HU191379B - Process for producing of 9/z/-tetradecen-1-yl-acetate - Google Patents

Abstract

Insect attractant compsn. for control of male white agrotis (scotia segetum) contains (Z)-dodecen-1-ol acetate of formula - (I) - and 9(Z)-tetradecen-1-ol acetate of formula - (II) - in a wt. ratio of (I) to (II) of 50-99 to 50-1, esp. 70- 98 to 30-2. The active constituents may be used with suitable solid or liq. adjuvants. - Used for control of agrotis (Scotia segetum) on tobacco, sugar beet, cereals, etc. The synergistic compsn. may be used to attract and trap the male insects or may be sprayed into the atmos. to confuse the insects and prevent mating. When used to trap the insects 0.01-10 mg, pref. 0.1-3.0 mg, total of (I) and (II) may be used in conjunction with a suitable trap or captive device. When sprayed in the atmos. to prevent mating 5.0-30 mg/ka/hr., pref. 10.0-20.0 mg/ka/hr of active cpds. are used.

Description

The present invention relates to a method for preparing 9 (Z) -tetetradecenyl acetate of formula (I) for use as an active ingredient in a composition for attracting male sow moth (Scotia segetum).

Sowing moths are one of the most important owl moths in Hungary. Specifically a multi-nutrient species, it regularly causes annual damage to almost all crops, mainly tobacco, sugar beet, other vegetable crops, and cereals. They defended themselves against phosphoric ester derivatives, which, however, are highly toxic to organisms other than the pest and even to humans. The use of phosphoric acid ester derivatives against sow moths is also complicated by the fact that older caterpillars have a hidden lifestyle in the soil and are therefore less accessible to the agent.

By using the natural sexual attractant of the pest moth species, the sex pheromone formulation instead of, or in addition to, conventional chemical control, environmental pollution problems associated with the use of broad-spectrum insecticides can be avoided or reduced.

The female pheromone sex pheromone of sow moth has been withdrawn from the female Otto et al. [Arch. Phytopathol u. Plantenschutz, Berlin, 12, 197-212 (1976)] but its chemical composition has not been disclosed.

Our experiments have shown that the combination of 9 (Z) -tetradecen-1-yl acetate (I) and 7 (Z) -dodecen-1-yl acetate (II) results in a synergistic effect. , which, when used in insect pads, has a strong seductive effect on male specimens of sow moths.

Two methods for the preparation of 9 (Z) -tetradecen-1-yl acetate of formula (I) were developed by Bestmann et al. According to one method, Chem. Wage. 104, 65 (1971)] was prepared in eight steps from the monoethyl ester of azelaic acid. The reaction is not economical due to its high rate of step, low yield, and expensive reactants. According to another method, Chem. Wage. 108, 3582 (1975)], formed from oleic acid and subjected to ozonolysis in the presence of triphenylphosphine. The resulting 9-acetoxy-nonanalized triphenylpentylphosphonium salt was reacted with a solution of Iide in potassium dissolved in hexamethylphosphoric acid amide to give the compound of formula (I). The industrial applicability of the process is limited by the fact that it requires expensive ozone depletion, which also hinders the increase in size. A further disadvantage is that an equivalent amount of the costly triphenylphosphine is required, which cannot be recovered from the reaction mixture.

According to the invention, 9 (Z) -tetradecen-1-yl acetate is prepared by reacting 9 (Z) -octadecen-1-yl acetate in the presence of an aprotic solvent with hydrogen peroxide-octadecan-1-ol acetate in ether. The resulting 9-acetoxynonanal is reacted with a phosphorane formed from the compound of formula (III), wherein X is a halogen substituent with a strong base at a temperature of 50 ° C, and the resultant -1-II-acetate is recovered from the reaction mixture.

To prepare the starting material for the synthesis, 9 (Z) -octadecn-1-yl acetate, the corresponding alcohol is acetylated in a manner known per se. The acetate is conveniently reacted with a mixture of hydrogen peroxide and acetic acid in an aprotic solvent, preferably chloroform. The resulting 9,10-epoxy-octadecane-1-ol acetate is cleaved with peoic acid in an ether-type 2 solvent, preferably dioxane, and the resulting 9-acetoxy-nonanalane is reacted with a strong base phosphorane of the compound of formula (III). A strong base is preferably a mixture of sodium hydride and dimethylsulfoxide or potassium and hexamethylphosphoramide. The captured 9 (Z) -tetradecen-1-yl acetate is isolated from the reaction mixture by methods known per se (e.g., distillation).

The process of the invention is illustrated by the following example.

Example

9 (Z) -Octadecen-1-yl acetate

A mixture of 12 ml (102 g; 0.379 mol) of 9 (Z) -octadecen-1-ol, 80 ml (86.5 g, 0.85 mol) of acetic anhydride and 80 ml of dry pyridine was allowed to stand at room temperature overnight. The reaction mixture was poured into a mixture of 50 ml of 10% sulfuric acid and 150 g of crushed ice and extracted with methylene chloride (2 x 200 ml), washed again with water, dried, then the solvent was distilled off and the residue was distilled under vacuum.

Yield: 104 g (88.3%); mp: 165-168 ° C (1.33 mbar; 156 ° C / O, 53 mbar) 0.4 mm.

NMR (CCl 4): δ 0.85 (3H, t, J = 6Hz), 1.1-1.6 (24H, m), 2 (311, s), 2.05 (4H, m), 4 (2H, t, J = 6Hz), 53 (2H, m).

Ms: M ⁺ 310 (3), 251 (28), 250 (70), 223 (3), 222 (7), 195 (3), 180 (6), 166 (8), 152 (14), 151 (7), 138 (26), 137 (20), 124 (40), 123 (28), 111 (20), 110 (52), 109 (40), 97 (46), 96 (100), 95 (80), 83 (60), 82 (100), 81 (85), 70 (16), 69 (70), 68 (52), 67 (85), 61 (20), 55 (95).

9,10-Epoxy-octadecan-1-yl acetate g (0.129 mol) 9 (Z) -octadecen-1-yl acetate to a solution of 0.5 g of sodium acetate in 100 ml of acetic acid and 200 ml of chloroform at room temperature, vigorous stirring while 40 ml of 70% hydrogen peroxide was added dropwise over 15 minutes

After 10 minutes, the reaction temperature rises to 35-40 ° C. Stir for six hours and allow to stand for a few minutes. The separated chloroform layer was separated, washed twice with distilled water (200 mL), extracted with 2% sodium sulfite solution (100 mL), washed again with distilled water (100 mL), dried and the solvent was distilled off. The residue was evaporated in vacuo.

Yield: 27 g (64.2%); mp: 164-170 ° C / 0.67 mbar.

NMR (CCl ₄ ): δ 0.85 (3H, t, J = 6Hz), 1-1.8 (28H, m), (311, s), 2.7 (2H, m), 4 (2H, t, J = 6Hz).

Ms: M ⁺ 326 (5), 252 (6), 249 (3), 224 (8), 213 (20), 203 (7), 201 (32), 199 (3), 185 (5), 155 (40), 154 (5), 153 (18), 141 (30), 140 (10), Π9 (21), 138 (7), 137 (6), 135 (8), 125 (38), 124 (68), 123 (56), 122 (24), 113 (8), 112 (10), 111 (22), 110 (12), 109 (18), 98

-2191,379 (14), 96 (66), 95 (52), 84 (20), 83 (82), 82 (97), 81 (88), 71 (24), 70 (34), 69 (100 ), 68 (50), 67 (74), 61 (58), 57 (50), 56 (30), 55 (98).

To a solution of 9-Acetoxynonanal g (0.11 mol) crystalline periodic acid (HJO ₄ '2H ₂ O) in water (25 ml) was added 25 g (0.076 mol) of 0.10-epoxyloctadecan-1-yl acetate in 220 ml of dioxane. solution in ten minutes.

The reaction mixture was stirred at room temperature for one hour and then poured into water (11). The aqueous suspension was extracted twice with a total of 500 ml of light petroleum, washed with water, dried over magnesium sulfate, the solvent was distilled off and the residue was distilled under vacuum under a nitrogen atmosphere. By distillation, the first by-product of the reaction was a nonanal (b.p. 80-85 ° C) of 18.7 mbar; 9.75 g, 90%) followed by distillation of 9-acetoxynonanal. 20

Yield: 10.5 g (68.6%), b.p. 160-162 ° C / 18.7 mbar.

IR (NaCl): 1735, 1715, 1360, 1030 cm ^-1 .

NMR (CCl ₄ ): δ 1.2-1.9 (12H, m), 2 (3H, s) 2.4 (2H, m), (2H, t, J = 6Hz), 9.65 (1H , t, J = 2Hz).

9 (Z) -Tetradecen-1-yl acetate (I) 30

A mixture of 1.0 g (0.041 mol) of sodium hydride and 20 ml of dry dimethylsulfoxide was stirred under argon at 70 ° C until hydrogen evolution ceased (0.5-1 hour).

After cooling to room temperature, a solution of 35 g (0.036 mol) of pentyltriphenylphosphonium bromide (III) in X = Br / 35 ml of dry dimethylsulfoxide was added and the mixture was heated at 50 ° C for half an hour. agitated. The resulting red solution was cooled to room temperature and, after the dropwise addition of 5 g (0.025 mol) of 9-acetoxynanone, was stirred at room temperature for 4 hours and then allowed to stand overnight. The reaction mixture was poured onto 150 g of crushed ice and extracted three times with a total of 300 ml of hexane. The extract was washed with twice distilled water, dried over magnesium sulfate, the solvent was distilled off and the residue was distilled under vacuum.

Yield: 3 g (47%), mp 114-118 ° C] 0.27 mbar.

IR (NaCl): 1730, 1360, 1230, 1040 ^cm-first

NMR (CCl ₄ ): δ 0.85 (3H, t, J = 6Hz), 1-1.6 (16H, m), 1.95 (3H, s), 1.85-2.05 (4H) , m), 3.9 (2H, t J = 6Hz), 5.2 (2H, m).

Ms .: M ⁺ 254 (1.5), 194 (38.4), 166 (6.3), 152 (5.6), 138 (13.3), 124 (20.5), 110 (36 , 8), 96 (82.6), 82 (100).

Claims (1)

A patent claim A process for the preparation of 9 (Z) -tetradecen-1-yl acetate of formula (1) wherein the (9) Z-octadecen-1-yl acetate is conveniently reacted with a mixture of hydrogen peroxide acetic acid in the presence of an aprotic solvent. 10-Epoxy-octadecan-1-ol acetate is cleaved with periodic acid in an ether-type solvent to give 9-acetoxy-nonanal from the compound of formula (erős), wherein X is halogen, with a strong base at 20-50 ° C. and recovering the resulting 9 (Z) -tetradecen-1-yl acetate of formula (I) from the reaction mixture.