CA2078163A1

CA2078163A1 - Diarylpyrazolinones

Info

Publication number: CA2078163A1
Application number: CA 2078163
Authority: CA
Inventors: Peter Mueller; Hilmar Wolf; Klaus Luerssen; Hans-Joachim Santel; Robert R. Schmidt
Original assignee: Individual
Current assignee: Bayer AG
Priority date: 1991-09-17
Filing date: 1992-09-14
Publication date: 1993-03-18
Also published as: EP0532996A1; BR9203623A; DE4130833A1; JPH05213892A

Abstract

Diarylpyrazolinones A b s t r a c t The invention relates to new diarylpyrazolinones of the general formula (I) (I) in which n, Q, X, R1 and R2 have the meanings given in the description, to two processes for their preparation, to various new intermediates, and to their use as herbicides.
Le A 28 654

Description

2078~ ~

The invention relates to new diarylpyrazolinones, to two processes for their preparation, to various new inter-mediates, and to their use as herbicides.

It has already been disclosed that certain pyrazolin-5-one derivatives such as, for example, 5-(3-methoxy-phenyl)-4-methylaminomethylene-2-phenyl-2,4-dihydro-3H-pyrazol-3-one have herbicidal properties (cf. EP-A
274,642). However, the herbicidal action of the pyrazo-lin-5-one derivatives which are known to date is not always entirely satisfactory.

There have now been found new diarylpyrazolinones of the general formula (I) F CH- ~ ¦ ,R1 2 ~ -N~ 2 (I) N`N o ~X) in which n represents the numbers O, 1, 2 or 3, Q represents oxygen or sulphur, Le A 28 654 - 1 -~78~
R1 represents hydrogen or C1-Cs-alkyl, R2 represents hydrogen, hydroxyl, amino, or a radical from the series comprising C1-C6-alkyl, C2-C6-alXen-yl, C2-C6-alkinyl, Cl-C6-hydroxyalkyl, C,-C4-alkoxy-Cl-C4-alkyl, C3-C6-cycloalkyl-C,-C4-alkyl, phenyl-C,-C4-alkyl,C,-C6-alkoxy, C3-C6-alkenyloxy, phenyl-C,-C2-alkoxy, C1-C6-alkylamino, C,-C4-alkylcarbonylamino or di-(C,-C4-alkyl)-amino, each of which is option-ally substituted by halogen, and 10 X represents hydrogen, halogen, or a radical from the series comprising C,~C4-alkyl or C,-C4-alkoxy, each of which i~ optionally substituted by halogen, the following compounds - disclosed in DE-OS (German Published Specification) 3,941,240, p. 44, 45, 95 and 96 - being excepted by disclaimer:

2-phenyl-, 2-(4-fluorophenyl)- and 2-(4-chloro-phenyl)-5-(2-difluoromethylthiophenyl)-4-(N-hydroxy-methylaminomethylene)-2,4-dihydro-3H-pyrazol-3-one, 2-phenyl-, 2-(4-fluorophenyl)- and 2-~4-chloro-phenyl)-5-(3-difluoromethylthiophenyl)-4-(N-hydroxy-methylaminomethylene)-2,4-dihydro-3H-pyrazol-3-one, 2-phenyl-, 2-(4-flusrophenyl)- and 2-(4-chloro-phenyl)-5-(2-difluoromethylthiophenyl)-4-dimethyl-: aminomethylene-2,4-dihydro-3H-pyrazoI-3-one as well as 2-phenyl-, 2-(4-fluorophenyl)- and 2-(4-chloro-phenyl)-5-(3-difluoromethylthiophenyl)-4-dLmethyl-aminomethylene-2,4-dihydro-3H-pyrazol-3-one.

Le A 28 654 - 2 -2~73~6~
If appropriate, the compounds of the formula (I) can exist in various stereoisomeric or tautomeric form~. The invention relates to the pure isomers as well as to the mixtures of these isomers. For simplicity's sake, the following text will always refer to compounds of the formula (I), this being understood as meaning the pure isomers as well as the various mixtures of these isomers which are possible.

The new compounds of the general formula (I) are obtained when (a) in the event that, in formula (I), R1 and R2 repres-ent methyl and n, Q and X have the abovementioned meanings, pyrazolinones of the general formula (II) F2CH- ~ (II) N~N

(x)n~3 ; in which n, Q and X have the abovementioned meanings, Le A 28 654 - 3 -2~78~
are reacted with dimethylformamide acetals of the general formula (III) (CH3)2N-cH(OR)2 (III) in which S R represents Cl-C4-alkyl or benzyl, i~ appropriate in the presence of a diluent, or when (b) diarylpyrazolinones of the general formula (Ia) F2CH-~
-NtCH~)2 tIa) N~N ~

tx in which n, Q and X have the abovementioned meanings, are reac~ed with amines of the general formula (IV) ,Rl H-N~ 2 ~ IV ) Le A ?8 654 - 4 -2~7~

in which R1 and R2 have the abovementioned meanings, if appropriate in the presence of a diluent.

The diarylpyrazolinones of the general formula ~I) according to the invention are distinguished by a power-ful herbicidal activity.

Surpri~ingly, the new compounds of the general formula (I) show a considerably better herbicidal action than the previously known pyrazolin-5-one derivatives, which are comparable substances from the point of view of their structure and profile of action.

The invention preferably relates to compounds of the formula tI) in which n represen~s the numbers 0, 1 or 2, Q represents oxygen or sulphur, R1 represents hydrogen, methyl or ethyl, : ~ R2 represents hydrogen, hydroxyl, amino, or represents : a radical from the series comprising C1-Cs-alkyl, C3-Cs-alXenyl, C3-Cs-alkinyl, Cl-Cs-hydroxyalkyl, Cl-C2-alkoxy-Cl-C2-alkyl, Cl-C4-alkoxy or C3-C4-alkenyloxy, each of which is optionally substituted Le A 2B 654 - 5 -2 ~
by fluorine and/or chlorine;

or represents a radical from the series comprising C3-C6-cycloalkyl-Cl-C2-alkyl, phenyl-Cl-C2-alkyl, phenyl-Cl-C2-alkoxy, Cl-C4-alkylamino, Cl-C4-alkyl-carbonylamino or dimethylamino, each of which is optionally substituted by fluorine, chlorine and/or bromine, and X represents hydrogen, fluorine, chlorine, bromine or a radical from the series comprising methyl, ethyl, methoxy or ethoxy, each of which is optionally substituted by fluorine and/or chlorine, with the : exception of the compounds being excepted by dis-claimer.

In particular, the invention relates to compounds of the formula (I) in which n represents the numbers 0, 1 or 2, Q represents oxygen or sulphur, R1 represents hydrogen or methyl, R2 represents hydrogen, hydroxyl, amino, or represents a radical from the series comprising methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, each of which is optionally substituted by fluorine, or repxesents allyl, propargyl, Le A 28 654 - 6 -- 2~78~3 l-methyl-propargyl, 1,l-dimethylpropargyl, hydroxy-ethyl, hydroxypropyl, methoxyethyl, ethoxyethyl, cyclopropylmethyl, cyclohexylmethyl, cyclohexyl-ethyl, phenylmethyl, phenylethyl, methoxy, ethoxy, propoxy, allyloxy, benzyloxy, methylamino, dimethyl-amino, acetylamino, propionylamino, butyrylamino or isobutyrylamino, and X represents hydrogen, fluorine, chlorine or tri-fluoromethyl, with the exception of the compounds being excepted by disclaimer.

If, for example, 1-(4-fluoro-phenyl)-3-(3-difluoro-methoxyphenyl)-pyrazolin-S-one and dimethylformamide dimethyl acetal are used as starting substances, the course of ~he reaction in process (a) according to the invention can be outlined by the following equation:

CH3~ N CH~Ç)CU3)2 ~-N(CH3)j N~N~o N`N

: F F

Le A 28 654 - 7 -2~7~

If, for example, 1-(2-chlorophenyl)-3-(4-difluoromethyl-thiophenyl)-4-dimethylaminomethylene-pyrazolin-5-one and O-methyl-hydroxylamine are used as ~tarting su~stances, : the course of the reaction in process (b) according to the invention can be outlined by the following equation:

F2CHS~
~C-N ~ CH3 12 ~ H2NOCH3 N~N~ - HN t CH3 ) 2 [~C

F2CHS~
~C - NHOCH3 ~N~o ~Cl Formula (II) provides a general definition of the pyrazo-linones to be used as starting substances in process (a) : according to the inventicn for the preparation of com-~: 10 pounds of the formula (I).

In formula (II), n, Q and X preferably, or in particular, :: have those meanings which have already been mentioned : above in connection with the description of the compounds : o the formula (I) according to the invention as being preferred, or particularly preferred, for n, Q and X.

Le A 28 654 - 8 -2~7~

The pyrazolinones of the formula (II) were hitherto unknown from the l~terature and, being new substances, are also a subject of the present patent application.

The new pyrazolinones of the formula (II) are obtained when aroylacetates of the general formula (V) F2cH-Q
~ O-CH2-CO-OR (V) in which Q represents oxygen or sulphur and R represents Cl-C6-al~yl, preferably methyl or ethyl, are reacted with arylhydrazines of the general formula (VI) H2N-NH ~ (X)n (VI) in which n represents the numbers 0, 1, 2 or 3 and 5 X represents hydrogen, halogen, or a radical from the series comprising Cl-C4-alkyl or Cl-C~-alkoxy, each of which is optionally substituted by halogen, at temperatures between -20C and +80Cj if appropriate Le A 28 654 - 9 -2 ~
in the presence of a diluent such as, for example, ethanol, and if appxopriate in the presence of a reaction auxiliary such as, for example, sodium acetate, and the product is worked up by customary methods (cf. the Preparation Examples).

The arylhydrazines of the formula (VI) are known and/or can be prepared by processes known per se (cf. US Patent 4,411,839; DE-OS (German Published Specification) 1,927,924; Khim. Farm. Zh. 10 (1976), 27-31 - cited in Chem. Abstracts 86: 139926a).

The aroylacetates of the formula (V) were hitherto unknown from the literature and, being new substances, are also a subject of the present patent application.

The new aroylacetates of the formula (V) are obtained when corresponding aroylmalonic diesters of the general formula (VII) F2~H - a ,COOR
O-CH (VII) ~~-~ COOR

in which Q represents oxygen or sulphur and R represents Cl-C6-alkyl, preferably methyl or ethyl, are refluxed with water in the presence of a catalyst Le A 28 654 - 10 -2~7~
such as, for example, p-toluenesulphonic acid, and the product is then worked up by customary methods (cf. the Preparation Examples).

The aroylmalonic diesters of the formula (VII) were hitherto unknown from the literature and, being new substances, are also a sub~ect of the present patent application.

The new aroylmalonic diesters of the formula (VII) are obtained when aroyl halides of the general formula (VIII) ~ o-X (VIII) in which Q represents oxygen or sulphur and X represents halogen, in particular fluorine, chlorine : or bromine, are reacted with malonic diesters of the general foxmula (IX) ,COOR
H2C~.~ ( IX) COOR

in which Le A 28 654 ~7~
R represents Cl-C6-alkyl, preferably methyl or ethyl, at temperatures between -20C and +50C, in the presence of a diluen~ such as, for example, acetonitrile, in the presence of a reaction auxiliary such as, for example, magnesium chloride, and in the presence of an acid binder such as, for example, triethylamine, and the product is worked up by customary methods (cf. the Preparation Examples).

The aroyl halides of the formula (VIII) are known and/or can be prepared by processes known per se (cf. US Patent Specification 4,832,879; JP 59,181,259 - cited in Chem.
Abstracts 102: 113480z; DE-OS (German Published Specifi-cation) 2,914,915; US Patent Specification 4,009,208; US
Patent Specification 3,960,945; US Patent Specification 3,895,036; Ukr. Khim. Zh. 47 (1981), 871-874 - cited in Chem. Abstracts 95: 186790x).

The malonic diesters of the formula (IX) are known chemicals for synthesis.

Formula (Ia) provides a general definition of the diaryl-pyrazolinones to be used as starting substances in process (b) according to the invention for the preparation of compounds of the formula (I).

In formula (Ia), n, Q and X preferably, or in particular, have those meanings which have already b~en mentioned above in connection with the description of the compound~

Le A 28 654 - 12 -of the formula (I~ according to the invention as being preferred, or particularly preferred, for n, Q and X.

The starting subætances of the formula (Ia) are a sub~et of the diarylpyrazolinones of the formula (I) according to the invention; they can be prepared by process (a) according to the invention.

Formula (IV) provides a general definition of the amines furthermore to be used as starting substances in process (b) according to the inven~ion.

In formula (IV), Rl and R2 preferably, or in particular, have those meanings which have already been mentioned above in connection with the de6cription of the compolnds of the formula (I) according to the invention as being preferred, or particularly preferred, for R1 and R2.

The starting substances of the formula (IV) are known chemicals for synthesis.

Processes (a) and (b) according to the invention for the preparation of the new diarylpyrazolinones of the formula (I) are preferably carried out using diluentsO Diluents which are suitable for this purpose are all inert organic solvents. These preferably include aliphatic and axomatic, optionally halogenated hydrocarbon~ such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chlorLdel chloroform, carbon Le A 28 654 - 13 -2~7~
tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether and di~utyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydro-furan and dioxane, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as, for example, acetonitrile and propio-nitrile, amides such as, for example, dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and hexa-methylphosphoric triamide.

When carrying out process (a) and ~b) according to the invention, the reaction temperatures can be varied within a substantial ran~e. In general, the process is carried out at temperatures between 0C and 100C, preferably at temperatures between 10C and 50C.

Processes (a) and (b) according to the invention are generally carried out under atmospheric pressure. How-ever, it is also possible to car~y out the process underincreased or reduced pressure.

For carrying out processes (a) and (b) according to the invention, the starting substances required in each case are generally employed in approxLmately equLmolar amounts. However, it i~ also possible to use one of the two components employed in each case in a larger excess.
In general, the reactions are carried out in a suitable Le A 28 654 - 14 -2~7~
diluent, and the reaction mix~ure is stirred for several hours at the temperature required in each case. Working-up i~ carried out in each case by customary methods (cf.
the Preparation Examples).

S The active compounds according to the invention can be used a~ defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according ~o the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants:

Dicotyledon weeds of the qenera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, ~anthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledon cultures of the ~enera: Goss~pium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Le A 28 654 - 15 -~7~
Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the qenera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the ~enera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Alli~m.

However, the use of the active compounds according to the invantion is in no way restricted to these genera, but also extends in the same manner to other plants.

The compounds are suitable, depending on the concentra-tion, for the total combating of weeds, for example onindustrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in peren-nial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plan~ations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture-land, and for the selective combating of weeds in annual cultures.

Le A 28 654 - 16 -~7~

The compounds of the formula (I) according to the inven-tion are particularly suitable for ~electiv~ly combating monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon cultures, both by the pre- and the post-emergence method.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concen-trates, natural and synthetic materials impregnated withactive compound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for : example by mixing the active compounds with extenders, : 15 that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsify-ing agents and/or dispersing agents and/or foam-forming agents.

In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene, or alkylnaph-thalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum frac-tions, mineral and vegetabl~ oils, alcohols, such as Le A 28 654 - 17 -2 ~ 6 ~
butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar sol-vents, such as dimethylformamide and dimethyl sulphoxide, as well as water.

As solid carriers there are suitable: for example ammon-ium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such Le A 28 654 - 18 -~ 36 as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.

It is possible to use colorants 6uch as inorganic pig-ments, for example iron oxide, titanium oxide and Prus-sian Blue, and organic dyestuffs, such as alizarin dyestuff 8, azo dyestuff 5 and metal phthalocyanine dye-stuffs, and trace nutrients such as salts of iron, manganese, bor~n, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between ; 0.5 and 90%.

~or combating weeds, the active compounds according to the invention, as such or in the form of their formula-tions, can also be u ed as mixtures with known herbi-cides, finished formulations or tank mixes being pos-sible.

Suitable herbicides for the mixtures are known herbicides such as anilides, such as, for example, diflufenican and propanil; arylcarboxylic acids such as, for example, dichlorpicolinic acid, dicamba and picloram; aryloxy-alkanoic acids such as, for example, 2,4 D, 2,4 DB, 2,4 DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy alkanoates such as, for ~xample, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones such as, for example, Le A 28 654 - 19 -~7~

chloridazon and norflurazon; carbamates such as, for example, chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides such as, for example, alachlor, acetochlor, butachlor, metazachlor, S metolachlor, pretilachlor and propachlor; dinitroanilines such as, for example, oryzalin, pendimethalin and tri-fluralin; diphenyl ethers such as, for example, acifluorfen, bifenox, fluoroglycofen, fomesafen, halo-safen, lactofen and oxyfluorfen; ureas such as, for example, chlortoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylamines such as, for example, alloxydim, clethodim, cycloxydim, sethoxydLm and tralkoxydim; imidazolinones such as, for example, imazethapyr, imazamethabenz, imazapyr and imazaquin;
nitriles such as, for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides such as, for example, mefenacet; sulphonylureas such as, for example, amido-sulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlor-sulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; thiocar-bamates such as, for example, butylate, cycloate, di-allate, EPTC, esprocarb, molina~e, prosulfocarb, thio-bencarb and tri-allate; triazines such as, for example, atrazin, cyanazin, simazin, simetryne, terbutryne and terbutylazin; triazinones such as, for example, hexa-zinone, metamitron and metribuzin; others such as, for example, aminotriazol, benfure~ate, bentazone, cin-methylin, clomazone, clopyralid, difen~oquatr dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, Le A 28 654 - 20 -~7~

isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird S repellants, plant nutrients and ayents which improve soil ~tructure, are also possible.

The active compounds can be used as ~uch, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-u~e solutions, suspensions, emulsions, powder~, pastes and granules.
They are used in the customary manner, for example by watering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied either before or after emergence of the plants.
They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a s~bstantial range. It depends essentially on the nature of the desired effect. In general, the amounts applied are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between S g and S kg per ha.

The preparation and use of the active compounds according to the in~ention can be seen from the following examples.

Le A 28 654 - 21 -2~7~

Preparation Exam~les:

Example 1 ; OCHF'2 ~C - N ( CH3 ) 2 ~ N~N~o I
F
(Process (a)) A mixture of 6.5 g (20 mmol) of 2-(4-fluorophenyl)-5-(3-difluoromethoxyphenyl~-4-dimethylaminomethylene-2,4-dihydro-3H-pyrazol-~-one, 2.7 g (22mmol) of dimethylform~ude dlmethyl acetal and 150 ml of toluene is stirred for 2 hours at 20C. It is : then concentrated under a water pump vacuum, the residue is triturated with petroleum ether, and the product which is obtained as crystals is isolated by filtration.

. 6.9 g (92% of theory) of 2-~4-fluorophenyl)-5-(3-~ difluoromethoxyphenyl)-4-dimethylaminomethylene-2,4-; dihydro-3H-pyrazol-3-one of melting point 103C are obtained.

;

Le A 28 654 - 22 -~ 3 Example 2 OCI~F2 H
-NHC~3 N`N~o (Process ~b)) A mixture of 2.8 g (7.5 mmol) of 2-(4-fluorophenyl)-5-(3-difluoromethoxyphenyl)-4 - methylaminomethylene-2,4-dihydro-3H-pyrazol-3-one, 50 ml of methanol and 3 ml of a 30% aqueou~ methylamine solution (10 mmol H2NCH3), is stirred for 3 hours at 20C. It is then concen~rated under a water pump vacuum, ~he residue is triturated with petroleum ether, and the product which has been obtained as crystals is isolated by filtration.

2.4 g t88.5% of theory) of 2-(4-fluorophenyl)-5-(3-difluoromethoxyphenyl)-4-methylaminomethylene-2,4-dihydro-3H-pyrazol-3--one of melting point 187C are obtained.

Other examples of compounds of the formula (I) which can be prepared analogously to Preparation Examples 1 and 2 and following the general description of the preparation processe~ according to the invention are those listed in Le A ?8_654 - 23 -~7g3 ~

Table 1 below.
F2CH_~ 7 Rl ~:C-N~ 2 ( I ) N~N~o ~X)n~

Le ~ 28 654 - 24 -Table 1: Examples of the compounds of tho formula (I) Ex. n (Posi- R1 R2 (Posi-Melting No. tion) tion)point (C) Q X
3 1(2-~S H CH3 (4-)F

4 2(2-~S CH3 CH3 (2,4-)F2122 0(3-)0 CH3 OH - 111 6 1(2-)S CH3 CH3 (4-)CF393 7 1~2-)S H CH3 (4-)CF3139 8 1(2-)S H NHCH3 (4-)F 125 9 1(2-)S H N(CH3)2 (4-)F 108 1(2-)S CH3 CH3 (3-)Cl104 11 0t2-)S H CH3 - 116 12 1(2-)S H NHCH3 (4-)CF3137 13 1(2-)S H N(CH3)2 (4-)CF3107 14 1(2-)S CH3 OH (4-)CF3118 2(2-)S H CH3 (2,4-)F275 16 0 (2-)S H NHCH3 17 0(2-)S H N(CH3)2 18 1(3-)0 H CH3 (2-)F 126 19 1(2-)S H CH3 (3-)C1138 1(2-)S H CH3 (4-)C1145 21 1(3-)0 CH3 OH (2-)F 78 22 2(2-)S CH3 OH (2,4-)F2141 Le A 28654 - 25 -Table 1 - Continuation Ex. n (Posi- Rl R2 (Posi-Melting No. tion) tion)point (C) 23 1 (2-)S H CH3 ~2-)F 127 24 1 (2-)S H NHCH3 (3-)Cl 88 0 (3-)O H CH3 - 137 26 1 (2-)S CH3 OH (3-)Cl 147 27 0 (3-)S H CH3 - 79 28 1 (3-)S CH3 CH3 t3-)C1 132 29 1 (3-)S CH3 CH3 (4-)CF3 121 1 (3-)S CH3 CH3 (3-)F 114 31 1 ~3-)S H N~CH3)2 ~4-)F
32 1 ~3-)S H CH3 ~4-)F 105 33 1 ~2-)S CH3 OH (2-)F
34 1 ~3-)0 CH3 OH (4-)F
1 (3-)S CH3 OH (3-)C1 105 36 1 ~3-)S CH3 OH (3-)F 58 37 1 (3-)S H CH3 (3-)Cl 97 38 1 (3-)S H CH3 ~3-)F 92 39 1 (2-)S H -C-C--CH (4-)F 99 40 1 (3-~S H CH3 (4-)CF3 127 Le A 28 654 - 26 -Table 1 - Continuation Ex. n (Posi- Rl R2 (Posi-Melting No. tion) tion)point (C) Q X

41 1 ~3-)S CH3 OH t4-~CF3 135 42 1 (3-)S H NHCH3 (3-)Cl 43 1 (2-~S H (R-)-CH~ (4-)F 49 44 1 (2-)S H -CH2C(CH3)3 (4-)F 105 1 (2-)S H -CH2 (4-)F 84 46 1 (2-)S H -CH2-C-CH ~4-)F 158 47 1 t2-)S H C4H9 (4-)F

48 1 (2-~S H (R)-CH ~ (4-)F 58 ,OH
49 1 (2-~S H -CH2-CH~ (4-)F 127 1 (2-~S H OCH3 (4-)F 46 51 1 (2-)S H -OCH2 ~ (4-)F

52 1 (2-)S H ~CH2CH20C2H5 (4-)F 61 53 1 (2-~S H -OCH ~ (4-)F

Le A 28 654 - 27 -Table 1 - Cantinuation ~ ~ 7 Ex. n (Posi- R1 R2 (Posi- Melting No. tion) tion) point (C) Q X
_ _ ~3 ~C~
54 1 (2-)S H -CH2-C - C-Cl (4-)F 113 1 (2-)S H -CH2CH20CH3(4-)F 81 56 1 ~2-)S H -CH~ (4-)F 45 57 1 (2-)S H -CHC3H7 (4-)F 62 58 1 (2-)S H -OCH2CH=CH2 (4-)F 48 59 1 (2-)S H H (4-)F
6Q 1 (2-)S H -C(CH3)3 (4-)F
61 1 (2-)S H -CH(CH3)2 (4-)F 99 62 1. (2-)S H CH2CH(CH~)2(4-)F
63 1 (2-)0 CH3 CH3 (4-)F 120 64 1 (2-)S H -CO-CH3 (4-)F
1 (2-)S H -CO-CH(CH3)2(4-)F 80 66 1 (2-)S H -CO-C2H5 (4-)F 96 67 1 (2-)O CH3 OH 14-)F 154 68 1 (2-)0 H CH3 (4-)F 193 69 o (3-)0 CH3 CH3 - 136 Le A 28 654 - 28 -2 ~ 7 .~
Table 1 - Continuation Ex. n (Posi- R1 R2 (Posi-Melting No. tion) tion)point (C) Q X
1(3-)0 CH~ OH t4-)F146 71 1(2-)S CH3 OH t2-)F124 72 O(3-)0 CH~ H - 137 73 1~2-)5 CH3 H (2-)F127 74 1(~-)O CH3 OH (2-)F78 1(3-)0 CH3 H (2-)F 126 Le A 28 654 - 29 -2 ~ 7 ~ - 6 3 Startina substances of the formula (IIl:

Example (II-1~

~H

To a solution of 4.06 g (25 mmol) of 4-fluorophenyl-hydrazine hydrochloride in 100 ml of ethanol there are ~ added 6.5 g (25 mmol) of ethyl t3-difluoromethoxy-- benzoyl)-acetate and 2.05 g (25 mmol) of sodium acetate, and the reaction mixture is stirred for 20 hours at 20C.
It is then concentrated under a water pump vacuum, the residue is stirred with petroleum ether, and the crystal-line product is isolated by filtration with suction, wa~hed with water and dried.

7.4 ~ (92~ of theory) of 2-(4-fluorophenyl)-5~(3-di-fluoromethoxyphenyl)-2,4-dihydro-3H-pyrazol-3-one of melting poiot 114C are obtained.

Le A 28 654 - 30 -Othex compounds of the formula (II) which can be prepa~d7 ~ J
analogously to Example tII-l) are those listed in Table 2 below.

F2CH- ~ H
N`NI ~o tx)n~

Table 2: Example of the compounds of the formula (II) Ex. n(Position) (Position) Nelting No. Q X point (~C) (II-2) 1 (2-)S (4-)F
(II-3) 1 (3-)S (4-)F 78 (II-4) 1 (2-)0 t4-)F
(II-5) 1 (2-)S (4-)C1 (II~6) 2 (2-)S (2,4-)F2 (II-7) S (2-)S (3-)C1 (II-8) 1 (3-)S t3-~C1 9) 1 t3-)S t4-)CF3 (II-10) 1 t2-)S (2-)F
(II-11) 1 (3-)0 t2-)F
(II-12~ 1 (3-)0 (4-~F
(II-13) 1 t3-)0 H

Le A 28 654 - 31 -2~7~
Starting substances of the formula (V!:

Example (V-l) ~CO- CH2 -COOC2H5 A mixture of 91.5 g (0.28 mol) of diethyl (3-difluoro-methoxybenzoyl)-malonate, 300 ml of water and 3 g of p-toluenesulphonic acid i~ refluxed for 8 hours. Ater cooling, the mixture is extracted with methylene chlor-ide, and the organic phase i5 ætirred with saturated sodium hydrogen carbonate solution, dried with sodium sulphate and fil~ered. ~he filtrate i3 concentrated under a water pump vacuum, and the residue is distilled under an oil pump vacuum.

21.2 g (30% of theory) of ethyl (3-difluoromethoxy-benzoyl)-acetate of boiling point 118C (at 0.01 torr) :~ 15 are obtained.

~ Startina substances of the formula ~YII~:
: ~ :
- Example (VII-l) ~ ,COOC H
: ~ O-C~ 2 5 ~ ~ COOC~H5 :
:~:

:: :
::
Le A 28 654 - 32 -2 ~ 7~
27.4 g (0.29 mol) of magnesium chloride are added in portions to 150 ml of acetonitrile, the lnternal ~emp~ra-ture being kept below 25C by external cooling with ice/
water. After the mixture has cooled to -10C, 46.1 g (0.29 mol) of diethyl malonate and 58.1 g (0.58 mol) of triethylamine are added dropwise in succession. After the mixture has been stirred at -10C for a further 30 minutes, 59.5 g (0.29 mol) of 3-difluoromethoxy-benzoyl chloride, dissolved in 120 ml of acetonitrile, are added dropwise, and the mixture is stirred for 12 hours at 20C. After 250 ml of 5N hydrochloric acid have been added, the mixture is extracted using methylene chloride, and the organic phase is dried using sodium sulphate and filtered. The solvent is carefully removed from the filtrate by distillation under a water pump vacuum.

92.4 g (97% of theory) of diethyl (3-(difluoromethoxy-benzoyl)-malonate as an oily residue of refractive index n24 : 1.4629 are obtained.

Use Examples:

In the Use Examples which follow, the compound shown below is used as comparison ~ubstance:

Le A 28 654 ~ 33 ~78~

l ~3 H
r 1l 1 ~ -NHCH~ tA) N~ IN~o 5-(3-~ethoxyphenyl)-4-methylaminomethylene-2-phenyl-2,4-: dihydro-3H-pyrazol-3-one : ~disclosed in EP-A 274,642~. -Example A

Post-emergence test ~: Solvent: 5 parts by weight of acetone ~: Emulsifier: 1 part by weight of alkylaryl polyglycol ether ~ 10 To produce a ~uitable preparation of active compound, l : part by weight of :active compound is mixed with the ~; stated amount of ~olvent, the stated amount of emulsifier i8 added and the concentrate is diluted with ~ater to the :~: desired concentration.
;
Tes'c pla~ts which have a~height of 5 - 15 cm ~re sprayed :

Le A 28 654 - 34 -~7~
with the preparation of the active compound in such a way a~ to apply the particular amounts of active compound desired per unit area. After three weeks, the degree of damage to the plants is rated in ~ damage in comparison to the development of the untreated control. The figures denote:

0% = no action (like untreated control) 100% = total destruction In this test, a powerful action against weeds is shown, for example, by the compounds of Preparation Examples 3, 5, 7, 8, 10, 11, 14, 15, 17, 19, 20, 26, 27, 32j 33, 36, 38, 40, 52, 55, 59 and 67, combined with good crop plant compatibility.

Example ~

Pre-emergence test .
Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol : 20 ether To produce a ~uitable preparation of active compound, 1 part by weight of active compound i~ mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate i5 diluted with water to the ;

Le A 28 654 - 35 -desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in ~ damage in comparison to the development of the untreated control. The figures denote:

0~ = no action (like untreated control) 100% = total destruction A clearly superior activity compared with the prior art is shown in this test, for example, by the compounds of the following Preparation Examples: 7 and 15.

Le A 28 654 - 36 -

Claims

1. A diarylpyrazolinone of the general formula (I) (I) wherein n represents the numbers 0, 1, 2 or 3, Q represents oxygen or sulphur, R1 represents hydrogen or C1-C4-alkyl, R2 represents hydrogen, hydroxyl, amino, or a radical from the series comprising C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C1-C6-hydroxyalkyl, C1-C4-alkoxy-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkyl, phenyl-C1-C4-alkyl, C1-C6-alkoxy, C3-C6-alkenyloxy, phenyl-C1-C2-alkoxy, C1-C6-alkyl-amino, C1-C4-alkylcarbonylamino or di-(C1-C4-alkyl)-amino, each of which is optionally substituted by halogen, and Le A 28 654 - 37 -X represents hydrogen, halogen, or a radical from the series comprising C1-C4alkyl or C1-C4-alko-xy, each of which is optionally substituted by halogen, with the exception of the compounds:

2-phenyl-, 2-(4-fluorophenyl)- and 2-(4-chloro-phenyl)-5-(2-difluoromethylthiophenyl)-4-(N-hydroxy-methylaminomethylene) 2,4-dihydro-3H-pyrazol-3-one, 2-phenyl-, 2-(4-fluorophenyl)-and 2-(4-chlorophenyl)-5-(3-difluoromethyl-thiophenyl)-4-(N-hydroxy-methylaminomethylene)-2,4-dihydro-3H-pyrazol-3-one, 2-phenyl-, 2-(4-fluorophenyl)- and 2-(4-chlorophenyl)-5-(2-difluoromethylthiophenyl)-4-dimethylamino-methylene-2,4-dihydro-3H-pyrazol-3-one as well as 2-phenyl-, 2-(4-fluorophenyl)- and 2-(4-chlorophenyl)-5-(3-difluoromethylthiophenyl)-4-dimethylæminomethylene-2,4-dihydro-3H-pyrazol-

3-one.

2. A diarylpyrazolinone of the general formula (I) according to Claim 1, wherein n represents the numbers 0, 1 or 2, Q represents oxygen or sulphur, R1 represents hydrogen, methyl or ethyl, R2 represents hydrogen, hydroxyl, amino, or Le A 28 654 - 38 -represents a radical from the series comprising C1-C5-alkyl, C3-C5-alkenyl, C3-C5-alkinyl, C1-C5-hydroxyalkyl, C1-C2-alkoxy-C1-C2-alkyl, C1-C4-alkoxy or C3-C4-alkenyloxy, each of which is optionally substituted by fluorine and/or chlorine, or represents a radical from the series com-prising C3-C6-cycloalkyl-C1-C2-alkyl, phenyl-C1-C2-alkyl, phenyl-C1-C2-alkoxy, C1-C4-alkylamino, C1-C4-alkylcarbonylamino or dimethylamino, each of which is optionally substituted by fluorine, chlorine and/or bromine, and X represents hydrogen, fluorine, chlorine, bro-mine or a radical from the series comprising methyl, ethyl, methoxy or ethoxy, each of which is optionally substituted by fluorine and/or chlorine, with the exception of the compounds:

2-phenyl-, 2-(4-fluorophenyl)- and 2-(4-chloro-phenyl)-5-(2-difluoromethylthiophenyl)-4-(N-hydroxy-methylaminomethylene)-2,4-dihydro-3H-pyrazol-3-one, 2-phenyl-, 2 (4-fluorophenyl)-and 2-(4-chlorophenyl)-5-(3-difluoromethyl-thiophenyl)-4-(N-hydroxy-methylaminomethylene)-2,4-dihydro-3H-pyrazol-3-one, 2-phenyl-, 2 (4-fluorophenyl)- and 2-(4-chlorophenyl)-5-(2-difluoromethylthiophenyl)-4-dimethylamino-methylene-2,4 dlhydro-3N-pyrazol-3-one as well Le A 28 654 - 39 -as 2-phenyl-, 2-(4-fluorophenyl)- and 2-(4-chlorophenyl)-5-(3-difluoromethylthiophenyl)-4-dimethylaminomethylene-2,4-dihydro-3H-pyrazol-3-one.

3. A diarylpyrazolinone of the general formula (I) according to Claim 1, wherein n represents the numbers 0, 1 or 2, Q represents oxygen or sulphur, R1 represents hydrogen or methyl, R2 represents hydrogen, hydroxyl, amino, or repre-sents a radical from the series comprising methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, each of which is optionally substituted by fluorine, or represents allyl, propargyl, 1-methyl-pro-pargyl, 1,1-dimethyl-propargyl, hydroxyethyl, hydroxypropyl, methoxyethyl, ethoxyethyl, cycloproplmethyl, cyclohexylmethyl, cyclo-hexylethyl, phenylmethyl, phenylethyl, methoxy, ethoxy, propoxy, allyloxy, benzyloxy, methyl-amino, dimethylamino, acetylamino, propionyl-amino, butyrylamino or isobutyrylamino, and X represents hydrogen, fluorine, chlorine or tri-fluoromethyl, with the exception of the com-pounds:

Le A 28 654 - 40 -2-phenyl-, 2-(4-fluorophenyl)- and 2-(4-chloro-phenyl)-5-(2-difluoromethylthiophenyl)-4-(N-hydroxy-methylaminomethylene)-2,4-dihydro-3H-pyrazol-3-one, 2-phenyl-, 2-(4-fluorophenyl)-and 2-(4-chlorophenyl)-5-(3-difluoromethyl-thiophenyl)-4-(N-hydroxy-methylaminomethylene)-2,4-dihydro-3H-pyrazol-3-one, 2-phenyl-, 2-(4-fluorophenyl)- and 2-(4-chlorophenyl)-5-(2-difluoromethylthiophenyl)-4-dimethylamino-methylene-2,4-dihydro-3H-pyrazol-3-one as well as 2-phenyl-, 2-(4-fluorophenyl)- and 2-(4-chlorophenyl)-5-(3-difluoromethylthiophenyl)-4-dimethylaminomethylene-2,4-dihydro-3H-pyrazol-3-one.

4. A compound according to claim 1, wherein such compound is 2-(4-fluorophenyl)-5-(2-difluorothiomethyl-phenyl)-4-methylaminomethylene-2,4-dihydro-3H-pyrazol-3-one of the formula Le A 28 654 - 41 -

5. A compound according to claim 1, wherein such compound is 2-phenyl-5-(3-difluoromethoxyphenyl)4-(N-methyl-N-hydroxyaminomethylene)-2,4-dihydro-3H-pyrazol-3-one of the formula

6. A compound according to claim 1, wherein such compound is 2-(2,4-difluorophenyl)-5-(2-difluorothiomethyl-phenyl)-4-methylaminomethylene-2,4-dihydro-3H-pyrazol-3-one of the formula

7. A compound according to claim 1, wherein such compound is 2-(4-fluorophenyl)-5-(2-difluoromethoxyphenyl)-4-(N-methyl-N-hydroxyaminomethylene)-2,4-dihydro-3H-pyrazol-3-one of the formula Le A 28 654 - 42 - .

8. A herbicidal composition comprising a herbicidally effective amount of a compound according to claim 1 and a diluent.

9. A method of combating unwanted vegetation which comprises applying to such vegetation or to a locus from which it is desire to exclude such vegetation a herbicidally effective amount of a compound according to claim 1.

10. The method according to claim 9 wherein such compound is 2-(4-fluorophenyl)-5-(2-difluorothiomethylphenyl)-4-methylaminomethylene-2,4-dihydro-3H-pyrazol-3-one, 2-phenyl-5-(3-dlflouoromethoxyphenyl)-4-(N-methyl-N-hydroxyaminomethylene)-2,4-dihydro-3H-pyrazol-3-one, 2-(2,4-difluorophenyl)-5-(2-difluorothiomethylphenyl)-4-methylaminomethylene-2,4-dihydro-3H-pyrazol-3-one, 2-(4-flouorophenyl)-5-(2-difluoromethoxyphenyl)-4-(N-methyl-N-hydroxyaminomethylene)-2,4-dihydro-3H-pyrazol-3-one.

11. A pyrazolinone of the general formula (II):

Le A 28 654 - 43 - (II) wherein n represents the numbers 0, 1, 2 or 3, Q represents oxygen or sulphur and X represents hydrogen, halogen, or a radical from the series comprising C1-C4-alkyl or C1-C4-alkoxy, each of which is optionally substituted by halogen.

12. An aroylacetate of the general formula (V) (V) wherein Q represents oxygen or sulphur and Le A 28 654 - 44 -R represents C1-C6-alkyl.

13. An aroylmalonic diester of the general formula (VII) (VII) wherein Q represents oxygen or sulphur and R represents C1-C6-alkyl.

Le A 28 654 _ 45 _