HU187780B - Composition for enticing gamma owlet moth males - Google Patents

Description

(57) EXTRAS

The present invention relates to a composition for attracting male gamma moths comprising 50-99.8% by weight of 7 (Z) dodecen-1-ol acetate and 50-0.2% by weight of 7 (Z) -dodccn-1-ol, preferably 80-99.5% by weight of a mixture of 7 (Z) -dodecen-1-ol acetate and 20-0.5% by weight of 7 (Z) -dodecen-1-ol, optionally a liquid and / or solid excipient - preferably with hexane, dichloromethane and / or viscous liquid, preferably sunflower oil or paralyn oil.

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The present invention relates to a composition for attracting male gamma owls (Autographa gamma); more particularly, the present invention relates to a composition comprising a synergistic combination of two active ingredients.

Gamma owl moth is one of the most important and most frequently occurring owl moth in Hungary. It is a multi-nutrient species that causes regular damage to the crops, tobacco, sugar beet and other crops every year. So far, the control has been mainly done with the help of phosphoric ester derivatives, which are highly toxic to pests and other organisms and even to humans. The application of phosphoric acid sclerite derivatives to gamma owl moth is further complicated by the fact that since the species is unable to overwinter in Hungary, the first damage is caused by the worms hatching from the eggs of butterflies that migrate from the Mediterranean to Hungary every year. its dates change annually depending on the weather.

The use of pheromone-active formulations in trapping can predict the time of pest appearance, and their use in air-saturation can eliminate some of the environmental problems associated with the use of broad-spectrum insecticides.

An advantage of pheromone traps over other trapping methods currently used in forecasting is that they are highly selective. In most cases, only the pests of the species in question, or some closely related species, are captured, so that, unlike light trap material, the processing of the captured material does not require a highly skilled insect tax expert. Another major advantage over light and UV traps is that pheromone traps do not require any source of energy, so they can be operated anywhere, that is to say, on any part of the crop to be protected, thus precisely locating the pest.

In gamma owl moths, by monitoring the appearance of moths with sex-pheromone traps, it is possible to select a time of control with conventional insecticides that is within the period of appearance of the caterpillars, thus making the control much more effective.

Pheromones are called "pheromones". Applying the airspace method, it is possible to prevent mating of male and female moths and thus to reduce the number of offspring. The method involves the release of relatively large amounts of pheromone into the airspace of the crop to be protected, which prevents male moths from detecting, locating and mating females, and by mating, of naturally occurring pheromones.

The advantage of using pheromones in this way is that they have a high degree of selectivity (inhibits the mating only of the pest species, does not affect the life of other organisms), low toxicity, and a few orders of magnitude less pollution than conventional insecticides. not expected (Birc, MC (ed.) Pheromones, North Holland Publ. Co. London-New York, 1974, p. 495).

The sex fcroinon of gamma moth has been removed from the female moth (Szőcs and Tóth, Acta Phytopath. 14, 453, 1979), but no structural determination has been made. According to Ghizdavu et al. (Rev. Roum. Bioi. Anim. 24, 87, 1979), the male was trapped in the field by 7 (Z) -dodecen-1-olacetate.

In our experiments, it was found that combining 50 99.8% by weight of 7 (Z) -dodccn-1-ol acetic acid with 50 0.2% by weight of 7 (Z) -dodecen-1-ol results in a synergistic combination which when used in an insect trap, it has a stronger sedative effect on gamma owl moths than when used alone with 7 (Z) -dodcccn-1-01 steel.

The composition according to the invention thus comprises a mixture of 50-99.8% by weight of 7 (Z) -dodecen-1-01-acetate and 50-0.2% by weight of 7 (Z) -dodecen-1-ol, optionally liquid and / or with solid excipients. Particularly preferred is a composition comprising 80-99.5% by weight of a mixture of 7 (Z) -dodecen-1-01-acetate and 20-0.5% by weight of 7 (Z) -dodecen-1-ol.

The discovery of the present invention is surprising because although sex component pheromone combinations are known in two relatives of the gamma owl moth, Trichoplusia ni and Autographa californica, the main component, besides 7 (Z) -dodecene-01-acetate, in the first case is dodecyl acetate. and in the other case 7 (Z) -tetradccn-1-01 steels are mentioned as the second component (Bjostad et al., J. Chem. Ecol., 6, 727, 1981); Steck et al., Can. Int., 1263 (1979)]. In contrast, the combination according to the invention contains 7 (Z) -dodecen-1-ol as a second synergistically active component.

The composition of the active compound combination according to the invention can be prepared by, for example, preparing a solution of the two components in a solvent which is chemically inert to the active ingredient (hexane, dichloromethane, methanol, acetone, etc.) and the capsule, microcapsule, microcapillary form. Once in the trap, the inhaled solvent quickly disappears, while the active ingredient gradually evaporates to attract.

Various viscous, low-volatile liquids which are chemically inert to the active ingredient (e.g., sunflower oil, olive oil, paraffin oil, mineral oils) are preferably used to slow the evaporation rate of the active ingredient. Such a liquid does not interfere with the attractive effect itself, but maintains the rate of evaporation of the active ingredient at a steady rate so as to maintain the efficacy of the formulation for an extended period of time.

In our experience, a side containing 12 to 67% by weight of sunflower oil, 80 to 30% by weight of hexane and 8 to 3% by weight of active ingredient. The amount of such solution used is such that, in a suitable formulation, the dosage will be from 0.001 to 10.0 mg of active ingredient.

The presence of a viscous liquid is not necessarily required to achieve the desired effect. It has been found that 50-90% by weight of inert solvent, preferably hex-23

A solution of 187,780 xane or dichloromethane and 50% by weight of the active ingredient in a suitable formulation, preferably in the form of a rubber, rubber or polyethylene capsule, in an amount such that the active ingredient is present in a dose of 0.001-10.0 mg.

The insect trap contains a combination of 0.001 to 10.0 mg of active ingredient, preferably 0.05 to 3.0 mg, preferably in one of the formulations described above.

To prevent mating, án. airflow rates of from 1.0 to 50.0 are preferably 5.0 to 20.0 mg / h.

The preparation of 7 (Z) -dodecene-1-O-1 and 7 (Z) -dodecen-1-01-acetate of formula (I) was solubilized from propargyl alcohol by literature analogues as follows:

The hydroxyl group of the propargyl alcohol was first protected from the resulting compound of formula (III): R is 2-tetrahydropyranyl, 1-ethoxyethyl, or the benzyl group is formed in an aprotic solvent with a strong base, preferably butyl lithium, and reacting the anion without isolation with a compound of formula IV (wherein X is chloro, bromo, or iodo; tosyloxy or mesyloxy).

From the reaction mixture, 2-octen-1-ol (VI; R = H) was prepared from the compound of formula (V), wherein R is as described above by acid catalysis in aqueous-alcoholic solution, preferably hydrochloric acid in methanol. The potassium salt of 3-diaminopropane was converted to the compound of formula VII (R = H). The hydroxy group of the compound is protected and the resulting compound of formula VI, where R is as defined above, is converted to an anion in a aprotic solvent with a strong base, preferably alkyl lithium, which, without isolation, has the formula (VII). X) is as defined above.

The protecting group of the compound (VIII) isolated from the reaction mixture, wherein R is as defined above, is deprotected by acid catalysis in an aqueous alcoholic solution, preferably hydrochloric acid in methanol, and the resultant compound of formula (VIII) (R = H) - preferably hydrogenated with palladium catalyst precipitated on barium sulfate - yields 7 (Z) dodecen-1-ol of formula (I).

For the preparation of 7 (Z) -dodecen-1-ol acetate (II), the compound (VIII) (R = H) is acylated in the presence of an acetic acid base, preferably acetic anhydride in pyridine, and the resulting compound (IX) hydrogenation is carried out with a supported, moderately active catalyst, preferably palladium catalyst precipitated on barium sulfate.

Details of our tests and procedures are given in the accompanying examples, but are not limited to the examples.

Example 1

Investigation of the attractiveness of 7 (Z) -dodecen-1-ol acetate (II) and 7 (Z) -dodecen-Ιοί (1) by outdoor trapping.

Our preliminary experiment was carried out in Pestimre, approx. 35 hectares of cabbage soil, July 1 - 30, 1979. Our second experiment was also carried out in Pestimre, ca. 180 hectares of cabbage land, from August 26 to October 27, 1981. For our third experiment in Vecsés, approx. It took place on 300 ha of cabbage land from 26 August to 27 October 1981.

The traps used are high, approx. They consisted of a 20 x 30 cm plastic sheet with a tent roof folded in the center. The sheets were fastened to each other at their corners so that the tent-like ridge was perpendicular to each other. The inside of the sheet below was smeared with adhesive to hold the butterflies flying there. The baits were suspended from the middle of the top panel, inside. The traps were placed 25 m apart and 0.5 m above the ground. In the first experiment, the dose of the active ingredient was 1 mg and the baits were changed weekly. In the second and third experiments, the dose of the active ingredient was 0.5 mg and the baits were not changed during the experiment. In the first experiment, one trap was used as treatment, in the second and third experiments three traps were used.

The captured animals were collected weekly and determined by species. Final data were statistically evaluated using the Duncan's New Multiple Rank Test. (Steel, R., Torric, J. (1960) Principles and Procedures of Statistics. New York: McGrawHill, p. 481).

In the first experiment, 16 male gamma owls were caught in a 95: 5% by weight mixture of 7 (Z) -dodecene-1-01-acetate and 7 (Z) -dodecene-10. 7 (Z) -dodecen-1-O1 acetate alone and other combinations of 7 (Z) -dodecen-1-O1 did not show an attractive effect (Table I).

Table 1

II II and mixtures of I and I by weight 1: 1 4: 1 95: 5 Caught male gamma 0 0 0 16 number of owls

In our second experiment, 7 (Z) -dodcccn-l-0-acetate alone and in the 7: 3 and 1: 1 mixtures of 7 (Z) -dodecen-1-1 showed little attractive effect, but most of the moths also showed 7 95: 5 mixture of Z) -dodecene-01-acetate and 7 (Z) -dodecene-1-01. Catches were significantly different from other treatments (Table 2) (P = 5%).

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Table 2

Mixtures of II and I in% by weight 1: 1 7: 3 95: 5 The number of male gamma owls caught 8a 3a 6a 25b

* Catch data with the same letter do not differ significantly at 5% level.

Our third experiment yielded similar results: the best catch was a mixture of 7 (Z) -dodecen-1-ol acetate and 7 (Z) dodecen-1-ol in a 95: 5 ratio, with significantly (P = 5%) fewer butterflies caught, respectively. mixtures of 7: 3, 1: 1; and 7 (Z) -dodecene-1-ol acetate alone (Table 3).

Table 3

Mixtures of II and I in% by weight 1: 1 7: 3 95: 5 The number of male gamma owls caught 6a 8a 18a 44b

* Catch data marked with the same letter are not significantly different at 5% level.

It can be stated that the most effective in all cases was a mixture of the two components in a ratio of 95: 5. 7 (Z) -dodecene-1-01-acetate alone is only minor

showed some activity. Table 4 Mixtures of II and I in% by weight 1: 1 95: 5 100: 1 Number of gamma ba-Iacac 2a moths caught 29bc 38b

^a Catch data marked with the same letter are not significantly different at the 5% level.

I = 7 (Z) -dodcccn-l-0l

II = 7 (Z) -dodcccn-1-O-acetate

Example 2

Preparation of 7 (Z) -dodecen-1-ol (I)

a) 3- (2-Tetrahydro-pyranyloxy) -propine [III: R = 2-ladder-hydro-pyranyl] g (1.03 mol) of propargyl alcohol in 100 ml of dry tetrahydrofuran, 0-5 ° To the solution cooled to C was added 2 g (0.16 mol) of p-toluene sulfonic acid, followed by 100 g (1.19 mol) of 3,4-dihydro

- 4H - pyran. After standing overnight at room temperature, the reaction mixture was diluted with 400 mL of ether and the solution was washed neutral with 5% sodium bicarbonate solution. After drying, the solvent is distilled off in vacuo and the residue is purified by fractional distillation. MP: 82 ° C / 30 mm Hg.

Yield: 95% o (137 g)

IR (film): 3200, 2900, 1440, 1380, 1340, 1240, 1215, 1180, 1100, 1010, 825, 880, 780. Λ H-NMR (CCl _4): 1.65 (6H, m, 3CHJ 2.4 (1H, t, J = 2Hz, O = CH), 3.65 (2H, m,

O-CH ₂ ), 4.22, (2H, d, J = 2Hz, O-CH ₂ -O ₂ C), 4.77 (1 H, m, O-CH-O).

b) 1- (2-Tetrahydropyranyloxy) -2-octine [V: R = 2-Tetrahydropyranyl]

2.1 g (0.015 mol) of 3- (2-tetrahydropyranyloxy)

To a solution of propine (III: R = 2-tetrahydro-pyranyl) in dry tetrahydrofuran (5 mL) at 0-5 ° C was added 0.015 moles of butyllithium (15 mL of 1 mmol) under argon with stirring. of hexane) and stirred for 2 hours at 0-5 ° C. To the reaction mixture was added 1.51 g (0.01 mol) of pentyl bromide (IV: X = Br) in dry hexamethylphosphoric acid amide (3 ml). ) was added dropwise and the mixture was allowed to stand at room temperature for 8 hours. The mixture was cooled to 0 °, neutralized with 1: 1 hydrochloric acid, diluted with ether (10 mL) and washed with water (5 mL). After drying, the solvent was distilled off in vacuo and the residue was purified by column chromatography.

Yield: 1.5 g (71%)

TLC: Rf 0.5 (hexane-ether 4: 0.7)

IR (film): 2900, 1460, 1440, 1370, 1320, 1270, 1140, 1200, 1120, 1060, 1010, 930, 860, 800, 745, 700 cm ^-1 .

1 H-NMR (CCl ₄ ): 0.9 (3H, t, J = 7Hz, CH J, 1.40 (6H, m, 3CH J, 2.05 (2H, m, C = CCH ₂ )), 1.65 (6H, m, ring), 3.3-3.6 (2H, m, O-CH ₂ , 4.2 (2H, t, J = 2Hz, -OCH ₂ C =), 4.5 (1H, m, --OCHO -).

MS: m / z 210 (<1 / M), 209 (<1 / M-1), 163 (<1), 113 (8) (THPO-CH 3 = (M-C = CCH ₂ CH ₂ CH ₂ CH). ₂ CHJ, 111 (7), 101 (30) (THPO), 95 (11), 85 (100) (THP), 81 (26), 79 (27), 67 (24), 55 (30), 53 (15), 41 (46).

c) 2-Octin-1-ol (V: R = h)

To a solution of 1.5 g of 1- (2-tetrahydropyranyloxy) -2-octine (V: R = 2-tetrahydropyranyl) in methanol (15 mL) was added 0.2 g of p-toluenesulfonic acid and the solution was stirred at room temperature for three hours. The methanol was evaporated in vacuo, the residue was dissolved in hexane, the hexane solution was washed with sodium bicarbonate solution, dried and the solvent was distilled off and the residue was purified by column chromatography.

Yield: 0.76 g (84%).

TLC: Rf 0.2 (hexane-ether 4: 0.7)

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IR (film): 3400, 2850, 1460, 1430, 1375, 1320, 1210, 1125, 1000 cm ^1st

1 H-NMR (CCl ₄ ): 0.9 (3H, t, J = 6Hz, CH ₃ ), 1.38 (6H, m, 3CH ₂ ), 2.15 (2H, m, C = CCH _2). )

3.2 (1H, m, OH, interchangeable with D ₂ O), 4.1 (2H, t, J = 1 Hz,

O-CH-O).

MS: m / z 126 (M +) (51), 111 (4) (M-CH 2), 108 (4) (M-H ₂ O), 95 (12) (M-HO-CH ₂ 93 (18) (M-H ₂ O-CH ₃ ), 83 (14) (M-CH ₂ -CH ₂ CH ₃ ), 79 (15), 70 (23), 67 (25), 55 (49) H ₂ CH _{2 -} C = C), or (C ₄ H ₇ ), 41 (89) (CH _{2 -} CH = CH ₂ ), 39 (100) (CH 3 - C = CH), 29 (65) (CH 3 CH 3), 27 (83) (OCH)

d) 7-Octin-1-ol (VI: R = H)

28 g of potassium hydride (18% in oil suspension) are washed three times with a total of 600 ml of dry hexane in a dry round-bottom flask under nitrogen, and 44 g of 1,3-diaminopropane are added dropwise at 0 ° C. (Hydrogen evolves during the addition and strong cooling is required.) The reaction mixture is allowed to stand at 0 ° C for 2 hours and then at room temperature for 8 hours. A solution of 2.56 g (0.02 mol) of 2-octinolol (V: R = H) in dry tetrahydrofuran (10 ml) was added at 0 ° C over 10 minutes and at 0 ° C leave for an hour. The reaction mixture was added dropwise to a vigorously stirred emulsion of 300 mL of hexane and 25 mL of acetic acid under cooling. The hexane solution was washed with acetic acid and water, dried, and the solvent was distilled off and the residue was purified by column chromatography.

Yield: 2 g (78%)

TLC: Rf 0.1 (hexane-ether 2: 2)

IR (film): 3400, 2800, 1460, 1430, 1250, 1150, 730 cm ^-1 . ¹ H-NMR (CCl ₄ ): 1.3 (8H, m, CH ₂ ), 1.95 (1H, t,

J = 1 Hz, C 1 -C 12), 2.5 (2H, m, CH, -C = C), 3.45 (2H, m, O-CH ₂ ), 2.10 (1 H, s, OH, Interchangeable with D ₂ O).

MS: m / z 126 (<1) (M ⁺ ), 125 (1) (M ⁺ -H), 111 (I) (M-15), 107 (1) (M-H-H ₂ O). , 95 (10) (M-HOCH ₂ - (CH _{2) s} OC H), 93 (28) (C ₇ H ₉ or C ₆ H ₅ O), 79 (44) (C _Ö H _7, or C ₅ H ₃ O), 67 (41), 56 (34), 42 (100) (C ₃ H ₆ , or C ₂ H ₂ O), 39 (58), 31 (55), 27 (47).

e) 1- (2-Tetrahydropyranyloxy) -7-octine [VI: R = 2-tetrahydropyranyl]

To a solution of 7-octin-1 -01 (VI: R-H) (2.56 g, 0.02 mol) and p-toluenesulfonic acid (0.1 g) in dry tetrahydrofuran was cooled to 0 ° C (2.0 g). Dihydropyran (0.024 mol) was added and the solution was stirred at 0-5 ° C for 5 hours. The reaction mixture was washed with sodium bicarbonate solution, dried and purified by column chromatography after distilling off the solvent.

Yield: 1.89 g (90%)

TLC: Rf 0.6 (4: 1 hexane) R (film): 2850, 1450, 1350, 1320, 1255, 1190, 1130, 1120, 1080, 1020, 860, 800 cm @ -1. 1 H-NMR (CCl ₄ ): 1.35-1.45 (12H, m, CH ₂ , ring)

CH ₂ -CH ₂ ), 1.15 (1H, t, J = 1 Hz, C-CH), 2.05 (4H, m, CH ₂ -C = C, ring CH ₂ ), 3.05-3 6 (4H, m, _O-CH2), 4.35 (IH, t,

O-CH-O).

MS: m / z 210 (<1) (M ⁺ ), 209 (1) (Μ-H), 109 (4) (Μ-THPO, or (CH ₂ ) _e OCH), 101 (20) (THPO) , 85 (100) (THP), 67 (37), 56 (25), 55 (23), 42 (45).

f) 1- (2-Telrahydropyranyloxy) -7-dodeccin [VII1: R = 2-tetrahydropyranyl group [

A stirred solution of 2.3 g (0.012 mol) of 1- (2-tetrahydropyranyloxy) -7-octine (VI: R = 2-tetrahydropyranyl) in dry tetrahydrofuran (15 ml) cooled to 0 ° C. while adding 0.012 moles of butyllithium (10.9 mL, 1.075 mmol / mL in hexane) under argon and stirring at 0 ° C for 2 hours. A solution of 1.6 g (0.012 mol) of butyl bromide (VII: X = Br) in dry hexamethylphosphoramide (4 mL) was added dropwise and the mixture was stirred at room temperature for 8 hours. The reaction mixture was cooled to 0 ° C, neutralized with 1: 1 hydrochloric acid, diluted with ether (20 mL), washed with ether (5 mL), dried and the residue was purified by column chromatography.

Yield: 2.58 g (81%).

TLC: Rf 0.6 (hexane-ethyl acetate 4: 0.3).

IR (film): 2900, 1470, 1450, 1360, 1330, 1260, 1200, 1140, 1120, 1080, 1030, 910, 810, 750, 710 cm ^-1 .

1 H NMR (CCl ₄ ): 0.9 (3H, t, J = 6Hz, CH ₃ ), 1.45 (12H, m, 6CH ₂ ), 2.1 (4H, m, CH ₂ CCH ₂ ), 1.6 (6H, m, ring),

3.3-3.8 (4H, m, _O-CH2), 4.55 (IH, m. O-CH-O).

MS: m / z 266 (3) (M), 223 (2) (M - CH ₂ CH ₂ CH ₃ ), 209 (4) (M - (CH ₂ ) 3 CH ₃ ), 181 (1) (M -). THP), 167 (3), 123 (4), 109 (14), 101 (30) (THPO), 95 (19) (C ₇ H 11, vag (CH ₂ ) ₄ OC), 85 (100), 82 (15), 67 (39), 56 (36), 42 (52).

g) 7-Dodecin-1-01 (Fruit: R = H)

Of a solution of 2.66 g (0.01 mol) of 1- (2-tetrahydropyranyloxy) -7-dodecin (VIII: R = 2-tetrahydropyranyl) in methanol (15 mL) at 0 ° C, 0.1 g of p-toluenesulfonic acid is added and the solution is stirred at room temperature for three hours. The solvent was evaporated in vacuo, the residue was dissolved in hexane (20 mL), the solution was washed with 5% sodium bicarbonate solution (4 mL) and water (5 mL), dried and the residue was purified by column chromatography. .

Yield: 1.6 g (91%).

TLC: hexane-ethyl acetate 2: 1 Rf 0.8.

IR (film): 3400, 2850, 1460, 1430, 1370, 1250, 1150, 730 cm ^-1 .

1 H-NMR (CCl ₄ ): 0.9 (3H, t, J = 6Hz, CH ₃ ), 135 (12H, m, 6CH ₂ ), 1.55 (1H, s, D ₂ O interchangeable) ), 2.05 (4H, m,

CH ₂ C = CCH ₂ ), 3.55 (2H, t, j = 6 Hz, O-CH ₂ ).

MS: m / z 182 (1) (M), 164 (1) (M-H ₂ O), 139 (2) (M-CH ₂ -CH ₂ -CH ₃ ), 122 (7) (M-H ₂ O-CH ₂ CH ₂ CH _2), 110 (38) (C ₈ H _I4 or C ₇ H ₁₀ O), 107 (15) (C ₈ H, "or C ₇ H ₇ O), 96

187780 (47) (C, H12, or C ₆ H ₈ O), 93 (43) (C ₇ H ₉ or C _e H ₆ O) 82 (83) (C _e H _10, or C ₅ H ₆ O), 79 (64) (C ₆ H ₇ O or C ₅ H ₃ O), 67 (96), 56 (74), 55 (89), 42 (100).

h) 7 (Z) -Dodecen-1 -01 (1) ⁵

Palladium barium sulfate, prehydrogenated in dry ethanol (40 mL) (0.165 g, 101% Pd), was treated with 0.25 g (0.014 mol) of 7-dodecin-I-01 (VIII: R = H) in dry ethanol ( 4 mL) was added, · θ and hydrogenation continued until uptake of one equivalent of hydrogen (33 mL) (10 min). The catalyst was filtered off and the solvent was evaporated in vacuo.

Yield: 0.23 g (90%). 15

TLC: Rf 0.35 (4: 1.5 hexane / ether)

IR (film): 3420, 1460, 1380, 1050 ^cm-first

1 H NMR (CCl ₄ ): 0.9 (3H, t, J = 7Hz, CH 3), 1.4 (12H, m, 6CH ₂ ), 2.0 (4H, m,

2CH ₂ -CH =), 4.1 (2H, t, J = 7Hz, 20)

0CH ₂ ), 5.34 (2H, m, t, d, J 1 = 6Hz, J _d = 1Hz, CH = CH), 2.3 (1H, s,

OH, interchangeable with D ₂ 0).

MS: m / z 184 (2) (M), 168 (10), 166 (10) (M-H ₂ O);

140 (7) (M-CH ₂ CH ₂ CH ₃ ), 111 (15) (C ₁₅ H ₁₅ ), 25

110 (16), 97 (31) (C ₇ H ₁₃ ), 96 (34), (29), 83 (48), (68), 81 (40), 69 (60) (C _S H ₉ ), 55 (100) (C ₄ H ₇ ), (53), 41 (78).

Example 3

Preparation of 7 (Z) -Dodecene-1-O1 Acetate (II) a) 7-Dodecin-1-O1 Acetate (IX)

To a solution of 1.82 g (0.01 mol) of 7-dodecin-1-O1 (VIII: R = H) and 35 0.95 g (0.012 mol) of pyridine in dry tetrahydrofuran (5 ml) was added 1.12 g (0.011 mol). Acetic anhydride was added and the solution was stirred at room temperature for 1 hour. The reaction mixture was diluted with hexane (20 mL), neutralized with 1: 1 hydrochloric acid, washed with water (40 mL, 5 mL), dried, and after evaporation of the solvent, the residue was purified by column chromatography.

Yield: 2.1 g (92%)

TLC: hexane-ether 4: 0.3 Rf 0.5.

IR (film): 2900, 1740, 1440, 1370, 1240, 1040 ^cm-first 1 H-NMR (CCl ₄ ): 0.9 (3H, t, CH ₃ ), 1.4 (12H, m,

6CH ₂ ), 2.0 (3H, s, 2, 15 (4H, CH ₂ = CCH ₂ ), 4.0 (2H, t, J = 6Hz, O-CH ₂ ).

MS: m / z 228 (1) (M), 135 (3), 122 (9) (C ₉ H _t6, or C _g H _l2 O, or C ₇ H _e O _2), 96 (36) 93 (42), 81 (38), 79 (53), 67 (47), 55 (32), 54 (36), 44 (100).

b) 7 (Z) -Dodecene-1-01 acetate (II)

7-Dodecin-1-OO acetate (IX) (0.4 g, 0.0018 mol) was added to Pd-BaSO ₄ (10% w / w) prehydrogenated in 210 mg methanol (40 mL) and the mixture was pressurized to atmospheric pressure. hydrogenated. After uptake of an equivalent amount of hydrogen (50 mL, about 30 min), the catalyst was filtered off and the solvent was distilled off.

Yield: 0.39 g (95%).

TLC: hexane Rf 0.7.

IR (film): 2850, 1745, 1470, 1365, 1230, 1040, 960 cm in ^{the first}

1 H-NMR (CCl ₄ ): 0.9 (3H, t, J = 7Hz, CH ₃ ), 1.35 (12H, m, 6CH ₂ ), 2.05 (3H, s, CH 3 -CO) , 2.0 (4H, m,

-C == 2 CH _2), 4.05 (2H, t, J = 8Hz, _OCH2), 5.35 (2H, m, t, d, J = 6 Hz, J _d = 1Hz, CH == CH);

MS: m / z 226 (1) (M ⁺ ), 166 (35) (M-AcOH), 123 (12) (IC-CH-CH ₂ -CH ₃ ), 110 (33) (C ₈ H ₁₄ ). , (CH ₂ ) _e —CH = CH), 109, 96 (69), (C ₇ H ₁₂ ), 95 (42) (C ₇ H 10), 82 (89) (C ₆ H ₁₀ ), 81 ( 65) (C _e H "). 68 (46) (C _$ H _e ), 67 (80) (C ₅ H ₇ ), 55 (80) (C ₄ H ₇ ), 43 (100), (CH ₃ C = O), 41 (67) (C ₃ H ₅ ).

A patent claim

Claims (2)

A composition for attracting male gamma moths, characterized in that 50 to 99.8% by weight of 7 (Z) -dodecene-1-O-acetate and 50-0.2% by weight of 7 (Z) -dodecen-1-ol, preferably 80- 99.5% by weight of a mixture of 7 (Z) -dodecene-01-acetate and 20-0.5% by weight of 7 (Z) -dodecene-01 -01, optionally a liquid and / or solid excipient, preferably hexane 45, in addition to dichloromethane and / or viscous liquid, preferably sunflower oil or paraffin oil. 2 do drawing -6187,780 International Classification: A 01 N 31/02; C 07 C 60/007; C 07 C 33/025 -0-Chg-C ^ CH ^ ich Ig C H == £ -íc ^ _-CH3 R-O-CH ₂ -C = CH II III X-Ch ^ -lC ^ -CHg IV R-0-CH2-ChC- _{(CH2) 4-CH 3} V R-O-CH ^ -CH ^ -CsCH VI -7187 780 International Classification: A 01 N 31/02; C 07 C 69/007; C 07 C 33/025 X-CH _{2 -} (CH ₂ -CH ₃₎ VII R-O-CH ₂ - (CH ₂ ) ₅ -C = C- (CH ₂ ) ₃ -Ch ₃ Vili CH-C-O-CH ^ ich -CxC-tC ^^ - ChL