DE102013003656A1 - New agrochemical active ingredients, their production and use - Google Patents

Abstract

Compounds of formula 1 are new, advantageous pesticides, in particular herbicides. As a rule, these can be prepared simply by starting from active ingredients which are weak acids by converting them into derivatives which contain at least one strong polar group, e.g. B. ionic functons - connected via a spacer. The compounds of formula 1 can be converted into agrochemical formulations and can thus be used to control harmful organisms.

Description

The invention relates to the technical field of agrochemical drug discovery.

Agrochemicals are well known. An overview of these can be found in The Pesticide Manual, 16 Edition (British Crop Protection Council).

However, some drugs have several drawbacks, such as "tight" selectivity in cultures, antagonistic effects when mixed with other drugs, or they have high vapor pressure, which can lead to drug losses on the field by elimination above the gas phase. This can be associated with other disadvantages, such as damage in crops that were grown in the neighborhood and in the volatile active ingredients - especially herbicides - are brought through the gas phase. Frequently such agents are agents having a molecular weight below 1000, especially below 500. In addition, it is often weak organic acids such. B. the natural or synthetic auxins.

The aim of the present invention was to find new drugs that do not have these disadvantages.

Surprisingly, it has been found that certain derivatives of the formula 1 of known active compounds completely or partially avoid the abovementioned disadvantages.

The present invention relates to compounds of formula 1, their preparation and use as agrochemically active compounds and their formulations. RAB compounds of the formula 1

Detailed description of the invention

Active substances of the formula 1 are new. They can be prepared by, for example, converting compounds of the formula 2 into a very polar active substance by targeted conversion (equation 1). Surprisingly, these derivatives 1 nevertheless show a high activity, a very good selectivity, an improved compatibility with other active ingredients and a greatly reduced vapor pressure.

Active ingredients of the formula 1 thus have at least 2 molecular fragments, one being a known active ingredient or a simple prodrug of an active ingredient, and one representing a polar or ionic group.

Molecules of formula 1 are characterized in that
R is an active substance or a prodrug of an active substance, the vapor pressure of the active ingredient and prodrug being higher than 10 ^-5 mPa, preferably higher than 10 ^-2 mPa,
A represents a single bond or a spacer which may be selected from a chain of up to 10 arbitrary atoms from the group C, N, O and S, where the spacer may be substituted or substituted, or saturated or unsaturated, or from a (hetero) cyclic group of up to 10 arbitrary atoms from the group C, N, O and S, wherein the (hetero) cyclic group may be substituted or unsubstituted or saturated, unsaturated or (hetero) aromatic or from a group of 10 atoms from the Group C, N, O and S, which contains both a chain and a (hetero) cyclic element, is
and
B represents a polar group which preferably contains at least one ionic or / and at least one zwitterionic group.

In a preferred embodiment, R represents the anion of pelargonic acid (nonanoic acid).

In a further preferred embodiment, R represents the anion or a prodrug of a natural or synthetic auxin.

Examples of auxins are 2,4-D or dicamba. Examples of a prodrug are alcohols which result from reduction of the carboxyl group from auxins.

In a further preferred embodiment, the spacer A is a linear chain of up to 10 atoms from the group C, O, N and S, wherein the chain may be unsaturated or saturated.

In a further preferred embodiment, the polar group B is at least one anionic function from the group consisting of sulfate, thiosulfate, sulfonate or phosphate, where the cations in question are cations which are relevant for agrochemical practice, such as, for example, K, Na, ammonium.

B1.1 -[NR¹R²R³]⁺M^–
B1.2 -[P(O)R⁴R⁵]⁺M^–
B1.3 -[SR⁶R⁷]⁺M^–
B1.4 -[S(O)R⁸R⁹]⁺M^–
B1.5 -[NR¹⁰-C(R¹¹)=NR¹²R¹³]⁺M^–
B1.6 -[NR¹⁴-C(NR¹⁵R¹⁶)=NR¹⁷R¹⁸]⁺M^–
R¹ (C1-C4)-Alkyl
R² analog R¹, aber unabhängig davon
R³ analog R¹, aber unabhängig davon
R⁴ (C₁-C₄)-Alkyl, Phenyl
R⁵ analog R⁴, aber unabhängig davon
R⁶ analog R⁴
R⁷ analog R⁶, aber unabhängig davon
R⁸ analog R⁴
R⁹ analog R⁸, aber unabhängig davon
R¹⁰ analog R¹, aber unabhängig davon
R¹¹ H, (C1-C4)-Alkyl
R¹² analog R¹⁰, aber unabhängig davon
R¹³ analog R¹⁰, aber unabhängig davon
R¹⁴ analog R¹
R¹⁵ analog R¹⁴, aber unabhängig davon
R¹⁶ analog R¹⁴, aber unabhängig davon
R¹⁷ analog R¹⁴, aber unabhängig davon
R¹⁸ analog R¹⁴, aber unabhängig davon
M^– agrochemisch relevantes Anion In a further preferred embodiment, the polar group B is at least one cationic group, preferably from an ammonium, sulfonium, sulfoxonium or phosphonium amidinium or a guanidinium group. The associated anions are anions that are relevant for agrochemical practice, such as. As Cl, Br, acetate, formate, propionate, sulfate, hydrogen sulfate or primary, secondary or tertiary phosphate. Examples of these are the following functional groups:

B1.1 - [NR ¹ R ² R ³ ] ⁺ M ^-
B1.2 - [P (O) R ⁴ R ⁵ ] ⁺ M ^-
B1.3 - [SR ⁶ R ⁷ ] ⁺ M ^-
B1.4 - [S (O) R ⁸ R ⁹ ] ⁺ M ^-
B1.5 - [NR ¹⁰ -C (R ¹¹ ) = NR ¹² R ¹³ ] ⁺ M ^-
B1.6 - [NR ¹⁴ -C (NR ¹⁵ R ¹⁶ ) = NR ¹⁷ R ¹⁸ ] ⁺ M ^-
R ^{1 is} (C ¹ -C 4) -alkyl
R ^{2 is} analogous to R ¹ , but independently
R ^{3 is} analogous to R ¹ , but independently
R ^{4 is} (C ₁ -C ₄ ) -alkyl, phenyl
R ^{5 is} analogous to R ⁴ , but independently
R ^{6 is} analogous to R ⁴
R ^{7 is} analogous to R ⁶ , but independent of it
R ^{8 is} analogous to R ⁴
R ^{9 is} analogous to R ⁸ , but independently
R ^{10 is} analogous to R ¹ , but independently thereof
R ^{11 is} H, (C 1 -C 4) -alkyl
R ^{12 is} analogous to R ¹⁰ , but independently
R ^{13 is} analogous to R ¹⁰ , but independently
R ^{14 is} analogous to R ¹
R ^{15 is} analogous to R ¹⁴ , but independent of it
R ^{16 is} analogous to R ¹⁴ , but independently
R ^{17 is} analogous to R ¹⁴ , but independent of it
R ^{18 is} analogous to R ¹⁴ , but independently
M ^- agrochemically relevant anion

In a further preferred embodiment, the underlying active ingredients (moiety R) are weak organic acids, preferably carboxylic acids, which are covered by the formula 3. Preferred spacers then represent linear molecular groups via which fragment B is connected.

Particularly preferred embodiments are those in which the molecular weight of the molecular fragments A and B does not exceed 400, in particular does not exceed 300.

X OH
R11 H, (C1-C2)-Alkyl
R20 analog R19, aber unabhängig davon
Hal Cl, Br oder I
R21 (C1-C4)-Alkyl
Y agrochemisch relevantes Anion
M agronomisch relevantes Kation
v 0–8
y 0–8
und v + w 1–8
R'-CO2H natürliches oder synthetisches Auxin oder Pelargonsäure The following preparation methods and examples illustrate the present invention

X OH
R11 is H, (C1-C2) -alkyl
R20 analog R19, but regardless
Hal Cl, Br or I
R21 (C1-C4) -alkyl
Y agrochemically relevant anion
M agronomically relevant cation
v 0-8
y 0-8
and v + w 1-8
R'-CO2H natural or synthetic auxin or pelargonic acid

Active ingredients of the formula 1 are usually converted into suitable formulations before they are used. Formulation types and technologies used in agrochemical formulations are well known to those skilled in the art and e.g. B. described in Proceedings from Formulation Forum '97, Formulation Science, Vol 1 (Chester L. Foy, David W. Pritchard, George B. Beestman) ; Chemistry and Technology of Agrochemical Formulations (ISBN 0-7514-0443-8; Ed .: DA Knowles, Kluwer Acaddemic Publishers 1998 ; Formulation technique (Hans Mollet, Arnold Grubenmann, Wiley-VCH Verlag GmbH, 2000) ; as well as cited literature.

Suitable formulations are solid and liquid formulations, such as. As dusts, powders and granules or solutions, emulsions, suspoemulsions

Preference is given to liquid, aqueous formulations, in particular those in which the active compounds of the formula 1 are dissolved, such as. B. Solutions. Very particular preference is given to liquid formulations which have a content of at least 200 g of compound 1 per liter.

Agrochemical formulations are characterized in that they
at least one active substance 1
at least one formulation adjuvant
optionally further agrochemical active ingredients
and
optionally include other agrochemicals such as adjuvants, fertilizers or trace minerals.

In a preferred embodiment, the active ingredient 1 is a herbicide.

Agrochemical formulations with compounds of formula 1 are also new and subject of this invention.

Agrochemical formulations of compounds 1 can be applied directly to target plants or target surfaces, in particular sprayed, or they can be previously treated with a suitable carrier such as. As water or organic solvents are diluted and then applied or sprayed. Preferred carrier is water.

For applications, the required application rates per hectare are diluted with water to a volume of 5 L to 5000 L, preferably to a volume of 50 L to 2000 L. In addition, more important for the agronomists products of the spray mixture can be added such. B. other crop protection agents, adjuvants, fertilizers or trace minerals.

Pesticides are, on the one hand, chemical agents that are either manufactured synthetically or are active substances of natural origin, or are called "biologicals", d. H. Plant protection products authorized in organic farming. An overview of these crop protection agents can be found in The Pesticide Manual, 16 Edition (British Crop Protection Council) and The BioPesticide Manual, 15th Edition.

Preferred crop protection agents are herbicides, fungicides, insecticides, accaricides, nematicides, safeners and rodenticides.

The method for controlling harmful organisms by applying agrochemical formulations of the compounds of formula 1 is also novel and subject of this invention.

Examples

Experiment 1 according to the invention

10 g of a potassium salt of 2,4-D are stirred in 100 ml of dimethylacetamide and admixed with 1.1 molar equivalents of 2-bromoethanol.

After completion of the reaction, all volatile components are removed in a high vacuum and the residue is purified by a short silica gel filtration with a solvent mixture of ethyl acetate and cyclohexane. The compound thus obtainable has a purity of more than 90% after a high vacuum and can be further reacted directly:

5 g of the compound thus obtained are taken up in 20 ml of dioxane and admixed with 1.1 equivalent of ClSO ₃ H with cooling. After completion of the reaction, air is passed through the apparatus to remove HCl formed. The resulting acid is then neutralized with dilute KOH solution to give compound 1.1. Subsequently, the volatile components are removed in a high vacuum. The residue can either be purified, for. B. by a "reversed phase chromatography", or it can be further processed directly.

Analogously to experiment 1 according to the invention, further compounds of formula 1 can be prepared. These are summarized by way of example in Table 1. Table 1: Herbicides of the formula 1 according to the invention

Experiment 2 according to the invention

0.01 g of Actizide MBS (biocide, Thor-Chemie) and 7.99 g of water are added to 2 g of compound 1.1. The resulting solution corresponds to an SL formulation and can be used directly in biological experiments,

Biological experiments

Inventive experiment 3

For a greenhouse experiment rapeseed is cultivated as a model plant for undesired plant growth. After the plants have reached a height of about 20 cm, they are mixed with a spray mixture of water and the formulation of experiment 2 of the invention. The spray mixture is 400 l / ha, the application rate of compound 1.1 is 100 g / ha.

Comparative test

Analogously to experiment 3 according to the invention 2,4-D is applied to rape plants (same molar equivalents as compound 1.1 in the inventive experiment 3, 400 L spray / ha).

Compound 1.1 shows an effect that is well comparable to 2,4-D.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited non-patent literature

• Proceedings from Formulation Forum '97, Formulation Science, Vol 1 (Chester L. Foy, David W. Pritchard, George B. Beestman) [0019]
• Chemistry and Technology of Agrochemical Formulations (ISBN 0-7514-0443-8; Ed .: DA Knowles, Kluwer Acaddemic Publishers 1998 [0019]
• Formulation technique (Hans Mollet, Arnold Grubenmann, Wiley-VCH Verlag GmbH, 2000) [0019]

Claims (3)

Molecules of formula 1, characterized in that R represents an active ingredient or a prodrug of an active ingredient, wherein the vapor pressure of active ingredient and prodrug is higher than 10 ^-5 mPa, preferably higher than 10 ² mPa, A represents a single bond or a spacer which from a chain of up to 10 arbitrary atoms from the group C, N, O and S, wherein the spacer may be substituted or substituted, or saturated or unsaturated, or from a (hetero) cyclic group of up to 10 arbitrary atoms the group C, N, O and S, where the (hetero) cyclic group may be substituted or unsubstituted or saturated, unsaturated or (hetero) aromatic or from a group of 10 atoms from the group C, N, O and S, which contains both a chain and a (hetero) cyclic element, and B represents a polar group which preferably contains at least one ionic or / and at least one zwitterionic group. Agrochemical formulations characterized in that they comprise at least one active ingredient 1, at least one formulation adjuvant optionally further agrochemical active ingredients and optionally other agrochemicals such as adjuvants, fertilizers or trace minerals. Process for the control of harmful organisms, characterized in that agrochemical formulations of the compounds of formula 1 are sprayed onto crops or target areas.