JPH0672961A - New ester of (1r(1alpha,3beta(z)))-2,2-dimethyl-3-(2-fluoro -3-methoxy-3-oxopropenyl)cyclopropanecarboxylic acid, its production and its use as agent for controlling noxious living organism - Google Patents

Abstract

PURPOSE: To obtain a new compound useful as an insecticide such as noxious insects, nematodes or mites.

CONSTITUTION: This compound of [1R[1α,3β(Z)]]-2,2-dimethyl-3-(2-fluoro-3- methoxy-3-oxopropenyl)cyclopropane-carboxylic acid(4-methoxymethyl-2,3,5,6- tetrafluoro)phenylmethyl is obtained by allowing (4-methoxymethyl-2,3,5,6- tetrafluoro)-benzylalcohol (functional derivative) to act on [1R[1α,3β(Z)]]-2,2- dimethyl-3-(2-fluoro-3-methoxy-3-oxopropenyl)cyclopropane-carboxylic acid (functional derivative).

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to [1R [1α, 3β
(Z)]]-2,2-Dimethyl-3- (2-fluoro-
It relates to a new ester of 3-methoxy-3-oxopropenyl) cyclopropanecarboxylic acid, a process for its production and its use as a pest control agent.

[0002]

SUMMARY OF THE INVENTION Therefore, the subject matter of the present invention is [1R [1
α, 3β (Z)]]-2,2-Dimethyl-3- (2-fluoro-3-methoxy-3-oxopropenyl) cyclopropanecarboxylic acid (4-methoxymethyl-2,3,3)
5,6-tetrafluoro) phenylmethyl (hereinafter referred to as compound A).

[0003]

BACKGROUND OF THE INVENTION Compound A is described in European Patent 0281
It is part of a group of known compounds described in No. 439.
This patent describes, among other things, the 1R, cis, ΔE stereoisomer corresponding to Compound A in Example 37 (hereinafter referred to as Compound B).

Here, compound A, which has not been synthesized so far, has a remarkable insecticidal activity, particularly, good insecticidal activity against flies and cockroaches, while it is orally administered to mammals. It has been found to have very low toxicity by both oral and intravenous administration. Therefore, compound A
Can be used as an insecticide indoors or outdoors for humans and animals, and as a place to store cereals and other products for food for humans and animals.

[0005] Therefore, Compound A is, for example, Jean-Jean in the yearbook of the 1986 “PARASITIS” conference.
As noted by Tessier, it meets the following generally accepted ecological criteria for the use of pesticides: "1. It is preferred to use the isomer with the highest potency rather than in the form of a mixture. This avoids diluting the activity with less potent insecticidal components. They are present in the environment. Can prove to be undesirable over the long term 2. Use as much of the costly chemical synthesis reaction as possible in terms of energy, solvent and reagents to produce the most effective structure and not the others. As we approach the end of the 20th century, obtaining inactive isomers is obsolete and wasteful from an economic standpoint: in short, users (especially in agriculture) have improved. It is preferable to benefit from compounds with increased potency due to isomeric purity, which takes into account stereochemical factors in order to obtain maximum activity. In addition, this method is commonly practiced for many types of drugs. "

The subject of the present invention is [1R [1α, 3
β (Z)]]-2,2-Dimethyl-3- (2-fluoro-3-methoxy-3-oxopropenyl) cyclopropanecarboxylic acid or a functional derivative of this acid with (4-methoxymethyl-2,3 , 5,6-Tetrafluoro) benzyl alcohol or a functional derivative of this alcohol is acted on. The acid used as starting material is described in EP 50534.
No. The alcohol used as a starting material is described in US Pat. No. 4,370,346.

Compound A has valuable properties which make it possible to use it for combating parasites. For example, they are effective in combating plant parasites and other pests, house nesting parasites and other pests and warm-blooded animal parasites. Therefore, compound A
Can be used for the control of plant and animal parasites pests, nematodes and drabs. In particular, the subject of the invention is the use of compound A for combating plant parasites, house nesting parasites and warm-blooded animal parasites.
Thus, the compound A can be used for combating pests in the field of agriculture, for example for combating larvae of the aphid, Lepidoptera and Coleoptera, and also for controlling pests in soil. It is 10g-300g per hectare
Used in amounts of active substance between. Compound A can also be used to control pests nesting in houses, especially flies, mosquitoes and cockroaches. Furthermore, Compound A is not toxic to mammals.

Compound A can also be used to combat the plant parasites acaridae and nematodes. In addition, Compound A is used to control animal parasites such as ticks, for example ticks, especially Boophilus spp. Hyalomnia.
) Species mites, Amblyomnia species mites, Phipicephalus mites control,
It can be used for the extermination of all kinds of mite, in particular sarcoptic mite, psoroptic mite and chorioptic mite. Accordingly, a subject of the invention is a composition for combating warm-blooded animal parasites, house nesting parasites and plant parasites, characterized in that it contains compound A.
In particular, a subject of the invention is an insecticide composition containing compound A as active ingredient. These compositions according to the invention are manufactured by the customary methods of the agrochemical industry, the veterinary medicine industry or the animal feed product industry.

In agricultural and home compositions, one or more other pesticides or synergists can be added to the active substance. These compositions may be powders, granules, suspensions, emulsions, solutions, aerosol solutions, flammable strips, poison baits, pyrolyzers (smoke pots) or other applications commonly used for compounds of this type. It can be provided in the form of a formulation. In addition to the active ingredient, these compositions generally contain, inter alia, a vehicle and / or a nonionic surfactant which allow a uniform distribution of the ingredients making up the mixture. The vehicle used is
Water, alcohols, hydrocarbons or other organic solvents, minerals, liquids such as animal or vegetable oils, talc, clay, powders such as silicates or diatomaceous earth, or combustible solids or nutritive or non-nutritive. It may be a suction substance. The insecticide composition according to the invention is preferably 0.005-1.
It contains 0% by weight of active substance.

For home use, in a useful embodiment, the compositions according to the invention are used in the form of fuming compositions. Then,
The composition according to the invention may consist of a flammable insecticide coil or a non-flammable fibrous base material for the non-active part. In the latter case, the smoke agent obtained after incorporating the active substance is placed in a heating device such as an electric mosquito trap. If an insecticide coil is used, the inert carrier may be, for example, pyrethrum cake, tab powder (Machilus thumber
gil leaf powder), pyrethrum trunk powder, cedar needle powder, wood flour (pine sawdust), starch and palm shell powder. In that case, the dose of active substance is, for example, 0.03 to 1% by weight. If a non-flammable fibrous substance carrier is used, the active substance dose may be, for example, 0.03 to 95% by weight. Also, the composition of the present invention for homes can be obtained by making a spraying oil mainly composed of an active ingredient and impregnating the oil into a lamp core, which is then burned. The concentration of the active ingredient incorporated in this oily substance is preferably 0.03 to 95% by weight.

Like the pesticides and nematicides, the pesticide compositions according to the invention can optionally be supplemented with one or more other pesticides. . Acaricides and nematicides are provided especially in the form of powders, granules, suspensions, emulsions, solutions or gels. For acaricide application, a foliar spray wettable powder containing 1 to 80% of the active ingredient, or a foliar spray liquid preparation containing 1 to 500 g / l of the active ingredient is preferably used. . 0.0
Leaf spray powders containing 5 to 3% of active substance can also be used. For nematicides, 300-500g /
A soil treatment solution containing 1 of the active ingredient is used.
The acaricidal and nematicidal compounds according to the invention are preferably used in a dose of 1 to 100 g of active substance per hectare.

To increase the biological activity of the compounds of the present invention, standard synergists used in such cases, such as 1- (2,5,8-trioxadodecyl)-
2-propyl-4,5-methylenedioxybenzene (piperonyl butoxide), or N- (2-ethylheptyl) bicyclo [2.2.1] -5-heptene-2,3-
Dicarboxamide, or piperonyl-bis-2- (2 '
-N-Butoxyethoxy) ethyl acetal (tropital) can be added. Also, compound A exhibits excellent systemic tolerance and therefore the subject of the present invention is the subject of ticks mite, especially in humans and animals.
s) in compound A as a drug for controlling the disorders caused by s). Compound A can be used to combat lice in particular, either prophylactically or therapeutically, and to combat scabies. The agents of the invention can be applied externally, by spraying, shampooing, bathing or applying. In addition, the veterinary medicine of the present invention can be administered by applying it to the back by a method called the "pour-on" method.

The subject of the invention is also the active substance:
Compound A and, on the other hand, chrysanthemic acid and allethlorone, 3,
4,5,6-Tetrahydrophthalimidomethyl alcohol, 5-benzyl-3-furylmethyl alcohol, 3-
Esters with phenoxybenzyl alcohol and α-cyano-3-phenoxybenzyl alcohol; 2,2-
Ester of dimethyl-3- (2-oxo-3-tetrahydrothiophenylidenemethyl) cyclopropane-1-carboxylic acid and 5-benzyl-3-furylmethyl alcohol; 2,2-dimethyl-3- (2,2 -Dichlorovinyl) cyclopropane-1-carboxylic acid esters of 3-phenoxybenzyl alcohol and α-cyano-3-phenoxybenzyl alcohol; 2,2-dimethyl-
3- (2,2-dibromovinyl) cyclopropane-1-
Ester of carboxylic acid and α-cyano-3-phenoxybenzyl alcohol; Ester of 2-p-chlorophenyl-2-isopropylacetic acid and 3-phenoxybenzyl alcohol; 2,2-Dimethyl-3- (1,2,2 2, 2
-Tetrahaloethyl) cyclopropane-1-carboxylic acid (where halo represents a fluorine, chlorine or bromine atom) and allethlorone, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, 5-benzyl-3-furylmethyl Alcohol, 3-phenoxybenzyl alcohol and α
Containing at least one pyrethrinoid ester selected from the group consisting of each ester with -cyano-3-phenoxybenzyl alcohol (wherein compound A and the acid and alcohol bond pairs of the above pyrethrinoid ester are all of them) A possible stereoisomeric form of), a composition having insecticidal, acaricidal or nematicidal activity.

The following examples illustrate the invention without limiting it in any way.

Example 1 : [1R [1α, 3β (Z)]]-
2,2-Dimethyl-3- (2-fluoro-3-methoxy-3-oxopropenyl) cyclopropanecarboxylic acid (4-methoxymethyl-2,3,5,6-tetrafluoro) phenylmethyl 1.4 g of dicyclohexylcarbodiimide , 60 mg
4-dimethylaminopyridine and 10 cc of methylene chloride are added to 1.3 g of [1R [1α, 3β (Z)]]-
2,2-dimethyl-3- (2-fluoro-3-methoxy-3-oxopropenyl) cyclopropanecarboxylic acid,
It is introduced at 0 ° C. ± 5 ° C. into a mixture containing 1.5 g of (4-methoxymethyl-2,3,5,6-tetrafluoro) benzyl alcohol and 60 cc of methylene chloride.
Hold the reaction mixture at 0 ° C ± 5 ° C for 15 minutes and increase the temperature to 20 ° C.
C. and the reaction mixture is kept at this temperature for 20 hours.
After filtration and concentration, the product obtained is chromatographed on silica, in a hexane-ethyl acetate mixture (85-
Elute with 15). After evaporating the solvent and drying, 2.
Obtained 05 g of the desired compound. [Α] _D = -12 ° ± 1 ° (c = 0.75%, CHCl
₃ ) NMR spectrum (CDCl ₃ , 250 MHz) H of methyl pair: 1.24 (s); 1.32 (s) H of the 1- and 3-positions of cyclopropane: 1.74 (dmJ =
5.5); 2.44 (dd, J = 5.5 and 10.5) M: methyl of methoxymethyl H: 3.41 (s) H: 3.82 (s) of methyl ester of methylene of methoxymethyl H: 4.59 (t) benzyl H: 5.25 (t) propenyl double bond H: 5.85 (dd, J = 10.
5 and 31)

Biological activity A) Study of insecticidal action on soybeans The pests used are four-day-old female soybeans. The operation is
It is carried out by direct spraying in a Kerns-March chamber at a concentration of 0.1 g / l. The test compound is dissolved in a mixture of 5% acetone and Isopar L (petroleum solvent) and sprayed with 2 ml of solution per second. Use 50 flies per treatment. Check every minute for 10 minutes, then 1
Do after 5 minutes. Time (minutes) when 50% of the flies were killed KT
Determine ₅₀ . The following results were obtained.

[0017]

[Table 1]

B) Knockdown effect on cockroaches The test was conducted on 12-week-old male cockroaches (Blattella german
ica). The operation is carried out by direct spraying in a glass chamber with a diameter of 13.5 cm. The test compound is a solution of Isopar. Spray the pre-positioned 20 dogs in the room with 0.75 ml of the solution in 2.5 seconds. Determine the KD (% knocked down cockroach) after 5 minutes at a dose of 100 mg / l. The following results were obtained.

[0019]

[Table 2]

C) Toxicity Studies on Mammals Toxicity by oral and intravenous administration was tested in rat rats by standard methods. Results are expressed as mg of active ingredient per kg of animal body weight. The following results were obtained.

[0021]

[Table 3]

D) Conclusion As described above, the compound A has activity comparable to that of the compound B, but has a considerably lower toxicity to mammals than the compound B.

Example of Composition of the Invention a) A spray formulation having the following formulation was prepared. Compound A: 0.1 g Deodorized petroleum: 99.9 g b) An aerosol agent having the following formulation was prepared. Compound A: 0.20 g Piperonyl butoxide: 1.0 g Methylene chloride: 7 g Deodorized petroleum: 21.80 g Propellant: 70.0 g c) An emulsifiable concentrate was prepared. Compound A: 2 g BHT (2,6-di-t-butyl-4-methylphenol): 0.1 g Acetic acid: 0.01 g Calcium dodecylbenzenesulfonate: 4 g Polyoxyethylenated castor oil: 4 g Cellosolve 100: 89. 89 g

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Pierre Pastel Marseille, France, Ryu Paradis, 550 (54) [Title of Invention] [1R [1α, 3β (Z)]]-2,2-Dimethyl- New ester of 3- (2-fluoro-3-methoxy-3-oxopropenyl) cyclopropanecarboxylic acid, its production method and its use as a pest control agent

Claims (4)

[Claims] 1. [1R [1α, 3β (Z)]]-2,2
-Dimethyl-3- (2-fluoro-3-methoxy-3-
(Oxopropenyl) cyclopropanecarboxylic acid (4-methoxymethyl-2,3,5,6-tetrafluoro) phenylmethyl. 2. A pesticide composition containing the compound according to claim 1 as an active ingredient. 3. An insecticide composition containing the compound according to claim 1 as an active ingredient. 4. [1R [1α, 3β (Z)]]-2,2
-Dimethyl-3- (2-fluoro-3-methoxy-3-
Oxopropenyl) cyclopropanecarboxylic acid or a functional derivative of this acid with (4-methoxymethyl-2,3,3
A process for the preparation of a compound according to claim 1, characterized in that 5,6-tetrafluoro) benzyl alcohol or a functional derivative of this alcohol is allowed to act.