JP3004888B2 - Plant protection formulation containing neofuan and azaneofuan - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
es) and water-dispersible powders (wetting agents) containing azaneophanes.

[0002]

BACKGROUND OF THE INVENTION Active substances from the group consisting of neophanes and azaneophanes are insects, arachnids and nematodes found in the field of pests, especially agriculture, forestry, protection of stored articles and materials, and hygiene. It is suitable for controlling insects and has little phytotoxicity to plants. They are effective against normally susceptible and resistant species and against whole or individual developmental stages (EP-A-224,024, EP 2 224
49,015 and 288,810). These documents also describe conventional formulations for insecticides or acaricides.

[0003] Particularly developed formulations of neophanes and azaneofuans for various crops and fields of application are described in European Patent Application Nos. 443,405 (concentrated aqueous emulsions) and in 443,412 (highly concentrated aqueous emulsions). Emulsions), 443,411 (water-dispersible granules) and DE-A-3,828,339 (stabilized powders).

[0004] In order to control pests in the cultivation of fruits and tea in Asia, especially in Japan, there is a need for water-dispersible powders, also called spray powders or wettable powders (WP).

[0005]

SUMMARY OF THE INVENTION Neophanes and azaneofuans, especially Silafluofen
Is a highly pulverulent storage preparation in liquid form, but a solid powdery preparation in which the liquid active substance is adsorbed on finely divided inert substances such as highly dispersed silica and aluminum silicate. Degradation is often observed in objects. Degradation of the active substance is particularly pronounced after storage of the sprayable powder formulation under warm conditions, for example after 14 days at 54 ° C. and after 3 months at 50 ° C. (see Table I). This property has already been observed for formulations as non-dispersible powders. [DE 38 28 339, "Stable powdered formulations of neofuans and azaneofuans (Stabile staubfoer)
mige Formulierungen von Neophanen und Azaneophane
n) "). The method for stabilizing these powders containing a low proportion of active substance (dilution of the active substance using certain high-boiling solvents) is described above in relation to the wettable powders containing a relatively high proportion of active substance. In the case of can not be used.

[0006]

Surprisingly, the present inventors have achieved a remarkable stabilization of neofuan and azaneofuan wettable powders by adding a combination of polypropylene glycol and bicarbonate. I found that it could be.

Accordingly, the present invention provides a compound of formula I

[0008]

Embedded image

(Wherein A and B are the same or different and each independently CH, CR ₄ or N
X is CH ₂ , O or S, Y is CH or N, Z is H or F, R ₁ and R ₄ are the same or different and are each independently H, Halogen, (C ₁ -C ₃ ) -alkyl, (C ₁ -C ₃ ) -haloalkyl, (C ₁ -C ₃ ) -alkoxy, (C ₁ -C ₃ ) -haloalkoxy, (C ₁ -C ₄ ) -Alkylthio or (C ₁ -C ₄ )-
Is haloalkylthio, or R ₁ and R ₄ together are —CH ₂ —O—CH ₂ —, and R ₂ is H, (C ₁ -C ₃ )
-Alkyl, ethynyl, vinyl, halogen or cyano, R ₃ is H, halogen, (C ₁ -C ₄ ) -alkyl or (C ₁ -C ₃ ) -alkoxy, and M is C or Si ) And novel compositions of plant protection products containing a combination of polyglycols and bicarbonates.

Alkyl is a linear or branched alkyl group. Haloalkyl is an alkyl group in which some or all of the hydrogen atoms have been replaced by halogens, as well as groups derived therefrom, such as haloalkylthio. Halogen is fluorine, chlorine,
It is to be understood as meaning bromine or iodine, especially fluorine or chlorine.

Preferably, in Formula I, A and B are
The same or different and is CH or N, X is CH ₂ , R ₁ is (C ₁ -C ₃ ) -alkoxy, R ₂ is H, R ₃ is H or F and M is Si.

Particularly preferred among the compounds of formula I are those wherein M is Si, R ₁ is ethoxy, and A
And B are each CH, X is CH ₂ , R
₂ is H, Y is CH, Z is F, and R ₃ is H (silaffluofene (silaf
luofen); formula Ia].

[0013] The polyglycol preferably used is polypropylene glycol. The polypropylene glycol used for the purpose of stabilization is 300 to 100
It has an average molar mass of 0 Dalton. The preferred ones are
Polypropylene glycol 750 with an average molar mass of 730-800 daltons, especially 750-760 daltons. The hydroxyl number (DIN 53240) of polypropylene glycol 750 is 140-154
mgKOH / g, preferably 147 to 148 mgKOH
/ G.

Since the above polypropylene glycols are all liquids, they are wettable powders (wettable powders).
It must be adsorbed on an adsorbent carrier material before it can be used as a formulation). For this purpose, customary finely distributed colloidal aluminum and / or magnesium silicates, such as bleaching earth, bentonite, fuller's earth (comprising attapulgite and montmorillonite), or diatomaceous earth, celite or precipitated, Spray-dried and optionally ground silica can be used. Preferably, in particular in the absorbent by milling, ^(R) Sipernat ^{((R) Sipernat)}
Spray dried silica, such as 50S (from Degussa).

In order to stabilize the neofuan and azaneofuan wettable powders, it is generally preferred to use 0.5 to 10% by weight of polyglycol, for example a 1: 1 adsorbate to carrier. 0 to 20% by weight is used. Particular preference is given to using 3.0 to 5.0% by weight of polypropylene glycol, ie 6.0% to 9.0% by weight of adsorbate, based on the absorbent silica.

The addition of adsorbates, such as the above-mentioned polypropylene glycols, to neofuan and azaneofuan wettable powders, already provides significant stabilization of the active substance after storage under warm conditions, but is not sufficient by itself. (See Table III).

However, when a bicarbonate, preferably an alkali metal bicarbonate, is further added, almost complete stabilization of the neophanes and azaneophanes in the wettable powder is achieved. Preference is given to using sodium bicarbonate and potassium bicarbonate. The use of sodium bicarbonate is particularly preferred. In principle, 0.5 to 12% by weight of bicarbonate is required, with 3 to 5% by weight being preferred.

Addition of only bicarbonate does not provide sufficient stabilization (see Table II). The addition of the mixture of polypropylene glycol and bicarbonate acting as a stabilizer can be in an amount of 1.0 to 22% by weight, or polypropylene mixed with bicarbonate adsorbed 50% on absorbent silica. In the case of glycols, the amount may be from 1.5 to 32% by weight.

For example, to stabilize 20% of neofuan and azaneofuan wettable powders, 3.0 to 5.0% by weight of sodium bicarbonate and ^(R) cypernat (
It is preferred to use a mixture of ^(R) Sipernat) 50S with 6% to 9% by weight of a 50% adsorbate of polypropylene glycol 750 supported on 50S.

The polypropylene glycol - by using the up Symbol mixed compound of Le and bicarbonate, degradation of the active substance in Shirasuruofuen based wettable powder after storage temperate conditions is completely prevented when the real That is, after 14 days at 54 ° C. , 5 months at 40 ° C. and 3 months at 50 ° C., and 2 years of storage at room temperature (22 ° ± 5 ° C.), no noticeable decomposition of the active substance occurs. Not observed ( see Table IV).

The above interactions are illustrated in the following tables:

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3]

[0025]

[Table 4]

The present invention also relates to a process for the preparation of the above-mentioned formulation, characterized in that the components are mixed in one or more steps. The invention furthermore treats pests or infested plants or cultivated lands with an effective amount of the formulation after diluting the formulation as defined by the invention to a concentration suitable for use. The present invention also relates to a method for controlling pests as described above.

For the preparation of wettable powders, known wetting and dispersing agents are used in order to obtain good wettability and dispersibility in water. Examples of wetting agents that may be used are: sodium diisobutylnaphthalenesulfonate [eg from BASF
^(R) Nekaru ^{((R) Nekal)} BX, Rhone-Poulenc, Inc. (Rh
one Poulenc) made of ^(R) Supurajiru ^{((R) Supragil)} N
K], sodium oleyl methyl tauride [for example, ^(R) Hostapon ( ^(R) Hostap manufactured by Hoechst AG)
on) T], α- C ₁₄ - C ₁₉ - olefinic sodium sulfonate [e.g., Hoechst (Hoechst AG) made of ^(R) Hosutapuru ^((R) Hostapur) OS], secondary C ₁₃ - C ₁₇ -
Alkanesulfonate (for example, Hoechst A
G) made of ^(R) Hosutapuru ^((R) Hostapur) SAS], isodecyl sodium sulfosuccinate [e.g., Hoechst (Hoechst AG) manufactured Nettsua (Netzer) IS]. In principle, the wetting agent is from 0.1 to 8.0% by weight, preferably from 0.2 to 3.0% by weight.

[0028] Examples of dispersants which can be used, calcium lignosulfonate, highly refined sodium lignosulfonate [e.g., Boregado Inc. (Borregard) manufactured by ^(R) Vani sparse ^{((R) Vanisperse)} CB], Hoechst (Hoechst
AG) made of SI and SS dispersing agent, sodium salt / formaldehyde condensation products of naphthalenesulfonic acid [e.g., DeSoto, Inc. (Desoto) made of ^(R) molar wet ^((R) Morw
et) D425 or BASF (BASF) made of ^(R) Tamol ^{((R) Tamol)} NN8906], sodium polycarboxylate [e.g., Rhone Poulenc (Rhone Poulenc) made of ^(R) Sopuropon ^((R) Sopropon ) T36]. In principle, they represent from 1 to 15% by weight of the formulation, preferably from 3 to 11% by weight.

To improve rain resistance, partially hydrolyzed polyvinyl acetate, which acts as an adhesive, for example,
^(R) Mowiol ( ^{(R) M} Mo manufactured by Hoechst AG)
wiol) 4/88 and ^{( R)} Mowiol
18/88) is mixed into the wettable powder. As a rule, the adhesive is 0.5 to 3.0% by weight, preferably 1 to 2%.
It is added in an amount of 5% by weight.

The adsorbents used for the oily liquid neophanes and azaneofuans are finely divided aluminum and / or magnesium silicates, such as kaolin, bleaching earth, bentonite, fuller's earth or diatomaceous earth, celite. Or precipitated, spray-dried and optionally ground silica, such as
^(R) Sipernat is ^{((R) Sipernat)} 50S. Mixtures of the above sorbents are also used. In principle, they represent from 45 to 80% by weight of the formulation, preferably from 50 to 75%.

[0031]

The following examples illustrate the invention without limiting it. Production Examples General description for evaluating and producing the above wettable powders.

Suspendability
Indicates the amount (% by weight) of the formulation found in 9/10 parts by volume above the suspension in water after the settling time of 30 minutes has elapsed [CIPAC Handbook Vol. 1 (1970)
Yearly, p. 861 (CIPAC Handbook Vol. 1 (19
70), p. 861). Example 1 First, in the blade type mixer plow ^(R) Sipernat ^((R) Sipe
rnat) 50S liquid active substance silafluofen (I
A 40% powder concentrate is prepared by adsorbing a). Add the necessary formulation aids to the concentrate and mix the batch until homogeneous. It is then ground in a pin disk mill at 12000 rpm.

The resulting wettable powder has the following composition: ^(R) Sipernat ^{((R) Sipernat)} 40% on 50S silafluofen adsorbate 50.0 wt% = silafluofen 20.0 wt% ^(R) Hosutapon ^{((R) Hostapon)} T 0.5 wt% ^(R) Vani sparse ^{((R) Vanisperse)} CB 5.0 wt% ^(R) Mowiol ^{((R) Mowiol)} 18/88 2.0 wt% kaolin 1777 42.5% by weight The total suspension (TS) is 72.2%. After storage for 14 days at 54 ° C. and 3 months at 50 ° C .: 0 degree of suspension (flocking by addition of water).

After storage at 54 ° C. for 14 days, the active substance decomposes from an initial value of 19.5% to <0.1%: after 14 days at 54 ° C., the silafluofene content is from 19.5% to 2.5%. It drops to 5%. Example 2 Preparation is as described in Example 1. The composition and properties of this wettable powder can be known from Table I. Example 3 Preparation is as described in Example 1. The composition of this formulation: ^(R) Sipernat ^{((R) Sipernat)} 40% on 50S Shirafuruo divorce adsorbate 50.0 wt% = silafluofen 20.0 wt% ^(R) Hosutapon ^{((R) Hostapon) T 0} . 5 wt% ^(R) Vani sparse ^{((R) Vanisperse)} CB 5.0 wt% sodium bicarbonate 4.0% by weight kaolin 1777 40.5 wt% TS = 54 82.7% after 14 days at ° C., TS = -
(Flocculation) After 3 months at 50 ° C., TS = − (Flocculation) Silafluofene content: Initial value: 19.5% After 14 days at 54 ° C .: 12.0% After 3 months at 50 ° C .: 2.1 % Examples 4 to 8 were prepared analogously to Example 1.

The composition and properties of these wettable powders are shown in Table I
I. Example 9 Preparation is as described in Example 1. The composition of the wettable powder formulations: ^(R) Sipernat ^{((R) Sipernat)} 40% of Shirafuruo divorce adsorbate 50.0 wt% on the 50S = silafluofen 20.0% by weight of calcium lignosulfonate 10.0 wt% ^(R) Hosutapon ^((R) Hostapon) T 1.0 wt% ^(R) Sipernat ^((R) Sipernat) 50% adsorbate 7.0 wt% kaolin of polypropylene glycol 750 on 50S 1777 32.0 wt% TS = 77.1%, after 14 days at 54 ° C, TS = 7
6.0% after 3 months at 50 ° C., TS = − (Flocculation) Silafluofene content: Initial value: 19.4% after 14 days at 54 ° C. 19.1% 17.7% after 3 months at 50 ° C. Example 10 To 13 are prepared as described in Example 1.

The compositions and properties of these formulations are listed in Table I
II. Example 21 The manufacture is similar to Example 1. Composition 40% silafluofen adsorbate 50.0 wt% = silafluofen 20.0 wt% ^(R) Vuanisupasu ^{((R) Vanisperse)} CB 5.0 wt% ^(R) Hosutapon ^{((R) Hostapon)} T 0.5 wt% ^(R) Sipernat ^((R) Sipernat) 50% adsorbate 7.0 wt% sodium bicarbonate 4.0% by weight of polypropylene glycol 750 on 50S kaolin 1777 33.5 wt% TS = 93.2%, 40 ℃ 5 months later, TS = 9
After 2 years at 0.5% room temperature (22 ° C. ± 5 ° C.), TS = 92.1
% Silafluofene content: Initial value: 21.6% After 5 months at 40 ° C., 21.3% After 2 years at room temperature (22 ° C. ± 5 ° C.) 21.5% Examples 14-20 and 22 It is manufactured in a similar manner.

The composition and properties of these silafluofene-based wettable powders can be known from Table IV.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ identification code FI A01N 43/40 101 A01N 43/40 101F 43/54 43/54 A (58) Investigated field (Int.Cl. ⁷ , DB name) ) A01N 55/00 A01N 25/22 A01N 31/14 A01N 43/40 A01N 43/54

Claims (10)

(57) [Claims] 1. A compound of the formula I Wherein A and B are the same or different and are each independently CH, CH ₄ or N; X is CH ₂ , O or S; Y is CH or N; Z is H or F, R ₁ and R ₄ are the same or different and each independently represents H, halogen, (C ₁ -C ₃ ) -alkyl,
(C ₁ -C ₃ ) -haloalkyl, (C ₁ -C ₃ ) -alkoxy,
(C ₁ -C ₃ ) -haloalkoxy, (C ₁ -C ₄ ) -alkylthio or (C ₁ -C ₄ ) -haloalkylthio, or R ₁ and R _{4 taken} together as CH ₂ -O -CH _2- , wherein R ₂ is H, (C ₁ -C ₃ ) -alkyl, ethynyl, vinyl,
R ₃ is H, halogen, (C ₁ -C ₄ ) -alkyl or (C
₁ -C ₃₎ - alkoxy, and M is a compound represented by a is) C or Si, plant protection formulations containing polyethylene glycol and bicarbonates. 2. In the formula I, A and B are the same or different and are each independently CH or N, X is CH ₂ , and Y and Z have the same meanings as in claim 1. R ₁ is (C ₁ -C ₃ ) -alkoxy;
₂ is H, R ₃ is H or F, and M is S
2. The composition of claim 1, wherein i is i. 3. In formula I, A and B each represent C
H, X is CH ₂ , Y is CH, and Z is F
R ₁ is ethoxy, R ₂ is H, R ₃
Is H, and M is Si. 4. The method according to claim 1, further comprising an adsorptive carrier.
A composition according to any one of the preceding claims. 5. The polyglycol of 300 to 1
5. The formulation according to claim 1, which comprises a polypropylene glycol having an average molar mass of 000 daltons. 6. The preparation according to claim 1, which comprises sodium hydrogencarbonate or potassium hydrogencarbonate as the hydrogencarbonate, preferably sodium hydrogencarbonate. 7. 0.5 to 10% by weight of polypropylene glycol, 0.5 to 12% by weight of bicarbonate, 0.5 to 10% by weight of an adsorbent carrier and optionally 1 to 10% by weight.
2. The composition according to claim 1, which contains one or more additives or auxiliaries, preferably those selected from the group consisting of wetting agents, dispersants and adhesives, wherein the preparation is in the form of a water-dispersible powder. A formulation according to any one of the preceding claims. 8. Use of a combination of polyglycol and bicarbonate for stabilizing a compound of formula I as defined in any one of claims 1 to 3. 9. A process for the preparation of a formulation according to claim 1, wherein the components are mixed in one or more steps. Method. 10. A method for controlling pests, comprising diluting an effective amount of the composition according to any one of claims 1 to 7 to a concentration suitable for its use. Or treating an infested plant or cultivated land.