DE1567166A1 - Pest repellants - Google Patents

Description

P! 5 67 166.6 · ·

■ ■ 'Patent Department

156716Q

Sohädl j.np ; abekämpfunft srctl tteX

The invention relates to a pesticide with increased activity containing mixtures of Carbaraaten and Form araidinen.

In the German Patent No. 1,169,194 means are with insecticidal and acaricidal effects are described which carbamates of the general formula

C ^ - O - C - NHR

in the ; ■,

Β * lower alkyl or cyclohexyl,

IU and R, lower alkyl or together with the nitrogen * "etoffatom a gegebeneηfalls contain further heteroatoms liinjj *

R ₄ j. Hydrogen, lower alkyl, lower alkenyl • -. "'or chlorine,

R- hydrogen or methyl _;

j mean included. 0 0 9822 / j | 85 7

• New documents lArt. V ai ^ u «. 2 No. 1 sentence 3 de8Anderung3gee.v. 4. Ö. IS * '.

VtattMl! Hwii-JSreM H «mMin · K« r | Ott «Mlttthtfn * di * h | Vortltitndtr d · «Au! <Ttht * mtai: Dr. Jur. Eduard v. 8diw «rtzkopp.n 1 Berlin« 6, Mqller «lr« e · 170-173 Pr. Rar, Mt Q »rh« nl Hup «<Dr.-Inf, Hont WIUeI SIU dtr G« * tlliob »Ri BwHn and Bcrgkcmm fonttxh 69

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It is also from German Patent No. 1.172.031 known that means containing forraaraidins of the general formula. .

Ί.

CH-H /

in the · , .

. R ₁ and Rg are alkyl radicals with up to 4 carbon atoms or R, hydrogen

and

Alkyl radicals as defined above

represent »and their salts have good acaricidal and especially acaricidal-ovicidal properties ·

It has now been found that pest control agents contain at least one carbamate of the general types mentioned above Formula mixed with at least one formamidine of the above general formula has a higher effect against plants «? and animal parasitic pests as the sum of effects /, of the individual components when used alone *

This significantly increases the effect of the individual components

the effect is surprising and was not predictable «because

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statements about this because of the lack of knowledge of the mechanisms underlying this effect are not. are suitable.

Connect with the use of the mixtures according to the invention There are significant advantages since, in order to achieve the same effect against many pests, smaller amounts of active ingredient than when using of the individual coraponents are required. The fight of pests can therefore be carried out more reliably, safely and economically, and it can be 2 B. the waiting periods, d. H. Significantly reduce the waiting times between treatment and harvest.

A particular advantage of the mixtures according to the invention is their increased action against all stages of animal and to evaluate plant-parasitic mites, as this is the only way to effectively control them · This effect is therefore unexpected, since * in almost all known acaricides the Main effect either only against the mobile stages of the pests (adulticidal effect) or against their eggs and mostly also directs their larvae (ovicidal effect). A population of mites z. B. consists of species of the family TETRANYCHIDAE namely always from different stages of development and there are always moving stages next to the eggs, so that often After a short period of time, new generations of the pests either from the intact eggs or from the mobile stages can emerge

The mixtures according to the invention not only avoid this

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Disadvantage of the known acaricides, but also work reinforced against both stages, which means a considerable technical advance. "

It has also been shown that the mixtures according to the invention also with regard to their acaricidal and / or acaricidal-ovicidal action, known acaricides are clearly superior, as from the comparison tests listed below.

Come as individual components for the mixtures according to the invention in particular the following active ingredients or their salts with inorganic or organic acids are suitable.

A carbamate

link

Physical constant

I '5-Dißiethylaminomethyleniminophenyl * N-methylcarbaraate

II 4-dimethylarainomethyleneirainophenyl N-methylearbaraat "

III Jl-DiBiethylaminoraethylenimino-3-methyl-phenyl-N-i-diethylcarbaoate

IV 4-Diethylarainoinethyleneimino-> methyl-pheny1-N-methylcarbamate

V'l-Dimethylaminonjethyleniraino ^ - methyl-phenyl-H-ethyl carbonate

VI ^ Dimethylaminomethyleneinino ^ - allyl-phenyl ~ ti-methylearbar.iat

VII 4-Ditnethy larainoinethyleniraino- ^, 5-diraethyl-pheny1-N-methylcarbamate

M.p. 102-103 ° C P. «82 - 85 ° C P. * 110 ° C

M. «178 · 179 ° C (hydrochloride)

oil

P. «120 - 121 ^U C (Chloraceta, t)

F. «156-157

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-5-

link

Physical constant

/ III

IX

XI

XIII

XIV

XV

χνΐί

XX

XXI

..4-Diethylaminorae thyleniniino-3, 5-diinethyl-phenyl-N-methylcarbaraate

4-Dimethylarninornethylenimino-3-

methyl-6-isupropyl-phenyl-N-raethyl-

carbaraat

4-diethy laininome thyleniininQ-3-

inethyl-6-isopropyl-phenyl-N-iaethyl-

carbamate

4-pissthylaniinoraethyleniinlno-2 «

methyl-5-isopropyl-phenyl-N-niethyl-

carbamate

^ -Diinethylaniinomethyleneimino-3-

aethyl-5-ia ° l> ropyl-phenyl-N-raethyl-

carbamate

• 4-DIilthy laminome thy lenimino-3-ir.e thyl · 5-isopropyl-phenyl "» N-methylcarbarflat

4- (N *, N ¹ -Tetrarne ethylene aminoraethylene carbamate

4- (H * # N * -Pentamethylene arainomothyleni "ino-3" 5 "" li "ie thy l" pheny l-N-ia · ethyl carb Junate.

Pllnoine thy l "nimino-3" 5-dieethylphenyl-K-raethylcarbam * t

y-Plmethylaminomtthylenimino-ή- «Ethyl-phenyl-N-methylcarbylate

XVIIX 3-DJ.ßi · thy laminome thy leniainophenyl-

XIX ^ -Dimethylaminoroethylcnirainophenyl-

^ -Diinethylarainoraethyleiiiinino-J-methyl-phenyl-M'-cyclohexylcarbamate

^ -Dimethylarainofnethylenirainophenyl " U-ethylearbainate

4-diraethylaminoethyleneinophenyl-N-butylcarbainate

4-Dimethylajninomethylenirainophenyl-3,5-dimethyl-phenyl-N-ethyl-barnate

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P. «86 - 87 ° C

P. * 127 * 5 - 128 ° C

P. " 92.0-92.5

P. -ι · α87 - 188 ° C (Hydrochloric!)

F- * 103 - 104.5 C oil

F. «« 185 ° C

F. m 85.0 ° C

F. - 144 * 145 ° C

F. - Π8 · 119 ° C

6i - »

F. m 118 - 119 ° C (chloroacetate)

P. »100 - 103 ° C

P. «* 105 - 108 ° C oil nj

1.5 ^ 50

P. «146-147 ° C

-6-

B Formaml dine

I N- (2-methi'l - ^ - chlorpheni ^r l) -H ^t -niethylforraaraldine

II N- (2-methyl-chlorophenyl) -NVN ^f -dimethylforraamidine

III N- ^l (2-metliyl- ⁱ r-chlorophenyl) '!> U, N ^l -diniethylformamidiniU2iichlürid

IV H- (2-ciothyl-4-chlorophenyl) -N *, N'-diethyl formalin aridin

V N- (2-iuethyl- ⁱ J-chlorophenyl) -K ¹ -n-propylforraaraidin

VI N-CS-raethyl- ^ chlorophenylJ-N'jN ^ dl-n-propylformajaidin

VII N- (2-methyl-'l-chlorophenyl) -N ^f -isobutylforraamidine

VIII N- (2-methyl-4r-chlorophenyl) -N * -sec • -butylformamidine

The mixtures according to the invention can be used alone or together with other pesticides, such as insecticides, acaricides or fungicides. Water »Mineral oil · or Lsungenilttelf suitable twt · Carriers are s. B. Benfconifc, Bleiehtrrt«, Oipe, XalH # Kiteelgur, Pyrophyllite, 3ilioiuodioxyd or Talcua · Di · Preparations can also additives such as Ejaulgienaittel, Net * - or Eindeoittel, Tr “ lbgaee _f fragrances »Stabiliiatoron * Attractive" toffe or flepellents containing · The agents can, among other things as dust, scattering agents or granules., as a sprayable, verspritz- or nebulizable liquids are used as aerosols or fumigants _t *

The amount of the mixture according to the invention »used in pesticides and crop protection agents, eg. B. in insecticides,

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Akarlziden u.a «, can be used within wide limits vary · It depends, among other things. on the ratio of the components, on the type of preparation, the method of application, the desired Beefing success and the type of pests to be controlled. Depending on the form of preparation, the content of the mixture be between about 0.1 and 90 percent by weight of the agent, those in concentrations as low as 0.001 percent by weight can be used «In general, however, result in use concentrations between about 0.023 and 10 percent in liquid or solid carriers give excellent results. Pure For some purposes, higher use concentrations up to about 25 percent by weight may be desired; be"

In the mixtures according to the invention, the weight ratio of the carbamates A to the forraainidines B can generally be from about 1 to 3 ^! be about 1 to 10

Particularly good results can be a Gewlchtsverhält- nis the carbamates A to the Foriaaioidinen B of 1: 2! · 1 to 1

The compounds contained in the mixtures according to the invention can be used as such or in the form of their salts, eg. B. the water-soluble hydrochloride, use.

These compounds, which, as already mentioned, are known per se, can be prepared in a manner known per se.

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The preparation of the components according to the invention containing the active compounds Mixing takes place in the usual way by means of grinding or mixing processes, inter alia. ·

Of the above-listed components of the mixtures to be used according to the invention, the active ingredients J-dimethylaniinoinethyleneiminophenyl-N-iJiethylcarbaiaat and 4-D1-niethylaininoraethylenifiiino-3-niethylphenyl-H-raethylcarbainat (compound, AI and A III) and N- (2- Methyl-4-chlorophenyl) -N ^! , N ^f diinethylformiamidine (compound B II) and salts thereof, in particular the hydrochlorides, have been shown to be suitable for combating plant-parasitic strokes. Preferred weight ratios of the components are carbamate AI to formamidine B II or their salts such as 1: 2 and carbamate A III to formamidine B II or their salts such as 1: 1.

Another advantage of the mixtures to be used according to the invention lies in their effectiveness against insects and other pests as well as their eggs, which opens up a variety of uses results.

As well combable are z. B. named the following pests:

Codling moth or Obstraade (Carpocapsa poraonella) Peach shoot borer (Cydia molesta) Peach moth (Anareia lineatella) Apple peel moth (Capua reticulana) Plum sawv.'espen (iloplocampa hapla and niinuta) Apple leaf suckers (Psylla mali)

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Leaf fleas (Empoasca ερ.)

ι San Jose Sqhildlaus (Quadraspidlotus perniciosus). Kreiseliainierniotte (Leucoptera scitella) Pocket miner moth (Lithocolletis blancardella)

The unexpected superiority of the mixtures according to the invention In comparison to the individual components, the following experiments show

example 1

The following results were obtained in 7 field tests with numerous repetitions in apple crops to control the fruit-growing spider mite (Metatetranychus ulmi Koch), where the number 100 is assigned to the mixed products and the effect of the individual coroponents is shown as a percentage. Agents tested were those containing I-dimethylaminoinethyleneiminophenyl-N- ■ * thylcarba "Ät (AI) and K" {2- ^{methyl- ^ - chlorophenyl) -N t} , H ^t diuethylforminophenyl (B II) in a weight ratio of 1 I 2 or 4-dime thy lawlnome thy lenimino-5-me thy lpiieny XN-cae thy lcarbamate (A III) and N- (2- ^ ethyl "4-ohlorphenyX) -N ^t _> N ^l " dimethylformamldine (B II) in a weight ratio of 1: X Im Compared to agents containing the individual components. For use aqueous suspensions of funds "came,

009822/185 7

• Means ent
holding JO Active ingredient in
100 liters
Prepare fuel 1567166 AI + B II • weight
behaves
nis
Λ: B 75 ßr Assessment of the
effect A III + B II 1: 2 80 gr 100 A I 1: 1
• 75 gr \ 100 A III 80 gr 79.6 B II 80 he 82.2 75.8

Example 2

The following table contains the LC ^ Q values of the agents according to the invention and some known acaricides.The determination was carried out by means of a leaf sticks test * in which round leaf pieces were punched out of bean leaves Ιο diameter of 18 mm, with the back facing up on foam pads in water-filled Petri For the experiments with eggs, they are left to lay their eggs for 24 hours and the females are then removed up to 4 concentration gradations in the range of the expected We _{0 were used} Bivereuche JJ sheet gap old 200 Eitrn used the Sterbllcnkeitswerto by j5 to 4 biw · J days as a percentage of the dead animals sur Oeaa "tflu * 's laboratory animal · calculated and so" \ Log frobiV Paper (WahrtcheinitcWceitsnetz)

gen. Through the respective point a straight line was laid and the values of the 50 £ l mortality read off in% active ingredient.

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The superiority of the agents according to the invention containing 5-diniethylaminoniethyleniminophenyl-N-ynethylcarbamate (Λ I) or 4-DiinethylaiJiinomeUiyleriiinino-3-inetlTylphenyl-N-methylcarbair.at (A III) as a mixture with N- (2-methyl-4-chlorophenyl) -N ', N'-diine thy 1-forraamidine (D II) in weight ratios of 1: 2 or 1: 1 is unambiguous because, in contrast to the comparison agents, an approximately uniform effect was exerted on all stages of the pests will. ·

Means ent
holding i loop Facial
behaved-
nis • ^LC 50
Adulticide in ppm
Ovicide or
Ovolarviaid 11.25 Invention barrel M . - 15.7 AI + B II 1: 2 8.1 A III + B II 1: 1 12.2 21.4 Single components about 40 AI • • 2.9 6.7 A III - 8th B II 62 Disposable means

O, O-dimethyl-S'-2- (ethylsulfinyl) ethylthiol phosphate

0,0-Dii: iethyl-U-: methylcarbaraoylmethyldithiophosphate

0,0-dimethyl-diethylaT.ldo-l-chloro crotonyl phosphate

pyrimidinyl thiophosphate 0,0-diethyl p-nitrophenyl thiophosphate

0.75

2.5

5.7

24

27

200

14 approx. ² 100

15.7 510

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Containing agents

Weight ratio

₀ in ppm

Adulticide Ovizid or Ovolarviζid

1,1-bis (p-chlorophenyl) - 2,2,2 -trichloroethane

2,4,5 »^ ^ Tetrachlorodiphenyl sulfone

p-chloro-pheriyl-p-chlorobenzene sulfonate "19

82

2000 1.2

2000

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Claims (4)

Pat e η ta η s ρ r ti c he 1. Containing pesticides with increased effectiveness as active component indicators a connection the general formula Y-CH-N ' -R ₂ 4 .0
-0 - C - NHR, in the R, * lower alkyl or cyclohexyl, . Rp and R_ β lower alkyl or together rait decj Nitrogen atom a ring optionally containing further heteroatoms, R ^ «hydrogen, lower alkyl, lower Alkenyl or chlorine, Rt - hydrogen or methyl mean, or their salts * la mixture with at least one Compound of the general formula 009822/1857 Neue Unleriaaen ^, ^, " -Φ- "156/166 / If in dor R ₁ and Rp are alkyl radicals with up to 4 carbon atoms or
R, hydrogen and
R _{2 is} alkyl radicals as defined above represent, or their salts. Containing J-Diinethylaminomethylenininophenyl-N-inethylcarbamat 2. Pesticide of claim 1 or -Diraethylarainoraethyleniroino ^ - ^ - ^ niethyl phenyl-H-raethylcarbamat Rait in the mixture of N- ^(S-methyl-i i-chloro-phenyl) -H ^t, N ^t dimethylforniai3idin or their salts; -. 5. Pesticides according to claims 1 and 2 containing the identified carbamates and pormamidines in a weight ratio of about 1 to 3 ^: about 1 to 10, preferably from 1: 1 to 1: 2, 00S822 / 1857 BAD OBJGlKAL