CA1078850A - Diphenylpyrazolium salts as herbicides and fungicides - Google Patents

Abstract

A B S T R A C T
A method for control of undesirable plant species and fungi by the application of an effective amount of a 1,2,4-trialkyl disubstituted pyrazolium salt having the formula:

Description

-~78~350 The present invention relates to a method for the control of undesirable plant species and fungi by applying to the ~
foliage of said undesirable plants or to soil containing seed of ` ~ :
undesirable plants, a herbicidally or fungicidally effective amount of a compound having the formula: ~;

. CH ~

R _ ~ m wherein R is alkyl C2-C5, allyl, propargyl, benzyl or carbethoxy-methyl; X represents an anion having a charge o-f from 1 to 3; and m represents an integer from 1 to 3. :~:

Y~l - 2 - ~

1~78~3S~

The present invention also relates to novel pyrazolium compounds represented by the formula:

I) 9 t ~

m wherein R is a member selected from the group consisting of alkyl C2-C5, allyl, propargyl, benzyl and carbethoxymethyl; X represents an anion with a charge of 1, 2 or 3 and preferably 1; m represents an integer selected from 1, 2 or 3.
As is known, certain 1,2-dialkyl-3,5-diphenylpyra-zolium salts and a method for the postemergence control of certain undesirable plant species therewith, are disclosed in Netherlands Application for Patent No. 7,217,015. Additionally, Elguero et al, Bull. Soc. Chim. Fr., 1121 (1970) describe the compound: 1,2,4-trimethyl-3,5-diphenylpyrazolium iodide. However, no utility for the compound is taught or suggested. Moreover, United States Patent No. 3,818,096, issued on June 18, 197~ to Margaret Sherlock, dis-cioses compositions of 1,2-lower dialkyl arylpyrazolium quaternary salts and a method of lowering blood sugar levels with said com-pounds. In no way does patentee suggest any preemergence or postemergence herbicidal activity util-t78~s~

1 izing any 4-benzyl, 4-propargyl or 4-carbethoxymethyl--1,2-dialkyl-3,5-disubstituted pyrazolium salt having enhanced herbicidal activity.
In the practice of the herbicidal methods of the present invention, compounds which have the herein-abovedefined structure (I) are highly efficacious for the postemergence control of crabgrass and wild oats and broadleaf weeds, such as lambsquarters, mustard, pig-weed, ragweed, velvetleaf and some grass plants. More- ;
over, they are highly selective in the presen~e of wheat and rice crops. Unexpectedly, the 4-alkyl compounds are also effective as preemergence herbicides and are useful for the preemergence control of crabgrass and wild oats and broadleaf weeds such as named above~
Among the 4-alkyl derivatives, the 3,5-di-phenyl-1,2,4-trimethylpyrazolium salts are especially notable for their outstanding postemergence herbicidal effect on crabgrass and wild oats in the presence of wheat and rice.
The compounds of this invention are also use-ful for the control of fungi which infect many living pIants. They are particularly effective for controlling powdery mildew, especially on grain5 such as barley and wheat, on vines such as cucumbers, grapes and pumpkin and on fruit and nut trees such as apples, pears and pecans. However, they are also effective for controll-ing fungi which are the causative agents for rice blast and apple scab. ~ -The pyrazolium salts of this invention are readily synthesized by reacting an alkali metal salt of .

.
~ ' .' gL07~3~3S0 1 an appropriate diketone with an alkylating, alkenylat-ing, alkynylating or benzylating agent. The thus-ob-tained substituted diketone is further reacted with a .
Cl-C4 alkylhydrazine to yield the appropriately substi-tuted pyrazole. Finally, the thus-obtained pyrazole is quaternized with the appropriate Cl-C4 alkylating agent to yield the desired pyrazolium salt. The above rèaction sequence may be graphically illustrated as follows:

.. . .. . , . .. . . . . ~ ., .
O O O M O
~t R~-C-CH -C-R ~ MY ~ R5-C-CH-C-R ` >
(v) li t4 11 ~IV) Solven~
~ Solvent R5-C-CH-~-R~ + ~1-NH-NH2 ~ a (III) R5~ ~ ~3 ; 5 ~ 3 1 xem N . ` N - ~

(II A) ~ ~ RI R2 m ~ S ~ ~ (I A) . . R5 ~ R~ R5 ~ 3 ~ - Rl . 2 1 . (II B) _ m . (I B) .

wheFein M is an alkali metal, such as sodium, potassium - ~078~350 1 or lithi~ and Y is hydrogen, hydroxide or alkoxide, such as methoxide, ethoxide, propoxide or butoxide; and wherein Rl to R5, X and m are as above defined. If R3 = R5, the pyrazolium compound identified as formula (I A) above is obtained.
In general, the alkali metal salt of 1,3-di-phenyl-1,3-propanedione or other appropriate diketone can be obtained by reacting an alkali metal hydride, preferably sodium hydride, with said 1,2 diphenyl-1,3--propane or other diketone in the presence of a solvent, such as diethyleth~r, methylether ether or di-n-propyl-ether. This reaction is usually conducted at a rela-tively l~w temperature, i.e., at 0C. to 20C. and pref-erably between 5C. and 15C. The thus-formed salt is then reacted with an alkylating reagent. Illustrative reagents for this reaction include: carbethoxymethyl Cl-C5 alkyl halide, allyl halide, propargyl halide, car-bethoxymethyl halide and benzyl halides, preferably the iodides, bromides or chlorides of the same.
The reaction is usually carried out at an ele-vated temperature, generally between about 50C. and 150C. and preferably between 50C. and 100C., in the presence of an anhydrous solvent such as a dry dialkyl ether, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF) or the like. Generally, about

2 to 3 moles of the alkylating reagent, per mole of the alkali metal ketonic salt are sufficient for effectively completing the reaction.
The thus-formed substituted 1,3- diphenyl-1,3-- 30 -propanedione or other appropriately substituted diketone . . . ....................... . .
.. .... .

~IL0~7~S0 1 is then reacted with a Cl-C4 alkylhydrazine.
Since the diketone and the alkylhydrazille com-pounds combine in equimolar quantities, it is preferable to maintain the molar ratio of reactants at about 1:1;
however, a slight excess (up to about 10%) of either re-actant may be used.
The ring forming reaction between the diketone and alkyl hydrazine is preferably carried out by combin-ing the reactants in a solvent and heating to the reac-tion temperature. Suitable temperatures are in therange of from about 70C. to about 150C. and, preferably, between 80C. and 120C. Suitable solvents include, for example, aprotic solvents, such as xylene, toluene, ben-zene, pyridine, DMSO and the like, or protic solvents, such as Cl-C4 alcohoLs, preferably n and i-propanol.
Where the latter solvents are employed, high rates of conversion are obtained at temperatures in the range of 80C. to 85C.
Quaternization of the l-aLkylpyrazole is ef-fected by reaction thereof with at least an equimolar :. , quantity of an R2X alkylating agent where R2 and X aredefined hereinabove. Exemplary agents are methyl chlor-ide, methyl bromide, methyl iodide, dimethyl sulfate, methyl hydrogen sul~ater trimethyl phosphate, methyl-p--toluene sulfonate, and equivalents thereof.
- This reaction is preferably conducted in the presence of a solvent, such as a lower alcohol Cl-C4: a ketone, such as acetone, methyl ethyl ketone, me`thyl lsobutyl ketone or cyclohexanone; an aprotic solvent, such as dimethylsulfoxide or dimethylformamide; or preferably, ~ 713l~5(~

1 an aprotic solvent, such as xylene, toluene, benzene or 1,2-dichloroethane.
The quaternization is usually carried out at temperatures maintained between 35C. and 150C., pref-erably between 50C. and 125C.
Generally, in the quaternization reaction, the reactants combine in equimolar quantities. It is pre-ferred to employ a 1:1 molar ratio thereof. However, a slight excess tup to 10~) of either reactant can be em- ;
- 10 ployed. Where the alkylating agent is volatile at the temperatures used, such as is in the case of methyl chlor-ide, i~ is preferred to conduct the reaction in an auto-clave. Further, where the diketone selected is asymmet-rically substituted and R3 differs from R5 in the pyra-zole to be produced, a mixture of isomers will result from the above-described reaction scheme. In such event, it is generally expedient to employ the isomer mixture in the herbicidal processes of the present invention.
However, should any separation of the isomers be desired, it can be affected by conventional separation techniques, such as for example, fractional crystalli2ation.
In carrying out the above ring closure and alkylation reactions, it may be expedient to initially form a salt having an anion other than that which it is 2~ desired to employ in the herbicidal processes of the present invention. In such cases, the exchange in anion can be effected by treating the initially forMed salt with an ion exchange resln. Among the suitable ion ex-change resins, one can mention a strong base organic anion exchanger. Exemplary exchangers contemplate quat--:~7885~

1 ernary ammonium salts. Where the resin is supplied as the salt of an anion other than that desired, it is pre-treated with an aqueous solution of a salt of the desir-ed anion. For example, if the resin is supplled as a quaternary ammonium chloride and it is desired to pro-duce a pyrazolium nitrate, one would pretreat the resin with an aqueous solution of sodium nitrate.
Other optional subsequent modifications of the anion in the pyrazolium salt may be effected. For ex-ample. a pyrazolium chloride may be conveniently convert-ed to the corresponding bromide or iodide by treatment with sodium bromide or sodium iodide, in a solvent, such as acetone. A pyrazolium salt, such as the chloride, may be converted to the correspondlng perchlorate by treatment of an aqueous solution of said salt with per-chloric acid~ Thi& results in the preparation of the less soluble perchlorate salt.
In applying the formula (I) pyrazolium salts to the foliage of the undesirable plant species, the salts are preferably formulated as postemergence herbi-cidal compositlons by admixing a herbicidal adjuvant with a herbicidally effective amount of the salt. Suit-able adjuvants include one or more conventional solid or liquid carriers, diluents and formulation aids, particu-larly surfactant~. The salts may be formulated alone,in combination with each other or with other pecticidal agents. The water-miscible (or emulsifiable) concentrates discussed below are especially advanta~eous. The pres-ent invention lS fuxther directed thereto as well as to methods for their preparation and use.

_ g _ ~C178~5~
1 Application o-f the salts as dusts, dust con-centrates, wettable powders and water-miscible (or emuls-ifiable) compositions using conventional application equipment at rates of from 0.27 to 22.4 kg. of active (i.e. cation) per hectare are preferred.
Dusts are generally prepared by grinding to-gether about 1% to 25% by weight of the active agent with from about 99% to 75% by weight of a solid diluent such as kaolln, attapulgite, talc, p~ice, diatomaceous earth, fullers earth, wood flour, or the like. Dust concentrates are prepared in similar fashion excepting that about 25% to 95% by weight of -the active agent is ground with about 75% to 5% by weight of the diluent.
Wettable powders are prepared in the same man-ner as the dust concentrates excepting that about 1% to5% by weight of a surfactant, such as polyoxyethylated vegetable oil, alkyl phenoxy polyoxyethylene ethanol, is also blended with the formulation.
The water-miscible (or emulsifiable) concen-trates are prepared by dissolving from 15~ to 70% of thecompound in 85~ to 30% of a water-miscible salv~nt, such as water itself or another polar water-miscible solvent, such as 2-methoxyethanol, methanol, propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, formamide, and methylformamide. Application of the ma-terial is made by adding a predetermined quantity of the water-miscible (or emulsifiable) concentrate to a spray tank and applying as such or in combination with a suit-- able diluent, such as after addition of a further quantity of water or one of the above polar solvents.

: ' : . ..

8~350 1 The performance of the product in all of the above formulations, which are applied as liquid sprays, is unexpectedly improved by adding a surfactant or blend of surfactants. Conventional, nonionic surfactants may be employed.
Exemplary nonionic surfactants include alkyl polyoxyethylene ethers, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monoolea~e, alkylarylpolyglycol ethers, alkyl phenol ethoxylates, trimethyl nonyl polyethylene glycol ethers, alkyl phenol ethylene oxide condensates, octyl phenoxy polyethoxy ethanols, nonylphenyl polyethylene glycol ethers, con-densates of polyoxy ethylenes, polyoxy propylenes, ali~
phatic polyethers, aliphatic polyesters, alkylaryl poly-oxyethylene glycols, and the like.
These surfactants are preferably added to thespray tank at the rate of 0.1% to 5% by volume to pro-vide good wetting of the spray solution on plant foliage.
The concentrates containing surfactants are preferably formulated as aqueous sprays containing ap-proximately 29% by weight of the appropriate salt, from about 26% to 50% by weight of water and the remainder of said for~ulation (26%-44% weight) of a selected surfact-ant. Surfactants, which have been used in preparing suitable surfactants containing concentrates, include an octylphenol ethylene oxide conden5ate, an ethanolic solution of an alkyl phenol ethoxylate, a polyglycolic ether condensate produced from ethylene oxide and an alkyl phenol and an alkyl aryl polyglycolic ether. Typ-ical formulations are (1) 28~6~ of a pyrazolium salt of ` ~7~385~

l the present invention, 22.0% of one of the above surfac-tants and 49.4% water; and (2) 28.6% of a pyrazolium salt of the present invention, 46.7% of one of the above surfactants and 24.7% water.
In control of wild oats, preferably about 4.68 liters, of the concentrate containing surfactant (l) would be admixed with 181 liters of water and applied as a dilute aqueous spray to cover l hectare of treated area. This spray solution would contain approximately 0.5~ by weight of the surEactant. Formulation (2) would preferably be used in a similar manner except that 4.68 liters of the formulation would be admixed with 374 liters of water and applied as the dilute aqueous spray to cover l hectare of treated area.
It is! of course, obvious that the formula-tions can be varied to provide dilute aqueous sprays containing from about O.l~ to 5.0% by weight of the sur-factant and an effective amount of the pyrazolium salt.
As previously noted, the water-miscible con-centrates of the present~invention are prepared by dis-solving 15~ to 70% of a pyrazolium salt of formula (I) in 85% to 30% of a water-miscible polar solvent. These compositions are unexpectedly improved with regard to their effectiveness by the further step of adding a sur-factant. Nonionic surfactants, especially those havinga hydrophilic-lipophilic balance (HLB) of from ll to 16, are preferred. This conventional surfactant classifica-tion test is described, for example, at page 232 e-t seq of Emulsion Theory and Practice by Paul Becher, Rheinholt Publishing Corporation, second edition (1965); also avail-~' 7~3~SO

1 able as No . 162 in the American Chemical society's Mon~~
graph Series.
Preferred methods employ water as the solvent and above one of the pyrazolium salts defined by form-ula (i) above as the active ingredient.
These compositions are effective when applied at a rate sufficient to provide 0.27-22.4 kg./hectare of active ingredient (i.e. cation). Application at rates from about 0.56 kg. to 11.2 kg. per hectare of said ac-tive material are more preferred.
The present invention and preparation of thestarting materials therefor are illustrated by the fol-lowing examples. UnlesS otherwise indicated, all parts and percentages are by weight, in the following illus-tration and examples as well as in the claims and thediscussion above.
Example 1 Preparation of 2-Sodium-1,3-diphenyl-1,3-propanedione Dibenzoylmethane (112.3 g., 0.5 mole) is dis~
solved in anhydrous diethyl ether (2 1.). The solution is stirred vigorously and sodium hydride (21.0 g., 0.5 mole) added in portions while maintaining the temperat-ure of the mixture between 7C. to 12C~ Upon comple-tion of the addition the reaction mixture is allowed`to stir for 3 hours. Additional anhydrous ether is added, the solid filtered off, reslurried in anhydrous ether, filtered and dried to give 109~0 g. (89%) of the sodium salt of 1,3-diphenyl-1,3-propanedione.
Example 2 Preparation of 1,3-Dipheny~-2-pentyl-l~3-propanedione 1~71~8SV
1 n-Pentylbromlde (22.6 g., 0.15 mole) is added to an anhydrous solution of 2-sodium-1,3-diphenyl~1,3--propanedione (15.7 g., 0.064 mole) in DMF (150 ml.), then the reaction mixture is heated at 80C. to 90C.
for 5 days. The reaction mixture is cooled, poured into ice water, stirred for 1 hour, and extracted with chloro-form (3 x 75 ml.). Evaporation of the chloroform layer gives an oil which is crystallized from 95% ethanol to give 3.7 g. (20%) of product, m.p. 68.5C. to 69.5C.
~nalysiS calculated for C2oH222 C, 81 H, 7.53. Found: C, 81.50; H, 7.63.
Example 3 Preparation of 2~Benzyl-1,3-diphenyl-1,3-propanedione Benzylbromide (25.6 g., 0.15 mole) is added to a partial solution of 2-sodium-1,3-diphenyl-1,3-pro-panedione (15.7 g., 0.064 mole) in dry acetone (200 ml.).
The reaction mixture is stirred at reflux for 39 hours, cooled and poured into ice water (600 ml.). The result-ing suspension is filtered, the collected solid is dried and recrystallized from 95% ethanol to give 14.6 g. (75%) of product, m.p. 102C. to 103C.
Analysis calculated for C22H18O2: C, H, 5.77. Found: C, 83.35; H, 5.89.
Exa~ple 4 Employing the procedure of Example 3, above, the following 2-substituted, 1,3~diphenyl-1,3-propane-diones are prepared:

:.

~ C-CH- ~

R Melting Point C
5 . 4 , - - _ C2H5 8~-84 n-C~H7 61-62 i-C3H7 81-82 C~2-CH-CH2 64-65 o CH2-C-OC~H5 82-8~

5 11 68.5-69c5 . Example 5 Preparation of 3,5-~phenyl-4-ethyl-1-methylpyrazole .
Methylhydrazine (2.86 g., 0.06 mole) is added to an isopropanol (100 ml.) solution of 1,3-dipheny,1-2--ethyl-1,3-propanedione (ll.O g., 0.044 mole) with con-stant stirring at 80C.- The reaction mixture is heated at reflux for 3 1/2 hours, then stirred at room temper-ature overnight. The reaction mixture is poured into ice-water, stirred for 1/2 hour, and the resulting mix-ture extracted with chloroform (3 x 50 ml.). Evapora-tion of the organic layer gives an oil,~which is crystal-lized from hexane with cooling to give 6.47 g. (56~) of product, m.p. 80C. to 81C.
Analysis calculated for C18H18W2: C~
H, 6.92; N, 10.68. Found: C, 82.35; H, 7.09; N, 10.75 - , .. , , . .. : . ~ .

0713B53:~

1 Example 6 Following the procedure of Example 5, above, the followin~ additional pyrazoles are prepared:

S ~ 14 N

R~ Meltin~_Point C

n-C H7 74-75 _ 3 7 oil CH -C~H 159-161 CH2-CH=CH2 79,5-80.5 0 oil Il` oil CH2 ~3 110 '~;
, Example 7 reparation of 3,5-Diphenyl-1,2,4-trimethylpyrazolium methyl sulfate Dimethylsulfate (7.5 g., 0.06 mole) is added to an anhydrous toluene (100 ml.) solution of 1,4-di-methyl-3,5-diphenylpyrazole (10 g., 0.04 mole) at 80C.
with stirring. The reaction mixture is stirred at 100C.
for 3 hours, cooled and a hygroscopic solid removed by filtration. The solid is dissolved in chloroform and ether is added to the solution gradually. The first fraction which precipitates is extremely hygroscopic, .

" .
. .. . . . , ... , ", ., .. , , , ... , .. , . ., , ,, . ,, .. , .. " " , , ~ .
., ,. , ... . . , .. . , . :
.. . . .. . .

-` ~07~8S0 1 m.p. 94C. to 96C.; the second fraction which precipi-tates is not hygroscopic, m.p. 103C. to 105C. as th~
methyl sulfate; total yield of product 12.6 g. t72%).
A 5.0 g. portion of the product is dissolved in water, the solution filtered and the filtrate treated with saturated sodium iodide solution. The precipitate is filtered off at 10C., air dried and then redissolved in warm water. The aqueous solution is extracted with ether, then with chloroform. The chloroform layer is evaporated, the residual oil triturated with ether to af-ford 2.8 g~ (54%) of the iodide salt of the above pyra-z~lium compound as a white solid, m.p. 196C. to 196.5C.
Similarly, a 3.0 g. portion of the pyrazolium methyl sulfate is dissolved in water, the solution filt-ered and treated with dilute perchloric acid; the precipi-tate formed is filtered, washed with water and dried to yield 2.5 g. (85%) of the perchlorate salt of the above pyrazolium compound.
Similarly prepared are:
1,2-Dimethyl~3,5-diphenyl-4-ethylpyrazolium methyl sul-fate, m.p. 115C. to 118C.;
1,2-Dimethyl-3,5-diphenyl-4-n-propylpyrazolium perchlor-ate, m.p. 134C. to 135C.;
1,2-Dimethyl-3,5-diphenyl-4-i-prOpylpyrazolium perchlor-ate, m.p. 149C. to 150C.;1,2-Dimethyl-3,5-diphenyl-4-n-pentylpyrazolium perchlor-ate, m.p. 51C. to 52.5C.;
1,2-Dimethyl-3,5-diphenyl-4-t2-propynyl)pyrazolium hy-drogen sulfate, m.p. 145~C. to 151C.; ~ -4-Allyl-1,2-dimethyl-3,5-diphenylpyrazolium hydrogen - 17 - ;~

.. .. . .. .

71~350 --1 sulfate, wax;
4-(Carboxymethyl)-1,2-dimethyl-3,5-diphenylpyrazolium iodidel~ ethyl ester; m.p. 148C. to 149C.;
~'~
L ~ j 4-Benzyl-1,2-dimethyl-3,5-diphenylpyrazolium hydrogen sulfate, m.p. 244C. to 264C.;
4-Benzyl-1,2-dimethyl-3,5-diphenylpyrazolium perchlor-ate, m.p. 180C~ to 180.5C.
Example 8 Preparation of 3,5-Dicyclohexyl-1,4-dime~lpyrazole Methylhydrazine (1.0 g., 0.022 mole) is added at 60C.-70C. with stirring to an isopropanol (200 ml.) ~ -solution of 1~3-dicyclohexyl-2-methyl-1~3-propanedione (5.0 g., 0.02 mole) having a m.p. of 36C.-37C. and prepared by the procedure of Example 3 above. The reac-tion is heated at reflux for 4 hours, then cooled, water ~300 ml.) added and the resulting solid filtered off.
The solid is dissolved in anhydrous toluene, methyl hy-drazine (1.0 g., 0.022 mole) added and the reaction mix-ture heated at 90C. for 4 hours. Then additional methyl hydrazine (1.0 g., 0.022 mole) is added and heating con-tinued for 3 hours. The reaction mixture is cooled. The solvent removed on a rotary evaporator and the resulting solid crystallized from hexane/benzene to give 1.7 g.
(32%) of the desired product, m.p. 120C. to 122C.
Analysis calculated for C17H28N2: , H, 10.84; N, 10.76. Found: C, 78.38; H, 10.91; N, 10.76.
Example 9 Preparation of 3,5-Dicyclohexyl-1,2,4-trime hylpyrazolLum methyl sulfate Dimethyl sulfate (1.26 g., 0.01 mole) is added ` 1~7~850 1 to an anhydrous toluene (50 ml.) solution of 3,5-dicyclo-hexyl-1,4-dimethylpyrazole (1.7 g., 0.0064 mole) with constant stirring at 80C. The reaction mixture is then heated to reflux and maintained at reflux, with stirringt for 6 hours, The reaction mixture is cooled, ether (75 ml.) is added and the mixture stirred for 3 hours. The resulting solid is filtered and dried to give 1.8 g. of the desirPd product, m.p. 176C. ~o 177C.
Analysis calculated for ClgH34N204S: C, 59.04;
H, 8.87; N, 7.25; S, 8.30. Found: C, 59.62; H, 9.54;
N, 7.21; S, 8.04.
Example 10 The preemergence activity of the compounds of the present invention is demonstrated by the following tests, wherein a 50/50 acetone/water (v/v) mixture and sufficient test compound to provide the amount per hec-tare of said compound as indicated in Table I when the mixture is applied to pots planted with seeds or propa-gules of test plant species~
The pots are prepared the day of herbicide treatment by pu~tting 100 ml. of soil in each plastic pot as a base, then morningglory and wild oat seeds are plac-ed on this base and covered with 50 ml. (1 cm. to 1.37 cm.) of soil. Seeds of the other 8 plant species identi-fied below are separately mixed with soil and 50 ml. of the soil seed mix added to the pot. The pots are then ~amped lightly to level the soil and the soil i9 wetted with water prior to herbicide application. This pre-wetting insures that the subsequently applied herbicide ;~

treatment solution spreads evenly over the surface of the ' - 19 - ::

, . , ' ~ , ~ . . : '.

~7~i~5~
l pot and protects the weed seeds from acetone injury.
Each o~ the 10 weed species is contained in a separate pot. The pots are then arranged in 25.4 x 30.4 cm.
flats prior to chemical treatment. -The planted pots are treated with 5 ml. of test solution and then placed on benches in the green-house. Pots are watered after treatment as needed and held in the greenhouse for 3 weeks at which time the re-sults are recorded, as reported in Table I below.
Plant Species Used in Preemergence Herbicide Evaluation .
Common Name Abbrevia-tion Sclentific Name Lambsquarters LA Chenopodium album Wild Mustard MU Brassica kaber Pigweed PI Amaranthus retroflexus 15 Ragweed RW ~mbrosia artemisiifolia Morningglory MG Ipomoca purpurea Barnyardgrass BA Echinochloa crusgalli Crabgrass CR Digitaria sanguinalis Green Foxtail FO -Setaria yiridis 20 Wild Oats WO Avena fatua Velvetleaf VL Abutilon theophrasti - Wheat ~ WH Triticum vulgare Rice RI Oryza sativa The rating system used in the evaluation of the experimental data is given below:

.~ .

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1 Rating System ~ Difference in growth from check*
0 - No effect 1 - Possible effect 1-10 2 - Slight effect 11-25

3 - Moderate effect 26-40 5 - Deflnite injury 41-60 6 ~ Herbicidal effect 61-75 7 - ~ood herbicidal effect 76-go 8 - Approaching complete kill 91-99 9 - Complete kill 100

4 - Abnormal growth, that is, a definite physiological malformation but with an over all effect less than 5 on the ratin~ scale.
15 * Based on visual determination of stand, size, vigor, : chlorosis, growth malformation and over-all plant - appearance.

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1 Example 11 The postemergence herbicidal activity of the compounds of the present invention is demonstrated by the following tests, wherein a variety of monocotyledon-ous and dicotyledonous plants are treated with test com-pounds dispersed in aqueous acetone mixtures. In the tests, seedling plants arP grown in jiffy flats for about 2 weeks. The test compounds are dispersed in 50/50 acetone/water (v/v) mixtures containing 0.5% TWEEN~ 20, a polyoxyethylene (2) sorbitan monolaurate surfactant by Atlas Chemical Industries, in sufficient quantity ~o provide the amount per hectare of active compound as in-.
dicated in Table II.when applied to the plants through a spray nozzle operating at 2.8 kg. per cm2 pressure for a predetermined time. After spraying, the plants are placed on greenhouse benches and cared for in the usual manner, commensurate with conventional greenhouse practices. Two weeks after treatment, the seedling , plants, with the exception of wild oats which are rated :. : 20 at 5 weeks, are examined and rated according to the rat-, .ingIsystem provided in Example 10.

. .The plant species used in the postemergence .

:herbicide activity evaluation are the same as those used .

in the .preemergence herbicide evaluation test and are listed in Example 10. The results are reported in Table II. .

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78~50 1 Example 12 To determine the effectiveness of the 4-sub-stituted 1,2-dimethyl-3,5-diphenylpyrazolium salts as fungicidal agents a variety of pathogenic fungi, host plants and salts are used in the ~ollowing tests. Path-ogents, host plants, the method of testing and the rat-ing system used are reported below along with the data obtained.
Pathogens:
Piricularia oryzae Cavara, the rice blast pathogen.
Venturia inaequalis (Cke.) Wint. which causes apple scab.
Erysiphe clchoracearum`DC, the cause of powd~ry mildew on cucurbits.
Podosphaera leucotricha (E. & E.) Salm., the cause of powdery mildew of apples and pears.
Erysiphe graminis f. sp~ tritici the cause of powdery mildew on wheat.
Erysiphe graminis f. sp. hordei the cause of powdery mildew on barley.
Host Plants:
.
Rice (~y__ sativa)(Cv. Nato) Cucumber (Cuc mis satlvus) (Cv. Marketer) Apple (Malus s~lvestris) (Seedling) Wheat (Triticum aestivum Cv. Bonanza) :
Barley (Hordeum vulgare Cv. Larker) ~ Plants are individually ~rown in 5.08 cm.
peat squares and assembled in 7.62 cm. x 25.4 cm. press-ed fibre flats the week pxior to spraying. With excep-~tion of rice, barley and wheat, a single specimen of each species is used. A separate flat is used for those 1 plants in the mildew evaluation. The complete test sys-tem is shown below:
series 1 Series 2 :
Rice: Rice Blast Apple: Powdery Mildew S Apple: Apple Scab Cucumber: Powdery Mildew Wheat: Powdery Mildew Barley: Powdery Mildew Spray solutions are prepared at a final con-centration of 100 ppm. or 500 ppm. in 50 ml. of 50%
aqueous aeetone. Acetone is added to solubilize the compound and solutions made to final volume with deion-ized water.
Two flats with plants for each treatment, one each from Series 1 and 2 (see above), are sprayed simul-taneously on a turntable with 50 ml. of the test solu-tion. Spray is provided by two fixed Spraying System Company nozzles mounted to deliver vertical and hori-zontal solid cone spray patterns. Immediately there-after, all plants are returned to the greenhouse to permit the deposit to dry. After the plants have dried, Series 1 and 2 are separately inoculated. Plants in Series 1 are inoculated with conidial suspensions of the respective pathogens using a DeVilbiss paint sprayer op-erated at air pressure 0.28-0.42 kg./cm2 and immediately transferred to a controlled temperature/humidity cab-inet (ambient temperature, RH. 95~. Plants in Series 2 are dusted with respective powdery mildew conidia and then removed to the controlled environment plant culture room (10 hours light, 22C., RH. 45%~ to await disease development. Plants in Series 1 are held 4 days ln the : ' . " " ' .

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Performance Rating:
All plants are rated for disease severity on a scale of 1 to 7 (clean to kill), as described below:
Rating Description 1 Clean 2 Trace disease 3 Slight disease 4 Moderate disease Heavy disease 6 Severe disease 7 Kill In the accompanying tables of results, the numerical rating is used for clarity.
Data obtained are reported in Tables III and IV below. The ratings reported represent data obtained from one or more individual tests. Where more than one test has been conducted the ratings are averaged and reported as a single value rating. For each table, there is also provided a rating value for the checks em-ployed. It is, of course, obvious that the lower the value, the more effective the disease controlO When a superscript is used in the table with a rating, it in-dicates some phytotoxicity. The legends, "S" meansslightj "M" means moderate, and "SV" means severe phyto-toxicity. Data are reported for minimum effective levels at which compounds are evaluated.

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Claims (17)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound having the formula:

wherein R is alkyl C2-C5, allyl, propargyl, benzyl or carbethoxymethyl;
X represents an anion having a charge of from 1 to 3; and m represents an integer from 1 to 3.

2. 4-Benzyl-1,2-dimethyl-3,5-diphenylpyrazolium hydrogen sul-fate.

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

4. 4-(Carboxymethyl)-1,2-dimethyl-3,5-diphenylpyrazolium iodide ethyl ester.

5. 1,2-Dimethyl-3,5-diphenyl-4-ethylpyrazolium methyl sulfate.

6. 1,2-Dimethyl-3,5-diphenyl-4-ethylpyrazolium methylsulfate/hydrogen sulfate (1:1).

7. 1,2-Dimethyl-3,5-diphenyl-4-n-pentylpyrazolium perchlorate.

8. 1,2-Dimethyl-3,5-diphenyl-4-n-propylpyrazolium perchlorate.

9. 1,2-Dimethyl-3,5-diphenyl-4-i-propylpyrazolium perchlorate.

10. 4-Allyl-1,2-dimethyl-3,5-diphenylpyrazolium hydrogen sulfate.

11. 1,2-Dimethyl-3,5-diphenyl-4-(2-propynyl)pyrazolium hydrogen sulfate.

12. A method for controlling fungi comprising contacting said fungi with a fungicidally effective amount of a compound as defined in claim 1.

13. A method for controlling undesirable plant species comprising applying to foliage of said species or to soil containing seeds of said species a herbicidally effective amount of a compound as defined in claim 1.

14. A method according to claim 12 or 13 wherein the cation of said compound is the 3,5-diphenyl-1,2,4-trimethylpyrazolium moiety, and the anion is selected from the group consisting of iodide, methylsulfate and perchlorate.

15. A method according to claim 12 wherein said compound is con-tacted with the fungi in the form of a liquid spray containing 50 ppm. to 500 ppm. of said compound.

16. A method according to claim 13 wherein said compound is applied in the form of a liquid spray containing 50 ppm. to 500 ppm. of said compound.

17. A method according to claim 12 or 13 wherein said compound is selected from 4-benzyl-1,2-dimethyl-3,5-diphenylpyrazolium hydrogen sul-fate, 4-benzyl-1,2-dimethyl-3,5-diphenylpyrazolium perchlorate, 4-(carboxy-methyl)-1,2-dimethyl-3,5-diphenylpyrazolium iodide ethyl ester, 1,2-dimethyl-3,5-diphenyl-4-ethylpyrazolium methyl sulfate, 1,2-dimethyl-3,5-diphenyl-4-ethylpyrazolium methylsulfate/hydrogen sulfate (1:1), 1,2-dimethyl-3,5-diphenyl-4-n-pentyl-pyrazolium perchlorate, 1,2-dimethyl-3,5-diphenyl-4-n-propylpyrazolium per-chlorate, 1,2-dimethyl-3,5-diphenyl-4-i-propylpyrazolium perchlorate, 4-allyl-1,2-dimethyl-3,5-diphenylpyrazolium hydrogen sulfate, and 1,2-di-methyl-3,5-diphenyl-4-(2-propynyl)pyrazolium hydrogen sulfate.