DE2009831A1 - Pesticide concentrates and preparations - Google Patents

Description

Applicant: SCIENTIFIC DEVELOIWENa) QOMPAlIX OP SOUXH AFHICA (PROPRIETARY) LIMITED, Johannesburg / South Africa.

Pesticide concentrates and preparations

The invention relates to pesticide concentrates which contain 1-haphthyltf-methylcarbamate, which compound is usually referred to as orbaryl. ! The term "carbaryl ¹¹ is used in the present application to denote the compound mentioned"

Carbaryl is an organic pesticide with a relatively low toxicity and a broad spectrum of activity. It has a fast to moderate speed of action. Along with its distinctive remaining properties is it is a valuable tool for combating various pests of animals and plants. In addition, Carbaryl appears to be im Organism cannot be stored to the same extent as certain other insecticides, for example as organic Dichlorodiphenyltriohlorethane). Rather, its metabolism occurs relatively quickly.

However, one disadvantage of carbaryl is that it is found in Solvents does not have sufficient solubility to acceptable emulsifiable concentrates for dilution with To produce water. Certain solvents that are known to dissolve the compound work on plants

009839/23 0 2

~ 2 or mammals cause undesirable toxicity.

The aim of the invention is to provide a concentrate in Solution of i-Haphthyl-N-methylcarbamst, duroh which essentially the problems described above can be solved.

Duroh the invention also provides a new method of manufacture of crystals of 1-naphthyl-N-methylcarbamate for Provided.

The pesticide concentrate according to the invention contains up to approximately 30 weight- ^ i-naphthyl-ii-methylcarbaioate, dissolved in Polyethylene glycol, preferably of molecular weight from 200 - 6000, which is stabilized with a suitable acid.

A preferred polyethylene glycol is one having a molecular weight of about 300, with the preferred stabilizing acid being consists of acetic acid, lactic acid or phosphoric acid in a concentration of about 0.1-15% by weight. For application to human or animal skin Lactic acid or acetic acid are preferred, while phosphoric acid is the preferred acid for application to plants is.

Suitable additives, such as alkyl polyglycol ether sulfates, can be added. These treatment funds increase the water dispersibility of the concentrated carbaryl solution.

Other additives _; bev-ipielowoAaf; das 3 ^r ond8nea1; j one product of oiled fatty acids., ·; ··; w't i; iitil ^:! v <.n · Κ »?!; | ;;. ^v ül. & n _: ^ fc with Π? λγ «ορι.Ιώ or

2009631

Ethyl taurine, can be added to your control of excess fat will·

The inventive whisk concentrates are in virtually everyone Ratio of ethanol, methanol, chloroform, di-chloroethane, J & ztttbjlfoxzzodd, Siaethylsulfoxyd, Nethylenohlorid, cyclohexanol, Hethyläthylketon or the like miscible.

Another feature of the invention is a pesticidal preparation which consists of a concentrate defined above, dissolved or dispersed in a suitable diluent. Suitable diluents are water ₉ polyethylene glycol or one of the above erwiQmten organic solvent.

It is known that carboxyl, together with many other insecticides, has a synergistic effect. One of the However, problems have hitherto been found in finding a suitable medium for both insecticides. Such a medium is provided for the present invention.

Other preparations such as those of the MGK series, β.B. USX II can be incorporated into the preparations according to the invention, these preparations having synergistic effects. Synergistic effects have been achieved also found when insecticides, such as _ Botenones, pyrethrins, piperonyl butylate, sulfoxide, malathion, liadane and chlordane (the last three are among other things registered trademarks), the preparation according to the invention services are added.

Compounds which have other properties and activities, for example fungicides or bactericides, can use the

009839/2302

Preparations for solving a common problem added will. Such additives are known.

The amount of stabilizing acid is chosen according to the dose hydrolysis of carbaryl, for example in cattle baths, is prevented.

Pas Eonsentrat is generally familiar with and in Usual catfish used! Propellants ?! mixable so that it isu aerosols can be formulated.

The field of application is very broad and includes veterinary medicine, agriculture, the poret economy and the Households, especially since the use of kerosene is dispensable. There can be different wordings for the individual uses are produced, for example

a) High concentrations (up to about 17 5 ^) for cattle baths, which are appropriately diluted in the bath or with water spray will.

b) aerosol sprays.

1. Preparations with a quick action and one remaining Effect can in addition to the carbaryl. Pyretbxins and piperonyibutylate. For the production of animal sprays the concentrations are chosen accordingly. The synergy tables Mixture of carbaryl and malathion is particularly suitable for preventing the occurrence of resistant ticks and similar parasites.

2. The preparation according to the invention is particularly suitable Way of making shampoos that dogs with sensitive skins can tolerate. A typical example

009839/2302

play for such a spray (so-called srock shampoo) or a liquid completely soapless shampoo is shown below specified

Oarbaryl concentrate

Genapol LRO paste (registered trademark)

Medialac EP or EA dto.

Phenonip dto.

Phenoxetol dto.

with or without the addition of lanolin or derivatives thereof.

According to a further feature of the invention, there is a method for the production of crystals of i-ffaphthyl-H-methyl- earbamat, which consists of the carbamate is dissolved in polyethylene glycol, which is a suitable stabilizing acid contains, whereupon the dissolved orbamate from the Solution precipitated and the precipitated carbamate crystals collected will. The carbamate can, for example, be precipitated from the solution by adding water.

i-Naphthyl-JT-ethylcarbamate, which is used in the above-described Manner has a pronounced crystal structure, and it was also found that as.

an increased effectiveness and an increased spectrum of activity in comparison to the 1-Naphthy1-N-methylcarbamate currently marketed.

The following examples explain the invention; without them, see below restrict.

example 1

800 g of a teoteisohexs Oaartjaasyls if®sd © s Ja®im® Slsiag @;

009839/2302

mixes 5500 g polyethylene glycol (molecular weight 300) and contains 130 g of a rainy lactic acid

This mixture is heated on a water bath to a temperature of 75 t ⁵⁰ G and kept at this temperature.

The carbaryl dissolves completely with occasional stirring.

The carbaryl solution obtained in this way is filtered through a fine wire mesh or through muslin in order to remove undissolved constituents. Ansohliessend is cooled to about 40 ⁰ C.

A surfactant such as 40 grams of one active polyglycol ether sulfate of lauryl alcohol, is then added to the solution, whereupon the solution is made up with ethyl alcohol (or another miscible organic solvent) any desired final concentration is diluted. One can at Place of lauryl alcohol polyglycol ether sulfate also any use other dispersants »

The concentrate described above is formulated into an aerosol spray preparation, whereupon the effectiveness of this the latter preparation is tested using tick-infested cattle.

Example 1 (a)

An AeroBol porn rating is made as follows: '.

A 16 $ igee Öa.rbaryl ~ Ko33Eöiitrat (as in Example 1) ssur with ethyl alcohol producing eimsr 3 v'lgeu JJSnwng is diluted.

A ΑθΓϋ £ ίϋι1 ~ · Β & 1ιβ '> .- icu. ¹ w.lrd immihl.ivsiwjiia al ^J ' dor A

0 0 9 8 3 9/2 M) 2

lieruag filled in the following way:

50 i> O £ lgen carbaryl-LÖ8ung

50 Jfi Frigen 11/12 50:50 (Erigen is a registered commodity

soak)

In this way, a finished spray consontration becomes one Obtain 4 J & gen carbaryl solution. This solution is the subject of extensive trials in the following described way:

Example 1 (b) - Biological marriage effectiveness

The aerosol, which stands at the top and contains 4 ^ Oarbaryl, is applied in small doses to an ear of a cattle infected with Zeolcon over a period of 15 seconds. During the same cell ₁ * rae, an application is made to a place below the tail (upper perineum). These places have the largest Zeokenkonontrationen.

For comparison, a commercially available so-called "tick fat ^{11" is} tested which contains a carbaryl preparation.

The results are summarized in Table I below.

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Table I.

Average attack by the ticks (both on the ears and on the swan)

Preparation Anssahl Before 1-2 4 8 12 1 2 4 12 18 24

of the hour hour hour hour day Sage Sage Sage! Cage! sweep

___ cattle brlnmmg _wmmmmm . «—_ _ _ _ _

"Zeoken fat ¹¹ ,

that I

_ difficult to 12 187 189 186 178 181 120.7 117.4 103.6 128 193.6 197.6 ^ bring ι

to lSeet oo

S '

^ Aerosol- (1) (2) (3) (4) (5) ifj (6) ^ 8)

n> solution that 30 212 212 209 208 207.9 180.8129 107.9 3.7 5.3 4.2 ω 4 ^ carbaryl ο contains

N) O O CO OO U)

(1) In an ELeeken examination, ie when 100 ticks are removed (arbitrarily), it is found that 43 % of them no longer move their legs and remain on the EUeken when they are brought into this position.

(2) In the same examination (as in 1), 100 # are the Ticks immobile and remain in this state until they are completely dry.

(3) The ticks shrink on the xers. m

(4) Some of the heavily blood-precipitated ticks are already dried out.

(5) All ticks are dry, with most of their heads being β have dug deep into the Saut.

(6) Some ticks are new Iiere _p but they are quite immobile.

(7) Most of the ticks counted after the 12th 3 * ag are new Pests that are already dead or noticeably restricted in their mobility. β

(8) Some animals do not have © ticks.

The following ticks are identified on these lizards

1. Boophilus decoloratiis

2. Ehipicephalus appendioialatus

3. Hhipiceph & Xu © © vertsi

4. HMpieephalmss © imu®

5. Hyalemma rufipes. ·

009839/2302

- ίο -

Aue of the foregoing it can be seen that the erfindungegemäese Carbaryl treatment a significant increase the effectiveness and was compared to a known orarbaryl preparation.

In addition, it should be noted that the preparation erfindungsgemäase kills ticks on the fours and not only nahmt ¹ ".

With a corresponding preparation of the above-described The preparation is not found to have streaked the skin, and neither on humans nor on animals * and neither was it after repeated administration of the solution.

Furthermore, a preparation with an adjustable concentration of active ingredient is able to prevent the occurrence of traveled strains. Such an occurrence was found with the commercially available carbaryl preparations. When laboratory tests were carried out, ticks (Boophilus decolorattiet) which were resistant to Qoxlmx ^ l were treated with formulations according to the invention. These ticks were received within the same period of time as comparative ticks that had been fetched from other sites.

Similar HersteXluugsinaQnahBieß, as described in Example 1 were "are made using high hormolecular polyethylejiglyJrole" a complied with, gel.ätoaliclia G'irbaryl-Zubocceitungezi received

Or rhi f '-:. ·.

CC 9 8 3 9 ': ^; 3

Carboxyl then dissolves the polythylene glycol when the latter is obtained to about 80 * 0, whereby a 25% carbaryl consistency is obtained. Consentration can be diluted 1st. Maintain this consensus at a temperature above 60 ⁴ G.

The product obtained is digestible and can be mixed with aqueous Shaaen Yermieohen, being a very fine QarTKryl-NieO.ezsohl & g is obtained, which dlsperglBrt in a simple Veiee.

Various foraalixungen are given below) the Wex'üen made from the ion concentrate in accordance with Example 2.

Example 2 (λ) - Manufacture of a £ 15 oarbarjl eutlleitenden

QeIa «« —i «——

Oarboryl-IonBentrat, produced according to Example 2 1500 g Polyethylene glycol 200 50Og ^ Ethyl alcohol (absolute) 300 g Hloht-iottisohes ^ ralglexaittel 200 g

Example 2 (b)

A preparation which is also suitable for stable floors, and especially if a broadband solution is required, is made as follows:

15 Jfciges Oarbaryl-Antiseptlkum - Ställ ~ / BundehllttenboAenwä8Ohe

Oarbaryl Consentrate gea. Example 2 1500 g Polyethylene glycol 300 250, g Ethyl alcohol (absolute) 150 g.

BensalkonluiBohlorld 90 1 » 500 g

Dispersing agent (see e.g. ice polyethylene glycol - 100 g

ether)

009839/2 ^ 02

In such a · »product, besides a seta distinctive pestislden effect auoh etaxk effective antiseptic Bigen-. shafts compared to a huge sound pathology Microorganisms "

Example 2 to)

Bine rerbeeeerte Ctobaryl ^ latieeptikum preparation around bathing ▼ on Bowls and on preventing a loathing naoh de » It is divided as follows:

15 t ^^ BHi ffflTlwrr? "* iAbtiffeptjLtaiBL **

Oarbaryl ionic rate 25 pounds 1500 g Polyethylene glycol 200 200 g Ethyl alcohol (abeolut) 200 g

<noor- <p- <phenoxatecl 375 g

Eriohlorhydroacydipheayl ether 75 g Dispersion medium 150 g

Me yore-standing Torumlierwigen are all in the hairy media stable during long lateral rumen.

Example 3 * YerwondT ^ np of polyethylene glycol 6000.

Bb similar preparations are made as described above, with the exception that polyethylene glycol 6000 is used in place of the embedded polyethyluglycols. In the process, some high-quality products are obtained from a waons-like latnr, which, however, can be consumed with water. Bas Oarbaryl remains in solution in the Konsentrat · BIE Work Tepe TUEX this mixture are mass increased to 100 ° 0 '

009839/2302

According to the invention, they are carbaryl preparations compared to known products, such as wettable ones Powder or dust »better. To treat obstacles . Sheep, horses and pigs, for example, have each other Eonsentcatioße », which is only 600 g Garbaryl per 1000 - 1200 1 Solution included to be effective in combating dagger infestations proven on such sires. This carbaryl concentration is considerably lower than the concentration used for GarbarjT! -Containing products is recommended that are already on dom market.

An extended aerosol spray toxicity test is performed using poultry It will be a £ 10 Garbary! Aerosol Poriaulieniag used. So be Chickens in an incubator for a period of Sprayed for a few weeks · Se will not lose any body weight noted the general:. The behavior of the chickens shows no signs of acute fosicity.

Example 4

This example shows the process of making Eristall of i-laphthyl-H-methyloarbaiBat.

A solution of carbaryl in polyethylene glycol is prepared in the manner described in Example 1. The solution is then dissolved in iron containing oil. The mixture is stirred & wiü g t. allowed to stand with occasional shaking for 30 minutes. Then mrö dl © Hi @ € & uiäg filtered through a filter paper (Wfeataan Mr. 1), whereupon the residue with distilled water as long as © gevüsehs: n wirä »Ms no further display forms

009839/2302

H -

Precipitation is poured, each medereohlag is at 55 ° 0 for a period of time το »24 - 30 hours in an oven dried.

The orbaryl base produced according to this example has a different quality than the known orbaryl crystals. Βλ © crystals are clear and "floky ¹ ", whereby the volume is approximately 2 "to 3 ~ fa © he deü Tolusoene of a finely ground GOTbaryl ^ tsubes, which is supplied by the Herste Hera. The dust flies easily with ¥ & ^ 0 @ r ml & Q & t ₉ -distributes atoh the naoh the above gssobilderton Hathodn kargoisteilte Oarbaryl relatively simple. Betraolit © t men dia? ®? Bi »& ang microscopically, then you put f @ et" daes the 'a,: - ista) la completely from the KrIo tall en varaoMeä ^ u eirtd; dl »for example duroh dissolutions of QeatbzxyX Xn Asetoii or DlmathylauliOacyd -and an-

zxb & zyla obtained with water

willβ

The crystals formed by the method of B © .ippi *, 14 have an extremely high affinity. die Baut, for the hair as well as for Ffl «fiieejQ3isttDr.lal (beXspidlsveise leaves or the like}» wa ^, ^ m ^ aaok öaap. ₉ v & nn aiö © dusting on the surface

'The UY-Spelr ^ /. Ci de hr / rgesSa'i >.:? -?

gen ®; Ι; πββ '"; ► · ■ ·". ^% ύΥ> effect. . ->. it &'; ·.!.

search

geachildex'ten method? ^ ^ but exactly demjeni ~ t Zms. Tmttm the biologi? _t * ,. ^! ,% 3 ie wi: cd following ver ~

· ^ Habmsa

j -i 3 3 9/2 3 0 2

200 & 831

a) a laboratory toxicity test and

b) in a Yereuohstierungshaus using Gorbaryl crystals, which are precipitated from a solution of ethylene glycol, bind.

Laboratory toxicity test Xeohnisohee carboxyl 98

20 g / M ² rice

Oarbaryl-irie parts, made detailed example? $ 98

of the dead animals nftoh *

1-2 5-5 6-10 10-20

12 killed animals, the number of dead the number of animals still multiplied multiplied

54 56

no cockroaches

♦ Tested with a fyrethrln preparation as a stimulant (stimulating effect of pyrethrins), with no cockroaches being detected for a period of a few days following the observations.

When performing a test in a TierajEtohtunga house similar results are obtained. Good control can be achieved if it is applied regularly,

As demonstrated by the preceding examples, those are according to the invention, benefits obtained saft! rich. The invention creates carbaryl preparations with a low toxicity and a high degree of effectiveness. The preparations are well tolerated by animals and plants. Further

009839/2302

means the ability to soluhillsieren that the C & rbaryl su known synergistic mixtures of Oarbaryl with others Inefficiencies can now be used to achieve greater efficiency "

Examples of synergistic mixtures are given below specified

Example 5

a) Oarbaryl-Sonsentrat 15 Jfc 66.7 £ 1,000 g

b) Plperonyl butylate $ 3.5 52.5 g o) Folyäthylengl ^ kolphenylKther 2.5 t 37.5 g d) ethyl alcohol (absolute) 27.3 56 410 g

This preparation forms a very effective synergistic one Misappropriation.

Example 6

a) Oarbaryl Consentrate 16 56 50 £ 8000 g

b) Piperonyl butflat 1.5 f> 240 g

o) HGK 264 (H-Oetylbieyolohepten-

dioarboxial (1.0 i> 160 g

d) sodium laurate sulfate 1.0 $ 160 g

e) Hethjlenohlorid 20 Ji 5200 g

f) Ethyl alcohol (absolute) 26.5 * 4240 g

The synergistic preparation can be used to produce a effective aerosol formulation can be used, with a Mixture of fluorine trichloromethane and difluorodiohloreathaa is used as a propellant.

009839/2302

Example 7

a) Carbarjl-Ionentrat 16 ft . 50 86 8000 g b) Pip # ronyl butylate ns * 240 g o) MoKH 326 (di-n-propyliso- oinohomeronate) no * 160 g d) polyethylene glycol lauryl ether 0.5 pc 80 g β) ethyl alcohol (abaalut) 47 Si 7520 g a) OarDaryl-Σοηιβηtrat 15 * 66.7 * 1000 g b) piperonyl butylate 2.0 * 30 g o) 25 + pyrethrins 4.0 * 60 g d) Ethoxylated a Rieinu oil 3.0Si 45 g β) ethyl alcohol (absolute) 24.3 * 365 g

009839/2302

Claims (1)

- 18 claims 1. Pestiaid concentrate, characterized in that it is up about 30 weights of 1-Haphthyl-I-aethylcarl) ejBat, dissolved in Polyäthylengljkol and stabilized by a suitable one Acid, contains. 2. Consent according to claim 1, characterized in that the polyethylene glycol has a molecular weight between 200 and 6000 owns. 3. Concentrate according to claim 2, characterized daduroli that the polyethylene glycol has a molecular weight of 300. 4. Concentrate according to one of claims 1-3, characterized in that the acid of acetic acid, lactic acid or Phosphoric acid. 5. Concentrate according to one of the preceding address, because * duroh characterized in that the acid in a consentration ▼ on 0.1 - 15% by weight, based on the preparation, is present. 6. A process for the production of crystals of 1-baphthyl-N-methyloarbamate, characterized in that the carbamate is dissolved in polyethylene glycol which contains a suitable stabilizing acid, the dissolved carbamate is precipitated from the solution and the precipitated carbainate crystals are jammed will. _l 7. The method according to claim 6, characterized in that the carbamate is precipitated from the solution duroh the addition of water. 009839/2302 β. i- it aaofe iron »procedure been made eats, 9. Yemendteig τβ » 8 ale Beetisld. ;, d & dureh gakenaseiohaet, dase iron of claim 6 or 7 that it passes Asspsfiohe 1-5 » Evaporation agent 10. Sestisid-iobereitimg, from a Xonsentrat according to "where this Eonsentrat i is dissolved or dispersed 11, PeetiBid-Preparationnog naoh Acepniofe 10 «by the fact that the ITerdQsmuisgeaittel consists of water or Poljäthyleijglytail. 00S83S / 2302