DD210195A5 - INSECTICIDE FORMULATIONS - Google Patents

Abstract

The present invention relates to novel insecticidal formulations which consist of one or more active substances from the group of pyrethroids and one or more phospholipids in addition to conventional Traeger-, Verduennungs-, solvents and / or other inert adjuvants, wherein the weight ratio drug or drug mixture to pure phospholipid or mixture of pure phospholipids 1:20 to 1:50 occupied.

Description

Title of the Invention: Insecticide Formulations

Field of application of the invention:

The invention relates to novel pyrethroid-containing insecticide formulations. The new formulations are particularly characterized by a strong adhesion and long-lasting effect.

Characteristic of the known technical solutions: Pyrethroids have become very important in recent years due to their high, rapidly occurring insecticidal activity and low toxicity to humans and animals. The natural as well as the synthetic pyrethroids are difficult to dissolve in water, are sensitive to heat and are easily inactivated in the air. In addition, pyrethroids are very costly products due to their elaborate isolation (natural pyrethroids) and elaborate syntheses.

Object of the invention:

The aim of the present invention is therefore to develop new insecticidal formulations containing pyrethroids as the active ingredient.

to provide that show with small amounts of active ingredient good, long-lasting efficacy and good adhesion to the protected goods.

Explanation of the essence of the invention:

It would "now" surprisingly found that one can obtain highly effective formulations for controlling pest insects, if the pyrethroids together with a phospholipid from the group phosphatidylcholine, phosphatidylethanolamine or N-Acylphosphatidylethanolamin or a mixture of several such phospholipids in the weight ratio 1: 2o to 1: 5o in addition to customary carrier, dilution, solution, spraying and / or other inert aids used.

The addition of phospholipids achieves a much better distribution and better adhesion and thus also a long-lasting efficacy. As a result, the application rate of active ingredient can be significantly reduced (up to 6o%).

Sine good distribution is therefore of great importance because for spraying fields, z.3. of cotton or tobacco fields, only 25 - 7o g active ingredient per hectare of commercial formulations are needed. In the new formulations, it is still possible to disperse effective amounts of Io-6o g per hectare without affecting its efficacy.

The new formulations are also suitable for the treatment of ectoparasites in domestic and grazing animals. They show good adhesion to the animal skin or the coat. When spraying barn walls, the active agent adheres well to the wall and provides long lasting protection against insects such as e.g. Fly, .

As phospholipids are natural or synthetic phospholipids from the group phosphatidylcholine, the hydrogenated phosphatidylcholines, phosphatidylethanolamine, the N-acyl-phosphate

idylethanolamines, phosphatidylinositol, phosphatidylglycerol or a mixture of several such phospholipids, but especially mixtures of phosphatidylcholine and phosphatidylethanolamine or phosphatidylcholine with phosphatidylethanolamine and N-acylphosphatidylethanolamine or other phosphatidyl mixtures with 15-75% phosphatidylcholine content ± x question.

Particular preference is given to natural phosphatidylcholines which can be obtained by the processes described in the following patents: DE-PS 1o 47 579, DE-PS Io 53 299, DE-PS 16 17 679, DE-PS 16 17 68o, DE-OS 3o 4 7 O48, DE-OS 3O 47 O12, DE-OS 3o 37 O11.

Suitable pyrethroids are natural or synthetic pyrethroids of the general formula I in question

^R i 2

^R 2

CH ₃ CH ₃

₁ = CH ₃ , COOH, COOCH ₃ , Cl, Br - = CH ₃ , Cl, Br, aryl, halo subst. aryl

^ = subst. Cyclopentene, substituted furylmethyl, phthalimidomethyl, phenoxybenzyl or phenalkenyl groups.

Examples of compounds of the formula I:

1. -CH ₀ -CH, CH--., CH ₉ -CH = CH-CH = CH. Pyrathrin I

3 3 3 Γ 2 L

2, -COOCH ₃ -CH ₃ CH ₃ -, = -.- CH ₂ -CH = CH-CH = CH ₂ pyrethrin II

-A-

3. -CH.

-CH, CH,----CH ₂ -CH = CH-CH ₃ cinerine I

₃ CH ₃

4. -COOCH- -CH,

C i η e r iπ II

5th

-CH

6. -COOCH ₃ -CH ₃

7. -CH, -CH

3 .. -CH, -CH

9 -CH

CH ₂ -CH = CH-C ₂ H ₅ O

CH

0

CH

CH.

J a s m o 1 i η I

Jasmine II

Fursthriπ

allethrin

C y c 1 e t h r i π

-w. ₂

CH * -.

11. -CH ₀ -CH

12. -CH ₀ -CH.

13, -CH ₃ . rCH

-CH

(f

3athri η

D i m e t h r i η

Phthaitnriπ

J a ρ ο t h r i η

H. -CH- -CH- -CH

Pyres ihri π

15. -CH- -CH, -CH ₀ -CH = C-CH

Cl

3 u t e t π π "π ·

15. -CH ₃ -CH ₃

Phenothriη

17. -Cl-Cl -CH.

P e rm e t h r i η

18. -Br -Sr

.ch to

CN

Decamethriπ

19th-CT-CT

Cypermethri π

.20 "Cl

The compounds of the formula I are known compounds which have already proven themselves as insecticides (Chemie der Pflanzenschutz- und Schädlingsbekungsmittel, Springer 197o, p. 87 ff).

For the preparation of the novel insecticidal formulations, the corresponding phospholipid is dissolved in a suitable solvent such as, for example. Toluene, ethyl acetate, xylene, gasoline, methanol or ethanol or mixtures of these solvents. The choice of solvent depends on the solution properties of the active ingredient used. If necessary, the active substance or a commercially available formulation is dissolved in the phospholipid solution while heating. After completion of the solution process, the solvent is distilled off under reduced pressure with heating. The product thus obtained is optionally processed by adding suitable inert auxiliaries, such as fillers, swelling agents, emulsifiers, disintegrants, spraying agents to conventional commercial products.

The novel insecticidal formulations may also be prepared by dissolving the active ingredient or a commercial formulation, the phospholipid and the desired adjuncts together in the solvent or solvent mixture by heating and then slurrying the solvent (s) in vacuo. Obtained is a ready-mix, which is ready for immediate use.

In the case of active substances which are soluble in water or water-alcohol mixtures, advantageously the active substance is first dissolved in water or water-alcohol mixtures and the phospholipid or the phospholipid mixture is processed by stirring or by the application of ultrasound to give a solution or emulsion , Dia optionally required emulsifiers can be added before or after this stirring. The emulsion or solution thus obtained is usually, as z.3. by distillation, spray drying, lyophilization, freed from the solvent mixture or water. The resulting product

can be used as a dry product if necessary. With the addition of auxiliaries and fillers. Also, the product can be emulsified or dissolved again in water with the addition of suitable excipients and used as a liquid product.

Preferably, emulsion concentrates are prepared by dissolving the phospholipid in the presence of co-emulsifiers in a solvent or solvent mixture and adding the pyrethrin with stirring and gentle heating. The concentrate obtained can be processed prior to use with the addition of the necessary amount of water to conventional spray mixtures.

Carriers are e.g. Talc, kaolin, bentonite, kieselguhr, lime or rock flour. Further aids are e.g. surface-active compounds, such as soaps (fatty acid salts), fatty alcohol sulfonates or alkyl sulfonates. As stabilizers or protective glycols gelatin, casein, albumin, starch or methylcellulose can be used. Furthermore, spreading agents, such as silicone oils, fatty acid esters, triglycerides, fatty alcohols or fatty acids may also be used.

As common synergists for pyrethroids, e.g. Piperonyl butoxide, safroxan, sesamex or sesamin are used.

The new formulations can be used in the form of spray, solutions, emulsions or suspensions.

example 1

2, ooo g of pyrethrum extract from INEXA, Quito-Ecuador

Lot 1o41 (pyrethrin content approx. 5 9.3%) 2.1o5 g phospholipid 1.595 g isophorone 0.800 g glycerol 0.265 g cremophor EL 0.235 g methanol

The phospholipid is dissolved in isophorone, glycerin, cremophor, methanol mixture with stirring and to this solution, the pyrethrum extract is added with stirring and gentle heating.

The following mixtures are prepared analogously to Example 1:

Example 2

0.4 g of permethrin 3, oo g of piperonyl butoxide 2, co g of phospholipid 1.75 g of isophorone o, 75 g of glycerol o, 25 g of cremophor EL o, 25 g of N- (2-hydroxyethyl) caproic acid amide

Beispiel.3

1, 7o g cypermethrin

1.7o σ piperonyl butoxide

2, oo g phospholipid

1.75 g of isophorone

ο, 75 g glycerol

0.25 g Cremophor EL

.0.25 g Softigen 767

Example 4

o, 9o g decamethrin

2.5 g of piperonyl butoxide

2, oo g phospholipid

1.75g isophorone

ο, 75 g glycerol

o, 25 g Cremophor SL

.0.25 g Softigen 767

Example 5

o, 2o g perinethrin

3.2o g of piperonyl butoxide

1.66 g phospholipid

o, 83 g Cremophor EL

o, o65 g of triethylamine

1.17 g of toluene

1.17 g of xylene

0.6 25. g DMSO

o, 33 g Pf lan ζ en oil.

o, 83 g of N- (2-hydroxyethyl) caproic acid amide

Example 6

1.7o g perinethrin

1.7o g of piperonyl butoxide

1.66 g phospholipid

1.66 g of isophorone

ο, 83 g Cremophor EL

o, 83 g of N- (2-hydroxyethyl) caproic acid amide

2.15 g of DMSO

o, 63 g of glycerol

o, 18 g of methanol

o, 33 g of vegetable oil

The phospholipid products used in the above Examples 1 to 6 had the following composition _r v; and the percentages by weight given are:

Example 1:

4o% phosphatidylcholine 28% phosphatidylethanolamine 27% N-acylphosphatidyl ethanolamine 5% other phospholipids

Example 2:

45% phosphatidylcholine 25% phosphatidylethanolamine 21% N-acylphosphatidylethanolamine 9% other phospholipids

Example 3:

42% phosphatidolcholine 25% phosphatidylethanolamine 25% N-acylphosphatidylethanolamine 8% other phospholipids

Example 4:

4o% phosphatidolcholine 3o% phosphatidylethanolamine 25% no-acylphosphatidylethanolamine 5% other phospholipids

Example 5:

96% 'phosphatidolcholine 4% other phospholipids

Example 6:

3o% phosphatidylcholine 16% N-acylphosphatidylethanolamine 24% phosphatidylethanolamine 3o% other phospholipids

Claims (11)

SrfindunqsanSprüche 1. Insecticidal formulations, characterized in that they are a) an insecticidal active substance from the group of pyrethroids and b) one or more phospholipids from the group phosphatidylcholine, the hydrogenated phosphatidylcholines, phosphatidylethanolamine, the N-acyl-phosphatidylethanoiamines, phosphatidylinositol, phosphatidylserine, lysolecithin and phosphatidylglycerol in the weight ratio a: b of 1: 2o to 1: 5o in addition to conventional carrier, dilution, solution, atomization and / or other inert HilfjitteJn consist. 2. Formulations according to item 1, characterized in that phospholipid mixtures of Phosphatidyleno1in and phosphatidylethanolamine or mixtures of phosphatidylcholine, phosphatidylethanolamine and N-acyl-phosphatidylethanolamine are used. 3. Formulations according to the items 1 and 2, characterized in that a phospholipid containing 15-75% phosphatidylcholine is used as the phospholipid. 4. Formulations according to the items 1 to 3, characterized in that as pyrethroid a compound of general formula I. C = CH COOR ₃ CH ₃ CH ₃ R ₁ = CH ₃ , COOH, COOCH-, Cl, Br
R ₇ = CH ₇ , Cl, Br, aryl, halo subst. aryl R-, = subst. Cyclopentene, subst. Fury! Methyl, phthalimidomethyl, phenoxybenzvi or phenalkenyl-Grupoen -Λ2 - is used. 5 .. formulations according to the items 1 to 4, characterized in that is used as the pyrethroid permethrin, decamethrin or cypermethrin. 6. Use of the formulations according to one or more of the items 1 to 5 for controlling insects, 7. A process for the preparation of formulations according to one or more of the items 1 to 5 / characterized in that the phospholipid is dissolved in an organic solvent or solvent mixture and dissolved in this solution, if necessary. By heating and / or stirring the active ingredient and then the Solvent or solvent mixture is removed in vacuo and the resulting mixture is transferred with the addition of conventional fillers and auxiliaries in a conventional application form ... , 8. A process for the preparation of formulations according to one or more of the items 1 to 5, characterized in that the one or more active substances with one or more phospholipids optionally. With the addition of conventional fillers and auxiliaries in an organic solvent dissolved or slurried and the solvent is deducted afterwards. 9. A process for the preparation of formulations according to one or more of the items 1 to 5, characterized in that one or more, water-soluble or alcohol-soluble active ingredients in water and water-alcohol mixtures together with one or more phospholipids with stirring and / or light heating and / or dissolved ultrasound and the solvent or solvent mixture is withdrawn. 10. A process for the preparation of formulations as an emulsion concentrate according to one or more of the items 1 to 5, characterized in that the phospholipid is dissolved in the presence of an emulsifier in an organic solvent or solvent mixture and in this solution, if necessary. By heating and / or stirring the active ingredient is dissolved. 11. Use of Emulsicnskonzentraten according to item 1o for controlling insects, characterized in that the concentrate is diluted with water and used as Spritζbrühe.