CA2127093A1 - Tablet formulation with internal desiccant - Google Patents

Abstract

A tablet formulation comprising a pesticide and a delivery system, the delivery system comprising a range of acid/base combinations, a dispersant, a wetting agent, polyvinylpolypyrrolidone, and a characterizing internal desiccant to ensure tablet stability, the tablet being selected to complement the particular class of base selected for the formulation.

Description

WO 93/1365~ P~/VS92/1 1305 : ` 212, ~93 TIT~E
TABLET FORMULATION WlTH INTERNAL DESIC(~
An effe~vescent tablet produces gas bubbles by the reaction be~ween an acid 5 and a base. Should the water level in the tablet e~ceed about 0.1%, the tablet will begin to lose itS effervescence even though it is stored in its container. Normally, an amount of water e~ceeding 0.1% is re~luired to forrnulate a tablet having acceptable integrity and strength.
One way to keep the water employed du~ing fonnulation from mining the 10 tablet dunng long-teIm storage is to package the tablet with a desiccant. Thewater in the tablet diffuses out and is taken up by the desiccant. This water isheld by the desiccant and so cannot cause the acid/b~se reaction tO occur.
However, the need for an e~temal desiccant complicates design of ~e tablet package.
One such tablet foImulation that does not have an internal desiccant is disclosed in WO 90/00007. Two formulations that contain an intemal desiccant are disclosed in CA-A-2,013,918 and WO 88109161. CA-A-2,013~918 discloses a tablet comprising potassium carbonate and/or potassiusn bicarbonate as bases anda desiccant which physically adsorbs water. WO 88/09161 discloses an effervescent tablet for cleaning dent~res comprising pancreatin, an acid component, a base component, and a drying agent.
~UMMARY OFTHE 1~NTION
This invention comprises a tablet formulation consis~ing essentially of by total weight of the foImulated composition:
(i) about 0.1% to 75% of apesticide;
(ii) about 25% to 99.9% of a delivery system characterized by a panel of componen~s complementary to the pesticide of (i) having the following components:
(a) about 5% to 75% of a dibasic or tribasic organic carbo~ylic acid or a mi~ture ~hereof:
- (b) about 5% to 75% of an ammonium. Iithium, sodium or potassium carbonatc or bicarbonate or a mi~turc thereof;
(c) about 0.5% to 20% of a dispçrsant;
(d) about 0.1% to 5% of ~at~r-insoluble cross-linked polyvinyl-polypyrrolidonc;

WO ~3/1365~ P~r/US92/1 1305 (e) about 0.1% to 5% of an anionic or nonion~c wetting a~ent; and (f) about 1% to 20% of an intemal desiccant being selected frorn the group:
(A) one or a mixture of desiccants tha~ chemically bind water, and S (B,~ one or a mi~ture of desiccants that physically adsorb water;
the desiccant being (A) when ~b) is potassium carbonatc or potassium bicarbonate.
This delivery system is characterized by the inter-relationship of componen~s (a) to (fl in the recited ran~es tO effect rapid disintegration of finely dispersed pesticide particles (i). Prefe~Ted ranges of the composition are 5% to70%, more prefera~ly 10% to 60% of the pesticide; and 30% to 95%, more preferably 40% to 90% of the delivery system.
By "tablet formulation" is meant the tablet made from the composition described herein, as well as the composition foImulated in accordance with this discIosure but not in tablet form. The preferred tablet formula~ion of the present invention is ~n the form of a tablet.
Contemplated pesticides include those selected from the ~ollowing classes, including mi~ r~s thereof: herbicides, ~ungicides, bactericides, insecticides, nematocides, acaricides, and growth regulants.
Preferred dibasic and tribasic organic carbo~cylic acids include citric, fumarie, phthalic, maleic, malic, o~salic, adipic, glutaric, 2-methyl glutaric, succinic, and tart~ric, or mixtures of any of them.
The term "dispersants" includes sodiwn, potassium, ammonium and calcium salts of naphthalene sulfonic acid-formaldehyde condensates; lithium, sodiurn, potassium, calcium, and ammoniom salts of lignosulfonates; sodium; potassium and ammoniwn salts of polyacrylates and carbo~cylates; sodium salts of maleic anhydride-isobutylene copolymers; and water soluble nonionic polymers such as polyvinyl-pyrrolidone, polycthylene o~ides and cellulose derivatives. Preferred dispersants include the sodium, potassium. ammonium and calcium salts of naphthalene sulfonic acid-formaldehyde condensates, With the ammonium salts more prcferred.
Water-insoluble, cross-linked polyvinylpolypy~rolidone disinte~rant refers to any of the generic, but is not limited tO, crospovidone disintegrating agents.
The term "anionic vctting a~ent" includes, but is not limited to, salts of alkylbcnzene sulfonates, alkyl and dialkylnaphthalene sulfonates, alkyl and WO 93/136~8 '~ 9 2~, v ~ PCI`/US92/1130S

alcohol sulfates, sulfoaL~lamides, carbo~ylates~ alpha-olefin sulfonates and di~L"yl sulfosuccinates. The term "nonionic wetting agent" includes acetylenic diols, ethylene o~cide-prQpylene o~ide copolymers, alkylphenol etho~ylates, fat~acid etho~ylates, alcohol etho~ylates, sorbitan fatty acid ester ethoxylates and5 castor oil etho~ylates The preferled wetting agents are sodium dialkyl sulfosuccinates of which sodium diisobutyl sulfssuccinate, sodium diamyl sulfosuccinate and sodium dicyclohe~yl sulfosuccinate are more preferred.
l~e intemal desiccants that "chemically bind" water are those that actually under~o chemical reac~ions with water to form a new compound. An e~ample of 10 this type of material is CaO which reacts with water to form Ca(OH~2. Other materials representative of those which react in this manner are ma~nesium oxideand boric anhydride.
The internal desiccants that "physically adsorb" water are those selected fr~m the group consisting of highly dispersed silicilic acids such as silica gel;
lS aluminum o~ide; clays such as montmorillonite; and amorphous ~nd crystalline aluminosilicates such as molecular sieves and zeolites. Combinations of these desiccants with those that fo~n hydro~ides and hydrates can be used. Kirk-Othmer's Encvclo~dia of Chemical Technolo~ (3rd ed., Vol. 8, p llS) describes desiccants suitable for use in the tablet formulation of this invcntion as Type 1 20 and Type 4 desiccants. Either type can bc employed, singly or in combination, as long as the desiccant does not e~cpand when it picks-up water, Such e~pansion causes the tablet to crack or cn~mble on long tenn s~orage.
Internal desiccants usefill in the tablet formulation of this invenuon also include materials that chemically bind water, not in the sense of a Chemical 25 reaction that fosms a hydro~ide, but in the sense of a chemical reaction thatproduces a hydrate. Representative of useful desiccants that form hydrates are CaS04, NaOAc, MgS04, ~a2SO4, CaC12, and ZnS04. Representative of the hydrate-form~ng reaction is that undergone by CaC12 to form CaC12 H20. One or more desiccants from each group, the hydro~ide-forming and the hydrate-30 forming, can be employed, alone or in combination, depending on the particularproperties sought by the formulator. In any event, the desiccants employed in the tablets of this invcntion are not thosc of the water-adsorbing type employed in prior art tabl~t formulations, Kirk-Othmer's EncyclQ~2edia ~f (~hemical Tcchnolo~ (Third Edition, Vol. 8, page 115) further describes desiccan~s of the 35 ~ype contcmplatcd for this invcntic~n as so-callcd Type 1 materials.

2 1 2 ~ ~ ~ 3 4 PCr~US92/1130$

A preferred tablet formulation is one wherein component (b) is an ammonium, sodium or lithium carbonate or bicarbonate or mix~ure thereof, and the in~emal desiccant is selected from (A), (B) and a mi~ture of (A) and (B).
Also preferred is a tablet forrnulation wherein (b) is potassium carbonate or S bicarbonate or mix~ure thereof, and the intemal desiccant is (A).
Preferred pesticides are those having a melting point of at leas~ about 100C
and solubility in pH 7 water at 20C of no more than about 5% by weight.
Representatives of sllch pesticides are herbicides such as: acifluorfen, asulam,atrazine, bensulfuron, bentazon, bromacil, bromo~ynil, chl~ramben, chlorimuron 10 ethyl, chloro~uron, chlorsulfuron, chlortoluron, clomazone, cyanazine, dazomet, desmediphan, dicamba~ dichlobenil, dichlorprop, diphenamid, dipropetryn, diuron, thiameturon, 2-[~r~N-~4^metho~cy-6-methyl-1,3,5-triazine-2-yl)-N- :
methylamino]carbonyl~amino~sulfonyl]benzoic acid, methyl ester, fenac, fenuron, fluometuron, fluridone, fomesafen, glyphosate, he~cazin~ne,imæamethabenz, 15 imazaquin, imazethapyr, io~ynil, isoproturon, isouron, iso~aben, karbutilate,lenacil, MCPA, MCPB, mefluidide, methaben~hia~uron, methazole, metribuzin, ::
metsulfuron methyl, monuron, naptalam, neburon, nitralin, nor~urazon, oryzalin, perfluidone, phenmedipham, picloram, prometlyn, pronamide, propazine, pyrazon, siduron, simazine, sul~ometllron methyl, tebuthiuron, terbacil, 20 terbuthylazine, tcrbutryn, triclopyr, 2,4-D, 2,4-DB, t~iasulfilron, primisulfuron, 2~ (4,6-bis(difluorometho~y)pyrimidin-2-yl~ureidosul~onyl)benzoic acid methyl ester, 5-pyrazolesulfsnamide,N~ l metho~y-6-methyl-pyrimidine-2-yl)-amino carbonyl~-4-metho~y-carbonyl-1-methyl-], N-[[(4,6-dimeths~cy-2-pyr~nidinyl)-amino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfon~mide, 2-[[[[(4,6 dimetho~v~-25 2-pynmidinyl)amino~carbonyl~amino]sulfonyl]-N,N~imethyl-3-pyridine-carbo~camide, methyl 2-[[[[[4-etho~y-6-(methylamino)-1,3,5-triazin-2-yl]-amino]carbonyl]amino]sulfonyl]be~oate, methyl 2-r[[[(4,6-dimethoxy-2-pyrimidinyl)amino}carbonyl~amino]sulfonyl~-6-(trifluoromethyl)-3-pyridine-carbo~ylate, 2-(2-chloroetho~cy)-~-~l(~metho~y-6-methyl-1,3,5-tIiazin-2-30 yl)amino]carbonyl~benzenesulfonamide, methyl 2-[[[~[4-(dimethyl-amino)-6-(2.2.2-trifluoroethoxy)-1 ,3,5-triazin-2-yl]amino]carbonyl]sulfonyl]-3-methyl-benzoate, sodium 2-chloro-6-[~4,~dimetho;sy-2-pyrimidinyl)thio]benzoate;
fun~icides such as: carbendazim, thiuram, dodine, chloroneb, cymoxaniI, captan, folpct, thi~phanatcmethyl, thiab~ndazole, chlorothalonil, dichloran, captafol, 35 iprodione, Yinclozolin. k~sugamycin, triadimenol, flutriafol, flusilazol, WO'~3/13658 ty ~ 9 ~ PCI/US92/11305 ~ 5 hexaconazole or fenarirnol; bactericides such as o~cytetracycline dihydrate;
~caricides such as: hexathiazo~, o~ythio~uino~, dienochlor or cyhe~satin;
insecticides such as: carbofuran, carbaryl, thiodicarb or deltamethrin.
More preferred pesticides are he;~azinone, 2,4-D, chlorsulfuron, 5 sulfometurcn methyl, chlorimuron ethyl, metsulfuron methyl, ethametsulfuron methyl, thifensulfuron methyl, tribenuron ethyl, bensulfuron methyl, primisulfuron, methyl 2-1~[(4,6-dimetho~y-2-pyrimidJnyl)amino~carbonyl]-arnino]sulfonyl]-6-(trifluoro-methyl)-3-pyridinecarbo~ylate, 2-(2-chloroetho~y)-N-[[(4-metho~y-6-methyl- 1,3 ,~-tria zin-2-yl)amino]carbonyl~benzenesulfonamide,ethyl 5-[[[[(4,6-dimetho~y-2-pyrirnidinyl)amino]carbonyl]amino]sulfonyl~-1-methyl-IH-pyrazole-4-carbo~ylate, ~V-[[(4,6-d~netho~cy-2-pyrimidinylamino]
carbonyl~-3-(e~hylsulfonyl)-2-pyridinesulfonamide, 2-t[~(4,6-dimetho~cy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-N,N-dimethyl-3-pyridine-carboxarnide, methyl 2-~[[[4^(dimethylarnino)-6-(2,2,2-tri~uoroetho~y)-1,3,5-triazin-2-yl]amino]carbonyl]sulfonyl]-3-methylben~oate, and sodium 2-chloro-6-(4,6-dirnetho~y-2-pyrimidinyl)thio]benzoate.
The most preferred pesticides are sulfonylurea herbicides such as chlorsul*lron, sulfomemron methyl, chlorimuron ethyl, metsulfuron methyl, e~hametsulfuron methyl, thifensulfuron methyl, tribenuron ethyl, bensulfuron mcthyl, primisulfuron, methyl 2-11tl(4,6~imethoxy-2-pyIimidinyl)~nino]-carbonyl~amino]sulfonyl3-6-(trifluoromethyl)-3-pyridinecarbo~cyla.e, 2-(2-chloroetho~cy)-N-[~(4-metho~y-6-methyl- 1,3 ,5-tria~in-2-yl)amino]carbonyl]-benzenesulfonamide, ethyl 5-[~[[(4,6-dimetho~cy-2-pyrimidinyl)amino~-carbonyl~arnino]sulfonyl]-l-methyl-lH-pyra~ole4-carbo~ylate, N-[[(4,6-dimetho~y-2-pyrimidinylarnino}carbonyl]-3-(çthylsulfonyl)-2-pyridine-sulfonamide, 2-[[[[(4,6-dimetho~y-2-pyrimidinyl)arnino]carbonyl]amino]-sulfonyl~-N,lV-dimethyl-3-pyridinecarbo~amide, and methyl 2-[[~[14-(dimethylammo)-6-(2,2,2-trifluoroetho~y)-1 ,3,5-triazin-2-yl]amino]carbonyl]-sulfonyl~ -3-methylbenzoate.
DETAILS OF THE I~VE~IlOI~
l~e most common method for applying watcr insoluble pes~icides is as frne aqucous dispcrsions which are sprayed onto the field or crop using ground or aerial spray rigs. Thc tablets of this in~venSiion combine a high level sf physical intcg~i~v with rapid break-up in water usin~ mir~imal or no agitation while providing fine dispersions of actiYe ingredient. Since the spray nozzles are WO g3/136~8 PCI/US92/l 1305 typically protected against clogging by 50 mesh screens (U.S. mesh size), the dispersions must be fine enough to pass through this size screen without plugging it. This ability is characteristic of pesticide dispersions delivered by the delivery system of t~s invention.
~igh physical integrity of the tablets is desirable so that the tablets themselves can withstand the tabletting operation and survive handling, packa~ing and shipping without breaking. An a~ial breaking strength of greater than about 9~c103 newtons is generally necessary for a tablet to survive such treatment.
Rapid break-up in water is desirable for the convenience of the growers who i O require ~uick ~naround times for the preparation of the dispersions. Generally, ~he tablets of the invention disperse completely in less than 10 minutes, most in less than 5 minutes using even the cold water drawn from wells in the early spring.
It is substantially impossible to obtain rapid break-up of a tablet of substantia y water-insoluble active ingredient in aqueous media wi~hout ~he use of effervescence. The reaction of the organic acid and carbonate or bicarbonate base affords carbon dio:1~ide gas which aids in this respect.
A dispersant is required so that the particles of the active ingredient formed during the disintegration of the tablet remain separated in the cold, hard water.
The disintegrant allows thc penetration of the water into the interior of the tablet through a wicking or swelling action. Common starch or cellulose-bæed disintegrants are unsuitable in agricultural applications as they typically fonn gels on the 50 mesh spray nozzle screens. Hence, a water insoluble cross-linked polyvinylpolypyrrolidone is uscd.
~ wetting agent is reql~ired to control the size of the carbon dio~ide bubbles fom-ed during the reaction of the acid base. The wetting agent reduces the surface tension between the bubbles and the solid tablet resulting in the fonnation of smaller bubbles which readily dct~ch from the tablet surface. As a consequence, the tablet remains submerged in the water for a longer pe~iod of time, thus Lmproving contact of the entire tablet surface with water.
If a tablet floats immediately after bein~ dropped in the water its top rapidly dries out and thc reaction slows down there This increases the tirne required for complete dispersion of active ingredient. When a tablet sinks, water wets the entire e~terior of the tablct, lllen, when the tablet floats to the surface (as a result of thc buoyancy of thc at~achtd carbsn dio~ide bubbles when the tablet hæ

WC~i ~3/136~8 ~ 1 2 7 ~ 9 ~ PCr/US92/1~305 partially dispersed and become lighter) the top remains wet so that e~fervescentreaction continues. Dispersion times for active ingredients ~ormulated as described herein are very much more rapid than in formulations that produce tablets designed for flotation. To ensure that the tablet will sink initially"nert S in~redients are employed that produce a tablet with a density grcater than that of water (specific gravity greater than l.00).
Inert ingredients up eo 99.9% of the total weight of the composition can be employed. Inert fillers such as sugar or clay can be added as long as they do not affec~ the chemical stability of the active in8redient(s). Ma~eri~1s such as glidants, anti-adherents, and lubricants can also be employed to facilitate production in the tablet press. The amounts and types of such ingredients will be readily determinab}e by one skil1ed in the tabletting ar~ given the disclosure herein.
The formulation ingredients are typically ground and mi ced in a mill, e.g., 1~ an air or hammermill. The ground premi~ is passed through a 50 or lO0 mesh (U.S.A. Standard Sieve Series) screen. The average particle size of the ground premi~ should be in the range of S to l5 microns. If it is much smaller, the tablet will be strong, but will not break up very fast. If the premi~c is much larger, the dispersion will not be ~me enough to pass a wet sçreen test used to indicate whether the dispersion will clog the spray nozzle and protective screen discussed previously.
The tablets can be prepared using conventional tablet-making equipment.
Their diameter can vary ~om about 1 crn or less, to 7.5 cm, depending on the tablet weight desired. Flat-faced, beveled-edge punches, with or withou~ a Z5 breakline, product a~tractive tablets.
To keep the tablet from sticking tO the die or punch faces, a lubsicant such as ma~nesium stearate or boric acid can be used. Such lubricants and anti-adherents can be brushed onto the die surface or incorporated into ~he fonnulation.
Tablets have been fonned in a hydraulic press with a capacity of 18,000 kg of force. Pressures between about 3A3:s107 to 6.86~107 pascals will produce stron~ tablets that break up rapidly. Break-up times are determined by dropping a tablet, typically S to 15 g into lO00 mL of water. Ihe "end point" of fLnal dispersion is easy to determinc because the tablet floats to the surface as it loses weigh~ shortly beforc it finally dispcrscs.

wn 93~1365g 2 ~ ~ r~ ~o 9 3 PCr/1)~92/1 1305 The resultant dispersion is then poured through a nest of 50/100/200 mesh screens (300 mm, 150 mm, 75 mm holes, respectively). A qualitative judgment is then ma~e about the amount of material that is retained on each screen. A good tablet will leave just a "trace" on the 200 mesh screen. and the larger screens will S be free of residue.
The strength of the tablet can be measured by a tester such as the Erweka0 Model TBH 28. The tablet is stood on end and the machine ~ip moves to the tablet along an a~cial path. The force to break the tablet in two is normally recorded in newtons (N). Good tablets normally have strengths in the r~nge of 8.896~103 to 4.448~104 N.

The following ingredients were weighed out and milled for l min in a Tekmar~ A-10 analy~ical laboratory mill. Thc premi~c was passed through a 50 mesh screen and blended well. A 15 g tablet, 4.34 cm in diameter, was made 15 with a hand-operated hydraulic press at a pressure of 525 kg/cm2.
Concentration, InFredient Wei~ht %
Thifensulfilron methyl 55.3 Citric Acid 10.0 Sodium Bicarbonate 25.4 Lomar PWA~ (ammonium salt of naph halene sulfonic acid-formaldehyde condensate) 5.7 Polyplasdone XL-1003 (polyvinylpolypyrrolidone) 1.22 Monawet MB-1003 (sodium diisobutyl sulfosuccinate) 1.05 Magnesium O~cide 1.33 The fresh tablet took 2 min and 23 sec to dissolve in 25C water with only a uace of solids on the screcns. A second 15 g tablet was allowed tO sit at room temperature for 3 days to allow the water in it to diffuse into the intemal desiccant 30 (MgO). The taUet was sealed in a tight jar and aged at 45C for 3 weeks. Thisaccelcratcd aging simulates about two years of storage at ambient conditions.
After aging, the tablet t90k 3 min and l0 sec tO dissolve in 25C water. The wetscrccns had only a trace of solids on them:

W0 93~3658 PC~/US92~11305 . ~1270~3 E~IPLE 2 The followLng ingredients were milled and ~ableted as in Example 1.
Concentration, In,ere~nt Wei,eht %
S Thi~ensulfuron methyl 52.7 Citric Acid 9.5 Sodium Bicarbona~e 24.2 Lomar PWA~ (ammonium salt of naphthalene sul~onic acid-fo~naldehyde condensate) 5.45 Polyplasdone~-100~ (polyvinylpolypyrrolidone) 1.15 Monawet MB-100~ (sodium diisobutyl sulfosuccinate) 1 00 Molccular Sieves S.00 The fresh tablet took 2 min and 50 s tO break-up in 25~C wateI. There was 1$ 03-1y a trace of solids on th screens. The second tablet was aged as in Example 1.
After aging, the ta~let took 2 min and 51 s to break-up. There was only a trace of solids on ~e wet screens.
~PLE$ 3 T0 1 In the same manner employed for E~ample 1, taUets can be prepared using 20 the active ingredients in the first column of Table 2 with one or more of thedesiccants listed in the second and third columnsl e~eept that when the base employed is potassium carbonate or bicarbonate, the desiccant~s) employed therewith are to be sdec~ed solely ~om Column A.

WO 93~136~8 PCI`~US92/1 1305 2~2~3 lo Desi~c~nt Active II~Eredient Columo (A) CQlumn (B) 3) he~azinooe selected from the selecled from Ihe group4) 2,~D group, CaO, MgO, highly dispersed silicilic S) chloIsulfuron B203, CaS4~ acids such as silica gel, 6) sulfometuron metbyl NaOAc, MgSO4, aluminum o~ide, clays 7) chlorimuron ethyl Na2S04. CaC12~ such as 8~ metsulfi~on methyl . . and ZnSO4 montmorillonite, and 9) ethametsulfuron me~yl amorphous alun~n~
10) tribenuroo ethyl silicates sach as I 1) bensulfuron methyl molecular sieves and 12) prin~isulfuron zeolites 13) methyl 2-[~[[~4,S dimetho~y-2-pyrinudinyl~
an~ino~car~onyl]asnino]sulfoDyl~(trifluoro methyl)-3-pyndinecarbo~cylate 14) 2-(2-chloroethoxy)-N-t[~4-methw~y-6-methyl-1,3,5-tnazin-2-yl)amino]calbonyl]-beDzeDesulfoDam~de 15) elhyl s-El~E(4~6 dimethw~y-~-py~imidinyl~
amioo]carbonyl~amioo~wlfoDylJ-l-methyl-lf~-pyrazole~carbo~tylate 16) ~-[~(4,6-dimetho~y-2-py irnidinylamino]-carbonyl]-3-~ethylsulfoDyl)-2-py~idiDe-sul~onan~ide 17) 2-t[[[(4,6-dimetho~y-2-pynmidinyl)arnino]-carbonyl]amino]sulfonyl]-NJV-dimetDyl-3-pyridinecarbo~amide 18) methyl 2-tE[[[(4-~dimetDylamino)-~(2,2,2-triBuoroethwcy~ 1 ,3,5-triazD-2-yl]amino]-carbonyl~sulforJyl~-3-metDylbcDwate 19~ sodium 2-chloro-~[(4,6-dimctho~cy-2-pyrimidinyl)tbio~benzoate WO 93/13~58 2 12~ ~ 9 ~ PCr~USg2/11305 By the general procedure of E;~ample 1, tablet fonnulations can be made whereby the active ingredient pesticide is æ described hereafter and the deliverv S system with itS characteris~ic internal desiccant is as defined herein.

The pesticide, described in more detail in U.S. 4,127,405, is a compound of the fonnula:

x Il // ~ :
Rl-S02-NH-C-NH~
N=~
Z

wherem Rlis ~R5 ~\ R ~Rlo `-R3 and R6 are independently hydrogen, fluorine, chlonne, bromine, iodine, aL~cyl of 1~ carbon atoms, alko~y of 14 carbon atoms, nitro, trifluoromethyl, cyano, CH3S(O~n- or CH3CH2S(O)n-;
R4 is hydrogen, fluorine, chlorine, bromine or methyl:
R5 is hydrogen, fluorine~ chlorine, bromine, methyl or metho:1~y;
R7 is hydrogen, fluorine, chlorine, bromine, alkyl of 1-2 carbon atoms or alko~y of 1-2 carbon atoms;
R8 is hydrogen, methyl, chlorine or bromine;
R9 and Rlo arc indepcndently hydrogen, methyl, chlorine or bromizle;

WO ~3~13~8 PCr/US92/11305 ~ ~ ~ r;~ ~ ~ 3 12 W and Q are independently o~y~en or sulfur;
nisO, 1 or2;
X is hydrogen, chlonne, bromine, methyl, ethyl, alkoxy of 1-3 carbon atoms, trifluoromethyl, CH3S- or CH30CH2-; and S :Z is methyl or metho~y, or their agriculturally suitable salts.
EXA~PLE 21 The pes~icide, desc~ibed in more detail in U.S. 4,394,506, is a compound of the formula: :
~-(heterocyclicaminocarbonyl)a~lsulfonamides in which the aryl radical is subs~ituted in the 2-position by a carboxy radical, ester, thioester, or amide thereof; e.g., N-1(4,6-dimethylpyrimidin-2yl)aminocarbonyl]-metho~ycarbonyl]benzenesulfo~amide orN-[(4,6-dimetho~cy-1,3,5-triazin-2-yl)amino-carbonyl]-2-methoxycarbonylbenz~nesulfonamide .
~ 22 The pesticide, described in more detail in U.S. 4,481,029, is a compound of the foImula: -A B B A

~B ' ~F3~A ' ~3 20 wherein W'isOorS;
A' is H, Cl, Br, Cl-C~ alkyl, OC~3, N02 or CF3;

A is -C-Q-R or -C-R where Q is 0, S or -N-;

~4 /
Tis O or=N
whcrc W~ 93/13S58 2 ~ 2 7 ~ ~ ~ PCI/US92/113~5 .. ..
: 13 Rm is H, Cl-C4 aL~cyl or C3-C4 aL~cenyl; when Q is O or S then RI is Cl-C6 aLtcyl C3-C6 alkenyl; C3-C6 alk~yl; C~-C6 a~yl substituted with 1-3 Cl, F or Br, or one of CN or OCH3; C3-C6 alkenyl substituted with 1-3 Cl; C3-C6 aL~cynyl substituled with C1; C5-C6 cycloaL~cyl; cyclohe~enyl; cyclohe:~yl substituted wi~ 1-3 CH,;
C4-C7 cyçloalkylalkyl or (cH2)n ~R7 Rg 10 where R7 and R8 are independently H, Cl, CH3 or OCH3;
nisOorl;and Rg is H or CH3;

Y X
~--< N~ N--N
Rl is --(O~Z; ~ ~N ~ ~O~ 1 X Yl Y

Y
1~1~ N ~/
--~0~ --<0 X~ o where 20Z~N,CHorC-F;
X-H, Cl, -CH~, -OCH3 or-OCH2CH3;
Y=H, Cl, Cl-C4 substiruted alkyl;
~vith thc pro~.riso that whcn X nd Y are both H, then RI and RII are less than 5 carbons;
Xl=H, Cl, OCH3, OCH2CH3 or CH3;
Yl=H, OCH3 or CH3; and ~ ~ 2 7 ~ 9 3 PCr/US92/11305 ~III=O r C~I~ and further provided that when A contains greater than 5 carbon atoms, then Y contains <4 carbon atoms,and their agriculturally suitab!e salts;
all other substituents being as defined in U.S. 4,481,029.
EXA~PLE 23 The pesticide, described in more detail in U.S. 4,435,205, is a compound of ~he formula:

~~ QSO2Rl :

R4 -:
~' where W is 5:) orS;
QisOorN~5;
Rl is CI-C4 al~l? Cl-C4 all~l substituted with 1-3 atoms of F, Cl or Br, CH2CH20CH3, CH2CH2CH20CH3 or ~R6 .

R2 is H, F, Cl, Br, OCH3, NO2, CF~ or Cl-C2 alkyl;
R3 is H, F, Cl, Br or CH3;
R4 is H, CH3 or OCH3;
Rs is Cl-C4 alkyl;
R6 and R7 are independcntly H, F, Cl, Br, CH3, CF3, NO~ or OCH3;

WO 93/1365X 15 2 1 2 ~ PCll/US92/~1305 A is ~Z, ~0~ ' ~ X,(CH2)n N--N N~X2 --< 0~ X2 or ~Q~N

X is NH2, N(CH3~2, NHCH3, Cl-C4 alkyl, Ci-C4 allyl subs~itu~ed with 1-3 atoms of F, Cl or Br, CH20CH3, CH20CH2CH3, Cl-C4 alko~y, Cl-C2 alkylthio, C3-C4 alkenylo~cy, C3-C4 alkynylo~y, OCH2CH20CH3 or C2-C4 alko~y subs~inlted with 1-3 a~oms of F, Cl orBr;
nis 1 OI2;
Y is H, CH3, OCH3 or Cl;
Xl is O or ~H2;
Yl is H, CH3, OCH3 or Cl;
X2 and Y2 are indcpendently CH3 or OCH3; and Z is CH, N, CCH3, CBr, CCl, CF, CI, CC2H5, CCH2CH2Cl or CCH2CH=C~2-~AMPLE 24 The pesticide, described in more detail in U.S. 4,420,325, is a compound of the formula:

2l~lQ I R3 wherein WO 93/136~ PCr/US92~1 1305 2~L2~9~ 16 Rl is F, Cl, Br, CF3, Cl-C3 aL~o7~y, Cl-C~ alkyl, NO~, C02R4. SO ,R~, SO~NR6R7, SO2N~OCH3)CH~. SO,OCH~CF3, OSO2R~ or CH,L;
L is S02NR6R7, OCH3, OC ,H5, CO~H5, CO ,CH~ or CO~C ,H5;
R2 is H, Cl, Br, F, C~3 or OCH3;
R4 is Cl-C3 alkyl, CH~CH=CH2. CH~CH~Cl or CH2CH~OCH3; ::
R5 is Cl-C3 ~lkyl or CF3;
R6 and R7 are independently Cl-C3 aL~cyl;
R8 is H or CH3;
Rg is H or Cl-C3 allcyl;
R3 is X X~ X

Z ~ --<0~ ' --(~

Xl X2 N

Nb N~
x3 --<O Z or --<O>--X3 Yl Y

W is O or S;
X is CH3, OCH3 or Cl;
Y is CH3, C ,Hs, OCH3, OC~Hs. CH2OCH3. NH2, NHCH3 or N(CH3)2;
Z is CH or N;
X} is H, Cl, CH3, OCH3 or OC ,H5;
X, is CH3. C2H5, OCH3 or OC2H5;
X3 is CH3 or OCH3; and Yl is CH3 or OCH3;

` WO` 93/13658 ~ 1 2 ~ O 9 3 P~/US92/tl3~s and their ~griculturally suitable salts. ~:

The pesticide, described in more de~ail in U.S. 4,514,211, is a compound o~
the fo~nula:
S R~

R4,~R2 L R
R5 ~R

,~--R7 . nr R5~R8 wherein QisO,S,SOorS02; .
QI is 0, S or S02;

L is S02NHCII`JA;

~-1 is H ~r Cl-C4 alkyl;

WO 93/1365~ PCr/US92J1 130 ~ ~ ,s~ ~ o ~ ~ 18 -R2 is H or Cl-C4 alkyl;
R3 is H or CH3;
R4 is H~ Cl, CH3, CF~, OCH~, Br, F, SCH3 or OCF2H;
R5 is H, CH3, OCH3. Cl, ~r, NO2~ C2R7- S2R8 OS~2Rg~
S02NR~ F, CF3, SCH3, OCF H or S02N(OCH3)CH3;
R6 is H, Cl, Br or Cl-C4 aL~cyl;
R is H, CH3, Cl or Br;
R7 is Cl-C3 a~kyl, CH2CH=CH2, CH2CH2OCH3 or CH2CH2Cl;
R8 is Cl-C3 alkyl;
Rg is Cl-C3 alkyl or CF3;
Rlo andRl~ are independen~ly Cl-C2 alkyl;
R12isHorCH3;
WisOorS;
Ris X X

' ~ 0 Xl X

~<0~ ' ~0 ,X~ N~

Y2 X .

X is H, CH3, OCH3. Cl. F. OCF.H or SCF,H;
Y is CH3, OCH3, OC2Hs, CH-,OCH3, ~JH2, NHCH3, N(CH3)2~
CH(OCH3)z, CH(OCH~CH3)2, C2Hs, CF3, CH2=CHCH2O, CH-CCHqO. CF3CH2O, OCH ,CH~Cl, OCH2CH ,Br, OCH~CH ,F, WO 93/13658 PC~/US92/113~5 ~ 1 2 ~ 18 R2 is H or Cl-C4 alkyl;
R3isHorCH3;
R4 is H, Cl, CH3, CF~ OCH~, Br, F. SCH3 or OCF2H;
R5 is H, CH3, OCH~, Cl, Br, ~02, C2~7, S2R8~ OS~2Rg~
SO.NR~ . F, CF3, SCH3, OCF H or S02~1tOCH3)CH3;
R6 is H, C1, Br or C l-C4 aL~cyl;
R is H, CH3, Cl or Br;
R7 is Cl-C3 alkyl, CH2CH-CH2, CH2CH20CH3 or CH2CH2Cl;
R8 is Cl-C3 alkyl;
Rg is Cl-C3 alkyl or CF3;
Rlo and Rl 1 are independentlY Cl-C2 alkyl;
Rl2 is H or CH3;
W is O or S;
Ais x o~
Y 1 ~.

N - N r ~ON ;

Y2 x~ .

X is H, CH3, OCH~,. Cl. F. OCF~H or SCF2H;
Y is CH3, OCH3, OC2Hs, CH OCH3, MH2, NHCH3, N(CH3)2, CH~OCH3)2, CH(OCH.CH3)2, C~H5, CF3, CH2-CHCH20, CH-CCH O. CF3CH20. OCH-,CH.Cl, OC}~CH~3r, OCH.CH~F, 2l27a~3 W~ 93/1365~ ~ PCI`/VS92/1 13~5 CN, CH2QCH~CH3, OCH2CH20CH3 or GCF2T wherein G is O or S
and T is H, CHCIF, CHBrF, CF,H or CHFCF3;
Z is CH, N, CCH3, CC2H5, CCl or CBr;
Yl is O or CH?;
X1 is CH3, OCH3, OC2H5 or OCF2H;
X2 is CH3, C2Hs or CH2C~;3;
Y2 iS C2H5. CH3, OCH3, QC2Hs~ SCH3 or SC2Hj; and X3 is CH3 or O~H3.

10The pesticide, described in more detail in U.S. 4,547,215, is a compound of the fonnula:

C~N~

N

15wherein R is C2Hs or CH(CH3)2;
and their agnculnlrally suitable salts.
E~AMPLE 27 The pes~icide, described in more detail ~ U.S. 4,548,638, is a compound of 20the formula:

[~ O NHCH3 502NHCN}~ (~

wherein 25R is CO2CH3. CO2CH2CH3~ C02CH CH~CH3, CO2CH2CH=CH2, CO2CH(CH3), C02CH2CH2Cl, S02N(CH3)2 or OSO~CH3.

WO 93/136~8 PCI`/US92/1130~

EXA~IPLE 2~
The pesticide, described Ln more detail in U.S. 4.479,821, is a compound of ~:
the formula:

R;! 1 5~2-NH-C-NH~

(X-A~m R4 wherein A is a Cl-C6 alkyl radical which is subs~i~uted by Cl-C4 alko~y, Cl-C4 alkylthio, Cl-C4 alkylsulfinyl or Cl-C4 aLkylsulfonyl;
X is oxygen. sulfur, a sulfinyl or sulfonyl bridge;
Z is o~ygen or sulfur;
m is 1 Ol 2;
R2 is hydrogen, halogen, Cl-C~ alL~l, C2-Cs al~;enyl, Cl-C4 haloalkyl, or a radical -Y-R5, -COOR6, -N02 or-CO-NR7R8;
R3 and R4, each independently of the o~er, are hydrogen, Cl-C4 alkyl, CI C4 ~O~CY, C1-C4 alkylthio, C1-C4 haloalkyl, halogen or alko~cy-alkyl of at most 4 carbon atoms;
R5 and R6, each independently of the other, are Cl-C5 alkyl, C2-Cs alkenyl or C2-C6 alkynyl;
R~ and Rg, each independently of the other, are hydrogen, Cl-C5 ~1, C2-C~ alkenyl or C~-C6 al~myl; and Y is w~ygen, sulfur, a sulfinyl or sulfonyl bridge, and salts of these compounds.
EXAMPI,E 29 The pesticide, described in more detail in U.S. 4,566,898, is a c~mpound of the formula:

~(~ C~ N--<
CJ SO ,~ICNH--<O N

WO ~3/136~8 P~r/US92/1130~ ~ -21 2127~

~XAMPLE ~0 The pesticide, described in more detail in U.S. 4,435,206, is a compound of the formula:
s R2~R
S02 1 -C- l wherem Ris X Xl Z ~N or --(O~XI

y Yl Yl Rl is H, Cl, Br, F, Cl-C4 alkyl, C~-C4 alko~cy, Cl-C4 alkylthio, NO2, CP3, COOR5 or SO2N:R6R,;
R2 is H, Cl, Br or CH3;
R3 and R4 are ind~pendently H or CH3;
R5 is Cl-C6 alkyl, C3-C6 alkenyl, CH ,CH20CH3, CH2CH20CH ,CH3, CH2cH2cH2ocH3 or CH ~CH2Cl;
R6 and R7 are independcntly CH3 or CH3CH2;
W is o~ygen or sulfur;
X is CH3 -OCH3 or -OCH ,CH3;
Y is H, CI, CH3, CF3, -NHCH3, -N(CH3)2-, -CH20R8, -CH~CH20R8, -OCH2CF3 or VR6;
Z is CH or ~;
~J is o~ygen or sulfur;
R8 is CH3, CH3CH2-, CH2CO2Rg, -CH2(: H20R6, C(CH3)HC02R8 or CH2C~2C02R8;
Yl is H, CH3 or OCH3; ar~d WO 93/1365~ PCI/US92/l13~5 7 ~ ~ 3 22 Xl is H, C1, -OCH3, -OCH2CH3 or CH3;
and agricultural salts thereof.
EXAI~T E ~1 The pesticide, descAbed in more detail in U.S. 4,514,212, is a compound of the fonnula:

~2 ~ SO2-NH-GNH ~ N

X-cH2-Q R4 and the salts thereof with amines, alkali metal or aL~caline earth metal bases or with quatema~y ammonium bases wherein:
Q is fluorine, fluoromethyl, chloromethyl, tnchloromethyl, 1,2~dichloro-e~hyl, 1,2-dibromoethyl, 1,2-dichloropropyl, 1,2-dibromopropyl, 1 ,2-dibromoisobutyl, 1,2-dichloro-1-methyl-ethyl or 1,2-dibromo-l-methylethyl;
~ is o~ygen, sulfur, a sulflnyl or sulfonyl bridge;
Z is oxygen or sulfur;
R2 is hydrogen, halogen, Cl-Cs alkyl, C2-Cs alkenyl, Cl-C4 haloalkyl, or a radical -Y-R5, -COOR6,-NO, or-CO-~lR7-R8;
R3 and R4, each independently of the other, are hydrogen, Cl-C4 alkyl, Cl-C4 alko~y, Cl-C4 alkylthio, Cl-C4 haloalkyl, halogen or alko~yaLkyl of at IllOSt 4 car~on atoms;
R~ andR6, each indcpendently of the other, are C1-Cs alkyl, C2-C5 a~enyl or C2-C,6 alkynyl;
R7 and Rg, each independently of the other, are hydrogen, Cl-Cs alkyl, Cz-Cs alkenyl or C2-C6 alkynyl; and Y is o~ygen. sulfur, a sulfinyl or sulfonyl bridge.
EXAMl?LE 32 l~e pesticide, described in more detail in U.S. 4,478,635, is a compound of the formula:

WO g3/136~8 P~/US~2/11305 2~127~3 X-SO?-NH-C-N~/ ~
~, R16 y wherein X is a radical of the ~oImula:
S

~ o- ~

Y is Cl-C3 alkyl, ~1-C3 haloalkyl, Cl-C3 aLIco~y, Cl-C3 haloalko~y, C~-C3 alkoscyalkyI, Cl-C3 alkylthio, ha!ogen or -~R16R17;
Z is o~ygen or sulfur;
Rl i~, hydrogen, halogen, cyano, nitro, Cl-C4 haloalkyl, Cl-C4 alkyl, Cl-C4 aiko~cy, -CO-R6, -N~7R8, -S(O)m-Cl-C4 allyl or-S02Rg;
R2 is hydrogen, fluorine, chlorine, bromine, nitro, ~ifluorome~hyl, -NR20R21, methyl, ethyl, metho~y, etho~cy or -S(O)m-Cl-C4 alkyl;
R3 is hydrogen, fluorine, chlorine, bromine, amino, nitro or metho~y;
R6 is hydrogen, Cl-C4 aLkyl, Cl-C3 alkcnylo~cy, C3-Cs alkynylo~y, Cl-C4 haloalkyl, C~-C5 alkylthio, pheno~y, benzylo:~y, -NRloRll or Cl-C5 alko~y which is unsubstituted or substituted by 1 to 3 halogen atoms or Cl-C3 aL~co~y;
ZO R7 is hydrogen, metho~y, etho~y, Cl-C4 ~lkyl or -CO-Rl2;
R8 is hydrogen or -CO-Rl2;
Rg is an -O-R13 or -NRl4Rl5 group;
Rll is Cl-C4 alkyl which is unsubstituted or substituted by 1 tO 3 halogen atorns, or is phenyl or bcnzyl;
R12 is hydrogen, Cl-C4 a~yl or Cl-C4 alkoxy; and misO,lor2;

WO 93/1365~ PCI'/VSg2/1 1305 2:~2~3 24 and R4 has the same meaning as R2; R5 has the same meaning as Rl; Rlo, Rl 1~ Rl4 and R20 each have the same meaning as R7; and R12, R15, R16, R17 and R21 each have the same meaning as R8.
E~LE ~ :
S The pesticide, described ln more de~ail in U.S. 4,634,465, is a compound of the fo~nula:

~SO~-NH-jj'-N ~ \~

A

wherein Z is o~ygen or sulfur;
E is nitrogen or =C-;
Rl is hydrogen, halogen, nitro, Cl-C4 alkyl, Cl-C4 haloalkyl, Cl-C4 alko~cy, Cl-C4 haloalko~cy, Cl-C4 alko~ycarbonyl, Cl-C4 aL~cylthio, Cl-C4 all~rlsulfinyl, Cl-C4 alkylsulfonyl or C2-C~ alko~yalko~y;
R2is hydlogen, Cl-C4 aLkylor Cl-C3alko~y;
R3 and R4t each independen~y ofthe other, &-e hydkogen, Cl-C4 alkyl, Cl-C4 alko~y, Cl-C4 haloalko~y, Cl-C4 haloalkylthio, Cl-C4 aLkylthio, halogen, C2-Cs a1ko~yaLkyl, C2-C5 aLko~yaLko~y or -NR5R6, wherein Rs and R4 are hydrogen or Cl-C4 alkyl; and A is an unsubstituted or substitutcd bridge of 3 or 4 atoms which contains 1 or 2 o~ygen, sulfur or nitrogen atoms and, together with the linking carbon atom, forms a non-aromatic S- or 6-membered heterocyclic ring system, with the proviso that two o~ygen atoms are separated by at least one carbon atom and that o~ygen and sulfur atoms are only linked to each other if the sulfur atom takes the form of the -SO- or -SO2- group.
EXAMPLE ~
The pesticide, de~cribed in more detail in EPA-202,830, is:
2-[[N-(4-mctho~y-6-mcthyl-1,3,5-tri~in-2-yl)-N-methylamino-carbonyl}aminosulfonyl]bcn~oic acid, methyl cster.

WO 93/136~8 2 1 2 7 1) 9 3 PC~/U~;92/11305 ~ he pesticide, described in more detail in EPA-237,292, is a compound of the foImula:
~OCH3 ~SO2N~ 1~0>

wherein J~

CNRlR~
R3 J~ , R3 ~¦
N N CNRlR2 J-l J-2 O
Il O
C~RlR2 l ll J-3 J.4 RisH ~rCH3;
Rl is H or Cl-C3 alkyl;
R2 ~ Cl-C3 a~yl or Cl-C2 alko~y; or Rl and R2 may be taken together to form -(CH2)n-, whercin n is 2, 3 or 4;
R~ is H, Cl, F, Br, CH3, CF3, OCH3 or COF2H; and X is CH3, CH2F, CH2CH3, OCH3, OCH~CH3, Cl, OCF2H or CH2OCH3.
E~Il~ 6 l~e pesticide, described in more detail in EPA-87,7~0, is a compound of the formula:

WO 93/136~8 P~US92/11~05 2 1 ~ 3 26 B

~ ~
C I ~=<
D y wherein A represents a hydrogen atom, a Cl-C8 alkyl group or a phenyl group which may be substitu~ed with Cl-C8 alkyl groups, halogen atoms or nitro groups; B and C represent independently hydrogen a~oms, halogen atoms~ nitro groups, Cl-C8 alkyl groups, arylalkyl groups, Cl-C8 aL~coxy groups; haloaL~cyl groups, -C02R [where R is a hydrogen atom, a Cl-Cg alkyl group, an allyl group or a propargyl group), -CONRlR2 (where Rl is a hydrogen atom, a Cl-C8 alkyl group or a phenyl group, R2 is a hydrogen a~om or a Cl-C8 alkyl group, or Rl and R2 taken together may represent -(CH2)m- (~ is 4, 5 or 6), -CH2CH2OCH2CH2-, or -CH2CH2N(CH3)CH2CH2-], -S(O)nR3 (where R3 is a Cl-Cg alkyl group, a phenyl group or an arylalkyl group and n is 0, 1 or 2), -S02NR4RS [where R4 is a Cl-C8 al~rl group, R5 is a hydrogen atom or a Cl-Cg alkyl group, or R4 and R5 taken together may represent -(CH2~p- (~2 is 4, ~ or 6), -CH2CH2OCH2CH2- or -CH2CH2N(CH3)CH2CH2-] or a phenyl group which may be substituted with Cl-Cg alkyl groups, halogen atoms or nitro groups, D represents a hydrogen atom or a Cl-C8 aL~cyl group; X and Y represent independently hydrogen atoms, halogen atoms, Cl-C8 aLkyl groups, Cl-C8 aL~oxy groups, Cl-C8 aLkoxyalkyl groups, -CF3 groups, Cl-Cg haloalko~y groups, alkylalTIino R
groups, dialkylamino groups, -OCHCO2R7 (where R6 and R7 cach represcnt hydrogen atoms or Cl-Cg alkyl groups) or either X or Y may foIm a five-membered ring contai ~ing an o~cygen atom together with X; and X represents a nitrogen atom or C-R~
~where Rg represcnts a hydrogen atom, a haloalkyl group or may WO 93JI3~58 2 1 2 ~ ~ ~ 3 PCr/USg2/11305 form 2 five^membered ring contai ~ing an oxygen atom ~ogether with X or Y) The pesticide, desclibed in more detail in IJ.S. 4,710,Z21, is a compound of S the formula:

~2 SO2NHCII~--<~

wherein R is H or CH3;
Rl is Cl-C3 aL~yl, C3-C4 al~o~yaL~cyl, C2-C4 haloalkyl, C3-C4 alkenyl o C3-C4 allcynyl;
R2 is C2-C6 alkoxy, C3-C6 cycloaLko~cy, C4-C6 cycloalkylaLkQxy, CI C6 haloalkoxy, C2-C~ alkenylo~y, CrC6 haloalke~ylo~y, C3-C6 1~ allynyloxy, C3-C6 haloaLt~ynylo~cy, C2-C4 all~o~cyalko~y, C2-C4 haloalko~yalko~cy, C2-C4 alkylthioaL~o~cy, C2-C4 haloalkylthio aLtco~cy, CrC4 all~ylsulfmylalko~y, C2-C4 haloal~ylsulfinylalko:~y, C2-C~ alkylsulfonylalko~y, C2-C4 haloalkylsulfonylaLko~cy, C2-C4 cyanoalkoxy, OCH2C(O)CH3, OCH2CH2C(O)CH3, C2-C4 am~noalko~y, Cl-Cg ~ylthio, C3-C~; cycloalkyl~hio, ~4-C~
cycloall~lalkylthio, Cl-Cg haloalkylthio, C2-C6 aL~cenylthio, C ,-C6 haloalkenylthio, C3-C6 alkynylthio, C3-C6 haloal~ynylthio, C2-C4 alko~cyalkylthio, C2-C4 haloalko~cyalkylthio, C2-C4 allylthio-alkylthio, C2-C4 haloal~lthioal~lthio, C2-C4 cy~noally}thio, SCH2C(O)CH3, SCH2CH2C(O)CH3, C2-C4 aminoalkylthio, SC6H5, SCH2C6H~, C~-Cg aLtcylsulfinyl, C3-C6 cycloalkylsulfinyl, C4-C6 cycloalkylaL~cylslllfinyl. C~-C8 haloalkylsulfinyl, C2-C6 alkenyl-sulfLrlyl, C2-C6 haloalkcnylsulfinyl, C3-C6 `alkynylsulfinyl, C3-C6 haloalkynyls~llfinyl, CrC4 aL~co~y~Lkylsulfinyl, Cz-C4 haloaL~coxy-alkylsulfinyl, C2-C4 cyanoalkylsulfinyl, S(O)CH2C~O)CH3, S(O)CH ,CH2C(O)CH3. C2-C4 aminoalkylsulfinyl, C2-Cg alkylsulfonyl, C3-C~, cycloaL~rlsulfonyl, C4-C6 cycloalkylalkyl-WO 93/136$8 P~/U!~92/1l~0~
2 ~ 3 28 : - ~
sulfonyl, Cl-C8 haloalkylsulfonyl, C2-C6 aLkenylsulfonyl, C2-C
haloaL'cenylsulfonyl, C3-C6 aL~cynylsulfonylt C3-C6 haloalkynyl-sulfonyl, C2-C4 aL~co;syaLkylsulfonyl, C2-C4 haloalkoxyalkylsulfonylt -~
C2-C4 cyanoalkylsulfonyl, S02CH2C(O)CH3, S S02CH2CH2C(O)CH3, C2-C4 aminoalkylsulfonyl, CH2F, CH2Cl, CHC12, CH2Br, CHBr2, C2-C6 a~kyl substin~ted with 1-3 atoms of F, Cl or Br, C2-C6 alkenyl, C2-C6 haloalkenyl, C-CH, C2-C6 haloalkynyl, OC(O)Cl-C4 alkyl. CH2C(O)NRaRb, NHCH3, NRbRC
or C~-C4 alkyl substituted with C~-C4 alkoxy, C3-C4 cycloaL~coxy, ryclopropylmetho~y~ Cl-C4 haloalkoxy, C2-C4 aL~enylo~y, (~2-C4 haloalkenyloxy, C3-C4 aLkynylo~y, C3-C4 haloalkynyloxy, C2-C4 ~lko~yaLko~cy, C2-C4 aminoalko~y, Cl-C4 alkylcarbonyloxy, Cl-C4 haloaL~cylca~oonylo~cy, Cl-C4 carbamoylo~y, Cl-C4 alko~y-carbonylo~y, OH, OP(O)(OCl-C2 alkyl)2, Cl-C4 alkylsulfonylo~y, Cl-C2 haloalkylsulfonylo~y. OSi(CH3)3, OSi(CH3)2C(CH3)3, Cl-C4 alkylthio, C3-C4 cycloalIylthio. cyclopropylmethylthio, Cl-C4 ha}oallcylthio, C2-C4 alkenylhio, C2-C4 haloaLt~enylthio, C3-C4 alkynylthio, C3-C4 haloal~rnylthio, C2-C4 alko~yalkyl~hiv, ~2-C4 aminoalkylthio, SH, SP(O)(OCl-C2 alkyI)2, Cl-C~ yl~finyl, C3-C4 cycloaLcylsulfonyl, cyclopropylmethylsulfinyl, Cl-C4 haloalkylsul~nyl, C2-C4 alkenylsulfinyl, C2-C4 haloalkenylsnlfinyl, C3-C4 alkynylsulfinyl, C3-C4 haloalkynylsulfinyl, C2-C4 alko~yalkyisulfinyl, C2-C4 aminoalkylsulfinyl, Cl-C4 alkylslllfonyl, C3-C4 cycloalkylsulfonyl, cyclopropylmethylsul~onyl, Cl-C4 haloalkylsulfonyl, C2-C4 alk~nylsulfonyl, C2-C4 haloalkenylsulfonyl, C3-C4 alkynylsulfonyl, C3-C4 haloal~nylsulfonyl, C2-C4 alko~yalkylsulfonyl or C2-C4 aminoalkylsulfonyl;
Ra and Rb are indepcndcntly H or Cl-C3 al~yl;
Rc is C2-C4 alkyl, cyclopropylmethyl. C2-C4 cyanoalkyl, CH2C(O)CH3, CH2CH;~C(O)CH3, Clo-C4 haloalkyl, C3-C4 alkenyl, C3-C4 haloalkenyl, C3-C4 alkynyl, C~-C4 haloall~ynyl, C~-C4 aL~nrl substitutcd with Cl-C4 alko~y, Cl-C4 alkylthio, CI-C4 alkylsulfimyl, Cl-C4 all~ylsulfonyl, OH, NH2, NHCH3 or N(CH3);;
X is CH3, OCH3, OC2Hs, Cl or Br;

` WO93/13658 21~79~3 PCI/llS92/11305 Y is Cl-C2 alkyl, Cl-C2 alko~y, OCH,CH2F, OCH2CHF~, OCH2CF3, NHCH3 or N~CH3)2; ~d Zis CH orN; and ~eir agriculturally suitable salts.

. .

Claims (8)

30What is claimed is:

1. A tablet formulation consisting essentially of by total weight of the formulated composition:
(i) about 0.1% to 75% of a pesticide;
(ii) about 25% to 99.9% of a delivery system characterized by a panel of components complementary to the pesticide of (i) having the following components:
(a) about 5% to 75% of a dibasic or tribasic organic carboxylic acid or a mixture thereof;
(b) about 5% to 75% of an ammonium, lithium, sodium or potassium carbonate or bicarbonate or a mixture thereof;
(c) about 0.5% to 20% of a dispersant;
(d) about 0.1% to 5% of water-insoluble cross-linked polyvinylpolypyrrolidone;
(e) about 0.1% to 5% of an anionic or nonionic wetting agent; and (f) about 1% to 20% of an internal desiccant being selected from the group;
(A) one or a mixture of desiccants that chemically bind water, and (B) an aluminosilicate;
the desiccant being (A) when (b) is potassium carbonate or potassium bicarbonate.

2. A tablet formulation according to Claim 1 wherein (b) is an ammonium, sodium or lithium carbonate or bicarbonate or a mixture thereof, and the internal desiccant is selected from (A), (B) and a mixture of (A) and (B).

3. A tablet formulation according to Claim 1 wherein (b) is potassium carbonate or bicarbonate or mixture thereof, and the internal desiccant is (A).

4. A tablet formulation according to Claim 1 in the form of a tablet.

5. A tablet formulation according to Claim 2 in the form of a tablet.

6. A tablet formulation according to Claim 3 in the form of a tablet.

7. A tablet formulation according to any one of Claims 1 to 6 wherein the pesticide is a sulfonylurea herbicide selected from the group consisting of chlorsulfuron, sulfometuron methyl, chlorimuron ethyl, metsulfuron methyl, ethamelsulfuron methyl, thifensulfuron methyl, tribenuron ethyl, bensulfuron methyl, primisulfuron, methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]-carbonyl]amino]sulfonyl]-6-(trifluoro-methyl)-3-pyridinecarboxylate, 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-pyrimidinylamino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide, 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-N,N-dimethyl-3-pyridinecarboxamide, and methyl 2-[[[[[4-(dimethylamino)-6-(2,2,2-trifluoro-ethoxy)-1,3,5-triazin-2-yl]amino]carbonyl]sulfonyl]-3-methylbenzoate.

8. A tablet formulation according to Claim 7 wherein the pesticide is a sulfonylurea herbicide selected from the group consisting of thifensulruron methyl, tribenuron ethyl, and bensulfuron methyl.