DE2834945A1 - THIADIAZOLYLBENZAMIDES, METHOD FOR THE PRODUCTION THEREOF AND INSECTICIDES CONTAINING THE SAME - Google Patents

Description

. ^ NNINQ-MAAS MEINIQ-LEMKE-Mockery 8CHLEISSHEIMERSTa 299 βΟΟΟ MUNICH 40

Χ-4472Η

Eli Lilly and Company, Indianapolis, Indiana, V. St. A.

Thiadiazolylbenzaitiides, process for their preparation and insecticidal agents containing them

(Addition to patent application P 27 04 288.2)

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The invention relates to thiadiazolylbenzamides, processes for their preparation and insecticidal agents containing them, and it is primarily aimed at a further refinement and improvement of patent application P 27 04 288.2.

In the patent application P 27 04 288.2 insecticidally active thiadiazolylbenzamides of the formula I are

_D 1O

HO

^v ΐ

described,

wherein R represents one of the following radicals:

R ⁰ -. '

R ¹ 'V

0OÖ8Ö9 / O82S

-R ⁴

ΛΛ

"V

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-R ⁵

\ / \ / or

• ο-

wherein at least one of the residues

R °, R and R denotes chlorine or bromine and these radicals,

which can be the same or different from one another, otherwise hydrogen, Mean chlorine or bromine,

X stands for oxygen or sulfur,

4th
R and R dxe are equal to or from one another

can be different, are hydrogen, chlorine, bromine or methyl groups, where R stands for hydrogen when X is oxygen,

R is hydrogen, chlorine, bromine, fluorine or a

Trifluoromethy! Group means and in which

7 8

1) R and R are hydrogen atoms and one of the radicals R

8th

and R is hydrogen and the other of the radicals R and

R is hydrogen, chlorine, methoxy, bromine, iodine, fluorine, a trifluoromethyl group _R is a methyl group, a hydroxyl group, a Phenyl group! Or monobromo-, chloro- or -fluorphenylgruppe or

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2) R and R are hydrogen atoms and R and R are mutually exclusive may be the same or different from one another, chlorine, fluorine or bromine or

6 8 7 9

3) R and R are hydrogen atoms and R and R are mutually exclusive may be the same or different from one another. Chlorine, fluorine, bromine or a trifluoromethyl group or

4) R and R are hydrogen atoms and R and R are mutually exclusive may be the same or different from one another, chlorine, fluorine or bromine or

5) R ⁷ , R ⁸ and R ^{9 are} hydrogen atoms and R ^{6 is} chlorine, fluorine or bromine or

6) R, R and R are hydrogen atoms and R. an acetamido, Mean nitro, amino or cyano group,

R and R, which can be the same or different from one another, represent hydrogen, chlorine, Fluorine, bromine, a methyl or methoxy group, where

1O 11

1) one of the radicals R and R only hydrogen

can be if the other of these two radicals is a methoxy group,

2) at least one of R and R is a methyl or methoxy group _R must be other than when

a) R does not represent a hydrogen atom and

6 7 9

R, R and R are hydrogen or

6 8

b) R and R are hydrogen atoms and one

7 9
or both radicals R and R trifluoromethyl

groups mean

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8 9

3) neither R nor R phenyl, acetamido, methoxy,

Nitro, amino, cyano or substituted phenyl groups if not both radicals R and R represent methoxy groups.

7 8 9

4) two of the radicals R, R and R are hydrogen,

if not both radicals R and R are methyl or methoxy groups, _r

10 11

5) both radicals R and R are methoxy or methyl groups

mean, if R stands for a pyridyl, naphthyl, furyl or thienyl radical,

6) both radicals R and R are methoxy groups when R is a benzthiazolyl, benzoxazolyl, benzthienyl, Represents benzofuryl, isoxazolyl, quinolyl or thiazolyl radical.

Patent application P 27 04 288.2 also relates to a process for the preparation of the thiadiazolylbenzamides Formula I given above, which consists in that either

1) a 2-amino-5-R-substituted-1,3,4-thiadiazole of the formula

: - ·. · —NH ⁷

NH

wherein R has the meanings given in connection with formula I, but not for an amino or acetamidopheny! group stands,

with a benzoyl halide of the formula

ο I.

Halo-C - <^ χ * 1

wherein halo is chlorine or bromine and R and R have the meanings given for formula I,

acylated or
2) a compound of the formula

X-NH-C-NH-C ~ - <^ . · \

R ¹¹

10 11

wherein R and R are those given in connection with formula I. Have meanings and X for the group

0
RC-NH- or R-CH = N-,

wherein R has the meanings given in connection with formula II Has,

Il

when X is R-C-NH-, with a dehydrating agent and, when X denotes R-CH = N-, is cyclized with an oxidizing agent and optionally a compound of

Formula I, in which R is a nitro group, is reduced to a compound in which R is an amino group,

and optionally the compound in which R is an amino group

means being acylated to a compound in which R is a Means acetamido group.

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-J

The present invention relates to a number of new N- (1,3,4-thiadiazol-2-yl) benzamides with a phenyl, naphthyl or heteroaryl group in position 5 of the thiadiazole ring and with substituents in positions 2 and 6 of the benzyl ring Processes for producing these compounds and insecticidal agents containing such compounds as an active ingredient.

Insect control is one of the first tasks tackled by chemical research in agriculture and needs constant further development. Insects of many orders not only attack natural plants of all kinds, but also also cause unsanitary conditions and spoilage through contamination of food and feed. The by insects Damage caused can no longer be recorded in numbers, which is why the control of harmful insects is inevitable the highest priority.

The withdrawal of the old residue insecticides has recently spurred the search for new and better insecticides.

Herbicidally effective 1,3,4-thiadiazol-2-ylureas are already known from U.S. Patent 3,726,892.

In Indian J. Chem. 8, 509-513 (1970) a method for the preparation of 2-amino-1,3,4-thiadiazoles described, and these Compounds are intermediates in the preparation of the instant compounds.

US Pat. No. 3,748,356 discloses N-benzoyl-N ¹ -phenylureas which are herbicidally and insecticidally active.

The invention is in the field of, and relates to, agrochemistry new thiadiazolylbenzamides of the formula I.

H 0? ^CHs

I Il * - ·

90980 ^Q ' ^neni *

45

wherein. R represents one of the following radicals:

τ ii \ y '

R ^s

• ·

or

ο--

whereby

Means oxygen or sulfur,

one of the substituents R ¹ or R ²

Is hydrogen and the other is fluorine, chlorine, bromine, trifluoromethyl or methoxy,

one of the substituents

• 3 A

R ° or R

Is hydrogen and the other is methoxy or trxfluoromethyl, '

9098I39 / 082S

one of
Substituents

R or R is hydrogen and the other is chlorine,

Bromine, fluorine, trifluoromethyl or hydrogen represents and

one of
Substituents

7 Q

R or R is hydrogen and the other is C ₁ -C ₃ -

Alkoxy means which is substituted by one or more fluorine atoms.

The invention also relates to a process for the preparation of the thiadiazolylbenzamxde of the formula given above I, wherein the substituent R has the abovementioned meaning, which is characterized in that either

(1) a 2-amino-5 ~ R-substituted-1,3,4-thiadiazole of the ■ Formula II

R— ·.

-NH II

wherein R has the meaning given above, with a benzoyl halide of the formula III

OCH ₃

° J- HaIo-C-

wherein halo is chlorine or bromine, acylated or

- γ-

(2) a compound of formula IV

. OCH ₃

S 0 I

C-NH-C- · ^% _Iv

3CH ₃ υ

Il

where E stands for R-C-NH- or R-CH = N-,

where R has the meaning given above, either with a Dehydratxsxerungsmxttel ·, if E for

0
RC-NH-

stands, or with an oxidizing agent, if E * is

R-CH = N-is treated.

The subject matter of the invention also includes insecticidal agents derived from the Thxadiazolylbenzamxden according to the invention Make use.

All ratios and percentages given below are based on weight. The specified temperatures are in degrees Celsius. Halogen is understood to mean fluorine, chlorine, bromine and iodine.

The present Thiadxazolylbenzamxde of the formula I are according to known or analogous processes manufactured. Leave all thiadxazolylbenzamxde

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-X- * 283A945

easily by acylation of 2-amino-5-R-substituted-1,3,4-thiadiazoles of formula II

R-. /.-NH ₂ II _;

wherein R has the meaning given above, with benzoyl halides of the formula III

GCH ₃

o I _β

HaIo-C- ·;

OCH ₃

where halo is chlorine or bromine.

The acylation is carried out in the presence of a base in a reaction solvent such as tetrahydrofuran, dimethylformamide, dimethyl sulfoxide or diethyl ether. The preferred base is sodium hydride, but organic bases such as pyridine, triethylamine or triethanolamine and other inorganic bases such as sodium hydroxide, potassium carbonate or lithium bicarbonate can also be used. The temperature range of this reaction is between about -10 and about 75 ^° C., preferably between about 0 ^° C. and about 25 ^° C.

The aminothiadiazoles required as starting materials are prepared by known processes. Generally will they by oxidative cyclization of a thiosemicarbazone, preferably with ferric chloride, or by dehydrating Cyclization of a thiosemicarbazide obtained with a strong acid. In this context, reference is made to what has already been mentioned Indian J. Chem. 8, 509-513 (1970) and the aforementioned US Pat. No. 3,726,892.

903803/0825

The thiadiazolylbenzamides of the formula I, in which R has the meaning already mentioned, can also be obtained by cyclizing a Compound of formula IV

OCHs S 0 I

¹¹ "/ \

E-NH-C-NH-C- ' \ IV,

OCHe

Il

where R is R-C-NH- or R-CH = N-,

where the substituent R has the meaning given above, · with either a dehydration tool if E is for

0
RC-NH-

stands, or with an oxidizing agent, if E is

R-CH = N- can be prepared.

Suitable dehydrating agents include phosphoric acid, formic acid, phosphorus pentachloride, phosphorus pentoxide in the presence a strong acid, and the chlorides and anhydrides of benzoic and alkanoic acids. The preferred dehydrating agents are the strong acids, especially methanesulfonic acid and concentrated sulfuric acid.

The dehydrating cyclization is carried out at temperatures of about 20 to 80 ^° C., preferably at room temperature. Usually, this reaction is preferably carried out without a solvent, but solvents can also be used if desired, and examples thereof are

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halogenated benzenes and halogenated alkanes such as chlorobenzene or methylene dichloride.

The preferred oxidizing agent is ferric chloride. It can but other strong oxidizing agents can also be used, such as calcium ferricyanide. Oxidative cyclizations are preferred in lower alkanols, such as ethanol or propanol, at reflux temperature of the reaction mixture carried out. In general Temperatures of about 50 to 100 ° C can be used when appropriate.

The starting materials required for the preparation of the thiadiazolylbenzamides of the formula I are for the average person skilled in the art readily accessible =

The following examples explain the synthesis of typical representatives the thiadiazolylbenzamides according to the invention, and the The preparation methods given show the synthesis of typical starting materials. All connections obtained are through nuclear magnetic resonance analysis, elemental microanalysis and, in some cases, infrared analysis and mass spectroscopy identified.

The first group of examples illustrates the preparation of thiadiazolylbenzamoxes of formula I by acylation by aminothiadiazoles

example 1

N- / 5- (4-trifluoromethoxyphenyl) -1,3,4-thiadiazol-2-yl / -2,6- d ime thoxyben ζ amide

A mixture of 1.8 ml of pyridine and 5.2 g of 2-amino-5- (4-trifluoromethoxyphenyl) -1, 3,4-thiadiazole in 50 ml of tetrahydrofuran is heated to reflux temperature. Then be 4.4 grams of 2,6-dimethoxybenzoylchloride dropwise over a period of 15 minutes added in 20 ml of tetrahydrofuran.

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The mixture is then refluxed for a further 45 minutes with stirring. The solvent is then removed in vacuo and the residue obtained is recrystallized from aqueous ethanol. In this manner, leads to 7.2 g of the title compound as white needle-like crystals, melting at 201 to 203 ⁰ C.

example

N- / 5- (6-methoxy-2-benzo / b / furyl) -1,3,4-thiadiazol-2-y] L / -2,6> dimethoxybenzamide

100 ml of tetrahydrofuran containing 0.7 g of 2-Amino ™ 5- (6-methoxy-2-benzo- / b / furyl) -1,3,4-thiadiazole are mixed with 0.3 g of sodium hydride. After the formation of bubbles has ceased, 0.62 g of 2,6-dimethoxybenzoyl chloride are added. The reaction mixture is stirred for 1 hour at room temperature, after which the solvent is removed by evaporation in vacuo. The residue is mixed with water, whereupon the whole thing is acidified with normal hydrochloric acid. The Peststoffe are filtered off, dried and recrystallized from benzene-hexane to give 0.12 g to the title compound enters, melting at 215-217 ⁰ C.

The process described in Examples 1 and 2 is used to prepare the further thiadiazolylbenzamides indicated below repeated. The aminothiadiazoles and benzoyl halides required as starting materials for this purpose Substituents result readily from the thiadiazolylbenzamide obtained in each case as a product. The in detail Connections made according to this are mentioned first in the following, while in the list that follows the amounts of reactants used and the amounts and melting points of the compounds obtained are summarized.

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-yf-

Example N- / 5- (2-Indenyl) -1, 3,4-thiadiazol-2-yl ₁ / -2, 6-dimethoxybenzamide

Example 4

N- / 5- (5-methoxy-2-benzo / b / furyl) -1,3,4-thiadiazol-2-yl / -2,6-dimethoxybenzamide

Example 5

N- / 5- (5-trifluoromethyl-2-benzo / b / furyl) -1,3,4-thiadiazol-2-y-1 / -2,6-dimethoxybenzamide

Example 6

N- / 5- (6-Trifluoromethyl-2-benzo / b / furyl) -1, 3, 4-thiadiazol-2-y] L / -2,6-dimethoxybenzamide

Example 7

N- / 5- (4-pentafluoroethoxyphenyl) -1,3,4-thiadiazol-2-yl / -2,6-d imethoxybenz amide

Example 8

N- / 5- (5-fluoro-2-benzo / b / furyl) -1,3,4-thiadiazol-2-yl / -2,6-dimethoxybenz amide

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On! Position

CO 00 O CO

Example no. Aminothiadiazole Benzoyl chloride product Melting point, ⁰ C OJ
\ 3 1.0 1.0 0.2 230-232 4th 2.0 1.8 1.3 255-257 5 2.8 2.2 2.5 242-245 6th 2.0 1.6 1.0 206-208 7th 3.1 2.2 1.7 227-229 8th 2.4 2.2 1.7 244-245

OO (JD

-yf-

The next group of manufacturing methods and examples illustrated typical cyclizations using dehydrating agents.

Manufacturing method 1

1- (4-pentafluoroethoxybenzoyl) -4- (2,6-dimethoxybenzoyl) thiosemi-

carbazid

0.54 g of ammonium thiocyanate is added to 10 ml of tetrahydrofuran, the reaction mixture is heated to reflux temperature and then 1.5 g of 2,6-dimethoxybenzoyl chloride, which is dissolved in 10 ml of further tetrahydrofuran, are added. The mixture is stirred for 20 minutes at reflux temperature, cooled to ambient temperature and finally 1.5 g of 4-pentafluoroethoxybenzoylhydrazine, which is dissolved in 20 ml of tetrahydrofuran, are added dropwise. The reaction mixture is then stirred for a further 1.5 hours at ambient temperature. The mixture is then evaporated to dryness in vacuo and the residue obtained is washed with diethyl ether. The diethyl ether solution obtained is concentrated under vacuum and the product recrystallized incurred, thus obtaining 1.1 g of the title compound enters, melting at 184-186 ⁰ C.

Example 9

N- / 5- (4-pentafluoroethoxyphenyl) -1,3,4-thiadiazol-2-yl / -2,6 · dimethoxybenzamide

1 g of the intermediate product formed according to preparation 1 above is slowly added to 5 g of methanesulfonic acid and the resulting mixture is then stirred for 5 hours at ambient temperature. The mixture is then slowly poured to 100 g

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Ice and stir the whole thing thoroughly. Then one brings the pH of the aqueous mixture by adding concentrated Ammonium hydroxide to 8.5, filtered the accumulated Solids are removed and recrystallized from aqueous ethanol. In this way, 0.6 g of crude product is obtained. The product is chromatographed on silica gel using a mixed solvent of 70% toluene and 30% ethyl acetate cleaned. This gives 200 mg of pure title compound which is identical to the product of Example 7.

Example 10

N- / 5- (4-trifluoromethoxyphenyl) -1,3,4-thiadiazol-2-yl / ~ 2,6- dimethoxybenzamide

Following the procedure described in Example 9 is used 1- (4-Trifluoromethoxybenzoyl) -4- (2,6-dimethoxybenzoyl) thiosemicarbazide with methanesulfonic acid, whereby one arrives at the compound mentioned in the title, which with the connection of Example 1 is identical.

Example 11

N- / 5- (6-methoxy-2-benzo / b / furyl) -1,3,4-thiadiazol-2-yl / -2,6- dimethoxybenzamide

A certain amount of 1- (6-methoxy-2-benzo / b / furylcarbonyl) is used -4- (2,6-dimethoxybenzoyl) thiosemicarbazide according to the Method described in Example 9 with methanesulfonic acid to give the title compound, which is identical to the compound of Example 2.

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Example 12 N- / 5- (2-Indenyl) -1,3,4-thiadiazol-2-yl / -2,6-dimethoxybenzamide

1- (2-Indenocarbonyl) -4- (2,6-dimethoxybenzoyl) -thiosemicarbazide is used according to the method described in Example 3 with methanesulphonic acid, resulting in the title compound which is identical to the compound of Example 3.

Example 13

N- / 5- (5-methoxy-2-benzo / b / furyl) -1,3,4-thiadiazol-2-yl / -2,6- dimethoxybenzamide

1- (5-Methoxy-2-benzo / b / furylcarbonyl) -4- (2,6-dimethoxybenzoyl) thiosemicarbazide is used according to the method described in Example 9 with methanesulfonic acid, whereby one reaches the title compound, which is identical to the compound of Example 4.

Example 14

N- / 5- (5-trifluoromethyl-2-benzo / b / furyl) -1,3,4-thiadiazol-2-yl / - 2,6-dimethoxybenzamide

A certain amount of 1- (5-trifluoromethy1-2-benzo / b / -fury! Carbonyl) -4- (2,6-dimethoxybenzoyl) thiosemicarbaz is used id according to the method described in Example 9 with methanesulfonic acid, whereby one arrives at the title compound, which with the compound of Example 5 is identical.

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Example 15

N- / 5-C6-trifluoromethyl-2-benzo / b / furyl) -1,3,4-thiädiazol-2-yl / - dimethoxybenzamide

1- (6-Trifluoromethyl-2-benzo / b / furylcarbonyl) -4- (2,6- (aimethoxybenzoyl) thxosemicarbazid according to the method described in Example 9 with methanesulfonic acid, whereby one reaches the Txtelverbindungen, which is identical to the compound of Example 6.

Example 16

N- / 5- £ 5-fluoro-2-benzo / b / furyl) -1,3,4-thiadiazol-2-yl / -2,6- dimethoxybenzamide

1- (5-Fluoro-2-benzo / b / furylcarbonyl) -4- (2,6-dimethoxybenzyl) thxosemicarbazide is used according to the method described in Example 9 with methanesulfonic acid, resulting in the title compound which is identical to the compound of Example 8 arrives.

To determine the range of their insecticidal effectiveness, the inventive thiadiazole benzamides of the formula I thoroughly examined against live insects. The following examinations are examples of the examinations carried out and the results obtained thereby.

In many cases, several tests are carried out with the same application ratio, and the results obtained in this way Results are then averaged. Spaces in the tables which follow later mean that no investigation was carried out at the application ratio mentioned. the Ornate connections are identified by the example number corresponding to them.

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Investigation 1 Mexican bean beetles and caterpillars of the cotton moth

Each compound to be tested is made by dissolving 10 mg of active ingredient in 1 ml of an anhydrous solvent mixture of a Part of ethanol and one part of acetone, the total of 36 g of a surfactant (23 g Toximul R and 13 g Toximul S) contains per liter. (Toximul is a mixture of surface-active sulfonates and non-ionic ones surfactants from Stepan Chemical Co., Northfield, Illinois, USA). Each sample is then dissolved in 9 ml of water dispersed, resulting in an active ingredient concentration of each 1000 ppm results in »By diluting this dispersion with water, lower concentrations can be obtained if desired form. The dispersion is then sprayed evenly over 10-day-old bean plants, whereupon the plants are allowed to dry put aside.

Leaves are then taken from the plants, the cut ends of which are wrapped in cotton wool soaked in water. Two leaves each are placed in a 100 mm plastic Petri dish, into which 5 larvae of the Mexican bean beetle (Epilachna varivestis) of the second or third instar and 5 larvae of the cotton moth (Spodoptera eridania) of the second or third instar are placed. For each compound to be examined, 3 Petri dishes are used. The Petri dishes are kept for 4 days at about 25 ^° C. and 51% relative humidity, after which the first assessment of the insecticidal effectiveness is carried out. Some Petri dishes are left under the conditions mentioned for a further 3 days and then subjected to a further evaluation.

The insecticidal effectiveness of the compounds examined is compared with the following rating scale

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OQ

Solvent blanks and untreated blanks are assessed :

Assessment scale

0 = no fight

1 = kill 1-7 larvae

2 = 8-14 larvae killed

3 = 15 larvae killed

The results obtained in the above tests are shown in Table I below.

Tabel

Application
amount in Mexican
Bean beetle 7 days Cotton moth
Caterpillar Days ppm 4 days 2 4 days 7 2 1000 2 2 2 2 100 1 1 1 3 1000 0 0 3 3 100 0 0 2 0- 1000 0 0 0 0 100 0 3 0 3 1000 0 2 3 3 100 0 2 3 3 1000 0 2 3 3 100 0 3 2 3 1000 2 3 3 3 100 2 2 3 3 1000 2 1 3 3 100 1 3

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The compound of Example 1 is following the same evaluation procedure assayed as above, but operating with a different application amount. Instead of the rating scale ranging from 0 to 3, the number of insect larvae killed is rated here in the form of the percentage of death. After a 4-day test on larvae of the cotton moth caterpillar, a 100% kill was obtained with this compound at an application rate of 5 ppm, and a 100% kill was also obtained after a test duration of 7 days with an application rate of only 2.5 ppm . In a corresponding study on Mexican bean beetles, after a test duration of 4 days with an application amount of 5 ppm, a 100 percent kill was obtained, while after a test duration of 7 days with an application amount of only 2.5 ppm, an 80 percent kill was obtained.

The test values given above show the good insecticidal effectiveness of the thiadiazolylbenzamides of the formula I. For Entomologists will readily see that the present compounds can be used in a wide variety of control of insects of various orders, which are detrimental to mankind and its economic ventures impact.

With the Thxadiazolylbenzamxden according to the invention, for example, the following organisms can be combated: Coleoptera, such as Anthonomus grandis, Crambus caliginosellus, Oulema melanopus, Leptinotarsa decemlineata, Hypera postica, Anthrenus scrophulariae, Tribolium confusum, Lyctidae species, Agriotes species, Sitophilus oryzae, Nodonota puncticollis and Conotrachelus neruphar; Diptera such as Musca domestica, Stomoxys calcitrans, Haematobia irritans, Phormia regina, Hylemya brassicae and Psila rosae; Lepidoptera such as Laspeyresia pomonella,

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Euxoa species, Plodia interpunctella, Tartricidae species, Heliothis zea, Ostrinia nubilalis, Hellula rogatalis, Trichoplusia ni, Thyridopteryx ephemeraeformis, Malacosoma americanum and Spodoptera frugiperda; and Orthoptera such as Blattella germanica and Periplaneta americana.

The present compounds are useful in reducing the "population" of insects. They are therefore also used in methods used to reduce an insect population, which consists in having an insecticidally effective amount such a compound applies to a substance that is consumed by the insects.

Insects can be made to ingest a particular active ingredient by looking at that particular compound brings up a substance that they consume. For example, insects infesting plants can easily be controlled by applying a compound to parts of plants that the insects eat, especially the Foliage »Insects that attack and consume textiles, paper or wood products can easily be combated by treating such products with the respective active ingredients. Such active ingredients can also be used in the same way Use to protect stored grain or seeds.

The present connections interfere with the training of the following Manifestations of insects that ingest these compounds. Take adult insects, for example these active ingredients, then they suffer on a large scale and no impairment whatsoever, but lay sterile eggs. If an insect larva takes up such a connection, then it dies without metamorphosis to the next larval form. Larvae of the last manifestation, ingesting such an active ingredient, pupate, but die in the pupal form.

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It will be readily apparent to entomologists that the use of a compound of formula I is not necessarily imperative must lead to the destruction of an entire insect population. In some cases, of course, the entire population will destroyed. In other cases, however, only some of the insects are killed, while others are treated with the respective one Active ingredient survive. The part of the population killed in each case depends on the type of insect that each compound used, the amount applied, the resistance of the insects, the weather and other well-known Factors. A decrease in an insect population is therefore understood to mean any decrease in the number of living insects, which in some cases also results in the disappearance of the entire population of the treated insects.

The amount of population depletion caused by a particular compound depends of course on the amount of compound used. However, it always has to be with a at least insecticidally effective amount are worked. This is understood to mean an amount of active ingredient through which a Can achieve measurable reduction in the treated insect population. Insecticidally effective amounts are generally in the range of about 1 to 1000 ppm.

The amount of insecticidal agent applied usually represents the concentration of the insecticidal agent in the dispersion in which it is applied. The application amount is determined because it is the most expedient a sufficient amount of the dispersion to cover the foliage or other material to be treated with one thin film of it results. The amount of dispersion used is therefore dependent on the surface area of the consumable to be treated Substance, and the amount of the compound depends on its concentration in the dispersion.

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The dispersions in which the present compounds are applied are prepared from conventional insecticidal preparations, which by the presence of the invention Connections, however, are new. Aqueous dispersions which can be obtained by mixing with a small one can be used to the greatest extent A quantity of a concentrated insecticidal agent can be mixed with a corresponding quantity of water, which will result in the gives the desired concentration of the respective compound. Such concentrated water-dispersible agents, in general contain about 5 to 90% active ingredient, are emulsifiable in the form Concentrates, wettable powders or suspensions can be used.

Wettable powders are intimate mixtures of the respective active ingredient with an inert carrier, which is a mixture of a fine inert powder and surfactants » The active ingredient concentration is usually 10 to 9O percent by weight - As inert powders, attapulgite clay, montmorillonite, diatomaceous earth or purified are usually used Used silicates. Useful surfactants, comprising about 0.5 to 10% of the wettable powder, are Among other things, the sulfonated lignins, the condensed naphthalene sulfonates, the naphthalene sulfonates, the alkylbenzenesulfonates, the alkyl sulfates and the nonionic surfactants Agents such as ethylene oxide adducts of alkyl phenol.

Exemplary emulsifiable concentrates of the present compounds can about 50 to 500 g of active ingredient per 1 liquid, which corresponds to an amount of about 5 to 50%, dissolved contained in an inert carrier which is a mixture of a water-immiscible organic solvent and Represents emulsifiers. Suitable organic solvents for this purpose are, for example, the aromatics, in particular the Xylenes, and the petroleum fractions, especially the high-boiling naphthalene and olefin fractions of petroleum, such as high-boiling aromatic naphtha. Other organic solvents too

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can be used, for example terpene solvents including natural resin derivatives and complex alcohols such as 2-ethoxyethanol. For egg-emulsifiable concentrates suitable emulsifiers belong to the same group of substances and are used in the same concentrations as the surface-active substances described above for the wettable powders Middle.

Suspensions of the present compounds contain one of the concentrations in an emulsifiable concentrate, for example a finely divided powder, similar amount of active ingredient in suspension in a suitable non-solvent Liquid. The most suitable non-dissolving liquid for this is a mixture of water and surface-active substances Means. The same surfactants are used to prepare the suspensions as they are used also used to form wettable powders. Occasionally a small amount of an inert diluent is also used s to thereby increase the suspension properties to enhance. Such inert diluents include Ättapulgittones, Montmorillonite, starches and especially purified silicates.

If desired, the active ingredient can also be in the form a solution in an organic solvent, usually a mild petroleum like one in agrochemicals by far Apply the amount of spray oil used.

The present compounds can also be in the form be used by dusts and aerosol preparations.

Stabilizers contain the respective compound in finely powdered form Form contained in a powdery inert carrier is dispersed. The carrier is usually powdered clay, such as pyrophyllite, bentonite, volcano layer or montmorillonite. Dusts normally contain the active ingredient in concentrations of about 0.1 to 10%.

909809 / 082S

283A945

Aerosol preparations contain a compound of the formula I dissolved or dispersed in an inert carrier which consists of a pressure-generating propellant mixture consists, and they are packed in a container from which the mixture through a fine distribution valve is released, propellant mixtures contain either low-boiling halogenated hydrocarbons in the mixture with organic solvents or aqueous suspensions, with inert gases or gaseous hydrocarbons under pressure to be brought.

800809/0825

Claims (22)

Claims 1. Thiadiazolylbenzamides of the formula I. HO? CHs wherein R represents one of the following radicals: ^Rl x ./ \ / V ^s , W R ^{6 /} X / ~ \ / ~ ° ^der whereby X means oxygen or sulfur, 9 0 9 8 0 9/0825 ORIGINAL INSPECTED ΧΑ one of
Subtituents R ¹ or R ² Is hydrogen and the other is fluorine, chlorine, bromine, trifluoromethyl or methoxy. one of
Substituents ? 4th
R or R Is hydrogen and the other is methoxy or trifluoromethyl, one of
Substituents R ⁵ or R ⁶ Is hydrogen and the other is chlorine, bromine, fluorine, trifluromethyl or hydrogen represents and one of
Substituents R ⁷ or R ⁸ Is hydrogen and the other is C ₁ -C ₂ alkoxy which is substituted by one or more fluorine atoms. 2. Compounds of the formula I according to. Claim 1, characterized in that the substituent R for •• -y \ stands. 909809 / 082S 3. Compounds of formula I according to claim 1, characterized in that the substituent R for stands. 4. Compound of formula I according to claim 3, characterized in that the substituent R represents substituted benzofuryl. 5. Compound of formula I according to claim 4, characterized in that the substituent R is 6-methoxy-2-benzo / b / furyl. 6. Compound of formula I according to claim 4, characterized in that the substituent R is 5-methoxy-2-benzo / b / furyl. 7. Compound of formula I according to claim 4, characterized in that the substituent R stands for 5-trifluoromethyl-2-benzo / b / furyl. 8. Compound of formula I according to claim 4, characterized in that the substituent R stands for 6-trifluoromethyl-2-benzo / b / furyl. 909809/0825 283Α945 9. Compound of formula I according to claim 4, characterized in that the substituent R stands for 5-fluoro-2-benzo / b / furyl. 10. Compounds of formula I according to claim 1, characterized in that the substituent R for XXJ stands. 11. Compound of formula I according to claim 10, d a dur.ch characterized in that the substituent R is 2-indenyl. 12. Compounds of formula I according to claim 1, characterized in that the substituent R for stands. 13. Compound of formula I according to claim 12, characterized in that the substituent R stands for hydrogen. 909803/0825 -X- 14, compound of formula I according to claim 13, characterized in that the sub- tuent R is Cj-C ^ perfluoroalkoxy. 15. Compound of formula I according to claim 14, characterized in that the substituent R represents 4-trifluoromethoxyphenyl. 16 compound of formula I according to claim 14, characterized in that the substituent R _f is 4-Pentafluorethoxyphenyl stands. 17. Insecticidal agent composed of an inert carrier and a thiadiazolylbenzamide as active ingredient, thereby characterized as having it as an active ingredient Thiadiazolylbenzamide of the formula I according to Claims 1 to 16 contains. 18. Insecticidal agent according to claim 17, characterized in that it is in the form of a wettable Powder has. 19. Insecticidal agent according to claim 17, characterized known that it is in the form of an emulsifiable concentrate. 20. Insecticidal agent according to claim 17, characterized characterized in that it is in the form of a suspension Has. 909809/0825 -3f- 21. Use of the thiadiazolylbenzamides of the formula I for lowering an insect population, thereby characterized in that a substance, which is ingested by the respective insects, with an insecticide effective amount of a thiadiazolylbenzamide of the formula I according to Claims 1 to 16. 22. Use of a thiadiazolylbenzamide of the formula I for lowering an insect population, thereby characterized in that a substance, which is ingested by the respective insects, with an insecticide effective amount of a thiadiazolylbenzamide of the formula I in the form of an insecticidal agent according to claim treated to 20. 909809/0825