DE3220883C2 - Salts of N- (4-trifluoromethylphenyl) tetrachlorophthalamic acid, process for their preparation and their use as pesticides - Google Patents

Abstract

The present invention relates to new salts of N- (4-trifluoromethylphenyl) tetrachlorophthalamic acid of the formula (I) (formula I) in which M stands for an alkali, alkaline earth, optionally substituted ammonium or heavy metal equivalent. They are obtained from the free acid by reaction with alkali, alkaline earth or optionally substituted ammonium hydroxide. The heavy metal salts are made from water-soluble salts by adding corresponding heavy metal salts. The new salts of N- (4-trifluoromethylphenyl) phthalamic acid can be used as pesticides and are distinguished by their high effectiveness and duration of action.

Description

a) N- (4-trifluoromethylphenyl) -tetrachlorophthalamic acid of the formula (II)

CO-OH

with a compound of the formula (NI)

X - OH (Π)

in which

X stands for an alkali, alkaline earth or optionally substituted ammonium cation, reacts in the presence of a diluent or solvent, or b) the water-soluble salts of N- (4-trifluoromethylphenyl) tetrachlorophthalamic acid of the formula (IV)

CO-OX

CO —NH- <> —CF ₃ (IV)

in which

X has the meaning given,

with a heavy metal salt of the formula (V)

Y-Z (V)

in which

Y for a heavy metal equivalent and
Z stand for an anion,

converts in aqueous solution.

8. Use of salts of N- (4-trifluoromethylphenyl) tetrachlorophthalamic acid according to the claims 1 to 6 for pest control.

The present invention relates to new salts of N- (4-trifluoromethylphenyl) -tetrachiorphthalamic acid, Process for their manufacture and their use as pesticides.

It is already known that tetrachlorophthalamic acids, e.g. B. a plant bactericidal effect own. For example, N- (2,3-dichlorophenyl) -tetrachlorophthalamic acid has a bactericidal effect against Xanrhomonas orvzae in rice (see GB-PS 13 55 849). N- (4-trifluoromethylphenyU-tetrachlorophthalamic acid belongs to the same class of substances also a good bactericidal effect (cf. DE-OS 29 32 689).

There were the new salts of N- (4-trifluoromethylphenyl) phthalamic acid of the formula (I) 5

Cl
Cl COOM

CONH- ^ f ^ CF ₃ (D

Cl

in which ^l:

M stands for an alkali, alkaline earth or heavy metal equivalent or for an optionally substituted ammonium radical,
found.
It has also been found that the new Saize of NH-TrifluormethylphenylHetrachlorphthalamid-

acid of formula d) ²⁰

Cl
Cl I COOM

CI

in which "°

M stands for an alkali, L; dalkali or heavy metal equivalent or for an optionally substituted ammonium radical,
received when one

a) N- (4-trifluoromethylphenyl) -tetrachlorophthalamic acid of the formula (II) .'5

Cl

COOH

_C / Y \ o-NH ^ V ^CF
r ·! N = /

Cl I CO —NH- <f ^ CF ₃ (Π)

Cl ^ = /

with a compound of formula (III) ⁴⁵

X-OH (CT)

in which

X denotes an alkali, alkaline earth or optionally substituted ammonium cation, 50

in the presence of a diluent or solvent, or if one b) the water-soluble salts of N-H-trifluoromethylphenyD-tetrachlorophthalamic acid of the formula (IV)

COOX ⁵⁵

Cl T CO -NH-ζ ^ -CF, (IV) _m

in which

X has the meaning given,

with a heavy metal salt of the formula (V)

Y-Z (V)

in which

Y has the meaning given above and
Z stands for an anion,

converts in aqueous solution.

The new salts of N- [4-trifluoromethylphenyl] -tetrachlorophthalamic acid mainly have a strong bactericidal effect. It is surprising that the compounds according to the invention have the same or in some cases better action and, above all, a longer duration of action against plant-damaging bacteria than the well-active free acid known from the prior art, N- [4-trifluoromethylphenyl] -tetrachloiphthalamic acid. In the case of the free acid as such and in its formulations, signs of degradation were already registered at room temperature. After 8 weeks at 40 ^° C., losses of activity of more than 30 ″ were observed, since the free acid cyclizes to form the dicarboximide derivative which is only slightly active.

The new compounds because of their equally good or partly better effect and their high Storage stability is an enrichment of the technology.

The salts of the N - ^ - trifluoromethylphenyl-tetrachlorophthalamic acid according to the invention are represented by the formula (I) defined.

The following are preferably mentioned:

the potassium salt of N - ^ - trilluormethylphenvIl-tetrachlorophthalamic acid, the magnesium salt of N - ^ - trilluomethylphenylj-tetrachlorophthalamic acid, the copper salt of N- [4-Trinuormethylphenyi] -tetrach! orphthalamic acid, das Marigansaiz der N - ^ - Triiliiurmethyiphenyij-ieirachiorphthalamidsäurc and the zinc salt of N- [4-Trinuorrne * iiylphenyl] -tetrachlorophtharamic acid.

If, for example, in process variant a) N - ^ - trifluoromethylphenyl tetrachlorophthalamic acid is used and sodium hydroxide as starting materials, the reaction can be represented by the following equation be reproduced:

CO-OH

+ NaOH

If you use z. B. in process variant b) the potassium salt of N- [4-trifluoromethylpnenyl] tetrachlorophthalamic acid and zinc chloride as starting materials, the course of the reaction can be as follows Formula scheme can be reproduced:

+ ZnCI ₂

CO - NH - <> - CF ₃

Zn

The starting material for the compounds to be prepared according to the invention according to the process variant a) N - ^ - trifluoromethylphenyl-tetrachlorophthalamic acid to be used is known and known from the literature Process can be produced (see e.g. DE-OS 29 32 689).

The hydroxides also to be used in process variant ui are defined by the formula (III) In this formula (III), X stands for the radicals which were given in connection with the preparation.

The water-soluble salts of N- [4-trifluoromethylphenyl] -tetraehlorphthalaniids; iure to be used in process variant b) are defined by the formula (IV) and are part of the inventive concept. They are new and according to the method described /. H. from the free acid by reaction with an Alka-Ii-, Alkaline earth or optionally alkyl-substituted ammonium hydroxide in aqueous or alcoholic Solution available.

Furthermore, in process variant b | Heavy metal salts used, which are defined by the formula (V) are. In this formula, M and Z stand for the radicals that are already in connection with the description A preparation of the substances according to the invention have been mentioned as preferred for these substituents.

Diluents or solvents are used for the reaction according to the invention according to process variant a) Alcohols such as methanol and F.thanol, and water in question.

The implementation according to the invention according to process variant b) is generally carried out in an aqueous medium carried out.

The reaction temperatures for both variants a) and b) can be varied over a wide range. i> One works in general between 0 to 50 ⁰ C, preferably between 20 to 40 ⁰ C.

The reaction is generally carried out under normal pressure.

When carrying out variant a) of the process according to the invention, the starting products are used generally in equimolar amounts. An excess of hydroxide does no harm.

When carrying out variant b) of the process according to the invention, the starting materials are generally used in equimolar proportions.

The end products in process variant a) are generally isolated by the Solution evaporated to dryness in vacuo.

A preferred embodiment in process variant b) according to the invention takes place in such a way that the water-soluble salt is produced in an aqueous or alcoholic solution from the acid and the hydroxide:? and without isolating the water-soluble salt, further work is carried out by adding an aqueous solution of the Heavy metal salt. The sparingly soluble heavy metal salts precipitate, are suctioned off and washed with water and dried.

The active ingredients according to the invention have a strong microbicidal effect and can be used for control can be used in practice by undesirable microorganisms. The active ingredients are for use as Suitable for pesticides.

So z. B. bactericidal agents in the plant school to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae are used.

The fact that the active compounds are well tolerated by plants in those necessary for combating plant diseases Concentrations allow a treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.

In particular, the compounds according to the invention are effective against bacteria of the genus Xanthorrionas, z. B. against Xanthomonas oryzae and Xanthomonas pelargonii; also against Erwinia mangiferae and Corynebacterium michiganense.

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, -to Suspensions, powders, foams, pastes, granulates, aerosols, active ingredient-impregnated natural and synthetic Substances, finest encapsulation in polymeric substances and in coating compounds for seeds, also in formulations with Burning sets, such as smoking cartridges, cans, spirals, etc., as well as ULV cold and warm mist formulations.

These formulations are produced in known manner, eg gerst open by mixing the Wirksgtoffe with extenders, that is liquid solvents, liquefied gases under pressure and / or solid carriers as, optionally with the use of surfactants, that is emulsifiers and / or dispersants, and / or foaming agents. In the case of the use of water as an extender, z. B. organic solvents can also be used as auxiliary solvents. The following liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols such as butanol, or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, e.g. B. aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carriers come into question: z. B. natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as highly disperse silica, aluminum oxide and silicates; Solid carriers for granules are: for example broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-producing agents come into question: z. B. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as dispersants there are: z. B. Lignin suifitabi eyes and Methyiceiiuiose.

There may be adhesives such as carboxymethyl cellulose, natural and synthetic in the formulations powdery, granular and iatexformige polymers can be used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferrocyan blue and organic Dyes such as alizarin, azole and metal phthalocyanine dyes and trace nutrients such as salts of iron, Manganese, boron, copper, coball, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and "0%.

The active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bactericides, insecticides, Acaricides, nematicides, herbicides, protective tunnels against bird damage, growth substances, plant nutrients and Soil structure improvement agents.

The active ingredients can be used as such, in the form of their formulations or that obtained therefrom by further dilution Prepared application names, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules can be used. It is used in the usual way, e.g. by pouring, dipping, Splashing, atomizing, atomizing, vaporizing, injecting, silting up, spreading, dusting, scattering, Dry pickling, wet pickling, wet pickling, slurry pickling or encrusting.

In the treatment of parts of plants, the drug concentrations in the use forms in can be varied over a larger area. They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

In the treatment of seeds, amounts of active ingredient of 0.001 to 50 g per kilogram of seed are generally used, preferably 0.01 to 10 g.

When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably of 0.0001 to 0.02%, required at the place of action.

Manufacturing examples
Example'l

40

COOK

CONH-

148 g (0.33 mol) of N ^ -Trifluormethylphenylj-tetrachlorphthalamidsäure be brought by the addition of 100 ml of methanol in 1 liter of water with! 9 g (0.33 Mo!) Kaüumhydroxid at 20-3O ⁰ C in reading. Small amounts of an insoluble fraction are filtered off and the filtrate is evaporated to dryness in vacuo. Here, 141 g (88% derTheorie) is obtained the potassium salt of NH-TrifluormethylphenylHetrachlorphthalamidsäure with the decomposition point of 170 ⁰ C.

Example 2

45

COO-

CONH-

Mg

55 60 65

135 g (0.3 mol) of N- (4-TrinuormethyIphenyl) tetrachlorophthalamic acid are brought into solution with the addition of 100 ml of methanol in 1 liter of water with 12 g (0.3 mol) of caustic soda. Then added dropwise a solution of 40 g (0.2 mol) of magnesium in 200 ml of water at 20-25 ⁰ C. The precipitated magnesium salt is filtered off with suction, washed with water and dried. This gives 115 g (84% of theory) of the magnesium salt of N- (4-trifluoromethylphenyl) -tetrachlorphthalarnidsäure having a melting point> 300 ⁰ C.

The following salts of the formula (I) are obtained in an analogous manner

COOM

CO-

example

No.

Analysis of the metal; Calculated Found

3 Copper (II) - 4th Manganese (II) - 5 zinc

6.65 7.3 5.8 5.5 5.75 6.6

Usage examples

In the following example, the known compound listed below is used as a comparison substance used:

CO-OH

Example agar plate test

Used medium

15 parts by weight 10 parts by weight 8 parts by weight 4 parts by weight 2 parts by weight 0.3 parts by weight

Agar Agar

Sucrose

Casein hydrolyzate

Yeast extract

Dipotassium hydrogen phosphate

Magnesium sulfate

are dissolved in 1000 ml of distilled water and ^{autoclaved at 121 °} C. for 30 minutes.

Solvent: 40 parts by weight of acetone.

Amount ratio of solvent to culture medium: 2: 100.

To produce an appropriate preparation of active ingredient, I part by weight of active ingredient is mixed with the specified Amount of solvent.

The concentrate is thoroughly mixed with the liquid nutrient medium in the specified proportions and 45 poured into petri dishes.

If the culture medium has cooled down and is solid, the plates are inoculated with the following microorganisms and ^{incubated at approx. 21 °} C:

Erwinia mangiferae like that

Xanthomonas oryzae Xanthomooas pelargonü Corynebacterium michiganense

The evaluation takes place depending on the growth rate of the microorganisms after 2 to 8 days, with 55 the growth inhibition is used as a measure of the effect of the preparations.

In this test, the compounds according to the following show a superiority over the prior art Production examples: 3, 4 and 5.

Claims (7)

Patent claims:
1. Salts of N- (4-tritluoromethylphenyl) tetrachlorophthalamic acid of the formula (I) CO - OM CO-NH- CI in which M stands for an alkali, alkaline earth, optionally substituted ammonium or heavy metal equivalent. 2. Potassium salt of N-H-trifluoromethylphenylhetrachlorophthalamic acid. 3. Magnesium salt of N - ^ - trifluoromethylphenylhetrachlorophthalamic acid. 4. Copper acid of N - ^ - trifluoromethylphenylj-tetrachlorophthalamic acid. 5. Manganese salt of N-H-trifluoromethylphenylhetrachlorophthalamic acid. 6. Zinc salt of N- (4-trifluoromethylphenyl) -tetrachlorophthalamic acid. 7. Process for the preparation of salts of N - ^ - trifluoromethylphenylHetrachlorophthalamic acid according to Claim 1 to 6, characterized in that one