CS209201B1 - Insecticide and its semisynthetic method of manufacture - Google Patents

Abstract

A process for the production of 2-acetyloxymethyl-5-acetyloxypyr-4- one comprises stationary or submergely cultivating penicillium sp. at 27 DEG C on the Czapek-Dox liquid media, extracting the supernatant and purifying it with methanol, adjusting the pH of said purified supernatant to 1.8 in order to crystallise out 2-hydroxymethyl-5- hydroxypyr-4-one and acetylating said compound with acetic anhydride in anhydrous pyridine. The substance is useful in insecticidal formulations.

Description

(54) The insecticide and its semi-synthetic production method

BACKGROUND OF THE INVENTION The present invention relates to an insecticidal composition for the preparation of an insecticide the protection of agricultural and aquaculture cultures against pests of a wide spectrum containing I as active substance [5-acetyloxy-2-acetyloxymethyl- | pyron- (4)] of the formula:

and its semi-synthetic method of production.

Fighting harmful insects is one of the most serious tasks of the world today. Population ⁴ , increasing demands on the quantity of food produced on the one hand, toxicity, low Specificity, danger of biosphere pollution by residues of synthetic chlorinated insecticides of DDT type, organophosphorus compounds, their cumulative and thus toxic effect in higher organisms, against these substances, on the other hand, are updating Madame's new ways of protecting agricultural plant crops from insect pests. The alarming phenomena of the universal spread of chlorinated preparations in the bodies of organisms, as a result of the gradual contamination of the food chain, are pushing the way of plant protection to the fore, with new, non-human and biodegrading preparations. This has been confirmed by research into bacterial and fungal toxins in practice. Natural insecticides of the aflatoxin and destruxin type are described in detail today. Known is the toxin produced by Bacillus thuringiensis, which produces endotoxin - crystalline formations. parasporal bodies containing a very toxic protein toxin. Various lecithinases, proteases and other enzymes have proven interesting.

The above-mentioned disadvantages are overcome by an insecticidal composition which contains [5-acetyloxy-2-acetyloxymethyl-pyrrone- (4)] of the formula as active ingredient:

dilution with acetone 1: 1, centrifugation at 5000 rpm. min ^-1 ,

I 209201 ............-........ - .......................... . ......

Stage výMálezu insektiddný composition was prepared by semi-synthetic process which is characterized in that the submerged or _stadonámou: kultivádou Penidlium sp. at 27 ° C on Czapek-Doxovom liquid medium followed extrakdou preferably acetone, and the other of purifikádou metanolům rekryátalizádou a pH of 1.8 is prepared [5-Hydroxy-2-hydroxy-metylpyron- (4) J, and _L is is further acetylated with acetic anhydride in anhydrous pyridine. Unreacted [5-hydroxy-2-hydroxymethylpyrone- (4)] is separated from the ballasts by acetylate and returned to the reaction cycle after concentration.

The following examples illustrate a process for producing an insecticide composition according to the invention and may characterize and confront! its properties.

EXAMPLE

a) Ϊ i [5-hydroxy-2-hydroxymethylpyrrone- (4) J - Fermentation method of preparation

Penidllium sp. (Collection No. 29, Collection of Microorganisms of the Department of Low-Molecular Biology, Institute of Molecular Biology of the Slovak Academy of Sciences, Bratislava) was cultured at 27 ° C for 14 days in 2000 ml Roux flasks per 200 ml Czapek- Dox's liquid medium. or in a submerged manner in laboratory tanks of 14 l of the above-mentioned above, for 5 days at a temperature of 27 ° C at room temperature ^. Agitation 150 ^min-1 and ¹ prevzduáňovaní 10 liters per minute. The mycelium, together with the fermentation liquid in an amount of 2800 ml, was homogenized; The mixture was centrifuged at 3000 rpm. min ^-1 , 10 min.

Further steps of the isolation of [5-hydroxy-2-hydroxymethyl-pyrrolidone (4)] according to the invention are given in the following, ¹ scheme:

supernatants

preparation of a saturated solution in distilled water at 90 ° C, acidification with HCl (5 mol. ^{1 1} ) to pH = 1.8; recrystallization from methanol [5-hydroxy-2-hydroxymethylpyrone- (4) J crystals]

In addition to the qualitative analytical reactions with FeCl ₃ , resp. with Fehling solutions, melting point determination, ultraviolet and infrared spectrum spectra of the compound. Comparison of the obtained data, together with the infrared and ultraviolet spectrum spectra, with the literature data was consistent (melting point: 152 ° C, UV absorption:

217.269 nm). The sum formula (C11H10N2) and the molecular weight (142.11) were determined by high resolution mass spectrometry.

) -

b)

The second stage of production according to the invention is acetylate with acetic anhydride in the anhydrous pyridine medium under the reaction:

2 (СН> С0)> 0

ABOUT

II

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In a 100 ml Erlenmeyer flask equipped with a stirrer and cooled to 0 ° C, 2.7 g (5-hydroxy-2-hydroxymethylpyrone- (4)) was mixed with 5.9 g acetic anhydride and 20.3 g pyridine. The reaction mixture was stirred for 4 hours at 0 [deg.] C. The precipitated white crystalline [5-acetyloxy-2-acetyloxymethylpyrone- (4)] was filtered, dried and recrystallized from methanol and washed from the traces, respectively. pyridine and several times with ether cooled to 4 ° C.

^On the original reaction mixture, after vacuum evaporation, respectively. it precipitates unreacted [5-hydroxy-2-hydroxymethylpyrone- (4)], thereby separating from any ballasts, which is capable of returning to the reactor for further acetylate. _______________ 'Evidence of the identity of the chemical synthesized'';

individuals were melting point, recording spectrum in ultraviolet and. IR (melting point: 102-103 ° C, absorption in UV spectrum: 212.255 nm). The sum formula (ОюНюОб) and molecular weight ´ (226,18) were determined by high resolution mass spectrometry.

Insecticidal. active chemical individual [5ί acetyloxy-2-acetyloxymethylpyrone- (4)] is well [soluble in ethanol, butanol, heated to 50 ° C, | it is possible to convert the substance prepared according to the invention into solutions, emulsions, etc. It is not necessary to 'combine the preparation' with other pesticide active substances ._________________________________ _______ _________ ___________ _______

Example 2 ..........

The insecticidal activity of [5-acetyloxy-2-acetyloxymethylpyrone- (4)] was determined using a model- | It is an organism from the range of agricultural and fruit pests, Scotch segetum Den. et Schiff.

Solutions of the title compound in ethanol. were prepared in graduated concentrations and added to the cultivation platform for cultivation of Scotia segetum Den larvae. et Schiff. In a set of 20 Petri dishes, 1 Scotia segetum Den larva was added for each concentration. et Schiff, 'just after hatching i; and the ontogenesis of said insect species was monitored over 60 days under optimal culture conditions. From the percentage of dead animals from the control group relative to · log-likelihood value of the fixed network ₅ 0 ED ED 50 value calculated from the equation fj registered ^^ snej line is shown in Table 1 .__

Table 1 ......

Example 3 ..... ......

: To assess toxicity of compound [5-acetyloxy-2- | 2-acetyloxymethylpyrone- (4)] according to the invention against pests of agricultural and fruit crops, for higher organisms, a method was used to determine acute toxicity. H, male mice of strain H were used as a model organism i 2 ° —25 8 ·. .. _v . !

Solutions of the title compound were prepared in. Six graduated concentrations and were administered intraperitoneally to 10 animals in each group. At 24 hours, the mortality of the animals was determined, the percentage of which, relative to the control group, the LD50 value was calculated on the logarithmic likely probability. LD50 value calculated from the regression line is shown in Table 2.

Table 2

compound Form of application LD50 ⁽ mg ^/ kg) ^ ^ Acetyloxy -acetyloxymetylpyron- (4)] i. p. 1,650.0 parathion (standard) per os 10.5

j Insecticidal product. according to the invention has a preferred form of application, maintained in the environment; biological activity in relatively small concentrations, is not toxic to higher animals, does not appear to have the cumulative effect of chlorinated organic hydrocarbons, has the ability to decompose into simple 1 non-toxic products capable of being included in the cycle of biogenic elements. in nature.

The semisynthetic production of the insecticide composition of the invention consists of undemanding fermentation technology with an accessible form of intermediate isolation and simple organic synthesis of the product, and thus predetermines its low cost.

Possibility of use is mainly in areas where increased concentration of insects is expected, e.g. in livestock production facilities, agricultural holdings, in farming; donations and fruit growing.

Claims (3)

OBJECT OF THE INVENTION . An insecticidal composition characterized in that it is an active ingredient. Contains [5-acetyloxy-2-acetyloxymethylpyon- (4)] of the formula: ^ ^ Acetyloxy -acetyloxymetylpyron- (4)] COMPOUND ED501 (ug. 895 О О ° ⁸ ° ^CHa CHF-O-C-O ^ ^ CHF ; ...... 8 ________________________- -..... ..... ’ 2. A method according to claim 1, characterized in that Penicilium sp. is cultured stationary or submerged at 27 ° C on a Čzapek-Oxo liquid medium, the supernatant is preferably extracted with acetone and further purified with methanol, and after adjusting the pH to 1.8 it is recrystallized and prepared [5-hydroxy-2-hydroxymethylpyrone] - (4) J is acetyl-I. is with acetic anhydride in anhydrous pyridine. -. Ί 3. The process according to claim 1 or 2, characterized in that unreacted [5-hydroxy-2-hydroxymethylpyrone- (4)] is separated from the ballasts by acetylate and returned to the reaction cycle after concentration.