HU189820B - Arthropocide preparations with improved duration of effect containing 4-amino-benzoic acid-ester-derivatives as photostabilizer - Google Patents

Abstract

The photodegradation of pyrethroid active agents in arthropodicide prepns. is suppressed by the incorporation of 4-amino-benzoic acid-ester derivs. in the wt. ratio range 40:1 to 1:20 with respect to the pyrethroid component. - In the formula R1 and R2 stand for hydrogen, methyl or ethyl, R3 is an alkyl or cyclo-alkyl gp. with 1-8 carbons, opt. substd. with an alkoxy gp. having 1-4 carbons.

Description

The present invention relates to compositions for controlling arthropods (insects and mites) which contain pyrethroids as the active ingredient of arthropodd and possibly other active ingredients of arthropodd (insecticide and / or acaricide) and excipients appropriate to the nature of the composition.

The improved potency of these formulations is achieved by providing photostability of the pyrethroid component by the addition of 4-aminobenzoic acid ester derivatives.

Eddis was also known to have chemical analogues of naturally occurring pyrethrins (pyrethrin I, II, cinerin I, II, etc.), the so-called pyrethroids, as one of the most potent arthropods currently known, that they are only slightly toxic to warmbloods.

However, although pyrethroid molecules are very stable in the dark, they are rapidly degraded by light, just like natural basic compounds, and so, especially in agriculture, the largest user of arthropods, pyrethroids have been able to replace the previously used chlorinated hydrocarbons, organic phosphoric acid esters.

Therefore, previously synthesized pyrethroids (tetramethrin, bioresmethrin, etc.) have been used almost exclusively for the control of health insect pests, in formulations (aerosols, fumigants, dusting agents, etc.) that require rapid killing, long-lasting effects are of little importance and are exposed.

Attempts have been made to eliminate this disadvantageous feature of pyrethroids by successfully microencapsulating them. In a comparative study of the effect of microencapsulated and non-encapsulated bioresmethrin poison fields with otherwise the same active ingredient concentration, only a small reduction in effect was seen after three months, whereas in the last two weeks virtually no efficacy was lost (GWBstett / ES, , 14-20, 1979). However, microencapsulation makes the formulations extremely expensive, so their use is only exceptionally possible - in the field of health care - and therefore, such formulations are rarely encountered even today.

They have also attempted to synthesize pyrethroid molecules that are highly resistant to light. Research to this end has yielded significant results in the preparation of compounds that significantly exceed the photostability of natural pyrethrins and the first generator of pyrethroids (M.Eliott, Pontifacae Sdenciarum Scripto Varia 41 157-175, 1977).

These are the new so-called. Photostable pyrethroids (permethrin, dpermetin, deltamethrin, fenvalerate) are already suitable for use in agriculture and are undergoing extensive research worldwide for the synthesis of additional photostable pyrethroids.

However, photostable pyrethroids are considered to be only photostable relative to natural pyrethrins and to previously synthesized pyrethroids, their photosensitivity is still quite significant and the efficacy of their formulations is largely limited by the photodegradation limit. A permethrin pl. (Which is a more glossy representative of photostable pyrethroids), applied to various specimens for approx. it loses its effect twice as fast as illumination (6,000 lux) than in darkness (The Wellcome Foundation Ltd., Berjhamsted, 1975).

It is therefore clear that any enhancement of the photostability of the active ingredient in any pyrethroid-containing formulation can significantly improve the efficacy and durability of the control of the formulation, and is thus highly advantageous.

The present invention is based on the discovery that pyrethroid-containing arthropodd formulations enhance the photostability of a 4-aminobenzoic acid ester derivative of formula (I) (Figure 1), and consequently the compositions retain their arthropodd activity for a much longer period of time. , as a preparation containing the same pyrethroid but not containing 4-aminobenzoic acid ester. In addition, some of these compounds (e.g., cycloaliphatic 4-aminobenzoic acid esters) significantly increase the activity of pyrethroid drugs.

The discovery of the beneficial effects of 4-aminobenzoic acid ester derivatives has led to the surprising observation that ethyl 4-aminobenzoate (benzocaine) mixed with a wide variety of pyrethroids (tetramethrin, bioresmethrin, fenvalerate, etc.) has a lasting effect on samples exposed to natural light multiplied it. No such difference was observed in the samples kept in the dark. This beneficial effect of benzocaine is thus explained by inhibition of the photodegradant.

Further investigations have shown that not only benzocaine but also other 4-aminobenzoic acid ester derivatives are effective, of which the compounds of formula (I) have significant advantages in terms of efficacy, formulation and costs.

The arthropod compositions of the present invention which are primarily:

- ready-to-use liquids, - emulsifiable concentrates, - suspensions, - dusts, - glazes, - aerosols in the range of 0.01-60% by weight of pyrethroid (s) and excipients, based on the pyrethroid content (40: 1) - (1: 20) contains by weight a 4-aminobenzoic acid ester derivative (s) of the formula (I).

In the formula (I):

Rj and Rj are methyl, ethyl or hydrogen,

R _{3 is an} aliphatic or dichloaliphatic hydrocarbon group optionally substituted with C 1-4 alkoxy.

Among the pyrethroid active substances, both photosensitive (tetramethrin: 3,4,5,6, -tetrahydro-phthalimidomethyl (1RS) -ds, trans-chrysanthemum) and photostable (permethrin: S-phenoxybenzyl-1S, 5'-cis, trans-3 (2,2-dichlorvinyl) -2,2-dimethyl-diclopropane carboxylate, dpermethrin: (S) -alpha-dano-3-phenoxybenzyl- (1 RS) ) -dsz-3 (2,2-dibrominoyl) -2,2-dimethyldkiopropane carboxylate) and to optimize the various effects (articulating ·, killing and killing) expected from the preparation, where necessary -21

189,820 should be used in combination with various plretroid agents.

Other arthropopicidic drugs include insecticides (DDVP: 2,2-dichlorvinyl dimethyl phosphate, diazinon: 0,0-diethyl-0-2-isopropyl-6-methylpyridin-4-yl phosphorothioate, propoxur: 2-isopropoxyphenylmethyl carbamate). its use, in addition to reducing the cost of the preparations, is particularly advantageous because their presence delays the development of pesticide resistance against pyrethroids and the presence of acaricides (tetradiphone: 4-chlorophenyl-2,4,5-trichlorophenylsulfone) most of which have only moderate or selective acarid effects - acaricidal effects.

Of the combined compositions, a fungidd, e.g. pentachlorophenol is required.

In addition to fungicides, the photostabilized pyrethroids according to the present invention may be combined with other sunscreens, flame retardants, disinfectants, repellents, etc. for various purposes. with active ingredients.

The excipients are liquid (n-butyl acetate, petroleum, methyl ethyl ketone, abs. Ethanol, toluene, xylyl. Isopropyl alcohol, cyclohexanol, isopropyl myrostate) and solid (kaolin, talc) carriers, preferably in most formulations. chemical stabilizers used (epichlorohydrin: 1-chloro-2,3-epoxypropane), antioxidants (butylhydroxytoluene: 2,6-di- (tert-butyl) -p-cresol), enhancers (piperonyl butoxide: 3,4-methylenedioxy-60-propylbenzyl-butyl-diethylene glycol ether) and emulsifiable concentrates also contain anionic (atlox 330µB) and non-ionic (Atlox 4995) emulsifiers, suspensions in powder form, wetting agents (Triton X 120) and dispersants (Tan 850) deactivators (tretylene glycol), tiling agents (Acronal 4 L) and possibly plasticizers in glazing materials, and propellant gas (Freon 11/12) in aerosols.

Of course, other formulations may require the use of other excipients.

The characteristics of the above-mentioned brand-name excipients are described in FIG. are summarized in Table.

Finally, the most preferred of the 4-aminobenzoate ester derivatives are ethyl 4-aminobenzoate, methyl (N-ethyl) 4-aminobenzoate, n-octyl (N, N'-dimethyl) 4 aminobenzoate, dclohexyl (N _# N'-dimethyl) -4-aminobenzoate, 2-methoxyethyl (N, N ₎ -dimethyl) 4-aminobenzoate, and 2-butoxyethyl The use of (N, N'-dimethyl) 4-aninobenzoate or mixtures thereof has been found.

The composition and preparation of the compositions of the present invention are illustrated by the following non-limiting examples:

Example No. 1: Ready-to-use Liquid kg of (RS) -alpha-dano-3-phenoxybenzyl (1RS) <sep> trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane carboxylate 3-Phenoxybenzyl- (1RS) -cis, trans-3- (2,2-dichloro-vinyl) -2- (2-dimethyl-cyclopropanecarboxylate) 1,5 kg of n-octyl- (N, N'-dimethyl) 4-amino- benzoate 2 kg 1-chloro-2,3-epoxypropane stabilizer 10 kg cyclohexanone

26.5 kg of kerosene

The composition, when sprayed on garbage or manure, is capable of killing insect larvae, especially fly larvae, which it develops, but also kills insects that visit such sites for ovulation. '

No. 2 Example: Emulsifiable concentrate and ready-to-use liquid

100 (RS) -alpha-cyano-3-phenoxybenzyl (lRS) -cis, trans-3- _Λ t (2,2-diÚorvinil) -2,2 <Jirnetil dklopropán ·-carboxylate 50 g of pentachlorophenol

550 g of 0.0-diethyl-2-isopropyl-6-methylpyridin-4-yl phosphorothioate,

100 g dclohexyl (NN-dimethyl) 4-aminobenzate 40 g l-chloro-2,3-epoxypropane g Atlox 33OOB (Atlas Chem.Ind) - anionic emulsifier g Atlox 4995 (Atlas Chem. Ind.) - no the mixture of ionic emulsifier is homogenized at 50 ° C.

The composition is suitable for protection of wood against fungal and insect pests in a single-phase operation. It may be applied by applying a ULV atomiser to the wood, or it may be prepared by preparing an aqueous emulsion of the composition and impregnating it by immersion. Its application is particularly suitable for the protection of freshly cut timber.

No. 3 Example 2: Suspended Powder Component A

2.0 kg of (RS) -alpha-cyano-3-phenoxybenzyl (1RS) -cis, m.p. trans-3- (2,2-dichlorvinyl) -2,2-dimethylcyclopropanecarboxylate

400 kg of 0.0-diethyl-0-2-isopropyl-6-methylpyridin4-yl phosphorothioate

20.0 kg 4-chlorophenyl-2,4,5-trichlorophenylsulfone 0.1 kg 2-butoxyethyl (N, N'-dimethyl) 4-aminobenzoate l? kg Triton X 120 Rohm and Haas Co). - wetting agent

10.0 kg Tamol 850 (Rohm and Haas Co.) dispersant

Component B:.

557.9 kg of kaolin

Component A was dissolved at 60 ° C with stirring, cooled to room temperature, and homogenized with Compound B, ground to a size of 6-9 micrometers. The product, when suspended in water, is a pest and insect pest (Disaphis sp., Especially in horticultural crops and orchards).

Eutetranychus sp., Aphis sp., Etc.).

No. 4 Example: Dust Component A:

g of 3,4,5,6-tetrahydro-phthalimidomethyl- (1RS) -cis, trans-chrysanthemate - 200 g of ethyl 4-aminobenzoate g of 2-isopropoxyphenol-methylcarbamate Component B:

g trimethylene glycol deactivator 735 g Chinese talc

The mixture of the components of Component A is ground in a jet of air to a powder having a particle size of 7 to 12 microns in diameter.

- Talc with a fine grain size of 20-40 micrometers in diameter is homogenized with the deactivator, allowed to stand for 2-3 hours, and then component A is homogenized with component B. Dust field60

-3189,820 protects against insect pests in the wild, effectively killing potato beetle larvae and larvae in potato cultures. No. 5 example: Glaze (varnish)

The components:

0.5 g 34.5.6, -tetrahydro-phthalimidomethyl- (1RS) -cis, trans-chrysanthemate

0.1 g of (RS) -alpha-cyano-3-phenoxybenzyl (1RS) -cis, trans-3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropanecarboxylate 1 θ

1.0 g of 0.0-diethyl-O-2-isopropyl-6-methylpyridin-4-yl phosphorothioate

1.0 g of 2-isopropoxyphenylmethylcarbamate 1.0 g of methyl (N-ethyl) -4-aminobenzoate 2.0 g of 2-methoxyethyl (N, N'-dimethyl) 4-aminobenzoate B component is:

1.0 g n-butyl acetate 16.0 g methyl ethyl ketone 3.0 g abs

33.5 g toluene

26.5 g xylene 20

Component C:

14.4 g Acronal 4 L (BASF) - film maker

In a mixture of components of Component B, the components of the Component are dissolved, the solution is filtered, and component C is dissolved therein.

The composition is a viscous liquid which, when applied by brush or spray gun to the surfaces, forms a colorless lacquer, which kills insects.

Use indoors to control domestic insect pests (eg cockroaches, ants, etc.).

No.6 Example: Aerosol (surface treatment)

The components:

g (S) -alpha-cyano-3-phenoxybenzyl (1RS) -3- (2,2-dibromo-vinyl) -2,2-dimethylcyclopropanecarboxylate 200 g of ethyl 4-aminobenzoate g of 2,6-di ( tert-butyl) -p-cresol - antioxidant component B:

g of 3,4-methylenedioxy-6-propylbenzyl-butyl-diethylene glycol ether

730 g 2,2-Dichloro-vinyl-dimethyl-phosphate 10 kg odorless petroleum 2 kg isopropyl myristate 27 kg isopropyl alcohol Component C:

kg Freon 11/12 1: 1 Mixture 'Dissolve the components of the Component in the component B component mixture and add 10045

It is filled into a 200 gram aerosol can and the component C is filled. Sprayed from the bottle to places visited by domestic insect pests (eg cockroaches, ants, etc.) for weeks, they form an effective poison box.

In addition to the above, other serum forms can be prepared, such as organic solvent-diluted concentrates (SC), granules, plastic gels (cream, ointment, paste), baits lubricants, baits molds, vaporizers, smokers, soaps, textile impregnates, etc too.

The quantitative effect of ethylaminobenzoate (benzocaine) on the photodegradation of tetramethrin is illustrated by the following experiment:

benzocaine or tetramethrin were prepared in methylethylketone solutions in which the tetramethrin-benzocaine was 25: 1, 5: 1, 1: 1 by weight respectively and did not contain any benzocaine at all. Each solution was then impregnated with 8-8 Petri dishes, of which 4-4 contained tetramethrin at 140 µg / cm, and 4-4 pegs at 28 µg / cm ¹ . Petri dishes impregnated in this way were then exposed for 2 minutes to biological light titration under the mercury vapor lamp (H 60-125) for 30 minutes (accelerated photostability test).

Plates kept in the dark and exposed were then plated under a plastic Petri dish cover (as measurements on flies from different populations may show significant dispersion greater than 50%), 20-20 female domestic flies (Musca domestico) and The number of dead flies was read every 2 hours.

The mortality data for the 2-2 replicate samples were then summarized and the LT50 values calculated by probit transformation method, the time required to kill 50% of the flies on the plate.

The shorter this time, the greater the concentration of active compound remaining on the plates.

Our measurement results are shown in Table 2. are summarized in Table. Comparison of LT 50 values in the dark-exposed and light-exposed 40 plates showed that the sample containing the smallest amount of benzocaine (25: 1) had a well-documented photostabilizing effect that increased to a 1: 1 ratio with benzocaine. In the case of tetramethrin mixture, the photodecomposition of the active ingredient was completely eliminated.

No. 1 Table 1 Characteristics of excipients Brand name chemical structure

Acronal 4 L

Atlox 3300 B Atlox 4995 Freon 11

Freon 12

Tamol 850 Trotin X 120 ·

Badische Anilin und Soda Fabrik.NSZ Atlas Chem. Ind., USA Atlas Chem. Ind., USA EIdu Pont de Nemours and Co., USA EIdu Pont de Nemours and Co., USA Rohm and Haas Co., USA Rohm and Haas Co., USA Poly (acrylic acid ester) alkylaryl sulfonate pclethylene glycol alkyl ether trichlorofluoromethane dichlorodifluoromethane naphthalenesulfonic acid formaldehyde condensate alkylphenol polyethylene glycol ether

189,820

Table 2

Investigation of photostabilization of tetramethrin and benaocaine mixtures in the dorsal cavity

Exposure time · 30 minutes with mercury vapor lamp

........... ^....... - · ΜΜ —i II i iu ^ t

LT 50 value (min)

Active ingredient concentration tetramethrin, benzocaln 140ug / cm ^J 28ug / cm ^J ratio dark light dark light

2.43 41.70 4.90 373.00 2.00 26.20 6.14 114.00 2.16 3.36 5.91 15.60 2.51 2.38 4.32 4.41

Claims

Claims (1)

Arthropod formulations with improved performance, preferably ready-to-use liquids and / or emulsifiable concentrates or dusts or suspendable powders or aerosols or glazes containing from 0.01 to 60% by weight of pyrethroid, preferably 3,4,5,6, -tetrahydrophthalimidomethyl- (1RS) -ds, from trans-chrysanthemate and / or (S) -alpha-dano-3-phenoxybenzyl- (1RS) -cis-3- (2,2-dibromovinyl) -2,2-dimethyldclopropanecarboxylate; / or (RS) -alpha-dano-3-phenoxybenzyl- (1RS) -dis, trans-3- (2,2-dichlorovinyl) -2,2-dimethyldclopropanecarboxylate and / or 3-phenoxybenzyl / 1 RS) -dis, trans-3- (2,2-dichloro-vinyl) -2,2-dimethyl-diclopropanecarboxylate, excipients, preferably liquid and / or solid carriers, chemical stabilizers, antioxidants, effecting agents, emulsifiers, wetting agents, dispersing agents, film-makers, haygans, at least one of them Characterized in that, as a photostabilizer, the 4-aminobenzoic acid ester derivative (I) is present in a weight ratio (40: 1) to 1:20 (w / w) of the total pyrethroid content, - R and Rj are methyl, ethyl or hydrogen, 30 - r; C1-C8-alkyl or C3-C6-cycloalkyl optionally substituted with C1-C4 alkoxy. 1 drawing