Note: Descriptions are shown in the official language in which they were submitted.
Title BA-8496
8ackground of the Invention
This invention relates to novel N-(heterocyclic-
aminocarbonyl3arylsul~onamides in which the aryl radi-
cal is substituted with a carboxyl radical. The com-
pounds of this invention and their agriculturally
suitable salts, are use~ul as agrioultural chemicals,
herbicides which may be selective and regulate growth.
lûIn EP0 Publication 7,687, there is disclosed
herbicidal compounds of the general formula within the
broad generic scope.
~ S02N-C NRl
R2 ~ R4 R5 (I)
R3 0
wherein
R may be Cl-C12 alkyl;
R2 and R3 may be hydrogen, as may R4
and R5;
Rl may be
25~ , or ~ O ~ Xl ;
Y Yl Y
R2 is H, Cl, Br, F, Cl-C3 alkyl, -N02,
-S02CH3, -OCH3, -SCH3, -CF3,
-N(CH3~2, -NH2 ~r -~N;
R3 is H, Cl, Br, F or CH3;
R4 is H or -CH3;
R5 is H, -CH3 or -OCH3;
38'7
X is H, Cl, ~CH39 -OCH3, -OCH2CH3 or
-OCH2CH20CH3;
Y is H; Cl; Cl-C4 alkyl; Cl-C4 alkyl
substituted with -OCH3, -OC2H5, -CN,
-C02CH3, -C02C2H5, or 1 to 3 atoms
of F, Cl, Br; C3-C4 alkenyl;
2C-CR13 where R13 is H, -CH3
-CH2Cl; ~A-(CH2)n~Al (Cl C3
alkyl), and n', A and Al are as
previously defined.
The presence of undesired vegetation causes sub-
stantial damage to useful crops, especially agricul-
tural products that satisfy man's basic food and fiber
needs, such as rice, corn and soybeans. Compounds
such as the ones indicated above, are extremely effec-
tive for killing or inhibiting the growth of undesired
vegetation; suoh materials are commonly referred to as
herbicides. The need still exists for more effective
herbicides.
0197
Summary of the Invention
This invention relates to novel compounds of
Formula I, agriculturally suitable compositions con-
taining them and their method-of-use as selective pre-
emergent or post-emergent herbicides.
~ C02R OCH3
~ 502NHCNH~O~
N ~
Cl
I
wherein
C2H5~ CH(~H3)2 or CH2CH=CH2;
and their agriculturally suitable salts.
Specifically preferred are:
2-t~(4-chloro-6-methoxypyrimidin-2-yl)aminocar-
bonyl]aminosulfonyl]benzoic acid ethyl ester, m.p.
198-201;
2-[[(4-chloro-6-methoxypyrimidin-2-yl)aminocar-
bonylaminosulfonyl]benzoic acid isopropyl ester,
m.p. 185-187~; and
2-~4-chloro-6-methoxypyrimidin-2-yl)aminocar-
bonyl]aminosulfonyl]benzoic acid 2-propenyl ester,
m.p. 180-18~.
.
~2~ 8'î~
Detailed Descri~tion_of the Invention
Compounds of Formula I are prepared by the pro-
cedure of Equation 1. This procedure is well known in
the art.
Equation 1
0 Cl
H2N
S2NC N ~
OCH3
a b
For details, sne may refer to EP0 Publication 0007587
and U.S. Patent 4,16g,719.
Sulfonyl isocyanates of Formula a are also known
in the art. For example, U.S. 4,305,884 teaches the
preparation of these compounds.
Agriculturally suitable salts of compounds of
Formula I are also useful herbicides and can be pre-
pared in a number of ways known to the art. For exam-
ple, metal salts can be made by contacting compounds
of For~ula I with a solution of an alkali or alkaline
earth metal salt having a sufficiently basic anion
(e.g., hydroxide, alkoxide, carbonate or hydroxide).
Quaternary amine salts can be made by similar tech-
niques.
Salts of compounds of Formula I can also be pre-
pared by exchange of one cation for another. Cationic
exchange can be effected by direct contact of an
aqueous solution of a sa.lt of a compound of Formula I
~e.g., alkali or quaternary amine salt) wlth a solu~
~ion containing the cation to be exchanged. This
; method is mGst effective when the desired salt con-
taining the exchanged cation is insoluble in water and
can be separated by filtration.
..
87
Exchange may also be effected by passing an
aqueous solution of a salt of a compound of Formula I
(e.g., an alkali metal or quaternary amine salt)
through a column packed with a cation exchange resin
containing the cation to be exchanged for that of the
original salt and the desired product is eluted from
the column. This method is particularly useful when
the desired salt is water-soluble.
Acid addition salts, useful in this invention,
lû can be obtained by reacting a compound of Formula I
with a suitable acid, e.g., p-toluenesulfonic acid,
trichloroacetic acid or the like.
The compounds of this invention and their pre-
paration are further illustrated by the following
examples wherein temperatures are given in degrees
centigrade and parts are by weight unless otherwise
designated.
2û
~5
. .
~9~7
Example 1
?-Amino-4-chloro-6-methoxypyrimidine
16.4 9 2-amino 4,6-dichloropyrimidine (purchased
from Aldrich Chemical Co., Milwaukee, WI 53201) was
added to 200 ml of CH30H. The mixture was cooled to
10 with an ice bath and 5.4 9 of NaOCH3 was added
in portions while maintaining the temperature. The
reaction mixture was allowed to warm to ambient tem-
perature and then heated to reflux for two hours. The
reaction mixture was then allowed to cool to ambient
temperature and it was stirred overnight. A yellow
solid was filtered and recyrstallized from butyl
chloride. The resulting solid was chromatographed on
a dry column of silica, and eluted with 40% EtOAc-
hexane. The resulting yellow solid was furtherpurified by recrystallization from butyl chloride.
9.4 9 of product with m.p. 163-166 was obtained.
Example 2
2-~[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]-
aminosulfonyl]benzoic acid ethYl ester
To 1.0 9 of 2-amino-4-chloro-6-methoxypyrimidine
suspended in 25 ml of dry CH2C12 was added 1.53 g
o~ ethyl 2-(isocyanatosulfonyl)benzoate (prepared by
procedures taught in U.S. 4,305,884). The reaction
mixture was stirred at ambient temperature for three
days. The solvent was stripped and the product was
recrystallized from butyl chlor~de to give a white
solid with m.p. 198-201~.
Using procedures analogous to Example 2, 2-E~(4-
chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]amino-
sulfonyl]benzolc acid isopropyl ester and 2-[~4-
chloro-6-methoxypyrimidln-2-yl)aminocarbonyl]amino-
sulfonyl]benzoic acid 2-propenyl ester may be pre-
pared.
~Z~ 7
The compounds of this invention may be used in
combination with other commercial herbicides. They
are particularly useful in combination with the
following herbicides.
5 Common Name Chemical Name
acifluorfen 5-[2-chloro-4-(tri~luoromethyl)phenoxy]-
2-nitrobenzoic acid
alachlor 2-chloro-2',6'-diethyl-N-(methoxymethyl)-
acetanilide
10 amitrole 3-amino-s-triazole
atrazine 2-chloro-4-(ethylamino)-6-(isopropyl-
amino)-s-triazine
barban 4-chloro-2-butynyl m-chlorocarbanilate
bentazon 3-isopropyl-lH-2,1,3-benzothiadiazin-
4(3H)-one-2,2-dioxide
benzoylprop N-benzoyl-N-(3,4-dichlorophenyl)-DL-
alaine
bromacil 5-bromo-3 sec-butyl-6-methyluracil
bromoxynil 3,5-dibromo-4-hydroxybenzonitrile
20 butylate S-ethyl-diisobutylthiocarbamate
; chloramben 3-amino-2,5-dichlorobenzoic acid
chlortoluron N'-(3-chloro-4-methylphenyl-N',N'-
dimethylurea
cyanazine 2-[[4-chloro-6-(ethylamino)-s-triazin-
2-yl]amino~-2-methylpropionitrile
diallate S-t2,3-dichloroallyl)diisopropylthio-
carbamate
dicamba 3,6-dichloro-o-anisic acid
dichloroprop 2-(2,4-dichlorophenoxy~propionic acid
30 diclofop 2-r4-(2,4-dichlorophenoxy)phenoxy]-
propanoic acid
difenzoquat l,2-dimethyl-3,5-diphenyl-lH-pyrazollum
dinoseb 2-sec-butyl-4,6-dinitrophenol
diuron 3-~3~4-dichlorophenyl)-1,1-dimethylurea
35 EPTC S-ethyl-dipropylthiocarbamate
~2Sa(~1~'7
Common Name Chemical Name
. _
~lamprop N-benzoyl-N-(3-chloro-4-fluorophenyl~-DL-
alanine
fluazifop-
butyl butyl 2-[4-[5-(trifluoromethyl)-2-pyri-
dinyloxy]phenoxy]propanoate
fluchloralin N-(2-chloroethyl)-2,6-dinitro-N-propyl-4-
trifluoromethyl)aniline
fluometuron l,l-dimethyl-3~ -trifluoro-m-tolyl)-
lû urea
fomesafen 5-(2-chloro-4-trifluoromethylphenoxy)-
N-methylsulfonyl-2~nitrobenzamide
fosamine ethyl hydrogen (aminocarbonyl)phosphonate
glyphosate N-(phosphonomethyl)glycine
hexazinone 3-cyclohexyl-6-(dimethylamino)-1-methyl-
1,3,5-triazine-2,4(1H,3H)-dione
ioxynil 4~hydroxy-3,5-diiodobenzonitrile
isoproturon N-(4-isopropylphenyl)-N',N'-dimethylurea
lenacil 3-cyclohexyl-6,7-dihydro-lH-cyclopenta-
pyrimidine-2,4(3H,5H)-dione
linuron 3-(3,4-dichlorophenyl)-1-methoxy-1-
: methylurea
MCPA ~(4-chloro-o-tolyl)oxy~acetic acid
: MCPB 4-~(4-chloro-o-tolyl)oxy~propionic acid
mefluidide N-[~,4-dimethyl~5-[~(tri~luoromethyl)-
sulfonyl]amino]phenyl]acetamide
methabenz-
thiazuron 1,3-dimethyl-3-(2-benzothiazolyl)urea
methoxuron N'-(3-chloro-4-methoxyphenyl)N9N-
dimethylurea
metolachlor 2-chloro-N-(~-ethyl-6-methylphenyl)-N-
(2-methoxy-1 methylethyl)acetamide
metribuzin 4-amino-5-tert-butyl-3-(methylthio~-as-
triazin-5(4H~-one
35 MSMA monosodlum methanearson~te
~Z~ 8~7
Common Name Chemical Name
neburon l-butyl-3 (3,4-dichlorophenyl)-1-methyl-
urea
oryzalin 3,4-dinitro-N,N-dipropylsulfanilamide
5 paraquat 1~1'-dimethyl-4,4'-bipyridinium ion
pendimethalin N-(l-ethylpropyl)-3,4-dimethyl-2,6-
dinitrobenzeneamine
profluralin N-(cyclopropylmethyl)-~,a,~-trifluoro-
2,6-dinitro-N-propyl-p-toluidine
10 propanil 3',4'-dichloropropionalide
sethoxydim 2-[1-(ethoxyimino)butyl]-5-[2-(ethyl-
thio)propyl]-3-hydroxy-2-cyclohexene-
l-one
siduron 1-(2-methylcyclohexyl)-3-phenylurea
15 supriox 2-[1-(2,5-dimethylphenyl)ethylsulfonyl3-
pyridine-N-oxide
terbacil 3-tert-butyl-5-chloro-6-methyluracil
triallate S-(2,3,3-trichloroallyl)diisopropylthio-
carbamate
trifluralin ~,~,a-trifluoro-2,6-dinitro-N,N-dipropyl-
p-toluidine
2,4-D (2,4-dichlorophenoxy)acetic acid
2,4-DB 4-~2,4-dichlorophenoxy)butyric acid
3,4-diaryl-4-cyanobutyrates
4-(6-chloroquinoxalinyl-2-oxy)phenoxy-
propionate Cl-C5 alkyl esters, such
as methyl ester, butyl ester, ethyl
ester, pentyl ester
ethoxyethoxyethyl 4-(6-chloroquinoxalin-
yl-2-oxy)phenoxypropionate
propargyl 2-t4-(3,5-dichloropyridin-2-
yloxy)phenoxy]propanoate
methyl 2-~4-(3-chloro-5-trifluoromethyl-
pyridin-2-yloxy)phenoxy3propanoate
oxyfluorfen 2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-
(trifluoromethyl)benzene
f ``~
:~2~ 87
Common Name ~
norflurazon 4-chloro-5-(methylamino)-2-[(3-(tri-
fluoro)phenyl~-3(2H)-pyridazinone
vernolate S-propyl dipropylthiocarbamate
ethyl 5-[2-chloro-4-(trifluoromethyl)-
phenoxy]-2-nitrobenzoic acid
Formulations
Useful formulations of the compounds of Formula
I can be prepared in conventional ways. They include
dusts, granules, pellets, solutions, suspensions,
emulsions, wettable powders, emulsifiable concentrates
and the like. Many of these may be applied directly.
Sprayable ~ormulations can be extended in suitablP
media and used at spray volumes of from a few liters
to several hundred liters per hectare. High strength
compositions are primarily used as intermediates for
further formulation. The formulations, broadly, con-
tain about 0.1~ to 9g~ by weight of active ingre-
dient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 1% to 9g.9% solid or li-
quid diluent(s). More specifically, they will contain
these ingredients in the following approxima~e propor-
tions:
3G
~Z9~37
11
Table I
Weight Percent*
Active
In~redient Diluent(s) Surfactant(s)
Wettable Powders 20-90 0-74 1-10
Oil Suspensions, 3-50 40-95 0-15
Emulsions, Solutions,
(including Emulsifiable
Concentrates)
Aqueous Suspension10 50 40-84 1-20
Dusts 1-25 70-99 0-5
Granules and Pellets0.1-95 5-99.9 0-15
High Strength 90-99 0-10 0-2
Compositions
* Active ingredient plus at least one o~ a Surfactant
or a Diluent equals 100 weight percent.
Lower or higher levels of active ingredient can,
of course, be present depending on the intended use
and the physical properties of the compound. Higher
ratios of surfactant to active ingredient are some-
times desirable, and are achieved by incorporation
into the formulation or by tank mlxing.
Typical solid diluents are described in Watkins,
et al., "Handbook of Insecticide Dust Diluents and
Carriersn~ 2nd Ed., Dorland Books, Caldwell, New
Jersey~ but other solids, either m~ned or manufac-
tured, may be used. The more absorptive diluents are
preferred for wettable powders and the denser ones for
dusts. Typical liquid diluents and solvents are de~
~cribed in Marsden, "Solvents ~uide,1' 2nd Ed.~ Inter-
scienc~, New York, 1950. Solubility under O.lX is
preferred for suspension concentrates; solution con-
centrates are preferably stable against phase separa-
~5 tion at 0C. "McCutcheon's Detergents and Emulsifiers
~L~Z~Ol37
12Annual", MC Publishing Corp., Ridgewood, New Jersey,
as well as Sisely and Wood, "Encyclopedia of Surface
Active Agents", Chemical Publishing Co., Inc., New
York, 196~, list surfactants and recommended uses.
S All formulations can contain minor amounts of addi-
tives to reduce foaming, caking, corrosion, microbio-
logical growth, etc.
The methods of making such compositions are well
known. Solutions are prepared by simply mixing the
ingredients. Fine solid compositions are made by
blending and, usually, grinding as in a hammer or
fluid energy mill. Suspensions are prepared by wet
milling (see9 for e~ample, Littler, U.S. Patent
3,060,084). Granules and pellets may be made by
spraying the active material upon preformed granular
carriers or by agglomeration techniques. See J. E.
Browning, "Agglomeration", Chemical Engineering,
December 4, 1967, pp. 147ff. and "Perry's Chemical
Engineer's Handbook", 5th Ed., McGraw-Hill, New York,
1973, pp. 8-57~f.
For further information regarding the art of
formulation, see for example:
H. M. Loux, U.S. Patent 3,235,361, February 15,
1966, Col. 6, line 16 through Col. 7, line 19 and
Examples lû through 41;
R. W. Luckenbaugh, U.S. Patent 3,309,19~,
March 14, 1~67, Col. 5, line 43 through Col. 7, line
62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132,
138-140, 162-164, 166, 167 and 169-182;
0 H. Gysin and E. Knusli, U.S. Patent 2,891,855,
June 23, 1959, Col. 3, line 66 through Col. 5, line 17
and Examples 1-4;
G. C. Klingman, "Weed Control as a Science",
John Wiley ~ Sons, Inc., New York, 1961, pp. 81-96; and
J. D. Fryer and S. A. Evans, "Weed Control Hand-
book", 5th Ed., Blackwell Scientific Publicat~ons,
Oxford, 1968, pp. 101-103.
~Z25~(~8~
In the following examples, all parts are by
weight unless otherwise indicated.
~e~
Wettable Powder
2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-
carbonyl]aminosulfonyl]ben~oic acid ethyl
ester 80%
sodium alkylnaphthalenesulfonate 2%
sodium ligninsulfonate 2%
synthetic amorphous silica 3%
kaolinite 13%
The ingredients are blended, hammer-milled until
all the solids are essentially under 50 microns, re-
blended, and packaged.
Example_4
Low Stren~h Granule
2-~[(4-chloro-6-methoxypyrimidin-2-yl)amino-
carbonyl]aminosulfonyl]benzoic acid 2-pro-
penyl ester 1%
N~N-dimethylformamide 9%
attapulgite granules 90%
(U.S.S. 20-40 sieve)
The active ingredient is dissolved in the sol-
vent and the solution is sprayed upon dedusted gran-
ules in a double cone blender. After spraying of the
solution has been completed, the blender is allowed to
run for a short period and then the granules are pack-
aged.
~0
~1 2~
14
Exam~le 5
Aqueous Suspension
2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-
carbonyl]aminosulfonyl~benzoic acid isopropyl
ester 40%
polyacrylic acid thickener 0.3
dodecylphenol polyethylene glycol ether 0.5~
disodium phosphate 1%
monosodium phosphate 0.5~
polyvinyl alcohol 1.0%
water 56.7
The ingredients are blended and ground together
in a sand mill to produce particles essentially all
under 5 microns in size.
Example 6
Granule
2-~(4-chloro-6-methoxypyrimidin-2-yl)amino-
carbonyl~aminosulfonylJbenzoic acid isopropyl
ester 8û%
wetting agent 1%
crude ligninsulfonate salt ~containing 10%
5 20~ of the natural sugars)
attapulgite clay 9%
The ingredients are blended and milled to pass
through a 100 mesh screen. This material is then
added to a fluid bed granulator, the air flow is ad-
~usted to gently fluidize the material, and a fine
spray of water is sprayed on~o the fluidized ma~
terial. The fluidizatlon and spraying are continued
until granules of the desired size range are made.
The spraying is stopped, but flu~d~zation is con-
tinued, optionally with heat, until the water content
is reduced to the desired level, generally less than
1%. The material is then discharged, screened to the
desired size range, generally 14-100 mesh (1410-149
microns)) ~nd packaged ~or use.
il7
~e~
High Strength Concentrate
2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-
carbonyl]aminosulfonyl]benzoic acid ethyl
ester 9~%
silica aerogel 0.5%
synthetic amorphous silica 0.5%
The ingredients are blended and ground in a
hammer-mill to produce a material essentially all
passing a U.S.S. No. 50 screen (0.3 mm opening). The
concentrate may be formulated further if necessary.
Example 8
Wettable Powder
2-[~(4-chloro-6-methoxypyrimidin-2-yl)amino-
carbonyl]aminosulfonyl]benzoic acid 2-pro-
penyl ester 90%
dioctyl sodium sulfosuccinate 0.1%
synthetic fine silica 9.9%
The ingredients are blended and ground in a
hammer-mill to produce particles essentially all below
100 microns. The material is sifted through a U.S.S.
; No. 50 screen and then packaged.
Example 9
Wettable Powder
2-~t(4-chloro-6-methoxypyrimidin-2-yl)amino-
carbonyl]aminosulfonyl~benzoic acid isopropyl
ester 40%
sodium ligninsulfonate 20
montmorillonite clay 40%
3û The ingredients are thoroughly blended, coarsely
hammer-milled and then air-milled to produce particles
essentially all below 10 microns in size. The ma-
terial is reblended and then packaged.
~z~
16
Wettable Powder
2 [[(4-chloro-6-methoxypyrimidin-2~yl)amino-
carbonyl]aminosulfonyl]benzoic acid ethyl
ester 50~
sodium alkylnaphthalenesulfonate 2%
1DW viscosity methyl cellulose 2%
diatomaceous earth 46
The ingredients are blended, coarsely hammer-
milled and then air~milled to produce particles essen-
tially all below 10 microns in diameter. The product
is reblended before packaging.
Example 11
Granule
Wettable Powder o~ Example 10 5%
attapulgite granules 95%
(U.S.S. 20-40 mesh; 0.84-0.42 mm)
A slurry of wettable powder containing x 25
solids is sprayed on the surface of attapulgite
granules in a double-cone blender. The granules are
dried and packaged.
Example l?
Extruded Pellet
2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-
carbonyl]aminosulfonyl]benzoic acid 2-pro-
penyl ester 25%
anhydrous sodium sulfate 10%
erude calcium ligninsulfonate 5%
sodium alkylnaphthalenesul~nnate 1
calcium~magnesium bentonite 59%
The ingredients are blended, hammer-milled and
then moistened with about 12% wa~er. The mixture is
extruded as oylinders about ~ mm diameter which are
out to produoe pellets about 3 mm long. These may be
used directly after dryin~, or the drled pellets may
~z~
17
be crushed to pass a U.S.S~ No. 20 sieve (0.84 mm
openings). The granules held on a U.S.S. No. 40 sieve
(0.42 mm openings) may be packaged for use and the
fines recycled.
Exam~le 13
ûil Suspension
2-~(4-chloro-6-methoxypyrimidin-2-yl)amino-
carbonyl~aminosulfonyl]benzoic acid isopropyl
ester 25%
polyoxyethylene sorbito~ hexaoleate 5%
highly aliphatic hydrocarbon oil 70%
The ingredients are ground together in a sand
mill until the solid particles have been reduced to
under about 5 microns. The resulting thick suspension
may be applied directly, but preferably after being
extended with oils or emulsified in water.
Example 14
Wettable Powder
~-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-
carbonyl~aminosulfonyl]benzoic acid ethyl
ester ~0~
sodium alkylnaphthalenesulfonate 4%
sodium ligninsulfonate 4%
low viscosity methyl cellulose ~%
attapulgite 69%
The ingredients are thoroughly blended. After
grinding in a hammer-mill to produce particles essen-
tially all below lO0 microns, the material is re-
blended and sifted through a U.S.S. No. 50 s~eve (0.3
mm opening) and packaged.
~22~187
Example 15
ûil Suspension
2-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-
carbonyl~aminosulfonyl]benzoic acid 2-pro-
penyl ester 35%
blend of polyalcohol carboxylic 6%
esters and oil soluble petroleum
sulfonates
xylene 59%
The ingred~ents are combined and ground together
in ~ sand mill to produce particles essentially all
below 5 microns. The product can be used directly,
extended with oils, or emulsified in water.
Example 16
Dust
~-[[(4-chloro-6-methoxypyrimidin-2-yl)amino-
carbonyl]aminosulfonyl]benzoic acid ethyl
ester 10~
attapulgite 10%
Pyrophyllite 80%
The active ingredient ~s blended with attapul-
gite and then passed through a hammer-mlll to produce
particles substantially all below 200 microns. The
ground concentrate is then blended with powdered pyro-
phyllite until homogeneous.
ExamPle 1?-
Emulsifiable Concentrate
,
2-C[(4-chloro-6-methoxypyrimidin-2 yl)amino-
carbonyl]aminosul~onyl~benzoic acid 2-pro-
penyl ester 20%
chlorobenzene 74%
sorbitan monostearate and polyoxyethylene
condensates thereof 6%
The ingredients 2re combined and stirred to pro-
duce a solution which can be emulsified in water ~or
application.
~2~187
UtilitY
The compounds of the present invention have high
herbicidal properties. They have utility for broad-
spectrum pre- and/or post-emergence weed control, in
particular selective weed control in soybeans.
~ he rates of application for the compounds of
the invention are determined by a number of factors,
including the types of weeds to be controlled, weather
and climate, formulations selected, mode o~ applica-
tion, amount of ~oliage present, etc. In yeneralterms, the subject compounds should be applied at
levels of around 0.004 to 1 kg/ha, the lower rates
being suggested for use on lighter soils and/or those
having a low organic matter content, or for situations
where only short-term persistence is required.
The compounds of the invention may be used in
combination with any other commercial herbicide,
examples of which are those of the triazine, triazole,
uracil, urea, amide, diphenylether, carbamate and
bipyridylium types.
The herbicidal properties of the sub~ect com-
pounds were discovered in a number of greenhouse
tests. The test procedures and results follow.
~o
Test A
Seeds of crabgrass ~Digitaria sp.), barnyard-
grass (Echinochloa crusgalli), wild oats (Avena
.
~atua), sicklepod (Cassia obtusifolia), morningglory
(Ipomoea sp.), cocklebur (Xanthium pensylvanicum),
sorghum, corn, soybean, sugar beet, rice, wheat and
purple nutsedge (Cyperus rotundus) tubers were planted
and treated pre emergence with the test chemicals dis-
solved in a non-phytotoxic solvent. At the same time,
these crop and weed species, along with cotton and
bush bean, were treated with a soil/foliage appl~ca-
tion. At the time of treatment, the plants ranged in
height from 2 to 18 cm. Treated plants and controls
were maintained in a greenhouse for sixteen days,
after which all species were compared to cont~ols and
visually rated for response to treatment. The rat-
ings, summarized in Table A9 are based on a numerical
scale extending from 0 = no injury, to 10 = complete
kill. The accompanying descriptive symbols have the
following meanings:
C = chlorosis/necrosis;
D = defoliation;
E = emergence inhibition;
G = growth retardation;
H = formative effects;
U = unusual pigmentation; and
6Y = abscised buds or flowers.
The data indicate the high herbicidal activity
o~ the compounds of the invention and their utility
for selective pre-emergence weed control in soybeans.
(3
21
Compounds
Compound 1
OCH3
S02-NH-C~NH--~
COOC2H5 Cl
Compound 2
OCH3
O N ~
~ " ~0>
~ N ~
COOCH(CH3)2 Cl
Compound 3
OCH3
O
502-NH-C-NH ~ 0~
COOCH2CH=CH~ Cl
22
Table A
Cmpd. 1 Cmpd. 2 Cmpd. 3 Cmpd. 3
5Rate kg/ha O . 05 U . 05 O . 4 O . 05
POST-EMERGENCE
Bush bean 9C gC 9D,9G,6Y 5C,8G,6Y
Cotton 2C, 9G 3C, 3H, 9G 6C, 9G 3C, 3H, 9G
Morningglory lOC 9C 9C lOC
10 Cocklebur lOC 9C 9C lOC
Sicklepod 9C 9C 5C, 9G 3C,7G
Nutsedge 9C 9G 7C,8G 5C,9G
Crabgrass 2C94G 2C,5G 2C,5H 5G
Barnyardgrass 5C,9H 3C,9H 9C 5C,9H
Wild Oats 6C,9G 8G 2C,5G lC,2G
Wheat 6C,9G 2C,9G lC,9G 5G
Corn 5U,9C 2C,8H 2U,9H 2C,7G
Soybean 4C,9G 2C,6G lC,6H lH,5G
Rice 5C, 9G 5C, 9G 6C, 9G 5C, 9G
Sorghum 5C, 9G 3C, 9G 5U, 9G lU, 9G
Sugar beet 5C,9G 4C,9G -
PRE -EMERGENCE
Morningglory 9C 9C 9C 2C,9G
20 Cocklebur - 9H 9H 9H
Sicklepod 9G 8G 3C, 9G 7G
Nutsedge lOE lOE lOE lOE
Crabgrass O 0 2C, 6G 5G
Barnyardgrass 2C,9H 4C,9H 5C,9H 3C,9H
Wild Oats 2C,8G 2C,6G 5C,9G 2C,7G
Wheat 9H 8G 2C, 9G 2C, 7G
Corn 2C, 9G lC, 9G 3C 1 9H 3C, 8G
Soybean O lC 3C, 6G 3G
Rice lOE lOE lOE 5C,9H
Sorghum 7C, 9H 2C, 9H 3C, 9H 2C, 9H
Sugar beet lOE lOE - -
~.~2~ 37
23
Test B
Two plastic bulb pans were filled with ferti-
lized and limed Woodstown sandy loam. One pan was
planted with corn, sorghum, Kentucky bluegrass and
several grassy weeds. The other pan was planted with
cotton, soybeans, purple nutsedge (Cyperus rotundus),
and several broadleaf weeds. The following grassy and
broadleaf weeds were planted: crabgrass (Digitaria
sanguinalis), barnyardgrass (Echinochloa crusgalli),
wild oats (Avena fatua), ~ohnsongrass (Sorqhum hale-
), dallisgrass (Paspalum dilatatum), giant fox-
tail (Setaria faberii), cheatgrass (Bromus secalinus)J
mustard (Brassica arvensis), cocklebur (Xanthium
pensylvanicum), morningglory (~ hederacea~,
sicklepod (Cassia obtusifolia), teaweed (Sida
spinosa), velvetleaf (Abutilon theophrasti), and
~imsonweed (Datura stramonium). A 12.5 cm diameter
plastic pot was also filled with prepared soil and
planted with rice and wheat. Another 12.5 cm pot was
planted with sugar beets. The above four containers
were treated pre-emergence with the test compounds of
the invention.
Twenty-eight days after treatment, the plants
were evaluated and visually rated for response to the
chemical treatments utilizing the rating system de-
scribed previously for Test A. The data are summar-
ized in Table B~ Note that the compounds are useful
as pre-emerger,ce treatments for weed control in
soybeans.
24
Table B
PRE-EMERGENCE ON
WOODSTOWN SANDY LO~M
Compound 1
Rate kg/ha 0.00175 0.0035 0.015
Crabgrass 5G 5G 3G
Barnyardgrass 6G 6G 9G
Sorghum 7G 9G,9C lOC
Wild Oats 3G 4G 8G
Johnsongrass O 0 8G
Dallisgrass 0 2G SG
15 Giant foxtail 0 2G 6G
Ky. bluegrass 0 2G 9G
Cheatgrass 8G 9G 9G,9C
Sugar beets 9G 9G lOC
Corn 2G 3G 6G
Mustard 9G 9G gG,9C
Cocklebur 7G aG 9G,3H
20 Pi9weed _ _ _
Nutsedge lOC lOC lOC
Cotton 8G 8G 9G
Morningglory 5G 7G 9G
Sicklepod 4G 6G 8G
Teaweed 0 4G ~G
Velvetleaf 4G 7G 8G
~lmsonweed 7G 9G,9C gG,9C
2S Soybean O n 2G
Rice 9G lCC lOC
Wheat 4G 7G 3G
Table O (continued)
PRE-EMERGENCE ON
WOODSTOWN SANDY LOAM
Compound 1
Rate kg/ha 0.030 0.060 0.500
Crabgrass 6G 6G 9E
Oarnyardgrass 9G,9C 9G,9C lOC
Sorghum lOC lOC lOC
Wild Oats 8G,3C 8G,5C 9G,9C
Johns~ngrass 8G 8G 9G,9C
Dallisgrass 7G 8G 9G
15 Giant foxtail 7G 7G 9G
Ky. bluegrass 9G 9E,9C lOC
Cheatgrass lOC lOC lOC
Sugar beets lOC lOC lOC
Corn 8G,5H 8G,7H lOC
Mustard 9G,9C lOC lOC
Cocklebur 9G,5H 9G,7H 9G,9C
Pigweed ~ - -
20 Nutsedge lOC lOC lOC
Cotton 9G 9G lOC
Morningglory 9G 9G gG,9C
: Sicklepod 9G 9G 9G,9C
Teaweed 9G ~G 9G19C
Velvetlea~ 9G 9G 9G,9C
: 3imsonweed 9C,9C 9G,9C 9G,9C
Soybean 2G 3G 7G
Rice lOC lOC lûC
Wheat 6G ~G 9G
:.
;L~Z9~3'7
26
Table B (cont~nued?
PRE-EMERGENCE ON
WOODSTOWN SANDY LOAM
Compound 2
Rate kg/ha 0.0017~ 0.0035 0.015 0.030
Crabgrass 2G 2G O 2G
Barnyardgrass 4G 5G SG 7G
Sorghum 5G 7G lOC lOC
Wild Oats 2G ~G 4G 5G
Johnsongrass O 0 7G 7G
Uallisgrass O 0 4G 5G
15 Giant ~oxtail 2G 2G 4G 5G
Ky. bluegrass 2G 5G 8G 9G
Cheatgrass 7G 8G 9G,9C 9G,9C
Sugarbeets 9G 9G 9G 9G
Corn 0 2G 4G 3G
Mustard 9G 9G 9G,9C 9G,9C
Cocklebur 7G 8G 9G,5H 9G,5H
Pigweed
20 Nutsedge 8G 9G lOC lOC
Cotton 6G 8G 8G 8G
Morningglory 5G 7G 9G 9G
: Sicklepod 0 4G 2G 5G
Teaweed O 0 8G 8G
Yelvetleaf 0 5G 7G 8G
Jimsonweed 6G 8G 9G 9G
Soybean O O O O
Rice 9G 9G lOC lOC
Wheat 4G 6G 5G 4G
~2~ 17
27
Table ~ (continued)
,,
PRE-~MERGENCE ON
WOODSTOWN SANDY LOAM
Compound 2
Rate kg/ha 0.060 0.120 0.500
Crabgrass 3G 5G 8G
Barnyardgrass 8G 8G 9G,9C
Sorghum lOC lOC lOC
Wild Oats 7G 7G 9G
Johnsongrass 8G 8G 9G,9C
Dallisgrass 5G 6G 9G
15 Giant foxtail 8G 9G 9G
Ky. bluegrass 9G 9G lOC
Cheatgrass 9G,9C lOC lOC
Sugar beets 9G,9C lOC lOC
Corn 6G 8G,5H lOC
Mustard lOC lOC lOC
Cocklebur 9G,7H 9G,7ff 9G,9C
20 Pigweed - -
Nutsedge lOC lOC lOC
Cotton 8G 9G 9G,9C
Morningglory 9G 9G 9G,9C
Sicklepod 8G 8G 9G
Teaweed 9G 9G 9G
Velvetleaf 9G 9G 9G~9C
Jimsonweed 9G,9C 9G,9C 9G r9C
25 Soybean 2G 2G 6G
Rice lOC lOC lOC
Wheat 5G 6G 8G
Table B (continued)
PRE-EMERGENCE ON
WOODSTOWN SANDY LOAM
Compound 3
Rate kg~ha O.û30 0~120
Crabgrass 2G 3G
aarnyardgrass 4G 5G
Sorghum SG,2H 8G,5H
Wild Oats 2G 2G
Johnsongrass 3G 4G
Dallisgrass 0 2G
15 Giant foxtail 3G 3G
Ky. bluegrass 2G 5G
Cheatgrass 2G 5G,3H
Sugar beets 8G,7C 9G,9C
Corn 2G 4G,2H
Mustard 8G,2C 9G,8C
Cocklebur - 9G~8C
20 Plgweed 8G lOE
Nutsedge lOE lOE
Cotton SG 9G,8C
; Morningglory 7G 8G
5icklepod 3G 9G,9C
Teaweed 0 2H,}G
Velvetleaf 5G,2H 7G,5H
Jimsonweed 4G 7G,}C
~ 25 Soybean 0 3G
i R~ce 8G,3H lOE
Wheat 2G 3G
~2~0~7
29
Test C
The test chemicals, dissolved in a non-phyto-
toxic solvent, were applied in an overall spray to the
foliage and surrounding soil of selected plant spe-
cies. One day after treatment, plants were observedfDr rapid burn injury. Approximately fourteen days
after treatment, all species were visually compared to
untreated controls and rated ~or response to treat-
ment. The rating system was as described previously
~or Test A. The data are presented in Table C.
All plant species were seeded in Woodstown sandy
loam soil and grown in a greenhouse. The ~ollowing
species were grown in soil contained in plastic pots
(25 cm diameter by 13 cm deep): soybeans, cotton,
alfalfa, corn, rice, wheat, sorghum, velvetleaf
(Abutilon theophrasti), sesbania (Sesbania exaltata),
sicklepod (Cassia obtusifolia), morningglory (Ipomoea
hederacea), ~imsonweed (Datura stramonium), cocklebur
(Xanthium pensylvanicum), crabgrass (Di~itaria sp.~,
nutsedge (CYperus rotundus), barnyardgrass (Echino-
chloa crusgalli), giant foxtail (Setaria faberii) and
wild oats (Avena f_tua). The following species were
grown in soil in a paper cup (1~ cm diameter by 13 cm
deep): sunflower, sugar beets, and mustard. All
plants were sprayed approximately 14 days after
planting. Additional plant species are sometimes
added to this standard test in order to evaluate
unusual selectivity.
The compounds tested by this procedure are use-
ful for the post-emergence control of weeds in soy-
beans.
Table C
Over the-Top Soil/Foliage Treatment
Compound 1
Rate kg/ha .004 .016 .063
Soybeans 0 5G 9G
Velvetlea~ 9G,4C lOC lOC
10 Sesbania lOC lOC lOC
Sicklepod 7G lOC lOG,4C
Cotton 8G lOC lOC
Morningglory 9G,2C lOC 9G,9C
Alfalfa 5G lOC 9G,8C
Jimsonweed 8G 9G,2C 9G
Cocklebur 9G,lH 8G,lH 9G
Sunflower lOC lOC lOC
15 Mustard 9G,5C lOC lOC
Sugar beets lOC lOC lOC
Corn 2G,2C 5G,lU 7G
Crabgrass O O
Rice 8G,2C 9G,8C 9G,8C
Nutsedge 9G 8G 8G,6C
Barnyardgrass 6G 8G,6C 9G,6C
20 Wheat 4G 8G 9G
Giant foxtail 6G 7G 8G
Wild Oats 2G 7G 8G
Sorghum 6G 8G,lU 9G,2U
~ohnsangrass 5G 8G,lU 8G,lU
Field Blndweed 0 8G 8G
3~
~ 229(~
31
Table C (continued)
Over-the-Top SoilJFoliage Treatment
Compound 2
Rate kg/ha .004 .016 .~63
Soybeans 0 7G BG,6C
Velvetleaf 9G lOC lOC
10 Sesbania lOC lOC lOC
Sicklepod 6G,4C lOC lOG,4C
Cotton lQC lOC lOC
Morningglory lOC 9G,8C lOC
Alfalfa lOC 8G,2C lOC
Jimsonweed 8G lOC lOC
Cocklebur - 9G lOC
Sunflower 9G,9C lOC lOC
Mustard 9G,6C 9G,6C 9G,4C
Sugar beets 9G lOC lOC
Corn lC 2G,2C 5G,2H
Crabgrass 0 2~ 0
Rice 6G 9G,7C 9G,4C
Nutsedge 7G 7G,6C 7G
Barnyardgrass SG 7G 8G,~C
20 Wheat o 6G 8G
Giant foxtail 3G 6G gG
Wild Oats 0 4G 7G
Sorghum 7G 7G,2U 7G,2U
Johnsongrass 5G 7G 7G,4U
Field Cindweed 6G 4G 8G
3~
~2290~7 -
Table C (continued)
Over-the-Top Soil/Foliage Treatment
. ~ .
Compound 3
Rate kgt'ha .004 .016 .063
Soybeans 2G,3C 3C 4G,2C
Velvetleaf - lOC lOC
10 Sesbania - 8G lOC
Sicklepod 2G 9G 9G
Cotton 8G 8G,2C 8G,4C
Morningglory 7G,2C 9G 8G,3C
Al~alfa 3G 3G 3G
Jimsonweed 3G 6G 8G
Coc~lebur 8G 8G,2H 9G
Sunflower 7G lOC lOC .
15 Mustard 9G,8C 9G lOC
Sugar beets 8~ 8G 9G~8C
Corn lG O O
Crabgrass û O O
Rice 3G 5G 8G
Nutsedge 3G 6G
Barnyardgrass 0 3G 9G
20 Wheat O O lS
Giant foxtail O SG O
Wild Oats O O O
Sorghum 0 3G gG
Johnsongrass 0 4G 4G,2U
Field B1ndweed 0 0 2G
?, 5
