DE2618421A1 - DIPHENYLPYRAZOLIUM SALTS - Google Patents

Description

PFENNING - MAAS - SEILER MEINIG - LEMKE - Mockery

8000 MÖNCHEN 40 SCHLEISSHEIMERSTR 299

25 653

American Cyanamid Company , Wayne, New Jersey, V.St.A.

Diphenylpyrazolium salts

The invention is concerned with the control of undesirable plant species and fungi by acting on the foliage of these unwanted plants or soil containing unwanted plants on the seeds of a herbicidally effective amount of a phenylpyrazolium salt of formula I.

(D

-ra

the substituents R ₁ and R _{0 are} each C ₁ -C ₄ -alkYl,

\ £ * I fr

is C ₂ -C ₄ -alkyl, C ^ -Cj -cycloalkyl, phenyl or benzyl,

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₁₅ allyl, propargyl, carbethoxy

is methyl or benzyl,

for C ₃ -C ₇ -CyClOaIlCyI, C ₂ -C ₄ -alkyl or phenyl,

is an anion with a charge of 1, 2 or 3 and

stands for 1, 2 or 3.

The invention also relates to new diphenylpyrazolium salts of formula I.

(D

.χ- ™,

in

is C ₁ -C ₅ -AlCyI, allyl, propargyl, benzyl or carbethoxymethyl,

an anion with a charge of 1, 2 or 3, preferably 1, and

is an integer of 1.2 or 3.

Certain 1,2-dialkyl-3,5-diphenylpyrazolium salts and one thereon Directed method for post-emergence control of certain undesirable Plant species are known from NL-OS 72 17 015. In Bull. Soc. Chim. Fr. 1121 (1970) also mentions 1,2,4-triethyl-3,5-diphenylpyrazolium iodide described. However, no indications or information are given about what this is for

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Lets use connection. Preparations are known from US Pat. No. 3,818,096 quaternary salts of 1,2-di-lower alkylarylpyrazolium compounds and a method for lowering blood sugar levels using these compounds. It however, no information is given anywhere that any 4-benzyl, 4-propargyl or 4-carbethoxymethyl-1,2-dialkyl-3,5-disubstituted-pyrazolium salt is present Can be used as a pre- or post-emergence herbicide.

It has now been found that the diphenylpyrazolium salts of the formula I mentioned at the outset are highly effective post-emergence herbicides for blood finger millet and wind oats as well as broad-leaved weeds such as white goose foot, wild mustard, field foxtail, ragweed, Native American mallow and some grasses are. You are in extremely highly selective in the presence of the crops wheat and rice. The 4-alkyl compounds also have a very surprising effect as pre-emergence herbicides and are suitable for combating pre-emergence of blood fingergrass and wind oats as well as broad-leaved weeds of the kind specified above.

Of the 4-alkyl derivatives, the 3,5-diphenyl-1,2,4-trimethylpyrazolium salts stand out due to a particularly pronounced effect as a post-emergence herbicide for blood finger millet and wind oats in the presence of wheat and rice.

The compounds according to the invention are also suitable for combating of fungi that attack many living plants. They are particularly effective in combating powdery meltau, especially with cereal grains such as barley or wheat, as well as climbing plants such as cucumbers, grapes or pumpkins, and in fruit and nut trees, such as apple trees, pear trees or pecano trees. They can also be used to combat of mushrooms, which are the cause of rice brandy and apple scab.

The compounds according to the invention are therefore generally pesticidal agents for combating a wide variety of harmful substances Influences on plants.

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The diphenylpyrazolium salts of the present invention can be easily prepared by adding an alkali salt a corresponding diketone is reacted with an alkylating, alkenylating, alkynylating or benzylating agent. The substituted diketone is then mixed with a C.-C.-alkylhydrazine implemented, whereby the corresponding substituted pyrazole is obtained. The pyrazole produced in this way is then finally with the corresponding Cj-C alkylating agent implemented, whereby the desired pyrazolium salt is formed. The above reaction sequence can be carried out by the following reaction scheme explain:

Reaction scheme

Il

solvent

+ MY

O R ^ O

NO.

• Ν

• (II A)

+ / 'Solvent ^: medium

(II B)

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η ¹ J π

Rc-C-CH-C-R, 5 3

(V)

Solution K ρ ||

: middle . R-C-CH-C-R, + »5 3

Δ (III)

solvent

(I B)

In the above reaction scheme, M stands for an alkali metal, such as Sodium, potassium or lithium, Y means hydrogen, hydroxide or alkoxide, such as methoxide, ethoxide, propoxide or butoxide, and the substituents R- to R ^ as well as X and the index m have the meanings given above.

In general, the alkali salts of 1,3-diphenyl-1,3-propanedione and other corresponding diketones can be prepared by reacting an alkali hydride, preferably sodium hydride, with 1,2-diphenyl-1,3-propane or another diketone in the presence a solvent, such as diethyl ether, methyl ethyl ether or di-n-propyl ether, is reacted. The reaction is usually carried out at a relatively low temperature, namely from 0 to 20 ^° C., preferably from 5 to 15 ^° C. The salt obtained in this way is then reacted with an alkylating agent. For this purpose, suitable alkylating agents are, for example, C.-C _g alkyl halides, allyl halides, Propargy! Halides, benzyl halides or Carbäthoxymethylhalogenide thereof, preferably each of the iodides, bromides or chlorides.

The alkylation is usually carried out at an elevated temperature, generally between about 50 and 150 ^° C., preferably 50 and 100 ^° C., in the presence of an anhydrous solvent such as dry dialkyl ether, acetone, methyl isobutyl ketone, cyclohexanone or dimethylformamide (DMF). In general, about 2 to 3 moles of alkylating agent per mole of alkali ketone salt are sufficient to terminate the reaction.

The substituted 1,3-diphenyl-1,3-propanedione formed in the above reaction or other appropriately substituted diketone is then reacted with a C1 -C4 alkylhydrazine.

After diketone and alkyl hydrazine in equimolar amounts with each other react, the molar ratio of the reactants is preferably kept at about 1: 1, but also with a small excess (up to about 10%) of one of the two reactants can be used.

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The ring formation reaction between the diketone and the alkylhydrazine is preferably carried out by bringing the reactants together in a solvent and then heating the reaction mixture to the reaction temperature. Temperatures of about 70 to 150 ^° C., preferably 80 to 120 ^° C., are suitable for this purpose. Examples of suitable solvents are aprotic solvents, such as xylene, toluene, benzene, pyridine or DMSO, or protic solvents, such as C ₁ -C ₄ -AlkOhOIe, preferably n- and iso-propanol. When using the latter solvents high ümwandlungsgeschwindigkeiten obtained at temperatures of 80 to 85 ⁰ C.

The 1-alkylpyrazole is quaternized by reacting it with at least an equimolar amount of an alkylating agent of the formula R ₂ ^X 'in which the substituents R and X have the meanings given above. Examples of suitable alkylating agents are methyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, methyl hydrogen sulfate, trimethyl phosphate or methyl p-toluenesulfonate.

This reaction is preferably carried out in the presence of a solvent, for example a Cj-C ₄ alcohol, a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, an aprotic solvent such as dimethyl sulfoxide or dimethylformamide, or preferably an aprotic solvent such as xylene, toluene, Benzene or 1,2-dichloroethane.

The quaternization is usually carried out at temperatures of 35 to 150 ⁰ C, preferably 50 to 125 C.

In general, the reactants go in the quaternization reaction in equimolar amounts. A molar ratio of 1: 1 is therefore preferably used. However, it can also a slight excess (up to 10%) of one of the reactants can be used. If the alkylating agent

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is volatile at the temperatures used, such as this for example applies to methyl chloride, then the reaction is preferably carried out in an autoclave. If you use also an asymmetrically substituted diketone, with the resulting pyrazole then having the 3 substituent from the 5 substituent is different, a mixture of isomers is obtained in the reaction described in the above reaction scheme. In this In this case, it is generally advisable to use the isomer mixture directly as a herbicide. However, there is a desire for separation of the isomers, this can be achieved by conventional separation techniques such as fractionated Crystallization.

In carrying out the ring closure and alkylation reactions noted above it may be useful to first form a salt which has a different anion than that which is then used according to the invention as a herbicide. In such cases, the required anion exchange can be achieved by treatment of the first set with an ion exchange resin. Suitable ion exchange resins for this purpose are for example strongly basic organic anion exchangers. An example of such an exchanger are quaternary ammonium salts. If you are dealing with a resin that has a different salt than the desired salt as an anion, then this salt is preferably treated beforehand with an aqueous solution of a salt of the desired anion. Is the exchange resin for example in the form of a quaternary ammonium chloride before and you want to produce a pyrazolium nitrate, then you treat the exchange resin initially with a aqueous sodium nitrate solution.

If necessary, the anion in the pyrazolium salt can also be used in other ways modify. For example, a pyrazolium chloride can be converted into the corresponding bromide or in a conventional manner Convert iodide by mixing the pyrazolium chloride with sodium bromide or sodium iodide in a solvent such as acetone, treated. A pyrazolium salt, such as the chloride,

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can be converted into the corresponding perchlorate, for example, by treating an aqueous solution of this salt with perchloric acid be convicted. In this way the less soluble perchlorate is obtained.

In order to apply the pyrazolium salts of the formula I according to the invention to the foliage of undesired plant species, these are used. Salts preferably formulated as post-emergence herbicide preparations / by combining a herbicidal adjuvant with a herbicid effective amount of the salt mixed. Adjuvants suitable for this purpose are the customary solid or liquid carriers, Diluents and formulation auxiliaries, especially surface-active agents. The salts can be used alone, in combination be formulated with each other or with other pesticides. The ones described below are particularly suitable water-miscible (or emulsifiable) concentrates. The invention also relates to such preparations as well as to methods directed towards their manufacture and use.

The application of the salts according to the invention in the form of dusts, dust concentrates, wettable powders or miscible with water (or emulsifiable) preparations are made with conventional application devices, preferably in amounts from 0.27 to 22.4 kg of active ingredient (cation) per hectare.

Dusts are generally produced by adding about 1 to 25 percent by weight of active ingredient with about 99 to 75 percent by weight a solid diluent such as kaolin, attapulgite, talc, pumice stone, diatomaceous earth, fuller's earth or wood flour. Dust concentrates are also produced in a similar manner, but with about 25 to 95 percent by weight of active ingredient about 75 to 5 percent by weight of diluent are ground.

The production of wettable powders is carried out in the same way as the production of dust concentrates, although this differs from this but additionally about 1 to 5 percent by weight of a surface-active agent such as polyoxyethylated vegetable oil or

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Alkylphenoxypolyoxyethylene ethanol, blended into the formulation will.

The production of water-miscible (or emulsifiable) concentrates is carried out by dissolving 15 to 70% active ingredient in 85 to 30% of a water-miscible solvent, such as water or another water-miscible solvent, like 2-methoxyethahol, methanol, propylene glycol, diethylene glycol, Diethylene glycol monoethyl ether, formamide or methylformamide. The material is used by adding a specified amount of a water-miscible (or emulsifiable) Concentrate to a spray tank and subsequent application as such or in combination with a suitable diluent, such as a further amount of water or one of the polar solvents indicated above.

The mode of action of the product is in all of the above formulations, which are used as liquid sprays, quite surprisingly by adding a surface-active agent or one Mixture of surfactants improved. Conventional nonionic surfactants can be used for this purpose will.

Examples of nonionic surfactants are alkyl polyoxyethylene ethers, Polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monooleate, Alkylaryl polyglycol ethers, alkylphenyl ethoxylates, Trimethylnonyl polyethylene glycol ether, alkylphenol ethylene oxide condensates, Octylphenoxypolyäthoxyäthanole, Nonylphenylpolyäthyleneglycolether, condensates of Polyoxyäthylenes, Polyoxypropylenes, aliphatic polyethers, aliphatic Polyesters or alkylaryl polyoxyethylene glycols.

These surfactants are preferably added to the spray tank in an amount of 0.1 to 5 percent by volume, and this results in good wetting of the plant foliage with the spray solution.

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The concentrates that contain surfactants will be preferably in the form of aqueous sprays from about 29 percent by weight of the respective salt, about 26 to 50 percent by weight Water and the selected surfactant as the remainder (26 to 44 percent by weight}. Examples of Surface-active agents for the production of such concentrates are octylphenol-ethylene oxide condensates, an ethanol solution an alkylphenol ethoxylate, a polyglycol ether condensate of ethylene oxide and an alkylphenol and an alkylaryl polyglycol ether. Two typical formulations consist of (1) 28.6% of the pyrazolium salt according to the invention, 22.0% of one of the above surfactants and 49.4% water or (2) from 28.6% of a pyrazolium salt according to the invention, 46.7% of one of the surface-active agents specified above and 24.7% Water.

For wind oat control it is preferred to mix about 4.68 liters of the above surfactant-containing agent Concentrate (1) with 187 liters of water and spray this diluted aqueous preparation then on one hectare of the area to be treated. The above spray solution thus contains about 0.5 percent by weight surfactant. The formulation (2) is preferably used in a similar manner, but differently However, 4.68 liters of this formulation are mixed with 374 liters of water and this diluted solution is then added one hectare of an area to be treated is sprayed.

Of course, the formulations can also be varied in such a way that dilute spray solutions with a content contains from about 0.1 to 5.0 weight percent surfactant and an effective amount of the pyrazolium salt. With Water-miscible concentrates according to the invention are, as already mentioned, prepared by adding 15 to 7O% of a Pyrazolium salt of the formula (I) in 85 to 3O% of one with water miscible polar solvent dissolves. Surprisingly, these preparations can still be effective in their effectiveness

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improve if you also use a surfactant Means shifted. Nonionic surfactants, especially those with a hydrophile to lipophile ratio (HLB) from 11 to 16, preferred. The attempt to investigate this conventional classification for a surfactant is, for example, in Emulsion Theory and Practice described by Paul Becher, Rheinholt Publishing Corporation, 2nd Edition (1965), pp. 232 ff., And he is also as No. 162 in the America Chemical Society Monograph Series.

Preferably, water is used as a solvent together with one of the pyrazolium salts given above by the formula (I) as an active ingredient.

These preparations are effective when applied in an amount that results in 0.27 to 22.4 kg of active ingredient (cation) per hectare. Order quantities from about 0.56 to 11.2 kg of active ingredient per hectare is preferred.

The invention is further illustrated by the following examples. All parts and percentages contained therein are based on weight, unless otherwise stated.

Example 1 2-Sodium-1,3-diphenyl-1,3-propanedione

Dibenzoylmethane (112.3 g, 0.5 mol) is dissolved in anhydrous diethyl ether (2 liters). The solution is stirred vigorously and sodium hydride (21.0 g, 0.5 mol) is then added in portions, the temperature of the mixture being kept at 7 to 12 ^° C. After the addition has ended, the reaction mixture is stirred for a further 3 hours. Further anhydrous ether is then added, the solid obtained is filtered off and slurried

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Solid again in anhydrous ether, filtered off again and the material obtained is dried, whereby one 109.0 g (89%) sodium salt of 1,3-diphenyl-1,3-propanedione receives.

Example 2 1,3-Diphenyl-2-pentyl-1,3-propanedione

n-Pentyl bromide (22.6 g, 0.15 mol) is added to an anhydrous solution of 2-sodium-1,3-diphenyl-1,3-propanedione (15.7 g, 0.064 mol) in DMF (150 ml) given, whereupon the reaction mixture is ^{heated to 80 to 90 °} C. for 5 days. The reaction mixture is then cooled, poured into ice water, stirred for one hour and finally extracted with chloroform (3 × 75 ml). Evaporation of the chloroform layer gives an oil which, after crystallization from 95 percent ethanol, leads to 3.7 g (20%) of product. Mp. 68.5 to 69.5 ⁰ C.

Analysis for C ₂₀ H ₂₂ O ₂ :

calculated: C, 81.6O; H 7.53; found: C, 81.50; H 7.63.

Example 3 2-Benzyl-1,3-diphenyl-1,3-propanedione

Benzyl bromide (25.6 g, 0.15 mol) is added to a partial solution of 2-sodium-1,3-diphenyl-1,3-propanedione (15.7 g, 0.064 mol) given in dry acetone (200 ml). The reaction mixture is stirred for 39 hours at reflux temperature, then cooled and finally poured into ice water (600 ml). The suspension obtained is filtered, whereupon the collected solid is treated

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dries and recrystallized from 95 percent ethanol. This gives 14.6 g (75%) of product which melts at 102 ⁰ C to 103 ⁰ C.

Analysis for ^C 22 ^H 18 ° 2 ^:

Calculated: C 84.25; H 5.77; Found: C, 83.35; H 5.89.

example

Using the procedure described in Example 3 the following 1,3-diphenyl-1,3-propanediones substituted in position 2 manufactured:

C-CH-

^R 4 melting point ° G

⁴ 3

CH, 82-83

83-8 ^ 61-62 81-82 98-99 6 ^ -65

CH-C ^ CH -CH = CH CH ₂ O
(I.
-C-OC ₂ H ₅ CH. ,
5 ii. CH ₂ Π "

82-83 68.5-69.5

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Example 5 3,5-Diphenyl-4-ethyl-1-methylpyrazole

Methylhydrazine (2.86 g _f 0.06 mol) is added under stirring at a temperature of 80 ⁰ C to an isopropanol (100 ml) of 1,3-diphenyl-2-ethyl-1,3-propane dione (11.0 g , 0.044 mol). The reaction mixture is heated to reflux temperature for 3.5 hours and then stirred at room temperature overnight. The reaction mixture is then poured into ice water, the whole is stirred for 0.5 hour and the resulting mixture is then extracted with chloroform (3 × 50 ml). Evaporation of the organic layer gives an oil which, on cooling, crystallizes from hexane to give 6.47 g (56%) of product; M.p. 80 to 81 ° C.

Analysis for C ^ gH ^ N »:

calculated: C 82.40; H 6.92; N 10.68; found: C 82.35; H 7.09; N 10.75.

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Example 6

The following further pyrazoles are prepared according to the process described in Example 5:

R.

CIL

CH ₂ -CH = CH ₂ - 5 11

Il

CH ₂ -C-OC ₂ H ₅

"Til • rO ι
CH Melting point ° .C 115-116 7 ^ -75 oil Ι59-Ι6Ι 79.5-8.5 oil oil 110

Example 7 3,5-Diphenyl-1,2,4-trimethylpyrazolium methyl sulfate

Dimethyl sulfate (7.5 g, O, 06 mol) is added under stirring at a temperature of 80 ⁰ C to an anhydrous toluene solution (100 ml) of 1 _# 4-dimethyl-3,5-diphenylpyrazole (10 g, 0.04 mol ) given. The reaction mixture is ^{stirred for 3 hours at 100 0} C, cooled and then filtered, whereby a hydroscopic

6-0 9847/099

Solid obtained. The solid is dissolved in chloroform and the solution is gradually treated with ether. The first fraction precipitated here is extremely hygroscopic and melts at 94 to 96 ^° C. The precipitated second fraction is not hygroscopic / and it melts in the form of methyl sulfate
(72%).

sulfate at 103 to 105 ⁰ C. The total yield is 12.6 g

5.0 g of the above product are dissolved in water, the solution is filtered and the filtrate is treated with saturated sodium iodide solution. The resulting precipitate is filtered off at a temperature of 10 ^° C., air-dried and then redissolved in warm water. The aqueous solution is extracted first with ether and then with chloroform. The chloroform layer is evaporated and the remaining oil is treated with ether. In this manner, 2.8 g (54%) of iodide salt obtained the above Pyrazoliumverbindung in the form of a white solid melting at 196 to 196.5 ⁰ C.

In a similar manner, 3.0 g of pyrazoliammethyl sulfate are dissolved in Water, and the resulting solution is filtered and then treated with dilute perchloric acid. The resulting precipitate is filtered off, washed with water and dried, yielding 2.5 g (85%) of perchlorate of the above pyrazolium compound receives.

In a similar way, the following connections are made:

1,2-dimethyl-3,5-diphenyl-4-äthylpyrazoliummethylsulfat, mp. 115 to 118 ⁰ C,

1,2-dimethyl-3,5-diphenyl-n-propylpyrasoliumperchlorat 4, mp. 134 to 135, ⁰ C,

609847/0931

- ι? - 26th

1,2-Dimethy1-3,5-diphenyl-4-isopropylpyrazoliumperchlorat, 149-150 ⁰ C mp.,

1,2-Dimethy1-3,5-diphenyl-4-n-pentylpyrazoliumperchlorat, mp. 51 to 52.5 ⁰ C,

1,2-dimethyl-3,5-diphenyl-4- (2-propynyl) pyrazoliumhydrogen · sulfate, 145 to 151 ⁰ C mp.,

4-allyl-1,2-dimethyl-3,5-diphenylpyrazolium hydrogen sulfate, Wax,

4- (carboxymethyl) -1, 2-diiuethyl-3,5-diphenylpyrazoliumjodidäthylester, mp. 148-149 ⁰ C.

4-Benzyl-1 ^, 2-dimethyl-3,5-diphenylpyrazolium hydrogen sulfate, m.p. 244 to 2β4 ⁰ C,

4-Benzyl-1,2-dimethyl-3PS-diphenylpyrasoliumperchlorat, 180 to 180.5 ⁰ C. mp.

example

3,5-dicyclohexyl -i _g 4-dimethylpyrazole

Methy! Hydraζin (1.0 g, 0.022 mol) is at a temperature of 60 to 70 ⁰ C with stirring to an isopropanol solution (200 ml) of 1 _{i of} 3-dicyclohexyl-2-methyl-1,3-propanedione (5, 0 g, 0.02 mol), which has a melting point of 36 to 37 C and has been prepared by the method described in Example 3. The reaction mixture is heated to reflux temperature for 4 hours, then cooled, treated with water (300 ml) and filtered. The pesticide obtained in this way is

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dissolved in anhydrous toluene, whereupon the solution is treated with methylhydraζin (1.0 g, 0.022 mol) and the reaction mixture is heated to 90 ° C. for 4 hours. Subsequently, further methylhydrazine (1.0 g, 0.022 mol) is added and the mixture is heated for a further 3 hours. The reaction mixture is then cooled. The solvent is then removed on a rotary evaporator and the solid obtained is recrystallized from hexane-benzene to give 1.7 g (32%) of the desired product. M.p. 120 ⁰ C to 122 ⁰ C.

Analysis for C ₁₇ H ₃₈ N ₂ :

calculated: C 78.40; H 10.84; N 10.76; Found: C, 78.38; H 10.91; N 10.76.

Example 9

' 3,5-Dicyelohexyl-i ^^ - trimethylpyrazolium methyl sulfate

Dimethyl sulfate (1.26 g, 0.01 mol) is added under constant stirring at a temperature of ⁰ SO C to an anhydrous toluene solution (50 ml) of 3,5-Dicyclohexyi-1,4-dimethylpyrazole (1.7 g _f 0 , 0064 mol). The reaction mixture is then stirred? Heated to reflux temperature for 6 hours. The reaction mixture is then cooled, ether (75 ml) is added and the mixture is stirred for 3 hours. The solid obtained is filtered off and dried, which generally leads to 1.3 g of the desired product. Mp. 176 ⁰ C to 177 ⁰ C.

Analysis for C ₁₉ H ₃₄ ^ ₂ Q ₄ S:

Calculated: C, 53.04; H 8.87; M 7.25; S 8.30; jafuncea: C, 59.52; H 9 ^ 54; K 7.21? SS _f 04.

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Example 10

The effect of the compounds according to the invention as pre-emergence herbicides is shown on the basis of the following studies. For this purpose, preparations are made from a 50/50 mixture Acetone and water (volume / volume) and such an amount of the respective active ingredient that is used in the following Table I gives the amount of active ingredient per hectare, if the mixtures obtained are sprayed onto pots which have been planted with seeds or offshoots of the specified plant species.

The pots are set up the day before the Herbicid treatment by filling each plastic pot with 100 ml of soil, then there are seeds for purple bindweed and wind oats, and the whole thing is finally covered with 50 ml (1 to 1.37 cm) of soil. Seeds of the other 8 types of plants listed below are mixed separately with soil, and each is then given 50 ml of the mixture of soil and seeds in the individual pots. The pots then become light to level the soil dammed, whereupon the earth is moistened with water before treatment with herbicide. This pre-moistening ensures that the subsequently applied herbicide solution is evenly distributed over the surface of the pot and provides protection the weed seeds before acetone. Each of the 10 types of weed is contained in a separate pot. The individual pots will be then before treatment with the active ingredient in 25.4 χ 30.4 cm large boxes placed.

In connection with this, the planted pots are treated with 5 ml test solution and then place it on appropriate tables. The pots are watered as needed after treatment and leave a total of 3 weeks in the greenhouse, after which the results obtained are determined, which are in the Table I below are summarized.

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Used as a pre-emergence herbicide to determine the effect

Plant species Scientific name Usual name abbreviation Chenopodium album White goosefoot LA Brassica kaber Wild mustard MU Amaranthus retroflexus Black foxtail PI Ambrosia artemisiifolia Ambrosia herb RW Ipomoca purpurea Purple bindweed MG Echinochloa crusgalli Chicken millet BA Digitaria sanguinalis Blood finger millet CR Setaria viridis Green millet FO Avena fatua Wind oats WHERE Abutilon theophrasti Indian mallow VL Triticum vulgar wheat WH Oryza sativa rice RI

The evaluation of the test results is carried out according to the following assessment system:

Appraisal system

Percentage difference in growth versus control

0 - no effect 0

1 - possible effect 1-10

2 - weak effect 11-25

3 - medium effect 26-40

5 - clear damage 41-60

6 - herbicidal effect 61-75

7 - good herbicidal effect 76-90

8 - almost complete death 91-99

9 - complete death 100

4 - abnormal growth, namely definite physiological malformation, with the overall effect with the above rating system but gives a value less than 5.

Based on a visual determination of the stand. Size, strength Chlorosis, growth and gas appearance of the individual Plants.

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Table I. Effectiveness of pyrazolium salts substituted in position 4 as a pre-emergence herbicide link

Treatment amount

kg / ha LA MU PI RW MG BA CR PO WO VL

3,5 ~ Diphenyl-1,2,4-trimethylpyrazolium methyl sulfate

3,5 ™ diphenyl-1,2,4-trimethylpyj; a52o 1 ium j odid

9999047248

9 9

0 3 6 0 7

3,5-diphenyl-1,2,4-trimethylpyrazolium perchlorate

9 9

0 8 9 0 4

1,2-dimethyl-3,5-diphenyl-4-ethylpyrazolium methyl sulfate hydrogen sulfate

2490005002

1,2-dimethyl-3,5-diphenyl-4-njropylpyrazolium perchlorate

1,2-dimethyl-3,5-diphenyl-4-isopropylpyrazolium perchlorate

7494478706

808043771

Table I.

(Continuation)

Effectiveness of pyrazolium salts substituted in position 4 as a pre-emergence herbicide

Verb i

Treatment amount

kg / ha LA MU PI RW MG BA CR FO WO VL

1,2-D j methyl-3,5-diphenyl-4-npentiylpyrazolium perchlorate

3,5-nicyclohexyl-1,2,4-trimethylpyrazolium methyl sulfate

2050005500

400089540

Example 11

The effect of the compounds according to the invention as post-emergence herbicides is shown on the basis of the following investigation. For this purpose, various monocot and dicot plants with the respective compounds to be investigated are used treated, which are dispersed in a mixture of water and acetone. For these examinations one leaves Grow plant seedlings in prick boxes for about 2 weeks. The compounds to be examined are in 50 to 50 mixtures dispersed from acetone and water (volume / volume) containing 0.5%

(R)
Tween ^v 20, namely a surfactant based on polyoxyethylene (20) sorbitan monolaurate from Atlas Chemical Industries. The amount of active ingredient is in each case

chosen so that after application of the preparations on

2 plants with one at a pressure of 2.8 kg per cm

operated spray nozzle for a predetermined time the amount of active ingredient given in the following Table II per ha results. After spraying, the plants are placed on greenhouse tables and tended there in the usual way. 2 weeks After the treatment, the plant seedlings are examined with the exception of the wind oat, which is treated for 5 weeks and evaluated according to the rating system described in Example 10.

The used for the investigation of this effect as a post-emergence herbicide The plant species used are the same as those used in Example 10 to determine the effect as pre-emergence herbicides have been used. The results obtained in these experiments are shown in Table II below.

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Tables Effectiveness of pyrazolium salts substituted in position 4 as post-emergence herbicide link

Treatment amount kg / ha

LA MU PI RW MG BA CR FO WO VL WH

RI

05 O CD OO

O CO CO

3,5-diphenyl-1,2,4-trimethylpyrazolium methyl sulfate

3,5-diphenyl-1,2,4-trimethylpyrazolium iodide

3,5-diphenyl-1,2,4-trimethylpyrazolium perchlorate

1,2-dimethyl-3,5-diphenyl-4-ethylpyrazolium methyl sulfate hydrogen sulfate

11.2
4.48 1.12 0.56

11.2
4.48 1.12 0.56

11.2
4.48 1.12 0.56

11.2
4.48 1.12 0.56

9 9 9 9 9 1 5 O 9 9 9 8th 9 2 9 1 9 9 9 6th 9 7th 5 2 9 9 9 9 9 9 9 9

2 2 O 1 9 8th 6th 7th 2 1 5 O 8th 8th 6th 5 O 1 3 O 9 7th 5 5 O 1 1 O 9 7th 2 2 2 3 8th 7th 8th 8th 1 1 O 9 9 6th 5 O O O O 9 3 5 5 O O O O 9 3 O 2 3 5 9 3 7th O 1 5 O 3 9 7th 5 O 1 2 O 3 9 5 2 O 1 1 O 2 9 3 9 7th 1 8th 9 9 O 1 9 3 5 6th 6th 9 O 9 1 5 6th 1 6th O O 1 O 3 1 O 6th

- 24 -

Table II

(Continuation)

Effectiveness of pyrazolium salts substituted in position 4 as post-emergence herbicide

CD O CD

O CO CO

link

1,2-Dimethyl 1-3,5-diphenyl-4-n-propylpyrazolium perchlorate

4-benzyl-1,2-dimethyl-3,5-diphenylpyrazoliura hydrogen sulfate

4-benzyl-1,2-dimethyl-3,5-diphenylpyrazolium perchlorate

1,2-dimethyl-3,5-diphenyl-4-isopropylpyrazolium perchlorate

1,2-dimethyl-3,5-diphenyl-4-n-pentylpyrazolium perchlorate

Treatment LA MU PI lot 9 9 9 kg / ha 9 9 11.2 9 9 4.48 9 9 1.12 9 9 9 0.56 9 9 11.2 9 9 4.48 9 8th 9 1.12 9 8th 11.2 9 9 9 4.48 9 9 11.2 9 9 4.48 9 9 9 1.12 9 9 11.2 9 9 4.48 1.12

RW MG BA CR PO WO VL WH RI

8th 5 5 6th 5 7th O m O CTf 6th O ui 3 O 3 O O V O O 5 3 O 2 O O 3 O O 1 6th 3 O 3 3 8th O 6th 5 O 1 6th O 5 O O O O O O 1 2 1 Γ 3 3 O O O ro O O 0 2 O O cn 9 3 2 1 5 8th O O CQ 5 O 5 3 1 3 O O ■ -e-> 5 O 5 3 O 1 - ISJ 7th 7th O 1 2 9 O O 9 O O 3 O 7th O O 1 O O 3 O 2 ■ 25

Table II

(Port setting)

Effectiveness of pyrazolium salts substituted in position 4 as post-emergence herbicide

CD O CO OO

O CO CO

link

1,2-dimethyl-3,5-diphenyl-4- (2-propynyl) pyrazolium hydrogen sulfate

4-allyl-1,2-dimethyl-3,5-diphenylpyrazolium hydrogen sulfate

Ethyl 4- (carboxymethyl) -1,2-dimethyl-3,5-diphenylpyrazolium iodide ester

3,5-dicyclohexyl-1,2,4-trimethylpyrazolium methyl sulfate

Treatment
lot
kg / ha LA MU PI RW MG BA CR FO WHERE VL WH RI •
σ * » 11.2
4.48
1.12 9 9
9
6th 9
9
9 5 7th
9
9 3
1
O 2
O
O 1
2
O 5
O
O 9
6th
1 O
O 3 \ 11.2
4.48
1.12 9 9
9
9 9
9
9 3 8th
9
8th 3
O
O 3
O
O 1
5
2 3
3
O 9
6th
5 1
O 6th
O cn 11.2
4.48 9 3
7th 8th
9 O 2
6th O
O O
O O
O 1
O 6th
3 O O GO
■ fr-
IS) 11.2
4.48
1.12 9 9
9
8th 9
9
8th 9 7th
9
9 9
8th
7th 3
8th
7th 8th
7th
5 8th
8th
8th 9
9
8th 1
O 3

Example 12

The fungicidal effectiveness of the erfindungsgeraektiven in position 4 substituted 1 ^ -dimethyl-S ^ -diphenylpyrazolium salts is determined on the basis of a number of pathogenic fungi, host plants and active substances through the following investigations. The pathogens, host plants, research methods used for this purpose and rating scales are below together with the test results obtained.

Pathogens;

Piricularia oryzae Cavara, namely the pathogen for rice brandy,

Venturia inaequalis (Cke.) / Namely the pathogen for apple scab,

Erysiphe cichoracearum DC, namely the cause of powdery Meltau on pumpkins,

Podosphaera leucotricha (E. & E.) Salm, namely the cause of powdery meltau in apples and pears,

Erysiphe graminis, f. Sp. tritici, namely the cause of powdery meltau in wheat,

Erysiphe graminis f. Sp. hordei, namely the cause of powdery melt dew in barley.

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Host plants

Rice (Oryza sativa) (Cv.Nato) Cucumber (Cucumis sativus) (Cv.Marketer)

Apple (Malus sylvestris) (saplings) Wheat (Triticum aestivura) (Cv.Bonanza)

Barley (Hordeura vulgar) (Cv.Larker)

The plants are allowed to grow individually in 5.08 cm square pieces of peat , which are then placed 1 week before treatment with active ingredient in 7.62 × 25.4 cm prick boxes made of compressed fibers. With the exception of rice, barley and wheat, only one sample of each plant species is used. A separate prick box is used for those plants that are to be examined for meltau. The entire investigation system looks like this:

Row 1 Row 2

Rice: rice brandy Apple: powdery meltau

Apple: apple scab, cucumber: powdery meltau

Wheat: powdery meltau. Barley: powdery meltau

There are corresponding spray solutions with a final concentration of 100 ppm or 500 ppm in each 50 ml of a 50 to 50 mixture of water and acetone. Acetone is added to dissolve the respective active ingredient, and the resulting solutions are then adjusted to their final volume with deionized water.

609847/0991

Two prick boxes provided with plants, namely each a box from row 1 and row 2 are filled with 50 ml at the same time for each treatment on a rotary table sprayed the solution to be examined. The spraying takes place using two fixed spray nozzles from Spraying System Company, which provide a vertically and horizontally solid cone-like spray pattern. Immediately after the treatment, all plants are put back into the Greenhouse given for the job to dry. After drying, the plants in row 1 and 2 are inoculated separately. The plants of row 1 are inoculated with conidia suspensions the respective pathogen using

a DeVilbiss paint spray gun operated at a pressure of 0.28-0.42 kg / cm and then immediately placed in a room with controlled temperature and humidity conditions (ambient temperature, relative humidity 95%). The plants of row 2 are dusted with the respective conidia for powdery meltau and then also placed in a room with controlled conditions (10 hours of light, 22 ^° C., 45% relative humidity), whereupon the development of the disease is awaited. The plants in row 1 are left in the room for 4 days, after which they are placed in the greenhouse and the disease is awaited.

Assessment system:

With regard to the severity of the disease infestation, all plants are classified according to one of 1 to 7 (no damage to death) rated as follows:

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- 3O -

Valuation numbers Description

1 clean 2 Trace of a disease 3 weak disease 4th medium disease 5 severe illness 6th very strong illness 7th Die

For the sake of clarity, the results obtained in the above investigations are in the following tables with the respective Valuation numbers given.

The individual test results are shown in Tables III and IV below. The listed rating numbers represent data from one or more individual experiments. If several examinations have been carried out, then represent the given evaluation numbers represent mean values which are given in the form of a single evaluation number. In each The table is also a rating number for the controls specified. The lower this rating number, the more effective it is the respective disease is of course combated. If there are letters in the following tables, this means the appearance of some phytotoxicity. The letter "S" means weak phytotoxicity, the letter "M" stands for medium phytotoxicity and the letters "SV" for very strong phytotoxicity. The ones given in the table Data refer to minimally effective concentrations at which the active ingredients have been tested.

609847/0991

Table III
■ Strength of the disease in plants that have been sprayed with the specified active ingredients (ppm) until they have dripped off

Link Untreated Controls

4-benzyl-1,2-dimethyl-3,5-diphenylpyrazolium hydrogen sulfate

ο 4-benzyl-1,2-dimethyl-3,5-diphenylpyrazolium perchlorate

oo 4- (carboxymethyl) -1,2-dimethyl-3,5-pyrazolium iodide ethyl ester

"^ ¹ 1,2-Dimethyl-3,5-diphenyl-4-ethylpyrazolium _o methyl sulfate / and hydrogen sulfate (1: I) J

tt> 1,2-dimethyl-3,5-diphenyl-4-n-pentylpyrazolium perchlorate

1,2-dimethyl-3,5-diphenyl-4-n-propylpyrazolium perchlorate 1,2-dimethyl-3,5-diphenyl-4-isopropylpyrazolium perchlorate 1,2-dimethyl-3,5-diphenyl-4- (2-propyl) pyrazolium hydrogen sulfate 3,5-diphenyl-1,2,4-trimethylpyrazolium methyl sulfate 3,5-diphenyl-1,2,4-trimethylpyrazolium perchlorate

Rice brandy 4.0 Apple scab 100 50_ 1 500 100 SO 500 6.0 4.8 5.0 4.0 SV ro
cn 5.0
4.0 4.5 5.0 5.0 4.0 5.0 3.0 SV 5.0

Table IV

Strength of the disease of plants which have been to runoff with the stated active ingredients (ppm) sprayed

link

500

Untreated controls

Cucumber 100

5.5

4.0 5.0

4-benzyl-1,2-dimethyl-3,5-diphenylpyrazolium hydrogen

sulfate 2.0

4 Benzyl 1,2-dimethyl-3,5-diphenylpyrazolium perchlorate 4.7

tf (carboxymethyl) -l, 2-dimethyl-3,5-diphenylpyrazolium iodide ethyl ester

ή, 2-dimethyl-3,5-diphenyl-4-ethylpyrazoliummethyl-

sulfate / and hydrogen sulfate (IrI _- ) / SV 3, OM

A _f 2-dimethyl-3,5-diphenyl-4-n-pentylpyrazolium perchlorate 5.0 5.0 '

1,2-dimethyl-3,5-diphenyl-4-n-propylpyrazolium perchlorate 4.7 1,2-dimethyl-3,5-diphenyl ~ 4-isopropylpyrazolium per-

chlorate 4.0

1,2-dimethyl-3,5-diphenyl-4- (2-propynyl) pyrazolium hydrogen sulfate 4.7

3,5-diphenyl-1,2,4-trimethylpyrazolium iodide 2

3,5-diphenyl-1,2,4-trimethylpyrazolium methyl sulfate SV 4.0 5 ", O 3,5-diphenyl-1,2,4-trimethylpyrazolium perchlorate

Powdery meltau at

wheat

Apples

500 100 50 5OO 100 50 6.5 5.9

2, O 3.3 4.3 4.7 5.5 5.5

2.0 2.0 2.8

1.5 2.0 3.0

1.3 3.0 3.3 5.0 5.5

2.5 2.0 3.0 4.5 5.0

2.0 2.0 2.8

2.3 4.0 5.3

2.0 4.0

1.5 4.0.

1.8 3.7

1.5 5.0

5.0 4.7 5.5

5.0 5M

4.0 4.3M 5.0

Barley 500 100

5.5

2.0

4.0 5.0

2.5 3.0

5.5 5.5 2.0

3.0 1.0 2.0 2.0

4.0 5.0

4.5 4.0 4.3

4.5 4.5

- 32 -

Claims (1)

Claims 1. / Diphenyl pyrazolium salts of the formula ? ^H 3 N-CH- * X -m is C ₂ -C ₅ -alkyl _f allyl, propargyl, benzyl or carbethoxymethyl, X is an anion with a charge of 1, 2 or 3 and m is an integer of 1, 2, or 3. 2. Diphenylpyrazolium salts according to claim 1, characterized indicated that these are the following compounds: 4-benzyl-1,2-dimethyl-3,5-diphenyIpyrazolium hydrogen sulfate, Ethyl 4- (carboxymethyl) -1,2-dimethyl-3,5-diphenylpyrazolium iodide ester. 609847/0991 1,2-dimethyl-3,5-diphenyl-4-ethylpyrazolium methyl sulfate (and hydrogen sulfate (1:! _) _ / » 1,2-dimethyl-3,5-diphenyl-4-n-pentylpyrazolium salt, 1,2-dimethyl-3,5-diphenyl-4-n-propylpyrazolium salt, 1, 2-dimethyl-3, S-diphenyl ^ -isopropylpyrazolium salt, 4-allyl-1,2-dimethyl-3,5-diphenylpyrazolium salt or 1,2-dimethyl-3,5-diphenyl-4- (2-propynyl) pyrazolium hydrogen sulfate. 3. Pesticides, especially fungicides, characterized by a content of a diphenylpyrazolium salt of the formula * X -m - m for Cj-Cc-alkyl, allyl, propargyl, benzyl or carbethoxymethyl, is an anion with a charge of 1, 2 or 3, and is an integer of 1, 2 or 3. as an active ingredient. 609847/0991 4. Means according to claim 3, characterized draws that it as an active ingredient 4-benzyl-1,2-dimethyl-3,5-diphenylpyrazolium hydrogen sulfate,
4-benzyl-1,2-dimethyl-3,5-diphenylpyrazolium salt, 1,2-dimethyl-3,5-diphenyl-4-ethylpyrazoliuramethyl sulfate / and hydrogen sulfate (1: 1j_ /, 1,2-dimethyl-3,5-diphenyl-4-n-pentylpyrazolium salt, 1,2-dimethyl-3,5-diphenyl-4-n-propylpyrazolium salt , 1,2-dimethyl-3,5-diphenyl-4- isopropylpyrazolium salt , 1,2-dimethyl-3,5-diphenyl-4- (2-propynyl) pyrazolium hydrogen sulfate or 4-alkyl-1,2-dimethyl-3,5-diphenylpyrazolium salt
contains. 5. Composition according to claim 3, characterized in that the cation of the active ingredient 3,5-diphenyl-1,2,4-trimethylpyrazolium and the anion is iodide, methyl sulfate or perchlorate. 6. Means according to claim 3, characterized dadu.rch that it is a liquid spray with an active ingredient content of 50 to 5600 ppm. € 09847/0 991 7. Pesticides, especially herbicides for Pre-emergence and post-emergence control of undesirable plant species, characterized by a content of a diphenylpyrazolium salt of the formula wherein the substituents
R. and R ₂ .LlJl N N ι i R ₁ R ₂ , X -in each denotes Cj-C.-alkyl, is C ₂ -C ₄ -alkyl, C ₃ -C ₇ -cycloalkyl, phenyl or benzyl, jj is allyl, propargyl, carbethoxymethyl or benzyl, represents C ₃ ~ C ₇ cycloalkyl, C ₂ -C ₄ alkyl or phenyl, is an anion with a charge of 1, 2 or 3 and stands for 1, 2 or 3, as an active ingredient. -6 09847/0991 8. Means according to claim 7, characterized draws that it as an active ingredient 1,2-dimethyl-3,5-diphenyl-4-ethylpyrazoliuntmethylsulfathydrogensulfat, 1,2-dimethyl-3, S-diphenyl ^ -n-propylpyrazolium perchlorate, 4-benzyl-t, 2-dimethyl-3,5-diphenylpyrazolium hydrogen sulfate, 4-benzyl-1,2-dimethyl-3,5-diphenylpyrazolium perchlorate , 1 , 2-dimethyl-3f 5-diphenyl-4-isopropylpyrazolium perchlorate _f 1,2-dimethyl-3,5-diphenyl-4-n-pentylpyrazolium perchlorate, 1,2-dimethyl-3, 5-diphenyl-4- (2-propynyl) pyrazoliumhydrogensulfat, 4-allyl-1,2-dimethyl-3,5-diphenylpyrazolium hydrogen sulfate, 4- (carboxymethyl) -1,2-dimethyl-3,5-diphenylpyrazolium iodide ethy ester or 3,5-dicyclohexyl-1, 2, 4-trimethylpyrazoliummethylsulfat contains. 9. Composition according to claim 7, characterized in that it is in an amount of 0.56 to 11.2 kg per hectare is applied. 1O. Agent according to Claim 7 _f, characterized in that it is used in an amount of 0.56 to 4.48 kg per ha. 609847/0991 1T. Means after. Claim 7, characterized in that it has 3,5-diphenyl-1,2,4-trimethylpyrazolium methyl sulfate, iodide or perchlorate as the active ingredient
contains. 12. Means according to claim 11, characterized in that that it is in an amount of 0.56 to 11.2 kg per hectare is applied. 13. Means according to claim 11, characterized that it is used in an amount of 0.56 to 4.48 kg per hectare. t X 60.9847 / 0991