Note: Descriptions are shown in the official language in which they were submitted.
213~15
The invention relates to new substituted phenylamino~
sulphonylureas, to processes for their preparation, and
to their use as herbicides.
It has been disclosed that the compound N-(4,6~
dimethoxy-pyrimidin-2-yl)-N'-(2-cyclopropyl-carbonyl-
phenylaminosulphonyl)-urea can be used as a selective ~ . t
herbicide (cf. EP-A 463287/US Patent 5009699).
Some alkylcarbonylphenylaminosulphonylureas ha~e been
disclosed in previous patent applications, but have not
10 gained importance (cf. EP-A 264467/US Patent 4622065). . .
'; ~ ,; ',"'''',''~
The new substituted phenylaminosulphonylureas of
general formula (I) ;.
R ~P' ~R2 `~
N~S4N~ ~N~
in which . `-
R1 represents hydrogen, halogen, or represents alkyl,
lS alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, ~ ~ :
alkylamino or dialkylamino, each of which has 1 to
4 carbon atoms in the individual alkyl groups and :~
~,
Le A 30 014-FC - 1 - ; -~:
2~34915 ~:~
, ~.
each of which is optionally substituted by halogen ~ ;
or Cl-C3-alkoxy, .
R2 represents hydrogen or halogen,
R3 represents halogen, or represents alkyl, alkoxy,
alkylthio, alkylsulphinyl, alkylsulphonyl,
alkylamino or dialkylamino, each of which has 1 to
4 carbon atoms in the individual alkyl groups and ~ -
each of which is optionally subs~ituted by halogen -
or Cl-C3-alkoxy, -~
R4 represents hydrogen, amino, halogen or formyl, or
represents alkyl, alkoxy, alkylthio, alkyl-
sulphinyl, alkylsulphonyl, alkylcarbonyl, alkoxy-
carbonyl, alkylcarbonylamino, alkoxycarbonylamino
or alkylsulfonylamino, each of which has 1 to
4 carbon atoms in the individual alkyl groups and
each of which is optionally substituted by halogen
or Cl- C3 - alkoxy, and
R5 represents hydrogen, or represents alkyl having 1 ~: ~
to 8 carbon atoms which is optionally substituted :.
by halogen, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-
alkylsulphinyl or Cl-C4-alkylsulphonyl, or
represents cycloalkyl, cycloalkyl-Cl-C4-alkyl,
cycloalkenyl or cycloalkenyl-Cl-C4-alkyl, each of
which has 4 to 7 carbon atoms in the cycloalkyl or ~. ~
cycloalkenyl groups and each of which is : ' h'
optionally substituted by halogen and/or Cl-C4- ~
'' '
Le A 30 014-FC - 2 ~
~ `,
2~3~915 ~ ~
alkyl, or represents phenyl or phenyl-C1-C4-alkyl,
each of which is optionally substituted by
halogen, Cl-C4-alkyl or C1-C4-halogenoalkyl, or
represents heterocyclyl or heterocyclyl-C1-C4-alkyl
having 2 to 6 carbon atoms and 1 to 3 nitrogen
atoms and/or one oxygen or sulphur atom and each
of which is optionally substituted by halogen,
C1-C4-alkyl or C1-C4-halogenoalkyl,
and salts of the compounds of the formula tI) have now ..
10 been found. .
The new substituted phenylaminosulphonylureas of the .
general formula (I) are obtained when aminopyrimidines
of the general formula (II)
in which .
R1, R2 and R3 have the abovementioned meaning,
are reacted with chlorosulphonyl isocyanate, if `~
appropriate in the presence of a diluent, and the :~
chlorosulphonylureas of the general formula (III) `- .
formed in this process
Le A 30 014-FC - 3 -
`'~
2 1 3 9~ 9 1
~ r
R
~O2-NHKX~NH ~ N'l R3 (tl~
in which --
R1, R2 and R3 have the abovementioned meaning;
are reacted with arylamines of the general formula (IV)
O
R ~ (IV)
in which
R4 and R5 have the abovementioned meaning,
if appropriate in the presence of an acid acceptor and
if appropriate in the presence of a diluent and, if
appropriate, the resulting compounds of the formula (I) ~ ~ `t,-
are converted into salts by customary methods. `~
A further preparation method for the compounds of the
formula (I) according to the invention which is
possible is outlined below, where R1, R2, R3, R4 and R5
have the abovementioned meaning and R represents alkyl
: Le A 30 014-FC - 4 ~
: -:, . -: :-
.. . :-
, :,. ..~:,..
2 1 3 ~
(in particular methyl or ethyl), aralkyl (in particular
benzyl) or aryl (in particular phenyl)~
o ~ . ~
4~H~ t a-S02N~ ~ R ~R
Q2NH2 i~
",i"
O R1 ~ ,.. ,- ~ .
~NI~SON~ R4~H/~R -~R
~'~,' .`-,' ~ ",,
., "~ ` ~, .,...,~ ..
:.'. ;`;-.-',,.
The new substituted phenylaminosulphonylureas of the
I general formula (I) are distinguished by a powerful and ';"-'¦ 5 selective herbicidal activity.
; Surprisingly, the new compounds of the formula (I) show
a considerably more powerful herbicidal activity than
the compound N-(4,6-dimethoxy-pyrimidin-2-yl)-N'-(2-
cyclopropyl-carbonyl-phenylaminosulphonyl)-urea, which -~
is known and which has a similar structure.
~ ;'""'~""'`''`
The invention preferably relates to compounds of the
formula (I) in which
" ~" ~ .''`'
Le A 30 014-FC - 5 - , ~`
: ~ ' , '`,',.''.,''`:
2 1 3 '1 ~
Rl represents hydrogen, fluorine, chlorine or : :
bromine, or represents alkyl, alkoxy, alkylthio,
alkylsulphinyl, alkylsulphonyl, alkylamino or :
dialkylamino, each of which has 1 to 3 carbon
atoms in the individual alkyl groups and each of :::
which is optionally substituted by fluorine,
chlorine, methoxy or ethoxy,
': ~``'
R2 represents hydrogen, fluorine, chlorine or ~:
bromine,
~:
10 R3 represents fluorine, chlorine or bromine, or ~ ;
represents alkyl, alkoxy, alkylthio,
alkylsulphinyl, alkylsulphonyl, alkylamino or
dialkylamino, each of which has 1 to 3 carbon
atoms in the individual alkyl groups and each of ::~
which is optionally substituted by fluorine,
chlorine, methoxy or ethoxy, ~ -
R4 represents hydrogen, amino, fluorine, chlorine, ~
bromine or formyl, or represents alkyl, alkoxy, ::
alkylthio, alkylsulphinyl, alkylsulphonyl, alkyl~
carbonyl, alkoxycarbonyl, alkylcarbonylamino,
alkoxycarbonylamino or alkylsulfonylamino, each of
which has 1 to 3 carbon atoms in the individual
alkyl groups and each of which is optionally
substituted by fluorine, chlorine, methoxy or
ethoxy, and :~
' , ., ,`.. '. ~.. -
Le A 30 014-FC - 6 ~
:.: :: - .-:::
2 13 ~
R5 represents hydrogen, or represents alkyl having 1
to 6 carbon atoms which is optionally substituted
by fluorine, chlorine, bromine, C1-C3-alkoxy,
Cl - C3 - alkylthio, C1- C3 - alkylsulphinyl or C1- C3 -
alkylsulphonyl, or represents cycloalkyl, cyclo-
alkyl-C1-C3-alkyl, cycloalkenyl or cycloalkenyl-
Cl-C3 -alkyl, each of which has 4 to 6 carbon atoms
in the cycloalkyl or cycloalkenyl groups and each
of which is optionally substituted by fluorine,
chlorine, bromine and/or C1-C3-alkyl, or represents ^~
phenyl or phenyl-C1-C3-alkyl, each of which is ~.-
optionally substituted by fluorine, chlorine, ".' .',',~"'.'~'!,.
bromine, C1-C3-alkyl or C1-C3-halo-genoalkyl, or
represents heterocyclyl or heterocyclyl-C1-C3~
alkyl, each of which has 3 to 5 carbon atoms and 1
to 3 nitrogen atoms and/or one oxygen or sulphur
atom and each of which is optionally su~stituted
by fluorine, chlorine, bromine, C1-C3-alkyl or
C1-C3-halogenoalkyl. :~
The invention furthermore preferably relates to sodium
salts, potassium salts, magnesium salts, calcium salts,
ammonium salts, C1-C4-alkyl-ammonium salts, di-(C1-C4-
alkyl)-ammonium salts, tri-(C1-C4-alkyl)-ammonium salts,
C5- or C6-cycloalkyl-ammonium salts and di-(C1-C2- -~
25 alkyl)-benzyl-ammonium salts of compounds of the ~ *
formula (I) in which R1, R2, R3, R4 and R5 have the
meanings given above as being preferred. - ~
; .. ..:. ,;
~,,',`~ .: '' '
;~ Le A 30 014-FC - 7 -
- ... ..
213~913
The invention particularly relates to compounds of the
formula ( I ) in which
R1 represents hydrogen, chlorine, methyl, ethyl, tri-
fluoromethyl, methoxy, ethoxy, difluoromethoxy,
methylthio, ethylthio, methylamino, ethylamino or
dimethylamino,
R2 represents hydrogen,
R3 represents chlorine, methyl, ethyl, :~ x
trifluoromethyl, methoxy, ethoxy, difluoromethoxy,
methylthio, ethylthio, methylamino, ethylamino or
dimethylamino, -
R4 represents hydrogen, amino, fluorine, chlorine,
bromine, methyl, trifluoromethyl, methoxy,
methylthio, methylsulphinyl, methylsulphonyl,
acetyl or methoxycarbonyl and
Rs represents hydrogen, or represents methyl, ethyl,
n- or i-propyl, n-, i- or s-butyl or n-, i- or s-
pentyl, each of which is optionally substituted by
fluorine and/or chlorine, or represents methoxy-
methyl, methoxyethyl, ethoxymethyl, ethoxyethyl,
methylthiomethyl, methylthioethyl, ethylthio-
methyl, ethylthioethyl, methylsulphinylmethyl,
ethylsulphinylmethyl, methylsulphonylmethyl or .
ethylsulphonylmethyl, or represents cyclobutyl, -~
cyclobutylmethyl, cyclopentyl, cyclopentylmethyl, .
"'';'''"'''`` ''''
~: Le A 30 014-FC - 8 - -
~` 2 1 3 4 ~
,::
cyclopentenylmethyl, cyclohexyl, cyclohexenyl~
methyl, phenyl, benzyl, phenylethyl, furyl, furyl-
methyl, thienyl, thienylmethyl, tetrahydrofuryl or
tetrahydrofurylmethyl, each of which is optionally
substituted by fluorine, chlorine and/or methyl.
A particularly preferred group of compounds according
to the invention consists of the compounds of the
general formula (Ia) below in which the radicals R1, R2,
R3, R4 and R5 have the meaning given above as being
particularly preferred.
O R
~SO2-N~NH 1~R ~ ~
R ~;
. ~,~ :,;
' ~"','~ ~ ';
The abovementioned general definitions of radicals, or
definitions of radicals whose preferred ranges have ~ .
been given, apply to the end products of the
formula (I) and, analogously, to the starting materials
or intermediates required in each case for the
preparation. These definitions of radicals can be ~'','' '~'!,"
combined with each other, that is to say combinations ~; `
.~. "'', '.-' '
Le A 30 014-FC - 9 ~
;: ' ~ - . : ` : :
2134~15
between ranges given as being preferred are also
possible.
The hydrocarbon radicals mentioned in the definitions
of the radicals, such as alkyl, also in combinations
with hetero atoms, such as in alkoxy, alkylthio or
alkylamino, are straight-chain or branched, even when
not mentioned expressly.
Halogen generally represents fluorine, chlorine,
bromine or iodine, preferably fluorine, chlorine or
bromine, in particular fluorine or chlorine.
If, for example, 4-chloro-6-methoxy-2-amino-pyrimidine,
chlorosulphonyl isocyanate and 2-propionyl-aniline are
used as starting materials, the course of the reaction
in the process according to the invention can be
outlined by the following equation~
cl cl
a~o2-N~o + ~ "-`, '
H2Nl OCH3 a-SO2-Nl~NH J~NJ~C~
O , , .~
~ ~C2Hs ~ ' S~'
- NHSO2-N~NH 1 OC~
`.. ~.:- .:
: ~ Le A 30 014-FC - 10 - .
,~ 213~915 :
: -
The aminopyrimidines of the formula (II) to be used as
starting substances in the process according to the
invention are known chemicals for synthesis, some of
which are commercially available. ~ -
The arylamines of the formula (IV) furthermore required
as starting substances are also known chemicals for
synthesis, some of which are commercially available
(re synthesis, cf. EP-A 325 247; J. Org. Chem. 44
(1979), 578-586 and the preparation examples).
The process according to the invention for the prepara-
tion of the new compounds of the formula (I) is
preferably carried out using diluents. Suitable
diluents are virtually all inert organic sol~ents.
These preferably include aliphatic and aromatic, -~
optionally halogenated hydrocarbons, such as pentane,
hexane, heptane, cyclohexane, petroleum ether, benzine,
ligroin, benzene, toluene, xylene, methylene chloride, -~ -.
ethylene chloride, ch~oroform, tetrachloromethane,
chlorobenzene and o-dichlorobenzene, ethers, such as
diethyl ether and dibutyl ether, glycol dimethyl ether
and diglycol dimethyl ether, tetrahydrofuran and -
dioxane, ketones, such as acetone, methyl ethyl ketone,
methyl isopropyl ketone and methyl isobutyl ketone,
esters, such as methyl acetate and ethyl acetate,
nitriles, such as, for example, acetonitrile and
propionitrile, amides, such as, for example,
dimethylformamide, dimethylacetamide and N-
., ...'~,-
., .~,:~,....
,' :. --,, .;
Le A 30 014-FC - 11 - - -
~" 213~91~ i
methylpyrrolidone, and also dimethyl sulphoxide, tetra-
methylene sulphone and hexamethylphosphoric triamide.
Acid acceptors which can be used in the process
according to the invention are all acid-binding agents
5 which can conventionally be used for such reactions. `~
Preferably suitable are alkali metal hydroxides, such
as, for example, sodium hydroxide and potassium
hydroxide, alkaline earth metal hydroxides, such as,
for example, calcium hydroxide, alkali metal carbonates
10 and alkali metal alcoholates, such as sodium carbonate -~
and potassium carbonate, sodium tert-butylate and
potassium tert-butylate, furthermore aliphatic,
aromatic or heterocyclic amines, for example
triethylamine, trimethylamine, dimethylaniline,
dimethylbenzylamine, pyridine, 1,5-diazabicyclo[4,3,0]-
non-5-ene (DBN), 1,8-diazabicyclo-[5,4,0]-undec-7-ene
(DBU) and 1,4-diazabicyclo[2,2,2]-octane (DABCO). -
. `':, ~.' -.
When carrying out the process according to the `
invention, the reaction temperatures can be varied -`
20 within a substantial range. In general, the process is `~- -
carried out at temperatures between -30C and +80C,
preferably at temperatures between -10C and +60C. " ' '.: !
: ' " .. , .: .
The process according to the invention is generally
carried out under atmospheric pressure. However, it is
also possible to carry out the process under elevated
or reduced pressure.
.
..... ~
..,..., ..~ ...
'',.~' ;.''
~'' ,'.~ ' '.,
Le A 30 014-FC - 12 - ~
r~ 2 1 3 ~ 1 3
To carry out the process according to the invention,
the starting substances required in each case are
generally employed in approximately equimolar amounts.
However, it is also possible to use one of the two
components employed in each case in a larger excess. In
general, the reactions are carried out in a suitable
diluent in the presence of an acid acceptor, and the
reaction mixture is stirred for several hours at the
temperature required in each case. Working-up in the
process according to the invention is carried out in
each case by customary methods (cf. the preparation
examples).
.~' '~'',.'
If appropriate, salts may be prepared with the
compounds of the general formula (I) according to the
invention. Such salts are obtained in a simple manner
by conventional salt formation methods, for example by
dissolving or dispersing a compound of the formula (I)
in a suitable solvent, such as, for example, methylene
chloride, acetone, tert-butyl methyl ether or toluene,
and adding a suitable base. The salts can then be
isolated by a concentration or filtration with suction,
if appropriate after prolonged stirring.
The active compounds according to the invention can be
used, for example, in connection with the following
plants~
~,', ."."",/
Dicotyledon weeds of the genera: Sinapis, Lepidium,
Galium, Stellaria, Matricaria, Anthemis, Galinsoga,
;~ ~ .''
'
'-
~ Le A 30 014-FC - 13 - ~
, , ' :~ .
. ~ ,".
i``) ':~','.. .. : . ,.. ' . ' . ' : ' `: .
`"` 213~91~
Chenopodium, Urtica, Senecio, Amaranthus, Portulaca,
Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania,
Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa,
Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex,
Datura, Viola, Galeopsis, Papaver, Centaurea,
Trifolium, Ranunculus and Taraxacum.
Dicotyledon cultures of the genera: Gossypium,
Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum,
Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon,
Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
.: ., ~.:.' :'
Monocotyledon weeds of the genera: Echinochloa, --
Setaria, Panicum, Digitaria, Phleum, Poa, Festuca,
Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus,
Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,
Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum,
Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and
Apera.
Monocotyledon cultures of the genera: Oryza, Zea,
Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, s ;~-
20 Saccharum, Ananas, Asparagus and Allium.; i;
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.
,,"
The compounds are suitable, depending on the concen~
tration, for the total combating of weeds, for example
, ~
.
Le A 30 014-FC - 14 - ~
~ ', " ~
~:
::
13~913
on industrial terrain and rail tracks, and on paths and
squares with or without tree plantings. Equally, the
compounds can be employed for combating weeds in peren~
nial cultures, for example afforestations, decorative
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 hopfields,
in lawns, turf and pasture-land, and for the selective
10 combating of weeds in annual cultures. .-~
The compounds of the formula (I) according to the
invention are particularly suitable for selectively ~ ~ ^
combating monocotyledon and dicotyledon weeds in
: ., ~
monocotyledon cultures by the pre- and post-emergence
methods.
The active compounds can be converted into the ;;~,
customary formulations, such as solutions, emulsions,
wettable powders, suspensions, powders, dusting agents,
pastes, soluble powders, granules, suspension-emulsion -
concentrates, natural and synthetic materials
impregnated with active compound, and very fine -~`~
capsules in polymeric substances.
These formulations are produced in a known manner, for ~-~
example by mixing the active compounds with extenders,
that is liquid solvents and/or solid carriers,
optionally with the use of surface-active agents, that
. :~' "."'
' :"'
Le A 30 014-FC - 15 -
213 19:1~
,
is emulsifying agents and/or dispersing agents and/or
foam-forming agents.
In the case of the use of water as an extender, organic
solvents can, for example, also be used as auxiliary
solvents. As liquid solvents, there are suitable in the
main: aromatics, such as xylene, toluene or
alkylnaphthalenes, chlorinated aromatics and
chlorinated aliphatic hydrocarbons, such as
chlorobenzenes, chloroethylenes or methylene chloride,
alipha-tic hydxocarbons, such as cyclohexane or
paraffins, for example petroleum fractions, mineral and
vegetable oils, alcohols, such as butanol or glycol as
well as their ethers and esters, ketones, such as
acetone, methyl ethyl ketone, methyl isobutyl ketone or
cyclohexanone, strongly polar solvents, such as
dimethylformamide and dimethyl sulphoxide, as well as
water.
., .
As solid carriers there are suitable~
~ -" .: ',.
fox example ammonium salts and ground natural minerals,
20 such as kaolins, clays, talc, chalk, quartz, - `
attapulgite, montmorillonite or diatomaceous earth, and . -~
ground synthetic minerals, such as highly disperse
silica, alumina and silicates, as solid carriers for
granules there are suitable: for example crushed and . ::
25 fractionated natural rocks such as calcite, marble, :.:
pumice, sepiolite and dolomite, as well as synthetic
granules of inorganic and organic meals, and granules
: :,
..
,,.
'..'
Le A 30 014-FC - 16 - -
~'
.'
. . ..
~ ',', ' ''` ,
213~
of or~anic material 9UCII as sawdust, coconut shells,
maize cobs and tobacco stalks; as emulsifying and/or
foam-forming agents there are suitable: for example
nonionic and anionic emulsifiers, such as
polyoxyethylene fatty acid esters, polyoxyethylene
fatty alcohol ethers, for example alkylaryl polyglycol
ethers, alkylsulphonates, alkyl sulphates,
arylsulphonates as well as albumen hydrolysis products;
as dispersing agents there are suitable: for example
lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural
and synthetic polymers in the form of powders, granules
or latexes, such as gum arabic, polyvinyl alcohol and
polyvinyl acetate, as well as natural phospholipids,
such as cephalins and lecithins, and synthetic
phospholipids, can be used in the formulations. Further
additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pig-
ments, for example iron oxide, titanium oxide and Prus-
sian Blue, and organic dyestuffs, such as alizarindyestuffs, azo dyestuffs and metal phthalocyanine dye-
stuffs, and trace nutrients such as salts of iron,
manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95
per cent by weight of active compound, preferably
between 0.5 and 90%.
Le A 30 014-FC - 17 -
v _.
.1 . -
.~-
.
:
:
'.,
:-
,
2 13 ~
For combating weeds, the active compounds according tothe invention, as such or in the form of their formula-
tions, can also be used as mixtures with known
herbicides, finished formulations or tank mixes being
possible.
Suitable herbicides for the mixtures are known
herbicides, for example anilides such as, for example,
diflufenican and propanil; arylcarboxylic acids such
as, for example, dichloropicolinic acid, dicamba and
picloram; aryloxyalkanoic acids such as, for example,
2,4 D, 2,4 DB, 2,4 DP, fluroxypyr, MCPA, MCPP and
triclopyr; aryloxy-phenoxy-alkanoic esters such as, for
example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-
butyl, haloxyfop-methyl and quizalofop-ethyl; azinones
such as, for example, chloridazon and norflurazon;
carbamates such as, for example, chlorpropham,
desmedipham, phenmedipham and propham;
chloroacetanilides such as, for example, alachlor,
acetochlor, butachlor, metazachlor, metolachlor,
pretilachlor and propachlor; dinitroanilines such as,
for example, oryzalin, pendimethalin and trifluralin;
diphenyl ethers such as, for example, acifluorfen,
bifenox, fluoroglycofen, fomesafen, halosafen, lactofen
and oxyfluorfen; ureas such as, for example,
chlortoluron, diuron, fluometuron, isoproturon, linuron
and methabenzthiazuron; hydroxylamines such as, for
example, alloxydim, clethodim, cycloxydim, sethoxydim
and tralkoxydim; imidazolinones such as, for example,
imazethapyr, imazamethabenz, imazapyr and imazaquin;
Le A 30 014-F~ - 18 -
~;'.'~' ' ' ' ' ' , ' ' ' ' ,, ' .
,,~
':,'' '
~:
~,.,: ., .
.~,,-.,,.--,
~. .:
-" 213~91~
nitriles such as, for example, bromoxynil, dichlobenil
and ioxynil; oxyacetamides such as, for example,
mefenacet; sulphonylureas such as, for example, amido-
sulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlor-
sulfuron, cinosulfuron, metsulfuron-methyl,
nicosulfuron, primisulfuron, pyrazosulfuron-ethyl,
thifensulfuron-methyl, triasulfuron and tribenuron-
methyl; thiocarbamates such as, for example, butylate,
cycloate, di-allate, EPTC, esprocarb, molinate,
prosulfocarb, thiobencarb and tri-allate; triazines
such as, for example, atrazine, cyanazine, simazine,
simetryn, terbutryn and terbutylazine; triazinones such
as, for example, hexazinone, metamitron and metribuzin;
others such as, for example, aminotriazole,
benfuresate, bentazone, cinmethylin, clomazone,
clopyralid, difenzoquat, dithiopyr, ethofumesate,
fluorochloridone, glufosinate, glyphosate, isoxaben,
pyridate, quinchlorac, quinmerac, sulphosate and
tridiphane.
Mixtures with other known active compounds, such as
fungicides, insecticides, acaricides, nematicides, bird
repellants, plant nutrients and agents which improve
soil structure, are also possible.
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, suspensions, emulsions, powders, pastes and
Le A 30 014-FC - 19 -
. -
,
.
.,
'
~,'
.' . ~,.
-`~ 213'~915
granules. They are used in the customary manner, for
example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be
applied either before or after emergence of the plants.
They can also be incorporated into the soil before
sowing.
The amount of active compound used can vary within a -
substantial range. It depends essentially on the nature ~
of the desired effect. In general, the amounts used are ~:
10 between 10 g and 10 kg of active compound per hectare ~
of soil surface, preferably between 50 g and 5 kg per -
ha.
The preparation and use of the active compounds
according to the invention can be seen from the
following examples.
Preparation Examples:
Example 1
O
N~SO2NI~ 1N~OCH3
4.2 g (33 mmol) of 2-amino-4-methoxy-6-methylpyrimidine -
are added at -5C with stirring to a mixture of 4.3 g
Le A 30 014-FC 20 -
. . ., ,~,,
,:: .
~ 213'~315
(30 mmol) of chloros~llphollyl isocyanate and 50 ml of
methylene chloride. The mixture is stirred for
30 minutes at 0C.
Then, 4.7 g (30 mmol) of 2-amino-propiophenone, 3.5 g
(35 mmol) of triethylamine and 50 ml of methylene
chloride are added, and stirring of the reaction
mixture is continued for 18 hours at 20C.
''"'.
The product is then washed using water and 10% strength
hydrochloric acid, dried using sodium sulphate and
filtered.
The filtrate is concentrated in vacuo, the residue is
crystallized by digestion with ethanol, and the product
is isolated by filtration with suction.
6.9 g (58.5~ of theory) of N-(4-methoxy-6-methyl-
pyrimidin-2-yl)-N'-(2-propionyl-phenylaminosulphonyl)-
urea of melting point 126C are obtained.
Other examples of the compounds of the formula (I)
which can be prepared analogously to Example 1 and
following the general description of the preparation
process according to the invention are those listed in
Table 1 below.
* ~
O R
H 54~C~H 1~R3 (I)
-
Le A 30 014-FC - 21 -
~''';':~' ' - .
'-, ~ ' ''
, ~; .
~,.......... .
~,
.~...
.,
213'191~
Ta~le 1: Examples of the compounds of the formula (I)
Ex.- Rl R2 R3(Position-) RS melting- - -
No. R4 point(C) -
,"
2 OCH3 H OCH3 H C2H5 184
3 OCH3 H OCH3 H CH3 145
4 CH3 H OCH3 H CH3 172
Cl H OCH3 H CH3 158 -~-
6 CH3 H CH3 H CH3 171
7 H H CH3 H CH3 171
8 CH3 H CH3 H C2H5 172
9 Cl H OCH3 H C2H5 152
OCH3 H OCH3 (6-)CI C2H5 162
11 OCH3 H CH3 (6-)CI C2H5 157
12 OCH3 H OCH3 (5-)Cl CH3 172 ---~
13 OCH3 H OCH3 (5-)CI CH(CH3)2 166 ~-~
14 CH3 H OCH3 H CH(cH3)2 149
15 OCH3 H OCH3 (6-)F CH3
16 OCH3 H OCH3 (6-)CH3 CH3 184 . ~:
` 17 OCH3 H OCH3 (6-)CI CH3 174 -
18 OCH3 H OCH3 (6-)OCH3 CH3
.. _ .. . , . _ .. . . .. . . ..
~;~ Le A 30 014-FC - 22 -
- :
. ,.~ ,
~ ,
: ;
`" 2134~1~
Tablel(Continuntion) .
Ex.- Rl R2 R3 (Position-) R5 melting-
No. R4 point(C)
19 OCH3 H OCH3 (6-)SCH3 CH3 162
OCH3 H OCH3 (6-)COOCH3 CH3
21 OCH3 H OCH3 (6-)F C2H5 155
22 OCH3 H OCH3 (6-)CH3 C2H5 164
23 OCH3 H OCH3 (6-)OCH3 C2H5
24 OCH3 H OCH3 (6-)SCH3 C2H5 220
OCH3 H OCH3 (6-)COOCH3 C2Hs ..
26 OCH3 H OCH3 (4-)CI n-C4Hg 165
27 OCH3 H OCH3 (5-)CI CH(CH3)2 160
28 CH3 H OCH3 (6-)F CH3 -
29 CH3 H OCH3 (6-)CI CH3
30 CH3 H OCH3 (6-)CH3 CH3 136 - -.
31 CH3 H OCH3 (6-)OCH3 CH
32 CH3 H OCH3 (6-)SCH3 CH3
33 CH3 H OCH3 (6-)COOCH3 CH3 ç~.
~ 34 CH3 H OCH3 (6-)F C2H5 161
: 3S CH3 H OCH3 (6-)CH3 C2H5 212
LeA30 014-FC
-23-
.
: ,
~.~
.. ..
- 213~
Table I (Continuation)
, .
Ex.- Rl R2 R3 (Position-) RS melting-
No. R4 point(C)
36 CH3 H OCH3 (6-)OCH3 C2H5
37 CH3 H OCH3 (6-)SCH3 C2H5 .
38 CH3 H OCH3 (6-)COOCH3 C2H5
39 Cl H OCH3 (6-)F CH3
Cl H OCH3 (6-)CI CH3 154
41 Cl H OCH3 (6-)CH3 CH3 145
42 Cl H OCH3 (6-)OCH3 CH3
43 Cl H OCH3 (6-)SCH3 CH3 .~.-
44 Cl H OCH3 (6-)COOCH3 CH3 -
45 Cl H OCH3 (6-)P C2H5 180
46 Cl H OCH3 (6-)CI C2H5 184 ~ .
47 Cl HOCH3 (6-)CH3 C2H5 158
48 Cl HOCH3 (6-?OCH3 C2H5
49 Cl HOCH3 (6-)SCH3 C2H5 196 -
50 Cl HOCH3 (6-)COOCH3 C2Hs
H H CH3 (6-)F CH3
52 H H CH3 (6-)CI CH3
~ ,
Le A 30 014-FC - 24 -
: '
,~ " . , . _, . .
~ '
i - -
;~ , ,
.:,, - .. .
.. ~ ..
. j~-::'~ ` '`'` , .
213~91~
T~biel (Continuation)
Ex.- Rl R2 R3 (Position-) RS melting-
No~ R4 point (C)
53 H H CH3 (6-)CH3 CH3
54 H H CH3 (6-)OCH3 CH3
H H CH3 (6-)SCH3 CH3 .
56 H H CH3 (6-)COOCH3 CH3
57 H H CH3 H C2H5
58 H H CH3 (6-)F C2H5
59 H H CH3 (6-)CI C2H5
H H CH3 (6-)CH3 C2H5
61 H H CH3 (6-)OCH3 C2H5
62 H H CH3 (6-)SCH3 C2Hs ~:
63 H H CH3 (6-)COOCH3 C2Hs : -~
64 H H OCH3 H CH
H H OCH3 (6-)F CH3
66 H H OCH3 (6-)CI CH3 ~-
67 H H OCH3 (6-)CH3 CH3
68 H H OCH3 (6-)SCH3 CH3
~: 69 H H OCH3 (6-)OCH3 CH3
Le A30014-FC
--25--
,~
....
--" 2134~1~
Table I (Continuation)
.
Ex~- Rl R2 R3 (Position-) R5 melting-
No~ R4 point(C)
'
H H OCH3 (6-)COOCH3 CH3
7I H H OCH3 H C2H5
72 H H OCH3 (6-)F C2H5
73 H H OCH3 (6-)CI C2H5
74 H H OCH3 (6-)OCH3 C H
H H OCH3 (6-)SCH3 C2H5
76 H H OCH3 (6-)CH3 C2H5
77 H H OCH3 (6-)COOCH3 C2H5
78 CH3 H CH3 (6-)F CH3 ~ -
79 CH3 H CH3 (6-)Cl CH3 158 -
80 CH3 H CH3 (6-)CH3 CH3 128
81 CH3 H CH3 (6-)SCH3 CH3
82 CH3 H CH3 (6-)OCH3 CH3
83 CH3 H CH3 (6-)COOCH3 CH3 ~.
CH3 H CH3 (6-)F C2H5 160 ~ ~ ~
85 CH3 H CH3 (6-)CI C2H5 -
86 CH3 H CH3 (6-)OCH3 C2H5 .
Le A 30 014-FC
-26-
~'~ ~ ' ', , `
~'''-'''' , .
~','"'," ,
213491S
Tnble I (Continuation)
Ex.- Rl R2 R3(Position-) RS melting-
No. R4 point(C)
g7 CH3 H CH3(6-)SCH3 C2H5 174
88 CH3 H CH3(6-)CH3 C2H5 178
89 CH3 H CH3(6-)COOCH3 C2H5
CF3 H CF3 H CH3
91 CF3 H CF3(6-)F CH3
92 CF3 H CF3(6-)CI CH3
93 CF3 H CF3(6-)CH3 CH3
94 CF3 H CF3(6-)SCH3 CH3
CF3 H CF3(6-)OCH3 CH3
96 CF3 H C~3(6-)COOCH3 CH3
97 ~F3 H CF3 H C2H5
98 CF3 H CF3(6-)F C2H5
99 CF3 H CF3(6-)Cl C2H5
100 CF3 H CF3(6-)OCH3 C2H5
101 CF3 H CF3(6-)SCH3 C2H5
102 CF3 H CF3(6-)CH3 C2H5 ..
103 CF3 H CF3(6-)COOCH3 C2H5
LeA30 014-FC
-27-
,~
;. ~. .
v',~
~. .-. ,~ . . `
" 213~1S
Tnblel(Continuation)
Ex.- Rl R2 R3 (Position-) R5 melting-
No. R4 point(C) -
104 CF3 H OCH3 H CH3
105 CF3 H OCH3(6-)F CH3
106 CF3 H OCH3(6-)CI CH3
107 CF3 H OCH3(6-)CH3 CH3
108 CF3 H OCH3(6-)SCH3 CH3
109 CF3 H OCH3(6-)OCH3 CH3
110 CF3 H OCH3(6-)COOCH3 CH3
111 CF3 H OCH3 H C2H5 ~ :;
112 CF3 H OCH3(6-)F C2H5
113 CF3 H OCH3(6-)CI C2H5
114 CF3 H OCH3(6-)OCH3 C2H5
115 CF3 H OCH3(6-)SCH3 C2H5
:~: 116 CF3 H OCH3(6-)CH3 C2H5
117 CF3 H OCH3(6-)COOCH3 C2H5 ;~
118 OCHF2 H OCHF2 H CH3
119 OCHF2 H OCHF2(6-)F CH3
120 OCHF2 H OCHF216-)CI CH3
. ~:
LeA30014-FC
-28-
.~,~".,, ~,
~j,,;-'.,, ', '.
.
--" 213~91~
Tablel(Continuntion)
P~ A, . ~
Ex.- Rl R2 R3 (Position-) R5 melting-
No. R4 point(C)
121 OCHF2 H OCHF2 (6-)CH3 CH3
122 OCHF2 H OCHF2 (6-)SCH3 CH3
123 OCHF2 H OCHF2 (6-)OCH3 CH3
124 OCHF2 H OCHF2 (6-)COOCH3 CH3 -.
125OCHF2 H OCHF2 H C2H5
126OCHF2 H OCHF2 (6-)F C2H5
127OCHF2 H OCHF2 (6-)CI C2H5 ~.
128OCHF2 H OCHF2 (6-)OCH3 C2H5
129OCHF2 H OCHF2 (6-)SCH3 C2H5
130OCHF~ H OCHF2 (6-)CH3 C2H5
131OCHF2 H OCHF2 (6-)COOCH3 C2H5
132 OCH3 H NHCH3 H CH3 .
133OCH3 H NHCH3 (6-)F CH3
134OCH3 H NHCH3 (6-)CI CH3
135OCH3 H NHCH3 (6-)CH3 CH3
136OCH3 H NHCH3 (6-)SCH3 CH3
137OCH3 H NHCH3 (6-)OCH3 CH3
LeA30 014-FC
-29-
. - . , .
;,-. .
~ '; , .
~'' ` ,
-`' 213~15 -
Tablel(Contimlation)
Ex~- Rl R2 R3 (Position-) R5 melting-
No. R4 point(C)
138 OCH3 H NHCH3 (6-)COOCH3 CH3
139 OCH3 H NHCH3 H C2H5
140 OCH3 H NHCH3 (6-)F C2H5
141 OCH3 H NHCH3 (6-)Cl C2HS
142 OCH3 H NHCH3 (6-)OCH3 C2H5
143 OCH3 H NHCH3 (6-)SCH3 C2H5
144 OCH3 H NHCH3 (6-)CH3 C2H5
145 OCH3 H NHCH3 (6-)COOCH3 C2H5
146 OC2H5 H NHCH3 H CH3
147 OC2H5 H NHCH3 (6-)F CH3
148 OC2Hs H NHCH3 (6-)CI CH3
149 OC2H5 H NHCH3 (6-)CH3 CH
150 OC2H5 H NHCH3 (6-)SCH3 CH3 - -.
151 OC2Hs H NHCH3 (6-)OCH3 CH3
152 OC2H5 H NHCH3 (6-)COOCH3 CH3
153 OC2H5 H NHCH3 H C2H5
154 OC2H5 H NHCH3 (6-)F C2H5
Le A 30 014-F
-30-
, . ..
~ A
~" - ~'' ' ~ '~' ~ . . ~' ' , ' '
~,','' , ' ~ ' ' ' `
',' ` ' " '
213~91~
Table I (Continuation)
Ex. - R I R2R3(Position-) R5 melting-
No. R4 point (C)
155 OC2H5 HNHCH3 (6-)Cl C2H5
156 OC2~5 HNHCH3(6-)OCH3 C2H5
157 OC2H5 HNHCH3(6-)SCH3 C2H5 ~ ~p
158 OC2Hs HNHCH3(6-)CH3 C2H5
159 OC2H5 HNHCH3(6-)COOCH3 C2H5
160 OCH3 HOCH3 H CH2SCH3 157
161 OCH3 HOCH3 H C3H7n 156
162 CH3 HOCH3 H C3H7n 149
163 CH3 H H H C3H7n 155 ~ `
164 OCH3 HOCH3 (6-)F c3H7n 142
165 OCH3 HOCH3 (6-)Cl c3H7n 133
166OCH3 HOCH3(6-)CH3 c3H7n 72
167OCH3 HOCH3 ~ 3 192
168OCH3 HOCH3 H ~ 188
169OCH3 HCH3 H ~ 172
"';' `' ~`' `.
Le A 30 014-FC -
-31- . .~
213'1~1S
Table I (Continuatio~
Ex.- Rl R2 R3 (Position-) R5 melting-
No. R4 point (C)
-
170OCH3 H OCH3 H CH(cH3)2 150
171OCH3 H OCH3 H (CH2)3CH3 156
172OCH3 H OCH3 H ~ 152
~ ~ '
173OCH3 H OCH3 (4-)C1 147 . -
174OCH3 H OCH3 (3-)F CH(CH3)2
175OCH3 H OCH3 (5-)CI CH3 163
176OCH3 H OCH3 (4-)CH3 CH(CH3)2
177OCH3 H OCH3 (4-)OCH3 CH(CH3)2 - ~- -
178OCH3 H OCH3 (4-)OCH3 CH3 --
,~ . . ~ .
179OCH3 H CH3 (4-)CI (CH2)3cH3 ~L.,,~
180OCH3 H CH3 (4-)CI ~
', .
181OCH3 HOCH3 H ~ 170
182OCH3 HOCH3 H {~ 165 ~ -
183OCH3 HOCH3 H t-C4Hg 103
~ -
Le A 30 014-FC - -
-32- - ::-
'- . .
; ~
,,
.. ~
.,.. - ~ .
213~91S
Tablel(Continuntion)
Ex~- Rl R2 R3 ~osition-) R5 melting-
No. R4 point (C) ; ~;,
. . . _ .
184OCH3 H OCH3 ~ ~ 172
185OCH3 H OCH3 H. ~ 150
186OCH3 H OCH3 ~4-)OCH3 n-C4Hg 149
187OCH3 H OCH3 (5-)OCH3 i-C3H7 165
188 CH3 H OCH3 (4-)OCH3 CH(CH3)2 162
189OCH3 H OCH3 (5-)CH3 CH(CH3)2 153
190 CH3 H OCH3 (5-)CH3 CH(CH3)2 164
191OCH3 H OCH3 (6-)C2H5 CH(C~3)2 152
192OCH3 H OCH3 (6-)CH(CH3)2 CH(CH3)2 176
193OCH3 H OCH3 (6-)C4Hg-s CH(CH3)2 162
194OCH3 H OCH3 (3-)OCH3 CH3 147 -
195OCH3 H OCH3 (5-)OCH3 n-C4Hg 170 .--
196OCH3 H OCH3 (3-)OCH3 n-C4Hg 158
197OCH3 H OCH3 (5-)C2Hs CH(CH3)2 176
198OCH3 H OCH3 (4-) CH(CH3)2 164 ~
NHCOOC2H5 ` . " ` . .
LeA30014-FC . :
-33- . ~-
. . . ~ .- ~ -
;, i . . - . .
213 I~l~
Table I (Continuation)
Ex.- Rl R2 R3 (Position-) R5 melting-
No. R4 point(C)
199OCH3 H OCH3 (6-)C2H5 CH3 159
200OCH3 H OCH3 (6-)C2HS C2H5 160 .
201OCH3 H OCH3 (6-)C2H5 n-C4Hg 116
202OCH3 H OCH3 (6-)CH(CH3)2 C2H5 161
203OCH3 H OCH3 (6-)CH(CH3)2 CH3 157
204OCH3 H OCH3 (6-) CH(CH3)2 160
NHCOOC2H5
205 Cl H OCH3 (6-)C2H5 C2H5 148
206OCH3 H OCH3 (6-)CH3 -(CH2)3-Cl 67
207OCH3 H OCH3 H ~3 128 :
208 CH3 HOCH3 H H 105 - ~- -
209OCH3 HOCH3 (6-)CH3 H 147
210Cl HOCH3 H H 158 ~.
211Cl HOCH3 (6-)CH3 H 194
212OCH3 HOCH3 (6-)C3H7-n CH3 144
213OCH3 HOCH3 (6-)C3H7-n C2H5 151 ~ ,
214OCH3 HOCH3 (6-)C3H7 n C3H7~n 148 . . ~.
` :~
LeA30014-~C -:
-34- :
t. ! . ~ ' '
,;'. -~ `
.~''' ~` . ' ` ' ` ' . `
',..................................... ` .` ' ' ' ' ' '
213 ~91~ ~
Table L (Continuation)
Ex.- R I R2 R3(Position-) R5 melting-
No. R4 point (C)
215 CH3 H OCH3(6-)C3H7-n CH3 133 '.
216 CH3 H OCH3(6-)C3H7-n C2H5 144
217 CH3 H OCH3(6-)C3H7-n C3H7~n 143
218OCH3 H OCH3(6-)C3H7-n CH(CH3)2 140
219 CH3 H OCH3(6-)C3H7-n CH(CH3)2 135
220 Cl H OCH3 H -CH2SCH3 136
221 CH3 H OCH3(6-)CH3 C3H7-n 128
222 Cl H OCH3(6-)CH3 C3H7-n 122 ~ ~-
223OCH3 H OCH3(6-)SC2Hs C3H7~n 150
224 Cl H OCH3(6-)Sc2Hs C3H7-n 125
225 CH3 H CH3 H ~ 190 - ,
226Cl HOCH3 H ~ 186 ~ ~.
227CH3 BrCH3 H C2H5 178
228CH3 BrCH3 (6-)F C2H5 168 : - .
229CH3 BrCH3(6-)CH3 C2H5 154
230OCH3 HOCH3(6-)soc2Hs C3H7-n 128 :
.
Le A 30 014-FC -` : . .
-35- ~ ~,
'' ```'~'`'
P~
.,,
~,;
213'~91~
Tab!e_L (Continuation)
Ex.- Rl R2 R3 (Position-) R5 melting-
No. R4 point(C)
231OCH3 H OCH3 (6-)SO2C2H5 C3H7~n 125
232OCH3 H OCH3 (6-)SCH3 C3H7~n 148
233 CH3 H OCH3 (6-)SCH3 C3H7-n 137
234OCH3 H OCH3 (6-)SO2CH3 C3H7~n 132
235 Cl H OCH3 H C3H7-n 129
236 Cl H OCH3 (6-)SCH3 C3H7~n 139
237 Cl H OCH3 (6-)Cl C3H7-n 148
238 CH3 H OCH3 (6-)Cl C3H7-n 145
239 CH3 H OCH3 (6-)Sc2H5 C3H7-n 168
240 CH3 H OCH3 (6-)F C3H7-n 149
241 Cl H OCH3 (6-)F C3H7-n 148
242OCH3 H OCH3 (6-)SO2CH3 CH3 182
243 CH3 H OC2H5 H CH3 180
244OCH3 H OCH3 (6-)Br C2H5 185
245 CH3 H OCH3 (6-)Br C2H5 169
246 Cl H OCH3 (6-)Br C2H5 161
247 CH3 H CH3 (6-)Br C2H5 181
Le A 30 014-FC
-36-
:. - -.. . . ..
~' '' " ' ` , , ,
,. . . .
:.
~13'i315
Table I (Continuation)
Ex.- R I R2 R3(Position-) R5 melting-
No. R4 point(C)
248 OCH3 H OCH3 (6-)Br CH3 195
249 CH3 H OCH3 (6-)Br CH3 191
250 OCH3 H OCH3(6-)CH3 -CH2SCH3 148
251 Cl H OCH3(6-)CH3 -CH2SCH3 102
252 CH3 H OCH3(6-)CH3 -CH2SCH3 85
253 Cl H OCH3(6-)CH3 -CH2SOCH3 112 ~ ~:
254 OCH3 H OCH3 (6-)Br C3H7-n 174
255 Cl H OCH3 (6-)Br C3H7-n 152
256 CH3 H OCH3 (6-)Br C3H7-n 148 - .. -
257 Cl H OCH3 (6-)Br CH3 182 -:
258 CH3 H CH3 (6-)Br CH3 177
259 Cl H OC2H5(6-)SCH3 CH3 150 ; ~ - -
260 Cl H OC2H5(6-)CI C2H5 174
261 Cl H OC2H5(6-)CI CH3 174
262 Cl H OC2H5 H C2H5 124 -- :
263 Cl H CH3 H C2H5 161 .
264 Cl H CH3 H CH3 196
' ' '~
Le A 30 014-FC
. -. .-~ ' . ' .
.
...
2134~1S
Table I (Continuation)
Ex. - R I R2 R3(Position-) R5 melting-
No. R4 point (C)
: ".: -;
265 Cl H CH3 (6-)CH3 CH3 201
266 Cl H CH3 (6-)SCH3 CH3 158
267 Cl H CH3 (6-)SCH3 C2H5 140
268 OCH3 H OCH3 H -CH2C1 244
269 Cl H OCH3 H -CH2C1 194
270 CH3 H OCH3 H -CH2C1 177 .
271 CH3 H CH3 H -CH2C1 156
272 Cl H CH3 H -CH2C1 140
273 Cl H OC2H5 H -CH2C1 112
274 CH3 H OC2H5 H -CH2C1 175
275 OCH3 H OCH3 (6-)CH3 -CH2C1 178 ` ~
276 Cl HOCH3 (6-)CH3 -CH2C1 128 ~`-
277 CH3 HOCH3 (6-)CH3 -CH2C1 153
278 CH3 H CH3 (6-)CH3 -CH2C1 164 -
279 Cl H CH3 (6-)CH3 -CH2C1 171 -
280 Cl HOC2H5(6-)CH3 -CH2C1 136
281 CH3 HOC2H5(6-)CH3 -CH2C1 15S ` -;
''~' :,
Le A 30 014-FC
--3~--
` '` ' ' '
,
~:',, -: - ` '
213'191~
Table I (Continuation)
Ex.- Rl R2 R3(Position-) R5 melting-
No. R4 point (C)
282OCH3 H OCH3 (6-)CI -CH2C1 155
283 Cl H OCH3 (6-)F -CH2C1 158
284OCH3 H OCH3 (6-)Br -CH2C1 155 . -. -
285 Cl H OCH3 (6-)Br -CH2C1 105
,~ ' "" .-'
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: -'
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213'1915
Starting ~4stances of ~le formula (IV):
Example(IV-1)
(C~
A mixture of 100 ml (0.1 mol) of boron trichloride and
100 ml of 1,2-dichloroethane is cooled to 0C. 12.3 g
5 (0.1 mol) of 4-methoxyaniline are added dropwise with ~-
stirring in the course of 15 minutes at this
temperature. A solution of 10.4 g (0.15 mol) of ~.
isobutyronitrile in 100 ml of 1,2-dichloroethane is
then added dropwise and, after the mixture has been -- ~i
stirred for 5 minutes, 14.7 g (0.11 mol) of aluminium -~ ~
trichloride are added to the mixture in portions at `
0C. The reaction mixture is then stirred for 5 hours '-
at 80C and subsequently subjected to ice-cooling, and
300 ml of water are added dropwise. The organic phase - : ~
15 is then separated off, and the aqueous phase is -~ -
reextracted three times using methylene chloride. The --
combined organic phases are dried over sodium sulphate
and filtered, and the filtrate is concentrated. The ;~
residue is separated by column chromatography (silica
20 gel; hexane/ethyl acetate: 4:1 by volume). ~ ~-
¦~ 5.3 g (27.5~ of theory) of4-methoxy-2-isobutyroyl-
~ aniline are obtained. ---~
. ~ .
.
Le A 30 014-FC
-40-
1. . . .
;'''''''" ' ' ' ' .~ .
: `
.~
, .:. ~:.
213491S
E a~Q_~
O
\~
'' - ~ '.
N~
10.9 g (72 mmol) of 2-cyano-4-chloro-aniline are dis-
solved in 30 ml of diethyl ether, and the mixture is
cooled to 0C. 100 ml of a two-molar solution of
5 cyclopentylmagnesium chloride in diethyl ether are --
added dropwise at this temperature, and the reaction -
mixture is stirred for a further 4. 5 hours at 20C. ~ -
After the mixture has been cooled to 0C, 150 ml of 10% ;
strength hydrochloric acid are added dropwise, and the
10 mixture is stirred for one hour at 20C. After the ~
mixture has again been cooled to 0C, 25 g of sodium ~ -
hydroxide are added to the mixture, the organic phase
is separated off, the aqueous phase is reextracted - -
three times using diethyl ether, and the combined ~
lS organic phases are dried over sodium sulphate and ~ -
concentrated. ~ ; -
-~.- . .~,
The residue is separated by column chromatography .~'.~,r."~
(silica gel; hexane/ethyl acetate: 4:1 by volume). ---
C ~
11.9 g (74~ of theory) of 4-chloro-2-cyclopentanoyl~
20 aniline of melting point 73C are obtained. -
Other compounds of the formula (Iv) which can be
prepared analogously to Example (IV-l) or (IV-2) are
those listed in Table 2 below. ~--
O
R ~ (IV)
Le A 30 014-FC
-41-
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'~ -
. . ., ," .~
.,, ~ . .
213'191~
Table 2: Examples of the compound~ of the formula (IV)
.. ,.. ~ . ~ _ _
Ex. (Position) R5 Melting ¦ ;.
¦NO. Rq point
¦IV-3 H CH(CH3)2 (oil)
5¦ IV - 4 ( 4 - ) Cl CH ( CH3 ) 2 6 4 C
IV-6 H ~ SgC
IV- 7 ( 4 - ) Cl CH
¦ IV-8 (4-) Cl (CH2) 3CH3 69C
IV-g t4-)Cl ~ 73C
10IV-10 (5-)Cl CH (CH3) 2 (oil)
I I .
¦ IV-11 ( 3 - ) F CH ( CH3 ) 2
IV- 12 ( 5 - ) Cl CH
I .
IV- 13 ( 4 - ) OCH3 CH ( CH3 ) 2 ( oil )
IV- 14 ( 4 - ) OCH3 CH ( CH3 ) 2 ( oil )
. _ _
15IV- 15 ( 4 - ) OCH3 CH3 ( oil )
IV-16 H CH2SCH3 ( oil )
.
Le A 30 014-FC
-~2-
,
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....
2 1 3 '~
Table 2: Continuation)
_
Ex. (Position) R5 Melting ¦ .
No R
IV-17 ¦H CH2SCH3 (oil) l : .
IV-l~ (6-)F C3H7n l ~ -.
IV-19 (6-)Cl C3H7n ¦¦
IV-20 (6-)CH3 C3H7n I .
11 ,, -,
IV-21 H -CH2 ~ 86C ~ ~
I . .
IV-22 (6-)Cl C2H
IV-23 (6-)F C2Hs I ::
IV-24 H d~ 4 03
H 1~'C
¦d=l 29
Le A 30 014-FC
~43-
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213'1~ 1~
Table 2: Contilluatioll)
_
Ex (Position) R5 Melting
No. R4 p(~oC)t
IV-27 (6-) Cl CH3
I
IV-28 (6-) CH3 CH, 48
I
IV-29 (6-) SCH3 C3H7 - n
IV-30 (6-) SCH3 CH3
IV-31 (6-) CH3 -CH2SCH3 :
IV-32 (6-)Br C3H7-n S9
- :'
- ~ i
" '
Use Examples
In the use examples, the compound (A) below is used as
comparison substance:
O S~
M~S02~KX}NH ~OC~ (A)
N-(4,6-Dimethoxy-pyrimidin-2-yl)-N'-(2-cyclopropyl-
carbonyl-phenylaminosulphonyl)-urea (disclosed in
EP-A 463287/US Patent 5009699).
Le A 30 014-FC
-44-
'~
.
'
.
.
213'1~1~
Example A
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 by weight of active compound is mixed with the
stated amount of solvent, the stated amount of I -
emulsifier is added and the concentrate is diluted with ~
lO water to the desired concentration. -
. ':
Test plants which have a height of 5 - 15 cm are ~
sprayed with the preparation of the active compound in ~-
such a way as to apply the particular amounts of active -
compound desired per unit area. The concentration of
the spray liquor is chosen such that the particular
amounts of active compound desired are applied in
2,000 l of water/ha. After three weeks, the degree of -
damage to the plants is rated in ~ damage in comparison
to the development of the untreated control.
20 The figures denote -
0~ = no action (like untreated control) -~-
100~ = total destruction.
: ', .
In this test, a considerably more powerful action -.-.
against weeds than in the case of compound (A) which is ~r.
25 known, combined with a very good tolerance by crop ::-
plants, such as, for example, wheat, is shown, for
example, by the compounds of Preparation Examples 1
and 2.
Le A 30 014-FC
-45-
,: '
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l ~
I ~
2134~1S
E~ample s
Solvent: 5 parts by weigllt of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
5 To produce a suitable preparation of active compound, ;
1 part ~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.
' '-. :.'
Seeds of the test plants are sown in normal soil.
After 24 hours the soil was watered with the
preparation of the active compound. It is expedient to
keep constant the amount of water per unit area. The
concentration of the active compound in the preparation
is of no importance, only the amount of active compound
applied per unit area being decisive. After three
weeks, the degree of damage to the plants is rated in
damage in comparison to the development of the
untreated control. The figures denote:
0~ = no action (like untreated control) ---
100~ = total destruction.
In this test, a considerably more powerful action
- against weeds than in the case of compound (A) which is
known, combined with a very good tolerance by crop
plants, such as, for example, wheat, is shown, for
example, by the compounds of Preparation Examples 1
and 2.
It will.be apprecisted that the instant specification and
claims are set forth by way of illustration and not limi-
tation, and that various modifications and changes may be
made without departing from the spirit and scope of the
present invention.
_,, , , . ... . _ . . . , .. _ . . . _, . . . . . .
Le A 30 014-FC
_46-
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,
.
