25 g of alcohol 11, 75 % yield as a mixture of stereoisomers. ¹H-NMR (400 MHz, CDCl₃) d 0.84-0.91 (m, 9H); 0.92 (d, ³J 6.8 Hz, 3H), 1.10-1.17 (m, 4H); 1.24-1.42 (m, 12H); 1.60-1.67 (m, 2H); 3.42 (dd, ³J 10.4 and 6.4 Hz, 1H); 3.50-3.54 (m, 1H); ¹³C-NMR (100 MHz, CDCl₃) d 11.4; 16.6; [19.2, 19.3]; 19.7; 24.4; 24.5; [29.4, 29.6]; 32.7; 33.4; 34.4; 35.8; 37.0; 37.3; 37.5; 68.5.

2,6,10-Trimethyltetradecan-1-ol (11a): As described above, compound 9a (1.64 g, 9.76 mmol) was converted into alcohol 11a (1.40 g, 65 %) as a mixture of stereoisomers. ¹H-NMR (400 MHz, CDCl₃) d 0.79-0.89 (m, 9H); 0.94 (d, ³J 7.0 Hz, 3H), 0.98-1.12 (m, 4H); 1.18-1.40 (m, 16H); 1.55-1.66 (m, 2H); 3.41 (dd, ³J 10.4 and 6.8 Hz, 1H); 3.44-3.52 (m, 1H)

Methyl-2,6,10-trimethyldodecanoate (1): Jones reagent (~20.0 cm³) was added to a solution of the alcohol 11 (1.30 g, 5.70 mmol) in acetone (100 cm³), and the mixture was stirred for 30 min at ¾5 °C. Excess of oxidant was destroyed with i-PrOH, and the mixture was concentrated in vacuo, diluted with water, and extracted with ether. The ether extract was washed with H₂O and satd NaCl solution, dried with MgSO₄, and concentrated. The residue obtained was diluted in ether (50 cm³) and treated with ethereal CH₂N₂ at 0° C, until the reaction mixture turned yellow. The solution was stirred for 30 min, concentrated, and the residual oil was chromatographed on silica gel using hexane/ethyl acetate (9.5:0.5 v/v) as eluent, yielding 1.10 g of 1 (75 %) as a mixture of stereoisomers. ¹H-NMR (400 MHz, CDCl₃) d 0.84 (d, ³J 7.2 Hz, 3H); 0.85 (d, ³J 6.8 Hz, 3H); 0.86 (t, ³J 7.2 Hz, 3H); 1.01-1.10 (m, 3H); 1.14 (d, ³J 6.8 Hz, 3H); 1.18-1.45 (m, 13H); 2.45 (sext, ³J 6.8 Hz, 1H); 3.67 (s, 3H); ¹³C-NMR (100 MHz, CDCl₃) d [11.42, 11.43]; [17.03, 17.14]; [19.21, 19.27]; [19.60, 19.65]; 24.47; 24.71; [29.47, 29.58]; 32.65; [34.12, 34.16]; 34.43; 36.84; [36.93, 36.97]; [37.31, 37.35, 37.36, 37.39]; [39.47, 39.50]; 51.44; 177.43; GC-EIMS m/z 256 (M⁺, 0.6 %); 232 (0.6); 203 (1.3); 152 (0.5); 119 (9.6); 101 (29.8); 88 (100); 69 (18.3); 55 (29.8).

Methyl-2,6,10-trimethyltetradecanoate (3): As described above, compound 11a (1.40 g, 5.47 mmol) was converted into 3 (1.32 g, 82 %) as a mixture of stereoisomers. ¹H-NMR (400 MHz, CDCl₃) d 0.83 (d, ³J 6.1 Hz, 3H); 0.84 (d, ³J 6.6 Hz, 3H); 0.89 (t, ³J 7.1 Hz, 3H); 1.00-1.12 (m, 4H); 1.14 (d, ³J 7.1 Hz, 3H); 1.18-1.31 (m, 13H); 1.32-1.44 (m, 3H); 2.44 (sext, ³J 7.1 Hz, 1H); 3.67 (s, 3H); ¹³C-NMR (100 MHz, CDCl₃) d 14.58; [17.43, 17.53]; [20.00, 20.05]; [20.10, 20.16]; 23.45; 24.85; [25.09, 25.11]; 29.76; 33.04; [33.14, 33.17]; [34.51, 34.56]; [37.15, 37.25]; [37.26, 37.33]; [37.71, 37.74]; [37.77, 37.82]; [39.87, 39.89]; 51.84; 177.44; GC-EIMS m/z 284 (M⁺, 1.0 %); 227 (0.6); 194 (2.0); 157 (6.7); 129 (3.66); 101 (34.3); 97 (14.4); 88 (100); 69 (24.3); 55 (45.5); 43 (73.0).

Results and Discussion

A brief retrosynthetic analysis is depicted for compounds 1 and 3 (Scheme 1). (±) ¾ Citronellol 4 serves as starting material to the synthesis of the key and common intermediate for both target molecule, aldehyde 6. From here, we have mainly utilized two Wittig reaction to build the skeleton of each molecule. The first one was employed to generate compounds 9 and 9a, which have the correct numbers of carbon atoms at the A portions of the molecules, and the second Wittig reaction afforded the B portions of alcohol 11 and 11a, the direct precursors of the desired molecules.

The transformation of (±)-citronellol 4 to the aldehyde 6 was performed according to Scheme 2. The first step involves the acetylation of 4 with Ac₂O-Py⁹ resulting in the respective acetate 5 in 95 % yield. This was oxidised by SeO₂ / ^tBuOOH to afford a mixture of the aldehyde 6 (40 % yield) and the corresponding allylic alcohol (38 % yield)^10,11. After purification by flash chromatography, the pure aldehyde 6 was subjected to the Wittig reaction with (triphenylphosphonium)methanide (CH₂=PPh₃) or (triphenylphosphonium)propanide (CH₃CH₂CH=PPh₃) to give compounds 7 (57 % yield) or 7a (65 % yield), respectively. These new acetates intermediates were straightforward transformed into methyl 2,6,10-trimethyl-dodecanoate (1) and methyl 2,6,10-trimethyltetradecanoate (3), as indicated in Scheme 3. Hydrolysis of 7 under basic condition yielded alcohol 8 in 99 % yield. Swern oxidation¹² of 8 gave the unstable aldehyde 9, which without purification was readily transformed in to the alcohol 10, by employing the second Wittig reaction of our synthetic plan, with ylide 12. Compound 10 and the respective analogue 10a, derived from acetate 7a, could not be adequately purified. The GC and TLC analyses of the crude residue obtained in this reaction shows a number of products, which are certainly related to the mixture of stereoisomers (resulting from the methyl branches and the double bonds). Thus, crude 10 was hydrogenated over Pd/C furnishing the alcohol 11 in 75 % yield over two steps. Finally, the routine Jones oxidation of 11 afforded the respective carboxylic acid, which was treated with CH₂N₂ to give the desired pheromone 1 in 75 % yield¹³ as a mixture of stereoisomers. Similarly, acetate 7a was converted into 3.

We have previously described the first synthesis of (2R, 6S, 10S) and (2S, 6S, 10S) isomers of methyl 2,6,10-trimethyldodecanoate (1)¹³, and recently we developed a new synthesis of a mixture of stereoisomers of pheromone 2⁷. A stereoisomeric mixture of methyl 2,6,10-trimethyltridecanoate (2) was firstly synthesized by Mori and Murata¹⁴, which later have described the synthesis of all of the eight possible isomers of pheromone 2¹⁵.

We have now achieved a new approach to the synthesis of these stink bugs pheromones. A positive feature of our synthesis is the fact that the starting material 4 and the bromide utilized to prepare ylide 12 (3-bromo-2-methyl-1-propanol), are commercially available in both enantiomeric forms. So, a number of stereoisomers of the final compounds 1 and 3 (even for 2) could be obtained.

However, we intend in to use the racemic compounds to carry out the bioassays, since these stink bugs are responding to the racemic mixture at the same level as to the pure isomers, as already mentioned⁶. This characteristic can be an economically important issue to define the usefulness of synthetic pheromones as an alternative method in pest management control for P. guildinii and E. heros.

Acknowledgments

We thank the IFS (International Foundation for Science ¾ Sweden, grant to PHGZ), CNPq (Brazilian Consul for Scientific and Technological Development), and Plantações E. Michelin for financial support, and Prof. Antonio Gilberto Ferreira (DQ-UFSCar) for running ¹H-NMR and ¹³C-NMR of the synthetic compounds.

Received: July 24, 2000

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Publication Dates

• Publication in this collection
  03 Apr 2007
• Date of issue
  Dec 2000

History

• Received
  24 July 2000