WO1998003506A1

WO1998003506A1 - Substituted pyrazolyl-pyrazole derivatives, process for their preparation and their use as agents with a herbicidal effect

Info

Publication number: WO1998003506A1
Application number: PCT/EP1997/003570
Authority: WO
Inventors: Helga Franke; Uwe Hartfiel; Michael Granzer; Eberhard Richter; Jürgen Bohner
Original assignee: Hoechst Schering Agrevo Gmbh
Priority date: 1996-07-18
Filing date: 1997-07-07
Publication date: 1998-01-29
Also published as: DE19630555A1; CA2261125A1; ZA976329B; TW355124B; EP0915873A1; KR20000067879A; CN1225635A; TR199900065T2; JP2000515142A; ID17533A; PL331287A1; BR9710494A; AU4009497A

Abstract

The invention concerns novel substituted pyrazole derivatives of general formula (I) in which R1 - R6 have the meanings given in the description. The invention also concerns a process for their preparation and their use as agents with a herbicidal effect.

Description

description

Substituted pyrazolyl-pyrazole derivatives, process for their preparation and their use as agents with herbicidal activity

The invention relates to substituted pyrazolyl-pyrazole derivatives, their preparation and intermediates for their preparation and their use as agents with herbicidal activity

No. 5,405,829 discloses pyrazolyl-pyrazoles with an unsubstituted amino group as herbicidally active compounds

WO 94/03999 describes herbicidally active pyrazolyl-pyrazoles, inter alia with a substituted amino group

Substituted pyrazolyl-pyrazoles with herbicidal properties are also known from WO 96/09303

However, the herbicidal activity of the known compounds is frequently inadequate, or selectivity problems arise in main agricultural crops

The object of the present invention is to provide new substituted pyrazolyl-pyrazoles which do not have these disadvantages and which are superior in their biological properties to the compounds known hitherto

It has now been found that substituted pyrazolyl-pyrazoles of the general formula I

in the

»1 C _r C ₄ alkyl,

RC _r C ₄ alkyl, C _r C ₄ -Alkylthιo, C _r C ₄ -Alkylsulfιnyl, C _r C ₄ alkylsulfonyl, C _r C ₄ - alkoxy, mono- or polysubstituted by halogen-substituted C _r C alkyl, C _r C ₄ - alkylthio, C _r C ₄ alkylsulfonyl, C _r C ₄ alkylsulfonyl or C _r C ₄ alkoxy,

R ¹ and R ² together form the group - (CH ₂ ) _n -,

R ^{3 is} hydrogen or halogen,

R ^{4 is} hydrogen or C _r C ₄ alkyl,

R = hydrogen, nitro, cyano, -COOR ⁷ , the group

-C-NR ⁸ R ⁹ -CR 10

II

X X or

R ^{b is} hydrogen, C _r C ₆ alkyl, C ₃ -C ₇ cycloalkyl, C3-C ₇ cycloalkyl-C _r C ₄ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or more times by halogen, hydroxy, cyano, C _r C ₄ alkoxy, C _r C ₄ -Alkthιo, C _r C ₄ alkoxy-carbonyl, hydroxycarbonyl, C ₁ -C alkylcarbonyl substituted C ₁ -C ₆ alkyl, C ₂ - C ₆ - alkenyl, C ₃ -C ₆ alkynyl, one or more times interrupted by oxygen or sulfur C _r C ₈ alkyl, C ₃ -C ₇ cycloalkyl, C ₃ -C ₇ cycloalkyl-C _r C ₄ alkyl , where appropriate cycloalkyl can be substituted one or more times by methyl, phenyl, benzyl, one or more times by halogen, nitro, cyano, CC ₄ -alkoxy or halo-C ₁ -C ₄ -alkyl-substituted phenyl or benzyl R ⁷ , R ⁸ and R ⁹ independently of one another are hydrogen or C ₁ -C ₄ -alkyl, R ⁸ and R ⁹ together with the adjacent nitrogen atom form a morpholmo group, a Pipeπdmo group or a pyrrolidino group, R ^{10 is} hydrogen, C ₁ -C ₄ alkyl, mono- or polysubstituted by halogen

C _r C ₄ alkyl, X is oxygen or sulfur, n is 3, 4 or 5, have a better herbicidal activity than the known compounds

Preferred compounds of the formula I are those in which

R ^{1 is} methyl,

R ² difluoromethoxy

R ¹ and R ² together form the group - (CH ₂ ) ₄ -,

R ³ chlorine or bromine,

R ^{4 is} hydrogen

R ⁵ nitro or cyano

R ^{6 is} hydrogen, C _r C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, by cyano, C _r C ₄ -

Alkoxy, C ₁ -C ₄ alkoxycarbonyl substituted C ₁ -C ₆ alkyl

The term "alkyl" stands for a straight or branched chain of carbon atoms

The term "alkylene" stands for a straight-line or branched chain of carbon atoms which is interrupted one or more times by double bonds

The term "alkynyl" stands for a straight-line or branched chain of carbon atoms which is interrupted once or several times by triple bonds

The compounds of general formula I according to the invention can be prepared by A) a compound of general formula II

in which R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meanings given in the general formula I, reacted with a suitable formylation reagent to give compounds of the general formula Ia

in the R .1 ¹ , R ^, R, R and R have the meanings given in the general formula I and R ^{6 is} hydrogen, or

B) a compound of the general formula Ia, in which R ¹ -R ^{5 have} the meanings given in the general formula I, with a suitable alkylating agent of the general formula Mb

R ⁶ -Z (llb),

in which R ^{6 has} the meanings given in the general formula I and Z represents a leaving group, or in the presence of a base C) a compound of the general formula

in which R - R have the meanings given in general formula I, reacted with a suitable formylating reagent, or

D) a compound of the general formula IV

in which R ¹ -R ^{3 have} the meanings given in the general formula I, reacted with a suitable formylation reagent and then nitrated, or

E) if R ^{2 is} C ₁ -C ₄ -alkylsulfinyl, C ₁ -C -alkylsulfonyl, one or more halogen-substituted CC ₄ -alkylsulfinyl or C _r C ₄ -alkylsuifonyl, a compound of the general formula IIa

in which R ^1, R ^3, R ⁴ and R ⁵ have the meaning indicated in formula I and R ¹¹ is C _r C ₄ alkyl or mono- or polysubstituted by halogen-substituted C _r C alkyl, is reacted with an oxidizing agent

For example, hydrogen peroxide, perbenzoic acids, sodium pirene iodate or potassium permanganate can be used as the oxidizing agent

For example, acetic acid formic anhydride or formic acid can be used as the formylating agent

For example, concentrated nitric acid or mixtures of fuming nitric acid with concentrated sulfuric acid can be used as the nitrating agent

The reactions are expediently carried out in such a way that the compounds are reacted at temperatures between -30 and 150 ° C.

Bases which can be used are, for example, alkali and alkaline earth metal hydroxides, alkali and alkaline earth metal carbonates and hydrogen carbonates, alcoholates, alkali metal hydrides, tertiary aliphatic and aromatic amines, such as tetrahydromamine and pyπdin, and heterocyclic bases

Escape groups are, for example, bromine, chlorine or iodine

The reaction in process variants A) and B), according to be carried out with or without solvent, whereby such Losungs- or diluents, if necessary, are used, which are inert to the respective reactants Examples of such solvents or Ver ^d are ünnungsmittel aliphatic, alicyclic and aromatic hydrocarbons, such as, for example, hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, ethers, such as, for example, diethyl ether, 1,4-dioxane and tetrahydrofuran, nitπle, such as, for example, acetonitrile, amides, such as, for example, dimethylformamide, dimethylacetamide or N. -Methylpyrrolidone, or sulfoxides, such as dimethyl sulfoxide The compounds of general formulas II and III used as starting material are known. Their preparation is described in EP 542388 and WO 9408999

The compounds of the general formula IIa used as starting material can be prepared by compound of the general formulas V or VI

in which R ¹ , R ² , R ^{3 have} the meaning given in the general formula I and m denotes 1 or 2, according to methods known per se, as described, for example, in JP 621 58 260, from compounds of the general formula VII or VIII produces

The compounds of general formulas VII and VIII, in which R ¹ , R ^{2 have} the meanings given in general formula I and R ^{3 is} halogen and m is 1 or 2, can be prepared by using compounds of general formula VII or VIII, in which R ^{3 represents} hydrogen, is reacted with a halogenating agent.

The compounds of general formula VII, in which R ¹ , R ² , R ^{3 have} the meaning given in general formula I and m is 1 or 2, can be prepared by reacting compounds of general formula VIII with an oxidizing agent The compounds of the general formula VIII, in which R ¹ and R ^{2 have} the meanings given in the general formula I and R ^{3 is} hydrogen, can be prepared by either a compound of the formula IX

with a hydrazine of formula X

R ¹ NHNH ₂ (X),

where R ^{1 has} the meaning given in general formula I, optionally in the presence of a solvent, first to give a compound of general formula XI

CN

in which R ^{1 has} the meaning given in the general formula I, and then reacted with a compound of the general formula XII

R ² Y (XII) in which R ^{2 has} the meaning given in the general formula I and Y represents a leaving group, for example chlorine or bromine, and the compound of the general formula XIII thus obtained is reacted

CN

(XIII)

according to methods known in nature (see, for example, Zeitschrift für Chemie 420, (1968) saponified and decarboxylated, or a compound of the general formula XIV

R2 _S CN

\ - / (XIV)

R ² S ^/

in which R ^{2 has} the meaning given in general formula I, with a hydrazine of formula X, optionally in the presence of a solvent, such as water, to give a compound of general formula XIII

The starting materials required for the preparation of these intermediates are known or can be prepared analogously to processes known per se

The preparation can be carried out with or without solvents, the solvents mentioned above being used if necessary

For example, hydrogen peroxide, perbenzoic acids, sodium pπodate or potassium permanganate can be used as the oxidizing agent

Examples of halogenating agents that can be used are sulfuryl chloride, sodium hypochlorite, N-chlorosuccinimide, N-bromosuccinimide, bromine or chlorine

As bases, for example, alkali and alkaline earth hydroxides, sodium methoxide, alkali hydrates, alkali and alkaline earth carbonate, tertiary aliphatic and aromatic amines, such as tetramethylamine and pyridine, and heterocyclic bases can be used. The reactions are carried out at a temperature between -30 and 150 ° C. carried out

The compounds according to the invention are worked up in the customary manner. Purification is carried out by 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, ethers such as diethyl ether or tetrahydrofuran, alcohols such as methanol or Ethanol, ketones such as acetone or butanone, amides such as dimethylformamide or sulfoxides such as dimethyl sulfoxide.

The compounds according to the invention have a good herbicidal action on broad-leaved weeds and grasses. A selective use is possible in different cultures, e.g. in rapeseed, beets, soybeans, cotton, rice, corn, barley, wheat and other types of goats. Individual compounds are also suitable as selective herbicides in beets, cotton, soybeans, corn and cereals. The compounds for weed control in permanent crops, such as e.g. can be used in forestry, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants.

The compounds of the invention can e.g. in the following

Plant genera are used.

Dicotyledon weeds of the genera such as Sinapsis, Lepidium, Galium, Stellaria,

Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senecio,

Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomea, Polygonum, Sesbania,

Ambrosia, Cirsium, Sochus.Solanum, Lamium, Veronica, Abutilon, Datura, viola,

Galeopsis, papaver, centaurea and chrysanthemum;

Monocot weeds of the genera such as Avena, Alopecurus, Echinochloa, Setaria,

Panicum, Digitaha, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Elymus,

Sagittaria, Monochoria, Fimbristylis, Eleocharis, Ischaemum and Apera.

Depending on the type of application, the application rates fluctuate between 0.001 and 5 kg / ha in the pre- and post-emergence.

The intensity and speed of action can be promoted, for example, by additives which increase the effectiveness, such as organic solvents, Wetting agents and oils can be achieved. Such additives may therefore allow the active ingredient dosage to be reduced

The active compounds according to the invention or mixtures thereof are expedient in the form of preparations such as powders, sprinkling agents, granules, solutions, emulsions or suspensions with the addition of liquid and / or solid carriers or diluents and, if appropriate, adhesives, wetting agents, emulsifiers and / or dispersants applied

Suitable liquid carriers are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethylsuloxide, dimethylformamide, mineral oil fractions and vegetable oils

Minerals such as bentonite, silica gel, talc, kaolin, attapulgite, limestone and vegetable products are suitable as solid carriers. For example, flours

Examples of surface-active substances include calcium lignin sulfonate, polyethylene alkylphenyl ether, naphthane sulfonic acids and their salts, phenol sulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates and substituted benzenesulfonic acids and their salts

The proportion of the active substance (s) in the various preparations can vary within wide limits. For example, the agents contain about 10 to 90% by weight of active ingredient, about 90 to 10% by weight of liquid or solid carriers and optionally up to 20% by weight. surfactants

The agents can be applied in a customary manner, for example using water as a carrier in spray boiling quantities of about 100 to 1000 liters / ha. The agents can be used in the so-called low-volume and ultra-low-volume method, as can their application in the form of so-called microgranules

These preparations can be prepared in a manner known per se, For example, by grinding or mixing processes. If desired, preparations of the individual components can also be mixed only shortly before they are used, as is carried out in practice in the so-called tank mixing process

The following examples describe the preparation of the compounds according to the invention

Example 1 2

I ^ S-Chlo .S ^ J-tetrahydropyrazolo-tl .S-aj-pyπdin ^ -y -δ-formylamino ^ - pyrazolcarbonsaurenitπl

147 g (1.44 mol) of acetic anhydride were added dropwise to 76.32 g (1.77 mol) of formic acid with stirring at 5-8 ° C. in the course of 15 minutes. The mixture was then heated to 60 ° C. for 2 hours. After cooling, this solution was dissolved in a suspension of 116.5 g (0.44 mol) of 5-amino (3-chloro-4,5,6,7-tetrahydropyrazolo- [1,5-a] -pyridium-2-yl) -4-pyrazolecarboxylic acid tril added dropwise in 850 ml of acetonitrile. The mixture was stirred for 20 hours at room temperature and for 4 hours at 60 ° C. The reaction mixture was concentrated, the residue was added to an ice-cold solution of 290 g (2.1 mol) of potassium carbonate in 3 l of water with stirring for one hour stirred, the solid filtered off and washed twice with 2 l of water each time. The solid was dried at 50 ° C. (200 mbar) and then re-installed from methanol

Yield 80.6 g (62.5% of theory) mp 186 ° C.

Example 1 17

1 - (3-Chloro-4,5,6,7-tetrahydropyrazolo- [1,5-a] -pyrιdιn-2-yl) -5- (N-formyl-N-propargylamιno) -4-pyrazolecarboxylic acid πππl

A suspension of 66.8 g (0.23 mol) 1 - (3-chloro-4,5,6,7-tetrahydropyrazolo- [1,5 a] -pyπdιn-2-yl) -5-formylamιno-4-pyrazolcarbonsaurenιtπl, 37.3 g (0.27 mol) of potassium carbonate and a spatula tip of potassium iodide in 500 ml of dimethylformamide were stirred for 30 minutes at a bath temperature of 80 ° C. Then 32.12 g (0.27 mol, 30.07 ml) of 3-bromo-1-propιπ (80% solution in toluene) were added dropwise and the mixture was stirred for 3 hours. The reaction mixture was poured into water, extracted with ethyl acetate and dried over sodium sulfate and concentrated The residue was first re-installed from dnsopropyl ether and then from methyl tert-butyl ether

Yield 47.8 g (63.2% of theory) mp 116-117 ^β C

The following compounds are prepared in an analogous manner, the preparation of the compounds marked with ^* ) having already been described above

The abbreviations used here mean

C = cyclo

Et = ethyl

Me = methyl

Ph = phenyl

Table 1:

General formula of Table 1

Table 2

General formula of Table 2

Table 3

General formula of Table 3

Table 4

General formula of Table 4

Table 5

General formula of Table 5

Table 6

General formula of Table 6

The following application example explains the invention:

Application example

In the greenhouse, the compounds listed in the table were applied by pipetting to a water surface of approximately 170 cm ² , the test plants being used both in the pre-emergence and in the 1-3-leaf statium.

After 2 weeks it was found that the compounds according to the invention were very effective against important rice weeds and did not cause any damage to the rice plants.

Claims

claims

Substituted pyrazolyl-pyrazoles of the general formula I

in the

R ¹ C _r C ₄ alkyl,

R ² C _r C ₄ alkyl, C _r C ₄ alkylthio, C _r C ₄ alkylsulfinyl, C _r C4 alkylsulfonyl, C ₁ -C ₄ alkoxy, one or more halogen-substituted CC ₄ alkyl, C _r C ₄ alkylthio, C _r C ₄ alkylsulfinyl, C _r C ₄ alkylsulfonyl or C _r C ₄ alkoxy,

R ¹ and R ² together form the group - (CH ₂ ) _n -,

R ^{3 is} hydrogen or halogen,

R ^{4 is} hydrogen or C _r C ₄ alkyl,

R ^{5 is} hydrogen, nitro, cyano, -COOR ⁷ , the group

-C-NR ⁸ R ⁹ -Cl, 10

II II

X or x

Hydrogen, C _r C ₆ alkyl, C ₃ -C ₇ cycloalkyl, C ₃ -C ₇ cycloalkyl-C _r C4 alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, one or more times by halogen, hydroxy, cyano, C _r -C 4 -alkoxy, C ₁ -C ₄ -Alkylt ^'nio, C _r C ₄ alkoxycarbonyl, hydroxycarbonyl, C _r C4 alkylcarbonyl substituted C _r C ₆ alkyl, C ₂ -C ₆ -Alkenyl, C ₃ -C ₆ -alkynyl, one or more CC ₈ -alkyl interrupted by oxygen or sulfur, C ₃ -C ₇ -cycloalkyl, C ₃ -C ₇ -cycloalkyl-C _r C ₄ -alkyl, optionally cycloalkyl one or can be substituted several times by methyl, phenyl, benzyl, one or more times by halogen, nitro, cyano, C ₁ -C ₄ alkoxy or halo-

C _r C ₄ alkyl-substituted phenyl or benzyl R ⁷ , R ⁸ and R ⁹ independently of one another form hydrogen or C ₁ -C alkyl, R ⁸ and R ⁹ together with the adjacent nitrogen atom form a morpholino group, a piperidino group or a pyrrolidino group, R ¹⁰ is hydrogen, C _r C ₄ alkyl, mono- or polysubstituted by halogen, C, -C ₄ alkyl, X is oxygen or sulfur, m 3, 4 or 5.

2. Compounds of the formula I in which R ^{1 is} methyl,

R ² difluoromethoxy or trifluoromethyl,

R ¹ and R ² together form the group - (CH ₂ ) ₄ -,

R ³ chlorine or bromine,

R ^{4 is} hydrogen,

R ⁵ nitro or cyano,

R ^{6 is} hydrogen, C _r C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or through

Cyano, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkoxycarbonyl substituted C _r C ₆ -

Mean alkyl.

3. agents with herbicidal activity, characterized by a content of at least one compound according to claims 1 and 2,

4. Agents with herbicidal activity according to claim 3, in a mixture with carriers and / or auxiliaries.

5. Use of compounds according to claims 1 and 2 for controlling monocotyledonous and dicotyledonous weed species in main agricultural crops.