WO2005053409A1 - Insecticidal premix and process for the preparation thereof - Google Patents

Insecticidal premix and process for the preparation thereof Download PDF

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Publication number
WO2005053409A1
WO2005053409A1 PCT/HU2004/000113 HU2004000113W WO2005053409A1 WO 2005053409 A1 WO2005053409 A1 WO 2005053409A1 HU 2004000113 W HU2004000113 W HU 2004000113W WO 2005053409 A1 WO2005053409 A1 WO 2005053409A1
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Prior art keywords
carrier
insecticidal
premix
methoxy
antioxidant
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PCT/HU2004/000113
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French (fr)
Inventor
Ferenc JURÁK
Attila Kolbert
Miklós NEMES
László KOCSIS
János HANÁK
Sándor JANI
Lászlóné PATKOLÓ
Péter RUDOLF
Péter SLÉGEL
Original Assignee
EGIS Gyógyszergyár Rt.
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Priority claimed from HU0303919A external-priority patent/HU0303919D0/en
Priority claimed from HU0402446A external-priority patent/HUP0402446A2/en
Application filed by EGIS Gyógyszergyár Rt. filed Critical EGIS Gyógyszergyár Rt.
Publication of WO2005053409A1 publication Critical patent/WO2005053409A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N49/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds containing the group, wherein m+n>=1, both X together may also mean —Y— or a direct carbon-to-carbon bond, and the carbon atoms marked with an asterisk are not part of any ring system other than that which may be formed by the atoms X, the carbon atoms in square brackets being part of any acyclic or cyclic structure, or the group, wherein A means a carbon atom or Y, n>=0, and not more than one of these carbon atoms being a member of the same ring system, e.g. juvenile insect hormones or mimics thereof

Definitions

  • This invention relates to an insecticidal premix and a process for the preparation thereof. More particularly, the invention is directed to an insecticidal premix comprising isopropyl-S- (2E,4E)-1 l-methoxy-3,7,11-trimethyl-dodecadienoate as active ingredient and a process for the preparation thereof.
  • the fodder may contain vitamin additives, medicines and insecticidal active ingredient.
  • S-methoprene is a compound regulating the growth of insects which is environmental friendly and belongs to the group of so-called third generation of insecticidal active ingredient (IGR). It is known that S-methoprene possesses a wide spectrum of effects and according to prior art it is effective against a number of insect pests [Chamberlain et. al.: J. Econ. Ent. 81- 1420-1425 (1988); CA. Henrick et. al.: J. Agr. Food Chem. 21, 354-59 (1973), 24, 207-17 (1976), 24 542-550 (1978); L.S. Mian et. al.: J. Econ. Ent. 75, 80- (1982)]. The toxicity of S-methoprene is extremely low.
  • US patent 5,194,264 relates to a pesticidal composition in the form of a solution free of solid substances and emulsions.
  • a composition is described which comprises an active ingredient containing hydrophobic core and a phospholipide coating surrounding said core.
  • US patent 5,612,047 relates to a pesticidal microemulsion.
  • the object of the invention is to develop an S-methoprene containing premix.
  • the above object is solved with the aid of the present invention.
  • an insecticidal premix comprising isopropyl-S- (2E,4E)-1 l-methoxy-3,7,11-trimethyl-dodecadienoate of the Formula I as active ingredient, a carrier and an anti-oxidant.
  • the insecticidal premix of the general Formula I contains generally 5.0-12.0 % by weight, preferably 9.0-11.5 % by weight, particularly advantageously 10.0-10.5 % by weight of S-methoprene of the Formula I.
  • the conventional carriers generally used in premixes of this type can be used, preferably natural ground minerals, e.g. kaolin, clay, talc, chalk, silica, attapulgit, monmorillonit, diatomaceous earth and artificial ground minerals, e.g. high dispersity silicic acid, aluminium oxide and silicate.
  • natural ground minerals e.g. kaolin, clay, talc, chalk, silica, attapulgit, monmorillonit, diatomaceous earth
  • artificial ground minerals e.g. high dispersity silicic acid, aluminium oxide and silicate.
  • the insecticidal premix of the present invention contains as antioxidant preferably 2-tertiary butyl-4-methoxy-phenol or 3- tertiary butyl-4-methoxy-phenol of the Formula
  • the antioxidant content of the insecticidal premix of the present invention is generally 3-10 % by weight, preferably 4-7 % by weight, most advantageously 4.5-5.5 % by weight.
  • carrier silicium dioxide being iron-free and having a suitable water content is used.
  • the present invention is based on the recognition that the stability of S-methoprene applied onto a carrier is effected by iron-ions present on the surface of the carrier in an adverse manner. It has also been found that a reduction of the iron content of the carrier, particularly below the detection limit, improves the stability of the composition significantly.
  • the iron content is preferably not higher than 0.03 % (Fe 2 0 3 ) but according to a particularly preferred embodiment of the present invention the carrier contains no iron on the surface (see test methods; Example 8, par. 1).
  • the iron-ions can be removed by acidic treatment which can be preferably performed by using diluted aqueous hydrochloric acid. It has been found that on a carrier subjected to acidic treatment the stability of S-methoprene is significantly increased.
  • the stability of S-methoprene can be increased by using a carrier which has a suitable water content.
  • the stabilizing effect of water is so much the more surprising as during the preparation of the product no sterile conditions were used.
  • the water content of the carrier used in the insecticidal premix according to the present invention is preferably 4-12 by weight, particularly preferably 6-8 by weight which can be adjusted by drying to the desired water content.
  • a process for the preparation of an insecticidal premix which comprises applying onto the surface of a carrier isopropyl-S-(2E,4E)-l l-methoxy-3,7,11-trimethyl- dodecadienoate of the Formula I and an antioxidant simultaneously or stepwise.
  • carrier natural ground minerals e.g. kaolin, clay, talc, chalk, attapulgit, monmorillonit, silica, diatomaceous earth, or artificial ground minerals, e.g. high dispersity silicic acid, aluminium oxide or silicates can be used.
  • carrier particularly preferably silicium dioxide made iron- free and having a suitable water content
  • silicium dioxide made iron- free and having a suitable water content
  • the removal of iron and the adjustment of the water content can be performed as described above.
  • iron-free silicium dioxide particularly advantageously amorphous silicium dioxide
  • the removal of iron can be done preferably by using iron-free diluted hydrochloric acid and ion-exchanged water.
  • the process can be carried out by suspending silicium dioxide -preferably an amorphous silicate - containing superficial iron at room temperature in diluted hydrochloric acid, preferably in 5 % hydrochloric acid, then washing acid- free (preferably by suspending, sedimentation and decanting), thereupon it is filtered and dried.
  • the solid and liquid phases are preferably separated by decanting, because in this manner by choosing a suitable sedimentation time the amount of particles having a small particle size can be minimized and thereby the iron-free silicium dioxide can be easily recovered from the suspension.
  • the carrier made thus iron-free is subsequently dried.
  • the stability of S-methoprene applied on the carrier can be further increased by suitable adjustment of the water content. It has been found that the water content is preferably 4-12 by weight, particularly advantageously 6-8 by weight.
  • the S-methoprene active ingredient and the antioxidant can be applied onto the carrier in one or two steps.
  • One-step coating can be carried out by preparing a homogeneous solution of the S-methoprene of the Formula I and an antioxidant, whereupon said solution is applied onto the surface of the carrier with the aid of usual homogenizing equipment.
  • the active ingredient and in the second step the antioxidant is applied onto the surface of the carrier.
  • Application of the antioxidant of the Formula II can be preferably carried out by slightly warming of the mixture because butylated hydroxy anizol is a greasy, soft substance consisting of soft crystals from which a homogeneous coating can already be prepared at a temperature below the melting point. This step is preferably carried out at 35-55°C, particularly advantageously at 50-55°C.
  • solvent-free coating is that the step of energy-consuming drying can be eliminated.
  • the homogeneity of the coating thus formed is monitored by micro-analytical methods and the stability of the product is determined by HPLC methods. Said methods are disclosed in the examples.
  • the advantage of the present invention is that it enables the solvent-free preparation of a stable, homogeneous S- methoprene containing premix which has good flowability.
  • amorphous silicate containing 0.0.3 % of superficial iron are suspended in 5000 g of 5 % aqueous hydrochloric acid.
  • the suspension is diluted to double of its volume, allowed to sediment for 20 minutes, whereupon the slightly opaque upper layer is filtered off in vacuo.
  • the diluting and stirring steps are repeated twice whereupon at least 90 % of the hydrochloric acid added are removed.
  • the superficial iron is dissolved in the form of ferric (III) chloride and can be removed with hydrochloric acid.
  • the residual thick suspension is diluted with 1000 ml of water, whereupon the pH is adjusted to 5.5-7.0 by adding a 4 % sodium hydroxide solution.
  • the mixture is filtered, whereupon the precipitate on the filter is dried as follows:
  • amorphous silicate is dried after removal of iron to a moisture content of 2.5 by weight.
  • Example 4 For use in Example 4 the amorphous silicate is dried after removal of iron to a water content of 9.5 by weight.
  • the homogeneity of the product is measured before the addition of butylated hydroxy anizol and at the end of the homogenizing period from 5 samples each. This is necessary because the stability test provides reliable results only if homogeneous samples are used.
  • Example 2 One proceeds as described in Example 2 except that S- methoprene and the antioxidant of the Formula II are applied onto the surface of the carrier in one step.
  • a homogeneous solution is prepared from S-methoprene and butylated hydroxy anizol at 45°C and said solution is applied onto the surface of the carrier.
  • the homogeneity of the coating thus prepared is measured according to Example 8.
  • the homogeneity of the sample is excellent.
  • Example 2 One proceeds as described in Example 2 except that as carrier amorphous silicate having a water content of 9.5 by weight is used. Homogenization is carried our for 7 hours each.
  • the homogeneity of the product is measured before the addition of butylated hydroxy anizol and at the end of the homogenizing period from 5 samples each as described in Example 2.
  • the homogeneity of the product obtained is excellent.
  • Example 2 One proceeds as described in Example 2 except that as carrier amorphous silicate not subjected to the iron-removal method of the present invention (iron content 0.03 by weight) is used.
  • the water content of the vehicle is 3.5 %.
  • the homogeneity, of the product is measured before the addition of butylated hydroxy anizol and at the end of the homogenizing period from 5 samples each as described in Example 2.
  • the homogeneity of the product is excellent.
  • Example 8 results of the stability test carried out as described in Example 8.
  • the S-methoprene content is determined by HPLC methods. The results are summarized in Table 5.
  • the stability of the product is determined by the HPLC method described in Example 8.
  • amorphous silicate 1 g are suspended in 5 ml of 1 : 1 diluted hydrochloric acid.
  • the suspension is filtered, whereupon the iron content is determined in a usual manner by using an iron measuring solution (Ph.Hg. VII. Volume I).
  • a "background” measurement is carried out by applying the hydrochloric acid used for suspending.
  • Amorphous silicate is an inorganic substance which does not contain carbon atoms. From the carbon content of the product formed after coating measured by micro-analytical methods one can conclude to the homogeneity of the coating.
  • Eluent Reference solution 50 mg of racemic methoprene are weighed in a 50 ml volumetric flask with analytical accuracy, whereupon it is dissolved in 40 ml of eluent, filled up to the mark and homogenized. Concentration of the solution: about 0.5 mg/ml (S)-methoprene. about 0.5 mg/ml (R)-methoprene.
  • Sample solution 250 mg of the sample are weighed into an 50 ml centrifugal tube. 40 ml of methanol are added, the mixture is shaken for 15 minutes, allowed to stand for 16 hours, shaken again for 15 minutes, whereupon it is centrifuged with 2000 r.p.m. for 10 minutes and the supernatant phase is measured. Concentration of the solution: about 0.5 mg/ml (S)-methoprene.

Abstract

The invention relates to an insecticidal premix comprising as active ingredient isopropyl-S-(2E,4E)-11-methoxy-3,7,11-trimethyl-dodecadienoate of the Formula (I), a carrier and an antioxidant. As carrier preferably silicium dioxide made iron-free and having a suitable water content can be used. The insecticidal premix of the present invention can be prepared by applying onto the surface of a carrier isopropyl-S-(2E,4E)-11-methoxy-3,7,11-trimethyl-dodecadienoate of the Formula I and an antioxidant simultaneously or stepwise.

Description

Insecticidal premix and process for the preparation thereof
FIELD OF THE INVENTION
This invention relates to an insecticidal premix and a process for the preparation thereof. More particularly, the invention is directed to an insecticidal premix comprising isopropyl-S- (2E,4E)-1 l-methoxy-3,7,11-trimethyl-dodecadienoate as active ingredient and a process for the preparation thereof.
TECHNICAL BACKGROUND
It is known that during feeding of animals several food additives can be administered to the organism of the animals. Thus the fodder may contain vitamin additives, medicines and insecticidal active ingredient.
It is also known that various fly species (Diptera species) lay their eggs into the fresh animal faeces. It is known further on that faeces can be treated by subsequent spraying or by passing an active ingredient through the digestive canal of the animal. The active ingredient can be administered into the digestive canal either with the fodder or the drinking water, or in case of cattle with the licking salt. It is known that isopropyl-S-(2E,4E)-l l-methoxy-3,7,11- trimethyl-dodecadienoate of the Formula
Figure imgf000003_0001
(S-methoprene) is a compound regulating the growth of insects which is environmental friendly and belongs to the group of so-called third generation of insecticidal active ingredient (IGR). It is known that S-methoprene possesses a wide spectrum of effects and according to prior art it is effective against a number of insect pests [Chamberlain et. al.: J. Econ. Ent. 81- 1420-1425 (1988); CA. Henrick et. al.: J. Agr. Food Chem. 21, 354-59 (1973), 24, 207-17 (1976), 24 542-550 (1978); L.S. Mian et. al.: J. Econ. Ent. 75, 80- (1982)]. The toxicity of S-methoprene is extremely low.
In patent literature various types of insecticidal compositions comprising racemic methoprene are known.
US patent 5,194,264 relates to a pesticidal composition in the form of a solution free of solid substances and emulsions. In US patent 5,221,535 a composition is described which comprises an active ingredient containing hydrophobic core and a phospholipide coating surrounding said core.
US patent 5,612,047 relates to a pesticidal microemulsion.
In US patent 5,660,844 a means for providing the sustained release of the pesticidal active ingredient is described, said means being adjustable on the neck or the ear of the animals.
In WO 98/05210 and WO 98/05211 and in European patent application EP-A 516,590 the effect of S-methoprene exerted against flea and the use thereof for the prevention of flea infection in the hair of various host animals (dogs, cats) is described.
SUMMARY OF THE INVENTION
The object of the invention is to develop an S-methoprene containing premix. The above object is solved with the aid of the present invention.
According to an aspect of the present invention there is provided an insecticidal premix comprising isopropyl-S- (2E,4E)-1 l-methoxy-3,7,11-trimethyl-dodecadienoate of the Formula I as active ingredient, a carrier and an anti-oxidant.
DETAILED DESCRIPTION OF THE INVENTION
The insecticidal premix of the general Formula I contains generally 5.0-12.0 % by weight, preferably 9.0-11.5 % by weight, particularly advantageously 10.0-10.5 % by weight of S-methoprene of the Formula I.
The conventional carriers generally used in premixes of this type can be used, preferably natural ground minerals, e.g. kaolin, clay, talc, chalk, silica, attapulgit, monmorillonit, diatomaceous earth and artificial ground minerals, e.g. high dispersity silicic acid, aluminium oxide and silicate.
The insecticidal premix of the present invention contains as antioxidant preferably 2-tertiary butyl-4-methoxy-phenol or 3- tertiary butyl-4-methoxy-phenol of the Formula
Figure imgf000006_0001
The antioxidant content of the insecticidal premix of the present invention is generally 3-10 % by weight, preferably 4-7 % by weight, most advantageously 4.5-5.5 % by weight.
According to a particularly advantageous embodiment of the present invention as carrier silicium dioxide being iron-free and having a suitable water content is used.
The present invention is based on the recognition that the stability of S-methoprene applied onto a carrier is effected by iron-ions present on the surface of the carrier in an adverse manner. It has also been found that a reduction of the iron content of the carrier, particularly below the detection limit, improves the stability of the composition significantly. The iron content is preferably not higher than 0.03 % (Fe203) but according to a particularly preferred embodiment of the present invention the carrier contains no iron on the surface (see test methods; Example 8, par. 1). The iron-ions can be removed by acidic treatment which can be preferably performed by using diluted aqueous hydrochloric acid. It has been found that on a carrier subjected to acidic treatment the stability of S-methoprene is significantly increased. In this manner a stable S-methoprene containing coating can be formed on the surface of the silicium dioxide carrier. This recognition is very surprising because on testing the decomposition of racemic methoprene on a glass surface a high light-sensitivity was observed [G.B. Quistad et. al. J. Agr. Food Chem. 21, 299-303 (1975)]. It is known that the most frequently used "normal glass" contains 73 % of silicium dioxide [O.-A. Neumϋller: Rδmpp vegyeszeti lexikon (ROMPPS CHEMIE LEXIKON), published by Mύszaki Kδnyvkiadό, Budapest, (1984)].
It has been found furtheron that the stability of S-methoprene can be increased by using a carrier which has a suitable water content. The stabilizing effect of water is so much the more surprising as during the preparation of the product no sterile conditions were used. According to prior art, on testing the aqueous metabolism of racemic methoprene, it has been found that during 9 days of storage a 56 % hydrolysis took place as a result of microbiological effect [D. A. Schooley et. al. J. Agr. Food Chem. 23, 293-298 (1975)]. The water content of the carrier used in the insecticidal premix according to the present invention is preferably 4-12 by weight, particularly preferably 6-8 by weight which can be adjusted by drying to the desired water content.
According to a further feature of the present invention there is provided a process for the preparation of an insecticidal premix which comprises applying onto the surface of a carrier isopropyl-S-(2E,4E)-l l-methoxy-3,7,11-trimethyl- dodecadienoate of the Formula I and an antioxidant simultaneously or stepwise.
According to the process of the present invention as carrier natural ground minerals, e.g. kaolin, clay, talc, chalk, attapulgit, monmorillonit, silica, diatomaceous earth, or artificial ground minerals, e.g. high dispersity silicic acid, aluminium oxide or silicates can be used.
One may proceed particularly preferably by using as carrier silicium dioxide, particularly advantageously amorphous silicate.
As carrier particularly preferably silicium dioxide made iron- free and having a suitable water content can be used. The removal of iron and the adjustment of the water content can be performed as described above.
According to a preferred embodiment of the present invention iron-free silicium dioxide, particularly advantageously amorphous silicium dioxide can be used. The removal of iron can be done preferably by using iron-free diluted hydrochloric acid and ion-exchanged water. The process can be carried out by suspending silicium dioxide -preferably an amorphous silicate - containing superficial iron at room temperature in diluted hydrochloric acid, preferably in 5 % hydrochloric acid, then washing acid- free (preferably by suspending, sedimentation and decanting), thereupon it is filtered and dried. The solid and liquid phases are preferably separated by decanting, because in this manner by choosing a suitable sedimentation time the amount of particles having a small particle size can be minimized and thereby the iron-free silicium dioxide can be easily recovered from the suspension.
The carrier made thus iron-free is subsequently dried. As already mentioned above, the stability of S-methoprene applied on the carrier can be further increased by suitable adjustment of the water content. It has been found that the water content is preferably 4-12 by weight, particularly advantageously 6-8 by weight. The S-methoprene active ingredient and the antioxidant can be applied onto the carrier in one or two steps.
One-step coating can be carried out by preparing a homogeneous solution of the S-methoprene of the Formula I and an antioxidant, whereupon said solution is applied onto the surface of the carrier with the aid of usual homogenizing equipment.
In case of two-step coating preferably in the first step the active ingredient and in the second step the antioxidant is applied onto the surface of the carrier. Application of the antioxidant of the Formula II can be preferably carried out by slightly warming of the mixture because butylated hydroxy anizol is a greasy, soft substance consisting of soft crystals from which a homogeneous coating can already be prepared at a temperature below the melting point. This step is preferably carried out at 35-55°C, particularly advantageously at 50-55°C. The significant advantage of solvent-free coating is that the step of energy-consuming drying can be eliminated.
The homogeneity of the coating thus formed is monitored by micro-analytical methods and the stability of the product is determined by HPLC methods. Said methods are disclosed in the examples.
The advantage of the present invention is that it enables the solvent-free preparation of a stable, homogeneous S- methoprene containing premix which has good flowability.
Further details of the present invention are to be found in the following Examples without limiting the scope of protection to said Examples.
Example 1
1000 g of amorphous silicate containing 0.0.3 % of superficial iron are suspended in 5000 g of 5 % aqueous hydrochloric acid. The suspension is diluted to double of its volume, allowed to sediment for 20 minutes, whereupon the slightly opaque upper layer is filtered off in vacuo. The diluting and stirring steps are repeated twice whereupon at least 90 % of the hydrochloric acid added are removed. The superficial iron is dissolved in the form of ferric (III) chloride and can be removed with hydrochloric acid. The residual thick suspension is diluted with 1000 ml of water, whereupon the pH is adjusted to 5.5-7.0 by adding a 4 % sodium hydroxide solution. The mixture is filtered, whereupon the precipitate on the filter is dried as follows:
a) For use in Examples 2 and 3 amorphous silicate is dried after removal of iron to a moisture content of 2.5 by weight.
b) For use in Example 4 the amorphous silicate is dried after removal of iron to a water content of 9.5 by weight.
As a result of the above removal of iron it has been found according to the test described in Example 8 the superficial iron content of the amorphous silicate is decreased below detection limit.
Example 2
416 g of amorphous silicate prepared according to Example 1 (water content 2.5 by weight) and 58.6 g of S-methoprene are mixed in a rotating homogenizer for 12 hours whereupon 25 g of butylated hydroxy anizol of the Formula II are added. The temperature of the mixture is raised to 50-55°C whereupon stirring is continued for a period of 12 hours.
The homogeneity of the product is measured before the addition of butylated hydroxy anizol and at the end of the homogenizing period from 5 samples each. This is necessary because the stability test provides reliable results only if homogeneous samples are used.
The homogeneity of the product prepared according to Example 2 is shown in Table 1. Line C(I) represents the results obtained after the application of S-methoprene, while line C(II) indicates the results obtained after the application of S- methoprene and butylated hydroxy anizol. (The C-values indicate the carbon content.) In view of the characteristics of the method used (very small product weight of some mg are used) the low relative deviation of about 2-3 % is very good.
Table 1
Figure imgf000014_0001
Example 3
One proceeds as described in Example 2 except that S- methoprene and the antioxidant of the Formula II are applied onto the surface of the carrier in one step. A homogeneous solution is prepared from S-methoprene and butylated hydroxy anizol at 45°C and said solution is applied onto the surface of the carrier.
The homogeneity of the coating thus prepared is measured according to Example 8.
The results obtained are summarized in Table 2. Table 2
No. of 2 2 3 4 5 Relative sample deviation C 12.67 12.85 12.48 12.82 12.66 2.8 %
The homogeneity of the sample is excellent.
Example 4
One proceeds as described in Example 2 except that as carrier amorphous silicate having a water content of 9.5 by weight is used. Homogenization is carried our for 7 hours each.
The homogeneity of the product is measured before the addition of butylated hydroxy anizol and at the end of the homogenizing period from 5 samples each as described in Example 2.
The results obtained are summarized in Table 3.
Table 3
Figure imgf000016_0001
The homogeneity of the product obtained is excellent.
Example 5 (Reference Example)
One proceeds as described in Example 2 except that as carrier amorphous silicate not subjected to the iron-removal method of the present invention (iron content 0.03 by weight) is used. The water content of the vehicle is 3.5 %.
The homogeneity, of the product is measured before the addition of butylated hydroxy anizol and at the end of the homogenizing period from 5 samples each as described in Example 2.
The results are shown in Table 4. Table 4
Figure imgf000017_0001
The homogeneity of the product is excellent.
Example 6
In this example the results of the stability test carried out as described in Example 8 are disclosed. The S-methoprene content is determined by HPLC methods. The results are summarized in Table 5.
Table 5
Figure imgf000017_0002
It can be seen from Table 5 that the best results are obtained when using amorphous silicate made iron-free according to the present invention and having a high water-content (Example 4). It has also been found that when using untreated amorphous silicate prepared according to Example 5 (iron content: 0.03 %, water content 3.5 %) the stability decrease of the product is significantly higher than that of the premix treated according to the present invention.
Example 7 Use of further antioxidants
A) 48 g of amorphous silicate having a suitable water content and a solution of 2.5 g of propyl gallate and 5.5 g of S- methoprene are mixed on a rotating homogenizer at 50-55°C for 20 hours. After preparing the coating the homogeneity of the product is measured according to the method described in Example 8.
The results obtained are summarized in Table 6.
The stability of the product is determined by the HPLC method described in Example 8.
The results are summarized in Table 7. B) One proceeds as described in Example 7/A) except that as antioxidant in place of propyl gallate 2.5 % of 2,6-di-tertiary butyl-4-methyl-phenol are used.
C) One proceeds as described in Example 7/A) except that as antioxidant in place of propyl gallate 2.5 g of E-vitamin are used.
Table 6
Figure imgf000019_0001
Table 7
Figure imgf000019_0002
Example 8 Analytical methods
1. Determination of iron content
1 g of amorphous silicate are suspended in 5 ml of 1 : 1 diluted hydrochloric acid. The suspension is filtered, whereupon the iron content is determined in a usual manner by using an iron measuring solution (Ph.Hg. VII. Volume I). A "background" measurement is carried out by applying the hydrochloric acid used for suspending.
2. Determination of homogeneity
Amorphous silicate is an inorganic substance which does not contain carbon atoms. From the carbon content of the product formed after coating measured by micro-analytical methods one can conclude to the homogeneity of the coating.
3. Determination of stability (HPLC method)
Apparatus: HP 1100 Autosampler HP 1100 Quaternery Pump HP 1100 Variable Wavelength Detector HP 1100 Column Thermostat HP l lOO Degasser
Characteristics ofchromatographic methods:
Mobile phase: Methanol: water = 98:2 Detector: UV detector 210 nm Injection: Volume: 10 μl Flow rate: 1 ml/min. Column pressure: max. 300 bar Stationary phase: Regis Val-u-pak HP 18.5 μm Column size: 25 cm x 4.6 mm Column temperature: room temperature Separating method: isocratic Evaluation: Performed under optimal integration conditions by HP ChemStation software
Solutions:
Background solution: Eluent Reference solution: 50 mg of racemic methoprene are weighed in a 50 ml volumetric flask with analytical accuracy, whereupon it is dissolved in 40 ml of eluent, filled up to the mark and homogenized. Concentration of the solution: about 0.5 mg/ml (S)-methoprene. about 0.5 mg/ml (R)-methoprene.
Sample solution: 250 mg of the sample are weighed into an 50 ml centrifugal tube. 40 ml of methanol are added, the mixture is shaken for 15 minutes, allowed to stand for 16 hours, shaken again for 15 minutes, whereupon it is centrifuged with 2000 r.p.m. for 10 minutes and the supernatant phase is measured. Concentration of the solution: about 0.5 mg/ml (S)-methoprene.

Claims

What we claim is,
1. Insecticidal premix comprising as active ingredient isoproρyl-S-(2E,4E)-l l-methoxy-3,7,11-trimethyl- dodecadienoate of the Formula
Figure imgf000023_0001
a carrier and an antioxidant.
2. Insecticidal premix according to Claim 1 comprising as carrier silicium dioxide.
3. Insecticidal premix according to Claim 2 comprising as carrier amorphous silicate.
4. Insecticidal premix according to any of Claim 1-3 comprising as antioxidant 2-tertiary butyl-4-methoxy-phenol or 3 -tertiary butyl-4-methoxy-phenol of the Formula
Figure imgf000024_0001
5. Insecticidal premix according to Claim 1 comprising as carrier silicium dioxide made iron-free and having a suitable water content.
6. Process for the preparation of insecticidal premix which comprises applying onto the surface of the carrier isopropyl-S- (2E,4E)-1 l-methoxy-3,7,11-trimethyl-dodecadienoate of the Formula I and an antioxidant simultaneously or stepwise.
7. Process according to Claim 6 which comprises silicium dioxide as carrier.
8. Process according to Claim 7 which comprises using amorphous silicate as carrier.
9. Process according to any of Claim 6-8 which comprises using as antioxidant 2-tertiary butyl-4-methoxy-ρhenol or 3- tertiary butyl-4-methoxy-phenol of the Formula II.
10. Process according to Claim 6 which comprises using as carrier silicium dioxide made iron-free and having a suitable water content.
11. Process according to Claim 10 which comprises using as carrier silicium dioxide made iron- free with aqueous hydrochloric acid.
PCT/HU2004/000113 2003-12-02 2004-12-02 Insecticidal premix and process for the preparation thereof WO2005053409A1 (en)

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Publication number Priority date Publication date Assignee Title
CN102349513A (en) * 2011-10-31 2012-02-15 湖南中烟工业有限责任公司 Biological insecticide containing methoprene as well as preparation and application methods thereof

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