DD154799A1 - AKARICIDAL AGENTS - Google Patents

Abstract

The invention relates to novel means of controlling mites which kill plants, which contain pyrimidines substituted as active ingredients and can be used for the protection of crop plants. The aim and object of the invention is the development of new effective, the well-known acaricides ebenbuertiger or superior means for mite mitigation, which take into account the necessary due to resistance training in the Schaedlingen rotation of the active ingredients and allow to keep the infestation below the economic damage threshold. It has been found that the hitherto only partially known pyridine (or N-oxide) carbonsaeureanilide of formula I are suitable as new active ingredients for acaricidal agents. In common formulations, e.g. used as a wettable powder, emulsion concentrate or Staeubepulver, show the inventive means in fruit growing good Bekaempfungserfolge and significant increases in yield.

Description

Acaricides agent

Field of application of the invention:

The invention relates to novel compositions for the control of plant-damaging mites, which are characterized by a content of substituted pyridines. The invention further relates to the use of the compounds or agents containing these active substances for controlling plant-damaging mites in arable crops.

Characteristic of the known technical solutions?

Plant-damaging mites are widespread worldwide and of great economic importance as direct pests in vegetable growing under glass or plastic, as well as in the field, in fruit and hops, in cotton, tea and other important crops. "Purely the fight against these mites are known a number of effective chemical compounds , which, however, have economic and technical defects. Thus, with repeated use of the same drugs resistance formation, which makes their substitution by new acaricides (rotation of the funds) required. As a result, there is a need to constantly develop new effective acaricides with the trend towards specialty acacia for certain crops. "Pyridinecarboxamides or N-oxides have been used in numerous patents

- ² - 2 25 5 24

DE OS 24 17 216, 25 58 278, 27 14-13 »DD AP 122 774» 115 421

as fungicides, anticoccidiosis, drugs and insecticides and pyridinecarboxylic anilides in JA-PS 5031-099 as fungicidally effective agents proposed »

Acaricidal active derivatives of pyridinecarboxylic acid have not previously been described

Aim of the invention!

The aim of the invention is the development of new effective means ziar combating plant-damaging mites, which are equal or superior to the already known acaricides in their effect on mite stages with great protection of crops and natural enemies ₈ so that the infestation can be kept below the economic damage threshold ^.

Explanation of the essence of the invention *

Technical Aufgabei

The invention has for its object ^ to develop new acaricidal agents based on new chemical agents to accelerate the currently particularly urgent rotation of acaricidal agents to overcome resistance phenomena and to avoid the associated loss of yield in arable crops and thus an advantageous control of pests zn gewährleisten'o '

Features of the invention:

It has been found that the previously only partially known substituted pyridine-carboxylic acid anilides or _e the N-oxides of the general formula I

225 524

1 2

in which R and R independently of one another are hydrogen, halogen

or alkyl and η is 0 and 1, have acaricidal properties which enable their use as agents for controlling plant-damaging mites.

The compounds of structure I, η = 0 are for the most part known and accessible by customary synthetic methods, for example by heating the pyridinecarboxylic acids with amines to higher temperatures. Soc, London 1960, 3371 J, Amer. former Soc. 67 (194-5) 1135, & n obezo Chimii I9 (1949) 356] · better in opposition of POCl i ~ Gazzo chim. Ital. 80 (1950) 456, J. prakt. Chem, (V 19 (1962) 45J, PCl ₅ [zh, obez. Chimii 16 (1946) 1719 »; fb Amer., Ehern, Soc. 80 (1958) 992 ~ | , Polyphosphoric acid [~ FR 1 3 & 4 (1964), BE 634 597 (1963) J or polyphosphoric esters Jchea »Pharm« Bull. I3 (1965) 1065], by reaction of the carboxylic acids with (ArNH) ₂ SO ₂ ί ~ Ζη _β obez. Chimii 22 (1952) 1616] or ArH = ^ P-NHAr FJ chem., Soc., London 1960, 33% BE 610 952 (1948) J, ^ by reaction of the carboxylic acid esters with the arylamines JJ Amer 67 (1945) 1135 »Gazz. Chim. Ital. 80 (1950) 456J or with magnes- lene ArN (MgX) ₂ ^ Zh. Obez. Chimii 33 (1963) 1261J or else by reaction of the acid chlorides or anhydrides with the amines jj. chem, Soc., 'London i960? 33? 1 ₉ J. Amer »former Soc. 6? (1945) 1135 · Gazz. chira. Ital. 80 (1950) 456, Cheia. Ber. 93 (I960) 3Ο83, HeIw. Chim. Acta 47 (19 ^ 4) I62I.

The compounds I, η = 0 listed in Table 1 were prepared by the "mixed anhydride method", ie. H. by reaction of the pyridinecarboxylic acids with chloroformate in the presence of triethylamine and subsequent aminolysis (Example 1) V

- '* - 22552A

For the preparation of the compounds in relatively large amounts, the reaction of the pyridinecarboxylic acids with aryl isocyanates bs * * has proven particularly useful (Example 2). The oxidation of the picoline, nicotine and isonicotinic anilides to the N-oxides I, η = 1 is carried out with 30% H "0 in glacial acetic acid (Example 3).

The compounds of the formula I can be used as such or in combination with a suitable additive as acaricidal agents. Suitable additives are, for example, solution diluents. Emulsifying agents and thickeners and other plants · »Protective and pest control agents ·

The agent _t contain the active compounds of formula I ^ may be administered in verschiedenster form, for example as emulsions, dusts, powders, dispersions, fog agents or microgranulate the administration is directed exclusively by the intended use · The preparation of the form suitable for various Anwondungsformen active ingredient formulations may in accordance with the mixing and grinding methods customary in forbreeding technology

In practice, depending on the nature of the treatment ₈ to be carried out, the compounds of formula I can be applied at the time and stage of development of the pest population in concentrations of 100 to 1000 ppm, especially in the concentration range from 200 to 500 ppm.

The compositions according to the invention can reduce the growth of spider mites in untreated by about 5 times more than 90 % already after 2 applications, which is regarded by the practice as a completely sufficient control success and is confirmed by the yield determination »'They reach after 3o Application an increase in yield of more than 600 % (compared to 100 % in untreated sV Tab. 4 and 5) and confirms enormous economical effects that can be achieved with an ovicidal special acaricide (Fentoxan). The following examples illustrate the preparation of the compounds according to the invention and their specific acaricidal properties

25 524

embodiments

example It

^ 2 ₉ 3 g _(0? 1 mol) of nicotinic acid v / ground in 200 ml of absolute tetrahydrofuran (THF) suspension. Is added dropwise with stirring, first 10.1 g (0.1 mol) of absolute triethylamine and after cooling to 0 ⁰ C, the solution of 10.9 g (0.1 mol) of ethyl chlorocarbonate in a little absolute THF hinzue then allowed 1 hr · 'Stirring and then the solution of 12.65 g (0.1 raol) 2-chloroaniline in 30 ml of THF, remove the ice bath and stirred for 1 h. At room temperature and 1 hr. Under reflux. The hot filtered solution is evaporated to dryness in vacuo and the reaction product is recrystallized from ethanol to give 13 * 9 g (60 % d "Th ₉ ) nicotinic acid""chloroanilide in the form of colorless needles, Schmp, 213-216 Ci

Example 2:

Ss brought 61t5 (0 ^»a 5 ° D picolinic absolute acetonitrile are suspended in 200 ml (by dropwise addition of 50.5 g 0.5 mol) of absolute triethylamine with stirring into solution. Subsequently, while stirring the solution of 76, 5 g (0.5 mol) of 4-chlorophenyl isocyanate in a little absolute acetonitrile, with evolution of gas (CO 2) and darkening of the solution, a colorless product separates out, and the mixture is refluxed for a further 0.5 h, cooled ? then sauf room temperature and filtered off the solid · After the usual work of the filtrate, which still contains small amounts of the reaction product is isolated a total of 10 '' 9 g (93 0 picolinic ~ 4 ~ ehloranilid _t, mp 135 ⁰ C. (Needles made of ethanol) ·.

Example 3t

11.6 g (0.1 mol) of isonicotinic acid-3-chloroanilide are dissolved in 50 ml of glacial acetic acid and mixed with 25 ml of 30 $ H ₂ O. The mixture is heated to 60 C for 16 h. During the reaction and subsequent cooling, the 4- (3-chloroanilino-carbonyl) -pyridine-1-oxide crystallizes out. It is filtered off with suction, thoroughly

~ ₆ ~ 225524

washed with water, sucked dry and made from toluene uracrystalline ^M »10? g (81.3 $) yellowish cuboid, mp, 248 «252 ⁰ C,

Example 4t

Ovizidwirkg against Tetranychus urtieae. Leaf discs of Phaseolus vulgaris were exposed to Tetranychus urticae summer eggs and sprayed with an aqueous solution of various concentrations of the test compound » ¹ After complete larval hatching on the untreated control, the number of hatched larvae in the treated test pieces was determined

The results calculated as percentage mortality rates are shown in Tables 2 and 3 »

Example 5?

AdultizidwirkuHg against females of Tetranychus urtica ^ 1 leaf of Phaseolus vulgaris was occupied by 25 females of Tetranychus urticae. 2 leaves per test element. were sprayed with aqueous emulsions of various concentrations of the test substance «After 48 hours» the number of females killed was determined «The results calculated as percentage mortality rate are shown in Tables 2 and 3»

Example 6?

Free range test against Panonychus ulmi Field plots of the apple variety «Gelber Köstlicher ¹¹ (5 trees each 4 m apart in two parallel rows) infested with Panonychus ulmi were sprayed with 10% aqueous emulsions at an application concentration of 400 ppm of the active substance to be tested (Appl took place on 26, 4 * _t 25v 5 * and 23 »6 _# ). The efficacy was determined by counting the mobile stages on 30 leaves per plot at 25x5x and 13x6x. In addition, the yield was determined by counting the apples on 15 trees (3x5 trees).

- 7 - 2 2 5 5 2 4

The compound was comparatively tested against the standard agent Fentoxan ax the host substance azoxybenzene (Fenazox) (see tables h and 5) *

225 524

Table 1

Position ^ CONHAr V · Ar r .CONHAr Training (SO No. η = 1 Schmp «( ⁰ C) Y. (SO 2 ^C 6 ^H 5 η = 0 Schmp »( ⁰ O 40 20 139 - 143 50 1 2 2-CH ₃ C ₆ H ₄ 74 « 76 40.5 21 131-134 46.5 2 2 4-CH ₃ C ₆ H ₄ 58 - 60 55 22 146 - 149 44.6 3 2 2-ClC ₆ H ₄ 105 - 108 60 23 140 - 143 25.0 4 2 > C1C ₆ H ₄ 106 - 107 48.2 24 149 - 153 46 _p. 7 5 2 4-ClC ₆ H ₄ 91 - 94 60J5 25 ^ I ^ i ^ t / inc % (I ^9m ι {j 30.8 6 2 VBrC ₆ H ₄ 135 58.3 26 18? - 191 47.1 7 2 2,5-Cl ₂ C ₆ H ₃ 142 - 143 49.5 27 203 - 207 34.0 8th 2 3,4-Cl ₂ C ₆ H ₃ 135 - 137 54.7 28 229-232 42.5 9 3 ^C 6 ^H 5 153 - 157 47.6 29 210-213 56.5 10 3 4-CH ₃ C ₆ H ₄ 111 ' 114 52.3 30 220 - 222 39.1 11 3 2-ClC ₆ H ₄ 137 - 140 60 12 3 4-ClC ₆ H ₄ 213 - 216 56.2 31 276 - 279 49.6 13 3 4 4-BrC ₆ H ₄ ^C 6 ^H 5 200 60.1 53.5 32 33 2? 5 - 279 220 - 222 67.5 39.9 14 15 4 2-ClC ₆ H ₄ 172 - 163- 175 166 56.2 34 I69-171 35.2 16 4 3-ClC ₆ H ₄ 136 - 139 61, '3 35 248 - 252 81.3 17 4 4-ClC ₆ H ₄ 162 - » 165 59.5 36 248 - 250 72.0 18 4 4-BrC ₆ H ₄ 139 - 141 62.0 37 246 - 249 58.1 19 198 - 200

225 524

Table 2

Acaricidal activity against Tetranychus urticae

Active ingredient (1000 ppm AS)

Mortality rate (%) ovicidal adulticide

31 1

6; a

100

7 8 0 6 6 10

Table 3

Acaricidal activity against Tetran y chus urticae after administration of various AS concentrations

Active substance verb; ^! 6

Mortality rate {%) at the concentration (ppm) 1000 800 400 200 100

ovicidal adulticide

100 11

100 11

100 5

96

Table 4 • mites Fentoxan untreated Outdoor test opposite Panonychus ulmi Per % to Milbea mites Boniturtermiae, verb. 6 Sheet unbeh'e Per % to Per sheet Contr " Sheet unbehv 4.2 I2 _r ; 1 · Contr 10.7 5.9 2 ^ 5 6.5 38.5 3.7 2.0 183.5 25. 5. 13. 6 *

~ 10 «

225 524

Table 5 Number per tree of apples 15 trees (3 x 5) • yield determination 249 * 7 374-6 Yield in % (compared to the non-control) Preparation or «active substance 269.7 4046 638'2 Verb. 6 39 ^ 1 587 689; ^: 3 Fentoxaa 100 "Neat control

For this 1 page formulas

-41- 2 25 524

CONH

Claims (1)

~ Ή- 2 25 5 24 Invention claim: Acaricidal agent, characterized in that it is the active ingredient in pyridine-carboxylic acid anilide or its N-oxide of the general. 1 2 Formula I ₉ in which R and E independently of one another hydrogen i halogen or alkyl andnO or 1, in addition to the usual carriers, solvents and / or formulation auxiliaries contain »