PROCEDE DE NETTOYAGE D'UN RESERVOIR CONTENANT UNE SOLUTION A PULVERISER

METHOD FOR SPRAY TANK CLEANOUT

Abrégé anglais

2130118 9316596 PCTABS00025
A method for facilitating cleanout of residual sulfonylurea
pesticide from spray tank equipment comprising (i) formulating the
sulfonylurea as an agriculturally suitable water-soluble salt
composition before spray tank application, (ii) applying the salt
composition to the crop and (iii) rinsing the tank substantially free
of residual sulfonylurea more easily than is possible when the
sulfonylurea is not formulated as a salt.

Revendications

WO 93/16596 PCT/US93/01295
CLAIMS
1. A method for reducing residual sulfonylurea
pesticide contamination of a spray tank from which the
sulfonylurea is applied, comprising the steps:
i) formulating the sulfonylurea as an
agriculturally suitable water soluble salt composition
before spray tank application, thereby increasing
solubility of the sulfonylurea and decreasing the
amount of insoluble sulfonylurea available for residual
contamination of the spray tank,
ii) applying the sulfonylurea salt composition to
the crop while minimizing buildup of insoluble
sulfonylurea in the spry tank, and
iii) rinsing the spry tank substantially free of
residual sulfonylurea, after application, in an
operation in which the sulfonylurea remaining in the
spray tank is reduced significantly versus the amount
remaining when sulfonylurea is not formulated as a
water-soluble salt before application.
2. A method according to Claim 1 employing, in
step i, the following sulfonylurea salt:
<IMG>
wherein:
J is selected from the group

WO 93/16596 PCT/US93/01295
21
<IMG> , <IMG> , <IMG> ,
J-1 J-2 J-3
<IMG> , <IMG> , <IMG> ,
J-4 J-5 J-6
<IMG> , <IMG> , <IMG> ,
J-7 J-8 J-9
<IMG> , <IMG> , <IMG> ,
J-10 J-11 J-12
<IMG> and <IMG> ;
J-13 J-14
R is selected from the group H and CH3;
R1 is selected from the group F, Cl, Br, NO2, C1-C4
alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C2-C4
haloalkenyl, C1-C4 alkoxy, C1-C4 haloalkoxy,

WO 93/16596 PCT/US93/01295
22
C2-C4 alkoxyalkoxy, CO2R12, C(O)NR13R14,
SO2NR15R16, S(O)nR17, C(O)R18, CH2CN and L;
R2 is selected from the group H, F, Cl, Br, CN,
CH3, OCH3, SCH3, CF3 and OCF2H;
R3 is selected from the group Cl, NO2, CO2CH3,
CO2CH2CH3, SO2N(CH3)2, SO2CH3, SO2CH2CH3, OCH3,
and OCH2CH3
R4 is selected from the group C1-C3 alkyl, C1-C2
haloalkyl, C1-C2 alkoxy, C2-C4 haloalkenyl, F,
Cl, Br, NO2, CO2R12, C(O)NR13R14, SO2NR15R16,
S(O)NR17, C(O)R18 and L;
R5 is selected from the group H, F, Cl, Br and CH3;
R6 is selected from the group C1-C3 alkyl, C1-C2
alkoxy, C2-C4 haloalkenyl, F, Cl, Br, CO2R12,
C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 and L;
R7 is selected from the group H, C1-C3 alkyl and
pyridyl;
R8 is selected from the group H, C1-C3 alkyl and
pyridyl;
R9 is selected from the group C1-C3 alkyl, C1-C2
alkoxy, F, Cl, Br, NO2, CO2R12, SO2NR15R16,
S(O)nR17, OCF2H, C(O)R18, C2-C4 haloalkenyl and
L;
R10 is selected from the group H, Cl, F, Br, C1-C3
alkyl and C1-C2 alkoxy;
R11 is selected from the group H, C1-C3 alkyl, C1-C2
alkoxy, C2-C4 haloalkenyl, F, Cl, Br, CO2R12,
C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 and L;
R12 is selected from the group allyl and propargyl
and C1-C3 alkyl optionally substituted by at
least one member independently selected from
halogen, C1-C2 alkoxy and CN;
R13 is selected from the group H, C1-C3 alkyl and
C1-C2 alkoxy;
R14 is C1-C2 alkyl;

WO 93/16596 PCT/US93/01295
23
R15 is selected from the group H, C1-C3 alkyl, C1-C2
alkoxy, allyl and cyclopropyl;
R16 is selected from the group H and C1-C3 alkyl;
R17 is selected from the group C1-C3 alkyl, C1-C3
haloalkyl, allyl and propargyl;
R18 is selected from the group C1-C4 alkyl, C1-C4
haloalkyl and C3-C5 cycloalkyl optionally
substituted by halogen;
n is 0, 1 or 2;
M is a cation;
L is
<IMG> ;
Rj is selected from the group H and C1-C3 alkyl;
W is selected from the group O and S;
X is selected from the group H, C1-C4 alkyl, C1-C4
alkoxy, C1-C4 haloalkoxy, C1-C4 haloalkyl, C1-C4
haloalkylthio, C1-C4 alkylthio, halogen, C2-C5
alkoxyalkyl, C2-C5 alkoxyalkoxy, amino, C1-C3
alkylamino and di(C1-C3alkyl)amino;
Y is selected from the group H, C1-C4 alkyl, C1-C4
alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4
haloalkylthio, C2-C5 alkoxyalkyl, C2-C5
alkoxyalkoxy, amino, C1-C3 alkylamino, di(C1-C3
alkyl)amino, C3-C4 alkenyloxy, C3-C4
alkynyloxy, C2-C5 alkylthioalkyl, C2-C5
alkylsulfinylalkyl, C2-C5 alkylsulfonylalkyl,
C1-C4 haloalkyl, C2-C4 alkynyl, C3-C5
cycloalkyl, azido and cyano;
Z is selected from the group CH and N;

WO 93/16596 PCT/US93/01295
24
provided that i) when one or both of X and Y is C1
haloalkoxy, then Z is CH; and ii) when X is halogen,
then Z is CH and Y is OCH3, OCH2CH3, N(OCH3)CH3, NHCH3,
N(CH3)2 or OCF2H.
3. A method according to Claim 2 employing a
sulfonylurea salt of a sulfonylurea selected from the
group: 2-chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-
2-yl)amino]carbonyl]benzenesulfonamide (chlorsulfuron);
methyl 2-[[[[(4,6-dimethyl-2-
pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate
(sulfometuron methyl); ethyl 2-[[[[(4-chloro-6-methoxy-
2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate
(chlorimuron ethyl); methyl 2-[[[[(4-methoxy-6-methyl-
1,3,5-triazin-2-yl)amino]-
carbonyl]amino]sulfonyl]benzoate (metsulfuron methyl);
methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]-
carbonyl]amino]sulfonyl]-6-(trifluoromethyl)-3-
pyridinecarboxylate; methyl 2-[[[[[4-ethoxy-6-(methyl-
amino)-1,3,5-triazin-2-yl]amino]carbonyl]amino]-
sulfonyl]benzoate (ethametsulfuron methyl); 2-(2-
chloroethoxy)-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-
yl)amino]carbonyl]benzenesulfonamide; ethyl 5-[[[[(4,6-
dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-
1-methyl-1H-pyrazole-4-carboxylate; N-[[(4,6-dimethoxy-
2-pyrimidinyl)amino]carbonyl]-3-(ethylsulfonyl)-2-
pyridinesulfonamide (rimsulfuron); methyl 3-[[[[(4-
methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]-
amino]sulfonyl]-2-thiophenecarboxylate (thifensulfuron
methyl); methyl 2-[[[[N-(4-methoxy-6-methyl-1,3,5-
triazin-2-yl)-N-methylamino]carbonyl]amino]sulfonyl]-
benzoate (tribenuron methyl); methyl 2-[[[[[(4,6-
dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-
methyl]benzoate (bensulfuron methyl); 2-[[[[(4,6-
dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-
N,N-dimethyl-3-pyridinecarboxamide (nicosulfuron);

WO 93/16596 PCT/US93/01295
methyl 2-[[[[[4,6-bis(difluoromethoxy)-2-
pyrimidinyl]amino]carbonyl]amino]sulfonyl]benzoate;
methyl 2-[[[[[4-dimethylamino)-6-(2,2,2-
trifluoroethoxy)-1,3,5-triazin-2-
yl]amino]carbonyl]amino]sulfonyl]-3-methylbenzoate; and
N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-1-
methyl-4-(2-methyl-2H-tetrazol-5-yl)-1H-pyrazole-5-
sulfonamide.
4. A method according to Claim 3 employing a
salt of at least one member of the group methyl 3-
[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-
yl)amino]carbonyl]amino]sulfonyl]-2-
thiophenecarboxylate (thifensulfuron methyl), methyl 2-
[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-
yl)amino]carbonyl]amino]sulfonyl]benzoate (metsulfuron
methyl), methyl 2-[[[[N-(4-methoxy-6-methyl-1,3,5-
triazin-2-yl)-N-methylamino]carbonyl]amino]sulfonyl]-
benzoate (tribenuron methyl) and 2-chloro-N-[[(4
methoxy-6-methyl-1,3,5-triazin-2-
y?)amino]carbonyl]benzenesulfonamide (chlorsulfuron)
wherein M is selected from the group sodium, potassium,
calcium, ammonium, and alkylammonium.
5. A method according to Claim 3 employing a
sulfonylurea salt in the absence of a tank mix partner.
6. A method according to Claim 4 employing a
sulfonylurea salt in the absence of a tank mix partner.
7. A method according to Claim 3 employing a
sulfonylurea salt in the presence of a tank mix
partner.
8. A method according to Claim 4 employing a
sulfonylurea salt in the presence of a tank mix
partner.
9. A method according to Claim 6 wherein spray
tank cleanout is improved by a factor of at least 4.

WO 93/16596 PCT/US93/01295
26
10. A method according to Claim 8 wherein the
spray tank cleanout is improved by a factor of at least
4.

Description

WO93/16596 2 1 3 0 1 1 8 PCT/US93/012g5
. - ' .
METHOD FOR SP~AY TANK C~E~NO~T
Sulfonylureas, as a cla~s, are highly active
pesticides. For this reason, care must be taken to
make sur2 that aLl traces of sulfonylurea are cleaned
out of the spray ~quipmen~ (hereafter referred to as
spray tank), ~hich iY u~ed ~o apply pe~icides to
crops, before an applicator uses thi3 equipment in a
lQ sub3~quent application to treat a crop tha~ is
sensitive or will be injured by the ~ul~onylurea used
in the pre~ious spray ~ank application. Adequate
cleanout may require a rinsi~g procedure that is time-
consuming and causes an enYironmental waste-water
dispo~al problem.
Salts of the sulfonylureas are generally known as
are methods for making them. What ha~ not been
appreciated until now is the advantage that can be
achieved in spray tank cleanout when the ~ulfonylurea
acti~e ingredi~nt is applied in its salt form rather
than in its acid form. The described salt formulations
can be applied oon~entionally or using ch~mical
injection tçchnology since the soluble formulation
gi~es a -~olution that can be uniformly injected into
the spray boom.
5~= Yl~
This invention concerns a method for reducing
residual sulfonylurea pesticide contamination of a
spray tank ~rom which the sulfonylur~a is applied,
39 comprising the steps:
i~ ormulating the sulfonylurea active
ingredient as ~n agriculturally suitable water soluble
salt composition before spray tank application, thereby
increasing solubility of the sulfonylurea and

WO ~3/165g~ PCr/US93/01~95
2130118 - -
decreasing the amount of insoluble sulfonylurea
a~railable for residual contamination of the spray tank,
ii) applying the sulfonylurea salt composition ~o
the crop while minimizing buildup of insoluble ~-
sulfonylurea in the spray tank, and
i.ii) rinsing the spray tank substantially free of
residual sulfonylurea, after application, in an
operation in which the sulfony}urea remaining in the
spray tank is reduced significantly versus the ~mount
remaining when sulfonylurea is not formulated as a
water-sQluble salt before application.
The sulfonylureas whose spray tank buildup is
curtailed by the method of this in~ention are the
sulfonylurea acids either when u~ed alone or w~th one
or more ~a~k mix partners. The benefits achieved by
this invention ha~e been found to be more pronounced
when the sulfonylurea is employed with a tank m~x -
part~er. The benefits are e~en more noteworthy when
earlier tank mixes have left organic deposits on inside --
spray ~ank surfaces. In such instances, it is believed
that undissolved particles of the sulfonylurea are held
by the organic deposit and kept from becoming
resuspended or dissol~ed in the spray tank water.
Thereafter, should the spray tank be employed on a crop
sensi~i~e to the ~ulfonylurea, damage may result either
from migration into the tank water of particles
formerly trapped by the organic deposit or by actual
sloughing off of the organic deposit carrying embedded
sulfonylurea particles with it.
The problem of difficult spray tank cleanout i3
exacerbated ~y sulfonylureas used at relatively high
concentrations. Since water solubility of the
3ulfonylurea acti~e ingredient in its acid form is so
low, tank mixes of the sulfonylureas are primarily
suspensions. Suspended particles can collect on tank

WO93/16~96 2 1 3 0 1 1 8 PCT/US93/0129~
:
walls, in tubing, or be trapped by organic deposits
that may be present inside the tank. If a later tank
mix sends the sulfonyluraa into solution or ~uspension,
sensiti~e crops can be damaged.
This problem is aYoided by employing sulfonylureas
in a water-soluble form. The sulfonylurea ~alt f~rm
shows a faster dissolution rate ~han the corresponding
sulfonylurea acid, particularly e~ident at low pH's.
Thus, at typical use rates, there will be ~ittle or no
sulfonylurea particles to build up on in~erior tank
surfa es or become imbedded in organic depos ts that
may ha~e formed on such surfaces. Use of sulfonylureas
in their sAlt form rather than their acid form has been
found, under a variety of circumstances, to result in a
grea~er than fourfold improvement in spray tank
cleanout.
Preferred salt cations (M) are the sodium,
potassium, calciumr magnesium, 2mmonium and
alkylammo~ium cations. Preferred sulfonylurea salts
are the sodium and calcium salts of tribenuron methyl,
the potassium salt of thifensulfuron methyl, the
ammonium salt of chlorsulfuron and the potassium salt
of metsulfuron methyl.
~RI~F DESCRIPTION OF TH~ DRAWIN~S
The Figures represent comparisons in bar graph
format of the data summarized in the Tables. Figure 1
shows a statistically significant distinction between
eaQe of cleanout of sulfonylurea-tank p~rtner mixtures
(37% failure rate) ~s. cleanout of correspondi~g
sulfonylurea salt-tank partner mixtures (8% failure).
Figure 2 shows an even greater distinction when no tank
partners are present (89% failure for sulfonylurea acid
and 11% failure for the salt formulation).

WO 93~16596 PCI/US93/0129~
213011B ~ -
- DE TsaILS ~F ~ VE~ION . ~;
Representati~e of the sulfonylureas whose salt ~:
f orms are contemplated f or u~e in the proces s of thi s
in~rention are those of the fonnula: ~
:.
wherein:
J is selected from ~he group
R4
R2~ ' ~C112
J-2
R4~ RS \~R4
J-4 ,~ ,~
R7~ ~R9 ~R
;r--7 J--8

wo g3/l6s96 2 1 3 0 11 ~ P~T~US~3/012Q~ :
. .
-
R7~
,~_~ `
~( and
~=;~ J-14
R is 3elected from the group H and C~3;
l is selected from the group F, Cl, Br, NO2, Cl-C4
alkyl, Cl-C4 haloalkyl, C3-C4 cycloalkyl, C~-C4
haloalkenyl, C1-C4 alkoxy! Cl-C4 haloalXoxy,
C2-C4 alkoxyalkoxy, C02Rl2, C~o)NRl3R14;
So2NR15Rl6, S~o~nRl7, C(O~Rl8, CH2&N and L;
R2 is selected from the group H, F, Cl, Br, CN,
CH3, OCH3, SC~3r CF3 and OCF2H;
R3 is ~elected from the group Cl, NO2, CO~CH3,
CO2C~2CH3, SO2N(CH3)2, SO2CH3, SO2CH2CH3, OCH3,
and OCH2CH3;
R4 is selected from the group Cl-C3 alkyl, Cl-C2
haloalkyl, C1-C2 alkoxy, C~-C4 haloalkenyl, F~
Cl, Br, NO2, CO2R12, C(o)NR13Rl4, SO~NRl5Rl6,
S(o)nR17, C~O)Rl8 and L;
R5 is selected from the group H, F, Cl, Br and C~3;
R6 is ~elected ~rom the group Cl-C3 alkyl, C1 C2
alkoxy, C2-C4 haloalkenyl, F, Cl, Br, CO2Rl2,
C(o)NR13R14, So2NR15R16, S(o)nRl7~ C~O)R~8 and L;
R7 iQ 3~1ected from the group H, F, Cl, CH3 and
CF3;

W~93~16S96 P~T/U593/01295
2 1 3 ~ 11 8 6
R8 is selected from the group H, C1-C3 alkyl and
pyridyl;
R9 is selec~ed from the group Cl-C3 alkyl, Cl-C2 ~-
alkoxy, F, Cl, Br, ~2~ CO2R1~, So2NRl5R~
S~o)nRl7, OCF2H, C(O)Rl8, C2-C4 haloalkenyl and
L;
R10 is selec~d from the group H, Cl, F, Br, Cl-C3
.alkyl and C1-C2 alkoxy~
Rll is selected from the group ~, Gl-C3 alkyl, Cl-C2
alkoxy, C2-C4 haloalkenyl, F, Cl, Br, CO2Rl2,
C~o)NRl3Rl4, S02NRl~R16, S(o)nRl7, CtO)R18 and L; ~-
Rl2 is selected from ~he group allyl and propargyl
and Cl-C~ alkyl optionally substituted by at ::
least one member independently selected from
halogen, C1-C2 alkoxy and CN;
R13 is selected from the group H, C1-C3 alkyl and
Cl-C2 alkoxy;
Rl4 is Cl-C2 alkyl;
R15 is selected from the group H, Cl-C3 alkyl, Cl C2
alkoxy, allyl and cyclopropyl; ~-
R~6 is selected from the group H and Cl-C3 alkyl;
R1? is selected from the group C1-C3 alkyl, C1-C3
haloalkyl, allyl and propargyl;
R18 is selec~ed from the group Cl-C4 alkyl, C1-C4 ~:
haloalkyl and C3-C5 cycloalkyl optionally --
substituted by halogen;
n is 0, 1 or 2;
M is a cation;
L is ;~
39
J i ;
N-- N
11 1 ; :
N~N

wo g3/l6~9S 2 1 3 0 11 ~ PCTiU~93~0129~
Rj is selected from ~he group H and Cl-C3 alkyl;
W is selected from ~he gxoup O and S;
X is 3elected from the group ~, Cl-C~ alkyl, C1-C4
alkoxy, Cl-C4 haloalkoxy, C1-C4 haloalkyl, Cl-C4
haloalkylthio, Cl-C~ alkylthio, halogen, C2-C
alkoxyalkyl, C2-C5 alkoxyalkoxy, amino, C1-C3
alkylamino and di(Cl-C3 alkyl)amino:
Y is selected fr~m the group H, Cl-C4 alkyl, Cl-C4
alkoxy, Cl-C4 haloalkoxy, Cl-C4 alkylthio, Cl-C4
haloalkyl~hio, C2-C~ alkoxyalkyl, C2-C5 alkoxy-
alkoxy, amino, Cl-C3 alkylamino, diSCl-C3
alkyl)amino, C3-C4 alkenyloxy, C3-C4 ~
al~ynyloxy, C2-C~ alkylthioalkyl, C2-C5
alkylsulfinylalkyl, C2-C~ alkylsulfonylalkyl,
Cl-C4 haloalkyl, C2-C4 alkynyl, C~-C5
cycloalkyl, azido and cyano;
Z is 3elacted from the group CH and N;
provided that i) when one or both of X and Y is C
haloalkoxy, then Z is CH; and ii) when X is halogen,
then Z is CH and Y is OCH3, OCH2C~3, N(OCH3)C~3, NHCH3,
N~CH3~2 or OCF~H.
Salt~ of the following sulfonylureas are preferred :
for use in the disclosed process: 2-chloro-N-~(4-
methoxy-6-methyl-1,3,5-triazin-2-yl)amino~carbonyl]-
benzenesulfonamide (chlorsul uron); methyl 2-~[~(4,6-
dimethyl-2-pyrimidinyl)amino~carbonyl~amino~sulfonyl3-
benzoata (~ulfometuron methyl); ethyl 2-[l[l(4-chloro- ~:
6-methoxy-2-pyrimidinyl)amino]carbonyl~amino]sulfonyl]-
benzoate (chloxLmuron ethyl); methyl 2-[~[[~4-methoxy- ~-
6-methyl-1,3,5-triazin-2-
yl)amino~carbonyl}amino]sulfonyl~benzoate (metsulfuron ~;
methyl); ms~hyl 2-[[[[(g,6-dimethoxy-2- ~:
pyrimidinyl)amino]carbonyl3amino]sulfonyl~-6- `;
(trifluoromethyl)-3-pyridine-carboxylate; methyl 2-
3~ [[ll~4-eth~xy-6-(methylamino)-1,3,5-triazin 2- :

WO~3/16~96 PCT~S~3/0129~
- 21~118 8
yl]amino~carbonyl]amino]sulfonyl]benzoate
~eth~metsulfuron methyl); 2-~2-chloroethoxy)-N-[[(4-
methoxy-6-methyl-1,3,5-triazin-2-yl)amino~carbonyl]-
benzenesulfonamide; ethyl 5-[[~[(4,6-d~methoxy-2-
pyrimidinyl)amino~carbonyl~amino]sulfonyl~ me~hyl~pyrazole-4-carboxylate; N-[[(4,6-dimethoxy-2- -
~pyrimidinyl)amino3carbonyl]-3-(ethylsulfonyl)-2-
pyridine-~ulfonamide ~rimsulfuron~; methyl 3-[[[[(4-
methoxy-6-methyl-1,3,5-triazin-2-
yl)amino~carb~nyl~amino~sul~onyl~-2-
thiophenecarboxylate tthifensulfuron methyl); methyl 2-
[[~[~-(4-methoxy-6-methyl-1,3~5-triazin-2-yl)-N-
methylamino~carbonyl]amino]sulfonyl~benzo~te
(~ribenuron methyl); methyl 2-~ [(4,6-dimethoxy-2-
pyrLmidinyl)amino]carbonyl]amino]-
sulfonyl~methyl]benzoate (bensulfuron methyl~;
2-[[[[(4,6-dimethoxy-2-
pyrimidinyl~amino]carbonyl~amino]sulfonyl3 -N, N-
dimethyl-3-pyridinecarboxamide ~nicosulfuron); methyl
2-1~[[[4,6-bis~difluoro-methoxy)-2-pyrimidinyl]amino]-
carbonyl]a~ino]sulfonyl]benzoate; methyl 2-E[1114-
dimethylamino)-6-~2,2,2-trifluoroethoxy~-1,3,5-triazin- :~
2-yl]amino]carbonyl~amino]sulfonyl]-3-methylbenzoate:
and N-l[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-1-
methyl-4-~2-methyl-2H-tetrazol-5-yl)-lH-pyrazole-5-
sulfonamide.
More preferred are sulfonylurea salts of the
followi~g sulfonylureas: 3-11[[(4-methoxy-6-methyl-
1,3,5-triazin-2-yl)aminoJcarbonyl~amino]sulfonyl~-2- :-
thiophenecarboxylate (thifensulfuron methyl), methyl 2-
[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino3-
carbonyl3amino]sulfonyl]benzoate (metsulfuron methyl),
methyl 2-1[llN-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-
N-methylamino3carbonyl]amino]sulfonyl3benzoate
(tribenuron methyl) and 2-chloro-N-[~(4.-methoxy-6-

W~93/1659~ ` 2 1 ~ ~ 1 1 8 PCT/US93~01295
methyl-l,3,5-triazin-2-yl)amino~carbonyl~benzene-
sulfonamide (chlorsulfuron) wherein M is ~elected from
the group ~odium, pota~sium, calrium, ammonium, and
alkyla~monium.
Sulfonylurea salts of thi~ in~ention can be used
alone or in combination with other commercial
herbicide.~ (includiny other ~ulfonylurea~ or
sulfonylurea ~altQ~, in~ecticides or fungicides.
Mixtures containing ~ulfonylurea salts are particularly
u~eful in minimizing spray tank cleanout when compared
to the same mixtures containing the corresponding
sulfonylurea acid.
The data summarized in Table I ~using Protocol I) :-
show that the ~ulfonyluraa acid plus tan~ mix partner
suffered a failure rate of 37~ (l0 failures out of 27)
whereas the corresponding alkali metal salt of the :~
sulfonylurea plus tank mix partner had a failure rate
of only about 8% (2 failures out of 24). ~NOTE: Test
failure corresponds to a greenhou~e result of >20%
20 in jury to ~ugarbeets in the bioassay test.~ The data :~
summarized in Table II (using Protocol II) show that in :
the abqence of a tank partner, cleanout of the
sulfonylurea sa}t formulation is equi~alent to or more
effec~ive than cleanout of the corresponding
sulfonylurea acid. The corresponding tank cleanout
Protocols I and II are described after each table,
followed by the bioaQ~ay protocol. Each of the percent -
in jury f igure~ in the tables i-Q the a~era~e of two
bioagsay re~ult3 of ~he two samples of the final
ammonia wash water: one sample taken from the tank and
one ~ample takan from the boom.

W ~ g3J16S~6 P ~ /US93/01295
2 1 3 ~ o
T~BLE I
~ra~er Cleanout ~:
~,
In~tial
Sulfonylur2a
Concentration Tank
in the Tank ~Pexcent ;
Thifensulfuron ~e~hyl 400 2,4-D 60
400 MCPA 100
500 propicona201e 90
Thifensulfuron met~yl 190 propiconazole 0
+ Metsulfuron 380 propic~nazole 100
m~t~yl ~10:1) 600 propico~Rscle 0
600 propiconazole 20
600 ~ropiconazole 0
600 flutriafol 70
600 ~lutria~ol 20
~hifensulfuron 600 2,4-D 0
+ Tribenuron 600 2,4-D 0
methyl ~2:1) 600 2,4-D 0
600 2,4-D 60
775 2,4-D o
1000 2,4-D 0
530 2,4-D/suractant 0
45Q MCPA 50
430 MCPA 0
750 MCPA 10
750 MCPA o
1070 ~CPA 0
835 propiconazole 100
~ribenuron methyl149 propiconazole 50
168 propiconazole
200 propiconazole 0
200 propiconazole 90

W ~ ~3/16596 2 1 3 0 1 1 ~ PCT/US~3/~1295
11 ,
Potassium Salt of232 propiconazole O
T~i~ensulfuron methyl 400 propiconazole 0. -~
500 propiconazole 90 ~-
400 2,4-D o
407 flutriafol
570 flutriafol 20 :.
Potassium Salt of660 propiconazole 30
Thi~ensulfuron methyl 660 propiconaz~le O
+ ~tsul~uron
m~yl tlO:l) --
Potassium Salt of700 2,4-D O ..
Thifensul~uron methyl 700 2,4-D O .
+ Sodium Salt ofllSO 2,4-D 5
Tribenuron 1150 2,4-D O
m2t~yl (2:1) 130 MCPA 2
675 ~CPA 2
700 ~CP~ O
720 ~CPA O
700 propiconazole O
770 propiconazole O
Sodium Salt of 117 2,4-D O
Tribenuron 200 propiconazole O
methyl 224 propiconazole O
246 propiconazole 2
268 propiconazsle O
281 propiconazole o
Percent injury to ~reenhouse ~ugarbeets after ~prayed with final
ammonia wash water from the tank cleanout proced~re.

WO 93/16596 PCI/US93/~1295
2 1 3 ~ 12 - ~
TANK CLE~OUT ~2TOCO~
(SU1fQ ylu~ea Pl ~ Tank MLx ~ar~ner) -~
~ -) '
Add water to the tank and when half-fi~led, add the
S sulfonylurea or the sulfonylurèa salt wi~h agitation.
Fill tank ~Q the 90~ level with water, add any tank mix
. partners, a~d finish filling the tank. Agitate the
tank mix for a minimum of 5 to 10 minutes.
~2 .-:
Spray the tank contents ~hrough the boom. Drain
any remainder from the ta~k. .
Step 3
Rinse the interior tank surfaces wi~h water; use
about 10% of the tank capacity. Spray this rinse :~
15 through the boom. Drain the remai~dex from the tank. :
,$tep 4 '~
Fill tank approximately half-full with fresh water
and add the desired cleaning solution. Finish fillins ,~
tank. Flush all lines and boom with cleaning ~olution ,:,
0 -~which can be water, or an ammonium hydroxide, or
sodium hypochlorite solution) and agitate for 15,min.
Spray 10 to 20 gallons of the wash through the boom.
Drain the remaining tank contents.
,Step S
Remove all nozzles, nozzle screens, in-line filters
or filters of any type and clean thoroughly in a bucket
of water and cleaning agent. Remo~e any residues or
deposits using a brush.
Rinse the interior tank surfaces with fresh water;
use about 10% of the tank capacity to remo~e 211 traces
of the cleaning solution. Spray the rinse through the
boom. Drain the remainder from the tank.

WO~3/16~96 2 13 O 1 1~ PCT/US93/0l295
~ .
13
$tep 7
Fill tank half full and add ammonium hydroxide to
gi~e a concentration of 0.3% of ammonia. Finish
filling the tank. Flush all lines and boom with ~he ~:
5 ammonium hydroxide solution, and let agitate for-15 ;
min. Sample ammonia water wash in tank (sample used -
for bioassay test). Spxay 10 to 20 gallo~s through tAe
boom and then sample at a nozzle ~sample used for -
bioassay test). Drain the remainder of the contents.
Rinse all remaining ammonium hydroxide solution from
the tank with fresh water. Note: Samples were .
buffered to an appropriate pH to ~nsure stability of
the sulfonylurea and then kept frozen prior to
analyses.
~A~
Initial Sulfonylurea
Concentration Percent
5~1~L5YI~SSJ in Tank ~i~ Ini~Y
Thifensulfuron methyl550 ~pm 28
550 ppm 32
550 ppm 17
Potassium Salt of 550 ppm O
Thifensulfuron methyl550 ppm O
550 ppm 18
Chlorsulfuron 275 ppm 50
275 ppm 100
275 ppm lOO
Ammonium Salt Of 275 ppm O
Chlorsulfuron 275 ppm O
275 ppm 5
Metsulfuron methyl 275 ppm 85
275 ppm lOO
275 ppm 30

WO93/1659~ P~TlUS93/01295
21~0118 - :
14
Potassium Salt of 275 ppm 8
Metsulf~n met~yl 275 p~m O
Sodium Salt of 275 ppm 64
Metsulfuron methyl
Percent injury to ~r~en~u~ sugarbeets after sprayed with final
ammonia was~ ~ater frGm the tank cleanout proced~re.
TANK ÇLE~NO~ P~OTQ~OL II
(SulfQnylurea With No Tank PaL~n~r
Ste~ 1
Divide the sulfonylurea sample to be tested into 2
equal portions. Prepare a concentrated slurry with one
10 portion, and a paste with the o~her portion. Spread ~-
a~d/or spray the pa~te and slurry onto the tank
interior and let sit oYernight. This procedure
produces dried deposits on the tank surfaces to
simulate worse-case field conditions.
St~p ~
Rinse the tank interior with clean water, using a
volume of 10-20~ of ~he tank capacity, ~llowing the
rinse to flush through the boom and hoses.
.Step 3
Fill the tank with clean water and agitate for 10
minutes. Discard the water, flushing at least 10-20%
through the boom and nozzles.
Step 4
Remove any nozzl~s, nozzle screens and in-line
2~ filters and clean with fresh water.
Step 5
Rinse the tank with cl~an water, usinq a volume of
10-20% of the tank capacity. Allow the rinse water to
accumulate in the tank and then discard through the
boom and nozzles. Drain any remaining rinse water from
the tank.

WO93/16S96 2 ~ ~ G 1 18 - PCT/US93/01295
,~,
Step 6
Fill the tank half full with water and add ammonium
hydroxide to gi~e a concentration of 0.3~ ammonia.
Finish ~illing the tan~. Flush all lines and boom with
the ammonium hydroxide solution and let agitate for 15
minutes. Sample ammonia water wash in tank (sample
used for bioas~ay te-~t). Spray 10-20% throush the boom
and then sample at a nozzle ~sample u-qed for bioassay
tes~). Drain the remainder of the tank cont~nts.
Rinse all remaining ammonium hydroxide ~olution from
the tank with fresh ~ater. NQTE: Samples are buffered
to an appropriate pH ~o insure stability of the
sulfonylurea and then kept frozen prior to analyses.
~I~A~S~Y PRQTOCOL
The bioassay protocol employed to determine the
percent injury of the crop (sugarbeets) sprayed with
the final rinse ~olution aft~r tank cl~anout of the
ingredients listed in the Tables is as follows.
Sugarbeet seedlings (at the two-leaf stage) ~ere grown
in ~he greenhouse (14 hour photoperiod at 21C with
light and lO hours at 17~C in the dark) and sprayed
with unmodified samples of effluent from various
sprayer cleanout procedures. An automatic belt spxayer
was used, and the samples were applied at a rate of
approximately 45 gal/A. Three replicate pots, with
four sugarbeet plants/pot, were treated with each
sample. The sprayer was rinsed 12 times between each
samp}e to ensure ~hat there would not be carryover
between samples.
Plants were held in the greenhouse until they were
evaluated, 14 to 23 days after treatment. Injury of
treated plants was aQ-Qessed visually on a scale of 0 to
lO0 (0-no injury, lO0=complete kill) comp2red to
control plants. Injury ratings were based on the
presence of variou~ symptoms including ~educed biomass,

WO93/1~5~ 2 1 ~ O 1 1 8 PCT/US~3/~1295
1~ :
stunting, inhibited development, chlorosis, necrosis,
le~f spotting, and leaf puckering or deformation.
E~ :
Compounds of this invention will generally be used
in formulation with an agriculturally suitable carrier
comprising a liquid or solid diluent or an organic
solvent. ~se formulations i~clude dusts, granules,
pelle~s, solutions, Table B, su~pensions, emulsions,
gels, actives in plastic, wettable powdersp
emulsifi~b~e concentrates, dry flowables a~d the like,
consistent with the physical prsperties of the acti~e
ingredient, m~de of application and en~ironmental
factors such as ~oil type, moisture and ~emperature.
Sprayabl~ formulations can be extended in suitable
media and u3ed at spray volumes from about one to
several hundred liters per hectare. High strength
compositions are primarily u-~ed as intermediates for
further formulation. The formulati~ns will typically --
contain effecti~ amounts of salts sf sulfonylurea(s),
diluent and surfactan~ within the following approximate
ranges which add up 100 wei~ht percent.
Weiqht Percent
Wettable Powders 5-95 0-95 0-10
Oil Suspensions, 1-50 40-99 0~15
Emulsions, Solutions,
~including Emulsifiable
Concentrates)
Pesticide Impregnated F~lm 1-80 20-99 0-15
Dusts 1-25 70-99 0-5
Granules 0.01-99 5-99.99 0-15
Water Dispersible 1-90 5-99 0-15
Granules/Pe}lets

WO ~/165~62 1 ~ PCI`~US93/~1295
17
Tablets 10--6040--99 0--5
High Strengt~ Cpositions 90-99 0-10 0-2
Gels 1--70 0--99 0-1~
Typical solid diluents are described in Watkins,
et al., ~andbook of Insecticide Dust Diluents and
Carriers, 2nd Ed., ~orland Books, Caldwell~ New 3ersey.
Typical liquid diluents and solYents are described in
Marsden~ Sol~ents Guide, 2nd Ed., Interscience, ~ew
York, 1950. ~cCutc~eon's Detergents and Emutsifiers
AnnuAl, Allursd Publ. Corp., Ridgewood, New Jersey, as
well as Sisely and Wood, Encyclopedia of Surface Active
10 Agents, Ch~mical Publ. Co., Inc., New York, 1964, list
surfacta~ts and recommended uses. All formulations can
contain minor amounts of additi~es to reduce foam,
caking, corrosion, microbiological growth, etc.
Solutions are prepared by simply mixing the
ingredients. Fine solid compositions are made by
blending and, usually, grinding as in a hz~mer mill or
; fluid energy mill. Wa~er-dispersible ~ranules can be
produced by agglomerating a fine powder composition;
see for example, Cross et al., Pesti~ide Fonmul~tions,
Washington, D.C., 1988, pp 251-259. Suspensions are
prepared by wet-milling; see, for example, U.S.
3,060,084. Granules and pellets can be made by
spraying the active material upon preformed granular
carriers or by agglomeration techniques. See Browning,
25 '1P.,gglomeration", Chemical Engineering, December 4,
1967, pp 147--48,Perry's Chemical Enginee~'s Handbook,
4th Ed., McGraw-~ill, New York, (1963), pages 8-57 and
~ollowing, and WO 91~13546. Pellets can be prepared as
described in U.S. 4,172,714. Water-dispersible and
water-soluble granules can also be prepared as taught
in DE 3,246,493.

W~93~16596 PCT/US93/012~5
213011~ 18
For further information regarding the art of
formulation, see U.S. 3,235,3Ç1, Col. 6, line 16 .
through Col. 7, line 19 and Examples 10-41, U.S.
3~ 309~ 192~ CO1D 5~ }ine 43 through Col. 7, line 62 and :~
Examples ~, 12, 15, 39, 41, 52, 53, 58, 132, 138-140,
162-}64, 166, 167 and 169-182; U.S. 2,89~,855, Col. 3,
line 66 through Col~ 5, line 17.and Examples 1-4;
Klingman, ~eed Control as a Science, John Wiley and
Sons, Inc., New York, (1961), pp 81-96; and ~ance et
al., Weed Cont~ol ~andbook~ 8th Ed., Blackwell
Scientific Publications, Oxford, (1989).
Tn the following Examples, all perc~ntages are by
weight and all formulations are worked up in
con~entional ways. Compound 1 is the amm~nium salt of
chlorsulfuron.
xample A
Hi~h Stren~th ~Qncentr~te
Compound 1 98.5%
silica aerogel 0.5%
synthetic amorphous fine silica 1.0%.
~xampl
We~ta~ powder
Compound 1 65.0%
30dium alkyl naphthalenesulfonate 2.0%
sodium ligninsulfonate 4.0
sodium silicoaluminate 6.0%
montmorillonite (calcined) 23.0%.
Ex~m~le C
Granule
Compound 1 10.0%
attapulgite granules ~low volatiYe
mat~er, 0.71/0.30 mm; U.S.S. No.
25-50 ~ieves) 90.0%.

W093/16~96 2 1 3 0 1 1 8 PCT/US~3/0~95
19
~xample P
Wa~ex Dis~rsible ~ra~le/Pellet
Compound 1 25.0
anhydrous sodium sulfate 10.0%
crude calcium ligninsulfonate 5.0
sodium alkylnaphthalenesulfonate 1.0%
calciumJmagnesium bentonite . 59.0%.
.