DE1792096A1 - Nematocidal agents and their uses - Google Patents

Description

DR. BERG DIPL.-ING. STAPF

PATENT LAWYERS Λ 7 Q 9 Π QR

8 MUNICH 2. HILBLESTRASSE 2O

Dr. Berg Dipl.-Ing. Stopf, 8 Munich 2, HilblestroBe 20 ·

Your sign

us.r sign. «v / My 17 498 d« * · ™ 22 · July 1968

Attorney's file 17 4-98

BOOTS PURE DRUG COMPANY LIMITED, Nottingham / England

Nematocidal agents and their uses

It has been found that compounds of the general formula I

"-IF-

(D

in which X is an oxygen or sulfur atom, Z is an oxygen atom or an H (OH) group, Y a) optionally one or more times through one

109847/1920 -2-

Halogen atom or a low molecular weight alkyl group eub-

substituted 2-thienyl group or
b) denotes a phenyl group which is optionally substituted one or more times by a halogen atom, a low molecular weight alkyl, alkoxy or alkylthio group or a nitro group, and

H is a hydrogen atom or one or more halogen atoms or represents one or more low molecular weight alkyl groups, have high nematocidal activity against plant-parasitic nematodes, e.g. against Heloidogyne spp. how Meloidogyne incognita and against Heterodera spp. like Heterodera rostochiensis.

The terms "low molecular weight alkyl group", "low molecular weight Alkoxy group "and" low molecular weight alkylthio group " denote beds with up to 7 carbon atoms and preferably up to 4 carbon atoms. The expression •• halogen atom " means a chlorine, bromine, fluorine or iodine atom and preferably a chlorine or bromine atom. When R is not a hydrogen atom R is preferably a single substituent in the 2- (or 5-) position of the furan or thiophene ring. If Y is a substituted 2-thienyl radical, so Y is preferably a single thienyl reet Substituents in the 5-position of the thiophene length. Palis Y denotes a substituted phenyl radical, then contains the-

109847/1920 - 3 -

This is preferably not more than 3 »in particular not more as 2, substituents.

The invention provides, inter alia, a method for controlling nematodes available, which consists in that one has a soil in which plants grow or are to be cultivated, with a combination of the foregoing general Formula 1 deals. Direct treatment of the soil with the active compound is the preferred embodiment of the method of the invention, but in some cases it is desirable to use the root system of a plant or treating the seed of a plant with the active compound prior to planting.

The term "soil" used here means any medium that can support the growth of plants. Thus, this expression means, in addition to soil itself, humus, compost, Sand and artificial plant growth media, including hydroponic media.

In soil treatment, a compound of general formula 1 is used as such or in one described below Preparation added to the soil in any way that allows intimate mixing with the soil. So can the mere nematocidal compound or preparation thereof

109847/1920

applied to the surface of the soil or below the surface of the soil and then mixed with the soil. The mere nematocidal compound can be applied in the form of powder or granules. Liquid preparations, including solutions, emulsions and dispersions, can be poured or poured onto the surface of the soil Injected into the soil. Aqueous emulsions or dispersions of the active ingredient can be incorporated into the irrigation water will. Granular and powdery preparations can be mixed with the soil.

The nematocidally effective dose of the active ingredient is generally 2.24 to 336 kg / ha, depending on the depth of the area to be treated Soil, which, depending on the plant variety and nematode species, can be up to 15 or 20 and even up to 30 and more cm can be. In general, amounts of 11.2 to 112 kg / ha (10 to 100 lbs. Per acre) are suitable.

For convenience and to get the maximum effect of the treatment to ensure, it is preferred to incorporate a compound of the general formula I into a suitable ZüTwereHruiig, which can be used according to the invention. Such nematocidal agents consist of a compound of the general Formula I in conjunction with a carrier material. Of the The carrier is generally an inert liquid carrier

109847/1920 _ ₅ _

together with a surfactant or a solid carrier with or without a surfactant. The surfactant can be made from a dispersant » Emulsifiers or wetting agents exist. The nematocidal agents can come in a variety of forms, e.g. in dispersions, emulsions, powders and granulates.

In particular, the dispersions and emulsions are available to the consumer as such and in the concentration of the active ingredient required for use or as primary preparations which still require the addition of water to either make them the one desired for use To dilute the concentration of the active ingredient or to first prepare the dispersion or emulsion.

The preparations contain essentially one or more of the active ingredients of the general formula as dispersions I dispersed in an aqueous medium. It is convenient to provide the consumer with a primary preparation, which can be diluted with water to produce a dispersion of the desired concentration; the primary preparation can be in one of the following forms.

The primary preparation can be used as a dispersible powder containing the active ingredient and a dispersant.

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be produced, which when mixed with water forms a dispersion.

The primary preparation can also be used as a solution of the active ingredient in a water-miscible solvent, e.g. acetone, can be supplied together with a dispersant, the solution diluted with water being a dispersion forms.

Another primary preparation contains an active ingredient of the general formula I in the form of a finely ground powder together with a dispersant that is old water intimately mixed into a paste or cream that after dilution forms a dispersion with water.

The above cream or paste containing a finely ground active ingredient can be added to an oil-in-water emulsion, a further type of primary preparation being obtained which is a dispersion of the active ingredient in an aqueous oil emulsion and which is further diluted with the kit water before use can be.

The preparations supplied as emulsions essentially consist of one or more active ingredients of the general type Formula I, which are dissolved in a solvent,

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- γ -

in the presence of an emulsifying agent with water in a Emulsion is converted. An emulsion of the desired concentration can be made from a primary preparation and the primary preparation can be in any of the following forms.

The primary preparation can be used as a concentrated stock emulsion | which contain an active ingredient of the general formula 1 together with an emulsifying agent, water and an organic Solvent, e.g. toluene, xylene or another aromatic solvent boiling between 80 and 300 C. contains.

A further, for the production of emulsions suitable primary composition may consist of the dissolved in an organic solvent and mixed with an emulsifying agent so as to obtain an emulsion when 'diluted primary prepared with water.

The powder and granulate preparations contain the Active ingredient in association with a solid carrier. The solid support is generally practically inert in the soil. In some In some cases, however, it may be desirable to use a non-inert carrier such as a fertilizer such as a Phosphate fertilizers or urea. Suitable inert carriers

109847/1920 " ⁸ "

are well known, e.g. bentonite, attapulgite, talc, diatomaceous earth, Puller earth and kaolin.

The powder powder and granulate preparations can be produced in a known manner. For example, the powder powder preparations can be produced by grinding or air-milling ψ a mixture of solid active ingredient and solid carrier. Granular preparations can be produced by soaking and / or coating carrier granules with the active ingredient or by granulating a pulverulent mixture of the active ingredient and the carrier.

The preparations described above, in which the active ingredients are in powder form, for example as dispersible powder and dust powder, contain the active ingredient preferably in the form of very small particles; the particle size is preferably such that the majority of the particles, on the order of at least $ 95, are smaller than 50 / u, of which about 75 $ are 5 to 20 / u. The solid supports usually used in such preparations generally have this or a smaller particle size.

The active ingredient concentration in the nematocidal agents described above can vary widely and can be 0.1

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- 9 -

up to 95% by weight of the preparation depending on the type of preparation and the application method. The essentials The requirement is that the habitat of the nematodes is brought into contact with a nematocidally effective amount of the active ingredient will.

In addition to a compound of the general formula I can ™ If the nematocidal preparations contain other active ingredients, e.g. additional nematocides, such as a mixture of Dichloropropane and dichloropropene, picryl chloride, dazomet, ethylene dibromide and 1,2-dibromo-3-chloropropane; insecticides like r * -benzene hexachloride, dieldrin, aldrin, dimethoate, parathion, Disulfoton and Phoratj fungicides such as Captan, Dicloran, Thiram, TGNB and PGNB; and herbicides, in particular Pre-emergence herbicides.

A group of compounds of the general formula is available for use in the process according to the invention

ο
preferred, in which R is a hydrogen or halogen atom, in particular a hydrogen, chlorine or bromine atom, and R ^ is a hydrogen atom, a low molecular weight alkyl group,

109847/1920

- ίο -

a low molecular alkoxy group, a nitro group or means one or two halogen atoms.

Particularly preferred compounds are those of the general

■ z

Formula II in which R is a tetravalent halogen atom, in particular means a tetravalent chlorine or tetravalent bromine atom. Such connections are not only very strong nematocidal effective but still have the advantage of being against many useful plants at nematocidally effective application doses are practically non-phytotoxic Planting or used after planting. However, it is preferred to treat the soil with the nematocidal compound 3 Treat up to 5 days before planting.

) The compounds of general formula II, in which R a means tetravalent halogen atom, can also be used for treatment the plants themselves are used, e.g. by spraying, to fight the nematodes that are in the air parts of the plant located parasitically attacked.

The nematocidal preparations of the invention also include those derived from a thiophene compound of the general formula III

- 11 109847/1920

1792Ü96

^E "Ο- S -fZf * (in)

in the Z gin oxygen atom or the group H (OH), R a Hydrogen atom or one or more halogen atoms or low molecular weight alkyl groups and R * one or more Halogen atoms, low molecular weight alkoxy groups, low molecular weight Mean alkylthio groups or nitro groups, and an inert liquid carrier together with a surfactant or a solid carrier with or without a tenside consists.

Many of the compounds falling under the general formula I. are known per se, but some compounds that have not been described so far are new. The new Compounds can be prepared by methods analogous to those known in the literature for those Connections are described.

For example, compounds of the general formula 1 in which Z is an oxygen atom can be prepared by a Friedel-Crafts reaction between a 2-thenoyl or 2-furoyl halide IV and a compound H - Y (V) or between

- 12 109847/1920

1792Ü96

an acid halide Y-CO-hal (VI) and a furan or Thiophene compound VII can be produced.

"O- 8-, al a-O

(IV) (VII)

Did Friedel-Crafts reactions are carried out in the presence of a metal halide catalyst, e.g. aluminum chloride, zinc chloride, Tin chloride or titanium tetrachloride.

The compounds of the general formula I in which Z is H (OH) can be prepared by reducing the corresponding compounds, in which Z is an oxygen atom, produced for example with aluminum isopropoxide. Such Compounds can also be made by means of a G-Rignard reaction an appropriate Grignard reagent, e.g. an appropriately substituted 2-thienyl or 2-furyl magnesium chloride, with the corresponding aldehyde, for example the correspondingly substituted benzaldehyde or thiophene-2-aldehyde, getting produced.

- 13 -

1 O 9 8 k 7/1 9 2 O

ORIGINAL

Examples of compounds which can be used according to the invention are:

2- (4-chlorobenzoyl) thiophene, 2- (4-bromobenzoyl) thiophene, 2- (4-fluorobenzoyl) thiophene, 2- (4-iodobenzoyl) -thiophene, 2-benzoyl-5-chlorotiiiophene, 2- (4-chlorobenzoyl) -5-chlorothiophene, 5-bromo-2- (4-chlorobenzoyl) thiophene, 2- (4-chlorobenzoyl) -5-iodothiophene, 2- (4-bromobenzoyl) -5-chlorothiophene, 2- (4-bromobenzoyl) -5-bromothiophene, 2- (3-bromobenzoyl) thiophene, 2- (3-fluorobenzoyl) thiophene, 2- (2-chlorobenzoyl) thiophene,

2- (3-chlorobenzoyl) thiophene, i

2-benzoylthiophene, 2- (2-bromobenzoyl) thiophene, 2- (2,6-dichlorobenzoyl) thiophene, 2- (2,4-dichlorobenzoyl) thiophene, 2- (2,4-dichlorobenzoyl) -5-chlorothiophene, 2- (2-chlorobenzoyl) -5-chlorothiophene, 2- (2-methylbenzoyl) thiophene, 2- (3-methylbenzoyl) thiophene, 2- (4-methylbenzoyl) thiophene,

109847/1920 -U-

-H-

2-benzoyl-5-methylthiophene, 2-benzoyl-5-ethylthiophene, 2- (2-methoxybenzoyl) thiophene, 2- (4-methoxybenzoyl) thiophene,

2- (4-methoxybenzoyl) -5-methylthiophene,

2- (4-ethoxybenzoyl) thiophane, 2- (4-n-butoxybenzoyl) thiophene, 5-0chloro-2-methoxybenzoylthiophene, 2- (4-methylthiobenzoyl) thiophene, 2- (2-nitrobenzoyl) thiophene, 2- (3-nitrobenzoyl) thiophane,

2- (4-CEbr-3-nitrobenzoyl) thiophene,

2-benzoylfuran,

2- (4-chlorobenzoyl) furan, 2- (4-bromobenzoyl) furan, 2- (4-Μβthoxybenzoyl) -furan, 2- (2-Thenoy1) -thiophene, 2- (2-puroyl) -thiophene, 2-0hlor-5- (2-thenoyl) -thiophene, 2-chloro-5- (2-furoyl) -thiophene, 2- (2-puroyl) -5-methylthiophene,

2- (2-Bromo-5-furoyl) -5-chlorothiopiient (4-bromophenyl) - (2-thienyl) methanol, (4-chlorophenyl) - (2-chloro-5-thienyl) -methanol, ^(4-c hlorphenyl) - (2-thienyl) methanol ·

10984 7/1920 - 15 -

Preferred connections are »

2- (4-chlorobenzoyl) thiophene, 2- (4-bromobenzoyl) thiophene, 2- (4-iodobenzoyl) thiophene and 2- (4-chlorobenzoyl) -5-chlorothiophene.

Those described above and which can be used according to the invention Compounds have a low level of mammalian ™ toxicity, which is a significant advantage.

The following examples illustrate the invention.

example 1

A solution was prepared from the following components:

2- (4-bromobenzoyl) thiophene ad 5 , 0 Ethylan CP 0 , 13 acetone 100 , 0

Ethylan CP, a trade name for an emulsifying and dispersing agent lubricant, is an ethoxylated octylphenol.

Similar solutions were prepared by using the following active ingredients instead of 2- (4-bromobenzoyl) thiophene were «2- (3-chlorobenzoyl) thiophene, 2- (4-chlorobenzoyl) thiophene and 2- (3-bromobenzoyl) thiophene.

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1 / 92Ü96

The above solutions form aqueous solutions when diluted with water Dispersions of the active ingredient suitable for soaking the soil.

Example 2

5 parts by weight were used to prepare a dust powder 2- (4-chlorobenzoyl) thiophene intimately with 95 parts by weight of kaolin mixed and the mixture ground using a hammer mill.

Example 3

A liquid concentrate was prepared from the following ingredients

Wt / IT oil.

2- (4-chlorobenzoyl) thiophene 10.0 Agrilan A 10.0 Dimethylformamide ad 100.0

Agrilan A, a trade name for an emulsifier, contains ethoxylated alkylphenol and an amine salt of an alkylarylsulfonate.

After dilution with water, this concentrate forms a dispersion of the active ingredient.

- 17 109847/1920

Example 4

A dispersible powder was prepared by mixing a mixture of the following ingredients with a hammer mill was ground:

2- (4-chlorobenzoyl) thiophene 25.0 Dyapol PT 2.5 Pentrone T 1.0 Ethylan MR 1.0 Kaolin, fine ad 100.0

Weight £

Dyapol PT, a trade name for a dispersant, is the sodium salt of an ethoxylated condensate of urea, Formaldehyde and cresol. Pentrone T, a trade name for a wetting agent, is the sodium salt of a sulfated one Fatty alcohol. Ethylan MR, a trade name for a wetting agent, is an ethoxylated alkylphenol.

A similar preparation was made using 2- (4-bromobenzoyl) thiophene manufactured as an active ingredient.

These preparations form dispersions of the solid active ingredients when mixed with water.

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- 18 ORIGINAL INSPECTED

Example 5

Portions of a soil medium infested by eggs and larvae of cotton root nematodes (Meloidogyne incognita acrita) were mixed with aqueous dispersions of a finely divided test compound at various concentrations. After 5 days of storage at 18.5 ⁰ C, the soil medium was placed into small pots and planted a healthy tomato seedling in each pot, and three pots were used for each concentration of test compound and three pots without test compound as a control. The pots were then ^{kept at 28 0} for 10 days} then the roots of each plant were examined for damage caused by the nematodes (knots on the roots). The degree of damage was classified according to the following rating system *

Root node index

0 1 2 3 4

Knot (gall) aahl at the root system (Durohsohnitt of 3 plants)

Hull

1 to 2, small 3 to 9> small 10 to 20, some large

over 2O _f generally large

The following results were obtained: 0 means di · Kon centering of the Teet compound in the soil medium in parts / mil lion (öew. / vol.).

7/1920 - 19 -

Root node index

C = 62, 5 C = 31 , 3 0 0 0 O • 0 1 0 1

- 19! Leased line

2- (4-chlorobenzoyl) thiophene 2- (4-bromobenzoyl) thiophene 2- (4-iodobenzoyl) thiophene

2- (4-chlorobenzoyl) -5-chlorothiophene

The other compounds listed before the examples gave root node index values below 1 at C = 250.

Some links had a Yairzel knot index of 0 at C = 125, and this value was kept at C = 62.5 for some compounds. The control plants gave one Root knot index of 4 at all four concentrations.

Claimsι

- 20 -

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Claims (1)

V / 92096 Claims 1. Nematocidal agent, characterized by a content on a thiophene compound of the general formula R - ^ jL 5 -f * in which Z is an oxygen atom or the group H (OH), R Hydrogen atom or one or more halogen atoms or one or more low molecular weight alkyl groups and R is or more halogen atoms or one or more low molecular weight alkoxy groups, low molecular weight alkylthio groups or nitro groups, and an inert liquid carrier together with a surfactant or a solid Carrier with or without surfactant. 2. Nematocidal agents according to claim 1, characterized in that that the thiophene compound has the general formula - 21 - YcT98A7 / 1920 ORWAL inspected 1 / 92Ü96 2 3 has, in which R is a hydrogen or halogen atom and R one or two halogen atoms, a nitro group or a mean low molecular weight alkoxy group. 3. nematocidal agent according to claim 2, characterized in that R is a tetravalent halogen atom . 4. Nematocidal agent according to claim 31, characterized in that that the thiophene compound is 2- (4-chlorobenzoyl) thiophene is. 5. Nematocidal agent according to claim 3 »characterized in that the thiophene compound 2- (4-bromobenzoyl) thio phen is. 6. A method for controlling nematodes, characterized in that a soil in which plants are to grow or waohsen, with a compound of the general formula - Y - 22 - 109847/1920 in which X is an oxygen or sulfur atom, Z is an oxygen atom or an H (OH) group, Y a) a 2-thienyl radical which is optionally substituted one or more times by halogen atoms and / or low molecular weight alkyl groups or b) one optionally single or multiple by halogen atoms, low molecular weight alkyl groups, low molecular weight Alkoxy groups, low molecular weight alkylthio groups and / phenyl radical substituted by nitro groups, and H represents a hydrogen atom or one or more halogen atoms and / or one or more low molecular weight alkyl groups. 7. The method according to claim 6, characterized in that the soil with a compound of the general formula κ ² -IQL s - ο
treated, in which E is a hydrogen or halogen atom and H is a hydrogen atom, a low molecular weight alkyl group, a low molecular weight alkoxy group, a nitro group or one or two halogen atoms. 8 «method according to claim 7ι daduroh characterized, dad Ir means a row halogen atom " 109847/1920 9. The method according to claim 8, characterized in that that the soil is treated with 2- (4-chlorobenzoyl) thiophene will. 10. The method according to claim 8, characterized in that that the soil is treated with 2- (4 - bromobenzoyl) thiophene will. 103847/1920