AU668706B2 - Tablet formulation with internal desiccant - Google Patents

Description

0PI DATE 03/08/93 APPLN. ID 34261/93 I| lllllll ||lllllll111 |1111I I I II AOJP DATE 14/10/93 PCT NUMBER PCT/US92/11305 AU9334261 uu, i.w uiNu trit vAI tN CUUPERATION TREATY (PCT) (51) International Patent Classification 5 (Il) International Publication Number: WO 93/13658 A01N 25/34, 47/36, 43/64 Al AOtN 39/04 (43) International Publication Date: 22 July 1993 (22.07.93) (21) International Application Number: PCT/US92/11305 (72) Inventor; and Inventor/Applicant (for US only) JACKISCH, David, Al- (22) International Filing Date: 30 December 1992 (30.12.92) lan [US/US]; 307 Walden Road, Wilmington, DE 19803

(US).

Priority data: (74) Agents: COSTELLO, James, A. et al.; E.I. du Pont de Ne- 07/817,247 6 January 1992 (06.01.92) US mours and Company, Legal/Patent Records Center, 07/817,248 6 January 1992(06.01.92) US 1007 Market Street, Wilmington, DE 19898 (US).

Parent Applications or Grants (81) Designated States: AU, BB, BG, BR, CA, CS, FI, HU, JP, (63) Related by Continuation KP, KR, LK, MG, MN, MW, NO, NZ, PL, RO, RU, US 07/817,247 (CIP) SD, UA, US, European patent (AT, BE, CH, DE, DK, Filed on 6 January 1992 (06.01.92) ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OAPI US 07/817,248 (CIP) patent (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, Filed on 6 January 1992 (06.01.92) SN, TD, TG).

(71) Applicant (for all designated States except US): E.I. DU Published PONT DE NEMOURS AND COMPANY [US/US]; With international search report.

1007 Market Street, Wilmington, DE 19898 (US).

6 6870 6 (54)Title: TABLET FORMULATION WITH INTERNAL DESICCANT (57) 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.

k WO 93/13658 PCT/US92/11305

TITLE

TABLET FORMULATION WITH INTERNAL DESICCANT An effervescent tablet produces gas bubbles by the reaction between an acid and a base. Should the water level in the tablet exceed about the tablet will begin to lose its effervescence even though it is stored in its container. Normally, an amount of water exceeding 0.1% is required to formulate a tablet having acceptable integrity and strength.

One way to keep the water employed during formulation from ruining the tablet during long-term storage is to package the tablet with a desiccant. The water in the tablet diffuses out and is taken up by the desiccant. This water is held by the desiccant and so cannot cause the acid/base reaction to occur.

However, the need for an external desiccant complicates design of the tablet package.

One such tablet formulation that does not have an internal desiccant "s disclosed in WO 90/00007. Two formulations that contain an internal desiccant are disclosed in CA-A-2,013,918 and WO 88/09161. CA-A-2,013,918 discloses a tablet comprising potassium carbonate and/or potassium bicarbonate as bases and a desiccant which physically adsorbs water. WO 88/09161 discloses an effervescent tablet for cleaning dentures comprising pancreatin, an acid component, a base component, and a drying agent.

SUMMARY OF THE INVENTION This invention comprises a tablet formulation consisting essentially of by total weight of the formulated composition: 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 having the following components: about 5% to 75% of a dibasic or tribasic organic carboxylic acid or a mixture thereof: about 5% to 75% of an ammonium, lithium, sodium or potassium carbonate or bicarbonate or a mixture thereof about 0.5% to 20% of a dispersant; about 0.1% to 5% of water-insoluble cross-linked polyvinylpolypyrrolidone; 1 1 j i 1

I

WO 93/13658 PCT/US92/11305 2 about 0.1% to 5% of an anionic or nonionic wetting agent; and about 1% to 20% of an internal desiccant being selected from the group: one or a mixture of desiccants that chemically bind water, and (B)an calumi no sil cla'e that physically adsorb water; the desiccant being when is potassium carbonate or potassium bicarbonate.

This delivery system is characterized by the inter-relationship of components to in the recited ranges to effect rapid disintegration of finely dispersed pesticide particles Preferred ranges of the composition are 5% to more preferably 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 formulated in accordance with this disclosure but not in tablet form. The preferred tablet formulation of the present invention is in the form of a tablet.

Contemplated pesticides include those selected from the following classes, including mixtures thereof: herbicides, fungicides, bactericides, insecticides, nematocides, acaricides, and growth regulants.

Preferred dibasic and tribasic organic carboxylic acids include citric, fumaric, phthalic, maleic, malic, oxalic, adipic, glutaric, 2-methyl glutaric, succinic, and tartaric, or mixtures of any of them.

The term "dispersants" includes sodium, potassium, ammonium and calcium salts of naphthalene sulfonic acid-formaldehyde condensates; lithium, sodium, potassium, calcium, and ammonium salts of lignosulfonates; sodium; potassium and ammonium salts of polyacrylates and carboxylates; sodium salts of maleic anhydride-isobutylene copolymers; and water soluble nonionic polymers such as polyvinyl-pyrrolidone, polyethylene oxides and cellulose derivatives. Preferred dispersants include the sodium, potassium, ammonium and calcium salts of naphthalene sulfonic acid-formaldehyde condensates, with the ammonium salts more preferred.

Water-insoluble, cross-linked polyvinylpolypyrrolidone disintegrant refers to any of the generic, but is not limited to. crospovidone disintegrating agents.

The term "anionic wetting agent" includes, but is not limited to, salts of alkylbenzene sulfonates, alkyl and dialkylnaphthalene sulfonates, alkyl and

I~

C

A

WO 93/13658 PCT/US92/11305 3 alcohol sulfates, sulfoalkylamides, carboxylates, alpha-olefin sulfonates and dialkyl sulfosuccinates. The term "nonionic wetting agent" includes acetylenic diols, ethylene oxide-propylene oxide copolymers, alkylphenol ethoxylates, fatty acid ethoxylates, alcohol ethoxylates, sorbitan fatty acid ester ethoxylates and castor oil ethoxylates. The preferred wetting agents are sodium dialkyl sulfosuccinates of which sodium diisobutyl sulfosuccinate, sodium diamyl sulfosuccinate and sodium dicyclohexyl sulfosuccinate are more preferred.

The internal desiccants that "chemically bind" water are those that actually undergo chemical reactions with water to form a new compound. An example of 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 magnesium oxide and boric anhydride.

The internal desiccants that "physically adsorb" water are those selected from the group consisting of highly-dispersed silicilic acids such as silica gel; aluminum oxide; clays such as montmorillonite; and amorphous and crystalline aluminosilicates such as molecular sieves and zeolites. Combinations of these desiccants with those that form hydroxides and hydrates can be used. Kirk- Othmer's Encvclovedia of Chemical Technology (3rd ed., Vol. 8, p 115) describes desiccants suitable for use in the tablet formulation of this invention as Type 1 and Type 4 desiccants. Either type can be employed, singly or in combination, as long as the desiccant does not expand when it picks-up water. Such expansion causes the tablet to crack or crumble on long term storage.

Internal desiccants useful in the tablet formulation of this invention also include materials that chemically bind water, not in the sense of a Chemical reaction that forms a hydroxide, but in the sense of a chemical reaction that produces a hydrate. Representative of useful desiccants that form hydrates are CaSO 4 NaOAc, MgSO 4 Na 2

SO

4 CaCl 2 and ZnSO 4 Representative of the hydrate-forming reaction is that undergone by CaCl 2 to form CaCl 2

-H

2 O. One or more desiccants from each group, the hydroxide-forming and the hydrateforming, can be employed, alone or in combination, depending on the particular properties sought by the formulator. In any event, the desiccants employed in the tablets of this invention are not those of the water-adsorbing type employed in prior art tablet formulations. Kirk-Othmer's Encyclopedia of Chemical Technology (Third Edition, Vol. 8, page 115) further describes desiccants of the type contemplated for this invention as so-called Type 1 materials.

WO 93/13658 PCI'/US92/11305 4 A preferred tablet formulation is one wherein component is an ammonium, sodium or lithium carbonate or bicarbonate or mixture thereof, and the internal desiccant is selected from and a mixture of and Also preferred is a tablet formulation wherein is potassium carbonate or bicarbonate or mixture thereof, and the internal desiccant is Preferred pesticides are those having a melting point of at least about 100'C and solubility in pH 7 water at 20'C of no more than about 5% by weight.

Representatives of such pesticides are herbicides such as: acifluorfen, asulamn, atrazine, bensulfuron, bentazon, bromacil, bromoxynil, chloraxnben, chiorimuron ethyl, chioroxuron, chiorsulfuron, chlortoluron, clomazone, cyanazine, dazomet, desmediphan, dicamba, dichlobenil, dichiorprop, diphenamid, dipropetryn, diuron, thiarneturon, 2-[[[[N-(4-methoxy-6-methyl- 1,3 ,5-triazine-2-yl)-Nmethylarnino]carbonyl]aminolsulfonyl]benzoic acid, methyl ester, fenac, fenuron, fluometuron, fluridone, fomesafen, glyphosate, hexazinone,imazamnethabenz, ixnazaquin, imazethapyr, ioxynil, isoproturon, isouron, isoxaben, karbutilate, lenacil, MCPA, MCPB, mefluidide, methabenzthiazuron, methazole, metribuzin, metsulfuron methyl, monuron, naptalamn, neburon, nitralin, norfiurazon, oryzalin, perfluidone, phenmedipham, picloram, prometryn, pronarnide, propazine, pyrazon, siduron, simazine, sulfometuron methyl, tebuthiuron, terbacil, terbuthylazine, terbutryn, triclopyr, 2,4-D, 2,4-DB, triasulfuron, primisulfuron, 2-/3-(4,6-bis(difluoromethioxy)pyrixnidin-2-yl)ureidosulfonyl)benzoic acid methyl ester, 5-pyrazolesulfonamide, N-IX4-methoxy-6-methyl-pyrimidine-2-yl)-aminocarbonyll-4-methoxy-carbonyl- I1-methyl-], N-[R(4,6-dimethoxy-2-pyrimnidinyl)amino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide, 2-[([[(4,6-dimethoxv- 2-pyrimidinyl)aminolcarbonyl] amino] sulfonyl] -NN-diniethyl-3 -pyridinecarboxamide, methyl 2-[[[[[4-ethoxy-6-(methylamino)-l1,': ,5-triazin-2-yl] amnino]carbonyl]amino]sulfonyl]benzoate, methyl 2-[[[[(4,6-dimethoxy-2pyrimidinyl)aminolcarbonyl]amino]sulfonyl]-6-(trifluoromethyl)3-pyridinecarboxylate, 2-(2-chloroethoxy)-N-[II(4-methoxy-6-methyl- 1,3,5-triazin-2yl)arnino]carbonyljbenzenesulfonamnide, methyl 2-[[[[[4-(dimethyl-amnino)-6- (2.2.2-trifluoroethoxy)- 1,3 ,5-triazin-2-yllaminolcarbonyllsulfonyl]-3-methylbenzoate, sodium 2-chloro-6-[(4,6-dimnethoxy-2-pyrimidinyl)thio]benzoate; fungicides such as: carbendazim, thiurarn, dodine. chioroneb, cymoxanil, captan, folpet. thiophanatemethyl, thiabendazole, chiorothalonil, dichioran, c'aptafol, iprodione, vinclozolin, kasugamycin, triadimenol, flutriafol, flusilazol, hexaconazole or fenarlinol; bactericides such as oxytetracycline dihydrate; acaricides such as: hexathiazox, oxythioquinox, dienochior or cyhexatin; insecticides such as: carbofuran, carbaxyl, thiodicarb or deltaxnethin.

More preferred pesticides are hexazinone, 2.4-D, chiorsulfuron, sulfomneturon methyl, chlorixnuron ethyl, metsulfuron methyl, ethaxnetsulfuron methyl, thifensulfuron methyl, tribenuron ethyl, bensulfuron methyl, primisulfuron, methyl 2-[[[[(4,6-dimethoxy-2-pyrimnidinyl)aniino]carbonyl]aminojsulfonyl]-6-(trifluoro-rnethyl)-3-pyridinecarboxylate, 2-(2-chloroethoxy)- N-[[(4-methoxy-6-methyl- 1,3 ,5-triazin-2-yl)amino~carbonyl~benzenesulfonamide, ethyl 5-[[[((4,6-dimethoxyv-2-pyrimidinyI )amino] carbonyl~aminosulfonyl 1methyl-lIf-pyrazole-4-carboxylate, N-[[(4,6-dinethoxy-2-pyrimidinylaminojcarbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide, 2- Wf[(4,6-dimethoxy-2pyrirnidinyl)amninolcarbonyllamino) sulfonyl] -NN-dirnethyl-3-pyridinecarboxaxnide, methyl 2-[[W]4-(dimnethylamino)-6-(2,2,2-trifluoroethoxy)- 1,3,5triazin-2-yl~aminojcarbonyl]sulfonyl]-3-methylbenzoate, and sodium 2-chloro-6- [(4,6-dirnethoxy-2-pyriznidinyl)thio]benzoate.

The most preferred pesticides are sulfonylurea herbicides such as chiorsulfuron, sulfomneturon methyl, chiorimuron ethyl, metsulfuron methyl, ethametsulfuron methyl, thifensulfuron methyl, tribenuron ethyl, bensulfuron methyl, primisulfuron, methyl 2-[[[(e4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-6-(trifluoromethyl)-3-pyridinecarboxylate, 2-(2chloroethoxy)-N-II(4-methoxy-6-methyl- 1.3 ,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide, ethyl 5-[[I(4,6-dimethoxy-2-pyrim idinyl)amino)carbonyl]amino~sulfonyl]- I-methyl- IH-pyrazole-4-carboxylate, dimethoxy-2-pyrirnidinylaxnino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide, 2- [[[[(4,6-dixnethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-N.I,N-dimnethyl-3-pyridinecarboxaxnide, and methyl (dimethylaxnino)-6-(2,2,2-trifluoroethoxy)- 1,3 ,5-triazin-2-yllamino]carbonyl)sulfonyl]-3-methylbenzoate.

DETAILS OF THE INVENTION (The most common method for applying water insoluble pesticides is as fine aqueous dispersions which are sprayed onto the field or crop using ground or aerial spray rigs. The tablets of this invention combine a high level of physical integrity with rapid break-up in water using minimal or no agitation while providing fine dispersions of active ingredient. Since the spray nozzles are WO 93/13658 PF S2 19 CN, CH 2

QOCH

2

CH

3

OCH

2

CH

2

OCH

3 or GCF 2 T wherein G is 0 or S and T is H, CHC1F, CHBrF, CF 2 H or CHFCF 3 typically protected against clogging by 50 mesh screens 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 this invention.

High physical integrity of the tablets is desirable so that the tablets themselves can withstand the tabletting operation and survive handling, packaging and shipping without breaking. An axial breaking strength of greater than about 9x10 3 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 require quick turnaround times for the preparation of the dispersions. Generally, the 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 substantially water-insoluble active ingredient in aqueous media without the use of effervescence. The reaction of the organic acid and carbonate or bicarbonate base affords carbon dioxide 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 the penetration of the water into the interior of the tablet through a wicking or swelling action. Common starch or cellulose-based disintegrants are unsuitable in agricultural applications as they typically form gels on the 50 mesh spray nozzle screens. Hence, a water insoluble cross-linked polyvinylpolypyrrolidone is used.

A wetting agent is required to control the size of the carbon dioxide bubbles formed during the reaction of the acid base. The wetting agent reduces the surface tension between the bubbles and the solid tablet resulting in the formation of smaller bubbles which readily detach from the tablet surface. As a consequence, the tablet remains submerged in the water for a longer period of time, thus improving contact of the entire tablet surface with water.

If a tablet floats immediately after being dropped in the water its top rapidly dries out and the reaction slows down there. This increases the time required for complete dispersion of active ingredient. When a tablet sinks, water wets the entire exterior of the tablet. Then, when the tablet floats to the surface (as a result of the buoyancy of the attached carbon dioxide bubbles when the tablet has WO 93/13658

I

PCT/US92/11305 SEXAMPLE S j The pesticide, described in more detail in U.S. 4,479,821, is a compound of i

II

L: WO 93/1P658 PCT/US92/11305 7 partially dispersed and become lighter) the top remains wet so that effervescent reaction continues. Dispersion times for active ingredients formulated 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, inert ingredients are employed that produce a tablet with a density greater than that of water (specific gravity greater than 1.00).

Inert ingredients up to 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 affect the chemical stability of the active ingredient(s). Materials such as glidants, anti-adherents, and lubricants can also be employed to facilitate production in th- tablet press. The amounts and types of such ingredients will be readily determinable by one skilled in the tabletting art given the disclosure herein.

The formulation ingredients are typically ground and mixed in a mill, e.g., an air or hammermill. The ground premix is passed through a 50 or 100 mesh Standard Sieve Series) screen. The average particle size of the ground premix should be in the range of 5 to 15 microns. If it is much smaller, the tablet will be strong, but will not break up very fast. If the premix is much larger, the dispersion will not be fine enough to pass a wet screen test used to indicate whether the disp: ;ion will clog the spray nozzle and protective screen discussed previously.

The tablets can be prepared using conventional tablet-making equipment.

Their diameter can vary from about 1 cm or less, to 7.5 cm, depending on the tablet weight desired. Flat-faced, beveled-edge punches, with or without a breakline, product attractive tablets.

To keep the tablet from sticking to the die or punch faces, a lubricant such as magnesium stearate or boric acid can be used. Such lubricants and antiadherents can be brushed onto the die surface or incorporated into the formulation. i Tablets have been formed in a hydraulic press with a capacity of 18,000 kg of force. Pressures between about 3.43x10 7 to 6.86x10 7 pascals will produce strong tablets that break up rapidly. Break-up times are determined by dropping a tablet, typically 5 to 15 g into 1000 mL of water. The "end point" of final dispersion is easy to determine because the tablet floats to the surface as it loses weight shortly before it finally disperses.

WO 93/13658 PCT/US92/11305 8 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 made 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 be free of residue.

The strength of the tablet can be measured by a tester such as the Erweka® Model TBH 28. The tablet is-stood on end and the machine tip moves to the tablet along an axial path. The force to break the tablet in two is normally recorded in newtons Good tablets normally have strengths in the range of 8.896x10 3 to 4.448x10 4

N.

EXAMPLE 1 The following ingredients were weighed out and milled for 1 min in a Tekmar* A-10 analytical laboratory mill. The premix was passed through a mesh screen and blended well. A 15 g tablet, 4.34 cm in diameter, was made with a hand-operated hydraulic press at a pressure of 525 kg/cm 2 Concentration, Ingredient Weight Tnifensulfuron methyl 55.3 Citric Acid 10.0 Sodium Bicarbonate 25.4 Lomar PWA* (ammonium salt of naphthalene sulfonic acid-formaldehyde condensate) 5.7 Polyplasdone XL-100* (polyvinylpolypyrrolidone) 1.22 Monawet MB-100* (sodium diisobutyl sulfosuccinate) 1.05 Magnesium Oxide 1.33 The fresh tablet took 2 min and 23 sec to dissolve in 25°C water with only a trace of solids on the screens. 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 internal desiccant (MgO). The tablet was sealed in a tight jar and aged at 45°C for 3 weeks. This accelerated aging simulates about two years of storage at ambient conditions.

After aging, the tablet took 3 min and 10 sec to dissolve in 25*C water. The wet screens had only a trace of solids on them.

WO 93/13658 PCT/US92/11305 22

X

1 is H, Cl, -OCH 3

-OCH

2

CH

3 or CH 3 and agricultural salts thereof.

FYAMPT F 1 WO 93/13658 P /US92/11305 EXAMPLE 2 The following ingredients were milled and tableted as in Example 1.

Concentration, Ingredient Weight Thifensulfuron methyl 52.7 Citric Acid Sodium Bicarbonate 24.2 Lomar PWA* (ammonium salt of naphthalene sulfonic acid-formaldehyde condensate) 5.45 Polyplasdone XL-100® (polyvinylpolypyrrolidone) 1.15 Monawet MB-1000 (sodium diisobutyl sulfosuccinate) 100 Molecular Sieves 6.00 The fresh tablet took 2 min and 50 s to break-up in 25 0 C water. There was only a trace of solids on the screens. The second tablet was aged as in Example 1.

After aging, the tablet took 2 min and 51 s to break-up. There was only a trace of solids on the wet screens.

EXAMPLES 3 TO 19 In the same manner employed for Example 1, tablets can be prepared using the active ingredients in the first column of Table 2 with one or more of the desiccants listed in the second and third columns, except that when the base employed is potassium carbonate or bicarbonate, the desiccant(s) employed therewith are to be selected solely from Column A.

I .A

U

WO 93/13658 PCT/US92/1 1305 3) bexazinone 4) 2,4-D chlorsulfuron 6) sulfometuron methyl 7) chlorin'uron ethyl 8) metsulfuron methyl 9) etbanietsulfuron methyl uribenuron ethyl 11) bensulfuron methyl 12) primisulfuron 13) methyl 2-[[(4,6-dimethoxy-2-pyrimidinyl).

amino~caxbonyl]amino]sulfonyl]-6-Qrifluoromczhyl).3-pyridinecarboxylate 14) 2-(2-chloroethoxy)-N-E[(4-methoxy-6methyl. l,3,5-triazin-2-yl)aminojcarbonyl]benzenesulionazmde ethyl 54([[[(4,6..dimethoxy-2.pynidinyl)aminolcarbonyllamninolsulfonyl]-1.methyl- IH-pyrazole-4-carbox:',ate 16) N-[[(4,6-dimethoxy-2-pyrimidinylamino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide 17) 2-1[[([(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amnino]sullonyl]-N,N-dimethyl-3pyridinecarboxainide 18) methyl 2.EE(E(4-(dimethylamino)-6.(2.2,2trifluoroethoxy)-1 ,3,5-triazin-2-yl]axnino]carbonyl]sulfonyl].3-methylbenzoate 19) sodium 2-chloro-64[(4,6-dimetboxy-2pyrimidinyl)thio]benzoate Colmn(A) selected from the group, CaO, MgO, B,)0 3 CaSO 4 NaQAc, MgSO 4 Na 2

SO

4 CaCI 2 and ZnSO 4 selected from the group highly dispersed silicilic acids such as silica gel, aluminum oxide, clays -ch as montmorillonite, and amorphous aluminosilicates such as molecular sieves and zeolites WO 93/1365P O 93/1365 PCT/US92/ 1305 11 EXAMPLES 20 TO 37 By the general procedure of Example 1, tablet formulations can be made whereby the active ingredient pesticide is as described hereafter and the delivery system with its characteristic internal desiccant is as defined herein.

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

X

11N R I-S0 2 -NH-C-NH-(V

N

z wherein R, Ris R3 R4 s R R Rg Q R9 Rio

R

7 R6 R3 and R 6 are independently hydrogen, fluorine, chlorine, bromine, iodine, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, nitro, trifluoromethyl, cyano, CH 3 S(O)n- or CH 3

CH

2 S(O)n-; R4 is hydrogen, fluorine, chlorine, bromine or methyl;

R

5 is hydrogen, fluorine, chlorine, bromine, methyl or methoxy;

R

7 is hydrogen, fluorine, chlorine, bromine, alkyl of 1-2 carbon atoms or alkoxy of 1-2 carbon atoms;

R

8 is hydrogen, methyl, chlorine or bromine;

R

9 and Rio are independently hydrogen, methyl, chlorine or bromine; /2 WO 9313658PCT/US92/1 1305 12 W and Q are independently oxygen or sulfur; n is 0, 1 or 2; X is hydrogen, chlorine, bromine, methyl, ethyl, alkoxy of 1-3 carbon atoms, trifluoromethyl, CH 3 S- or CH 3 OCH-7-; and Z is methyl or methoxy, or their agriculturally suitable salts.

EXAMRLE ZI The pesticide, described in more detail in U.S. 4,394,506, is a compound of the formula: N-(heterocyclicarninocarbonyl)arylsulfonaxnides in which the aryl radical is substituted in the 2-position by a carboxy radical, ester, thioester, or amide thereof; N-[(4,6-dumethylpyrimnidin-2yl)amninocarbonyl]methoxycarbonyllbenzenesulfonamnide or N-[(4,6-dimethoxy- 1,3,5triazin-2-yl)amino-carbonyl]-2-methoxycarbonylbenzenesulfonarnide.

EAMPLE2 The pesticide, described in more detail in U.S. 4,481,029, is a compound of the formula: A B B A B A wherein WisO0 or S; A' is H, 0, Br, C 1

-C

4 alkyl, OCH 3

NO

2 or CF 3 0 T A is or -C-R 11 where Q is0, S or

ORII'

T is 0or =N where

I.

I'

WO 93/13658 PCT/US92/1 1305 RHI is H, C I-C 4 alkyl or C 3

-C

4 alkenyl; when Q is 0 or S then RI is C 1

-C

6 alkyl C 3

-C

6 alcenyl; C 3

-C

6 alkynyl; C-7-C 6 alkyl substituted with 1-3 Cl, F or Br, or one of CN or OCH 3

C

3

-C

6 alkenyl substituted with 1-3 Cl; C 3

-C

6 alkynyl substituttd with CI; -'5-C 6 cycloalkyl; cyclohexenyl; cyclohexyl substituted with 1-3 CH;;

C

4 -Cy cycloalkylalkyl or

CH(C

2 )n 9 R9 8 where

R

7 and R 8 are independently H, Cl, CH 3 or OCH 3 nisOor 1; and

R

9 is H or CH 3 y NR-4s

IQN

Y

1

I

where Z is N, CH or C-F; X=H, Cl, -CH 3

-OCH

3 or -OCH 2

CH

3 Y=H, Cl, C 1

-C

4 substituted alkyl; with the proviso that when X and Y are both H, then RI and RII are less than 5 carbons;

X

1 Cl, OCH 3

OCH

2

CH

3 or CH 3

Y

1

OCH

3 or CH 3 and agriculturally suitable salts; all other substituents being as defined in U.S. 4,481,029.

5EXME23 The pesticide, described in more detail in U.S. 4,435,205, is a compound of the formula: QS0 2

RI

SO

2

NHCNA

R3 where W is 0or S; Q is 0or NR 5 RI is C 1

-C

4 alkYl, C 1

-C

4 alkyl substituted with 1-3 atoms of F, Cl or Br,

CH

2

CH

2

OCH

3

CH

2

CH

2

CH

2

OCH

3 Or

R

2 is H, F, Cl, Br, OCH 3

NO

2 CF; or C 1 alkyl;

R

3 is H, F, Cl, Br or CH 3

R

4 is H, CH 3 or OCH 3

R

5 is C 1

-C

4 alkyl;

R

6 and R 7 are independently H, F, Cl, Br, CH 3

CF

3

NO

2 or OCH 3 WO 9313658PCTIUS92/ 11305 28 sulfonyl, CI-C 8 haloalkylsulfonyl, C0,-C 6 alicenylsulfonyl, C 2

-C

6 haloalkenylsulfonyl, C 3

-C

6 alkynylsulfonyl, C 3

-C

6 haloalkynylc~,,fnn1 Cfl.~i~nrv1v,ifnvi r-r hn21nUd-nvvn1IcvIqt1fnnvI t_

A

WO 93/13658 PCr/US92/11305 A is x 1I

N

W N x (CH2)nt Y 1 X2

N-N

KO X 2 or 0N Y2 Y2 X is NI 2

N(CH

3 2

NHCH

3

C

1

-C

4 alkyl, C 1

-C

4 alkyl substituted with 1-3 atoms of F, Cl or Br, CH-,OCH 3

CH

2

OCH

2

CH

3

C

1

-C

4 alkoxy,

C

1

-C

2 allcylthio, C 3

-C

4 alkenyloxy, C 3

-C

4 alkynyloxy,

OCH

2

CH

2

OCH

3 or C 2

-C

4 alkoxy substituted with 1-3 atoms of F, Cl or Br; n is 1 or 2; Y is H, CH 3

OCH

3 or Cl; X, is Oor CH 2

Y

1 is H, CH 3

OCH

3 or Cl;

X

2 and Y 2 are independently CH 3 or OCH 3 and Z is CH, N, CCH 3 CBr, CCI, CF, CI CC 2

H

5

CCH

2

CH

2 C1 or

CCH

2

CH=CH

2 EXAMPLE 24 The pesticide, described in more detail in U.S. 4,420,325, is a compound of the formula: wherein L is SO-7NR 6

R

7

OCH

3 0C 2

)H

5 CO-,Hs, CO 2 7CH 3 or

R

2 is H, Cl, Br, F, CF 3 or OCH 3 R4 is CI-C 3 alkyl, CH,,CH=CH-7, CH 2 )CHCl or CH 2

CH,

2

OCH

3

R

5 is C 1

-C

3 alkyl or CF 3

R

6 and R 7 are independently CI-C 3 alkyl;

R

8 is H or CH 3

R

9 is H or C I-C 3 alkyl;

R

3 is x xl Ixi N- N y 0 0 X,

X

0 0x 3

H

y W isO0 or S X is CH 3

OCH

3 or Cl; Y is CH 3

C,H

5

OCH

3 0C-71- 5

CH

2 )OCHI. NH 2

NHCH

3 or NC32 Z is CH or N; X, is H, Cl, CH 3

OCH

3 or OCH 9 is CHi, C 2

H

5

OCH

3 or OC2H 5

X

3 is CHa or OCH 3 and Y, is CH 3 or OCH 3 The claims defining the invention are as follows: r!'I j WO 93/13658 PCF/US92/11305 17 and their agriculturally suitable salts.

EXAMPLE The pesticide, described in more detail in U.S. 4,514,211, is a compound of the formula: R4 R2 R Q R 3 L)

Q

L

Q R 3 Q R 7 *or

Q

L

L

R

R

O6\R8 wherein Q is 0, S, SO or SO 2 Q, is 0, S or SO 2 w L is SO 2

NHCNA;

R, is H or C 1

-C

4 alkyl;

R

4 is H, Cl, CH 3 CFI, OCH 3 Br, F, SCH-A or OCF 2

H;

R

5 is H, CH 3 OCH., Cl, Br, N0 2 C0 2

R

7 S0 2

R

8 0S0 2

R

9 S0 2 NR OR, I, F, CF 3

SCH

3

OCF

2 H or SO.,N(OCH 3

)CH

3

R

6 is H, Cl, Br or C I-C 4 alkyl; R 6is H,CH 3 CIor Br;

R

7 is C 1

-C

3 alkyl, CHr-H 2

C

2

CH

1 )OCH3 or CH 2

CH

2 Cl;

R

8 is C 1

I-C

3 ailkyl;

F.

9 is CI-C 3 ailkyl or CF 3 R 10 and R I are independently C I-C alkyl;

RU

2 is H or CH 3 W isO0 or S; A is N,

X

N

Y

2 or -KON X is H, CH 3 OCHi. Cl. F. OCF-7H or SCFH; Y is CH 3

OCFI

3 0C, 2

H

5

CH

2

)OCH

3

NH

2 NHCH;, N(CH 3 2

CH(OCH

3 2

CH(OCHCH

3 2

C

2

H

5

CF

3

CH

2

=CHCH

2

O,

CH=.CCH

2

CFACH

2 O, OCHC, OCH,CH,)Br, OCH 2

CHIF,

,Iv I INTERNATIONAL SEARCH REPORT IntuatiSSA Afflkac, No PCT/US 92/11305 i. EASSMJCAMIN OF SUDJEC HAT=I (Of uvumI daldfldbe *UoIS qIY, IMIMS uJ06 AcwIftg to IstamIo Fame aaggft.Ao. (IV or to booh Nadomw aanaillm aai mrc Int.C1. 5 A01N25/34; A01N47/36; A01N43/64; A01N39/04 U. VEWLS SUMMOED Miolum DocumudomSdud CN, i-IOCH 2

H

3 ,OCH7CH 2

OC

3 or GCF 2 T wherein G is 0 or S and T is H, CHClF, CHBrF, CF-,H or CHFCF 3 Z is CH, N, CCH 3

CC

2

H

5 CCl or CBr; Yj is 0or CH 2

X

1 is CH 3

OCH

3 0C 2

H

5 or OCF-,H;

X

2 is CH 3

C

2

H

5 or CH 2

CF

3 Y2 is C 2

H

5

CH

3

OCH

3 0C 2

H

5

SCH

3 or SC 2

H

5 and

X

3 is CH 3 or OCH 3 The pescicide, described in more detail in U.S. 4,547,215, is a cornpound of the formula:

CQ

2

)R

OCH

3

C

wherein R is C 2

H

5 or CH(CH 3 2 and their agriculturally suitable salts.

EAMELE 27 The pesticide, described in more detail in U.S. 4,548,638, is a compound of the formula: a

R

0

NN~Q

-'THCH

3

I

Ii ii wherein R Is COCH 3

CO

2

CH-CH

3

CO

2

)CH

2

,CH

2 CH,, CO 2

CH-,CH=CH-,.

Co 2

,CH(CH

3

CO

2

CH

2

CH

2 CI, 50 2

N(CH

3 2 or OSO,CHq.

PCT/US 92/11305 IntwutoWa Application No MD. DOCUMENTS CONSIDERED TO NE NEVANT (CONTINUED FROM THE SECOND SHEETr) Categ. Ol..i Of Dominmt, with jlice, W'me spruiat. of the imimat P"090g Rd~W to Oai No.

WO,A,9 000 007 (E.I.DU PONT DE NEMOURS) 11 January 1990 1,2,4,5, 7,8 W093/3658PCr/US92/11305 The pesticide, described in more detail in U.S. 4,479,821, is a compound of the formula: SO.,.NH-C-NIH N

R

wherein A is a C 1

-C

6 alkyl radical which is substituted by CI-C 4 alkoxy, CI-C 4 alkylthio, C I-C 4 alkylsulfinyl or C I-C 4 alkylsulfonyl; X is oxygen, sulfur, a sulfinyl or sulfonyl bridge; Z is oxygen or sulfur; mn is!I or 2;

R

2 is hydrogen, halogen, C 1

-C

5 ailkyl, C,)-C 5 alkenyl, C 1

-C

4 haloalkyl, or a radical -Y-R 5

-COOR

6

-NO

2 or -CO-NR 7

R

8

R

3 and R 4 each independently of the other, are hydrogen, C I-C 4 alkyl,

C

1

-C

4 alkoxy, C 1

-C

4 alkylthio, C 1

-C

4 haloalkyl, halogen or alkoxyalkyl of at most 4 carbon atoms;

R

5 and R 6 each independently of the other, are C 1 5 alkyl, C 2

-C

5 alkenyl or C 2

-C

6 alkynyl;

R

7 and R 8 each independently of the other, are hydrogen, C I-C 5 ailkyl,

C

2

-C

5 alkenyl or C 2

-C

6 alkynyl; and Y is oxygen, sulfur, a'sulfinyl or sulfonyl bridge, and salts of these compounds.

The pesticide, described in more detail in, U.S. 4,566,898, is a compound of the formula:

CO

2

CH(CH

3 C1 SOnNHCNHK 9N

CH

3

L

WO 93/13658 PCT/US92/11305 21 EXAMPLE The pesticide, described in more detail in U.S. 4,435,206, is a compound of the formula:

O

2

N-C-NR

R

3

R

4 wherein R is

NN

R, is H, Cl, Br, F, C 1

-C

4 alkyl, C 1

-C

4 alkoxy, C 1

-C

4 alkyithia, N0 2

CF

3

COOR

5 or SO 2

NR

6

R

7

R

2 is H, Cl, Bror CH 3

R

3 and R 4 are independently H or CH 3

R

5 is C 1

-C

6 alkyl, C 3

-C

6 alkenyl, CH 2

)CH

2

OCH

3

CH

2

,CH

2

OCH-CH

3 CH,CH-,CH7OCH- 3 or CH 2

)CH

2 Cl;

R

6 and R 7 ar-e independently CH 3 or CH 3

;CH

2 W is oxygen or sulfur; X is CH 3

-OCH

3 or -OCHiCH 3 Y is H, Cl, CH 3

CF

3

-NHCH

3

-N(CH

3 2

-CH

2

OR

8

-CH-,CH

2

OR

8 -OCI-I,CF.; or VR 6 Z is CH or N; V is oxygen or sulfur;

R

8 is CH 3

CH

3 CH-71, CH-,C0 2

R

8 -CX,CH,0R 6

C(CH

3

)HCO-,R

8 or

CHCH

2

CO

2

R

8 Yj is-H, CH 3 or OCH 3 and WO 93/13658 PCF/US92/1 1305 22 X, is Cl, -OCH 3

-OCH

2

CH

3 or CH 3 and agricultural salts thereof.

The pesticide, described in more detail in U.S. 4,514,212, is a compound of the formula: zNK

NK

X-CH

2 -Q

R

and the salts thereof with amnines, alkali metal or alkaline earth metal bases or with quaternary ammonium bases wherein: Q is fluorine, fluoromethyl, chioromethyl, trichioromethyl, I ,2-dichloroethyl, 1 ,2-dibronioethyl, 1 ,2-dichloropropyl, 1 ,2-dibl-omopropyl, I ,2-dibromoisobutyl, 1 ,2-dichloro- 1-methyl-ethyl or 1 ,2-dibromo- 1 -methylethyl; X is oxygen, sulfur, a sulfinyl or sulfonyl bridge; Z is m..ygen or sulfur;

R

2 is hydrogen, hslogen, CI-C 5 alkyl, C 2

-C

5 alkenyl, C 1

-C

4 haloalkyl, or a radical -Y-R 5 -COORs. or -CO-NR 7

-RF;

R

3 and R 4 each independently of the other, are hydrogen, CI-C 4 alkyl, cl-c 4 alkoxy, C 1

-C

4 alkylthio, C 1

-C

4 haloalkyl, halogen or alkoxyalkyl of at most 4 carbon atoms;

R

5 and R 6 each independently of the 'other, are CI-C 5 alkyl, C 2

-C

5 alkenyl or C 2

C

6 alkynyl;

R

7 and R 8 each independently of the other, are hydrogen, C 1

-C

5 alkyl,

C

2

-C

5 alkenyl or C 2

-C

6 alkynyl; and Y is oxygen, sulfur, a sulfinyl or sulfonyl bridge.

EAMPLE 32 The pesticide, described in more detail in U.S. 4,478,635, is a compound of the formula:

R-

16 wherein X is a radical of the formula: or- R2-t

RI

Y is C 1

-C

3 alkyl, Ci-C 3 haloalkyl, CI-C 3 alkoxy, C 1

-C

3 haloalkoxy, C 2

-'C

3 alkoxyalkyl, C 1

-C

3 alkylthio, halogen or -NR 16

R

1 7 Zis oxygen or sulfur; R, is hydrogen, halogen, cyano, nitro, C 1

-C

4 haloalkyl, C 1

-C

4 alkyl, CI-C 4 alkoXy, -C0-R 6

-NR

7

R

8 -S(O)mnC 1

-C

4 alkyl. or -S0 2 Rq;

R

2 is hydrogen, fluorine, chlorine, bromine, nitro, trifluoromethyl,

-NR

20

R

2 1 methyl, ethyl, methoxy, ethoxy or -S(O)m-Cl-C4 alkyl;

R

3 is hydrogen, fluorine, chlorine, bromine, amino, nitro or methoxy;

R

6 is hydrogen, CI-C 4 alkyl, C 1

-C

3 alkenyloxy, C 3

-C

5 alkynyloxy, C 1

-C

4 haloalkyl, CI-C 5 alkylthio, phenoxy, benzyloxy, -NRIGRII or -C alkoxy which is unsubstituted or substituted by 1 to 3 halogen atoms or C I-C 3 alkoxy;

R

7 is hydrogen, methoxy, ethoxy, C 1

-C

4 alkyl or -OR2

R

8 is hydrogen or -OR2

R

9 is an -0-R 13 or -NR 14

R

1 5 gr'OuP;

R

11 is CI-C 4 alkyl which is unsubstituted or substituted by 1 to 3 halogen atoms, or is phenyl or benzyl; 215 R 1 2 is hydrogen, C I-C 4 alkyl Or C I-C 4 alkoxy; and m is 0, 1 or 2; WO 93/13658PC/S2I10 24 and R 4 has the same meaning as R 2

R

5 has the same, nieaning as RI; Rio, RI I, R 14 and R 20 each have the same meaning as R 7 and R 1

R

15

R

16

R

17 and each have the same meaning as R 8 EXAMPLEf The pesticide, described in more detail in U.S. 4,634,465, is a compound of the formula: SO -NH-fj N -K E 2p~ A

F

wherein Z is oxygen or sulfur; E is nitrogen or R I is hydrogen, halogen, nitro, C I-C 4 alkyl, C I-C 4 haloalkyl, C I-C 4 alkoxy, C 1

-C

4 haloalkoxy, C 1

-C

4 alkoxycarbonyl, CI-C 4 allcylthio,

C

1 -CA alkylsulfinyl, 0 1

-C

4 alkylsulfonyl or C 2

-C

5 alkoxyalkoxy;

R

2 is hydrogen, C I-C 4 alkyl or C I-C 3 alkoxy;

R

3 and R 4 each independently of the other, are hydrogen, C 1

-C

4 a1y,

C

1

-C

4 alkoxy, C 1

-C

4 haloalkoxy, CI-C 4 haloalkylthio, CI-C 4 allcylthio, halogen, C 2

-C

5 allcoxyalkyl, C 2

-C

5 alkoxyalkoxy or

-NR

5

R

6 wherein R 5 and R 4 are hydrogen or C 1

-C

4 alkyl; and A is an unsubstituted or substituted bridge of 3 or 4 atoms which contains 1 or 2 oxygen, sulfur or nitrogen atoms and, together with the linking carbon atom, forms a non-aromatic 5- or 6-membered heterocyclic ring system, with the proviso that two oxygen atoms are separated by at least one carbon atom and that oxygen and sulfur atoms are only liniked to each other if the sulfur atom takes the form of the -SO- or group.

T(he pesticide, described in more detail in EPA-202,830, is: 3Ce 2-[jN-(4-methoxy-6-methyl-1 ,3 ,5 -triazin-2-yl)-N-methylaminocarbonyl]amninosulfonyllbenzoic acid, methyl ester.

WO 93/13658 WO 9313658PCr/US92/1 1305 EXAMPLE 3 The pesticide, described in more detail in EPA-237,292, is a compound of the formula: 0CH 3 ISO NHCN-( R x wherein R3

K

R -LI 3 N

CNR

1

R

2 1?

CNR

1

R

2 0 11 or R3#&

CRR

"N

R is H or CH 3 R, is H or CI-C 3 alkyl;

R

2 is CI-C 3 alkyl or C 1

-C

2 alkoxy; or R, and R 2 may be taken together to form -(CH 2 wherein n is 2, 3 or 4; is H, CI, F, Br, CH 3

CF

3 0C11 3 or COF 2 H; 'and X is CH 3

CH

2 F, CH, 2

CH

3

OCH

3

OCH

2

)CH

3 Cl, OCF 2 H or CH 2

OCH

3 Tlh. pesticide, described in more detail in EPA-87,780, is a compound of the iormula: S. i WO 93/13658 PCT/US92/11305 26

B

N= 0 X A SO 2 NHC-N-- Z I N= D

Y

wherein A represents a hydrogen atom, a C 1

-C

8 alkyl group or a phenyl group which may be substituted with C

I

-Cg alkyl groups, halogen atoms or nitro groups; B and C represent independently hydrogen atoms, halogen atoms, nitro groups, CI-C 8 alkyl groups, arylalkyl groups,

CI-C

8 alkoxy groups; haloalkyl groups, -CO 2 R [where R is a hydrogen atom, a CI-C 8 alkyl group, an allyl group or a propargyl group), -CONRiR 2 (where RI is a hydrogen atom, a CI-C 8 alkyl group or a phenyl group, R 2 is a hydrogen atom or a CI-Cg alkyl group, or RI and R 2 taken together may represent -(CH2)m- (m is 4, or -CH 2

C

2

CH

2

CHC

2 or -CH 2

CH

2

N(CH

3

)CH

2

CH

2

-J,

-S(O)nR 3 (where R 3 is a CI-C 8 alkyl group, a phenyl group or an arylalkyl group and n is 0, 1 or -SO 2

NR

4

R

5 [where R 4 is a CI-C 8 alkyl group, R 5 is a hydrogen atom or a CI-C 8 alkyl group, or R 4 and

R

5 taken together may represent -(CH 2 (p is 4, 5 or 6),

-CH

2 CH20CH 2

CH

2 or -CH 2

CH

2

N(CH

3

)CH

2

CH

2 or a phenyl group which may be substituted with Ci-Cg alkyl groups, halogen atoms or nitro groups, D represents a hydrogen atom or a CI-C 8 alkyl group; X and Y represent independently hydrogen atoms, halogen atoms, CI-C 8 alkyl groups, CI-C 8 alkoxy groups, CI-C 8 alkoxyalkyl groups, -CF 3 groups, C 1

-C

8 haloalkoxy groups, alkylamino

R

groups, dialkylamino groups, -OCHCO 2

R

7 (where R 6 and R 7 each represent hydrogen atoms or CI-C 8 alkyl groups) or either X or Y may form a five-membered ring containing an oxygen atom together with X; and X represents a nitrogen atom or C-Rg (where R 8 represents a hydrogen atom, a haloalkyl group or may 4 WO 93/13658 PCr/US92/11305 27 form a five-membered ring containing an oxygen atom together with X or Y).

EXAMPLE 3 The pesticide, described in more detail in U.S. 4,710,221, is a compound of the formula: C0 2 PRI x R2 SO 2 NHCN J I N- R Y wherein R is-HorCH 3 RI is C 1

-C

3 alkyl, C 3

-C

4 alkoxyallcyl, C 2

-C

4 haloalkyl, C 3

-C

4 ailkenyl or

C

3

-C

4 ailkynyl;

R

2 is C 2

-C

6 alkoxy, C 3

-C

6 cycloalkoxy, C 4

-C

6 cycloalkylalkoxy, CI-C 6 haloalkoxy, C 2

-C

6 alkenyloxy, C 2

-C

6 haioalkenyloxy, C 3

-C

6 alkynyloxy, C 3

-C

6 haloalkynyloxy, C 2

-C

4 alkoxyalkoxy, C 2

-C

4 haloalkoxyalkoxy, C 2

-C

4 alkylthioalkoxy, C 2

-C

4 haloalkylthioalkoxy, C 2

-C

4 alkylsulfinylalkoxy, C 2

-C

4 haloalkylsulfinylalkoxy,

C

2

-C

4 alkylsulfonylalkoxy, C 2

-C

4 haloalkylsulfonylalkoxy, C 2

-C

4 cyano 'alcoxy, OCH 2

C(O)CH

3

OCH

2

CH

2

C(O)CH

3

C

2

-C

4 aminoalkoxy, C 1

-C

8 alkylthio, C 3

-C

6 cycloalkylthio, C 4

-C

6 cycloalkylalkylthio, C 1

-C

8 haloalkylthio, C 2

-C

6 allcenylthio, 07-C 6 haloalkenylthio, C 3

-C

6 alkynylthio, C 3

-C

6 haloalkynyirhia, C 2

-C

4 alkoxyalkylthio, C 2

-C

4 haloalkoxyalkylthio, C 2

-C

4 allcylthioalkylthio, C 2

-C

4 haloalkylthioalkylthio, C 2

-C

4 cyanoalkylthio,

SCH

2

C(O)CH

3

SCH

2

CH

2

C(O)CH

3

C

2

-C

4 amninoalkylthio, SCAH,

SCH

2

C

6

H

5

CI-C

8 alkylsulfinyl, C 3

-C

6 cycloalkylsulfinyl, C 4

-C

6 cycl oalkylalkylsulfinyl, C 1

I-C

8 haloalkylsulfinyl, C 2

-C

6 alkenylsulfinyl, C 2

-C

6 haloalkenylsulfinyl. C 3

-C

6 alkynylsulfinyl, C 3

-C

6 haloalkynylsulfmnyl, C 2

-C

4 alkoxyalkylsulfinyl, C 2

-C

4 haloalkoxyalkylsulfinyl, C 2

-C

4 cyanoalkylsulfinyl, S(O)CH 2

C(O)CH

3 S(OCHiCH 2

C(O)CH

3

C

2

-C

4 ammnoalkylsulfinyl, C 2

-C

8 alcylsulfonyl, C 3

-C

6 cycloalkylsulfonyl, C 4

-C

6 cycloalkylalkyl- WO 931~;RPCF/US92/1 1305 28 sulfonyl, C 1

-C

8 haloalkylsulfonyl, C',-C 6 alicenylsulfonyl, C 2

-C

6 haloalkenylsulfonyl, C 3

-C

6 alkynylsulfonyl, C 3

-C

6 haloalkynylsulfonyl, C 2

-C

4 alkoxyalkylsulfonyl, C 2

-C

4 haloalkoxyalkylsulfonyl,

C

2

-C

4 cyanoalkylsulfonyl, SO 2 7CH 2

C(O)CH

3

SO

2

CH-

2

CH

2

C(O)CH

3

C

2

-C

4 aminoalkylsulfonyl, CH4 2 F, CH-,CI, CHC1 2

CH

2 Br, CHBr 2

C-.-C

6 alkyl substituted with 1-3 atoms of F,a Cl or Br, C 2

-C

6 alkenyl, C 2

-C

6 haloalkenyl, C=-CH, C 2

-C

6 haloalkynyl, OC(O)CI-C 4 alkyl. CH 2 C(O)NRaRb, NHCH 3 NP-bRc or CI-C 4 alkyl substituted with C 1

-C

4 aikoxy, C 3

-C

4 cycloalcoxy, cyclopropylmethoxy, C 1

-C

4 haloalkoxy, C 2

C

4 alkenyloxy, C 2

-C

4 haloalkenyloxy, C 3

-C

4 alkynyloxy, C 3

-C

4 haloalkynyloxy, C0,-C 4 alkoxyalkoxy, C 2

-C

4 aminoalkoxy, C 1

-C

4 alkylcarbonyloxy, Cl-C 4 haloalicylcarbonyloxy, C 1

-C

4 carbamoyloxy, CI-C 4 alkoxycarbonyloxy, OH, OP(O)(0C 1

-C

2 alk-Yl) 2

C

1

-C

4 alkylsulfonyloxy,

CI-C

2 haloalklcysulfonyloxy, OSi(CH 3 3 OSi(CH 3 2

C(CH

3 3

C

1

-C

4 alkyithio, C 3

-C

4 cycioalklcythio. cyclopropyimethylthio, C 1

-C

4 haloallcylthio, C 2

-C

4 aikenylthio, C 2

-C

4 haloalkenylthio, C 3

-C

4 allcynylthio, C 3

-C

4 haloalkynylthio, C 2

-C

4 alkoxyalkylthio, C 2

-C

4 aminoalkylthio, SH, SP(O)(0CI-C 2 allcyl) 2

C

1

-C

4 alkylsulfinyl,

C

3

-C

4 cycloalklcysulfonyl, cyclopropylxnethylsulfznyl, C 1

I-C

4 haloalkyisulfinyl, C 2

-C

4 alkenyisulfmnyl, C 2

-C

4 haloalkenyisulfifyi,

C-C

4 alkynylsulfinyl, C-C 4 haloalkynylsuifinyl, C 2

-C

4 alkoxyalkylsulfinyl, C 2

-C

4 aminoalkylsuLfinyl, C 1

I-C

4 aikylsuifonyl,

C

3

-C

4 cycloalkylsulfonyl, cyclopropylmethyisulfonyl, CI-C 4 hrloalkylsulfonyl, C 2

-C

4 alkeriyisulfonyi, C 2

-C

4 haloalkenylsulfonyl,

C

3

-C

4 alkynylsulfonyl, C 3

-C

4 haloalkynylsulfonyl, C 2

-C

4 aikoxyalklcysulfonyi or C 2

-C

4 aminoalkylsulfonyl; Ra and Rb are independently H or C I-C 3 alkyl; Rc is C 2

-C

4 alkyl, cyclopropyhnethyl, C 2

-C

4 cyanoalkyl, CH 2

C(O)CH

3

CH

2

CH

2

C(O)CH

3

CI

0

-C

4 haloalkyl, C 3

-C

4 alkenyl, C 3

-C

4 haloalkenyl, C 3

-C

4 alkynyi, C 3

!-C

4 haloalkynyl, CI-C 4 alklcv 4substituted with C 1

I-C

4 alkoxy, C I-C 4 alkyithia, C I-C 4 alkylsuifinyl,

C

1

-C

4 alkylsulfonyl, OH, NH 2

NI{CH

3 or NC32 is CH',OCH '-O2H Cl or Br; ZisCH orN; and their agriculturally suitable salts.

B ft i -1 i

I

J IJ

Claims (9)

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

2. A tablet formulation according to Claim 1 wherein is an ammonium, sodium or lithium carbonate or bicarbonate or mixture thereof, and the internal desiccant is selected from and a mixture of and I" 3. A tablet formulation according to Claimi wherein is potassium carbonate or bicarbonate or mixture thereof, and the internal desiccant is

4. A tablet formulation according to Claim 1 in the form of a tablet. 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. 15/3/9t6SAIP7750.SPE,30 I

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, sulfomneturon methyl, chlorimuron ethyl, metsulfuron methyl, ethametsulfuron methyl, thifensulfuron methyl, tribenuron ethyl, bensulfuron methyl, primisulfuron, methyl 2-i[1 [(4,6-dimethoxy-2-pyrimidinyl) amino]- carbonyllaminolsulfonyl]-6-(trifluoro-methyl)-3-pyridinecarboxylate, 2-(2- chloroethoxy)-N-[[(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)aminolcarbonyll- benzenesulIf onamide, ethyl 5-I[[[[(4,6-dimethoxy-2-pyrimidinyl)aminolcarbonyl]- amin-olsulfonyll-1 -methyl-i H-pyrazole-4-carboxylate, N-l[(4,6-dimethoxy-2- 1 0 pyrimidinylaminolcarbonyll-3-(ethylsulfonyl)-2-pyridinesulfonanlide, dimethoxy-2-pyrimidinyl)aminolcarbonyllamino]5ulfonyl]-N,N-dimethyl-3- pyridinecarboxamide, and methyl 2-[[[[4-(dimethylamino)-6-(2,2,2-trifuloro- ethoxy)-1 ,3,5-triazin-2-yllaminocarbonyllsulfonyl]-3-methylbenzoate.

8. A tablet formulation according to Claim 7 wherein the pesticide is a 1 5 sulfonylurea herbicide selected from the group consisting of thifensulfuron methyl, tribenuron ethyl, and bensulfuron methyl.

9. A tablet formulation according to any one of the preceding claims substantially as hereinbefore described with reference to any one of the examples. DATED this 1 5th day of March, 1 996. ElI DU PONT DE NEMOURS AND COMPANY By Their Patent Attorneys: CALLINAN LAWRIE IWTERNATI0NAL SEARCH REPORT Iteratihnal Appicaiol; No PCT/US 92/11305 1. CLASSIXICATION OF SUUJECr MATTERt (if seera classificaton Symbols apply, tndlC116 W06) Acoordiag to Interational Patent asulfictlo. (IPC or to both Natinal Casificaiee and INC Int.Cl. 5 A01N25/34; AO1N47/36; A01N43/64; A0IN39/04 U. FIELDS SEARCEED Nsimum Documentatihn Settled Ctl Citatho of Documnt, 1 1 with Indicatimn, whee appropriate, of the relevat passages' 2 Relevat to aio No.0 X EP,A,0 391 851 (CIBA-GEIGY) 1,2,4,5, October 1990 7,8 see column 1, line 1 line 24 see column 2, line 1 line see column 2, line 36 column 4, line 16 see column 5, line 2 column 9, line Y 3,6 CA,A,2 013 918 cited in the application Y PATENT ABSTRACTS OF JAPAN 3,6 vol. 9, no. 1 (C-259)(1724) 5 January 1985 JP,A,59 155 311 (NISSAN )4 September 1984 see abstract Sr~AW categories of cited icaime to lae documn published after the international filing date we' documet dininag the genera state of the art wic is s. or prioritv 4te and no.,t on fict with the apicative but matlmi t he f citedvt. -,stand the princile or theory underlying the 'E aler documet bet published em or after the Iateanatioeal -r docmen of p lit relevance; the claimed Invention filing date cannot be osidered novel or cannot be consieed to IV document which my throw doubts on piority, dlam(s) or Involve in inventive step which is dWe to establish the publicatin date of another 'Y documet of particular relevanix; the claimed Inventlon citation or other special re (as specified) cannot he considered to involve an inventive step when the 0' document refering to an oral disclosure, tno, "lbition or doc t iIs combined with one or more other such dorm- othersun mts, such combination being obvious to a peso.s skilled 1w document published prier to the aIntletinl fil date but In the amt later time the priority daue dtimd W document mumber of the same patent faily MV CRTIFICATION Date of the Acted Comnpletion of the latmotioel Smoft Date of Mailing of this Intatsoal Earchb Repert 18 MARCH 1993 2 0. 04. 93 11tatema Saching Authority signature it Authorized Officer EUROPEAN PATENT OFFICE LAM4ERS W. Utedook of Mount, with isdicadon, wbere appropdate, of the rakvut passages I mm i P,x A A A A WO,A,9 000 007 (E.I.DU PONT DE NEMOURS) 11 January 1990 see the whole document GB,A,2 242 130 (INFOWISE) September 1991 see page 4, line 2 line 19 see page 6; example B see page 7, line 7 line 12 EP,A,0 488 660 (SUMITOMO CHEMICAL) 3 June 1992 see page 2, line 10 page 7, line see page 7, line 21 line 24 EP,A,O 415 688 (AECI) 6 March 1991 see the whole document EP,A,0 367 887 (CIBA-GEIGY) 16 May 1990 see the whole document US,A,4 180 467 (J.B.BARTH) December 1979 see column 1, line 11 line 26 see column 1, line 65 column 2, line 22 DE,A,2 710 107 (HOVER) 14 September 1978 see page 2; claims 9,10 see page 8, paragraph 3 page 9, paragraph 3 1,2,4,5, 7,8 1,2,4,5, 7,8 1-8 1-8 1-8 1-8 1-8 F-r IPCrIMMO Wir 000Wy I"S ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 9211305 SA 68875 th& -MM b"u th ptn family nembrs relabo to die patnt doumnt cited in the sinvewatismed intaodom'i4 search report. The um Mb as contained in the Europaean Patent Office EDP file on The European Patent Office is inine way fiabl for these particlars wtich are umirey given for the purpose of infemadston. 18/03/93 Paten doomanu Pulieti's, pan famiy Publication citedm inwsach report d"M member(s) date EP-A-039 1851 10-10-90 AU-B- AU-A- CA-A- JP-A- 625467 5304290 2013918 2290801 09-07-92

11-10-90 07-10-90

30-11-90 WO-A-9000007 11-01-90 AU-B- 626551 06-08-92 AU-A- 3691189 23-01-90 CN-A- 1039948 28-02-90 EP-A- 0422026 17-04-91 JP-T- 3505451 28-11-91 US-A- 5180587 19-01-93 GB-A-2242130 25-09-91 None EP-A-0488660 03-06-92 JP-A- 5000903 08-01-93 EP-A-0415688 06-03-91 AU,0-A- 6204390 07-03-91 CA-A- 2024291 01-03-91 JP-A- 3163004 15-07-91 EP-A-0367887 16-05-90 US-A- 4933000 12-06-90 AU-B- 625412 09-07-92 AU-A- 2588608 08-02-90 JP-A- 2048506 19-02-90 US-A-4 180467 25-12m79 None m DE-A-2710107 14-09-78 None mm id For maers dotr& ab" an van Offidd Joured of do Enroposs P"M Ofllco, No. 12182