DE4137872C2 - - Google Patents

Description

The invention relates to new substituted pyrazolylpyrazoles, their Manufacture and intermediates for their manufacture and their Use as a herbicidal agent.

It is already known from EP 1 54 115 A1, DE 34 02 308 A, EP 34 945 A2 and GB 21 23 420 known that 1-phenylpyrazoles have herbicidal properties.

However, the herbicidal activity of the known compounds is frequent not sufficient, or it occurs with a corresponding herbicide problems of selectivity in main agricultural crops on.

The object of the present invention is to provide new substituted pyrazolylpyrazoles that do not have these disadvantages have and the biological properties of the previous known connections are superior.

It has now been found that substituted pyrazolylpyrazoles of general formula I.

in the
R1 methyl,
R ² C ₁ -C ₄ alkyl, C₁-C₄-alkylthio, C₁-C₄-alkoxy, mono- or polysubstituted by fluorine-substituted C₁-C₄-alkyl, C₁-C₄-alkylthio or C₁-C₄-alkoxy,
R ^{3 is} hydrogen or chlorine,
R ^{4 is} hydrogen or C ₁ -C ₄ alkyl,
R ^{5 is} hydrogen, nitro, cyano or the group -COOR ⁶ or -CONR ⁷ R ⁸ ,
R ^{6 is} hydrogen, C ₁ -C ₆ alkyl,
R ⁷ and R ^{8 are} hydrogen or C ₁ -C ₆ alkyl or
R ⁷ and R ⁸ together with the neighboring nitrogen atom form a piperidino group, mean that they have a better herbicidal activity than the known compounds.

Substituted pyrazolyl pyrazoles of the general formula I, in which
R ^{1 is} methyl,
R ^{2 is} methyl, trifluoromethyl, methylthio, difluoromethylthio, methoxy or difluoromethoxy,
R ^{3 is} hydrogen or chlorine,
R ^{4 is} hydrogen or methyl,
R ^{5 is} hydrogen, nitro, cyano or the group -COOR ⁶ or -CONR ⁷ R ⁸ ,
R ^{6 is} hydrogen, methyl or ethyl and
R ⁷ and R ^{8 are} hydrogen, methyl or isopropyl or
R ⁷ and R ⁸ together with the neighboring nitrogen atom form a pipido group.

The term "alkyl" means that the carbon chain branches or can be unbranched.

The invention further relates to intermediates of the general NEN formula II

in which R ¹ , R ² and R ^{3 have} the meanings given under the general formula I, with the exception of the intermediates, in which R ^{1 is} methyl or butyl and R ^{2 is} methyl when R ^{3 is} hydrogen. The intermediates of the general formula II are suitable for the preparation of compounds of the general formula I.

The compounds of general formula I according to the invention leave establish yourself by

• A) a compound of general formula II in which R ¹ , R ² and R ^{3 have} the meanings given under the general formula I, with compounds of the general formula III in which R ⁴ and R ^{5 have} the meanings given under the general formula I and Y represents C ₁ -C ₆ alkoxy, hydroxy or halogen, or
  if R ^{5 is} hydrogen
• B) a compound of the general formula II with 2-haloacrylonitriles of the formula (IIIa) or with 2,3-dihalopropionitriles of the formula (IIIb) in which Hal stands for halogen.

The compounds of general formula I according to the invention leave also in DE 34 02 308 A, EP 34 945 A2 and EP 1 54 115 A1 Manufacture described method by instead of there substituted phenylhydrazines set the compounds of general formula II,

in which R ¹ , R ² and R ^{3 have} the meanings given under the general formula I, are implemented.

The compounds of general formula I according to the invention in which R ^{5 represents} nitro or the group -CONR ⁷ R ⁸ can also be obtained from compounds of general formula Ia

in which R ¹ , R ² and R ^{3 have} the meanings given in general formula I and R ^{5 represents} hydrogen, cyano or the group -COOR ⁶ , are prepared by known methods (DE 34 02 308 A, EP 34 945 A2 and EP 1 54 115 A1).

The reactions are conveniently carried out in such a way that the compounds of general formulas II and III in a ge suitable solvents at temperatures between -30 and 150 ° C, preferably at room temperature.

The preparation can be carried out with or without a solvent the being such solution or Ver fertilizers are used, compared to the respective Reactants are inert. Examples of such solvents be either diluents are aliphatic, alicyclic and aromatic hydrocarbons, each optionally can be chlorinated, such as hexane, cyclohexane, Pe trole ether, ligroin, benzene, toluene, xylene, methylene chloride, chloro roform, carbon tetrachloride, ethylene chloride, trichlorethylene and chlorobenzene, ethers such as diethyl ether, methyl ethyl ether, methyl t-butyl ether, diisopropyl ether, dibutyl ether, Dioxane and tetrahydrofuran, ketones such as acetone, Me ethyl ethyl ketone, methyl isoproyl ketone and methyl isobutyl ketone, Ni trile such as acetonitrile and propionitrile, alcohols, such as methanol, ethanol, isopropanol, butanol, tert.- Butanol, tert-amyl alcohol and ethylene glycol, esters, such as for example play ethyl acetate and amyl acetate, acid amides such as Dimethylformamide and dimethylacetamide, sulfoxides such as Dimethyl sulfoxide, and sulfones, such as sulfolane, bases, such as pyridine and triethylamine, carboxylic acids such as Example acetic acid and mineral acids, such as sulfur acid and hydrochloric acid.  

The compounds according to the invention are worked up in the usual way. Purification takes place through Crystallization or column chromatography.

The compounds according to the invention are generally colorless or pale yellow colored crystalline or viscous substances some of which are readily soluble in chlorinated hydrocarbons, such as methylene chloride or chloroform, alcohols such as for example methanol or ethanol, ketones, such as Acetone or butanone, amides, such as dimethylformamide, or also sulfoxides, such as dimethyl sulfoxide.

The compounds of the general required as intermediates Formula II

in which R ¹ , R ² and R ^{3 have} the meanings given in the general formula I, can be carried out analogously to processes known per se (for example: JP 6 21 58 260) from the compounds of the general formula IV

in which R ¹ , R ² and R ^{3 have} the meanings given in the general formula I, produce.

The compounds of the general formula IV in which R ¹ and R ^{2 have} the meanings given in the general formula I and R ^{3 is} halogen can be prepared by using compounds of the general formula IV in which R ^{3 is} hydrogen a halogenating agent.

The for the preparation of the compounds of general formula IV required starting materials of the general formula V

in which R ^{1 has} the meaning given in the general formula I can be prepared, for example, if R ^{2 is} C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkyl which is substituted one or more times by halogen,

• A) a compound of the general formula VI or VII in which R ^{2 represents} C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyl which is mono- or polysubstituted by halogen, with compounds of the general formula VIIIR¹-NHNH₂ (VIII), in which R ^{1 is} the one in general Formula I has the meaning indicated, if appropriate in the presence of a solvent, or if R ^{2 is} C ₁ -C ₄ -alkylthio or C ₁ -C ₄ -alkylthio which is mono- or polysubstituted by halogen,
• B) a compound of the general formula IX in which R ^{9 is} C ₁ -C ₄ alkyl, with compounds of the general formula VIII, if appropriate in the presence of a solvent, first to give compounds of the general formula X. in which R ^{1 has} the meaning given in the general formula I and R ^{9 is} C ₁ -C ₄ alkyl, and then reacted with compounds of the general formula XIR¹⁰X (XI) in the R ¹⁰ for C ₁ -C ₄ alkyl or represents one or more halogen-substituted C ₁ -C ₄ alkyl and X represents a leaving group, can react and the resulting compound of the general formula XII according to methods known from the literature (e.g. Zeitschrift für Chemie 420, (1968)) saponified and decarboxylated, or
• C) a compound of the general formula XIII in which R ^{9 is} C ₁ -C ₄ alkyl and R ^{10 is} C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyl which is substituted one or more times by halogen, with compounds of the general formula VIII to give compounds of general formula XII, or if R ^{2 is} C ₁ -C ₄ alkoxy or one or more halogen-substituted C ₁ -C ₄ alkoxy
• D) Compounds of the general formula XIV in which R ^{1 has} the meaning given in the general formula I, with compounds of the general formula XI in the presence of a base.

The intermediate products can be prepared with or without a solution medium are carried out, if necessary mention the above th solvents are used.

The starting materials mentioned are known or can be produce analogous to known methods.

Escape groups according to process variants B and D are chlorine and Bromine.

For example, sulfuryl chloride, Na trium hypochloride, N-chlorosuccinimide, N-bromosuccinimide, bromine or Chlorine can be used.

The compounds according to the invention show a good herbicidal we in broad-leaved weeds and grasses. A selective one Use of the active ingredients according to the invention is in different kul structures possible, for example in rapeseed, beets, soybeans, cotton, Rice, corn, barley, wheat and other cereals. Are there individual active substances as selective herbicides in beets, cotton, sun yes, corn and cereals are particularly suitable. Likewise, the Ver bindings for weed control in permanent crops, such as for play forest, ornamental wood, fruit, wine, citrus, nut, banana, Coffee, tea, gum, oil palm, cocoa, berry fruit and hops systems are used.  

The compounds of the invention can, for example, in the the following plant species are used:

Dicotyledon weeds of the genera
Sinapis, Lepidium, Galium, Stel laria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Ur tica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipo moea, Polygonum, Sesbania, Ambrosia, Cirsium, Sonchus, Solanum, Lamium, Veronica , Abutilon, Datura, Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum.

Monocotyledonous weeds of the genera
Avena, Alopecurus, Echino chloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Elymus, Sagittaria, Monochoria, Fim bristylis, Eleocharis, Ischaemum and Apera.

The application rates fluctuate depending on the type of application Post-emergence in limits between 0.001 to 5 kg / ha.

The active compounds according to the invention can also be used as defoliants, Desiccant and used as an herbicide.

The compounds of the invention can either alone, in Mixture used with each other or with other active ingredients will. If necessary, other crop protection or damage  pesticide added depending on the desired purpose will. If there is a broadening of the spectrum of activity other herbicides can be added. At for example, are suitable as herbicidally active mixture partners those active ingredients that are described in Weed Abstracts, Vol. 40, No. 1, 1991 under the title "List of common names and abbreviations employed for currently used herbicides and plant growth regulators " are listed.

A promotion of the intensity and speed of action can be achieved, for example, through additives that enhance the effects, such as organic Solvents, wetting agents and oils can be achieved. Such additions may therefore cause a reduction in the drug dose tion to.

The active compounds according to the invention or their Mi. in the form of preparations such as powders, sprinkling agents, Granules, solutions, emulsions or suspensions, with addition of liquid and / or solid carriers or Ver fertilizers and optionally adhesives, wetting agents, emulsifying agents and / or Dispersing aids applied.

Suitable liquid carriers are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclo hexanone, isophorone, dimethyl sulfoxide, dimethylformamide, further Mineral oil fractions and vegetable oils.  

Minerals are suitable as solid carriers, for example Ben tonite, silica gel, talc, kaolin, attapulgite, limestone and herbal products, for example flour.

Examples of surface-active substances include calci umlignin sulfonate, polyethylene alkylphenyl ether, naphthalene sulfone acids and their salts, phenolsulfonic acids and their salts, form aldehyde condensates, fatty alcohol sulfates and substituted benzene sulfonic acids and their salts.

The proportion of the active ingredient (s) in the various The preparations can vary within wide limits. Example the agents contain about 10 to 90 percent by weight of active ingredient substance, about 90 to 10 weight percent liquid or solid carrier fabrics and possibly up to 20% by weight of surfaces active substances.

The funds can be distributed in the usual way to Example with water as a carrier in spray liquor quantities of about 100 up to 1000 liters / ha. An application of funds in the so-called low Volume and ultra-low-volume processes are just as possible as theirs Application in the form of so-called microgranules.  

These preparations can be prepared in a manner known per se and manner, for example by grinding or mixing methods leads. If desired, preparations of the individual com components are only mixed shortly before they are used, such as it, for example, in the so-called tank mix process in practice is carried out.  

For the preparation of the various preparations, the following components are used:

• A) Spray powder:
  20 percent by weight of active ingredient,
  35% by weight of bleaching earth,
  8 percent by weight calcium salt of lignin sulfonic acid,
  2 percent by weight sodium salt of N-methyl-N-oleyl-taurine,
  35 weight percent silica;
• B) Paste:
  45 percent by weight of active ingredient,
  5% by weight sodium aluminum silicate,
  15 percent by weight of cetyl polyglycol ether with 8 moles of ethylene oxide,
  2% by weight spindle oil,
  10% by weight polyethylene glycol,
  23 weight percent water;
• C) Emulsion concentrate:
  20 percent by weight of active ingredient,
  75 percent by weight isophorone,
  5 percent by weight of a mixture based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of liginsulfonic acid.

The following examples illustrate the preparation of the Invention according connections:

example 1 5-amino-4-cyano-1- (1-methyl-5-trifluoromethyl-3-pyrazolyl) pyrazole

0.85 g (4.72 mmol) 3-hydrazino-1-methyl-5-trifluoromethylpyrazole and 0.59 g (4.72 mmol) of ethoxymethylene malononitrile in 10 ml of etha nol are 10 hours at room temperature and 2 hours at 50 ° C. touched. After adding 50 ml of ethyl acetate with saturated Na trium hydrogen carbonate solution, washed over sodium sulfate dries and evaporates. The crude product is by column chromatography graph on silica gel (hexane / ethyl acetate) cleaned.

Yield: 0.48 g (39.7% of theory).
Mp: 165-167 ° C.

Preparation of the starting compounds 1. 3-amino-1-methyl-5-trifluoromethylpyrazole (I) and 5-amino-1- methyl-3-trifluoromethylpyrazole (II)

To a solution of 38.0 g (0.3 mol) of 4,4,4-trifluoro-3-oxobutyro nitrile in 150 ml ethanol at room temperature 13.8 g (0.3 mol) Dropped methylhydrazine. The reaction mixture is 3 hours heated to reflux, then volatile parts removed in vacuo and the oily residue over silica gel (Ethyl acetate) filtered. To separate the isomers, the crude pro  product by column chromatography on aluminum oxide (hexane / vinegar ester) cleaned.

Yield:
3.2 g (6.5% of theory) of I; Mp: 41 ° C,
11.5 g (23% of theory) of II; Mp .: 91 ° C

2. 3-hydrazino-1-methyl-5-trifluoromethylpyrazole

0.52 g (7.44 mmol) of sodium nitrite in 2 ml are added to a solution of 1.0 g (6.06 mmol) of 3-amino-1-methyl-5-trifluoromethylpyrazole in 15 ml of 6N hydrochloric acid at 5 ° C Water slowly added dropwise. The mixture is stirred for 1.5 hours at the same temperature. Then 3.35 g (14.85 mmol) of tin chloride (SnCl ₂ × 2 H ₂ O) in 3 ml of concentrated hydrochloric acid are added dropwise. The mixture is allowed to come to room temperature, stirred for 2 hours and made alkaline with 8N sodium hydroxide solution while cooling with ice. The residue is extracted with methylene chloride, dried over sodium sulfate and concentrated. 0.85 g of 3-hydrazino-1-methyl-5-trifluoromethylpyrazole are obtained, which are reacted further without further purification.

Example 2 5-amino-1- (4-chloro-1-methyl-5-trifluoromethyl-3-pyrazolyl) -4-cy anopyrazole

1.4 g (6.5 mmol) of 4-chloro-3-hydrazino-1-methyl-5-trifluoromethylpy razole and 0.81 g (6.5 mmol) of ethoxymethylene malononitrile in 20 ml  Ethanol will be at room temperature for 10 hours and at 2 hours 50 ° C stirred. After adding 100 ml of ethyl acetate, it is saturated with ter sodium bicarbonate solution washed over sodium sulfate dried and concentrated. The crude product is by column chromatography Topography on silica gel (methylene chloride) cleaned.

Yield: 0.38 g (20% of theory).
Mp: 183 ° C.

Production of raw materials 4-chloro-3-hydrazino-1-methyl-5-trifluoromethylpyrazole

2.0 g (12.1 mmol) 3-amino-1-methyl-5-trifluoromethylpyrazole in 20 ml Acetonitrile is mixed with 1.8 g (13.3 mmol) of sulfuryl chloride sets and stirred for 2 hours at room temperature. The reaction mi is in an aqueous saturated sodium bicarbonate solution solution, extracted with ethyl acetate, over sodium sulfate dries and evaporates. 2.24 g of 3-amino-4-chloro-1-methyl 5-trifluoromethylpyrazole obtained without further purification 4-chloro-3-hydrazino-1-methyl-5-trifluoromethylpyrazole as under 2. (Example 1) are implemented.

Yield: 1.4 g.

The following compounds are used in an analogous manner produced:

The following examples explain the possible applications of the compounds according to the invention:

Example of use A

The plant species listed were in the greenhouse before Accumulation with the listed connection in one application rate treated of 0.03 kg of active ingredient / ha. The connection became the purpose as an emulsion with 500 liters of water / ha evenly above sprayed the plants. Here shows two weeks after treatment tion, the compound of the invention has a high crop selectivity in cotton (GOSHI) and corn (ZEAMX) at marked effect against weeds. The comparative showed not the same selectivity.

In the following table mean:

0 = no damage,
1 = 1-24% damage,
2 = 25-74% damage,
3 = 75- 89% damage,
4 = 90-100% damage,
GOSHI = Gossypium hirsutum,
ZEAMX = Zea mays,
IPOSS = Ipomoea purpurea,
MATCH = Matricaria chamomilla,
POLSS = Polygonum sp.,
SOLSS = Solanum sp.,
VERPE = Veronica persica,
VIOSS = Viola sp.

Example of use B

In the greenhouse, the plant species listed after Accumulation with the listed compounds in one application rate treated with 0.3 kg of active ingredient / ha. The connections were too this purpose as an emulsion with 500 liters of water / ha evenly sprayed over the plants. The compounds of the invention show an effect against this 2 weeks after treatment Weed.

In the following table mean:

0 = no damage,
1 = 1-24% damage,
2 = 25-74% damage,
3 = 75- 89% damage,
4 = 90-100% damage,
ABUTH = Abutilon theophrasti,
SEBEX = Sesbania exaltata,
SOLSS = Solanum sp.

Example of use C

The compounds listed in the table were in the greenhouse applied with the application rates also mentioned. For this the active ingredients were pipetted onto the water surface.

ORYSA (Oryza sativa), CYPDI (Cyperus diformis) and MOOVA (Monochoria vaginalis) in the pre-emergence and in the 1-3 leaf stage used.

In the following table mean:

0 = no damage,
1 = slight damage,
2 = moderate damage,
3 = severe damage,
4 = totally destroyed.

As the results of the table show, the invention is Compounds highly effective against CYPDI and MOOVA (important Rice weeds) and at the same time selectively to water rice.

Claims (5)

1. Substituted pyrazolylpyrazoles of the general formula I in the
R1 methyl,
R ^{2 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkoxy, mono- or poly-substituted by fluorine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylthio or C ₁ -C ₄ alkoxy,
R ^{3 is} hydrogen or chlorine,
R ^{4 is} hydrogen or C ₁ -C ₄ alkyl,
R ^{5 is} hydrogen, nitro, cyano or the group -COOR ⁶ or -CONR ⁷ R ⁸ ,
R ^{6 is} hydrogen or C ₁ -C ₆ alkyl,
R ⁷ and R ^{8 are} hydrogen or C ₁ -C ₆ alkyl or
R ⁷ and R ⁸ together with the adjacent nitrogen atom form a piperidino group. 2. Substituted pyrazolylpyrazoles according to Claim 1 of the general formula I in which
R ^{1 is} methyl,
R ^{2 is} methyl, trifluoromethyl, methoxy, difluoromethoxy,
R ^{3 is} hydrogen or chlorine,
R ^{4 is} hydrogen or methyl,
R ⁵ nitro, cyano or the group -COOR ⁶ and
R ^{6 is} methyl or ethyl
mean. 3. Compounds of the general formula II in which R ¹ , R ² and R ^{3 have} the meanings given in the general formula I, with the exception of the compounds in which R ^{1 is} methyl or butyl and R ^{2 is} methyl when R ^{3 is} hydrogen, as intermediates for the preparation of compounds of general formula I. 4. A process for the preparation of compounds of general formula I, characterized in that

• A) a compound of general formula II in which R ¹ , R ² and R ^{3 have} the meanings given under the general formula I, with compounds of the general formula III in which R ⁴ and R ^{5 have} the meanings given under the general formula I and Y represents C _1-6 alkoxy group, hydroxy or halogen, or
  if R ^{5 is} hydrogen
• B) a compound of the general formula II with 2-haloacrylonitriles of the formula (IIIa), or with 2,3-dihalopropionitriles of the formula (IIIb), in which Hal stands for halogen.

5. Agents with herbicidal activity, characterized by a Content of at least one compound according to claims 1 and 2, in a mixture with conventional carriers and / or auxiliaries.