CA 02129528 2003-07-29
1
Herbicidal N-ftgvrimidin-2-yl]aminocarbonyll
benzenesulfonamides
The present invention relates to N-[(pyrimidin-2-
yl)aminocarbonyl]benzenesulfonamides of the general
formula I
R3 O RS
R4
II
SO2--NH--C-I~ --C/
N- I
R2
ORi
where
R1 is methyl or ethyl;
R' is hydrogen or methyl;
R3 is Cl-C,-alkyl which may carry from one to three
methoxy groups or fluorine atoms;
or R3 is a group ER6 in which E is O or S, R6 being C1-C2-
alkyl, which may carry from 1 to 3 or 1 to 5 fluorine
atoms, with the exception of difluoromethoxy, and, if E is
O and at the same time R5 is trifluoromethyl, R6 may
furthermore be methylsulfonyl, ethylsulfonyl, trifluoro-
methylsulfonyl, allylsulfonyl or propargylsulfonyl;
N02 or OH;
or R3 is di-C1-C3-alkylaminosulfonyl if R5 is fluorine;
or R3 is C1- or C2-alkylsulfonyl which may carry 1-3
halogen atoms;
R° is hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine,
chlorine, methylthio, ethylthio or C1-Cz-haloalkoxy;
and Rs is fluorine or trifluoromethyl,
and their environmentally compatible salts.
The present invention furthermore relates to a
process for the preparation of the compounds I and to
CA 02129528 2003-07-29
2
their use as herbicides.
The prior art includes a number of patents which
relate to sulfonylureas having a herbicidal action.
EP-A 44 808 lists the compounds A -D in the form
of a table, without further characterization.
OCH3 A: R1 - CFA; RZ - OCF2C1
N B: R1 - F; RZ - OCF2C1
SOZNHCONH---~/ ~ C : Rl - CF3 ; R2 - OCHF2
1 0 N - D: R1 - F; RZ - OCHF2
R1
The sulfonylurea E is mentioned in EP-A 44 807,
likewise without physical characteristics.
CF3
0
N
SOzNHCON'H--~/ ~ E
N
OCH3
EP-A 338 424 describes methyl benzoates, for
20 example F.
C02CH3 CF3
N
SOZNHCONH ~---~/
N- F
ocH3
DE-A 39 00 472 relates to benzoates and
benzamides and o-halogen-substituted sulfonylureas, for
example having the structures G-I.
CA 02129528 2003-07-29
2a
R~
1 F
G : Rl - C02CH3 ; R2 - H
N H: Rl - C1; RZ - H
S02NHCONH--~~
N - I: R1 - CON(CH3)Z; RZ - 3-F
OCH3
EP-A 101 308 describes higher sulfones, for
example J-M.
, ~~~~~~V
-' '3 ° Ooze o05 43041
~-~ ~~rSO Rl ' OR2 J : ~C' ~ xs-i:3lH~; R~ ..., ~;~3
it : Rl - CH ( CH3 ) CHaCH~ ; RZ - CHI
N .
S02NHCONH----~/ ~ L: Rl ~ CH? --!~ , RZ ~ CH3
N '° M: R1 - C(CH3)3; RZ ' C2Hs
F
US-s 4 120 691 (DS-A 27 15 786) mentions the
sulfonylureas N and O.
C1 OCH3 .
N
SQ2NHCONH---~~ ~ N
N - a
CF3
CF3 OCH3
N
S02NHCONH--~/
CH; N -
C1
U.S. Patent 4,310,346 discloses sulfonamides
havia~g the structure P.
so2N a ocH3
s
~02NHCONH-~-~/ ~ P
CFA
bim~thgrlcarba~noyl-substituted sulfonylureas
havi.r~g the etructur~ R
' pS02N (CHg3 2 OCH~
~ N
S02NHCONH---~,
N_
CF3
are disclosed in U.S. Patent 4,515,624.
Sulfonylurea derivatives substituted by fluoro-
alkoxy, sulfamoyl, aeyl or alkyl in the ortho position of
the phenyl radical are represented by general structural
formulae in EP-A 173 312, US-B 4 515 624, US.-U 4 425 153
i i
CA 02129528 2003-07-29
4
and EP-A 44 209, respectively, without any detailed
information on specific structures.
The earlier German Applications DE40 38 430A of
December 1, 1990 and DE 41 05 518 A of February 22, 1991
describe herbicidal sulfonamides which, compared with the
novel compounds, have different substituents in the ortho
position of the phenyl radical and/or in the 3/5 posi-
tions of the triazine radical.
It is an object of the present invention to
synthesize sulfonylureas which have improved properties
compared with the known members of this herbicide class.
We have found that this object is achieved by the
N-[(pyrimidin-2-yl~aminocarbonyl]benzenesulfonamides of
the formula I which are defined at the outset.
In view of their intended use, suitable sub-
stituents are, for example, the following radicals:
Rl is methyl or ethyl;
R~ is hydrogen or methyl;
R' is C1-C'-alkyl, such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl,
which may carry from one to three methoxy groups or
fluorine atoms;
a group ER6 in which E is 0 or S, R6 being C1-CZ-alkyl,
which if R6 is methyl may carry 1 to 3 fluorine atoms and
if R6 is ethyl may carry 1 to 5 fluorine atoms, with the
exception of difluoromethoxy, and, if E = 0 and at the
same time RS - trifluoromethyl, R6 may furthermore be
methylsulfonyl, trifluoromethylsulfonyl, ethylsulfonyl,
allylsulfonyl or propargylsulfonyl;
NOZ or OH;
di-(C1-C,-alkyl)aminosulfonyl, such as dimethylamino-
sulfonyl or diethylaminosulfonyl if RS is fluorine;
C1-CZ-alkylsulfonyl, such as methylsulfonyl or ethyl-
sulfonyl, where up to three hydrogen atoms may be
replaced by halogen atoms;
R' is hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine,
chlorine, methylthio, ethylthio or C1-Cz-haloalkoxy such
~l~~~h~
- 5 - O.Z. 0050/43041
as t.~ra.f~.uorome~thoxy or difluoromethoxy; and
RS is fluorine or trifluoromethyl.
Halogen is in general fluorine, chlorine, bromine
or iodine, in particular fluorine, chlorine or bromine.
~ Compounds with Rl = methyl and R~ = hydrogen are
preferred.
Preferred definitions of R3 are: methylsulf
onyloxy, trifluaromethyl, trifluoromethoxy, thiomethyl,
vitro, methylsulfonyl, ethylsul'fonyl, methoxymethyl and
P1,~1-dimethylsulfamoyl.
Particularly preferred compounds I arise as a
result of the following combinations of radicals:
a) Rl = methyl, Ra, R° = H, R3 = methylsulfonyloxy, RS = . .
trifluoromethyl;
b) R1 - methyl, R2, R~ = H, R3 - trifluoromethyl, Rg = ,'
trifluoromethyl or fluorine;
c); Rl = methyl, R2, R° ° H, R3 = trifluoro~nethoxy, RS =
trifluoromethyl or fluorine;
d ) R~ _ methyl, R2 ~ H, R~ = thiomethyl or methoxy, R° _
s-methyltha:o, R5 - trifluoromethyl or fluorine;
a) RL - methyl, R2, R° - H, R3 - methoxymethyl, RS - .
trifluoromethyl or fluorine;
f) Rs _ methyl, Rz, R° - H, R3 = vitro, RS = trifluorome-
thyl or fluorine;
g) Rl methyl, R28 R° - H, R' - methyl- or ethylsul
f~nyl, RS _ tra:fluorc~methyl or fluorine;
h ~ . R' - in~thyl, R2, R4 = g, R3 = fit, I~-dimethylsulfamoyl,
~5 ~ fluorine
The novel su3.fonylureas of the formula I are
obtainable by various methods which.are described in the
literature. Particularly advantageous methods (A-D) are
described in detail below by way of example~
<IMG>
~ ~~~~.~~~
- ? - o.z. 0050/43041
I~,a . ~~ s~slfo~ay:E isocyaa~aate l.:t is x~eac;c~ri xri a cc~ar~r~sax-
,'g,'x. ..
tional manner (EP-A-162 723) with about the stoichio-
metric amount of a 2-aminopyrimidine derivative III at
from 0 to 120°C, preferably from 10 to 1.00°C. The
reaction can be carried out under atmospheric pxessure or
superatmospheric pressure (up to 50 bar), preferably at
from 1 to 5 bar, continuously or batchwise.,..,.
Solvents and diluents which are inert under the
particular reaction conditions' are advantageously used
for the reactions. Examples of suitable solvents are
halohydrocarbons, in particular chlorohydrocarbons, eg.
tetrachloroethylene, 1,1,2,x- or 1,1,1,2-tetrachloro-
ethane, dichloropropane, methylene chloride, dichloro-
butane, chloroform, chloronaphthalene, dichloro-
naphthalene, carbon tetrachloride, 1,1,1- or 1,1,2-
trichloroethane, trichloroethylene, pentachloroethane,
o-, m- or p-difluorobenzene, 1,2-dichloroethane, 1,I-
dichloroethane, 1,2-cis--dichloroethylene, chlorobenzene,
fluorobenzene, br~iaobenzene, iodobenz~ne, o-, m- or p-
dichlorobenzene, o-, p- or m-dibramobenz~ne, o-, m- or p-
chlorotoluene or 1,2,4-trichlorobenzene; ethers, eg.
ethyl propyl ether, methyl: tert-butyl ether, n-butyl
ethyl ether, di-n-butyl. ether, diisobutyl ether, diiso-
amyl ether, dii~opxoplrl ether, anisole, phenetole,
~yclohexyl,methyl ethero diethyl ether, ethylene glycol
da.~ethyl ether, tet~ahyelrofuran, dioxan~, thioanisole or
a.~:-dichlvr~die~hyl ~tlaer; nitrohydrocarbons, such as :.:;
raitrometlaane, nitr~ethane, . nitrobenzene, o-, m- or p--
chlbronitr~benzene or o~nitrotoluene; nitriles, such as
acetonitrile, btttyronitrile, isabutyronitrile, benzo-
nitrile or m-chlorobenzonitrile; aliphatic or cyclo-
aliphatic'hydrocarbons, eg. heptane, pinane, nonane, o-,.
m- ~r p-cyr~ene, gasoline fractions boiling within a range
froze: 70 to 190°C, cycloh~xane, azaethylcyclohexane,
decalin, petroleum ether, hexane, naphtha, 2,2,4-tri-
methylpentane, 2, 2, 3~triaa~ethylpentane, 2, 3, 3-tra.methyl-
Pehtane or octane; esters, eg. ethyl acetate, ethyl
,. .
y
r .. ~,
f..::
1 3..
a
a0...
T , r!. -,.
f . .
n.. "5
1.
i.., :.
Y ..
..:. . , : ., . .;.. ~, ..::. . , ~ ~;.. .: ,.
. . i.
f s
..1
~ Y''P,:
'..9 ~. ;h, r w. :~i.:. ,
.. . ,.. . /. ~ . ... ., . .,... .. .....w . G ,.-.~.. ......,... . ~
_>.r.~....".. ...,.,. w....r. .. , ., , .:
... ... .,,,.... ...,. . ,.. ,,, ... .. ..... .... ..... . .
' - 8 -' OeZ. 0050!43041
acetaacetate or ~.sobuty~. acetate; amides, eg. for~~amide,
"fir.
methylformamide or dimethylformamide; ketones, eg.
acetone or methyl ethyl ketone, and corresponding mix-
tutee. The solvent is advantageously used in an amount
of from 100 to 2, 000, preferably from 200 to 700, ~ by
wei.c~ht, based on the starting material II.
The compound II required for the,reaction is
generally used in about equianolar amounts (for example
from 80 to 120, based on the particular starting mater-
7.0 ial TII). The starting material ITT in one of the above-
mentioned diluents may be initially taken and the start-
ing material II then added:
However, the process for the preparation of the
novel compounds is advantageously carried out by initial
I5 ly taking the starting material II, if necessary in one
of the abovementioned diluents, and then adding the
starting material III:
To terminate -the reaction, stirring is carried
out for a further 20 ma.nutes to 24~ hours at from 0 to
20 120°C, p=eferably from 10 t~ 100°C, after the addition of
the components.
A. tertiary amine, eg: pyridine, a,~i-y-picoline,
2,4- or 2,6-lutidine, 2,4,6-collidine, p-dimethylamino-
py~idi.ne, trimethylamine, triethylamine, tri-n-propyl-
25 amine, 1,4-diaza[22.2,bi:cyclooctane [DABCO~ or l,8-
diazabicycto[5:4.0~undec--7.~ene, gay advantage~usly be
used as a reaction accelerator, in an amount of from 0.01
to l mol per mol of starting material IT.
The end product I is isolated from the reaction
30 mixture in a conventional manner, for example by distil
ling off solvents or directly by filtration unde~c suc
tion.' The residue can be washed with water or dilute.
amid to remove basic impurities: However, the residue
can also be dissolved in a water-immiscible solvent and
35 waahed in the manner desdribed. The desired end products
are obtained Mere in pure form; if necessary, they can be
purified by recrystallszation, stirring in an organic
~~.~~~2~~
- Oa~e 0050!43041
solv~~t.yahich takes up the impurities or chromatography.
This reaction is preferably carried out in aceto- ,
nitrite, methyl tent-butyl ether, toluene or methylene
chloride, in the presence of from 0 to 100, preferably
from 0 to 50, molar equivalents of a tertiary amine, such y
as 1,4-dia~abicyclo[2.2.2]octane or triethylamine.
B: A corresponding suifonyl carbamate of .:the formula
IV is reacted in a conventional manner (EP-A-120 814,
EP-A-101 407), in an inert o~ga~ic solvent at from 0 to
120°C, preferably from 10 to 100°G, with a 2-amino
pyrimidine derivative III. Bases, such as tertiary
aanines, may be added here, with the result that the ,
reaction is accelerated and the product quality improved.
Suitable bases for this purpose are, for example,
tertiary amines as stated under A, in particular tri
ethylamine or 1,4-diazabicyclo~2.2.2]octane, in an amount
of from 0.0I to 1 mot per mot of starting material IV. .
Advantageously used solvents are those stated
under A.
The solvent is used in an amount ~f from 100 to
2, 000, preferably from 200 to ?00, ~ by raeight, based on .
the starting material IV.
The compound IV required for the reaction is used
in general in about equimolar amounts (for example from
50 to'120%, based on the particular starting material
III). The starting material IV in one of the above-
mehtz~ned diluents may be initially taken and the start-
ing material ILI then added.
gowever, the starting material III in one of the
stated solvents or diluents may also be initially taken
and the sulfonyl carbamate, IV added.. ,
In both cases, a base may be added as a catalyst
hefore or during the ruction.
The end product I can be obtained from the
reaction mixture in a conventional manner, as stated
under Ao
A sulfonamide of the formula V is .reacted in a
.-.-.... ~emrr..ww.. ,. .....,.,.:.J.3'.-.,. ...:iJ. , ....J.~:~Y. . .r.:":j
,4~.~.:~... . < t;:...
~~:~~~~~
- 10 - O.Z. 0050/43041
conv.~ntional manner (Ep-A-141 777 and EP-A-101 670), in
an inert organic solvent, with about the stoichiometric
amount of a phenyl carbamate VI at from 0 to 120°C,
preferably from 20 to 100°C. The reaction can be carried
out at atmospheric or superatmospheric pressure (up to 50
bar), preferably at from 1 to 5 bar, continuously or
batchwise.
Bases such as tertiary amines, which accelerate
the reaction and improve the product quality, may be
ZO added here. Suitable bases for this purpose are those
stated under A, in particular triethylamine, 2,4,6-
collidine, 1,4-diazabicyclo[2:2.2]octane [DABCO] or 1,8-
diazabicyclo[5.4.0]undec-7-ene (DHU), in an amount of
from 0.01 to 1 mol per mol of starting material V.
Advantageously used solvents or diluents are
those stated under A:
The solvent is used in an amount of from 100 to
2,.000, preferabl~t from 200 to ?00, ~ by weight, based on
the starting material V:
The compound V'required for the reaction is used
in general in about equimolar amounts (for example from
to 120%, based on the particular starting materials
VI). The starting material VI in one of the above
mentioned diluents may be initially taken and the start
ing material V then added:
However,, the starting' material; V in one of the
stated solvents may also be initially taken and the
carbamate VI then added. In both cases, one of the
stated bases may be added as a catalyst before or during
3~ the reaction.
To terminate, the reaction, stirring is earrie.d
out for a further 20 minutes to 24 hours at from 0 to
I20°C, preferably from 10 to 100°C, in particular from 20
to 80°C, after the addition of the components.
The sulfonylureas of the formula I are isolated
from the reaction mixture by conventional. methods as
described under A.
CA 02129528 2003-07-29
11
D: ~ sulfonamide of the formula V is reacted in a
conventional manner (EP-A-234 352), in an inert organic
solvent, with about the stoichiometric amount of an iso-
cyanate VII at from 0 to 150°C, preferably from 10 to
100°C. The reaction can be carried out under atmospheric
or superatmospheric pressure (up to 50 bar), preferably
at from 1 to 5 bar, continuously or batchwise.
Bases such as tertiary amines, which accelerate
the reaction and improve the product quality, may be
added before or during the reaction. Suitable bases for
this purpose are those stated under A, in particular
triethylamine or 2,4,6-collidine, in an amount of from
0.01 to 1 mol per mol of starting material V.
Advantageously used solvents are those stated
under A. The solvent is used in an amount of from 100 to
2,000, preferably from 200 to 700, % by weight, based on
the starting material V.
The compound V required for the reaction is used
in general in about equimolar amounts (for example from
80 to 120$, based on the starting materials VII). The
starting material VII in one of the stated diluents may
be initially taken and the starting material V then
added. However, the sulfonamide may also be initially
taken and the isocyanate VII then added.
To terminate the reaction, stirring is carried
out for a further 20 minutes to 24 hours at from 0 to
120°C, preferably from 10 to 100°C, in particular from 20
to 80°C, after the addition of the components. The end
product I can be obtained from the reaction mixture in
the conventional manner, as described under A.
The sulfonyl isocyanates of the formula II which
are required as starting materials can be obtained in a
conventional manner from the corresponding sulfonamides
by phosgenation (Houben-Weyl 11/2 (1985) 1106,
US 4 379 769 ) or by reacting the sulfonamides with chloro
sulfonyl isocyanate (German Laid-Open Application DE 3,132,944).
The sulfonamides of the formula V can be obtained
~1 ~3~~~~
- 12 - .O.Z. 0050/43041
by r~ae:~ing the correspondling sulfon~r:l chlorides w.~th
ammonia ,,(M. Quaedvlieg in Houben-Weyl, Methoden der
organischen Chemie, Georg Thieme Verlag, Stuttgart, 9_
(1955), 398-400, F. Muth, ibid., 605 et seq.j. However,
it is also possible for an o-halobenzenesulfonamide to be.
subjected to a nucleophilic substitution reaction, for
example with an alcohol or thiol, and, for,example, far
the resulting corresponding thioether to be oxidized to
the sulfoxide or sulfone (cf. process examples).
The corresponding sulfonyl chlorides for pregara-
Lion of the sulfonamides of the formula V are obtained in
general by a Meerwein reaction (diazotization of suitable . y
amides and sulfochlorination with sulfur dioxide under
catalysis by a copper salt: F_. Muth in Houben-Weyl,
15. Methoden der organischen Chemie, Georg Thieme Verlag,
Stuttgart, ~ (1955), 579, S. Pawlenko in Houben-Weyl,'
Methoden der organischen Chemie, Georg.Thieme Verlag,
Stuttgart, Vol. E 11/2 (1985), 1069), from the corres
ponding sulfonic acids (F~ Muth in Houben-Weyl, Methoden
der organischen Chemie, Geo~rg Thieme Verlag, Stuttgart,
9 ( 1955 j , 564 j , by chlorosulf ovation of suitable aromatic
intermediates (F. Muth, ibid:, page 572) or by oxidative
chlorination of Iow-valence sulfur intermediates (mercap-
tan$,'diaryl disulfides or S-benzylmercaptansj (F. Muth,
iba.d., page 580, S. Pawlenko, Ioc. cit., page 1073).
The sulfonyl carbamates of the formula IV were
prepared by conventional reactions or'similarly to such
reactions (for example EP-A 120 814'. However, the
sulfvnyZisocyanates of the formula II, i.n an inert
solvent, such as ether or:dichloromethane, can also be
donverted with phenol into;the carbamates,of the formula
IV.
Carbamates of'the formula VI are obtainable by
known reactions or similarly to such reactions (for
exampl~ EP-A 101 670), but can also be prepared from the
.corresponding isocyanates VII by reaction with phenol.
The isocyanates of the formula VII are obtained
( N
~~< ~~~~
- 13 - O.Z. 0050/43041
from the amines of the formula~III by treatment with
oxalyl chloride or phosgene (similarly to Angew. Chem. 83
(1971), 407 or EP-A 388 873).
The synthesis of 2-amino-4-fluoro-6-methoxy
pyrimidine and 2-amino-4-ethoxy-6-fluoropyrimidine is
disclosed in DE-A-39 00 471.
2-Amino-4-chloro-6-trifluromethylpyra.midine is
known from the literature (J. Heterocycl. Chem. 20
(1983), 219). The 4-alkoxy-2lamino-6-trifluoromethyl-
pyri.midines III (Rl ~ methyl or ethyl; Rs - Vii) can be
obtained from this intermediate by reaction with corres-
a
ponding alcoholates (cf. process examples).
. 4-Methoxy-2-methylmercapto-6-trifluoropyrimidine
(J. Heterocycl. Chem: 20 (1983), 219) can be converted
with HzO2 into the 2°methylsulfone, which is reacted with
amines and hydroxylamines to give the starting materials
of the general formula III (cf. process examples).
The salts of the compounds I are obtainable in a
conventional manner (EP-A-304 282 or US-A 4,599,412).
They are obtained by deprotonation of the corresponding
sulfonylureas I in water or i~ an inert organic solvent
at from -80 to 120°C, preferably from 0 to 60°C, in the
presence of a tease: .
Examples of suitable bases are alkali metal or
alkaline earth,metal hydroacides, hydrides, oxides or
alcoholates,.such as sodium hydroxide, patassium hydrox
ide, lithium hydroxide, sodium methylate, sodium
ethylate, sbdium tert-butylat~, sodium hydride, calcium
hyd~:ide or calcium.-oxide.
,. ,.
..~, ..
.r
:. ,. ,; ,. - ....' . ; .~:., z . ,:,;_.... ..' , . ,
'; r.,
",,~.... ..._r..r:.. .. ..:.,,..:.~. ~.:~~....:,.... ...,.~..~ ~ ,. . ~
.,:.:,,.,.,.,
f , .,
~~.~~J~c~
~eZe ~~50/43041
-..Lxamples of suitable solvents in addition to
.~tx. '
water are alcohols, such as methanol, ethanol and tent-
butanols, ethers, such as tetrahydrofuran and dioxane,
acetonitrile, dimethylformamide, ketones, such as acetone
and methyl ethyl ketone, and halahydrocarbonse
The deprotonation can be carried out at atmos-
pheric pressure or at up to 50 bar, preferably at from
atmospheric pressure to 5 bar gage pressure.
The compounds I or tie herbicides containing
them, and their environmentally compatible salts of
alkali metals and alkaline earth metals, can very readily
control weeds in crops such as wheat, rice and corn,,
without damaging the crops, an effect which occurs in
particular at low application rates. They can be used,
for example, in the form of directly sprayable solutions,
powders, suspensions, including concentrated aqueous,
oily or other suspensions or dispersions, emulsions, oil .
dispersions, pahtes, dusts, broadcasting agents or
granules, by spraying, nebulizing, dusting, broadcasting
or pouring. The application forms depend on the ~.ntend~d
uses; they should in'any'case ensure vei°y fine distribu-
tion of the nswel activ~'ingredients:
The compounds' I are suitable in general for the
preparation of directly sprayable s~lutions, emulsions,
pastes or' oil dispersions. Suitable inert additives
include mineral oil fractions having s medium to high
bailing p~int, such as kerosene or diesel oil, and coal
tar oils and oils of vegetable or animal origin, alipha-
tic, cyclic and aromatic hydrocarbons, eg. toluene,
x~tlene, paraffan, tetrahydronaphthalene, alkylated
naphthalenes or derivatives thereof, methanol, ethanol,
propanol; butanol, cyclohexanol, cyclohexanone, chloro
benxene, isophorone ~r strong polar solvents, such as
N, I~i-dimethylf ormamide, diethyl sulfoxid~, N-methyl
pyrr~lidone or wai:~r:
l~queous application forms can be prepared from
emulsion concentrates, dispersions, pastes, wettable
_ ___ ..... _. ...... _._. ..... ... .. . , . .. . .. . , .. ... . .. . ... ..
.:.~....... :~..,..-..,.f:..,. ~ .~....,.~~ .. ... .. , .~.,.._. . ..
- 15 - p.Z. 0050!43041
.. ~rnwa~e~g ~r,r ~r~atcexwdi~cpers~in:~e g~ca~x~u:~e~ ri~r a,dd~.r~g w~:x~;e~
.six. ~.
For the. preparation of emulsions, pastes or oil diaper-
s~.ons, the substances, as such or dissolved in an oil or
solvent, can be homogenized in water by means of Wetting
agents, adherents, dispersants or emulsifiers. Sowever,
concentrates which consist of active ingredient, wetting
agents', adherents, dispersants or emulsifier"s and pos-
sibly solvents or oil and which are suitable far dilution
with water can also be prepared.
lU Suitable surfactants are the alkali metal,
alkaline earth metal, amacnonium salts of aromatic sulfonic
acids, for example lignin-, phenol-, naphthalene- and
dibutylnaphthalenesulfonic acid, and of fatty acids,
alkyl- and alkylarylsulfonates, alkylsulfates, laur~rl
ether sulfates and fatty alcohol sulfates, and salts of
sulfated hexa-, hepta- and octadecanols, and of fatty
alcohol glycol ethers, condensates of sulfonated naph-
thalene and its derivates with formaldehyde, condensates
of naphthalene and of naphthalenasulfnnic acids with
phenol and formaldehyde, polyoxyethyle~ne oetylphenol
ether, ethoxylated isc~octyl~, octyl- os nonylphenol,
alkylphenol polyglycol-ether, tributglphenyl polyglycol
eth~r, alkylaryl polyether alcohols, isotridecyl alcohol,
fatty alcohollethylene oxide condensates, sthoxylated
castor oil, polyoxyethylene alkyl ether or polyoxy-
propylene, lauryl- alcohol polyglycol ether acetal,
sarbit~1esters, lignineulfite v~aste liquors or
methyl.dellulose.
Powders, broadcasting agents and dusts can be
30- p~egared by mixing or milling the active ingredients
together with a s~lid Barrier.
Granules, for example coated, impregnated and
hog~geneous granules can be prepared by binding the
active ingredients to solid carrier. Solid carriers are
~u:neral acids, such as silicas, silica gels, silicates,
talc, kaolin, limestone, lime, chalk, bole, loess, clay,
do~.omite, kieselguhr, calcium sulfate, magnesium sulfate,
CA 02129528 2003-07-29
16
magnesium oxide, milled plastics, fertilizers, such as
ammonium sulfate, ammonium phosphate, ammonium nitrate and
ureas, and vegetable products, such as grain flour, bark
meal, wood meal and nutshell meal, cellulosic powders or
other solid carriers.
The formulations contain in general from 0.01 to
95, preferably from 0.5 to 90, °s by weight of active
ingredient.
It is worth mentioning that a definition of each
chemical compound identified by a specific compound number
hereinbelow (i.e. compound N° 1) can be found in Table 1 on
pages 26 to 28 of the present specification.
Examples of formulations are:
I. 90 parts by weight of compound No. 1 are mixed
with 10 parts by weight of N-methyl-a-
pyrrolidone, and a solution which is suitable for
use in the form of small drops is obtained.
II. 20 parts by weight of compound No. 2 are dis-
solved in a mixture of 80 parts by weight of
xylene, 10 parts by weight of the adduct of from
2 0 8 to 10 mol of ethylene oxide with 1 mol of N-
monoethanololeamide, 5 parts by weight of the
calcium salt of dodecylbenzenesulfonic acid and
5 parts by weight of the adduct of 40 mol of
ethylene oxide with 1 mol of castor oil. By
pouring the solution into 100, 000 parts by weight
of water and finely distributing it therein, an
aqueous dispersion which contains 0 . 02 % by weight
of the active ingredient is obtained.
III. 20 parts by weight of compound No. 7 are dissolved
in a mixture Which consists of 40 parts by weight
of cyclohexanone, 30 parts by weight of
isobutanol, 20 parts by weight of the adduct of 7
mol of ethylene oxide with 1 mol of isooctylphenol
and 10 parts by weight of the adduct of 40 mol of
CA 02129528 2003-07-29
16a
ethylene oxide with 1 mol of castor oil. By
pouring the solution into 100,000 parts by weight
of water and finely distributing it therein, an
aqueous dispersion which contains 0.02% by weight
of the active ingredient is obtained.
IV. 20 parts by weight of active ingredient No. 8 are
2~.~~~~8
. _ ~,7 _ l7. Z . 005
~ .. dissolved in a mixture which consists of 25 pasts
~'g~ x ~ ~
. by weight of cyclohexanone, 65 parts by weight of
a mineral oil fraction boiling within a range
from 230 to 280~C and 10 parts by weight of the
adduct of 40 mol of ethylene oxide with 3 mol of
castor oil. ~y pouring the solution into 300,000
parts by weight of water and finely, distributing
it therein, an aqueous dispersion which contains
0.02% by weight of the active ingredient is
30 obtained.
V. 20 parts by weight of active ingredient ~to. 34
are thoroughly mixed with 3 parts by weight of '
the sodium salt of diisobutylnaphthalene-a--
sulfonic acid, 37 parts by weight of the sodium
35 salt of a ligninsulfonic acid obtained from a
sulfite waste liquor and 60 parts by weight of
silica gel powder, and the mixture is milled in
a ha~uner x.11: ~y finely distributing the
~.xture in 20,000 paste by weight of water, a
20 spray liqu~~ which contains 0.3~ by wea.ght of the
active ingredgert i~ obtained.
VI. 3 parts by 'aei~ht of active ingredient ~Io. 27 are
mixed with 97 parts by weight of finely divided
ka~lin. pr dust which contains 3~ by weight of
25 the active ingredi~n~ is obtained in this manner.
Y~~. 30 p.$rts by weight of active ingredient No. Z0
ire tlaor~ughly ~t3.xed pith a anixtnre ~f 92 parts ~
~y soaeight of sil~.ca gel powder and 8 parts by
weight of liquid paraffin, which was sprayed onto
30 the surface of the silica gel. A preparation of
the active ingred~.ent having good adhesion is
~btained in this manner.
Vf~.T. 20 parts by weight of active ingredient No. 3 are
thoroughly ynixed with 2 parts by weight of the
35 calcium salt of dodecylbenzenesulfonic acid, 8
parts by wegght of a fatty alcohol polyglycol
ether, 2 parts by Weight of the sodium salt of a
~1~~~~t~
1g ~ O.Z. 0050/43041
~~x--.~.,,phenol/urea/formaldehyde condensate and ~g parts
by weight of a garaffinic mineral oil. A stable
oily dispersion is obtained.
Application may be effected by the preemergence
or postemergence meth~d. If the active ingredients are
less well tolerated by certain crops, it is possible to
use application methods in which the herbicides are
sprayed with the aid of the sprayers in such a way that
the leaves of the sensitive craps are as far as gossible
not affected, whereas the active ingredients reach the
leaves of undesirable plants growing underneath or the
uncovered soil, surface (post-directed, lay-by).
The app~.ication rates of active ingredient are
from 0.001 to 3, preferably from 0.01 to l, kg/ha of
active ingredient, depending on the aim of control, the
season, the target plants and the stage of growth.
In view of the versatility of the application
methods, the novel compounds or agents containing them
may also be used in a further number of crops for eli.min~
sting undesirable plants. For example, the followa.ng
crops ass suitablet
Botanical name Com~.non name
Allium ceps onions
Ananas comosus pineapples ,
Arachis hypogaea peanuts (groundnuts)
Asparagus offic~inalis . asparagus
Beta vt~lgaris spP, altissima ~ sugarbeets
Beta vulgaris sppraga fodder beets
Hrassica magus var. napus: rapeseed
Hrassica napus var. napobrassica swedes
Brassica raga var. silvestris beets
Camelli.a~sinensis tea plants
Carthamus tinctorius safflower
Citrus limon lemons
Citrus sinensis orange trees
Coffee arabica (Coffee canephora,
Coffee liberica) coffee plants
P
19 _ O.Z. 0050/43041
Hc~ta~xxca:l name Cc~~ia~un trauae-- -
"jpx. '
Cucumis.~sativus cucumbers
Cynodon dactylon Bermudagrass in turf
and lawns
Oaucus carota carrots
Elaeis guineensis . oil palms
Fragaria vesca strawberr.~.es
Glycine max soy beans
Gossypium hirsutum
(Gossypium arboreum cotton
Gossypium herbaceum
Gossypium vitifolium)
Helianthus annuus sunflowers
Hevea brasiliensis rubber plants
,
Hordeum vulgate barley
Humulus lupulus hops
Ipomoea batatas sweet potatoes
Juglans regia walnut trees
L~ns culinaris lentils
Linum usitatiseimum' flax
Lycopersicon lycopersicum tomatoes
Males sPP aPPle trees -
~nihot esculenta- cassava
Medic:~go sativa alfalfa ( lucerne ~
Musa spp. banana plants
Nicotiana abacum tobacco
(N ~sticaj
Olea europaea olive trees
Oryza sativa rice
Phaseolus lunatus limabeans
Phaseolus vulgaris , ; snapbeans, green
~, beans, dry beans .
Picea abies Norway spruce
Pines'sPP pine trees
Pisum sativum gnglish peas
Prunes avium cherry trees
- Prunes persica peach trees
Gd eJ v W l
_ ~.Z. 0050/43041
I~otani:cal name - ~'°mu~on name
----
T~yrus communis pear trees
Ribes sylvestre redcurrants
Ribes uva-crisps gooseberries
Ricinus communis castor-oil plants
Saccharum officinarum sugar cane
Secale cereals rYe . ...
Solanum tuberosum Trish gotatoes
Sorghum bicolor (S. vulgare) ' sorghum
Theobroma cacao cacao plants
Trifolium pretense red clover
Triticum aestivum wheat
Triticum durum durum wheat
Vicia faba tick beans
Vitis vinifera grapes
Zea ways Indian corn, sweet
corn, mal2e
In order to broaden the action spectrum to
achieve synergistic effects, the pyrimidinyl-substituted
sulfonylureas of the fonaula I can be mixed and applied
together with many members of other herbicidal or growth-
regulating groups of active ingredients. For example,
dia2inee, 4H-3,1-benzoxaza.ne derivatives, ben2othia-
diazinones, 2,6-dinitsoanilines, N-phenylcarbamates,
thiocarbamates, halocarboxylic acids, triazines, amides,
ureas, diphenyl.ethers, triazinones, uracils, ben2ofuran
derivatives, cyclohexane-1,3-dune derivatives,
cyuinolinecarboxylic acid derivatives, phenoxy- and
hetaryloxyphenylpropionic acids and their salts, esters
and amides, and ~thers, are suitable as components of the
mixture .
It may also be useful to apply the compounds of
the formula I, alone or in combination with other herbi-
cides, also as a mixture together with further crop
protection agent, for example with pesticides or agents
for controlling phytopathogenic fungi or bacteria. The
mi.sc~.bility with mineral salt solutions which are used
~1~.~:~
- 21 - O. Z . 0050/43041
for ~ liminating nutrient and trace element deficiencies
is also, of interest. Nonphytotoxic oils and oil con-
centrates may also be added.
Typical examples of the preparation of the
intermediates II-VII are given below.
1. 2-Amino-4-methoxy-6-trifluoromethylpyrimidine
28.1 g of a 30% strength by weight ..,solution of
sodium methylate (O. x6 mol) in methanol (internal tem-
perature below 40°C) were added'dropwise to a solution of
25.? g of 2-amino-4-chloro-b-trifluoromethylpyrimidine
(0.13 mot) in 200 ml of methanol. Stirring was carried
out for one hour at 20-25°C, the volatile components were '
removed under reduced pressure from a water pump at 65°C,
the residue was taken up in l 1 of dichloromethane, the.
solution was washed with water, the dichloromethane phase
was dried over NaZSO, and the solvent was removed under
seduced pressure from a water pump. 23.4 g of the
product (93% of theory) were obtained as colorless
crystals of melting point 208-109°C.
2-Amino-4--ethoxy-6-trifluosomethylpyrimidine of
melting point 114-116°C was obtained in a similar manner
by reacting 2-amino-4-chloro=6-trifluorontethylpyrimidine
with sodium methylate im ethanol.
2. 4-~Iethoxy-2-methylsulfonyl-6-trifluoromethyl-
Pyr~dirne
? .1 g of a 30% strength by we~.ght solution of $z02
(63 mmol) a.n water were added dropwise to ~ solution of
5.0 g of 2,4-methoxy°2-methylsulfonyl-S-trifluoromethyl-
pysimidine (22 'mmol) in 50 ml of glacial acetic acid.
The mixture was heated slawly to an internal temperature
of 90°C and stirred for 1 hour at ,this temperature, and,
the reaction batch was cooled to 25°C and then .introduced
into 2 1 of glacial acetic acid. The product was ex-
traced with 200 ml of dichloromethane, the organic phase
wa.~ we.shed With a dilute sodium thiosulfate solution and
then with water, the solution of the product was dried
over NazSO, and the solvent was removed under reduced
~~r.~~
22 - O. Z . 0050/43041
pres~ur~ from a water pump. 5. ~. g of the product ( ~0% of
.~x~ ' . '
theory'. were obtained as colorless crystals of melting
point 88-90°C.
3. 2-(~I-Methoxyamino)-4-methoxy-6-trifluoromethyl-
pyrimidine
66.6 g of a 1.6 molar solution of n-butyllithium
( 0 .156 mol j in n-hexane were added dropwise to a solution
of 6.5 g of O-methylhydroxylammonium chloride (?8 mmolj
in 200 ml of tetrahydrofuran ~at -ZO°C. Stirring was
carried out for I0 minutes at -10°C, and 20 g of 4-
methaxy-2-methylsulfonyl-6-trifluoromethylgyrimidine
(?8 mmol) were added to the cloudy solution. Stirring '
was carried out for 1 hour at 25°C, the reaction batch
was introduced into 200 n1. o~ water, and the organic
ghase was separated off, washed with water and dried.
Removal of the solvent gave an oily, slightly impure
product, which could be crystallized in pentane at -78°C.
7;,5 g of the product (43% of theory) were obtained as
colorless crystals of melting point 44-46°C.
4. 2-Iaocyanato-4-methoxy-6-~rifluoromethylpyrimidine
38. 3 g of oxalyl chloride ( 0. 3 mol' were added
dropwise to a suspension of 2-amino-4-methoxy-6-tri
fluoramethylpyrimidine (78 mmol) in 1d0 ml of toluene.
The refluxing mixture was stirred for 4 hours, after
which the homogeneous solution obtained was subjected to
fractional distillation: The-title compound (9.9 g; 58%
of theory) was obtaihed as an oil of boiling point 44
,~OoC ~~~5 mbar).
5. 4-Methoxy-2-[(phenoxycarbonyljamino~-6-trifluoro-
methylpyrimidine
4.2 g of phenol (45 mmoly were added at 25°C to
a solution of 9.~9'~g of 2-isocyanato-4-methoxy-6-tri-
floor~methylpyrimidine ( 45 m~nol j in 50 ml caf methylene
chloride. Stirring was carried out for 16 hours at 25°G,
the pnethylene chloride was distilled off under reduced
pressure and the residue was stirred vigorously with
a00 ml of a dii opr~pyl ether/hexane mix~c~ure (v/v
2~.~~~~8
23 _ O.Z. 0050/43041
, 1 : ~l(1 j., ~,rhereupon crystallization occurred. ~'he product
was filtered off with suction and dried under reduced
pressure from a water pump at 50°C. The title compound
(12.2 g; 87% of theory] was obtained as colorless crys-
tale of melting point 85-88°C.
6. 2-(Methylsulfinyl)benzenesulfonamide
14.8 g of hydrogen perox~.de (0.13.. mol), 30%
strength in HTO, were added dropwise at from 25 to 30°C
to a suspension of 26.5 g of 2-(methylthiojbenzene-
sulfonamide ( 0.13 mol ) and 2.1 g of NaTWO~ ~ 2Hz0 in 88 ml
of glacial acetic acid. Stirring was carried out for 45
minutes at 25'°C, the reaction mixture was poured onto 400
ml of water and the precipitate was filtered off with
suction. Tt was washed with water and dried under
reduced pressure from a water pump at 40°C. 24.3 g (85%
of theory] of the title compound Were thus obtained.
1H-1NMR spectrum ( 250 MHz, CD3SOCD3, int. TMS ) : 8 .16 d
(1H), 7.82-8.0 m (2H), 7.77 b= (2S), 7.63-7.85 m (2Hj,
2.76 s (3H),
? : lei- ( n-Hutylaa:ino ) carbonyl-2~methylsulfinylbenzene-
sulf onamide
10.2 g of n-Butyl isocyanate (0.10 molj Were
added drogwise at 25°C to a suspension of 20.1 g of 2-
(methylsulfinyl ) benzenesulfonamide ( 0:09 anol j in 250 ml
of acetonitrile. 13.9 g of potassium carbonate
(0:10 mol) were'added, after which the refluxing mixture
was stirred fo= 4 hours. After cooling to 0°C, the
mixture ~aa poured onto 400 ml ice/water, brought to a pH
of ~, by adding concentrated hydrochloric acid and ex-
tracted with methylene chloride. The organic extracts
were washed neutral with water and dried. After removal
of the solvent, 25~ g of the title compound (85% of
th~oryj were obtained as a gale brown oil.
I~-NI~R spectrum (250 MHz, CDCl~, int. TMSj: 8.28 d (1B),
gWaO d (lHj, 7.89 t (2Hj, 7.?3 t (1H), 6.03 t (IH),
3.13 m (2H), 2.95 s (3H), 1.38 m (2Hj, 1.24 m (2Hj,
w 85 t ( 3H j .
. 212~j~8
r 24 _ O.Z. 0050!43041
ii . ' l-._( l~et~yylsu~.finyl ) be.uzenesulfonyl . ~-gocy~.ri~ate
,Phosgene was slowly passed into a refluxing
solution (cooled with solid carbon dioxide) of 25 g of N
[(n-butylamino)carbonyl-2-methylsulfinyl]benzenesulfon
amide and 0.4 g of 1,4-diazabicyclo[2.2.2]octane in
400 ml of xylene, until an internal temperature of 110°C
was reached. The Cooling was removed and the volatile
components were distilled off under reduced pressure from
a water pump at 80°C. The remaining sulfonyl isocyanate
was reacted without further purification.
9. N-[(n-Butylamino)carbony!-2-(N,N-dimethylamino-
sulfonyl)]benzenesulfonamide .
18.6 g of n-butyl isocyanate (0.18 mol) were
added dropwise at 25°C to a suspension of 44.2 g of 2
[N,N-dimethylaminosulfonyl]benzenesulfonamide (0.17 mol)
(prepared similarly to 2-[N,N-diethylamino)-sulfonyl]
benzenesulfonamide in US-B-4,310,346) in 450 ml of
acetonitrile: A-fter the addition of 25.4 g of potassium
carbonate (0:18 mol), the refluxing mixture was stirred
for 3 hours. After cooling to 0°C, the reaction mixture
was pou=ed onto 400 ml of ice/~ater andvbrought to a pH
of I by adding concentrated hydrochloric acid, and the
precipitate-formed was filtered off with suction, washed
neutral with water and dried under reduced pressure from
a water pump at 44°C. 60 g of the title compound (99% of
theory) were obtained in this manner:
1H-NMR spectrum (250 MHz, CDCl~ int. TMS): 8.55 br (1H),
~ . 30 d ( 1H ) , 8 . 05 d ( 1H ) , 7 : 7-7 . 9 m ( 1H ) , 6 . 52 t ( 1H ) ,
3.17 qua (28), 2.94 s '(6H), 1.43 qui (2H), 1.25 sext
(2Hj, 0:85 t (3H).
10. 2-[N,:N-(,Dimethylam~.no)sulfonyl]benzenesulfonyl
isocyanate
The sulfonylurea obtained in Example 9. was
converted into the corresponding sulfonyl isocyanate,
similarly to the preparation of 2-(methylsulfinyl)
benzenesulfonyl isocyanate.
Typical examples of the synthesis of the
21~~~~~
-- 25 - O.Z. 0050143041
su~.fr~nylureas ~ and their salts are described below.
~~a'-
11. 2-Nitro-1-N-[4-methoxy-6-trifluoromethylpyrimidine-
2-yl)aminocarbonyl]benzenesulfonamide
g of 2-nitrobenzenesulfonyl isocyanate
(35 mmol) in 10 m1 of 1,2-dichloroethane were added at
25°C to a mixture of 6.7 g of 2-amino-4-methoxy-6-tri-
fluoromethylpyrimidine (35 mmol) in 10 ml, ~f dichloro-
methane. Stirring was carded out for 14 hours at 25°C,
after which the solvent was removed under reduced pres-
sure from a water pump at 40°C and the residue was
stirred vigorously for 2 hours with 50 m1 of diethyl
ether. The product was filtered off with suction and
dried under reduced pressure from a water pump at 40°C.
3 g of the title compound (20% of theory] were obtained
as colorless crystals of melting point 204-205°C. ~ v
12: Sodium 2-nitro-1-N-[(4-methoxy-6-trifluoromethyl-
pyrimidin-2-yl)aminocs,rbonyl]benzenesulfonami.de
0.65 g (36 mmol) of a solution of sodium meth=
ylate (30% by weight) in methanol was added at 25°C to a
ZO susgension ref 1.5 g of 2-vitro-I-N-[(4-a~eethoxy-6-tri
fluoromethylpyri~nidin-2-yl)aminocarbonyl]benzn~nesulfon-
amide (3:6 Col) in 20' ml of methanol. Shirring was
carried nut for '10 minutes at 25 °C after which the
homogeneous solution was evaporated down under reduced
pressure from a water gump at 50°C: The title compound
was obtained in~duantitative yield as colorless crystals
having a decomposition temperature of 1.64-166°C.
13 , 2-[ [ (;~~Fluor~-6-a~ethoxyPYrimidin~2-yl ) amir~o
carbonyl]aaninosulfonyl]benzenesulfonic acid N,N
dir~thygamide
~ .1 g of ~- ( diu~ethylami.no ) sulfonylbenzenesulf on~rl ;
isc~cyanate (2S mmol) ~ae~re added at 25°C to~a suspension
of 4:0 g of 2-amino-4-fluoro-6-methoxypyrimidine
(2~ mmol)-in 30 ml of ethylene chloride. Stirring was
carried'out for 16 hours at 25°C and the precipitated
product was filtered -off with suction. To eliminate
unconverted pyrimidine, the precipitate was stirred
~1 ~~r~3
28 ~ O.Z. 0050/43041
wigp,~ously With diisopropyl~ether. The product was
filtered off with suction, washed with n-hexane and dried
at 40°C under reduced pressure from a water pump.
7.2 g (59%) of the title compound (decomposition
temperature 138°C) were obtained in this manner. Further
product could be isolated from the mother liquor.
1H--NMR spectrum (Z50 MHz, CD3COCD" int. TMS,.. E (gpm) )
2.91 s (6H), 4.17 s (6H), 6.24 s (1H), 7.8-8.0 m (2H),
8.04 m (1H), 8.50 m (1H), 9.63 br (1H), 12.25 br (1H).
14. [(4-Fluoro-6-methoxypygimidine-2-yl)aminocarbonyl]-
2-methylsulfonylbenzenesulfonamide
4.7 g of 2-(methylsulfinyl)benzenesulfonyl
isocyanate (19 mmol) were added at 25°C to a solution of
2.7 g of 2-amino-4-fluoro-6-methoxypyrimidine (19 mmol)
in 30 ml of methylene chloride. Htirring was carried out
for 16 hours at 25°C, after which the precipitated
product was filtered off, with suction, washed with a
little ether and dried under reduced pressure from a
v~rater Bump at 50°C. 0.9 g ~f the title ct~mpound ( 10% of
theory) at melting 'pointc 161-176°~ was obtained in this
manner: Further product could be isolated from the
mother liquor.
The active ingredients stated in Table 1 below
were obtained by a sinni.lar separation method.
.25 TABLE 1
R3 R~
R9
N
SO--~~1-~6 ' ~
RZ
OR1
N
_ 2? _ 0.~. 0050/43041
AcAll~ ~1 R~ Rd
r .
' ~
~n~rEd!!at
Na
1 CH3 S02NICH3?ZH F 198
2 CH3 S02N(CH3j2H F 161-168"
3 CH3 S02NtCH3)2H F 184-I92"'
4 CHI OCFzCFZH H F 135-139
CH3 (~F3 H F 181-182
6 CH3 t7CF3 H . F 140146'
? CH3 N02 H F 159-16?
8 CH3 N02 H F 214"
9 CH3 SOZICZH5~2H F 206
CH; S02~C2Hg)2H F 200"
11 CHg CF3 . H F 181
12 CH3 CF3 H F 178'
13 CH3 CH3 H F 185-193 due.
14 CH3 CH3 H F 166'
1~ CH3 OCH3 H F 20?-209
16 CH3 ~H3 , H g 1?0''
Z7 CHI cF3 6-CH3 F 206=209 air.
lg CH3 CF; 6-CH3 F ~ 250*
19 CH3 N02 H CF3 204_ZOS
CHI N02 H CFA 164-166
21 CH3 CF3 H CF3 194-196
22 CH3 CFA H CF3 1?4-179'
23 CH3 CF3 H CF3 156-160..
24 CFi3 SOzCH3- H CF3 202-204
CH3 OSOZCH3 H CF3 19?-200
26 CND OCFZCF2H H F I64t
2? CHI SCH3 H F 192-193
28 CH3 SCH3 H F 120-135*
Na alt oo~,)
(~ oomP.)
a w K
alt
(de
~1~~~~8
2g _ O.Z. 0050/43041
,~,~ . R3 R4 RS trc.P. [ ~C
" _ R1 1
~
io~dime
Na "
2 9 CH; SCH; H F 2 0 5--210'
30 CH; CH~OCH3 H F 167-169
31 CH; SCH3 H CF; 163-166
32 CH3 SCH; H CF; 146-151*
33 C~HS SCH3 H CF; 172=173
34 CH; CH20CH3 H CF3 165
35 CH3 OCF; H CF; 153-154
36 CH; OCF3 H CF3 107*
37 CH; SCH; 6-SCH; CF3 190-192 ,
38 CH; SCH3 6-SCH; CF; 1?4'
39 CH; SCH; 6=SCH; F 191-193
40 CH; SCH; 6-SCH~ F 186*
4I CH; OCH2CF3 5-OCHZCF; F 189-190
42 CH; f7CHZCF3 5-OCHZCF3 F 152* ~w
43 CH3 Sp2C2H5 5-Cl F 205-209
' Na
tit
(dip,)
a r ~d)
K ~
The compounds shown can
below also
be
obtained
in
a similar .
manner:
~~ o _ CF3 ,
R4
N
'
S0--C~-~/
OCH3
NOZ F
O
R~
SOZ--NH-C-NH-~/ ~
OCH3
or'the Na is
salts hydrogen,
thereof, 3-methyl,
where
R'
i
- 29 - a.Z. 0050!43041
4-~r~~ ~,t~y~.. W-~athy~., 6-a~~tl~yl., :i-ethyl, 4-ethyl, 5~att~y~.,
.,~ ~'
6-ethyl, 3-fluoro, 4-fluoro, 5-fluoro, 6-fluoro, 3-
ch~.oro, 4-chloro, 5-chloro, 6-chloro, 3-~thoxy, 4-
~ethoxy, 5-anethoxy, 6-anethoxy, 3-ethoxy, 4-ethoxy, S-
ethoxy, 6-ethoxy or 6-methylthioP
0CH3 ~ Cg3
...
N
s0~-~-~--C~TH
-
N , ,-.
OCFi3
s
OCH3 ~ g
R4
N
S02-.-NH-C-~.~!
N°
~CH~
or the Ira salts there~~, where ~' is hyc~rnge~a, 3-ynethyl,
4-methyl. p 5-nctethyl, 6-methyl, 3-ethyl, 4-~thyl, 5-ethyl,
6-ethyl, 3-fluoro, 4-fl.txoro, 5-fl~orci, 6-fluoro, 3-
chloro, 4~chloro, S-chloro, 6-chloro, 3-~ethoxy, 4-
m~t~oxy~ 5~~nethoxy, 6~~ethoxy, 3-ethoxy, 4-ethoxy, 5-
etho~cy, 6-ethoxy or 6~~~thylthio;
~~,3 ~ ~
~g
N
~~~NH~.-c~---~!
~~3
OCF'3 ~ CFA
R9 ~~ N
1 S02-,-.NH--~~~/
OCH3
~lw~~~~
V s i1 0 ~~~
or tYa~ Vila ~a~.t~ thereof, where ~4 ~.~ hyc~ogen~o v ~-methyl.,
~~la-
4-methyl, 5-methyl, S-methyl, 3-ethyl, 4~ethyl, ~-ethyl,
6--ethyl, 3~fluoro, 4r~fl.uoro, 5~fluoro, 6~fluoro, 3°
chlaro, 4-~chlaro, a-chl.oro, 6-chloro, 3°m~thox~', ~-
methoxy, 5-methaxy, 6-methoxy, 3-ethaxy, 4-ethaxy, 5-
ethaxy, 6~ethoxy or 6-methylthio;
CF3 0 CF3 . ...
\ 502.x--c~-_(/ \
N-
aC~i3
CF3 0 F
~4
S02-~TFi--~CC~1I3~
I3_
0CH3
ar the Ira pelts thereof, where Vita ,~.s hydrogen, 3-methyl,
4-methyl, 5-methyl, 6-methyl, 3-ethyl, 4--etk~yl, ~°-ethyl,
6-ethyl, 3-fluoro, ~-fluoro, 5-flu~ro, 6-fluosa, 3-
chloro, 4-~hloro, 5-chloro, 6-chloro, 3-aaethaxy,
methoxy, 5~methoxy, s-methoxy, 3-ethoxy, ~-ethoxy, ~-
ethoxy, ~-ethaxy or g-~ethylthlo;
~FZCF~H 0 CFg
N
\ sod--c-~~l \
OCFZCFzH ~ g
soy-~x..~~--
~_
OCH3
- 31 - ~~ ~ ~ 0050/43041
dr iG~~~-- Na ~~s:1'~~- 't~~~e~ewcrof o va'he~'~-.-R~ .is .h~.~~',~rt~exa,
3~~ote'~f~~'1,
.~ ~ _ ~'
4-methyl, 5-methyl, 6-methyl, 3-ethyl, 4-ethyl, 5-ethyl, .
6-ethyl, 3-fluoro, 4-fluoro, 5-fluo~ro, 6-fluoro, 3-
chloro, 4-chloro, 5-chloro, ~-chloro, 3-methoxy, 4
methoxy, 5-methoxy, 6-methoxy, 3-ethoxy, 4-ethoxy, 5
ethoxy, 6-ethoxy or 6-methylthio;
CH3 O ~~,3 ...
R9
N
S~z~--~~~/ a
N_
OCH~
CH3 ~ F
H~ .
N
S0--C~--.~l
N_
~C~I3
or tlae Na salts thereof, where R' is hydxogee, 3-methyl,
4-methyl, 5-methyl, 5--methyl, 3-ethyl, 4-ethyl, 5-ethyl,
6-ethyl, 3-fluoro, 4~fluoro, 5-fluoro, 6--fluoro, 3-
chloro, 4-~chlo~o, 5-chloro, 6-chloxo, 3-methoxy, 4-
methox~r, 5~methoxy, 6-methoxy, 3-ethoxy, 4-ethoxy, 5-
ethoxy, 6-ethoxy ~r 6-methylthio;
or the Na salts thereof, ' where R3 is hy~lrog~n, 3-methyl,
4s~~,~h~l, 5-methyl, ~-methyl, 3~ethyl~ 4-ethyl, 5-ethyl,
.15 6-ethyl:, 3-fluoro, 4-~f~.u~ro, 5-fluoro, s-fluoro, 3- .
ch~:o~o, 4°chloro, 5-chl~ro, 6-ehloro, 3-methoxy~ 4-
~e.~hoxy, 5-methoxy, 6-anethoxy, 3-ethoxy, 4-ethoxy, 5-
~thoxy, 5-sthoxy or 6-methylthio;
~~~~ ~%r~
- ~2 - OoZ. ~05~D1~3041
CFIaOCH~ ~ Cg3
R4
N
SO~~,--C.~,pgi--
N~ , .
OCH3
CHZ0CH3 g
Ft9 ,I . N
S02--~~c[ -.-~--(!
o~ N -
or the Na salts thereof, where R' is hydrog~r~, 3-methyl,
~-methylo 5-methyl, 6-methyl, 3-ethyl, ~-ethyl, 5-ethyl,
6-ethyl, 3-fluoro, 4-fluoro, 5-fluoro, 6-fluoro, 3-
chloro, ~-chloro, 5-~hloro, 6-chloro, 3-~tethoxy, 4- :::;
me~hoxy, 5-methcxy, s-methoxy, 3-ethoxy, 4-ethoxy, 5-
ethoxy, 6~ethoxy or 6-~etkaylthio;
SCF~ ~ 0 CF3
Rq (~ N
~ SOa-----r~e-C
OCH3
. SCF3 ~ F
~I i
sox-c-~H-
OCH3
or the Na silts thereof, v~here I~° is h~rlroc~en, 3-methyl,
4-me~.hyl, 5-methyl, ~-methyl, 3-ethyl, ~-ethyl, 5-ethyl,
5-~~hyl, 3-fluoro, 4-fluoro, 5-fluoro, 6-fluoro, 3-
1Q . ~hloro, 4-chloro~ 5-chloro, 5-chioro, 3-methoxy,
methoxy, 5-methoxy, 6-methoxy, 3-ethoxy, 4-ethoxy, 5-
2~.~,~~w~
~lr ._, 3~ .~ VoZo ~~ .
eth~x~,~;, 6-ethoxy or 6-anetlaylthio~
OSOaCHC3 0 Cg~
N
!i
soy--c.~--~e ~
N_
OCH3
t~S02CIi3 O . ~
R4
ii ~ ~
~~.--~-.~--~--.~
--
OCH3
or the Ids salts thereof, where
R4 is hydrogen,
3-methyl,
4-methyl, 5-methyl, 6~m~thyl,
3-ethyl, ~-ethyl,
5-ethyl,
6-ethyl, 3-fl~oro, ~~-fluoro,
5-fluoro, 6-fl~aoro,
3-
ch3.oro,
4-chloro,
5-chhro, 6-chloro,
3-a~etlaoxy,
4- .
methoa~y, 5a~tethc~xy, 6~methoxy,
3-ethoxy, 4-~thoxy,
5-
eth~~y, s.~~t~~~y
~r s~~~thy~ah~.~;
OSO~t:F3 ~ CF3
R~
ii N
sod--.c-~-(e'
~-
0CH3
O~OZCF3
R~
ii N
S~~-~~1H~~TH--~e
:
_.. N ~ :.. '.::
..
OCH3
or the Na salts thereof, where
R' is hydrogen,
3mme~hy3.,
~4-metlhyl, 5~a~aethyl, 6-methyl,
3-ethyl, 4-ethyl;,
5-~thy3l,
6-ethyl, 3-fluoro, ~-fluoro,
5-fluoro~ 6-flaasaro~
3-
ohloro, 4-chloro, 5-chloro,
6-chloro, 3~metho~cy,
. 4-methc~xy, 5-methoxy, 6-methoxy, 3-ethoxy, ~-ethoxy, 5-
~'a' ~r - '
ethoxy, 6-ethoxy o= C-methylthio.
Use Examples
The herbicidal action of the N-[(pyrimidin-2
yljaminocarbonyl~benzenesulfonamide of the formula f on
the growth of the test plants is demonstrated by the
following greenhouse experiments. '°
The culture vessels used are plastic flower pots
having a capacity of 300 cm$ and containing loamy sand
with about 3.0% of humus as a substrate. The seeds of
the test plants are sown shallow and separately according
to species.
For the purpose of the postemergence treatment,
the plants which are e~.ther directly sown or grown in the
same vessehs are selected, or they are first grown
segarately as seedlings and transplanted into the test
vessels a few days laefore the treatment.
The test plants, at a height of growth of from 3
to 15 cm, depending on the form of growth, are then
treated with the active'ingredients which are suspended
or emulsified in water as a distributing' medium and which
aye sprayed through finely distributing nozzles. The '
application rate for the postemergence treatment is 0.06
and 0:03 kg/ha a.i. (acti~re 3.ngredient,.
The test vessels are placed in a~ greenhouse,
w~rm~s areas (from 20 ~~ 35°C~' being g~referred fos
sr~armth-loving species and fgom 10 to 20°C being preferred
fir those of temperate climates: The test period extends
over fr~m 2 t~ ~ weekso During this time, the plants are
tended and their r~act~on to the individual treatments is
evaluated.
Evaluation i~ based~on a scale of from 0 to 100:
100 means no e~aergence of the plants or complete destruc-
tio~t of at least the above-ground pa$-ts, and 0 means no
~5 damage or normal course of growth.
The plants used in the greenhouse experiments
consisted of the following species:
. ~~.29~~~
35 _ ~.Z. 0050/43041
~otarW xJL xiarne ~:ommori ndjotte
.~,r-
Alopecurus myosuroides slender foxtail
Echinochloa crus-galli barnyard grass
Setaria italics foxtail millet
Zea mat's corn
When used at a rate of 0.06 and 0.03 kg/ha a.i.
by the postemergence method, Example No.,,.ll controls
u:adesirable plants very well while at the same time being
compatible with the example crap corn.
1~ Compound No. 11 was compared with the comparative
substance J disclosed in EP-A 101 308. The results,
,..~.. .
which are listed in Table I, demonstrate the substantial- .
ly better herbicidal activity in conjunction with high
selectivity in the example crop corn.
Co~gounds No.' 23, 25 'and 19 were compared with
the comparative substances N and O disclosed in DE--A
27 15 786 (US 4,120,691)° The results listed in Tables
I:I to IV demonstrate the better herbicidal act%vity in
conjunction with high selectivity in the example crop
minter wheat ;(Triticum aestivum):
Table I: Herbicidal activity in postemergence applica-
ti.on in the greenhouse
S02-- R
SQz-NIiCON~i--~~ ~
r"
r~ ..i
- 36 O.Z.
- 0050/43041
Exle No. I1 J
Cz$s n-CaH7
~rpplication rate
(kg/ha a.i.) 0.06 0.03 0.06 0.03
Test plants
(damage in %)
F.lopecurus myosuraides 95 . 80 55 0
Echinochloa crux-galli 100 98 30 10
Setaria italics 85 85 20 15
Zea ways 15 15 ZO 0
Table II: Herbicidal.activity in postemergence applies-
tion in the greenhouse
R CF3
SOZ-I~THC~IE~i--~~
C Ex~a~le No.~~~ 25 .":"'~...~r.,o _,N ~.......,.~..~..~...
, ' OSO2CH3 Cl
I R
Application rate
(kg/ha a.i.) (0.06 ~U.03 10.06 0.03
Test plants
damage in % ) ~
'
Triticum sestivum 20 0 1~l 5
Echinochloa crux-galli 85 70 40 30
Amaranthus retroflexus 100 100 98 98
Sinapis alba 100 100 90 80
Solanum nigrum 100 100 40 30
Veronica spp. 85 T5 40 30-
Table III: applica-
Herbicidal
activity
in postemergence
tion in greenhouse
the
R CF3
$pZ---NHCONH-~~
OCN3
21~~a?~
- 38 - O.Z. 0050/43041
_'af x .'
Example Nos 23 N
?ti, CF3 C1
Application rate
(kg/ha a.i.) 0.06 0.03 0.06 0.03
Test plants
(damage in %)
Echinoehloa crus-galli 88 60 40 30
Abutilon theoprasti 95 95 50 40
Chenopodium album 100 100 95 90
Chrysanthemum corinarium 100 100 75 65
Galium aparine 90 90 40 20 '
Solanum nigrum 100 100 40 30
Polygonum persicaria 100 95 80 50
Table'IV. activity postemergen~e applica-
Herbicidal in
tion greenhouse
in the
CF3 R
g pZ
~.
NFICONFi--~/
. - . N_
CH3 ' OCH3
a
- , . ... ,,.
. , .. _
. .. , ..,.,a:
.,. .. .
:.r,..:..
..
.,.
..
..
.
..
..
"
............,vn
>.....,...,
....
.
,.,
,
.
,..
,.
..c
..
,..
.
.,....
..
.
....
n...
.
.
N
" Os4.
~~ 00
-
adx '~ .:..
.
Example No. 19 O
C . . ..;;
.. .:
Application rate
(kg/ha a.i.j 0.06 0.03 0.06 0.03
Test plants
(damage in %)
Triticum aestivum 10 10 50 40
Echinochloa crux-galli 75 65 80 80
Amaranthus retroflexus 100 100 100 I00
Sinapis albs 75 75 90 90
Solanum nigrum 100 95 98 90
