Note: Descriptions are shown in the official language in which they were submitted.
~oo~
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Herbicidal sulfonylureas, the preparation and use thereof
The present invention relates to substituted
sulfonylureas of the general formula I
R3 A O F
~SO 2--NH--C--N~
Rl oR2
in which the substituents have the following -=ning
S Rl is hydrogen, Cl-C3-alkyl, C3-C~-alkenyl or C3-C6-alkynyl;
R2 is C1-C4-alkyl;
R3 is hydrogen or halogen and
A is halogen or
~ B--R 4
where B is oxygen or alkylimino
N-R5
R4 i~ hydrogen, Cl-C~-alkyl which can carry up to three of
the following: halogen, Cl-C4-alkoxy, Cl-C4-alkylthio,
Cl-C4-halogenoalkoxy, Cl-C"-alkoxy-Cl-C2-alkoxy, C3-C7-
cycloalkyl and/or phenyl; C5-C,-cycloalkyl which can carry
up to three C~-C4-alkyls; C3-C~-alkenyl or C3-C~-alkynyl and
R5 is hydrogen, Cl-C~-alkyl, or together with R~ is a C4-C6-
alkylene chain in which one methylene can be replaced by
oxygen or Cl-C~-alkylimino.
The present invention furthe - a relate~ to a
process for the preparation of the co~pounds I as well a3
to the use thereof as herbicides.
US-A 4 547 215 discloses varlous herbicidal
~ulfonyl-pyrimidyl-ureas which are ~ubstituted in the
pyrimidyl moiety by chlorine. IIo.~.~ver, these compounds
are unsatisfactory becau~e of the low selectivity for
weed~ and ~ecA~7qe of the relatively hiqh application
rate~.
Hence the ob~ect of the invention was to find
novel compounds from the sulfonyl~pyrimidyl-urea class
with improved herbicidal p,~e,Lie~.
In accordance with this ob~ect, we have found the
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sulfonylureas defLned in the introduction.
We have furthermoxe found that the compounds I,
a~ well as the alkali metal and alkaline earth metal
salts thereof, have good selectivity for weeds in crops
such as corn.
In addition, we have found some special chemical
pr~cesses for preparing the compounds I. In particular,
the synthesis of the precursor III entails, by comparison
with the state of the art (J. Med. Chem. 6, (1963) 688;
J. Chem. Soc. 6 (1970) 1280), less expense and ha~
greater regioselectivity and thus a higher yield, which
is a crucial advantageO
The sulfonylureas of the formula I according to
the invention can be obtAi n~ in a variety of ways:
R3 A F
A: ~SO 2NCO ~ R I -NH~/ ~> _
oR2
Il 111
R3 A F R3 A Rl F
B: ~SO 2--NH--C~3 + R ~--NH~ ~ ~SO 2--NH--I l-N~(N~>
IV III
C: ~SO z--NH 2 + ~ 7~N~
Rl OR2
X Xl
As A sulfonyl isocyanate II is reacted in a con-
ventional manner (EP-A 162 723) with approximately the
sto~ch-- -tric amount of a 2-aminopyrimidine derivative
III in an inert organic solvent at from 0 to 120~C,
preferably 10 to 100~C. The reaction can be carried out
under atmospheric or superatmospheric pressure (up to
50 bar), preferably under 1 to 5 bar, continuou~ly or
disc~ntinuou~ly.
Suitable solvents are listed in tha above-
ment~ons~ literature.
Bs An app op~iate sulfonylcarbamste of the formula
IV is reacted in a convenLional manner (EP-A-162 723)
with a 2-aminopyrimidine derivative III in an inert
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organic solvent at from 0 to 120~C, preferably 10 to
100 ~C . It is possible to add bases such as tertiary
amines, which increases the reaction rate and improves
the quality of the product.
Examples of bases suitable for this purpose are
tertiary - ines such as pyridine, the picolines, 2,4- and
2,6-lutidine, 2,4,6-collidine, p-dimethylaminopyridine,
1,4-diazabicyclo[2.2.2]octane [DABC0] and 1,8-diazabi-
cyclo[5.4.0]undec-7-ene.
The solvents which are ~Y~e~iently used are those
specified in the literature and/or halogenated hydro-
carbons such a8 dichloromethane and chlorobenzene, ether
~uch as diethyl ether, tetrahydrofuran and dioxane,
acetonitrile, dimethylformamide and/or ethyl acetate in
an amount of from 100 to 4000 ~ by weight, preferably
1000 to 2000 ~ by weight, based on the starting materials
II, IV and X.
Of the int -liAtes III required according to
the invention, 2-amino-4-ethoxy-6-fluo~opyLimidine has
been disclosed (J. Med. Chem. 6 (1963) 688). It hag
hitherto been necessary to prepare it in an elaborate
-nner from 2-amino-4,6-difluo~opy~ in9 and sodium
ethylate in dry toluene with a change of the solvent and
working up in ether, concentration and crystallization
from a large volume of petroleum ether, the yield of
crude product being, ho aver, only 61 %.
It i8 even more difficult to obtain the 2-amino-
4~6-difluoro~y imidine required as starting material,
this having been obt~ined in 66 ~ yield by aminolysis of
2~4~6-trifluo~opy imidine in absolute ethanol followed by
precipitations and washings of the residue and filtrate
as well as a steam distillation to separate the isomers,
other products being an isomeric 4-amino compound and
hydrolysis p oducLs.
In a similar way, R.E. Banks et al.
(J. Chem. Soc. 6 (1970) 1280) obt~ine~ on aminolysi3 of
trifluoropyrimidine in aqueous ammonia at 0~C, a mixture
of isomers, with a yield of 53 % of the 2-amino and 26 %
of the 4-amino compound.
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In view of the un~olved problem with i~omer~, the
yields and the reaction conditions, all the known pro-
cesses are unsatisfactory in terms of simplicity and
cost, especially on the industrial scale.
However, the int~ -~iAte~ III can be obtAine~ in
a considerably more advantageous -nn~r during the
preparation of the compound~ according to the invention:
F~ FR I NH 2 ( V I )R l-NHY~
F RlNHMI (VIa) F '.
V VII
R20H or
R 20Ml R 20H or
.VIIIa VIII R20Ml
. VIIIa
F
F--(~N~ RINH2 (Vl) F
OR2 RINHMl (Vla) Rl~
IX OR2
III
The c~ pcunds III are prepared in two in~sp~n~nt
reaction stages, the sequence of which can be inverted.
Thus, for example, 2,4,6-trifluoLopy~imidine can
be reac~ed in an aprotic polar solvent
a) with an amine VI, which can be in aqueous ~olu-
tion, in the presence or Ahsen~e of a base and, if the
reaction i~ carried out in two phA~es~ in the presence of
a phase-transfer catalyst or
b) with a metal amide VIa, in the Ahssnce or pres-
ence of a base, and, if the reaction iq carried out intwo phases, in the presence of a phase-transfer catalyst
at from -~0 to +20~C, after which the 2-aminopyrimidine
derivative VII which ha~ been obtA i n9~ in this way is
reacted withou~ solvent or in the presence of an inert
organic solvent
c) with an Alcoholate VIII in the presence or
Ahgsn~e of a base or
d) with an alcoholate VIIIa in the pre~ence of the
co~La~o~ding alcohol VIII
at from 0 to 140~C to give the aminopyrimidine III.
.
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These reaction~ can be carried out under atmospheric or
superatmospheric pressure (1 to 10 bar, preferably 1 to
5 bar), continuously or discontinuously.
Ml in each of formulae VIa and VIIIa i5 an alkali
metal cation such as lithium, sodium or potassium cation
or the equivalent of an alkaline earth metal, such as
magnesium, calcium or barium cation.
The following solvent~ are cuitable for the
reaction of 2,4,6-trifluoropyrLmidine V with the amine
RlNH2 (VI) to give VII:
ethers such as methyl tert.-butyl ether, diethyl
et~er, ethyl propyl ether, n-butyl ethyl ether, di-n-
butyl ether, diisobu~yl ether, dii~oamyl ether, diiso-
propyl ether, cyclohexyl methyl ether, tetrahydrofuran,
1,2-dimethoxyethane, diethylene glycol dimethyl ether and
anisole; chlorinated hydrocarbons such as 1,1,2,2-tetra-
chloroethane, 1,1-dichloroethylene, chlorobenzene, 1,2-
dichlorobenzene and 1-chloronaphthalene as well as
corresponding mixtures.
The solvent i~ e~re~;ently used in an amount of
from 100 to 2000 ~ by weight, preferably 500 to 1500 ~ by
weight, based on the starting material V.
It is advantageou~ to use as acid acceptor an
excess of amine or the ~lkAli metal or AlkAlin~ earth
metal salt thereof. The amine is advantageously added in
twice the equ1valent ; -unL, or up to 15 % above or below
this, ba~ed on the starting material V, within 1 to 2
hour~, to a mixture of starting material V in one of the
abo~ 1,;0~9~ sol~ent~ at from -80 to 20~C, preferably
-30 to -10~C, and the mixture is then stirred for up to
one hour where app o~,iate and then allowed to warm to
25~C for the ~orking out.
When the primary amine RlNH2 (VI, R1 ~ H) is em-
ployed as aqueous solution, it is eYre~ient to add to the
reaction solution a phase-transfer cataly~t.
Suitable for thi~ purpose are, for example, crown
ethers such as 15-crown-5 or 15-crown-6 and corresponding
benzo-fu~ed derivatives such as ~;hen7o-18-crown 6,
polyethylene glycol dialkyl ethers of the type
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V- ( 0~'~0 ) n~
(n = 5 to 7 and v and w, independently of one another,
Cl-C4-alkyl) as well as quaternary ammonium salts such as
benzyltriethylammonium chloride, tetrabutylammonium
iodide, tetrabutylammonium hydroxide and tetrabutyl-
ammonium bisulfate.
In this case the reaction is preferably carried
out at from -15 to 20~C with addition of from 0.002 to
0.02 mol-equivalents of catalyst.
Reaction of starting materials VII and VIII is
expediently carried out in excess alcohol VIII as sol-
vent. Where appropriate, an alkali metal alcoholate
VIIIa is added, in an equivalent amount or up to 5 %
above or below this, based on the starting material VII,
to a suspension of the starting material VII in 5 to 20
times the amount by weight of alcohol VIII as solvent,
based on starting material VII, within up to one hour at
from 20 to 80~C. The reaction is then completed by
stirring at from 0 to 140~C, preferably 20 to 100~C, for
1/2 to 8 hours.
Example~ of basic compounds which can be used are
lithium, sodium, potas~ium, calcium, barium and gnesium
in the form of their alcoholates; however, also suitable
are organic bases ~uch a~ tximethylamine, ~riethyl r ine,
N-ethyldii~opLopylamine~ triiSGpLo~yli i ne~ N,N-dimethyl-
An~l~ng, N,N-dimethylcyclohexylamine, N-methylpyrroli-
dine, pyridine, quinoline, ~,~ or 7-picoline, 2,4- and
2,6-lutidine and triethylene~ii ine.
When the reaction sequence i8 reversed, 2,4,6-
trifluo opyLi~i~;ns (V) is reacted in the fir~t stage
either with an alcohol VIII or with its ~alt VIIIa to
give the pyrimidine derivative IX which i8 then
derivatized with an amine VI or its salt VIa to give the
aminopyr~ ~ins derivative III.
These reactions are carried out in the same
solvents and using the ~ame acid acceptors and ~ame
ratio~ of amount~ as in the conditionq described above.
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The temperature for the reaction of V with the
alcohol VIII or its salt VIIIa is from -20 to 140~C,
preferably from 0 to 100~C, and for the reaction of IX
with an amine VI or its salt VIa is from -40 to 100~C,
preferably from -20 to +20~C.
The aminopyrimidines III are isolated by the
method~ of working up described in the literature.
Compared with the ~tate of the art, the process
according to the invention provides the compounds I in a
more straightforward and eco - ic ~nn~r with better
yields and purity in all steps.
C: A sulfonamide of the formula X i8 reacted in a
conventional ~nn~r (Ep A 141 777) with approximately the
stoichiometric amount of a phenyl carbamate XI in an
lS inert organic solvent at from 0 to 120~C, preferably 20
to 100~C. The reaction can be carried out under at-
mospheric or superatmo~pheric pressure (up to 50 bar),
preferably under 1 to 5 bar, continuously or
discontinuously.
Example~ of suitable solvents, besides those
listed in the literature cited above, are nitrated
hy~ocarbons such as nitroethane and nitrobenzene,
nitrile~ such as acetonitrile and benzonitrile, esters
such as ethyl acetate, amicles such as dimethylformamide
and/or ketone~ such as acetone.
The reaction is preferably carried out in ethyl
acetate as solvent and with pyridine or one of the
ab~ tions~ tertia~y _mines as base.
The sulfonamides required as startin~ materials
of the fc 1~ IV can be prepared from 6-halogeno-
anthranilic esters by the Meerwein reaction and sub-
sequent reaction with ammonia.
Compounds of the formula I in which R4 is hydro-
gen are obtAineA by hydrolysis of e~ters of the formula
I in which R~ is C1-C5-alkyl. The hydrolysis is carried
out with not less than twice the ~mount of a ba~e, ~uch
as sodium or pota~sium hydroxide, expediently in a mixed
solvent contAining 2 to 8 times the amount of methanol
and 10 to 40 times the amount of water, based on the
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weight of the appropriate ester of the formula I, at from
30 to 80~C for from 1 to 20 hour~. The sulfonamide
carboxylic acids of the formula I are precipitated by
acidification.
With regard to the biological activity, preferred
compounds of the formula I are those in which the sub-
stituents have the following -~ni ngs:
Rl is hydrogen and methyl,
R2 is methyl, ethyl,n-propyl and i~opropyl,
R3 is hydrogen, fluorine, chlorine and bl~ i ne,
A is chlorine, carboxyl and aminocarbonyl,
R4 is alkyl such as methyl, ethyl, n-propyl and isoplop~l,
alkenyl such as allyl, methallyl, crotyl and
but-1-en-3-yl,
alkynyl such as propargyl, but-1-yn-3-yl and but-2-ynyl,
haloge~oAlkyl such as 2-chloroethyl, 2-chloro-n-propyl,
3-chloro-n-propyl, 1-chloro-2-butyl, 2-chloro-iso-butyl,
4-chloro-n-butyl, chloro-tert.-butyl, 3-chloro-2-propyl
and 2,2,2-trifluoroethyl,
alkoxyalkyl such as 2-methoxyethyl, 2-ethoxyethyl, 3-
methoxy-n-propyl, 2-methoxy-n-propyl, 3-methoxy n-butyl,
1-methoxy-2-butyl, methoxy-tert.-butyl, ethaxy-tert.-
butyl, 2-methoxy-n-butyl, 4-methoxy-n-butyl, 2-ethoxy-n-
propyl, l-methoxy-2-propyl, 2-ethoxy-1-butyl and
4-e~hoxy-n-butyl,
alkoxyalkoxy~lkyl such as 2-methoxy-ethoxy-methyl, 2-
(ethoxy)-ethoxy-methyl, 2-(pLopoxy)-ethoxy-methyl~ 2-
methoxy-ethoxy-ethyl, 2-(ethoxy~-ethoxy-ethyl and 2-
(methoxy-methoxy)-ethyl,
hAlogQno~lk~yyalkyl such as 2-(~-chloroethoxy)ethyl, 3-
t~-chloroethoxy)-n-propyl and 3-(~-chloro-n-propoxy)-n-
propyl,
cycloalkyl such as cyclo~en~yl and cyclohexyl,
R5 is hydk~yall~
alkyl such as methyl, ethyl, n-propyl, 180PLOPY1 and
n-butyl,
or together with R~ is tetramethylene, pentamethylene,
hexamethylene, ethyleneo~yethylene and ethylene-N-
methyliminoethylene.
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9 O.Z. 0050/40473
Examples of suitable salts of the compounds of the formula I are agri-
culturally useful salts, for instance alkali metal salts such as potassium
and sodium salts; alkaline earth metal salts such as calcium, magnesium
and barium salts; manganese, copper, zinc and iron salts, and ammonium,
5 phosphonium, sulfonium and sulfoxonium salts, e.g., ammonium salts, tetra-
alkylammonium salts, benzyltrialkylammonium salts, trialkylsulfonium salts
and trialkylsulfoxonium salts.
The novel herbicidal and growth-regulating agents I, or agents containing
10 them, may be applied for instance in the form of directly sprayable
solutions, powders, suspensions (including high-percentage aqueous, oily
or other 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
15 purpose for which the agents are being used, but they must ensure as fine
a distribution of the active ingredients according to the invention as
possible.
The compounds I are generally suitable for the manufacture of solutions,
20 emulsions, pastes and oil dispersions to be sprayed direct. Suitable inert
additives are mineral oil fractions of medium to high boiling point, such
as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or
animal origin, aliphatic, cyclic and aromatic hydrocarbons such as
benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated
25 naphthalenes and their derivatives such as methanol, ethanol, propanol,
butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone,
chlorobenzene, isophorone, and strongly polar solvents such as N,N-di-
methylformamide, dimethyl sulfoxide, N-methylpyrrolidone and water.
30 Aqueous formulations may be prepared from emulsion concentrates, pastes,
dispersions, wettable powders or water-dispersible granules by adding
water. To prepare emulsions, pastes and oil dispersions the ingredients as
such or dissolved in an oil or solvent may be homogenized in water by
means of wetting or dispersing agents, adherents or emulsifiers. Concen-
35 trates which are suitable for dilution with water may be prepared fromactive ingredient, wetting agent, adherent, emulsifying or dispersing
agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and
40 ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids,
phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl
sulfonates, alkali metal and alkaline earth metal salts of dibutyl-
naphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates,
alkali metal and alkaline earth metal salts of fatty acids, salts of
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O.Z. 0050/40473
sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated
fatty alcohol glycol ethers, condensation products of sulfonated
naphthalene and naphthalene derivatives with formaldehyde, condensation
products of naphthalene or naphthalenesulfonic acids with phenol and
5 formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl
phenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol
polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether
alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates,
ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated poly-
lO oxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters,tignin, 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 silicic acid, silica gels,
silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole,
20 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, bark meal, wood meal, and nutshell meal,
cellulosic powders, etc.
The formulations contain from 0.1 to 9S, and preferably 0.5 to 90, % byweight of active ingredient. The active ingredients are employed in a
purity of from 90 to 100, preferably from 95 to 100, % (according to the
NMR spectrum).
The cc .a:.ds I according to the invention may be formulated for instance
as follows:
1. 90 parts by weight of compound no. 1.010 is mixed with 10 parts by
35 weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which is
suitable for application in the form of very fine drops.
Il. 20 parts by weight of compound no. 1.001 is dissolved in a mixture
consisting of 80 parts by weight of xylene, 10 parts by weight of the
40 adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-
monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-
sulfonic acid, and 5 partS by weight of the adduct of 40 moles of ethylene
oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts
by weight of water and uniformly distributing it therein, an aqueous dis-
persion is obtained containing 0.02% by weight of the active ingredient.
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11 O.Z. 0050/40473
Ill. 20 parts by weight of compound no. 1.002 is dissolved in a mixture
consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of
isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide
and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of
5 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the
solution into 100,000 parts by weight of water and finely distributing it
therein, an aqueous dispersion is obtained containing 0.02% by weight of
the active ingredient.
10 IV. 20 parts by weight of compound no. 2.006 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 280~C, and
10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole
of castor oil. By pouring the solution into 100,000 parts by weight of
15 water and uniformly distributing it therein, an aqueous dispersion is
obtained containing 0.02% by weight of the active ingredient.
V. 20 parts by weight of compound no. 1.009 is well mixed with 3 parts by
weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid,
20 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained
from a sulfite waste liquor, and 60 parts by weight of powdered silica
gel, and triturated in a hammer mill. By uniformly distributing the
mixture in 20,000 parts by weight of water, a spray liquor is obtained
containing 0.1% by weight of the active ingredient.
VI. 3 parts by weight of compound no. 1.058 is intimately mixed with
97 parts by weight of particulate kaolin. A dust is obtained containing 3%
by weight of the active ingredient.
30 Vll. 30 parts by weight of compound no. 1.059 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.
VIII. 20 parts by weight of compound no. 2.004 is intimately mixed with
2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a
fatty alcohol polyglycol ether, 2 parts of the sodium salt of a
phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a
40 paraffinic mineral oil. A stable oily dispersion is obtained.
IX. 90 parts by weight of compound no. 2.001 is mixed with 10 parts by
weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which is
suitable for application in the form of very fine drops.
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12 O.Z. 0050/40473
x. 20 parts by weight of compound no. 1.009 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 and 1 mole of oleic acid-N-
monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-
5 sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil. By pouring the solution into 100,000 parts
by weight of water and uniformly distributing it therein, an aqueous dis-
persion is obtained containing 0.02% by weight of the active ingredient.
10 XI. 20 parts by weight of compound no. 1.001 is dissolved in a mixture
consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of
isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide
and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of
40 moles of ethylene oxide and I mole of castor oil. By pouring the
15 solution into 100,000 parts by weight of water and finely distributing it
therein, an aqueous dispersion is obtained containing 0.02% by weight of
the active ingredient.
Xll. 20 parts by weight of compound no. 2.007 is dissolved in a mixture20 consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a
mineral oil fraction having a boiling point between 210 and 280~C, and
10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole
of castor oil. By pouring the solution into 100,000 parts by weight of
water and uniformly distributing it therein, an aqueous dispersion is
25 obtained containing 0.02% by weight of the active ingredient.
XIII. 20 parts by weight of compound no. 3.001 is well mixed with 3 parts
by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid,
17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained
30 from a sulfite waste liquor, and 60 parts by weight of powdered silica
gel, and triturated in a hammer mill. By uniformly distributing the
mixture in 20,000 parts by weight of water, a spray liquor is obtained
containing 0.1% by weight of the active ingredient.
35 XIV. 3 parts by weight of compound no. 1.059 is intimately mixed with
97 parts by weight of particulate kaolin. A dust is obtained containing 3%
by weight of the active ingredient.
XV. 30 parts by weight of compound no. 1.009 is intimately mixed with a
40 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.
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13 O.Z. 0050/40473
XVI. 20 parts by weight of compound no. 1.001 is intimately mixed with2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a
fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenol-
sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic
5 mineral oil. A stable oily dispersion is obtained.
The herbicidal or growth-regulating active ingredients, or agents contain-
ing them, may be applied pre-or postemergence. If certain crop plants
tolerate the active ingredients less well, application techniques may be
10 used in which the herbicidal agents are sprayed from suitable equipment in
such a manner that the leaves of sensitive crop plants are if possible not
touched, and the agents reach the soil or the unwanted plants growing
beneath the crop plants (post-directed, lay-by treatment).
lS The application rates for the herbicidal use of the active ingredients
depend on the objective to be achieved, the time of the year, the plants
to be combated and their growth stage, and are from 0.001 to 3.0, prefer-
ably 0.01 to 1, kg of active ingredient per hectare.
20 The compounds of the formula I may exercise a variety of influences on
practically all plant development stages, and are therefore used as growth
regulators. The diversity of action of growth regulators depends especial-
ly on
25 a) the type and variety of plant;
b) the time applied, with reference to the development stage of the
plants and the time of the year;
c) the place and method of application (seed treatment, soil treatment,
or application to foliage);
30 d) climatic factors, e.g., average temperature, amount of precipitate,
sunshine and duration;
e) soil conditions (including fertilization);
f) the formulation of the active ingredient; and
g) the concentration at which the active ingredient is applied.
A description of some of the various possibilities of using the growth
regulators according to the invention in agriculture and horticulture is
given below.
40 A. Vegetative plant growth can be inhibited to a considerable extent, a
fact which is manifested particularly in a reduction in plant height.
The treated plants thus have a compact habit; furthermore, the leaf
color is darker.
Z~055~
14 O.z. 0050/40473
Of advantage in practice is for example the reduction in grass growth
on roadsides, hedges, canal embankments and on areas such as parks,
sportsgr~unds, fruit orchards, lawns and airfields, thus reducing
expensive and time-consuming mowing~
A further feature of economic interest is the increase in the rigor of
crops which tend to lodge, such as cereals, Indian corn, sunflowers
and soybeans. The shortening and strengthening of the stem thus caused
reduces or eliminates the danger of lodging under unfavorable weather
conditions.
The use of growth regulators is also important for inhibiting plant
height and changing the time of ripening in cotton. It is thus pos-
sible for this important crop to be harvested completely mechanically.
Pruning costs can be saved in fruit and other trees. Furthermore,
growth regulators can break up the alternate bearing of fruit trees.
Growth regulators may also increase or inhibit lateral branching. This
is of interest when, for instance in tobacco plants, it is desired to
inhibit the formation of lateral shoots (suckers) in favor of leaf
development.
With the growth-regulating compounds, it is possible for instance in
winter rape to considerably increaSe the resistance to freeze injury.
On the one hand, upward growth and the development of a too luxuriant
(and thus particularly frost-susceptible) leaf or plant mass are
inhibited; on the other, the young rape plants are kept, in spite of
favorable growth conditions, in the vegetative development stage
before winter frosts begin. The danger of freeze injury is thus
eliminated in plants which tend to lose prematurely their inhibition
to bloom and pass into the generative phase. In other crops, too,
e.g., winter cerea1s, it is advantageous if the plants are well
tillered in the fall as a result of treatment with the compounds
according to the invention, but enter winter with not too lush a
growth. This is a preventive measure against increased susceptibility
to freeze injury and - because of the relatively low leaf or plant
mass - attack by various (especially fungus) diseases. The inhibition
of vegetative growth also makes closer planting possible in numerous
crops, which means an increase in yield, based on the area cropped.
B. Better yields both of plant parts and plant materials may be obtained with the novel agents. It is thus for instance possible to induce
increased formation of buds, blossom, leaves, fruit, seed grains,
20(~5~3' ~
O.Z. 0050/40473
roots and tubers, to increase the sugar content of sugarbeets,
sugarcane and citrus fruit, to raise the protein content of cereals
and soybeans, and to stimulate the increased formation of latex in
rubber trees.
The compounds of the formula I may raise the yield by influencing
plant metabolism or by promoting or inhibiting vegetative and/or
generative plant growth.
10 C. It is also possible with growth regulators to shorten or lengthen
growth stages and to accelerate or retard the ripening process in
plant parts either before or after harvesting.
A factor of economic interest is for example the facilitation of har-
vesting made possible by a chemical, temporally concentrated loosening
(abscission) of the adherence of stalks to the branches of citrus
fruit, olive trees, and other kinds of pomes, drupes and indehiscent
fruit. The same mechanism, i.e., promotion of the formation of separ-
ation layers between fruit or leaf and stem of the plant, is also
essential for a readily controllable defoliation of crop plants, e.g.,
cotton.
D. Further, transpiration in crop plants may be reduced with growth
regulators. This is particularly important for plants growing in
agricultural areas which are expensive to irrigate, e.g., in arid or
semi-arid areas. Irrigation frequency can be reduced by using the
compounds according to the invention, making for lower costs. As a
result of the use of growth regulators, the water available can be
better utilized, because, inter alia,
- the size of the stomata opening is reduced;
- a thicker epidermis and cuticle are formed;
- penetration of the soil by the roots is improved;
- the micro-climate in the stand is favorably influenced by the
more compact growth.
The active ingredients of the formula I to be used in accordance with the
invention may be applied not only to the seed (as a disinfectant), but
also to the soil, i.e., via the roots, and - the method particularly
40 preferred - to the foliage by spraying.
As a result of the good crop plant tolerance, the application rates may
vary within wide limits.
~(~05'~-~9S
- 16 O.Z. 0050/40473
In view of the number of application methods possible, the herbicidal and
growth-regulating agents according to the invention, or agents containing
them, may be used in a further large number of crops for removing unwanted
plants.
To increase the spectrum of action and to achieve synergistic effects, the
compounds I according to the invention may be mixed and applied together
with numerous representatives of other herbicidal or growth-regulating
active ingredient groups. Examples of suitable components are diazines,
10 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines,
N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines,
amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran deriva-
tives, cyclohexane-t,3-dione derivatives, quinolinecarboxylic acid
derivatives, aryloxy- or heteroaryloxy-phenoxypropionic acids and salts,
15 esters and amides thereof, etc.
It may also be useful to apply the compounds I, either alone or in combin-
ation with other herbicides, in admixture with other crop protection
agents, e.g., agents for combating pests or phytopathogenic fungi or
20 bacteria. ~he compounds may also be mixed with solutions of mineral salts
used to remedy nutritional or trace element deficiencies. Non-phytotoxic
oils and oil concentrates may also be added.
2005595
- 17 - 0.2. 0050/40473
Synthesis examples
The procedures given in the examples which follow
have been used with appropriate modification of the
starting compounds to obtain further compounds of the
formula I; the resulting compounds are li~ted with
physical data in the table~ which follow; c ~unds
without these data can be synthesized from the appro-
priate ~ub-ctance~ in a ~imilar ~nner. On the ba~is of
their close structural relations to the compound~ which
have been prepared and investigated, they are expected to
have similar effects.
Svnthesis example~
1. Preparation of the inte ~ tes III
R I ~
oR2
1.1 2-A~ino-6-fluoro-4-methoxy~yLimidine (variant a)
F
H2N~
OCH3
a) 2-amino-4~6-difluo~opyrimidine
69.7 g (4.1 mol) of liquid ammonia were added at
-30 to -20-C to a stirred mixture of 250 g (1,865 mol) of
2~4~6-trifluo.v~y~imidine in 3.3 1 of diethyl ether
within one hour. For the working up, the reaction
mixture wa~ sllowed to warm to 25-C and the precipitate
was filtered off. Washing with ether, stirring in water,
~enewed filtration and drying resulted in 203 g (83 % of
theory) of the title compound of melting point 214-216~C.
Concentration of the ether filtra~e to about 1/3 of its
vol,ume allowed a further 20 g (8 ~ of theory) of the
title compound of melting point 193-196~C to be isolated
as a 1s1 mixture with the isomeric 4-amino compound. ,
'
' .:
:
~o~ss9s
- 18 - O.Z. 0050/40473
b) 2-Amino-6-fluoro-4-methoxypyrLmidine
27 g of 3Q % strength sodium methylate (0.15 mol)
were added to a stirred suspension of 19.7 g (0.15 mol)
of 2-amino-4,6-difluoropyrLmidine in 250 ml of absolute
methanol at 65~C within 20 minutes. The reaction
solution was stirred under reflux for 5 hours and then
cooled to 25~C, and the precipitate was L. -ved, wa~hed
with a little methanol and then ~tirred in water.
Filtration, washing with water and drying resulted in
16 g (74 % of theory) of the title compound of melting
point 172~C. Concentration of the filtrate, washing with
methanol and subsequently with water resulted in iso-
lation of a further 3 g (14 % of theory) of the title
compound of melting point 161-169~C.
1.2 2-Amino-4-ethoxy-6 fluo,opy i i~ine
H 2
O~
A ~olution of 25.2 g (0.3 mol) of pota ~ium
ethylate in 200 ml of absolute ethanol was added to a
stirred suspension of 39.3 g (0.3 mol) of 2-amino-4,6-
difluoL~yL~ ~ln9 (1 la) :Ln 150 ml of absolute ethanol
.
at 78~C within 40 minute~. The mixture wa~ stirred under
reflux for 5 hours and then cooled, and the solvent was
removed under reduced pressure. The residue was ~tirred
with water, filtered off, washed with wster and dried.
39 g (83 ~ of theory) of the title compound of melting
point 121-123~C were obt~ ed (cf. Lit. J. Med. Chem. ~
(1963) 688; 61 % yield of crude product; melting point
after recrystallizations 120.5-123~C).
1.3 2-Amino-6-fluoro-4-propyloxypyrimidine
H 2N~
O~
29.4 g (O.3 mol) of potas~ium propylats were
reacted in a ~imilar manner to 1.2 with 39.3 g (0.3 mol)
Z 0 0 S~ 9 5
- 19 - O.Z. 0050/40473
of 2-amino-4,6-difluoropyrimidine (l.la) in a total of
400 ml of n-propanol. The solvent was removed from the
reaction mixture under reduced pressure, and the residue
was washed with petroleum ether. It was subsequently
stirred in water, filtered off, washed and dried, result-
ing in 36.1 g (70 ~ of theory) of the title compound of
melting point 63-66~C.
1.4 2-Amino-6-fluoro-4--isopropyloxypyrimidine
H2N~
ol
29.4 g (0.3 mol) of pota~ium isopropylate were
reacted in a 8i il~r ~nner to 1.2 with 39.3 g (0.3 mol)
of 2-amino-4,6-difluoropyrimidine (l.la) in a total of
400 ml of i~opropanol. Working up, washing with petro-
leum ether and water in the u~ual ~nner resulted in
38.5 g (75 % of theory) of the title compound of melting
point 66-68~C.
1.5 4-Allyloxy-2-amino-6-fluoropyrimidine
H 2N~
0
1.14 g (O.0382 mol) of 80 % sodium hydride
(emulslon in linseed oil) were added under a nitrogen
atmosRhere to 70 ml of allyl alcohol at 25~C. The
mixture was stirred at 40~C for 20 minutes and then 6.0 g
(0.0382 mol) of 2-amino-4,6-difluo.epy.imidine (l.la)
were added to the clear solution, and the mixture was
then stirred at 97~C for 1.5 hours. For tha working up,
the exce3s alcohol was 1 ~ed by distillation under
reduced pressure, the resulting residue wa~ taken up in
methylene chloride, and the solution wa~ washed with
water, dried over magne3ium ~ulfate and then the ~olvent
wa~ removed. The resulting viscous oil crystallized on
trituration with n-pentane. Piltration, washing with
water and drying resulted in 4.6 g (71.2 % of theory) of
the title compound of melting point 62-56~C.
Z(~55 9~
- 20 - O.Z. 0050/40473
1.6 2-Amino-6-fluoro-4-methoxypyrimidine (variant b)
H2N~
OCH3
a) 2,4-Difluoro-6-methoxypyrimidine
335.8 g (1.865 mol) of 30 ~ ~trength sodium
methylate (in methanol) were added to a mixture of 250 g
(1.865 mol) of 2,4,6-trifluoropyrLmidine in 1.4 1 of
methanol at -20~C within 45 minutes, and the mix~ure was
stirred at this temperature for a further 30 minute~.
~he re~ctio~ mixture wa~ subsequently allowed to warm to
25~C and then concentrated to about 1/3 of its volume.
The mixture obt~;n~ in this way wag partition~
between diethyl ether and water, and the organic pha~e
was dried over magne~ium sulfate and concentrated.
Distillation (1.1 m column, 3 mm V-shaped packing3
re~ulted in 141.6 g (52 % of theory~ of the title com-
pound of boiling point 144-145~C.
Di~tillation of the distillation residue without
a column re~ulted in 114.4 g (42 % of theory) of 4,6-
difluoro-2-methoxypyrimidine of boiling point 157-161~C.
b) 2-Amino-6-fluoro-4-metho~ypyLimidine
13.6 g (0.8 mol) of ammonia in 30 ml of methyl
tert. butyl ether were added at -20 to -10~C to a stirred
mixture of 52 g (0.356 mol) of 2,4-difluoro-6-methoxy-
pyrimidine in 300 ml of methyl tert.-butyl ether within
20 minutes. After a further 2 hours at -lS~ and 3 hour~
at 25~C, the precipitate was filtered off with suction,
washed with methyl tert.-butyl ether, ~tirred with water,
filtered off, washed again and subsequently dried,
re~ulting in 36.1 g (71 % of theory) of the title com-
pound of melting point 171-173~C.
2005~
- 21 - O.Z. 0050/40473
1.7 4-Fluoro-6-methoxy-2-methylaminopyrimidine
N <
CH3~ >
Ny
OCH 3
46.8 g of a 40 % strength solution of methylamine
in water (0.605 mol) were added at 0 to 2~C to a stirred
mixture of 41.9 g (0.287 mol) of 2,4-difluoro-6-methoxy-
pyrimidine (1.6a) and a spatula-tip of triethylbenzyl-
ammonium chloride (pha~e-transfer catalyst) in 100 ml of
methyl tert.-butyl ether within 30 minutes. After 1 hour
at 0~C and 3 hours at 25~C, the organic phase was separ-
ated off, washed with water and concentrated under
reduced pres~ure. The residue was stirred with pentane,
resulting in 39.9 g (88 % of theory) of 4-fluoro-6-
methoxy-2-methylaminopyrimidine of melting point 78-80~C.
2. Preparation of inte~ Ate3 X
R3 A
~SO 2N~ 2
2.1 ~ethyl 2-aminosulfonyl-6-chlorobenzoate
Ct CO2CH3
~ SO2~H2
a) 4-Chloro-1,2-benzoisothiazol-3-one l,l-dioxide
S04 g (2.02 mol) of methyl 6-chloro-2-amino-
sulfonylhan~cAte were added a little at a time to a
solution of 80 g (2.0 mol) of sodium hydLoxide in 2.5 1
of water, during which the temperature rose from 25~C to
50~C. After 30 minutes at this temperature, the mixture
was cooled to 25~C and extracted with methyl t-butyl
ether, and the aqueous phase was stirred into 2 N hydro-
chloric acid. The precipitate was isolated, w4shed with
water and dried. 330 g (75.8 % of theory) of the title
cl r~-~nd of melting point 210-212-C were obtA~ne~.
~oo~
- 22 - ~-Z- 0050/40473
b) Methyl 2-aminosulfonyl-6-chlorobenzoate
93 g (0.427 mol) of 4-chloro-1,2-benzoisothiazol-
3-one 1,1-dioxide were suspended in 0.8 1 of methanol and
stirred under reflux, while passing in gaseous hydrogen
chloride, for 3 hours. Cooling to 20~C, filtration with
suction and drying resulted in 60 g (56.3 ~ of theory) of
the title compound of melting point 152-153~C. Con-
centration of the f iltrate under reduced preasure and
trituration of the residue with methyl tert.-butyl ether,
renewed filtration and drying re~ulted in 42 g (39.4 % of
theory) of a ~econd fraction of thi3 compound, of melting
point 144-149~C.
The following compoclnds were obtainFed in a
~imilar ~nner~ for example: I I
~CO 2R ~CO 2R
~SO 2NH 2 ~SO 2NH 2
R Melting point Melting point
( ~C) ( ~C)
C2H, 97-101 129-131
n-C3H~ 111-113 104-107
i-C3~, 145-147 84- 87
CH2CH~CH2 105-108
Cl 130-134 109-110
102-104 135-136
~u~c~zocu~r~cl 124-126
2.2 Nbthyl 2-aminosulfonyl-6-fluorobenzoate
F CO 2CH 3
~50 2NH 2
a) Methyl 2-chlorosulfonyl-6-fluorobenzoate
108 g (0.639 mol) of methyl 6-fluoroanthranilate
and 45 g of sodium nitrite in 106 ml of water were added
~eparately but simultaneously at 5~C with ~tirring to
250 ml of concentrated hy~lochlorlc acid within 1 hour in
such a way that the ester c~ r,~nent was pre~ent in
excess. After the reaction mixture had been stirred at
2(~055~3~
- 23 - o.z. 0050/404~3
S to 8~C for 20 minute~ it was poured all at once into a
prepared solution of 53 g of sulfur dioxide, 1.7 g of
copper(II) chloride in a little water in 200 ml of 1,2-
dichloroethane and then st:irred for 10 minute~. The
mixture was slowly heated to 50~C and, while passing in
46 g of sulfur dioxide, stirred for 1 1/2 hours. It was
then cooled to 20~C and 5.5 g of chlorine were passed in
within 20 minute~ while stirring. After stirring for
20 minute~, the organic pha~e was separated off, washed
with water and dried. 105 g (65 ~ of theory) of the
title compound were obt~i n~A as a brownish oil in thi~
way.
b) Nethyl 2-aminosulfonyl-6-fluorobenzoate
42.5 g of gaseous ammonia were pas~ed at 20 to
2~~C into a stirred mixture of 252.5 g (1 mol) of methyl
2-chlorosulfonyl-6~fluorohen70~te in 700 ml of anhydrous
tetrahydrofuran. After the mixture had been ~tirred at
25~C for 1 hour, the precipitate wa~ filtered off with
suction, dissolved in water and extracted once with ethyl
acetate. Acidification of the aqueous phas3e with con-
centrated hrdLochloric acid resulted in 8.8 g (4.4 ~ of
theory) of 4-fluoro-1,2-benzoisothiazol-3-one l,l-~1o~e
of melting point 210-212-C.
The tetrahydrofuran filtrate was conc0ntrated,
and ths re~idue was washed with water, filtered off,
~- ~hg~ with diethyl ether, again filtered off and dried.
186 g (79.8 % of theory) of the title c _ of melting
polnt 155-159-C were obtA1ned.
3. Preparation of intermediates II
R3 A
~SO 2NCO
3.1 3-Chloro-2-methoYycarbonylbenzenesulfonyl
it30cyanate Cl CO2CH3
~SO 2NCO
2~0~S~
- 24 - O.Z. 0050/40473
100 g (O.4 mol) of methyl 6-chloro-2-amino-
sulfonylbenzoate were suspended in 300 ml of 1,2-di-
chloroethane and, while stirring, 123 g (1.03 mol~ of
thionyl chloride were added, and the mixture was 510wly
heated to reflux. After the mixture had been stirred
under reflux for 5 hours it was cooled to 55~C, 1.5 ml of
pyridine were added and, while passing in phosgene, the
mixture was again heated to reflux. After ga~ had been
passed in for 4 hour~, the reaction mixture was con-
centrated under reduced preY~ure and ventilated withnitrogen. The L~ -ining oil (105 g, 95.2 % of theory)
was employed for the next stage without further
purification.
4. Preparation of active ingredients I
4.1 Methyl 6-fluoro-2-[N-(4-fluoro-6-methoxy-2-
pyrimidinyl)aminocarbonylaminosulfonyl]benzo~te
F CO2CH3 8 F
~S02-NH-C~
OCH 3
4.3 g (0.03 mol) of 3-fluoro-2-methoxycarbonyl-
bsn~~~0sulfonyl isocyanate in 15 ml of 1,2-dichloroethane
were added at 25~C to a stirred ~uspension of 4.3 g
(0.03 mol) of 2-amino-4-fluoro-6-methoxypyrimidine
(1.1/1.6) in 70 ml of 1,2-dichloroethane within
15 minutes, and the mixture wa3 stirred at 25~C for
12 hour~. The precipitate was filtered off with suction,
stirred first with 1 N hydlochloric acid, washed with
water, then stirred with diethyl ether, filtered off with
~uction, w~hsA and dried, resulting in 8.1 g (67 % of
theory) of the title c~ _w~d of melting point 203-C
(decomposition) (active ingredient example 2.001).
4.2 1-Chloro-2-[N-(~-fluoro-6-methoxy-2-pyrimidinyl)-
aln~ no~Ar~Qnyl~mino8ulfonyl ]h~!n~~~ 9
Cl ,O F
~SO ~H--C~
OCH~
200559~
_ 25 - O.Z. 0050/40473
10.9 g (0.05 mol) of chlorobenzene-2-~ulfonyl-
isocyanate in 10 ml of 1,2-dichloroethane were added at
25~C to a stirred suspension of 7.15 g (0.05 mol) of 2-
amino-4-fluoro-6-methoxypyrimidine (1.1/1.6) in 150 ml of
1,2-dichloroethane within 20 minutes, and the mixture was
stirred for 8 hours. The reaction mixture was con-
centrated under reduced pressure, and the residue was
stirred with methyl tert.-butyl ether, filtered off and
washed. It was then stirred with 2 N hydrochloric acid,
filtered off, washed with water and dried, resultin~ in
8.6 g (47.7 % of theory) of title compound of melting
point 148-151~C (active ingredient example 3.001).
4.3 Methyl 2-tN-(4-fluoro-6-methoxy-2-pyrimidinyl)-
N-methylaminocA-bonylaminosulfonyl]b9n7Q~te
CH3 o
CH3 OCH3
6.3 g (0.04 mol) of the compound 1.7 were intro-
duced into 80 ml of 1,2-~chloroethane and, while stirr-
ing at 25-C, 9.6 g (0.04 mol) of 2-methoxycArhonyl-
bQn~r~ fonyl isocyanate were added within 5 minutes.
The reaction mixture was stirred at 25-C for 12 hours and
then cDr-- Lrated under ~e~--ce~ pres3sure. The residue
wa~ treated in the usual way with lsl diethyl
ether/petroleum ether and with 1 N l.~l~ochloric acid and
with water. Drying resulted in 10.4 g (65 ~ of theory)
of the title compound of melting point 148-150~C (active
in~ nt ex~mple 1.002).
4.4 Sodium salt of eth~l 2-[N-(4-fluoro-6-methoxy-2-
pyrimidinyl)a~noc~r~Q~ylaminosulfonyl]h~n7QAte
C N~
ÇO2CH2CHJ F
~ SO2-*i H ~
_ OCH3
4.2 g (0.0109 ~ 1) of ethyl 2-tN-(4-fluoro-6-
methoxy-2-pyrimidinyl)am~nncArh~nylam~ 1fonyl]h~n~QAte
(active ingredient example 1.009) were suspe~sd in 80 ml
, ~- .~ ' '. '
.
.
~.
Z005595
- 26 - O.Z. OOS0/40473
of methanol and, at 25~C, 1.9 g ~0.0109 mol) of 30 ~
strength sodium methylate solution in methanol were
added, and the mixture was stirred for 10 minuteq. The
solvent was 1~ ved by di~tillation under reduced pre~-
sure, resulting in 4.4 g (99.1 % of theory) of the titlecompound of melting point 175~C (decomposition) (active
ingredient example 1.009 sodium salt).
' ~
''''
ZC)05595
880556
27 0. Z . 005040473 ' '
Table 1
~ 502-NH-C-N-~
Rl oR2
No. Rl R2 R4 mp. (~C)
5 1.001 H CH3 CH3 186-188
1.002 CH3. CH3 CH3 148- 150
1.003 H CH2CH3 CH3 169-170
1.004 CH3 CH2CH3 CH3
1.005 H (CH2)2CH3 CH3 156-158
10 1.006 CH3 (CH2)2CH3 CH3
1.007 H CH(CH3)2 CH3 134-135
1.008 CH3 CH(CH3)2 CH3
1.009 H CH3 CH2C~3 165- 168
175 [sodium salt]
lS 1.010 CH3 CH3 CH2CH3 141-146
1.011 H CH3 (CH212CH3 143-147
1.012 CH3 CH3 (CH2)2CH3
1.013 H CH3 CH(CH3)2 172-175
1.014 CH3 CH3 CH(CH3)2
20 1.015 H CH3 CH2CH=CH2
1.016 CH3 CH3 CH2CH=CH2
I.Ot7 H CH3 CH2C~CH
1.018 CH3 CH3 CH2C_CH
1.019 H CH3 CH2CH=CHCH3
25 1.020 CH3 CH3 CH2CH=CHCH3
1.021 H CH3 CH2C--CCH3
1.022 CH3 CH3 CH2C-CCH3
1.023 H CH3 CH2C(CH3)=CH2
1.024 CH3 CH3 CH2C(CH3)=CH2
30 1.025 H CH3 (CH2) 2C1 168-170
1.026 CH3 CH3 (cH2)2cl
1.027 H CH3 (CH2)20CH3 154-156
1.028 CH3 CH3 (CH2)20CH3
1.029 H CH3 (CH2)2O(CH2)2CCH3
35 1.030 CH3 CH3 (CH2)20(CH2)20cH3
1.031 H CH3 CH20(CH2)20cH2cH3
1.032 CH3 CH3 CH20(CH2)20CH2cH3
Z00559S
880556
28 O.Z. 005040473
Table 1 ~contd.)
No. Rl R2 R4 mp- (~C)
5 1.033 H CH3 CH2CF3
1.034 CH3 CH3 CH2CF3
1.035 H CH3 C(CH3)2cH20cH3
1.036 CH3 CH3 C(CH3)2cH20cH3
1.037 H CH3 CH2o(cH2)2ocH3
10 1.038 CH3 CH3 CH20(cH2)20cH3
1.039 H CH3 -cyclopentyl
1.040 CH3 CH3 cyclopentyl
1.041 H CH3 cyclohexyl
1.042 CH3 CH3 cyclohexyl
15 1.043 H CH3 (cH2)2scH3
1.044 CH3 CH3 (CH2)25CH3
1.045 H CH3 (CH2)20CH2cF3
1.046 CH3 CH3 (CH2)20CH2cF3
1.047 H CH3 CH2C6H5
20 1.048 CH3 CH3 CH2C6H5
1.049 H CH3 (CH2)3CH3
1.050 CH3 CH3 (CH2)3CH3
1.051 H CH3 CH2CH(CH3)2
1.052 CH3 CH3 CH2CH(CH3~2
25 1.053 H CH3 C(CH3)3
1.054 CH3 CH3 C(CH3)3
1.055 H CH3 CH(CH3)CH2cH3
1.056 CH3 CH3 CH(CH3)CH2cH3
1.057 H CH3 (CH2)20CH3 142 (decomp.)
[sodium salt]
1.058 H CH3 (cH2)2cl 152 (decomp.)
[sodium salt]
1.059 H CH3 CH3 144 (decomp.)
tsodium salt]
35 1.060 H CH3 CH3 164 (decomp.)
[sodium salt]
1.061 H CH3 CH(CH3)2 184 (decomp.)
[sodium salt]
1.062 H CH3 (CH2)2CH3 186 (decomp.)
[sodium salt]
z~o~9s
880556
- 29 O.Z. 005040473
Table 2
R3 CO2R4 O F
so2-NH-C-~
R1 OCH3
NO. R1 R3 R4 mp- (~C)
5 2.001 H F CH3 203 ~decomp.)
2.002 CH3 F CH3 152-155
2.003 H F CH2CH3
2.004 CH3 F CH2CH3 138-140
2.005 H F ICH2)2CH3
10 2.006 CH3 F (CH2)2CH3 142-144
2.007 H Cl CH3 222-225
2.008 CH3 C1 CH3
2.009 H Cl CH2CH3 185-188
2.010 CH3 Cl CH2CH3
15 2.011 H Cl (CH2)2CH3
2.012 CH3 Cl (CH2)2CH3
2.013 H 8r CH3 220-225 (decomp.)
185 ( decomp.)
sodium SaIt
Z0 2.014 CH3 Br CH3
2.015 H Br CH2CH3
2.016 CH3 Br CH2CH3
2.017 H Br (CH2)2CH3
25 2.018 CH3 Br (CH2)2CH3
2.019 H C1 CH(CH3)2
2.020 CH3 C1 CH(CH3)2
2.021 H F CH(CH3)2 194-196
2.022 CH3 F CH(CH3)2
30 2.023 H F CH2CH=CH2
2.024 CH3 F CH2CH=CH2
2.025 H Cl CH2CH=CH2 116-120
2.026 CH3 C1 CH2CH=CH2
2.027 H C1 (CH2)2O(CH2)2CI 148-151
180 (decomp.)
sodium Sa1t
2.028 CH3 C1 (CH2)2O(CH2)2C1
2.029 H F (CH2)2O(CH2)2C1
2.030 CH3 F (CH2)2O(CH2)2
200~595 880556
-- 30 O.Z. 005040473
Table 3
R3 Cl 0 F
~SO 2--NH--C~
Rl OR2
No. Rl R2 R3 mp- (~C)
5 3.001 H CH3 H 148-151
3.002 CH3 C~3 H 116-118
3.003 H CH3 Cl
3,004 CH3 CH3 Cl
3.005 H CH2CH3 H
10 3.006 CH3 CH2CH3 H
3.007 H CH2CH3 Cl
3.008 CH3 CH2CH3 Cl
3.009 H (CH2)2CH3 H
3.010 CH3 (CH2)2CH3 H
15 3.011 H (CH2)2CH3 Cl
3.012 CH3 (CH2)2CH3 Cl
3.013 H CH(CH3)2 H
3.014 CH3 CH(CH3)2 H
3.015 H CH(CH3)2 Cl
20 3.016 CH3 CH(CH3)2 Cl
3.017 H (CH2)3CH3 H
3.018 CH3 (CH2)3CH3 H
3.019 H (cH2~3cH3 Cl
3.020 CH3 (CH2)3CH3 Cl
~oos~9s
880556
. 31 O.Z. 005040473
Table 4
R4 R5
N
R3 Lo o F
~SO 2--NH--C--IN~
Rl oR2
No. Rl R2 R3 R4 R5mp. (~C)
5 4.001 H CH3 H CH3 H
4.002 CH3 CH3 H CH3 H
4.003 H CH2CH3 H CH3 H
4.004 CH3 CH2CH3 H CH3 H
4.005 H (CH2)2CH3 H CH3 H
10 4.006 CH3 ~CH2)2CH3 H CH3 H
4.007 H CH3 F CH3 H
4.008 CH3 CH3 F CH3 H
4.009 H CH3 F CH3 CH3 178-179
192(decomp.)
[sodium salt]
4.010 CH3 CH3 f CH3 CH3
4.011 H CH3 Cl CH3 H
4.012 CH3 CH3 Cl CH3 H
4.013 H CH3 Cl CH3 CH3
20 4.014 CH3 CH3 Cl CH3 CH3
4.015 H CH3 Br CH3 H
4.016 CH3 CH3 Br CH3 H
4.017 H CH3 Br CH3 CH3
4.018 CH3 CH3 Br CH3 CH3
25 4.019 H CH3 H CH3 CH3
4.020 CH3 CH3 H CH3 CH3
4.021 H CH3 H CH2CH3 H
4.022 CH3 CH3 H CH2CH3 H
4.023 H CH3 H (cH2)2cH3 H
30 4.024 CH3 CH3 H (cH2)2cH3 H
4.025 H CH3 H CH~CH3)2 H
4.026 CH3 CH3 H CH(CH3)2 H
4.027 H CH3 F CH2CH3 H
4.028 CH3 CH3 F CH2cH3 H
35 4.029 H CH3 F (cH2)2cH3 H
4.030 CH3 CH3 F (cH2)2cH3 H
4.031 H CH3 F CH(CH3)2 H
4.032 CH3 CH3 F CH(CH3)2 H
200s~g5
880556
32 O.Z. 005040473
Table 4 (contd.)
No. Rl R2 R3 R4 R5 mp- (~C)
5 4.033 H CH3 Cl CH2CH3 H
4.034 CH3 CH3 Cl CH2CH3 H
4.035 H CH3 Cl (CH2)2CH3 H
4.036 CH3 CH3 Cl (CH2)2CH3 H
4.037 H CH3 Cl CH(CH3)2 H
10 4.038 CH3 CH3 Cl CH(CH3)2 H
4.039 H CH3 H CH2CH3 CH3
4.040 CH3 CH3 H CH2CH3 CH3
4.041 H CH3 H CH2CH3 CH2CH3
4.042 H CH3 F CH2CH3 CH2CH3
15 4.043 H CH3 H (cH2)2cH3 (CH2)2CH3
4.044 H CH3 F (cH2)2cH3 (CH2)2CH3
4.045 H CH3 H (cH2)3cH3 (CH2)3CH3
4.046 H CH3 F (cH2)3cH3 (CH2)3CH3
4.047 H CH3 H (cH2)2ocH3 H
20 4.048 H CH3 F (cH2)2ocH3 H
4.049 H CH3 H (cH2)2ocH3 CH3
4.050 H CH3 F (cH2)2ocH3 CH3
4.051 H CH3 H CH2CH=CH2 H
4.052 H CH3 F CH2CH=CH2 H
25 4.053 H CH3 H CH2CH=CH2 CH3
4.054 H CH3 F CH2CH=CH2 CH3
4.055 H CH3 H(CH2)20(cH2)2ocH3 H
4.056 H CH3 F(CH2)20(CH2)2OCH3 H
4.057 H CH3 H-(CH2)4-
30 4.058 H CH3 F -(CH2)4-
4.059 CH3 CH3 H-(CH2)4-
4.060 CH3 CH3 F -(CH2)4-
4.061 H CH3 H -(CH2)5-
4.062 CH3 CH3 H -(CH2)5-
35 4.063 H CH3 F -(CH2)5-
4.064 CH3 CH3 F -(CH2)5-
4.065 H CH3 H -(CH2)6-
4.066 CH3 CH3 H -(CH2)6-
4.067 H CH3 F -(CH2)6-
40 4.068 CH3 CH3 F -(CH2)6-
4.069 H CH3 H -~CH2)2O(cH2)2
4.070 CH3 CH3 H -(cH2)2o(cH2)2
4.071 H CH3 F -(cH2)2o(cH2)2
~, .
2~05S95
880556
33 O.Z. 005040473
Table 4 (contd.)
No. Rl R2 R3 R4 R5 mp- (~C)
5 4.072 CH3 CH3 F -(cH2)2o(cH2)2
4.073 H CH3 H -(cH2)2NcH3(cH2)2-
4.074 CH3 CH3 H -(CH2)2NCH3(CH2)2-
4.075 H CH3 F -(cH2)2NcH3~cH2)
4.076 CH3 CH3 F -(CH2)2NCH3(CH2)2-
Use examples:
The herbicidal action of sulfonylureas of the formula I on the growth of
the test plants is demonstrated by the following greenhouse experiments.
The vessels employed were plastic flowerpots having a volume of 300 cm3and filled with a sandy loam containing about 3.0% humus. The seeds of the
test plants were sown separately, according to species.
20 For the postemergence treatment, either plants sown directly in the pots
and grown there were used, or plants which were cultivated separately as
seedlings and were transplanted to the vessels a few days before treat-
ment.
25 Depending on growth form, the plants were grown to a height of 3 to 15 cm
before being treated with the active ingredients, which were suspended or
emulsified in water and sprayed through finely distributing nozzles. The
application rate for postemergence treatment was 0.125 kg/ha.
30 The pots were set up in the greenhouse, species from warmer climates in
warmer areas (20 to 35~C) and species from moderate climates at 10 to
20~C. The experiments were run for from 2 to 4 weeks. During this time the
plants were tended and their reactions to the various treatments assessed.
35 The assessment scale was 0 to 100, 100 denoting nonemergence or complete
destruction of at least the visible plant parts, and 0 denoting no damage
or normal growth.
The plants used in the greenhouse experiments were Amaranthus retroflexus,
40 Brassica napus, Chrysanthemum corinarium, Cyperus esculentus, Echinochloa
crus-galli, Malva neglecta, Matricaria inodora, Sinapis alba, Solanum
nigrum, Stellaria media, Veronica spp. and Triticum aestivum.
Z00559~
34 O.Z. 0050/40473
The compound of Example 1.001, applied pre- or postemergence at a rate of
0.125 kg/ha, gives excellent control of unwanted plants.
Compounds 1.009, 1.058 and 1.059, applied at a rate of 0.15 kg/ha, combat
5 unwanted broadleaved plants very well without causing any appreciable
damage to wheat as an example of a crop plant.
