CA2130118A1 - Method for spray tank cleanout - Google Patents

Abstract

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.

Description

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 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 R2~ ' ~C112 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 ;~

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 60 500 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 0 750 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 ~ .

$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 - :

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 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 ~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%.
.

Claims (10)

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:

wherein:
J is selected from the group , , , , , , , , , , , , and ;

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, 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;

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 ;

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;

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);

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.

10. A method according to Claim 8 wherein the spray tank cleanout is improved by a factor of at least 4.