CH570759A5 - 2-Acylamino-5-halo-1,3,4-thiadiazoles as pesticides - e.g. 2-chloroacetamido-5-bromo-1,3,4-thiadiazole - Google Patents

Abstract

Agents for combatting pests contain as active component at least one 2-acylamino-5-halo-1,3,4-thiadiazole of formula (I) (where Hal is Cl or Br and R is H, COOH, COOM (M=monovalent metal), phenyl, opt. substd. 1-8C alkyl, 2-5C alkenyl or 2-5C alkynyl), e.g. 2-chloroacetamido-5-bromo-1,3,4-thiadiazole or 2-formamido-5-bromo-1,3,4-thiadiazole. The agents can be used for cobatting various animal and vegetable pests, and as plant growth regulators and defoliants. (I) are partic. useful for combatting phytopathogenic nematodes. (I) also have activity against Thallophyte, e.g. viruses, bacteria and fungi, and can be used as fungicides against phytopathogenic fungi on crops such as cereals, vegetables, fruits trees, ornamental plants etc.

Description

  

  
 



   The present invention relates to an agent for combating pests which contains at least one compound of the formula I as the active component
EMI1.1
 contains where
Hal chlorine or bromine and
R is hydrogen, -COOH, -COOMe, phenyl, unsubstituted or substituted C1-C8-alkyl, C2-C5-alkenyl or C2-C5-alkynyl and
Me mean a monovalent metal.



   The alkyl, alkenyl or alkynyl groups at R can be straight-chain or branched. Possible substituents on these groups are, for example, halogen atoms, such as fluorine, chlorine, bromine or iodine, cyano, carboxyl, phenyl, alkoxy or alkylthio groups. Examples of such alkyl, alkenyl or alinyl groups are u. a .: methyl, chloromethyl, dichloromethyl, bromomethyl, trichloromethyl, ethyl, isopropyl, propyl, n-hexyl, vinyl, 2,2,2-trichlorovinyl, allyl, propargyl, -CH2-CH2-COOH, = = CH-COOH.



   Preferred monovalent metals in Me are the alkali metals, especially sodium and potassium.



   The compounds of the formula I can be prepared by the following, known method:
EMI1.2

In the formulas II and III, Hal and R have the meaning given for the formula I and X stands for hydroxyl, halogen or alkoxycarbonyl, alkenyloxycarbonyl or alkynyloxycarbonyloxi. When preparing the formyl and oxaline derivatives, the free carboxylic acid or a mixed anhydride can be used. Suitable acid-binding agents are: tertiary amines, e.g. B. trialkylamines, pyridine. Dialkylanilines; inorganic bases such as hydrides, hydroxides: carbonates and bicarbonates of alkali and alkaline earth metals.



   The process is carried out at a temperature of from -20 to 100 ° C., preferably from 10 to 40 ° C., under normal pressure, and preferably in water-immiscible solvents such as ether, benzene, toluene, chloroform or methylene chloride.



   The starting materials of the formula II can be prepared analogously to known methods.



   The compounds of the formula I can be used for combating a wide variety of animal and plant pests, as plant regulators and as defoliants.



   The compounds of formula I have above all nematicidal properties and can be used to combat z. B.



  The following phytopathogenic nematodes are used: Meloidogyne species, Heterodera species, Ditylenchus species, Pratylenchus species, Paratylenchus species, Anguina species, Belonolaism species, Trichodorus species, Longidorus species, Aphelenchoides species.



   The active ingredients of the formula I are also suitable for combating representatives of the Thallophyta department such. B. viruses, bacteria and fungi. They have fungicidal properties against phytopathogenic fungi on various crops such as cereals, maize, rice, vegetables, and ornamental plants. Fruit trees, vines, field crops, etc. They are particularly effective against the phytopathogenic fungi belonging to the following classes: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes.



   According to the invention, the compounds of the formula I are used together with suitable carriers and / or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances customary in formulation technology such as. B. natural or regenerated substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders and / or fertilizers.



   For application, the compounds of the formula I can be added to dusts, emulsion concentrates, granules.



  Dispersions, sprays, solutions or slurries in the usual formulation, which is part of general knowledge in application technology.



   The agents according to the invention are prepared in a manner known per se by intimately mixing and / or grinding active ingredients of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active ingredients.



  The active ingredients can be present and used in the following working-up forms: solid working-up forms:
Dust, grit,
Granulates, coated granulates,
Impregnation granules and
Homogeneous granules Liquid processing forms: a) Active substance concentrates dispersible in water:
Wettable powders, pastes, emulsions; b) Solutions
The active ingredients are mixed with solid carriers for the production of solid forms (dusts, grit).

  Carrier materials include kaolin, talc, bolus, loess, chalk, limestone, lime grit, attapulgite, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminum silicates (feldspars and mica), calcium and magnesium sulfates, magnesium oxide, ground plastics, Fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products such as grain flour, tree bark flour, wood flour, nutshell flour, cellulose powder, residues of plant extracts, activated charcoal, etc., each individually or as mixtures with one another.



   Granules can be produced very easily by dissolving an active ingredient of the formula I in an organic solvent and applying the resulting solution to a granulated mineral, e.g. B. Attapulgite, SiO2, Granicalcium Bentonite etc.



  applies and then the organic solvent evaporates again.



   Polymer granules can also be produced by mixing the active ingredients of the formula I with polymerizable compounds (urea / formaldehyde; dicyandiamide / formaldehyde; melamine / formaldehyde or others), whereupon a gentle polymerization is carried out which does not affect the active substances, and granulation taking place while the gel is being formed. It is more favorable to use finished, porous polymer granules (urea / formaldehyde, polyacrylonitrile, polyester and others) with a certain surface area and a favorable, predeterminable adsorption / desorption ratio with the active ingredients such. B. to impregnate in the form of their solutions (in a low-boiling solvent) and remove the solvent.

  Such polymer granules can also be applied in the form of microgranules with bulk weights of preferably 300 g / liter to 600 g / liter with the aid of atomizers. The atomization can be carried out over large areas of crops with the help of aircraft.



   Granules can also be obtained by compacting the carrier material with the active ingredients and additives and then comminuting.



   These mixtures can also be added to stabilize the active ingredient and / or nonionic, anionic and cationic substances, which, for example, improve the adhesion of the active ingredients to plants and parts of plants (adhesives and adhesives) and / or better wettability (wetting agents) and dispersibility (dispersants ) guarantee.



   For example, the following substances are possible: olein / lime mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethylene glycol ethers of mono- and dialkylphenols with 5-15 ethylene oxide residues per molecule and 8-9 carbon atoms in the alkyl residue, ligninsulphonic acid, its alkali and alkaline earth salts, polyethylene glycol (Carbowax), fatty alcohol polyglycol ether with 5-20 ethylene oxide residues per molecule and 8-18 carbon atoms in the fatty alcohol part, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidones, polyvinyl alcohols, condensation products of urea / formaldehyde and latex products.



   Active ingredient concentrates dispersible in water, d. H.



  Wettable powders, pastes and emulsion concentrates are agents that can be diluted with water to any desired concentration. They consist of active ingredient, carrier, optionally additives stabilizing the active ingredient, surface-active substances and anti-foaming agents and optionally solvents.



   The wettable powders and pastes are obtained by mixing and grinding the active ingredients with dispersants and powdery carriers in suitable devices until homogeneous. Suitable carriers are, for example, those mentioned above for the solid work-up forms. In some cases it is advantageous to use mixtures of different carriers.

  The following can be used, for example, as dispersants: condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, and alkali, ammonium and alkaline earth salts of ligninsulfonic acid, further alkyl aryl sulfonates, alkali metal sulfates, alkali metal sulfates, alkali metal sulfates and alkali metal sulfates , such as salts of sulfated hexadecanols, heptadecanols, octadecanols and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleyl methyl tauride, ditertiary ethylene glycols, dialkyldilaurylammonium chloride and fatty acid alkali and alkaline earth salts.



   Silicone oils, for example, can be used as antifoam agents.



   The active ingredients are mixed, ground, sieved and passed with the additives listed above in such a way that the solid portion of the wettable powders does not exceed a particle size of 0.02 to 0.04 and of the pastes 0.03 mm. To produce emulsion concentrates and pastes, dispersants such as those listed in the previous sections, organic solvents and water are used. Examples of suitable solvents are alcohols, benzene, xylenes, toluene, dimethyl sulfoxide and mineral oil fractions boiling in the range from 120 to 350 ° C. The solvents must be practically odorless, non-phytotoxic and inert to the active ingredients.



   The agents according to the invention can also be used in the form of solutions. For this purpose, the active ingredient is bez. several active ingredients of the general formula I are dissolved in suitable organic solvents, solvent mixtures or water. Aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alkylnaphthalenes, mineral oils, alone or as a mixture with one another, can be used as organic solvents.



   The content of active ingredient in the agents described above is between 0.1 and 95%.



   The active ingredients of the formula I can be formulated as follows, for example: Dusts:
The following substances are used to produce a) 5% and b) 2% dust: a) 5 parts of active ingredient
95 parts of talc b) 2 parts of active ingredient
1 part of highly dispersed silica
97 parts of talc
The active ingredients are mixed and ground with the carrier substances.



  Granules:
The following substances are used to produce 5% granules:
5 parts of active ingredient
0.25 part epichlorohydrin
0.25 part of cetyl polyglycol ether
3.50 parts of polyethylene glycol
91 parts of kaolin (grain size 0.3-0.8 mm)
The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution obtained in this way is sprayed onto kaolin and the acetone is then evaporated in vacuo.

 

  Wettable powder:
The following ingredients are used to produce a) 40%, b) and c) 25% d) 10% wettable powder: a) 40 parts of active ingredient
5 parts of lignin sulfonic acid sodium salt
1 part dibutylnaphthalenesulfonic acid sodium salt
54 parts of silica b) 25 parts of active ingredient
4.5 parts calcium lignosulfonate
1.9 parts of champagne chalk / hydroxyethyl cellulose
Mixture (1: 1)
1.5 parts of sodium dibutyl naphthalene sulfonate
19.5 parts of silica
19.5 parts of champagne chalk
28.1 parts of kaolin
25 parts of active ingredient
2.5 parts of isooctylphenoxy-polyoxyethylene ethanol
1.7 parts of champagne chalk / hydroxyethyl cellulose
Mixture (1:

  :1)
8.3 parts of sodium aluminum silicate
16.5 parts of diatomaceous earth
46 parts of kaolin d) 10 parts of active ingredient
3 parts mixture of the sodium salts of saturated
Fatty alcohol sulfates
5 parts of naphthalenesulfonic acid / formaldehyde
condensate
82 parts of kaolin
The active ingredients are mixed with the in suitable mixers
Aggregates intimately mixed and on appropriate
Grind mills and rollers. Wettable powders are obtained which can be diluted with water to form suspensions of any desired concentration.



  Emulsifiable concentrates:
The following substances are used to produce a 25% emulsifiable concentrate: b) 25 parts of active ingredient
2.5 parts epoxidized vegetable oil
10 parts of an alkylarylsulfonate / fatty alcohol poly glycol ether mixture
5 parts of dimethylformamide
57.5 parts of xylene
Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.



  Spray:
The following ingredients are used to make a 5% spray:
5 parts of active ingredient
1 part epichlorohydrin
95 parts gasoline (boiling limit 160-190 C)
Example 1 a) Preparation of 2 -chloroacetamino-5-bromo -
1,3,4-thiadiazole
To 180 g of 2-amino-5-bromo-1,3,4-thiadiazole in 1000 cm3 of toluene, 170 g of chloroacetic anhydride are added dropwise over 10 minutes with stirring. The temperature rises to 40 ° C. Stirring is continued for 30 minutes, heated to 80 ° C. for 1 hour and then the mixture is cooled to 10 ° C. The precipitated product is filtered and washed with petroleum ether. The compound of the formula is obtained
EMI3.1
 with a melting point of 211-212 C (dec.).



   Example 2 b) Preparation of 2-formylamino-5-bromo-1,3,4-thiadiazole 7.8 g of anhydrous formic acid and 17.2 g of acetic anhydride are heated to 50 ° C. for 2 hours. The mixed formic acid-acetic anhydride obtained in this way is dissolved in 50 cm3 of dry toluene and added dropwise to a suspension of 27 g of 5-bromo-2-amino-1,3,4-thiadiazole in 100 cm3 of dry toluene over a period of 10 minutes. Stirring is continued for 5 hours at 30 ° C. and the mixture is then cooled to 0 ° C. The precipitated white product is filtered off and washed with a little toluene and ether.



   The compound of the formula is obtained
EMI3.2
 with a melting point of 200-202 C (dec.).



   The following connections are also established in the same way:
EMI3.3

EMI3.4


<tb> Hal <SEP> R <SEP> Physical <SEP> data
<tb> Br <SEP> -CHC12 <SEP> Smp .: <SEP> 181-187 "C
<tb> Br <SEP> -CH3 <SEP> Smp .: <SEP> 243245 <SEP> C <SEP> (decomp.)
<tb> Cl <SEP> -CH = CH-CH3
<tb> Cl <SEP> -CH-CH3 <SEP> m.p .: <SEP> 184-185 C
<tb> <SEP> I
<tb> <SEP> Cl
<tb> Cl <SEP> -CCI3 <SEP> Smp .: <SEP> 174-175 C
<tb> Cl <SEP> 4 <SEP> Smp .: <SEP> 240-2410C
<tb> Cl <SEP> -C3H7 (n) <SEP> Smp .: <SEP> 219-220 <SEP> C
<tb> Br <SEP> -CH2Br <SEP> Smp .: <SEP> 196-197 "C <SEP> (decomp.)
<tb> Br <SEP> 4 <SEP> Smp .: <SEP> 2452460C
<tb> Br <SEP> -C7HIs (n) <SEP> Smp .: <SEP> 158 "C
<tb> Br <SEP> -COOH <SEP> Smp .: <SEP> 2200 <SEP> C <SEP> (decomp.)
<tb> Br <SEP> -COONa
<tb> Br <SEP> -CH2CH2COOH <SEP> Smp .: <SEP> 2250 <SEP> C <SEP> (decomp.)
<tb> Br <SEP> -CH2CH2COONa
<tb> Cl <SEP> -C2Hs <SEP> Smp .:

  <SEP> 2570 <SEP> C <SEP> (dec.)
<tb> Cl <SEP> -CH2Br <SEP> Smp .: <SEP> 211-213 C <SEP> (decomp.)
<tb> Br <SEP> -CH = CH-COOH <SEP> Smp .: <SEP> 1590 <SEP> C <SEP> (decomp.)
<tb> Br <SEP> -CH2CN <SEP> Smp .: <SEP> 209-2100C
<tb>
Example 3
Effect against soil nematodes
To test the action against soil nematodes, the active ingredients were added in the concentration to be tested to soil infected by root cell nematodes (Meloidogyne arenaria) and thoroughly mixed. In the soil prepared in this way, tomato seedlings were planted immediately afterwards in one test series and tomatoes were sown in another test series after a waiting period of 8 days.

 

   To assess the nematocidal effect, the galls present on the roots were counted 28 days after the plants or after the sowing.



   In this test, the active ingredients according to Examples 1 and 2 showed a good action against Meloidogyne arenaria.

 

Claims (1)

PATENT CLAIM 1 Agent for combating pests, characterized in that it contains at least one compound of the formula I as the active component EMI4.1 contains where Hal chlorine or bromine and R is hydrogen, -CO OH, -COOMe, phenyl, unsubstituted or substituted C1-C8-alkyl, C2-Cs-alkenyl or C2-Cs-alkynyl and Me mean a monovalent metal. PATENT CLAIM II Use of an agent according to patent claim I for combating plant-parasitic nematodes.