Note: Descriptions are shown in the official language in which they were submitted.
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Substituted N-cyano-amidines
The invention relates to novel substituted N-cyano-amidines, to a process for
their
preparation and to their use as herbicides.
It is already known that certain substituted N-cyano-guanidines have
herbicidal prop-
erties (cf. DE-A-2505301, US-A-4661520, US-A-4684398, US-A-4689348, J. Agric.
Food Chem. 37 (1989), 809-814). However, various aspects of the properties of
the
substituted N-cyano-guanidines of the prior art do not meet the high
requirements for
modern crop treatment agents.
This invention now provides the novel substituted N-cyano-amidines of the
general
formula (I),
R2
R' N ~
H
N (I)
RCN
in which
R' represents hydrogen or represents in each case optionally substituted
alkyl,
alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl, aryl or arylalkyl and
RZ represents in each case benzo-fused, pyrido-fused or t:hieno-fused cyclo-
alk(en)yl, oxacycloalk(en)yl or thiacycloalk(en)yl, where all cyclic and
hetero-
cyclic groupings may be substituted.
The general formula (I) includes the E and Z configuration isomers which are
possible
in each case.
In the definitions, the hydrocarbon chains, such as alkyl, alkenyl or alkinyl,
are in each
case straight-chain or branched.
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Preferred substituents of the radicals listed in the formulae mentioned above
and be-
low are illustrated below.
Rl preferably represents hydrogen, represents optionally cyano-, halogen-,
C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulphinyl- or C1-C4-alkyl-
sulphonyl-substituted alkyl having 1 to 6 carbon atoms, represents in each
case
optionally halogen-substituted alkenyl or alkinyl having in each case 2 to 6
carbon atoms, represents in each case optionally cyano-, halogen- or C1-C4-
alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6
carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in
the alkyl moiety, or represents in each case optionally nitro-, cyano-,
halogen-,
CI-C4-alkyl-, C1-C4-halogenoalkyl-, C~-C4-alkoxy- or C1-C:4-halogenoalkoxy-
substituted aryl or arylalkyl having in each case 6 or 10 carbon atoms in the
aryl groups and optionally 1 to 4 carbon atoms in the alkyl moiety.
R2 preferably represents in each case benzo-fused, pyrido-fused or thieno-
fused
cycloalk(en)yl, oxacycloalk(en)yl or thiacycloalk(en)yl from the list below,
/ /
O ~ S N~
I/ I/ I/ I/
,v
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\
\ / / \ / ~
s. \ s
s
s ~ \ /
where all cyclic and heterocyclic groupings may preferably be substituted by
one of the groupings listed below:
nitro, hydroxyl, amino, cyano, carbamoyl, thiocarbamoyl, formylamino, halo-
gen, C1-CQ-alkyl, C1-C4-halogenoalkyl, C1-CQ-alkoxy, C~-C4-halogenoalkoxy,
C,-C4-alkylthio, C,-C4-halogenoalkylthio, C1-C4-alkylsulphinyl, C1-CQ-halo-
genoalkylsulphinyl, C1-C4-alkylsulphonyl, C~-C4-halogenoalkylsulphonyl, Cl-
C4-alkylamino, di-(C,-C4-alkyl)-amino, C1-C4-alkyl-carbonyl, C1-C4-alkoxy-
carbonyl, C~-C4-alkylamino-carbonyl, di-(C1-C4-alkyl)-amino-carbonyl, CI-
C4-alkyl-carbonyl-amino, C1-C4-alkoxy-carbonyl-amino, CI-C4-alkyl-amino-
carbonyl-amino, C~-C4-alkyl-sulphonyl-amino.
R' particularly preferably represents hydrogen, represents in each case
optionally
cyano-, fluorine, chlorine-, bromine-, methoxy-, ethoxy-., n- or i-propoxy-,
methylthio-, ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-
,
n- or i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or i-propyl-
sulphonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
repre-
sents in each case optionally fluorine-, chlorine- or bromine-substituted
ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, represents in each
case
optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-
propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo-
propylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or
represents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bro-
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mine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-,
trifluoromethyl-,
methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy- or trifluoromethoxy-
substituted phenyl or benzyl.
S R2 particularly preferably represents one of the cyclic and hete;rocyclic
groupings
mentioned above, where the substituents may be selected from one of the
groupings listed below:
nitro, hydroxyl, amino, cyano, carbomoyl, thiocarbomoyl, formylamino, fluo-
rine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
di-
fluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodi-
fluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- o:r i-propoxy, difluo-
romethoxy, trifluoromethoxy, chlorodifluoromethoxy, fluorodichloromethoxy,
methylthio, ethylthio, n- or i-propylthio, difluoromethylt:hio, trifluorometh-
ylthio, chlorodifluoromethylthio, fluorodichloromethylthio, methylsulphinyl,
ethylsulphinyl, trifluoromethylsulphinyl, methylsulphonyl, ethylsulphonyl, tri-
fluoromethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, di-
methylamino, diethylamino, acetyl, propionyl, n- or i-butyroyl, methoxy-
carbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl,
ethylaminocarbonyl, n- or i-propylaminocarbonyl, dimethylaminocarbonyl,
diethylaminocarbonyl, acetylamino, propionylamino, n- or i-butyroylamino,
methoxycarbonylamino, ethoxycarbonylamino n- or i-propoxycarbonylamino,
methylaminocarbonylamino, ethylaminocarbonylamino, n- or i-propylamino-
carbonylamino, methylsulphonylamino, ethylsulphonylarr~ino, n-or i-propyl-
sulphonylamino.
R' very particularly preferably represents hydrogen and represents in each
case
optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-,
methylthio-, ethylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl-,
ethylsulphonyl-substituted methyl, ethyl, n- or i-propyl.
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RZ very particularly preferably represents benzo-fused cycloalk(en)yl from the
list
above
\ ~\ ~\
/ / / i~
where all cyclic groupings may be substituted by one of the groupings listed
below:
[lacuna]
R' most preferably represents hydrogen, methyl, ethyl of n- or i-propyl.
RZ most preferably represents one of the groupings below:
NHZ
~ , ~ ~ ~ , off
CH3
Preference according to the invention is given to the compounds of the formula
(I)
which contain a combination of the meanings listed above as being preferred.
Particular preference according to the invention is given to the compounds of
the
formula (I) which contain a combination of the meanings listed above as being
par-
ticularly preferred.
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Very particular preference according to the invention is given to the
compounds of the
formula (I) which contain a combination of the meanings listed at>ove as being
very
particularly preferred.
Most preference according to the invention is given to the compounds of the
formula
(I) which contain a combination of the meanings listed above as being most
preferred.
The abovementioned general or preferred radical definitions apply both to the
end
products of the formula (I) and, correspondingly, to the starting materials or
interme-
diates required in each case for the preparation. These radical definitions
can be com-
bined with one another as desired, i.e. including combinations between the
given
preferred ranges.
The novel substituted N-cyano-amidines of the general formula (I) have
interesting
biological properties. In particular, they have strong herbicidal activities.
The novel substituted N-cyano-amidines of the general formula (I) are obtained
when
N-cyano-imidates of the general formula (II)
R'
R' O
(II)
N~CN
in which
R' is as defined above and
R' represents alkyl
are reacted with amino compunds of the general formula (III)
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R2
(III)
H'N~H
in which
R2 is as defined above,
if appropriate in the presence of a reaction auxiliary and if appropriate in
the presence
of a diluent.
Using, for example, ethyl N-cyano-propaneimidate and indan-2-yl-amine as
starting
materials, the course of the reaction in the process according to the
invention can be
illustrated by the formula scheme below:
CZHS
H5C2 O
+ --
N~CN
H~N~H HSCZ~N~H
INI~CN
The formula (II) provides a general definition of the N-cyano-imidates to be
used as
starting materials in the process according to the invention for preparing
compounds
of the general formula (I). In the general formula (II), Rl preferably has the
meaning
which has already been mentioned above, in connection with the; description of
the
compounds of the general formula (I) according to the invention, as being
preferred,
particularly preferred, very particularly preferred or most preferred for Rl;
R' prefer-
ably represents alkyl having 1 to 4 carbon atoms, in particular methyl or
ethyl.
The N-cyano-imidates of the general formula (II) are known and/or can be
prepared by
processes known per se (cf. J. Am. Chem. Soc. 104 (1982), 235-239; loc. cit.
106
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_g_
(1984), 2805-2811; J. Org. Chem. 28 (1963), 1816-1821; loc. cit. 46 (1981),
1457-
1465; Synthesis 1983, 402-404; Tetrahedron Lett. 21 (1980), 909-912).
The formula (III) provides a general definition of the amino compounds further
to be
used as starting materials in the process according to the invention for
preparing com-
pounds of the general formula (I). In the general formula (III), RZ preferably
has that
meaning which has already been mentioned above, in connection with the
description
of the compounds of the general formula (I) according to the invention, as
being pre-
ferred, particularly preferred, very particularly preferred or most preferred
for R2.
The amino compounds of the general formula (III) are known ancL'or can be
prepared
by processes known per se (cf. J. Am. Chem. Soc. 88 (1966), 2233-2240; loc.
cit. 95
(1973), 4083-4084); J. Chem. Soc. C 1966, 717-722; Synthesis 1980, 695-697;
Tetra-
hedron 24 (1968), 3681-3696; loc. cit. 50 (1994), 3627-3638).
The process according to the prevention for preparing compounds of the general
for-
mula (I) is, if appropriate, carried out using a reaction auxiliary. Reaction
auxiliaries
suitable for the process according to the invention are, in general, the
customary inor-
ganic or organic bases or acidic acceptors. These preferably include alkali
metal or
alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides,
hydroxides
or alkoxides, such as, for example, sodium acetate, potassium acetate or
calcium ace-
tate, lithium amide, sodium amide, potassium amide or calcium amide, sodium
car-
bonate, potassium carbonate or calcium carbonate, sodium bicarbonate,
potassium
bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium
hy-
Bride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium
hydroxide
or calcium hydroxide, sodium methoxide, ethoxide, n- or i-propoxide, n-, i-, s-
or t-
butoxide or potassium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-
butoxide;
furthermore also basic organic nitrogen compounds, such as, for example,
trimethyl-
amine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine,
N,N-
dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N-di-
methyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-
methyl-
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2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-
2-
methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabi-
cyclo[2,2,2]-octane (DABCO), 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), or 1,8-
diazabicyclo[5,4,0]-undec-7-ene (DBL..
In most cases, the use of one of the reaction auxiliaries mentioned above can
be dis-
pensed with.
The process according to the invention for preparing compounds of the general
formula (I) is preferably carned out using a diluent. Suitable diluents are,
in addition
to water, especially inert organic solvents. These include, in particular,
aliphatic, ali-
cyclic or aromatic, optionally halogenated hydrocarbons, such as, for example,
benz-
ine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum
ether, hex-
ane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers,
such as
1 S diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene
glycol dimethyl
ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or
methyl
isobutyl ketone, nitrites, such as acetonitrile, propionitrile or
butyronitrile; amides,
such as N,N-dimethylformamide, N-dimethylacetamide, N-methyl-formanilide, N-
methyl-pyrrolidone or hexamethylphosphorie triamide; esters such as methyl
acetate
or ethyl acetate, sulphoxides such as dimethylsulphoxide, alcohols, such as
methanol,
ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol
mono-
ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl
ether,
mixtures thereof with water or pure water.
When carrying out the process according to the invention, the reaction
temperatures
can be varied within a relatively wide range. In general, the process is
carned out at
temperatures between 0°C and 150°C, preferably between
10°C and 120°C.
The process according to the invention is generally carned out under
atmospheric
pressure. However, it is also possible to carry out the process according to
the inven-
tion under elevated or reduced pressure - in general between 0.1 bar and 10
bar.
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For carrying out the process according to the invention, the starting
materials are
generally employed in approximately equimolar amounts. However, it is also
possible
to use a relatively large excess of in each case one of the components. The
reaction is
generally carried out in a suitable diluent in the presence of a reaction
auxiliary, if
appropriate, and the reaction mixture is generally stirred at the required
temperature
for a plurality of hours. Work-up is carried out by customary methods (cf. the
Prepa-
ration Examples).
The active compounds according to the invention can be used as defoliants,
desic-
cants, haulm killers and, especially, as weed killers. By weeds in the
broadest sense
there are to be understood all plants which grow in locations where they are
undesired.
Whether the substances according to the invention act as total or selective
herbicides
depends essentially on the amount used. The active compounds according to the
in-
vention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,
Matricaria,
Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xan-
thium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus,
Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon,
Emex,
Datum, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus,
Phaseolus,
Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis,
Brassica,
Lactuca, Cucumis, Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum,
Digitaria,
Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus,
Sor-
ghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis,
Scir-
pus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus,
Apera, Aegilops, Phalaris.
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Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Ho:rdeum, Avena,
Se-
cafe, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
However, the use of the active compounds according to the invention is in no
way
restricted to these genera, but also extends in the same manner to other
plants.
Depending on the concentration, the active compounds according to the
invention are
suitable for total weed control, for example on industrial terrain and railway
tracks and
on paths and areas with or without tree growth. Equally, the active compounds
ac-
cording to the invention can be employed for controlling weeds in perennial
crops, for
example forests, ornamental tree plantings, orchards, vineyards, citrus
groves, nut
orchards, banana plantations, coffee plantations, tea plantations, rubber
plantations, oil
palm plantations, cocoa plantations, soft fruit plantings and hop fields, on
lawns and
turf and pastures and for selective weed control in annual crops.
The compounds of the formula (I) according to the invention have strong
herbicidal
activity and a broad activity spectrum when used on the soil and on rough-
ground
parts of plants. To a certain extent, they are also suitable for selective
control of
monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyle-
donous crops, both by the pre-emergence and by the post-emergence method.
The active compounds can be converted into the customary formulations, such as
solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes,
soluble
powders, granules, suspo-emulsion concentrates, natural and synthetic
substances
impregnated with active compound, and microencapsulations in polymeric
substances.
These formulations are produced in a known manner, for example by mixing the
ac-
tive compounds with extenders, that is to say liquid solvents and/or solid
earners,
optionally with the use of surfactants, that is to say emulsifiers and/or
dispersants
and/or foam formers.
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If the extender used is water, it is also possible to use, for example,
organic solvents as
auxiliary solvents. Liquid solvents which are suitable are mainly: aromatics,
such as
xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated
aliphatic
hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride,
ali-
phatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum
frac
tions, mineral and vegetable oils, alcohols, such as butanol or glycol, and
also their
ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl
isobutyl ke
tone or cyclohexanone, strongly polar solvents, such as dimethylformamide and
di
methyl sulphoxide, and water.
Suitable solid carriers are for example ammonium salts and ground natural
minerals,
such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or
diato-
maceous earth, and ground synthetic minerals, such as finely divided silica,
alumina
1 S and silicates; suitable solid Garners for granules are for example crashed
and fraction-
ated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and
synthetic
granules of inorganic and organic meals, and granules of organic material,
such as
sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers
and/or
foam formers are for example nonionic and anionic emulsifiers, such as
polyoxyethyl-
ene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example
alkylaryl poly-
glycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein
hydroly-
sates; suitable dispersants are for example lignosulphite waste liquors and
methylcel-
lulose.
Tackifiers, such as carboxymethylcellulose, natural and synthetic polymers in
the form
of powders, granules or latices, such as gum arabic, polyvinyl alcohol and
polyvinyl
acetate, and also natural phospholipids, such as cephalins and lecithins and
synthetic
phospholipids can be used in the formulations. Other possible additives are
mineral
and vegetable oils.
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It is possible to use colorants, such as inorganic pigments, for example iron
oxide,
titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin
dyestuffs, azo
dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as
salts of iron,
manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of
active
compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as
such or in
the form of their formulations, can also be used as mixtures with known
herbicides,
finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example
acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium),
ametryne,
amidochlor, amidosulphuron, anilofos, asulam, atrazine, azafenidin,
azimsulphuron,
benazolin(-ethyl), benfuresate, bensulphuron(-methyl), bentazone,
benzobicyclon,
benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium),
bromo-
butide, bromofenoxim, bromoxynil, butachlor, butroxydim, butylate,
cafenstrole,
caloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben,
chlor-
idazon, chlorimuron(-ethyl), chlornitrofen, chlorsulphuron, chlorotoluron,
cinidon-
(-ethyl), cinmethylin, cinosulphuron, clefoxydim, clethodim, clodinafop(-
propargyl),
clomazone, clomeprop, clopyralid, clopyrasulphuron(-methyl), cloransulam(-
methyl),
cumyluron, cyanazine, cybutryne, cycloate, cyclosulphamuron, cycloxydim,
cyhalo-
fop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-
methyl), diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican,
diflufenzopyr, dime-
furon, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam,
dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epropodan, EPTC,
espro-
carb, ethalfluralin, ethametsulphuron(-methyl), ethofumesate, ethoxyfen,
ethoxysul-
phuron, etobenzanid, fenoxaprop(-P-ethyl), fentrazamide, flamprop(-isopropyl),
flam-
prop(-isopropyl-L), flamprop(-methyl), flazasulphuron, florasulam, fluazi-
fop(-P-butyl), fluazolate, flucarbazone, flufenacet, flumetsulam, flumiclorac(-
pentyl),
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flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone,
fluoroglyco-
fen(-ethyl), flupoxam, flupropacil, flurpyrsulphuron(-methyl, -sodium),
flurenol(-butyl), fluridone, fluroxypyr(-methyl), flurprimidol, flurtamone,
fluthi-
acet(-methyl), fluthiamide, fomesafen, glufosinate(-ammonium), glypho-
sate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), haloxy-
fop(-P-methyl), hexazinone, imazamethabenz-(-methyl), imazamethapyr, imazamox,
imazapic, imazapyr, imazaquin, imazethapyr, imazosulphuron, iodosulphuron(-
methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron, isoxaben,
isoxachlortole,
isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet,
mesotrione, metamitron, metazachlor, methabenzthiazuron, metobenzuron, meto-
bromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsul-
phuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon,
nico-
sulphuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon,
oxasulphuron,
oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin,
pendralin,
pentoxazone, phenmedipham, piperophos, pretilachlor, primisulphuron(-methyl),
prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide,
prosul-
phocarb, prosulphuron, pyraflufen(-ethyl), pyrazolate, pyrazosulphuron(-
ethyl),
pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyriminobac(-methyl),
pyrithio-
bac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl),
quizalo-
fop(-P-tefuryl), rimsulphuron, sethoxydim, simazine, simetryn, sulcotrione,
sulphen
trazone, sulphometuron(-methyl), sulphosate, sulphosulphuron, tebutam,
tebuthiuron,
tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr,
thidi
azimin, thifensulphuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim,
triallate,
triasulphuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and tri
flusulphuron.
A mixture with other known active compounds, such as fungicides, insecticides,
acar-
icides, nematicides, bird repellents, plant nutrients and agents which improve
soil
structure, is also possible.
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The active compounds can be used as such, in the form of their formulations or
in the
use forms prepared therefrom by further dilution, such as ready-to-use
solutions, sus-
pensions, emulsions, powders, pastes and granules. They are used in the
customary
manner, for example by watering, spraying, atomizing, scattering.
S
The active compounds according to the invention can be applied both before and
after
the emergence of the plants. They can also be incorporated into the soil
before sowing.
The amount of active compound used can vary within a relatively wide range. It
de-
pends essentially on the nature of the desired effect. In general, the amounts
used are
between 1 g and 10 kg of active compound per hectare of soil surface,
preferably
between 5 g and 5 kg per ha.
The preparation and the use of the active compounds according to the invention
can be
seen from the examples below.
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Preparation Examples:
Example 1
H3C NCH
N~CN
S
A mixture of 0.98 g (10 mmol) of methyl N-cyano-ethaneimidate, 1.42 g (10
mmol) of
1,2,3,4-tetrahydro-1-naphthylamine and 20 ml of water is stirred at room
temperature
(about 20°C) for 12 hours. The resulting crystalline product is then
isolated by filtra-
tion with suction, washed with a little water and diethyl ether and dried on a
disc made
of clay.
This gives 1.3 g (62% of theory) of N'-cyano-N-(1,2,3,4-tetrahydro-1-naphthyl)-
ethaneimideamide of melting point 113°C.
Analogously to Example 1, and in accordance with the general description of
the
preparation process according to the invention, it is also possible to
prepare, for ex-
ample, the compounds of the general formula (I) listed in Table 1 below.
R2
R1 NCH
(I)
N~CN
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Table 1: Examples of compounds of the formula (I)
Ex. No. R1 R Melting point (°C)
2 H NH2 162°C
3 H ~ 148
/
4 CH3 NHZ 180
CH3 ...., 139
6 CH3 -,. 176
HO ~ '''
(1R,2S)
7 CH3 .-_ 173
HO ~ "
( 1 S,2R)
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Ex. No. ~ Rl R Melting point (°C)
8 C2H5 ~ 117
I /
9 C3H7-n ~ 149
/
CZHS NH2 203
11 CZHS -,. 140
HO ~ "
(1R,2S)
12 CZHS ~ 141
HO ~ "
( 1 S,2R)
13 C3H7-n NH2 194
14 C3H7-n ~. (amorphous)
HO ~ "
(1R,2S)
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Ex. No. RI R2 Melting point (°C)
15 C3H7-n -.~ (amorphous )
/
HO ~ '''
(1 S,2R)
16 H H3C ...~ 223
/
17 H -,. 149
HO ~ "
(1R,2S)
18 H ~ 156
HO ~ "
( 1 S,2R)
19 H / \ 136
20 CH3 / ~ 206
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Ex. No. R1 R Melting point (°C)
21 CZHS / \ 150
22 C3H7-n / ' 126
23 H , 105
24 C2H5 .~ 133
25 C3H7-n -," 84
26 CH3 ~ ,,.''
OCH3
27 CH3 i H3 152
o
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Ex. No. . R1 R Melting point (°C)
28 CH3 OCH3 144
/ ,,,.
29 CH3 OCH3 142
30 CH3 ~ ..~~~ 228
Br
31 CH3 B~ 205
\ ,,,,,
/
32 CH3 Br 204
33 CH3
/ CHs
34 CH3 -_
H3C
H3C
3 5 H -,
H3C
HsC ~ r
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Use Examples:
Example A
S Pre-emergence Test
Solvent: S parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of
active
compound is mixed with the stated amount of solvent, the stated amount of
emulsifier
is added and the concentrate is diluted with water to the desired
concentration.
Seeds of the test plants are sown in normal soil. After about 24 hours, the
soil is
sprayed with the preparation of active compound such that the particular
amount of
active compound desired is applied per unit area. The concentration of the
spray liquor
is chosen such that the particular amount of active compound desired is
applied in
1000 litres of water per hectare.
After three weeks, the degree of damage to the plant is rated in% damage in
compari-
son to the development of the untreated control.
The figures denote:
0% - no effect (like untreated control)
100% - total destruction
In this test, for example, the compound of Preparation Example 1 shows strong
activ-
ity against weeds.
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Example B
Post-emergence Test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part b;y weight of
active
compound is mixed with the stated amount of solvent, the stated amount of
emulsifier
is added and the concentrate is diluted with water to the desired
concentration.
Test plants of a height of 5 - 15 cm are sprayed with the preparation of
active com-
pound such that the particular amounts of active compound desired are applied
per
unit area. The concentration of the spray liquor is chosen such that the
particular
amounts of active compound desired are applied in 10001 of waterlha.
After three weeks, the degree of damage to the plants is rated in "/°
damage in com-
parison to the development of the untreated control.
The figures denote:
0% = no effect (like untreated control)
100% = total destruction
In this test, for example, the compound of Preparation Example 1 shows strong
activ-
ity against weeds.
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