CA1078394A - Pyrazolium salts - Google Patents
Pyrazolium saltsInfo
- Publication number
- CA1078394A CA1078394A CA218,846A CA218846A CA1078394A CA 1078394 A CA1078394 A CA 1078394A CA 218846 A CA218846 A CA 218846A CA 1078394 A CA1078394 A CA 1078394A
- Authority
- CA
- Canada
- Prior art keywords
- halogen
- denotes
- lower alkyl
- lower alkoxy
- spp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention relates to new and valuable pyrazolium salts having the general formula:
, where X denotes an anion and D denotes identical or different lower alkyl radicals, and a) C denotes hydrogen, lower alkyl, halogen or lower alkoxy, A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, and B denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or b) B denotes halogen or lower alkoxy, A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, and C denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or c) C denotes hydrogen, lower alkyl, lower alkoxy or halogen, A denotes hydrogen, lower alkyl, lower alkoxy or halogen, and B denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or d) C denotes hydrogen, lower alkyl, lower alkoxy or halogen, B denotes hydrogen, lower alkyl, lower alkoxy or halogen and A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or e) A, B and C
simultaneously denote identical or different halogen radicals.
These pyrazolium salts have a good herbicidal action.
The present invention relates to new and valuable pyrazolium salts having the general formula:
, where X denotes an anion and D denotes identical or different lower alkyl radicals, and a) C denotes hydrogen, lower alkyl, halogen or lower alkoxy, A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, and B denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or b) B denotes halogen or lower alkoxy, A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, and C denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or c) C denotes hydrogen, lower alkyl, lower alkoxy or halogen, A denotes hydrogen, lower alkyl, lower alkoxy or halogen, and B denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or d) C denotes hydrogen, lower alkyl, lower alkoxy or halogen, B denotes hydrogen, lower alkyl, lower alkoxy or halogen and A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or e) A, B and C
simultaneously denote identical or different halogen radicals.
These pyrazolium salts have a good herbicidal action.
Description
`` iO78394 The present invention relates to new and valuable pyrazolium salts, herbicides containing these compounds, and a process for controlling the growth of unwanted plants with these compounds.
It is known (German Laid-Open Application DOS 2,260,485) to use pyrazolium salts, especially l,2-dimethyl-3,5-diphenyl-pyrazolium methyl sulfate, as herbicides. However, their herhicidal action is not always satisfactory.
We have now found that pyrazolium salts of the formula 10 ' _ r ~
~. ~
.
~ where X denotes an anion and D denotes~identical or different ; lower alkyl radicals, and .~ :
- a) C denotes hydrogen, lower alkyl, halogen or lower alkoxy, A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, and B denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or b) B denotes halogen or lower alkoxy, A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, and C denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or c) C denotes hydrogen, lower alkyl, lower alkoxy or halogen, A denotes hydrogen, lower alkyl, lower alkoxy or halogen, and B denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or ?
':
d) C denotes hydroyen~ lower alkyl~ lower alkoxy or halo~en, B denotes hydrogen, lower alkyl, lower alkoxy or halogen and A denotes unsubs-tituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or e) A, B and C simultaneously denote identical or different halogen radicals, have a strong, and particularly selective, herbicidal action.
Examples of lower alkyl groups are methyl, ethyl, n-propyl, isopropyl and tert-butyl, and examples of lower alkoxy ; 10 substituents are methoxy, ethoxy, n-propoxy, isopropoxy and tert-butoxy.
Examples of halogens are chlorine, bromine and iodine.
Anions are for example the anions of the following salts:
halides, e.g., chlorides and bromides; sulfates, hydrosulfates; r perchlorates, lower alkyl sulfates, e.g., methyl sulfate, lower ,~ alkane sulfonates, substituted benzene sulfonates, aminosulfona-tes and alkylaminosulfonates.
The pyrazoles used as starting materials for the preparation of the pyrazolium salts may be prepared by either 20 condensing a 1,2-dicarbonyl compound in accordance with the i~ following schemes with an alkyl hydrazine, or by alkylating it, ; after reaction with hydrazine hydrate, with an alkylating agent such as a dialkyl sulfate or an alkyl halide to give l-alkylpyrazole, ' A, B, C and D having the above meanings except that A, C and advantageously B are neither halogen nor alkoxy:
.: .
~ ~ 2 -`"" 1~78394 ~ ' :
B
A C ~ CH C ~ C NH 2 -N~l-D A~,C
~ D
or ¦~N 2H 4 , r 1 0 A~,~C
'i ' ~ :'' or N N D~ C
, H ~ --N
~, D
~j .
;,~, '.:
':
- 2a -, ~ .
. . ' , ' ' , ,: , ~ ,, ~.
~078394 In the case of l-H or l-alkylpyrazoles, hydrogen may be replaced by halogen in A or B, A and B, or A,B and C by adding elementary halogen, e.g., chlorine, bromine and iodine, if desired in the presence of catalytic amounts of Lewis acids, e.g., iron (III) bromide and aluminum (III) chloride, or by the action of halo-genating agents, e.g., sulfuryl chloride.
The halogenation reactions are carried out in conventional solvents such as methylene chloride, chloroform, carbon tetra-chloride, ethers and lower organic carboxylic acids.
The l-alkylpyrazoles are quaternized by reaction with at least one mole equivalent of an alkylating agent in known manner .j', , ;~ at temperatures of from 30 to 150C. Suitable alkylating agents are the ones usually employed for this purpose, e.g. lower alkyl halides such as methyl iodide, or lower alkyl sulfates such as diethyl sulfate. The reaction may also be carried out in aprotic ~ !
solvents, e.g., chlorinated, aliphatic or aromatic hydrocarbons or ketones.
The quaternary pyrazolium salts are usually obtained in crystalline form. In reactions with alkylating agents in the absence of solvents it may at times be advantageous to fully crystallize the crude products by stirring them with lower ketones or suitable mixtures of lower alcohols or ethers.
If the anion of the pyrazolium salt is to be different from that provided by the alkylating agent, it may be replaced by means of ion exchange resins.
PREPARATION OF THE STARTING COMPOUNDS
A) l-methyl-3,4-(4,5)-_iphenYl~ zole At 25 C, 84 parts (by weight) of methyl hydrazine was dripped under nitrogen into 183 parts of -formyl deoxybenzoin in 1,000 parts of isopropynol. The mixture was stirred for 2 hours at 25C and boiled for 1 hour under reflux. After evaporation of the solvent in vacuo, the residue was distilled. Theze was obtained 127 parts of 1-methyl-3,4-(4,5)-diphenylpyrazole at 182 C
.
`` 1078394 186C/0.3 mm.
B) l-methyl-4-bromo-3,5-diphenylpyrazole -~
At room temperature and over a period of 3 hours, a solution of 103 parts of bromine in 100 parts of chloroform was dripped into a solution of 150 parts of 1-methyl-3,5-diphenyl-pyrazole in 900 parts of chloroform. The mixture was then stir-red for a further 2 hours. After removal of the solvent in vacuo, recrystallization from ethanol gave 160 parts of the desired product; m.p.: 111 to 112 C.
'.' ,10 C) 1~
At 80 to 85C, 9 parts of methyl hydrazine was dripped into a solution of 23 parts of l,l-dibenzoylethane in lOO parts of isopropanol, and the mixture heated for 2 hours under reflux.
After coolin~, 21 parts of the desired product having a melting point of 108 to 109 C was obtained.
D) l-methYl-3~4,5-tribromopYrazole 45.5 parts of 3,4,5-tribromopyrazole was introduced into 26.3 parts of a 30% (by weight) sodium methylate solution in methanol; 17 parts of methanol was then added. Subsequently, 27.6 parts of methyl iodide was added and the mixture stirred at 50C until it had a neutral reaction. The precipitated sodium iodide was removed by suction filtration, and the filtrate was concentrated in vacuo, suction filtered and washed with water.
42 pa`rts of the desired product was obtained; m.p.: 86 to 87C.
E X A M P L E
1,2-dimethYl-3,4-diphenylEyrazolium methYl sulfate 90 parts of 1-methyl-3,4-(4,5)-diphenylpyrazole was dissolved in 400 parts of dry and warm xylene. 50.7 parts of dimethyl sulfate was then dripped in and the mixture stirred for 8 hours at 105 to 110C. The xylene upper phase was decanted and the residue stirred with dry acetone until all has crystallized. After suction filtration and drying, 82 parts of the desired product was obtained; m.p.: 153 to 154 C.
10783~4 o.z. 30,364 1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium methyl sulfate A mixture of 63 parts of 1-methyl-4-bromo-3,5-diphenylpyrazole and 33,6 parts of dimethyl sulfate was stirred for 2 hours at 150C. The crude product was cooled, pasted with dry acetone and suction filtered. After dissolution in ethanol and precipita-tion with ether, 60 parts of the desired product melting at ` 164 to 165C was obtained.
1,2,4-trimethyl-3 5-diphenylpyrazolium methyl sulfate 20.4 parts of 1,4-dimethyl-3,5-diphenylpyrazole was dissolved at 60 to 65C in 100 parts of dry xylene. 10.8 parts of dimethyl sulfate in 15 parts of dry xylene was added and the mixture stirred for 8 hours at 105 to 110C. The mixutre was then cooled, the upper xylene phase was decanted and the residue stirred with dry ~ acetone. Suction filtration gave 14.2 parts of the desired product;
3 m.p. 86 to 88C.
1,2-dimethyl-3,4,5-tribromopyrazolium methyl _ulfate 20 parts o~ 1-methyl-3,4,5-tribromopyrazole was mixed with 10.4 parts of dimethyl sulfate and stirred for 3 hours at 105 to 110C. After cooling, the crystalline residue was stirred with 150 parts of dry acetone. Suction filtration ga~e 19 parts of the desired product;
m.p.: 210C.
The following compounds for instance may be prepared analogous-ly: :
1,2-dimethyl-3-phenyl-4-bromo-5-chloropyrazolium methyl sulfate (m.p.: 200 to 201C) 1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium perchlorate (m.p O 300 to 302C) 1,2-dimethyl-4-bromo-3-phenyl-5-p-chlorophenylpyrazolium methyl sulfate O.Z. 30,364 1,2-dimethyl-3-bromo-4,5-diphenylpyrazolium methyl sulfate (m.p.: 128 to 130C) 1,2-dimethyl-4-methoxy-3,5-diphenylpyrazolium methyl sulfate characteristic infrared bands at 2850, 1230, 1060, 1010 cm 1,2-dimethyl-3,4-dichloro-5-phenylpyrazolium methyl sulfate 1,2-dimethyl-4-chloro-3,5-diphenylpyrazolium methyl sulfate (m.p.: 135 to 136C) 1,2,4-trimethyl-3,5-diphenylpyrazolium trifluoromethyl sulfonate (m.p.: 128 to 130~C) 1,2-dimethyl-4-ethyl-3,5-diphenylpyrazolium methyl sulfate (m.p.: 130 to 132C) 1,2-dimethyl-4-n-propyl-3,5-diphenylpyrazolium methyl sulfate (m.p.: 122 to 124C).
The compounds have a strong herbicidal action and may therefore be used as weedkillers or for controlling the growth of unwanted plants. Whether the new active ingredients are used as -total or selective agents depends in essence on the amount of in-gredient used per unit area.
By weeds and unwanted plant growth are meant all monocotyledonous and dicotyledonous plants which grow in loci where they are not desired.
Thus, the present invention also relates to a process for controlling the growth of unwanted plants, wherein the plants or the soil are treated with a herbicidally effective amount of a compound of the formula C 1 ~
N-N
D D X
where X denotes an anion and D denotes identical or different lower alkyl radicals, and ., i,, 1078394 o. æ . 30, 364 a) C denotes hydrogen, lower alk.yl, halogen or lower alkoxy, A denotes unsubstituted pheny; or phenyl substituted by lower alkyl, lower alkoxy or halogen, and B denotes unsub-'! stituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen or b) B denotes methyl,-halogen or lower alkoxy, A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, and C denotes unsub-stituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or c) C deno*es hydrogen, lower alkyl, lower alkoxy or halogen, A denotes hydrogen, lower alkyl, lower alkoxy, or halogen, - and B denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or d) C denotes hydrogen, lo~Jer alkyl, lower alkoxy or halogen, B denotes hydrogen, lower alkyl, lower alkoxy or halogen and A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or e) A, B and C simultaneously denote identical or different halogen radicals.
: The agents according to the invention may therefore be used for controlling for instance Gramineae,such as Cynodon spp. - Dactylis spp.
Digitaria spp. Avena spp.
Echinochloa spp. Bromus spp.
Setaria spp. ` Uniola spp.
Panicum spp. Poa spp.
Alopecurus spp. Leptochloa spp.
Lolium spp. Brachiaria spp.
Sorghum spp. Eleusine spp.
Agropyron spp. Cenchrus spp.
; - 6a -' ' ~ ~078394 o. z . 30,~64 Phalaris spp. Eragrostis spp.
Apera spp. Phragmites communis etc.;
Cyperaceae, such as Carex spp. Eleocharis spp.
Cyperus spp. Scirpus spp.
etc.;
dicotyledonous weeds, such as ~ Malvaceae, e~g.
., 10 Abutilon theoprasti Hibiscus spp.
Sida spp. Malva spp.
etc~;
Compositae, such as Ambrosia spp. Centaurea spp.
Lactuca spp. Tussilago spp.
Senecio spp. Lapsana communis Sonchus spp. Tagetes spp.
Xanthium app. Erigeron spp.
Iva spp. Anthemis 8pp.
Galinsoga spp. Matricaria spp.
Taraxacum spp. Artimisia spp.
Chry~anth~mum spp. Bidens 9pp.
Cirsium spp. etc.;
Convolvulaceae, such as Convolvulus spp. Cuscuta spp.
Ipomoea spp. Jaquemontia tamnifolia etc.;
Cruciferae, such as Barbarea vulgaris Arabidopsis thaliana Brassica spp. Descurainia spp.
Capsella spp. Draba spp.
. . . ..... . .. - . .
~78394 Z. 30,364 3isymbrium spp. Coronopus didymus ; Thlaspi spp. Lepidium spp.
Sinapis arvensis Raphanus spp.
etc.;
, ~ -Geraniaceae, such as 1 Erodium spp. Geranium spp.
etc.;
, Portulacaceae, such as Portulaca sppO etc.;
Primulaceae, such as Anagallis arvensis Lysimachia spp.
etc.;
Rubiaceae, such as Richardia spp. Diodia spp.
Galium spp. etc.;
Scrophulariaceae, such as Linaria spp. Digitali~ spp.
Veronica spp. etc.;
Solanaceae, such as Physalis spp. Nicandra spp.
Solanum spp. Datura spp.
etc.;
Urticaceae, such as Urtica spp.
Violaceae, such as Viola spp. etc.;
Zygophyllaceae, such as Tribulus terrestris etc.;
Euphorbiaceae, such as Mercurialis annua Euphorbia spp.
Umbelliferae, such as Daucus carota Ammi majus Aethusa cynapium etc.;
, . .. . ~ . .: . ,.... ,. . :
Commelinaceae, such as Commelina spp. etc.;
Labiatae, such as Lamium spp. Galeopsis spp.
etc.;
Leguminosae, such as Medicago spp. Sesbania exaltata Trifolium spp. Cassia spp.
Vicia spp. Lathyrus spp.
etc.;
Plantaginaceae, such as Plantago spp. etc.;
Polygonaceae, such as Polygonum spp. Fagopyrum spp.
Rumex spp. etc.;
Aizoaceae, such as Mollugo verticillata etc.;
Amaranthaceae, such as Amaranthus spp. etc.;
Boraginaceae, such as Amsinckia spp. Anchusa spp.
Myostis spp. Lithospermum spp.
etc.;
Caryophyllaceae, such as Stellaria spp. Silene spp.
Spergula spp. ~erastium spp.
Saponaria spp. Agrostemma githago Scleranthus annuus etc.; ' Chenopodiaceae, such as Chenopodium spp. Atriplex spp.
Kochia spp. Monolepsis nuttalliana Salsola Kali etc.;
: ~:
~78394 o.z. 30,364 Lythraceae, such as Cuphea spp. etc.;
Oxalidaceae, such as ~, Oxalis spp.
Ranunculaceae, such as Ranunculus spp. Adonis spp.
Delphinium spp. etc.;
Papaveraceae, such as Papaver spp. Fumaria offinicalis etc.;
Onagraceae, such as Jussiaea 9pp. etc.;
Rosaceae, such as Alchemillia spp. Potentilla spp.
etcO;
Potamogetonaceae, such as Potamogeton spp. etc.;
' Najadaceae, such as Najas spp, etc.;
Equisetaceae Equisetum spp. etc.;
~' Marsileaceae, such as Marsilea quadrifolia etc.;
Polypodiaceae, Pteridium quilinum Alismataceae, such as Alisma spp. Sagittaria sagittifolia etc, The herbicides according to the invention may be employed in cereal crops such as Avena spp. Sorghum Triticum spp. Zea mays ` 1~78394 o.z. 30,364 Hordeum spp. Panicum miliaceum Secale spp. Oryza spp.
; Saccharum offinicarum and in dicotyledon crops such as Cruciferae, e.g.
Brassica spp. Raphanus sppt Sinapis spp. Lepidium spp, Compositae, e.g.
Lactuca spp. Carthamus spp.
Helianthus spp. Scorzonera spp.
Malvaceae, eOg.
Gossypium hirsutum Leguminosae, e.g.
Medicago spp. Phaseolus spp.
Trifolium spp. Arachis spp.
Pisum spp. Glycine max.
Chenopodiaceae, e.g.
Beta vulgaris Spinaoia spp. ' Solanaceae, eOg.
Solanum spp. Capsicum annuum Nicotiania spp.
Linaceae, e.g.
Linum spp.
Umbelliferae, e.g.
Petroselinum spp. Apium graveolens Daucus carota Rosaceae, e.g. Fragaria Cucurbitaceae, e.g.
Cucumis spp. Cucurbita spp.
Liliaceae, e.g.
Allium spp.
Vitaceae, e.g.
Vitis vinifera Bromeliaceae, e.g.
Ananas sativus.
The amount used of the agents according to the invention may vary and depends in essence on the type of effect to be achieved; it is generally from 0.1 to 15 (and more~, preferably from 0.2 to 6, kg per hectare of active ingredient. The agents according to the invention may be used once or several times before or after planting, before sowing, and before, during or after emergence of the crop plants and unwanted plants.
Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc. and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene,xylene, paraffin, tetrahydronaphthalene, alkyl-ated naphthalenes and their derivatives such as methonal, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chloro~enzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, ~-methyl-pyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion concen-tratesj pastes, oil dispersions or wettable powders by adding water.
To prepare emulsions, pastes andoil dispersions the ingredients as such or dissolved in an oil or solventmay be homogenized in water ~78394 o.z. 30,364 by means of wetting or dispersing agents, adherents or emulsi-fiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emul-sifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are; alkali metal, alkaline earth metal and ammonium salts of ligninsuifonic acid, naphthalene-sulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfa~ed fatty alcohol glycol ether, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and form-aldehyde~ polyoxyethylene octylphenol ethers, ethoxylated isooctyl-phenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkyl-phenol polyglycol ethers, tributylphenyl polyglycol ethers~ alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryi alcohol polyglycol ether acetal, sorbitol esters~ lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers.
Examples of solid carriers are mineral earths such as silica gel, silicic acid, silica gels, silicates, talc, kaolin, Attaclay, lime-stone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth,calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, 1~78394 .Z. 30,364 barK meal, wood meal, and nutshell meal, cellulosic powders, etc. , The formulations contain from 0.1 to 95, and preferably 0.5 to 90% by weight of active ingredient.
There may be added to the compositions or individual active in~redients (if desired, immediately before use (tar.kmix)) oils of various types, herbicides, fungicides, nematocides, insectici-des, bactericides7 trace elements, fertilizers, antifoams (e.g., silicones), growth regulators, antidotes and other herbicidally effective compounds such as substituted anilines substituted aryloxycarboxylic acids and salts, esters and amides thereof, substituted ethers ^
substituted arsonic acids and their salts, esters and amides substituted benzimidazoles substituted benzisothiazoles substituted benzothiadiazinone dioxides substituted benzoxazines substituted benzoxazinones substituted benzothiadiazoles substituted biurets substituted quinolines substituted carbamates substituted aliphatic carboxylic acids and their salts, esters and amides substituted aromatic carboxylic acids and their salts, esters and amides substituted carbamoylalkylthiol- or -dithiophosphates substituted quinazolines substituted cycloalkylamidocarbothiolic acids and their salts, esters and amides -~78394 o,z. 30,364 substituted cycloalkylcarbonamidothiazoles substituted dicarboxylic acids and their salts, esters and amides substituted dihydrobenzofuranyl sulfonates substituted disulfides substituted dipyridylium salts substituted dithiocarbamates substituted dithiophosphoric acids and their salts, esters and amides substituted ureas substituted hexahydro-lH-carbothioates substituted hydantoins substituted hydrazides substituted hydrazonium salts :~
substituted isoxazole pyrimidones substituted imidazoles substituted isothiazole pyrimidones substituted ketones substituted naphthoquinones substituted aliphatic nitriles substituted aromatic nitriles substituted oxadiazoles substituted oxadiazinones substituted oxadiazolidine diones substituted oxadiazine diones :
substituted phenols and their salt~ and esters substituted phosphonic acids and their salts, esters and amides substituted phosphonium chlorides substituted phosphonalkyl glycines substituted phosphites substituted phosphoric acids and their salts, ester and amides substituted piperidines substituted pyrazoles ~ 8394 O.Z. 30,364 substituted pyrazole alkylcarboxylic acids and their salts, esters and amides substituted pyrazolium salts substituted pyrazolium alkyl sulfates substituted pyridazines substituted pyridazones substituted pyridine carboxylic acids and their salts, esters and amides substituted pyridines substituted pyridine carboxylates subestituted pyridinones substituted pyrimidines substituted pyrimidones substituted pyrrolidine carboxylic acid and its salts, esters and amides substituted pyrrolidines ; substituted pyrrolidones substituted arylsulfonic acids and their salts, esters and amides substituted styrenes substituted tetrahydrooxadiazine diones substituted tetrahydroxadiazole diones substituted tetrahydromethanoindenes substituted tetrahydroxadiazole thiones substituted tetrahydrothiadiazine thiones substituted tetrahydrothiadiazole diones substituted aromatic thiocarbonylamides substituted thiocarboxylic acids and their salts, esters and amides substituted thiol carbamates ~ubstituted thioureas substituted thiophosphoric acids and their salts, esters and amides O.Z. 30,364 substituted triazinessubstituted triazoles substituted uracils, and substitu~ed uretidine diones.
The last-mentioned herbicidal compounds may also be applied before or after the active ingredients or compositions thereof according to the invention.
These agents may be added to the herbicides according to the invention in a ratio by weight of from 1:10 to 10:1. The same applies to oils, fungicides, nematocides, insecticides, bac-: tericides, antidotes and growth regulators.
. E X A M P L E 5 In the greenhouse the plants listed below were treated at a growth height of from 4 to 18 cm with 1.0 and 2 kg per hectare of each of the following active ingredients, each being dispersed or emulsified in 500 liters of water per hectare:
1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium methyl sulfate II 1,2,4-trimethyl-3,5-diphenylpyrazolium methyl sulfate IV 1,2-dimethyl-3,5-diphenyl-4-bromopyrazolium perchlorate III 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate (prior art compound used for comparison purposes) ~
After 3 to 4 weeks it was ascertained that active ingredients :-I, II and IV had better crop plant compatibility and a better her-bicidal action than compound III.
The results are given below:
Active ingredient I II III IV
kg/ha 1.0 2.0 1.0 2.0 1.0 2.01.0 2.
Crop plants:
Triticum aestivum o o 0 n lo 25 0 0 Hordeum vulgare o 0 0 0 20 30 0 0 Secale cereale o 0 0 0 20 35 0 0 -Beta vulgaris 0 10 0 0 20 30 0 0 Brassica napus o 5 0 5 0 10 0 0 10 Unwanted plant: -Avena fatua 90 100 85 100 75 95 90 100 0 ~ no damage 100 = complete destruction The action of 1,2-dimethyl-3,4-diphenylpyrazolium methyl sulfate, 1,2-dimethyl-3,5-diphenyl-4-chloropyrazolium methyl sulfate and 1,2-dimethyl~3,4,5-tribromopyrazolium methyo sulfate corresponds to that of I, II and IV above.
90 parts by weight of the compound of Example 1 is mixed with 10 parts by weight of N-methyl-~-pyrrolidone. A mixture ` is obtained which is suitable for application in the form ofvery fine drops.
20 parts by weight of the compound of Example 2 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole ofcastor oil.
By pouring the solution into 100,000 parts by weight of water and .: ~ ;
_ ~78394 o,z. 30,364 uniformly distributing it therein, an aqueous dispersion i8 ob- ;
tained containing 0.02% by weight of the active ingredient.
; E X A M P I. E 8 20 parts by weight of the compound of Example 3 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone~
30 parts by weight of isobutanol, 20 parts of weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aque-ous dispersion ia~obtained containing 0.02% by weight o~ the active ingredient.
20 parts by weight of compound I is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles . .
of ethylene oxide to 1 mole of castor oil. By pouring the solu-tion into 100,000 parts by weight of water and uniformly dis-tributin~ it therein, an aqueous dispersion is obtained contain-ing 0.02% by weight of the active ingredient.
20 parts by weight of compound II is well mixed with 3 parts ~ by weight of the sodium salt of diisobutylnaphthalene- ~ -sulfonic ; acie, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uni-formly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.
O.Z. 30,364 3 parts by weight of compound I is intimately mixed with 97 ~
parts by weight of particulate kaolin. A dust is obtained containing , 3% by weight of the active ingredient.
30 parts by weight of compound II is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
E X A ~ P L E 13 In the greenhouse, various plants were treated at a growth -height of from 4 to 18 cm with the following amounts of the follo-wing individual active ingredients and compositions thereof as emul-sions:
I 1,2-d~methyl-4-bromo-3,5-diphenylpyrazolium methyl sulfate, 0.75 kg/ha II 1,2,4-trimethyl-3,5-diphenylpyrazolium methyl sulfate, 0.75 kg/ha IV adduct of 6 to 7 moles of ethylene oxide to 1 mole of isooctyl-phenol (spreader-sticker), 2 kg/ha I+II and II+IV, each at a rate of 0.75+2 kg/ha.
After 3 to 4 week~ it was ascertained that the compositions I+IV and II+IV had a better herbicidal action than I and II when used singly, combined with the same crop plant compatibility~
`` ~8394 o.z. 30,364 The results are given below: ' Active ingredient I II IVI+IV II+IV
kg/ha 0,75 0.75 20.75+2 0.75+2 Crop plants:
Triticum aestivum 0 0 0 0 0 Hordeum vulgare 0 0 0 0 0 Secale cereale 0 0 0 0 0 Unwanted plant:
Avena fatua 55 60 0 90 90 .;~
0 = no damage 100 = complete destruction '~ .
In the greenhouse, various plants were treated at a growth height of from 6 to 20 cm with the following amounts of the following active ingredients, each being emulsified in 500 liters of water per hectare: ~-I 1,2-dimethyl-3,4-diphenylpyrazolium methyl sulfate + IV, 1.0 ~ l.Q kg/ha : II 1,2-dimethyl-4-methoxy-3,5-diphenylpyrazolium methyl sulfate + IVg 1.0 + 1.0 kg/ha 10 IV adduct of 6 to 7 moles of ethylene oxide to 1 mole of isooctyl- :
phenol, 1.0 and 2.0 kg/ha.
After 2 to 3 weeks it was ascertained that the active ingre-dients had a good action on wild oats, cobined with good grop plant compatibility.
~ .
, ~ - 21 -. ~ - .
,, :
1~78394 O.Z. 30,364 ; !
The results are given below:
Active ingredient I+IV II+VI IV
kg/ha l.0+1.0 l.0+1.0 1.0 2.0 :
Crop plants:
Hordeum vulgare 0 0 0 0 Triticum aestivum 0 0 0 0 Secale cereale 0 0 0 0 Unwanted pIant:
Avena fatua 85 80 0 0 0 = no damage ~00 = complete destruction The following compounds have the same biological action:
1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium trifluoromethyl sulfate 1,2-dimethyl-4-methyl-3,5-diphenylpyrazolium trifluoromethyl sulfate 1-methoxy-2-methyl-3,5-diphenylpyrazolium methyl sulfate.
The active ingredients I 1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium methyl julfate II 1,2,4-trimethyl-3,5-diphenylpyrazolium methyl sulfate III 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate (comparative agent) were sprayed on various plants in amounts of 1.5 kg/ha dispersed or emulsified in 500 liters of water per hectare. The growth height of the plants was from 5 to 15 cm.
After 4 weeks it was ascertained that the herbicidal action of I and II w~s superior to that of III.
~ ~- 1078394 o.z. 30,364 The results are given below:
Active ingredient I II III
kg/ha 1.5 1.5 1.5 __ Unwanted plants:
Cyperus difformis 60 60 50 Cyperus esculentus 55 65 50 Cynodon dactylon 40 50 30 Digitaria sanguinalis 65 70 60 Echinochloa crus-galli 50 60 40 Panicum virgatum 40 40 30 Sorghum halepense 45 40 25 0 = no damage 100 - complete destruction .
"
,. .
. .
. - 23 -
It is known (German Laid-Open Application DOS 2,260,485) to use pyrazolium salts, especially l,2-dimethyl-3,5-diphenyl-pyrazolium methyl sulfate, as herbicides. However, their herhicidal action is not always satisfactory.
We have now found that pyrazolium salts of the formula 10 ' _ r ~
~. ~
.
~ where X denotes an anion and D denotes~identical or different ; lower alkyl radicals, and .~ :
- a) C denotes hydrogen, lower alkyl, halogen or lower alkoxy, A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, and B denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or b) B denotes halogen or lower alkoxy, A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, and C denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or c) C denotes hydrogen, lower alkyl, lower alkoxy or halogen, A denotes hydrogen, lower alkyl, lower alkoxy or halogen, and B denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or ?
':
d) C denotes hydroyen~ lower alkyl~ lower alkoxy or halo~en, B denotes hydrogen, lower alkyl, lower alkoxy or halogen and A denotes unsubs-tituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or e) A, B and C simultaneously denote identical or different halogen radicals, have a strong, and particularly selective, herbicidal action.
Examples of lower alkyl groups are methyl, ethyl, n-propyl, isopropyl and tert-butyl, and examples of lower alkoxy ; 10 substituents are methoxy, ethoxy, n-propoxy, isopropoxy and tert-butoxy.
Examples of halogens are chlorine, bromine and iodine.
Anions are for example the anions of the following salts:
halides, e.g., chlorides and bromides; sulfates, hydrosulfates; r perchlorates, lower alkyl sulfates, e.g., methyl sulfate, lower ,~ alkane sulfonates, substituted benzene sulfonates, aminosulfona-tes and alkylaminosulfonates.
The pyrazoles used as starting materials for the preparation of the pyrazolium salts may be prepared by either 20 condensing a 1,2-dicarbonyl compound in accordance with the i~ following schemes with an alkyl hydrazine, or by alkylating it, ; after reaction with hydrazine hydrate, with an alkylating agent such as a dialkyl sulfate or an alkyl halide to give l-alkylpyrazole, ' A, B, C and D having the above meanings except that A, C and advantageously B are neither halogen nor alkoxy:
.: .
~ ~ 2 -`"" 1~78394 ~ ' :
B
A C ~ CH C ~ C NH 2 -N~l-D A~,C
~ D
or ¦~N 2H 4 , r 1 0 A~,~C
'i ' ~ :'' or N N D~ C
, H ~ --N
~, D
~j .
;,~, '.:
':
- 2a -, ~ .
. . ' , ' ' , ,: , ~ ,, ~.
~078394 In the case of l-H or l-alkylpyrazoles, hydrogen may be replaced by halogen in A or B, A and B, or A,B and C by adding elementary halogen, e.g., chlorine, bromine and iodine, if desired in the presence of catalytic amounts of Lewis acids, e.g., iron (III) bromide and aluminum (III) chloride, or by the action of halo-genating agents, e.g., sulfuryl chloride.
The halogenation reactions are carried out in conventional solvents such as methylene chloride, chloroform, carbon tetra-chloride, ethers and lower organic carboxylic acids.
The l-alkylpyrazoles are quaternized by reaction with at least one mole equivalent of an alkylating agent in known manner .j', , ;~ at temperatures of from 30 to 150C. Suitable alkylating agents are the ones usually employed for this purpose, e.g. lower alkyl halides such as methyl iodide, or lower alkyl sulfates such as diethyl sulfate. The reaction may also be carried out in aprotic ~ !
solvents, e.g., chlorinated, aliphatic or aromatic hydrocarbons or ketones.
The quaternary pyrazolium salts are usually obtained in crystalline form. In reactions with alkylating agents in the absence of solvents it may at times be advantageous to fully crystallize the crude products by stirring them with lower ketones or suitable mixtures of lower alcohols or ethers.
If the anion of the pyrazolium salt is to be different from that provided by the alkylating agent, it may be replaced by means of ion exchange resins.
PREPARATION OF THE STARTING COMPOUNDS
A) l-methyl-3,4-(4,5)-_iphenYl~ zole At 25 C, 84 parts (by weight) of methyl hydrazine was dripped under nitrogen into 183 parts of -formyl deoxybenzoin in 1,000 parts of isopropynol. The mixture was stirred for 2 hours at 25C and boiled for 1 hour under reflux. After evaporation of the solvent in vacuo, the residue was distilled. Theze was obtained 127 parts of 1-methyl-3,4-(4,5)-diphenylpyrazole at 182 C
.
`` 1078394 186C/0.3 mm.
B) l-methyl-4-bromo-3,5-diphenylpyrazole -~
At room temperature and over a period of 3 hours, a solution of 103 parts of bromine in 100 parts of chloroform was dripped into a solution of 150 parts of 1-methyl-3,5-diphenyl-pyrazole in 900 parts of chloroform. The mixture was then stir-red for a further 2 hours. After removal of the solvent in vacuo, recrystallization from ethanol gave 160 parts of the desired product; m.p.: 111 to 112 C.
'.' ,10 C) 1~
At 80 to 85C, 9 parts of methyl hydrazine was dripped into a solution of 23 parts of l,l-dibenzoylethane in lOO parts of isopropanol, and the mixture heated for 2 hours under reflux.
After coolin~, 21 parts of the desired product having a melting point of 108 to 109 C was obtained.
D) l-methYl-3~4,5-tribromopYrazole 45.5 parts of 3,4,5-tribromopyrazole was introduced into 26.3 parts of a 30% (by weight) sodium methylate solution in methanol; 17 parts of methanol was then added. Subsequently, 27.6 parts of methyl iodide was added and the mixture stirred at 50C until it had a neutral reaction. The precipitated sodium iodide was removed by suction filtration, and the filtrate was concentrated in vacuo, suction filtered and washed with water.
42 pa`rts of the desired product was obtained; m.p.: 86 to 87C.
E X A M P L E
1,2-dimethYl-3,4-diphenylEyrazolium methYl sulfate 90 parts of 1-methyl-3,4-(4,5)-diphenylpyrazole was dissolved in 400 parts of dry and warm xylene. 50.7 parts of dimethyl sulfate was then dripped in and the mixture stirred for 8 hours at 105 to 110C. The xylene upper phase was decanted and the residue stirred with dry acetone until all has crystallized. After suction filtration and drying, 82 parts of the desired product was obtained; m.p.: 153 to 154 C.
10783~4 o.z. 30,364 1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium methyl sulfate A mixture of 63 parts of 1-methyl-4-bromo-3,5-diphenylpyrazole and 33,6 parts of dimethyl sulfate was stirred for 2 hours at 150C. The crude product was cooled, pasted with dry acetone and suction filtered. After dissolution in ethanol and precipita-tion with ether, 60 parts of the desired product melting at ` 164 to 165C was obtained.
1,2,4-trimethyl-3 5-diphenylpyrazolium methyl sulfate 20.4 parts of 1,4-dimethyl-3,5-diphenylpyrazole was dissolved at 60 to 65C in 100 parts of dry xylene. 10.8 parts of dimethyl sulfate in 15 parts of dry xylene was added and the mixture stirred for 8 hours at 105 to 110C. The mixutre was then cooled, the upper xylene phase was decanted and the residue stirred with dry ~ acetone. Suction filtration gave 14.2 parts of the desired product;
3 m.p. 86 to 88C.
1,2-dimethyl-3,4,5-tribromopyrazolium methyl _ulfate 20 parts o~ 1-methyl-3,4,5-tribromopyrazole was mixed with 10.4 parts of dimethyl sulfate and stirred for 3 hours at 105 to 110C. After cooling, the crystalline residue was stirred with 150 parts of dry acetone. Suction filtration ga~e 19 parts of the desired product;
m.p.: 210C.
The following compounds for instance may be prepared analogous-ly: :
1,2-dimethyl-3-phenyl-4-bromo-5-chloropyrazolium methyl sulfate (m.p.: 200 to 201C) 1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium perchlorate (m.p O 300 to 302C) 1,2-dimethyl-4-bromo-3-phenyl-5-p-chlorophenylpyrazolium methyl sulfate O.Z. 30,364 1,2-dimethyl-3-bromo-4,5-diphenylpyrazolium methyl sulfate (m.p.: 128 to 130C) 1,2-dimethyl-4-methoxy-3,5-diphenylpyrazolium methyl sulfate characteristic infrared bands at 2850, 1230, 1060, 1010 cm 1,2-dimethyl-3,4-dichloro-5-phenylpyrazolium methyl sulfate 1,2-dimethyl-4-chloro-3,5-diphenylpyrazolium methyl sulfate (m.p.: 135 to 136C) 1,2,4-trimethyl-3,5-diphenylpyrazolium trifluoromethyl sulfonate (m.p.: 128 to 130~C) 1,2-dimethyl-4-ethyl-3,5-diphenylpyrazolium methyl sulfate (m.p.: 130 to 132C) 1,2-dimethyl-4-n-propyl-3,5-diphenylpyrazolium methyl sulfate (m.p.: 122 to 124C).
The compounds have a strong herbicidal action and may therefore be used as weedkillers or for controlling the growth of unwanted plants. Whether the new active ingredients are used as -total or selective agents depends in essence on the amount of in-gredient used per unit area.
By weeds and unwanted plant growth are meant all monocotyledonous and dicotyledonous plants which grow in loci where they are not desired.
Thus, the present invention also relates to a process for controlling the growth of unwanted plants, wherein the plants or the soil are treated with a herbicidally effective amount of a compound of the formula C 1 ~
N-N
D D X
where X denotes an anion and D denotes identical or different lower alkyl radicals, and ., i,, 1078394 o. æ . 30, 364 a) C denotes hydrogen, lower alk.yl, halogen or lower alkoxy, A denotes unsubstituted pheny; or phenyl substituted by lower alkyl, lower alkoxy or halogen, and B denotes unsub-'! stituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen or b) B denotes methyl,-halogen or lower alkoxy, A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, and C denotes unsub-stituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or c) C deno*es hydrogen, lower alkyl, lower alkoxy or halogen, A denotes hydrogen, lower alkyl, lower alkoxy, or halogen, - and B denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or d) C denotes hydrogen, lo~Jer alkyl, lower alkoxy or halogen, B denotes hydrogen, lower alkyl, lower alkoxy or halogen and A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or e) A, B and C simultaneously denote identical or different halogen radicals.
: The agents according to the invention may therefore be used for controlling for instance Gramineae,such as Cynodon spp. - Dactylis spp.
Digitaria spp. Avena spp.
Echinochloa spp. Bromus spp.
Setaria spp. ` Uniola spp.
Panicum spp. Poa spp.
Alopecurus spp. Leptochloa spp.
Lolium spp. Brachiaria spp.
Sorghum spp. Eleusine spp.
Agropyron spp. Cenchrus spp.
; - 6a -' ' ~ ~078394 o. z . 30,~64 Phalaris spp. Eragrostis spp.
Apera spp. Phragmites communis etc.;
Cyperaceae, such as Carex spp. Eleocharis spp.
Cyperus spp. Scirpus spp.
etc.;
dicotyledonous weeds, such as ~ Malvaceae, e~g.
., 10 Abutilon theoprasti Hibiscus spp.
Sida spp. Malva spp.
etc~;
Compositae, such as Ambrosia spp. Centaurea spp.
Lactuca spp. Tussilago spp.
Senecio spp. Lapsana communis Sonchus spp. Tagetes spp.
Xanthium app. Erigeron spp.
Iva spp. Anthemis 8pp.
Galinsoga spp. Matricaria spp.
Taraxacum spp. Artimisia spp.
Chry~anth~mum spp. Bidens 9pp.
Cirsium spp. etc.;
Convolvulaceae, such as Convolvulus spp. Cuscuta spp.
Ipomoea spp. Jaquemontia tamnifolia etc.;
Cruciferae, such as Barbarea vulgaris Arabidopsis thaliana Brassica spp. Descurainia spp.
Capsella spp. Draba spp.
. . . ..... . .. - . .
~78394 Z. 30,364 3isymbrium spp. Coronopus didymus ; Thlaspi spp. Lepidium spp.
Sinapis arvensis Raphanus spp.
etc.;
, ~ -Geraniaceae, such as 1 Erodium spp. Geranium spp.
etc.;
, Portulacaceae, such as Portulaca sppO etc.;
Primulaceae, such as Anagallis arvensis Lysimachia spp.
etc.;
Rubiaceae, such as Richardia spp. Diodia spp.
Galium spp. etc.;
Scrophulariaceae, such as Linaria spp. Digitali~ spp.
Veronica spp. etc.;
Solanaceae, such as Physalis spp. Nicandra spp.
Solanum spp. Datura spp.
etc.;
Urticaceae, such as Urtica spp.
Violaceae, such as Viola spp. etc.;
Zygophyllaceae, such as Tribulus terrestris etc.;
Euphorbiaceae, such as Mercurialis annua Euphorbia spp.
Umbelliferae, such as Daucus carota Ammi majus Aethusa cynapium etc.;
, . .. . ~ . .: . ,.... ,. . :
Commelinaceae, such as Commelina spp. etc.;
Labiatae, such as Lamium spp. Galeopsis spp.
etc.;
Leguminosae, such as Medicago spp. Sesbania exaltata Trifolium spp. Cassia spp.
Vicia spp. Lathyrus spp.
etc.;
Plantaginaceae, such as Plantago spp. etc.;
Polygonaceae, such as Polygonum spp. Fagopyrum spp.
Rumex spp. etc.;
Aizoaceae, such as Mollugo verticillata etc.;
Amaranthaceae, such as Amaranthus spp. etc.;
Boraginaceae, such as Amsinckia spp. Anchusa spp.
Myostis spp. Lithospermum spp.
etc.;
Caryophyllaceae, such as Stellaria spp. Silene spp.
Spergula spp. ~erastium spp.
Saponaria spp. Agrostemma githago Scleranthus annuus etc.; ' Chenopodiaceae, such as Chenopodium spp. Atriplex spp.
Kochia spp. Monolepsis nuttalliana Salsola Kali etc.;
: ~:
~78394 o.z. 30,364 Lythraceae, such as Cuphea spp. etc.;
Oxalidaceae, such as ~, Oxalis spp.
Ranunculaceae, such as Ranunculus spp. Adonis spp.
Delphinium spp. etc.;
Papaveraceae, such as Papaver spp. Fumaria offinicalis etc.;
Onagraceae, such as Jussiaea 9pp. etc.;
Rosaceae, such as Alchemillia spp. Potentilla spp.
etcO;
Potamogetonaceae, such as Potamogeton spp. etc.;
' Najadaceae, such as Najas spp, etc.;
Equisetaceae Equisetum spp. etc.;
~' Marsileaceae, such as Marsilea quadrifolia etc.;
Polypodiaceae, Pteridium quilinum Alismataceae, such as Alisma spp. Sagittaria sagittifolia etc, The herbicides according to the invention may be employed in cereal crops such as Avena spp. Sorghum Triticum spp. Zea mays ` 1~78394 o.z. 30,364 Hordeum spp. Panicum miliaceum Secale spp. Oryza spp.
; Saccharum offinicarum and in dicotyledon crops such as Cruciferae, e.g.
Brassica spp. Raphanus sppt Sinapis spp. Lepidium spp, Compositae, e.g.
Lactuca spp. Carthamus spp.
Helianthus spp. Scorzonera spp.
Malvaceae, eOg.
Gossypium hirsutum Leguminosae, e.g.
Medicago spp. Phaseolus spp.
Trifolium spp. Arachis spp.
Pisum spp. Glycine max.
Chenopodiaceae, e.g.
Beta vulgaris Spinaoia spp. ' Solanaceae, eOg.
Solanum spp. Capsicum annuum Nicotiania spp.
Linaceae, e.g.
Linum spp.
Umbelliferae, e.g.
Petroselinum spp. Apium graveolens Daucus carota Rosaceae, e.g. Fragaria Cucurbitaceae, e.g.
Cucumis spp. Cucurbita spp.
Liliaceae, e.g.
Allium spp.
Vitaceae, e.g.
Vitis vinifera Bromeliaceae, e.g.
Ananas sativus.
The amount used of the agents according to the invention may vary and depends in essence on the type of effect to be achieved; it is generally from 0.1 to 15 (and more~, preferably from 0.2 to 6, kg per hectare of active ingredient. The agents according to the invention may be used once or several times before or after planting, before sowing, and before, during or after emergence of the crop plants and unwanted plants.
Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc. and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene,xylene, paraffin, tetrahydronaphthalene, alkyl-ated naphthalenes and their derivatives such as methonal, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chloro~enzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, ~-methyl-pyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion concen-tratesj pastes, oil dispersions or wettable powders by adding water.
To prepare emulsions, pastes andoil dispersions the ingredients as such or dissolved in an oil or solventmay be homogenized in water ~78394 o.z. 30,364 by means of wetting or dispersing agents, adherents or emulsi-fiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emul-sifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are; alkali metal, alkaline earth metal and ammonium salts of ligninsuifonic acid, naphthalene-sulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfa~ed fatty alcohol glycol ether, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and form-aldehyde~ polyoxyethylene octylphenol ethers, ethoxylated isooctyl-phenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkyl-phenol polyglycol ethers, tributylphenyl polyglycol ethers~ alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryi alcohol polyglycol ether acetal, sorbitol esters~ lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers.
Examples of solid carriers are mineral earths such as silica gel, silicic acid, silica gels, silicates, talc, kaolin, Attaclay, lime-stone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth,calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, 1~78394 .Z. 30,364 barK meal, wood meal, and nutshell meal, cellulosic powders, etc. , The formulations contain from 0.1 to 95, and preferably 0.5 to 90% by weight of active ingredient.
There may be added to the compositions or individual active in~redients (if desired, immediately before use (tar.kmix)) oils of various types, herbicides, fungicides, nematocides, insectici-des, bactericides7 trace elements, fertilizers, antifoams (e.g., silicones), growth regulators, antidotes and other herbicidally effective compounds such as substituted anilines substituted aryloxycarboxylic acids and salts, esters and amides thereof, substituted ethers ^
substituted arsonic acids and their salts, esters and amides substituted benzimidazoles substituted benzisothiazoles substituted benzothiadiazinone dioxides substituted benzoxazines substituted benzoxazinones substituted benzothiadiazoles substituted biurets substituted quinolines substituted carbamates substituted aliphatic carboxylic acids and their salts, esters and amides substituted aromatic carboxylic acids and their salts, esters and amides substituted carbamoylalkylthiol- or -dithiophosphates substituted quinazolines substituted cycloalkylamidocarbothiolic acids and their salts, esters and amides -~78394 o,z. 30,364 substituted cycloalkylcarbonamidothiazoles substituted dicarboxylic acids and their salts, esters and amides substituted dihydrobenzofuranyl sulfonates substituted disulfides substituted dipyridylium salts substituted dithiocarbamates substituted dithiophosphoric acids and their salts, esters and amides substituted ureas substituted hexahydro-lH-carbothioates substituted hydantoins substituted hydrazides substituted hydrazonium salts :~
substituted isoxazole pyrimidones substituted imidazoles substituted isothiazole pyrimidones substituted ketones substituted naphthoquinones substituted aliphatic nitriles substituted aromatic nitriles substituted oxadiazoles substituted oxadiazinones substituted oxadiazolidine diones substituted oxadiazine diones :
substituted phenols and their salt~ and esters substituted phosphonic acids and their salts, esters and amides substituted phosphonium chlorides substituted phosphonalkyl glycines substituted phosphites substituted phosphoric acids and their salts, ester and amides substituted piperidines substituted pyrazoles ~ 8394 O.Z. 30,364 substituted pyrazole alkylcarboxylic acids and their salts, esters and amides substituted pyrazolium salts substituted pyrazolium alkyl sulfates substituted pyridazines substituted pyridazones substituted pyridine carboxylic acids and their salts, esters and amides substituted pyridines substituted pyridine carboxylates subestituted pyridinones substituted pyrimidines substituted pyrimidones substituted pyrrolidine carboxylic acid and its salts, esters and amides substituted pyrrolidines ; substituted pyrrolidones substituted arylsulfonic acids and their salts, esters and amides substituted styrenes substituted tetrahydrooxadiazine diones substituted tetrahydroxadiazole diones substituted tetrahydromethanoindenes substituted tetrahydroxadiazole thiones substituted tetrahydrothiadiazine thiones substituted tetrahydrothiadiazole diones substituted aromatic thiocarbonylamides substituted thiocarboxylic acids and their salts, esters and amides substituted thiol carbamates ~ubstituted thioureas substituted thiophosphoric acids and their salts, esters and amides O.Z. 30,364 substituted triazinessubstituted triazoles substituted uracils, and substitu~ed uretidine diones.
The last-mentioned herbicidal compounds may also be applied before or after the active ingredients or compositions thereof according to the invention.
These agents may be added to the herbicides according to the invention in a ratio by weight of from 1:10 to 10:1. The same applies to oils, fungicides, nematocides, insecticides, bac-: tericides, antidotes and growth regulators.
. E X A M P L E 5 In the greenhouse the plants listed below were treated at a growth height of from 4 to 18 cm with 1.0 and 2 kg per hectare of each of the following active ingredients, each being dispersed or emulsified in 500 liters of water per hectare:
1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium methyl sulfate II 1,2,4-trimethyl-3,5-diphenylpyrazolium methyl sulfate IV 1,2-dimethyl-3,5-diphenyl-4-bromopyrazolium perchlorate III 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate (prior art compound used for comparison purposes) ~
After 3 to 4 weeks it was ascertained that active ingredients :-I, II and IV had better crop plant compatibility and a better her-bicidal action than compound III.
The results are given below:
Active ingredient I II III IV
kg/ha 1.0 2.0 1.0 2.0 1.0 2.01.0 2.
Crop plants:
Triticum aestivum o o 0 n lo 25 0 0 Hordeum vulgare o 0 0 0 20 30 0 0 Secale cereale o 0 0 0 20 35 0 0 -Beta vulgaris 0 10 0 0 20 30 0 0 Brassica napus o 5 0 5 0 10 0 0 10 Unwanted plant: -Avena fatua 90 100 85 100 75 95 90 100 0 ~ no damage 100 = complete destruction The action of 1,2-dimethyl-3,4-diphenylpyrazolium methyl sulfate, 1,2-dimethyl-3,5-diphenyl-4-chloropyrazolium methyl sulfate and 1,2-dimethyl~3,4,5-tribromopyrazolium methyo sulfate corresponds to that of I, II and IV above.
90 parts by weight of the compound of Example 1 is mixed with 10 parts by weight of N-methyl-~-pyrrolidone. A mixture ` is obtained which is suitable for application in the form ofvery fine drops.
20 parts by weight of the compound of Example 2 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole ofcastor oil.
By pouring the solution into 100,000 parts by weight of water and .: ~ ;
_ ~78394 o,z. 30,364 uniformly distributing it therein, an aqueous dispersion i8 ob- ;
tained containing 0.02% by weight of the active ingredient.
; E X A M P I. E 8 20 parts by weight of the compound of Example 3 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone~
30 parts by weight of isobutanol, 20 parts of weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aque-ous dispersion ia~obtained containing 0.02% by weight o~ the active ingredient.
20 parts by weight of compound I is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles . .
of ethylene oxide to 1 mole of castor oil. By pouring the solu-tion into 100,000 parts by weight of water and uniformly dis-tributin~ it therein, an aqueous dispersion is obtained contain-ing 0.02% by weight of the active ingredient.
20 parts by weight of compound II is well mixed with 3 parts ~ by weight of the sodium salt of diisobutylnaphthalene- ~ -sulfonic ; acie, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uni-formly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.
O.Z. 30,364 3 parts by weight of compound I is intimately mixed with 97 ~
parts by weight of particulate kaolin. A dust is obtained containing , 3% by weight of the active ingredient.
30 parts by weight of compound II is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
E X A ~ P L E 13 In the greenhouse, various plants were treated at a growth -height of from 4 to 18 cm with the following amounts of the follo-wing individual active ingredients and compositions thereof as emul-sions:
I 1,2-d~methyl-4-bromo-3,5-diphenylpyrazolium methyl sulfate, 0.75 kg/ha II 1,2,4-trimethyl-3,5-diphenylpyrazolium methyl sulfate, 0.75 kg/ha IV adduct of 6 to 7 moles of ethylene oxide to 1 mole of isooctyl-phenol (spreader-sticker), 2 kg/ha I+II and II+IV, each at a rate of 0.75+2 kg/ha.
After 3 to 4 week~ it was ascertained that the compositions I+IV and II+IV had a better herbicidal action than I and II when used singly, combined with the same crop plant compatibility~
`` ~8394 o.z. 30,364 The results are given below: ' Active ingredient I II IVI+IV II+IV
kg/ha 0,75 0.75 20.75+2 0.75+2 Crop plants:
Triticum aestivum 0 0 0 0 0 Hordeum vulgare 0 0 0 0 0 Secale cereale 0 0 0 0 0 Unwanted plant:
Avena fatua 55 60 0 90 90 .;~
0 = no damage 100 = complete destruction '~ .
In the greenhouse, various plants were treated at a growth height of from 6 to 20 cm with the following amounts of the following active ingredients, each being emulsified in 500 liters of water per hectare: ~-I 1,2-dimethyl-3,4-diphenylpyrazolium methyl sulfate + IV, 1.0 ~ l.Q kg/ha : II 1,2-dimethyl-4-methoxy-3,5-diphenylpyrazolium methyl sulfate + IVg 1.0 + 1.0 kg/ha 10 IV adduct of 6 to 7 moles of ethylene oxide to 1 mole of isooctyl- :
phenol, 1.0 and 2.0 kg/ha.
After 2 to 3 weeks it was ascertained that the active ingre-dients had a good action on wild oats, cobined with good grop plant compatibility.
~ .
, ~ - 21 -. ~ - .
,, :
1~78394 O.Z. 30,364 ; !
The results are given below:
Active ingredient I+IV II+VI IV
kg/ha l.0+1.0 l.0+1.0 1.0 2.0 :
Crop plants:
Hordeum vulgare 0 0 0 0 Triticum aestivum 0 0 0 0 Secale cereale 0 0 0 0 Unwanted pIant:
Avena fatua 85 80 0 0 0 = no damage ~00 = complete destruction The following compounds have the same biological action:
1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium trifluoromethyl sulfate 1,2-dimethyl-4-methyl-3,5-diphenylpyrazolium trifluoromethyl sulfate 1-methoxy-2-methyl-3,5-diphenylpyrazolium methyl sulfate.
The active ingredients I 1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium methyl julfate II 1,2,4-trimethyl-3,5-diphenylpyrazolium methyl sulfate III 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate (comparative agent) were sprayed on various plants in amounts of 1.5 kg/ha dispersed or emulsified in 500 liters of water per hectare. The growth height of the plants was from 5 to 15 cm.
After 4 weeks it was ascertained that the herbicidal action of I and II w~s superior to that of III.
~ ~- 1078394 o.z. 30,364 The results are given below:
Active ingredient I II III
kg/ha 1.5 1.5 1.5 __ Unwanted plants:
Cyperus difformis 60 60 50 Cyperus esculentus 55 65 50 Cynodon dactylon 40 50 30 Digitaria sanguinalis 65 70 60 Echinochloa crus-galli 50 60 40 Panicum virgatum 40 40 30 Sorghum halepense 45 40 25 0 = no damage 100 - complete destruction .
"
,. .
. .
. - 23 -
Claims (8)
1. A pyrazolium salt of the formula , where X denotes an anion and D denotes identical or different lower alkyl radicals, and a) C denotes hydrogen, lower alkyl, halogen or lower alkoxy, A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, and B denotes unsubs-tituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or b) B denotes halogen or lower alkoxy, A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, and C denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or c) C denotes hydrogen, lower alkyl, lower alkoxy or halogen, A denotes hydrogen, lower alkyl, lower alkoxy or halogen, and B denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or d) C denotes hydrogen, lower alkyl, lower alkoxy or halogen, B denotes hydrogen, lower alkyl, lower alkoxy or halogen and A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or e) A, B and C simultaneously denote identical or different halogen radicals.
2. 1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium methyl sulfate.
3. 1,2-dimethyl-3,4-diphenylpyrazolium methyl sulfate.
4. 1,2-dimethyl-4-methoxy-3,5-diphenylpyrazolium methyl sulfate.
5. A process for controlling the growth of unwanted plants, wherein the plants or the soil are treated with a herbicidally effective amount of a compound of the formula , whereX denotes an anion and D denotes identical or different lower alkyl radicals,and a) C denotes hydrogen, lower alkyl, halogen or lower alkoxy, A denotes unsubstituted phenyl of phenyl substituted by lower alkyl, lower alkoxy or halogen, and B denotes unsub-stituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or b) B denotes halogen or lower alkoxy, A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, and C denotes unsub-stituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or c) C denotes hydrogen, lower alkyl, lower alkoxy or halogen, A denotes hydrogen, lower alkyl, lower alkoxy or halogen, and B denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or d) C denotes hydrogen, lower alkyl, lower alkoxy or halogen, B denotes hydrogen, lower alkyl, lower alkoxy or halogen and A denotes unsubstituted phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen, or e) A, B and C simultaneously denote identical or different halogen radicals.
6. A process as claimed in claim 5, wherein the pro-cess is carried out using the compound 1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium methyl sulfate.
7. A process as claimed in claim 5, wherein the process is carried out using the compound 1,2-dimethyl-3,4-diphenylpyrazolium methyl sulfate.
8. A process as claimed in claim 5, wherein the process is carried out using the compound 1,2-dimethyl-4-methoxy-3,5-diphenylpyrazolium methyl sulfate.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2404795A DE2404795C2 (en) | 1974-02-01 | 1974-02-01 | 1,2-Dimethyl-3,5-diphenylpyrazolium salts and their use as herbicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1078394A true CA1078394A (en) | 1980-05-27 |
Family
ID=5906314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA218,846A Expired CA1078394A (en) | 1974-02-01 | 1975-01-28 | Pyrazolium salts |
Country Status (23)
| Country | Link |
|---|---|
| JP (1) | JPS5826323B2 (en) |
| AT (1) | AT340197B (en) |
| BE (1) | BE825071A (en) |
| BR (1) | BR7500579A (en) |
| CA (1) | CA1078394A (en) |
| CH (1) | CH613605A5 (en) |
| CS (1) | CS185671B2 (en) |
| DD (1) | DD117335A5 (en) |
| DE (1) | DE2404795C2 (en) |
| DK (1) | DK137423C (en) |
| ES (1) | ES434312A1 (en) |
| FR (1) | FR2259828B1 (en) |
| GB (1) | GB1486984A (en) |
| HU (1) | HU171225B (en) |
| IL (1) | IL46490A (en) |
| IT (1) | IT1044116B (en) |
| LU (1) | LU71764A1 (en) |
| NL (1) | NL180008C (en) |
| NO (1) | NO750266L (en) |
| PL (1) | PL96751B1 (en) |
| SE (1) | SE7501113L (en) |
| SU (1) | SU545242A3 (en) |
| ZA (1) | ZA75654B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3963742A (en) | 1974-07-12 | 1976-06-15 | American Cyanamid Company | 1,2-Dialkyl-3,4,5-trisubstituted pyrazolium salts as herbicidal agents |
| IL49410A (en) * | 1975-05-02 | 1980-06-30 | American Cyanamid Co | Methods for control of undesirable plant species comprising the use of 3,5-diphenyl pyrazolinium derivatives,certain such derivatives,their preparation and their additional use as fungicides |
| US3963741A (en) * | 1975-05-02 | 1976-06-15 | American Cyanamid Company | 4-Alkyl-1,2-dimethyl-3,5-diphenylpyrazolium salts and derivatives thereof as fungicidal agents |
| US4041046A (en) | 1975-06-06 | 1977-08-09 | American Cyanamid Company | 1,2-Dialkyl-3,4,5-trisubstituted pyrazole compounds |
| DE2747531A1 (en) * | 1977-10-22 | 1979-04-26 | Basf Ag | SUBSTITUTED 3-AMINOPYRAZOLE |
| JPS61197954U (en) * | 1985-05-29 | 1986-12-10 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3158620A (en) * | 1962-06-12 | 1964-11-24 | American Cyanamid Co | Pyrazole compounds and process therefor |
| DE2260485C2 (en) * | 1971-12-17 | 1983-12-29 | American Cyanamid Co., Wayne, N.J. | 1,2-dialkyl-3,5-diphenylpyrazolium salts and herbicidal agents containing them |
| BE792801A (en) * | 1971-12-17 | 1973-06-15 | American Cyanamid Co | NEW HERBICIDE COMPOSITIONS |
| FR2179559A1 (en) * | 1972-04-12 | 1973-11-23 | Cetrane Laboratoire | Antiglycemiant compsns - contg 1,2-dialkyl-3-or4-aryl-3-pyrazolines |
-
1974
- 1974-02-01 DE DE2404795A patent/DE2404795C2/en not_active Expired
-
1975
- 1975-01-17 JP JP50007177A patent/JPS5826323B2/en not_active Expired
- 1975-01-22 IL IL46490A patent/IL46490A/en unknown
- 1975-01-28 CA CA218,846A patent/CA1078394A/en not_active Expired
- 1975-01-29 NL NLAANVRAGE7501049,A patent/NL180008C/en not_active IP Right Cessation
- 1975-01-29 CS CS7500000583A patent/CS185671B2/en unknown
- 1975-01-29 FR FR7502715A patent/FR2259828B1/fr not_active Expired
- 1975-01-29 NO NO750266A patent/NO750266L/no unknown
- 1975-01-29 BR BR579/75A patent/BR7500579A/en unknown
- 1975-01-30 LU LU71764A patent/LU71764A1/xx unknown
- 1975-01-30 HU HU75BA00003198A patent/HU171225B/en unknown
- 1975-01-30 CH CH108575A patent/CH613605A5/en not_active IP Right Cessation
- 1975-01-30 SU SU2102625A patent/SU545242A3/en active
- 1975-01-31 PL PL1975177717A patent/PL96751B1/en unknown
- 1975-01-31 GB GB4266/75A patent/GB1486984A/en not_active Expired
- 1975-01-31 DK DK33575A patent/DK137423C/en not_active IP Right Cessation
- 1975-01-31 BE BE152959A patent/BE825071A/en not_active IP Right Cessation
- 1975-01-31 ZA ZA00750654A patent/ZA75654B/en unknown
- 1975-01-31 AT AT71875A patent/AT340197B/en not_active IP Right Cessation
- 1975-01-31 SE SE7501113A patent/SE7501113L/xx unknown
- 1975-01-31 ES ES434312A patent/ES434312A1/en not_active Expired
- 1975-02-03 DD DD183972A patent/DD117335A5/xx unknown
- 1975-10-23 IT IT47953/75A patent/IT1044116B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CH613605A5 (en) | 1979-10-15 |
| DK33575A (en) | 1975-10-06 |
| NO750266L (en) | 1975-08-25 |
| AU7760775A (en) | 1976-07-29 |
| FR2259828A1 (en) | 1975-08-29 |
| LU71764A1 (en) | 1975-06-24 |
| SU545242A3 (en) | 1977-01-30 |
| IL46490A0 (en) | 1975-04-25 |
| CS185671B2 (en) | 1978-10-31 |
| AT340197B (en) | 1977-11-25 |
| IL46490A (en) | 1978-09-29 |
| GB1486984A (en) | 1977-09-28 |
| DE2404795A1 (en) | 1975-08-14 |
| DK137423B (en) | 1978-03-06 |
| NL180008B (en) | 1986-07-16 |
| IT1044116B (en) | 1980-03-20 |
| JPS5826323B2 (en) | 1983-06-02 |
| DK137423C (en) | 1978-08-14 |
| ES434312A1 (en) | 1976-11-16 |
| NL180008C (en) | 1986-12-16 |
| BR7500579A (en) | 1975-11-18 |
| SE7501113L (en) | 1975-08-04 |
| HU171225B (en) | 1977-12-28 |
| ATA71875A (en) | 1977-03-15 |
| DE2404795C2 (en) | 1983-03-24 |
| BE825071A (en) | 1975-07-31 |
| ZA75654B (en) | 1976-02-25 |
| FR2259828B1 (en) | 1979-05-25 |
| JPS50116642A (en) | 1975-09-12 |
| PL96751B1 (en) | 1978-01-31 |
| DD117335A5 (en) | 1976-01-12 |
| NL7501049A (en) | 1975-08-05 |
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