Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
`` 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
?
1078394
':
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
E X A M P L E 2
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.
E X A M P L E 3
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.
X A M P L E 4
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
1078394
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.;
-- 8 --
, . .. . ~ . .: . ,.... ,. . :
1078394
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
-- 10 --
` 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.
-- 11 --
1078394
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
-12-
~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,
- 13 -
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
- 14 -
-
~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
- 1
~ 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
- 16 -
8394
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.
- 17 -
1C978394
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.
E X A M P L E 6
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.
E X A M P L E 7
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
-18-
.: ~ ;
_ ~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.
E X A M P L E 9
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.
E X A M P L E 10
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.
- -- 19 --
-- 1078394
O.Z. 30,364
E X A M P L E 11
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.
E X A M P L E 12
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~
- 20 -
`` ~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
'~ .
E X A M P L E 14
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.
E X A M P L E 15
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.
- 22 -
~ ~- 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 -
