JPS58219153A - Salts of n-(4-trifluoromethylphenyl)- tetrachlorophthalamic acid, manufacture and insecticide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to /V-(4-)lifluoromethylphenyl)
- A novel salt of tetrachlorophthalamic acid, its production method and its use as a pest control agent.

For example, it has already been disclosed that tetrachlorophthalamic acid has a bactericidal effect on plant bacteria. Immediately, N-
(2,a-te dichlororenyl)-tetrachlorophthalamic acid is derived from rice xanthomonas oryza x (Xant
homonas oryzae) (see British Patent No. 1,355.849). From the same class of substances, N-(4-)lifluoromethylphenyl)-tetrachlorophthalamic acid also shows good bactericidal action (see German Published Patent No. 2,
No. 934689).

This time, the formula (#-(4-)lifluoromethylphenyl) of the formula (where M represents 1 equivalent of an alkali metal, alkaline earth metal, optionally substituted ammonium or heavy metal) -tetrachlor7-thalamic acid A new salt has been discovered.

Furthermore, #-(4-) of formula (1) [wherein M represents 1 equivalent of the alkali residue, alkaline earth metal, optionally substituted ammonium or heavy metal]! The novel salt of 7fluoromethylphenyl)-tetrachlorophthalamic acid is prepared by a) formula (1) % formula % trachlorphthalamic acid in the presence of a diluent or solvent. %() [wherein X represents an alkali metal, alkaline earth metal or an optionally substituted ammonium cation] or b) a compound of the formula (Gin I) [wherein X represents the above-mentioned meaning] #-(4-)IJfluoromethylphenyl)-tetrachlorophthalamic acid having the formula (V)
d, one of the heavy metals and Z represents an anion] was discovered to be produced by reacting with a heavy metal Pj4 salt.

#-()17fluoromethylphenyl] - The new surface salt of tetrachlorophthalamic acid has a particularly strong bactericidal action. Surprisingly, the compound according to the invention has a good effect in some cases on the same minerals as well as against the previously known and good action against batataeria, which are harmful to plants. Free acid A-(47
)1fluoromethylphenyl)-Tetrachlorophthalamic acid. In the case of free acids, the phenomenon of decomposition is observed even in their mixtures at room temperature. After 8 weeks at 40 DEG C., a decrease in activity of more than 30% was observed, as the free acid gave rise to a dicarboxylic acid imide conductor, which had only a slight bactericidal effect.

The new compounds therefore represent an advance in technology on the basis of their equally good or in some cases even better action and high storage stability.

The formula ([) gives the definition of AI-(4-)lifluoromethylphenyl)-tetrachlor7-talamic acid according to the invention. In this formula, y is preferably sodium, potassium, calcium or magnesium, or a di- or tri-alkylated ammonium group in which the number of moieties in the alkyl group is from 1 to 4, such as diethylamine or tributylamine, or copper, titanium, iron, Represents nickel, manganese or zinc.

When using -(4-)lifluoromethylphenyl]-tetrachlorophthalamic acid and sodium hydroxide as starting materials in process embodiment α),
The reaction process can be expressed by the following equation: l For example, N-(4-)! 7fluoromethylphenyl)-tetrachlor 7 thalamic acid and zinc chloride in process embodiment b)
The course of the reaction can be represented by the following equation: 1 In the case of compounds that can be prepared according to the invention, #-(4-) can be used as starting materials for process embodiment α). (Lifluorometerphenyl)-tetrachlor7-thalamic acid is known and can be prepared by methods known from the literature (see, for example, DE 2.932689).

The following formula gives a definition of the hydroxides that can be used in process embodiment α). In this formula (1), X represents the group already mentioned above in connection with the production.

Furthermore, the water-soluble salt solution of #-(4-)trifluoromethylphenyl)-tetrachloro7-thalamic acid, which can be used in process aspect mb), is defined by formula (■) and is part of the concept of the invention. Eggplant. They are novel, e.g. prepared from free acids by reaction with alkali metal hydroxides, alkaline earth metal hydroxides or optionally alkyl-substituted ammonium hydroxides in aqueous or alcoholic solution. be able to.

Heavy metal salts defined by formula (V) are also used in process embodiment b). In this formula, Y and Z represent the radicals mentioned as suitable for these substituents in connection with the description of the preparation of the substances according to the invention.

Possible diluents or solvents for the reaction in process embodiment a) according to the invention are alcohols such as methanol and ethanol, and water.

The reaction in step h b) of the process according to the invention is generally carried out in an aqueous medium.

The reaction temperatures for both embodiments a) and b) can vary within a substantial range. The reaction is generally carried out at 0-50°C, preferably 20-40°C.

The reaction is generally carried out under normal pressure.

When carrying out embodiment α) of the process according to the invention, the starting materials are generally used in equimolar amounts. Excessive amounts of hydroxide are not harmful.

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

In process embodiment α), the final product is generally separated by evaporating the solution to dryness under vacuum.

A preferred embodiment of embodiment b) of the process according to the invention provides that the water-soluble salt is prepared from the acid and the hydroxide in an aqueous or alcoholic solution and that the water-soluble salt is further converted into a heavy metal salt without separation. The treatment is carried out by the addition of an aqueous solution of Barely soluble heavy metal salts precipitate. This is separated, washed with water, and dried.

The active compounds according to the invention exhibit a strong microbicidal action and can be used for the combating of practically undesired microorganisms. The active compounds are suitable for use as plant protection agents.

Thus, for example, the bacteriocide may
seudotnonadeeae), Rhizobacteriaceae (Rh
i-gobiacaag), Enterobacteriaceae (E%tgro
baatariaaaam ) Corynebacteriaceae (C
odecinabα6t-diαC-α-) and Streptomycidae, (St uptown Shiroatα-tea
m) is used in plant protection for the control of fungi.

The good tolerance of the active compounds by plants at the levels necessary for combating plant diseases makes it possible to treat the aboveground parts of plants, the growing stems and seeds, as well as the soil.

The compounds according to the invention are suitable for use with bacteria of the genus Xanthomonas, such as Xanthomonas oryzae.
naa oryzaa) and Xanthomonas pelargonii (Xanthomonas pglargon)
tt) 1 and further Erwinia 9 Mangihuelae (Er
sot-nia mangifarag) and Corynebacterium miciganens.
It is particularly effective against rixmmicrutga*gnag).

, the active compounds are combined in the customary formulations, e.g. solutions, emulsions,
bm agents, powders, foams, pastes, granules, aerosols, natural and synthetic substances impregnated with active compounds, microcapsules in polymeric substances, coating compositions for seeds and combustion devices such as fumigation cartridges, for fumigation. Compounds used with cans and fumigation coils, and ULV? 91
Can be converted into mist and warm mist formulations.

These formulations are prepared in a known manner, for example by combining the activated metal with an extender, i.e. a liquid diluent, a gaseous and/or solid carrier liquefied under pressure, and optionally a surfactant, i.e. an emulsifying agent and/or a dispersing agent. It can be produced by mixing/or using a foaming agent. Furthermore, when water is used as an extender, for example, an organic solvent can also be used as an auxiliary solvent. as a liquid diluent or carrier, especially a solvent;
Mainly aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, polyethylene, methylene chloride, aliphatic or cycloaliphatic hydrocarbons such as cyclohexane or para7. Suitable are mineral oil fractions, alcohols such as butanol or glycols and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone or cyclohexanone, strong polar solvents such as dimethyl lumamide and trimethyl sulfoxide, and water; liquefaction By gaseous diluent or carrier is meant a liquid that is a gas at normal temperature and pressure, such as halogenated hydrocarbons and aerosol propellant bases such as butane, propane, nitrogen and carbon dioxide; solids; As carriers, crushed natural minerals, such as kaolin, clay, talc, chalk, quartz, athanofurgite, montmorillonite, or quartzite, and synthetic minerals, such as highly dispersed silicic acid, alumina, and silicates, are suitable. Solid carriers for the granules include crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as inorganic and organic synthetic granules such as sawdust, coconut shell, Corn cob and tobacco bases are suitable; emulsifiers and/or
Examples of blowing agents include nonionic and ionic emulsifiers, such as polyoxyethylene monofatty acid esters, polyoxyethylene fatty alcohol ethers, alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates, and alpamine. Hydrolysis products are suitable; examples of dispersants are lignin sulfite waste liquor and methylcellulose.

Adhesives such as Cal oxymethyl cellulose as well as powder,
Particulate or latex natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate can be used in the composition.

Colorants such as inorganic pigments such as iron oxide, titanium oxide and Prussian blue and organic dyes such as alizarin dyes, azo dyes or phthalocyanine dyes, and trace nutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc. Salt can be used.

The formulations generally contain from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90% by weight.

The active compounds according to the invention may be present in formulations or in combination with other known active compounds, such as fungicides, bacteriicides, insecticides,
They can be present in various forms of use as mixtures with acaricides, nematicides, herbicides, bird repellents, growth factors, plant nutrients and soil conditioners.

The active compounds may be used as such or in the form of their formulations or in the application forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. Can be done. These conventional methods include, for example, watering, dipping,
spray, atomiaing, atomization, evaporation, injection, slurry application, brushing, powder application, granulation, dry application, wet application, liquid application, slurry application, or ancrua
t i%g).

For the treatment of plant parts, the concentration of active compound in the application forms can be varied within a substantial range. They generally range from 1 to 0.0001% by weight, preferably from 0.5 to
Existing at 0.0011.

For the treatment of seeds, amounts of active compound of from 0.001 to 50 V, preferably from 0.01 to 10 f per seed weight are generally required.

For soil treatment, 0.00001 at the place of action
A concentration of active compound of from 0.1% by weight, preferably from 0.0001 to 0.02%, is required.

Production Examples Example 1 I A-(4-trifluoromethylphenyl)-tetrachlor 7tara i y 148 V (0.33 mol),
Together with potassium hydroxide 19F (0.33 mol), methanol ioo- was added and dissolved in water at 20°C.

The insoluble material from the dinner was separated from F and the F solution was evaporated to dryness under vacuum. As a result, #-(4
141f (theoretical amount of 88 t) of the potassium salt of chlor7-thalamic acid was obtained.

Example 2 #-(4-)Lifluoromethylphenyl)-tetrachlorophthalamic acid 135'7 (0.3 mol) was added with 12t (0.3 mol) of sodium hydroxide and methanol 1001Rt. Dissolved in 1 ton of water.9.

Next, in water 200-Medium chloride, 6H, 040F
(0.2 mol) was added dropwise at 20-25°C. The precipitated magnesium salt was separated by suction F, washed with water, and dried. Magnesium #-(4-trifluoromethylphenyl)-tetrachlorophthalate 115f (84% of theory) with a melting point higher than aOO<0>C was obtained.

A salt of the following formula was prepared in a similar manner: 1 3 Copper-(1) 6.65 7.34
Manganese - 〇) & 85J 5 Zinc 5.75 6.6 Usage Examples The following known compounds were used as control substances in the following experimental examples; Experimental Examples Agar plate test Medium used: Agar 15 parts by weight Sucrose 1O Jushabu Casein hydrolyzate, 8 parts II parts Yeast extract 4 parts by weight Dipotassium hydrogen phosphate 2 parts by weight Magnesium sulfate 0.3 parts by weight was dissolved in 1000 ml of distilled water, and the solution was maintained at 121°C for 30 minutes in an autoclave. .

Bath medium: 40 parts by weight of acetone Volume ratio of solvent to medium: 2:100 To prepare the active compound preparation, lfi parts of the active compound were mixed with the abovementioned amounts of solvent.

This concentrate was mixed thoroughly with liquid culture medium in the proportions mentioned above, and then the mixture was poured into Petri dishes.

After cooling and solidifying the medium, the following organisms were grafted onto agar plates and cultured at approximately 21°C:
gifgrae ) Xanthomonas Φ oryzae
ryzae) Xanthomonas beral is a stingray (Xantho-mon
as pelargonit) Corynebacterium fistulae (Corynm-b)
Depending on the growth rate of the microorganism, the evaluation is carried out after 2 to 8 days,
Inhibition of growth was used as a measure of the activity of the preparation.

In this test, the compounds of Examples 3.4 and 5 clearly showed superiority compared to the known ones.

Claims (1)

[Claims] 1. #-(4- )-trifluoromethylphenyl)-tetrachlorophthalamic acid salt. 2. In formula 0), M represents the lfi amount of sodium, potassium, calcium, magnesium, optionally alkyl-substituted ammonium, copper, iron, nickel, manganese or zinc, #-(4-)lifluoromethylphenyl)-tetrachlorophthalamic acid salt. 1 N-(4-9fluoromethylphenyl)-f trachlorophthalate of formula (1) [wherein M represents 1 equivalent of an alkali metal, alkaline earth metal, optionally substituted ammonium or heavy metal] When producing a salt of lamic acid, α) A'-(4-)lifluoromethylphenyl)-tetrachlorophthalamic acid of formula (I+) C'l in the presence of a diluent or solvent, (III) x-on (1) [wherein X represents an alkali metal, an alkaline earth metal or an optionally substituted ammonium cation]; #-(4-)lifluoromethylphenyl)-tetrachlorophthalamic acid in an aqueous solution,
Formula (V) y −z (V) [wherein,
#-(4-)lifluoromethylphenyl)- of formula (1) is reacted with a heavy metal salt of Y represents a heavy metal 1st needle and Z represents an anion.
Method for producing tetrachlorophthalamic acid. 4. Formulas (A'-
(4-Trifluoromethylphenyl) - A pest control agent containing at least one salt of tetrachlorophthalamic acid. 5. Claims 1 and 3 for exterminating pests
Use the salt of A'-(4-)difluoromethylphenyl)-tetrachloro7-thalamic acid of formula (1) described in item 4. Scope of 6-phase W+ii cultivation Pests in which the salt of A'-(4-trifluoromethylphenyl)-tetrachlorophthalamic acid of formula (1) described in items 1 and 3 is applied to the pests and/or their environment. How to get rid of it. 7. A- of formula (1) described in claims 1 and 3
(4-) A method for producing a drug for exterminating pests, which comprises mixing a salt of (4-)tetrachloromethylphthalic acid with an extender and/or a surfactant.