TABLET FORMULATION WITH INTERNAL DESICCANT

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: TITLE TABLET FORMULAΗON WITH INTERNAL DESICCANT γ An effervescent tablet produces gas bubbles by the reaction between an acid " 5 and a base. Should the water level in the tablet exceed about 0.1%, 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 10 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. 15 One such tablet formulation that does not have an internal desiccant is 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 20 effervescent tablet for cleaning dentures comprising pancreatin, an acid component, a base component, and a drying agent. SUMMARY OF THE INNENTION This invention comprises a tablet formulation consisting essentially of by total weight of the formulated composition: 25 (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 30 or a mixture thereof; (b) about 5% to 75% of an ammonium, lithium, sodium or potassium » carbonate or bicarbonate or a mixture thereof; j (c) about 0.5% to 20% of a dispersant; (d) about 0.1% to 5% of water-insoluble cross-linked polyvinyl- 35 polypyrrolidone; (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) one or a mixture of desiccants that physically adsorb water; the desiccant being (A) when (b) is potassium carbonate or potassium bicarbonate. This delivery system is characterized by the inter-relationship of components (a) to (f) in the recited ranges to effect rapid disintegration of finely dispersed pesticide particles (i). Preferred ranges of the composition are 5% to 70%, 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 a-nhydride-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 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 Encyclopedia of Chemical Technology (3rd ed., Nol. 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 , ΝaOAc, MgSO 4 , Νa 2 SO 4 , CaCl 2 , and ZnSO 4 . Representative of the hydrate-forming reaction is that undergone by CaCl2 to form CaC^-^O. One or more desiccants from each group, the hydroxide-forming and the hydrate- forming, 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. A preferred tablet formulation is one wherein component (b) is an ammonium, sodium or lithium carbonate or bicarbonate or mixture thereof, and the internal desiccant is selected from (A), (B) and a mixture of (A) and (B). Also preferred is a tablet formulation wherein (b) is potassium carbonate or bicarbonate or mixture thereof, and the internal desiccant is (A). 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, asulam, atrazine, bensulfuron, bentazon, bromacil, bromoxynil, chloramben, chlorimuron ethyl, chloroxuron, chlorsulfuron, chlortoluron, clomazone, cyanazine, dazomet, desmediphan, dicamba, dichlobenil, dichlorprop, diphenamid, dipropetryn, diuron, thiameturon, 2-[[[[N-(4-methoxy-6-methyl-l,3,5-triazine-2-yl)-N- methylamino]carbonyl]amino]sulfonyl]benzoic acid, methyl ester, fenac, fenuron, fluometuron, fl.uri.done, fomesafen, glyphosate, hexazinone,imazamethabenz, imazaquin, imazethapyr, ioxynil, isoproturon, isouron, isoxaben, karbutilate, lenacil, MCPA, MCPB, mefluidide, methabenzthiazuron, methazole, metribuzin, metsulfuron methyl, monuron, naptalam, neburon, nitralin, norflurazon, oryzalin, perfluidone, phenmedipham, picloram, prometryn, pronamide, propazine, pyrazon, siduron, simazine, sulfometuron methyl, tebuthiuron, terbacil, terbuthylazine, terbutryn, triclopyr, 2,4-D, 2,4-DB, triasulfuron, primisulfuron, 2-/3-(4,6-bis(difluoromethoxy)pyrimidin-2-yl)rc^ ester, 5-pyrazolesulfonamide, N-[(4-methoxy-6-methyl-pyrimidine-2-yl)-amino- carbonyl]-4-memoxy-carbonyl-l-me yl-], N-[[(4,6-dimethoxy-2-pyrimidinyl)- amino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide, 2-[[[[(4,6-dimethoxy- 2-pyrimidinyl)amino]carbonyl] amino] sulf onyl] -NN-dimethyl-3 -pyridine- carboxamide, methyl 2-[[[[[4-ethoxy-6-(methylamino)-l,3,5-triazin-2-yl]- amino]carbonyl]amino]sulfonyI]benzoate, methyl 2-[[[[(4,6-dimethoxy-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]-6-(trifluoromethyl)-3-pyridine- carboxylate, 2-(2-chloroethoxy )-N-[[(4-methoxy-6-methyl-l ,3 ,5-triazin-2- yl)amino]carbonyl]benzenesulfonamide, methyl 2-[[[[[4-(dimethyl-amino)-6- (2.2.2-trifluoroethoxy)-l,3,5-triazin-2-yl]amino]carbonyl]sulfonyl]-3-methyl- benzoate, sodium 2-cUoro-6-[(4,6-d^methoxy-2-pyrimidinyl)thio]benzoate; fungicides such as: carbendazim, thiuram, dodine, chloroneb, cymoxanil, captan, folpet, thiophanatemethyl, thiabendazole, chlorothalonil, dichloran, captafol, iprodione, vinclozolin, kasugamycin, triadimenol, fhitriafbl, flusilazol, hexaconazole or fenarimol; bactericides such as oxytetracycline dihydrate; acaricides such as: hexathiazox, oxythioquinox, dienochlor or cyhexatin; insecticides such as: carbofuran, carbaryl, thiodicarb or deltamethrin. More preferred pesticides are hexazinone, 2,4-D, chlorsulfuron, sulfometuron methyl, chlorimuron ethyl, metsulfuron methyl, ethametsulfuron 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-l,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide, ethyl 5-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-l- methyl-lH-pyrazole-4-carboxylate, N-[[(4,6-dimethoxy-2-pyrimidinylamino]- carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide, 2-[[[[(4,6-dimethoxy-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]-NN-dimethyl-3-pyridine- carboxamide, methyl 2-[[[[[4-(dimethylamino)-6-(2,2,2-trifluoroethoxy)-l ,3,5- triazin-2-yl]amiαo]carbonyl]sulfonyl]-3-methylbenzoate, and sodium 2-chloro-6- [(4,6-dimethoxy-2-pyrimidinyl)thio]benzoate. The most preferred pesticides are sulfonylurea herbicides such as chlorsulfuron, sulfometuron methyl, chlorimuron ethyl, metsulfuron methyl, ethametsulfuron methyl, thifensulfuron methyl, tribenuron ethyl, bensulfuron methyl, primisulfuron, methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]- carbonyl]amino]sulfonyl]-6-(trifluoromethyl)-3-pyridinecarboxylate, 2-(2- chloroethoxy)-N-[[(4-methoxy-6-methyl-l,3,5-triazin-2-yl)ammo]carbonyl]- benzenesulfonamide, ethyl 5-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]- carbonyl]amino]sulfonyl]-l-methyl-lH-pyrazole-4-carboxylate, N-[[(4,6- dimethoxy-2-pyrimidinylamino]carbonyl]-3-(ethylsulfonyl)-2-pyridine- sulfonamide, 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]- sulfonyl]-N^-dimethyl-3-pyridinecarboxamide, and methyl 2-[[[[[4- (dimethylamino)-6-(2,2,2-trifluoroethoxy)- 1 ,3 ,5-triazin-2-yl]amino]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 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 tfiis 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^ 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 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 the 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 (U.S.A. 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 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 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 anti- adherents can be brushed onto the die surface or incorporated into the formulation. Tablets have been formed in a hydraulic press with a capacity of 18,000 kg of force. Pressures between about 3.43xl0 7 to 6.86xl0 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. 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 d e machine tip moves to the tablet along an axial path. The force to break the tablet in two is normally recorded in newtons (N). Good tablets normally have strengths in the range of 8.896xl0 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 50 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 % Thifensulfuron methyl 55.3 Citric Acid 10.0 Sodium Bicarbonate 25.4 LomarPWA ® (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 die 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. EXAMPLE 2 The following ingredients were milled and tableted as in Example 1. Concentration, Ingredient Weight % Thifensulfuron methyl 52.7 Citric Acid 9.5 Sodium Bicarbonate 24.2 Lomar PWA ® (ammonium salt of naphthalene sulfonic acid-formaldehyde condensate) 5.45 Polyplasdone XL-100 ® (polyvinylpolypyrrolidone) 1.15 Monawet MB-100 ® (sodium diisobutyl sulfosuccinate) 1.00 Molecular Sieves 6.00 The fresh tablet took 2 min and 50 s to break-up in 25°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. 10 TABLE : Desiccant Active Ingredient Column (A) Column CB 3) faexazinone selected from the selected from the group 4) 2,4-D group, CaO, MgO, highly dispersed silicilic 5) chlorsulfuron B2O3, CaS0 4 , acids such as silica gel, 6) sulfometuron methyl NaOAc, MgS0 , aluminum oxide, clays 7) chlorimuron ethyl Na 2 S0 , CaCl 2 , such as 8) metsulfuron methyl and.ZnS0 montmorillonite, and 9) ethametsulfuron methyl amorphous alumiπo- 10) tribenuron ethyl silicates such as 11) bensulfuron methyl molecular sieves and 12) primisulfuron zeolites 13) methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)- amino]carbonyl]amino]sulfonyl]-6-(tιifluoro- methyl)-3-pyridinecarboxylate 14) 2-(2-chloroethoxy)-N-[[(4-methoxy-6- methyl-l,3,5-tria-rin-2-yI)amino]carbonyl]- benzenesulfona ide 15) ethyl 5-[[[[(4,6-dimethoxy-2-pyrimidinyl)- amino]caιbonyl]amino]sulfonyl]-l-methyl- lff-pyrazole-4-caιboxylate 16) N-[[(4,6-dimethoxy-2-pyrimidinylamino]- carbonyl]-3-(ethylsulfonyl)-2-pyridine- sulfonamide 17) 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]- carboπyl]amino]sulfonyl]-N^V-dimethyl-3- pyridinecarboxamide 18) methyl 2-[[[[[(4-(dimetfaylamino)-6-(2,2,2- trifluoroethoxy)-! ,3,5-triazin-2-yl]amino]- carbonyl]sulfonyl]-3-methylbenzoate 19) sodium 2-chloro-6-[(4,6-dimethoxy-2- pyrimidinyl)thio]benzoate 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 20 The pesticide, described in more detail in U.S. 4,127,405, is a compound of the formula: wherein R^s R3 and Rg are independendy 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 -; R 4 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; Rg is hydrogen, methyl, chlorine or bromine; R 9 and RJ Q are independently hydrogen, methyl, chlorine or bromine; 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 2 -; and Z is methyl or methoxy, or their agriculturally suitable salts. EXAMPLE 21 The pesticide, described in more detail in U.S. 4,394,506, is a compound of the formula: N-(heterocyclicaminocarbonyl)arylsulfonamides in which the aryl radical is substituted in the 2-positiσn by a carboxy radical, ester, thioester, or amide thereof; e.g., N-[(4,6-dimethylpyrimidin-2yl)aminocarbonyl]- methoxycarbonyl]benzenesulfonamide or N-[(4,6-dimethoxy-l,3,5- triazin-2-yl)amino-carbonyl]-2-methoxycarbonylbenzenesulfonamide. EXAMPLE 22 The pesticide, described in more detail in U.S. 4,481,029, is a compound of the formula: wherein W' is O or S; A is H, α, Br, C r C 4 alkyl, OCH 3 , ΝO 2 or CF 3 ; O T A is -C 11 - -R 1 I or -C "-R E u where Q is O, S or -N-; OR / T is O or =N where R m is H, C r C 4 alkyl or C 3 -C alkenyl; when Q is O or S then R 1 is C r C 6 alkyl C 3 -C 6 alkenyl; C 3 -C 6 alkynyl; C 2 -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 substituted with Cl; C 5 -C 6 cycloalkyl; cyclohexenyl; cyclohexyl substituted wid 1-3 CH^; C -C7 cycloalkylalkyl or where R 7 and Rg are independently H, Cl, CH 3 or OCH 3 ; n is 0 or 1 ; and R 9 is H or CH 3 ; where Z is N, CH or C-F; X=H, Cl, -CH 3 , -OCH 3 or -OCH 2 CH 3 ; Y=H, Cl, C C 4 substituted alkyl; with the proviso that when X and Y are both H, then R 1 and R π are less than 5 carbons; X 1= H, Cl, OCH 3 , OCH 2 CH 3 or CH 3 ; Y 1= H, OCH 3 or CH 3 ; and X j τχ=O or CH 2 and further provided that when A contains greater than 5 carbon atoms, then Y contains <4 carbon atoms,and their agriculturally suitable salts; all other substituents being as defined in U.S.4,481,029. EXAMPLE 23 The pesticide, described in more detail in U.S.4,435,205, is a compound of the formula: where W is O or S; Q is O orNR 5 ; R x is C j -C 4 alkyl, C r C alkyl substimted 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 3 or C r C 2 alkyl; R 3 is H, F, Cl, Br orCH 3 ; R 4 is H, CH 3 or OCH 3 ; R 5 is C r C alkyl; R 6 and R 7 are independently H, F, Cl, Br, CH 3 , CF 3 , NO 2 or OCH 3 ; 15 A is X is NH 2 , N(CH 3 ) 2 , NHCH 3 , C r C 4 alkyl, C r C 4 alkyl substimted with 1-3 atoms of F, Cl or Br, CH 2 OCH 3 , CH 2 OCH 2 CH 3 , C r C 4 alkoxy, Cι-C 2 alkylthio, C 3 -C alkenyloxy, C 3 -C 4 alkynyloxy, OCH 2 CH 2 OCH 3 or C 2 -C 4 alkoxy substimted with 1-3 atoms of F, Cl or Br; n is 1 or 2; Y is H, CH 3 , OCH 3 or Cl; X j is O or CH 2 ; Y l 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, CC1, CF, Cl, 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 R j is F, Cl, Br, CF 3 , C r C 3 alkoxy, C r C 3 alkyl, NO 2 , CO 2 R , SO 2 R 5 , SO 2 NR 6 R 7 , SO 2 N(OCH 3 )CH 3 , SO 2 OCH 2 CF 3 , OSO 2 R 5 or CH 2 L; L is SO 2 NR 6 R 7 , OCH 3 , OC 2 H 5 , CO 2 H 5 , CO 2 CH 3 or CO 2 C 2 H 5 ; R 2 is H, Cl, Br, F, CF 3 or OCH 3 ; R 4 is C C 3 alkyl, CH 2 CH=CH 2 , CH 2 CH 2 C1 or CH 2 CH 2 OCH 3 ; R 5 is C r C 3 alkyl or CF 3 ; Rg and R are independendy C^-C 3 alkyl; R 8 isHorCH 3 ; R 9 is H or C r C 3 alkyl; R 3 is WisOorS; XisCH 3 ,OCH 3 orCl; Y is CH 3 , C 2 H 5 , OCH 3 , OC 2 H 5 , CH 2 OCH 3 . NH 2 , NHCH 3 or N(CH 3 ) 2 ; Z is CH or N; Xi is H, Cl, CH 3 , OCH 3 or OC 2 H 5 ; X 2 is CH 3 , C 2 H 5 , OCH 3 or OC 2 H 5 ; X 3 is CH 3 or OCH 3 ; and YiisCHgorOCH^ 17 and dieir agriculmrally suitable salts. EXAMPLE 25 The pesticide, described in more detail in U.S. 4,514,211, is a compound of the formula: wherein Q is O, S, SO or SO 2 ; Qi is O, S or SO 2 ; W I! L is SO 2 NHCNA; R 12 R j is H or C r C 4 alkyl; R 2 is H or C r C 4 alkyl; R 3 is H or CH 3 ; R 4 is H, Cl, CH 3 , CF 3 , OCH 3 , Br, F, SCH 3 or OCF 2 H; R 5 is H, CH 3 , OCH 3 , Cl, Br, NO 2 , CO 2 R 7 , SO 2 R 8 , OSO 2 R 9 , SO 2 NR 10 R n , F, CF 3 , SCH 3 , OCF 2 H or SO 2 N(OCH 3 )CH 3 ; R 6 is H, Cl, Br or C, -C 4 alkyl; R is H, CH 3 , Cl orBr; 6 R 7 is C r C 3 alkyl, CH 2 CH=CH 2 , CH 2 CH 2 OCH 3 or CH 2 CH 2 C1; R 8 is C r C 3 alkyl; R 9 is C r C 3 alkyl or CF 3 ; R i0 andR j ^ are independentiy Cι~C 2 alkyl; R 12 is H or CH 3 ; W is O or S; Ais X is H, CH 3 , OCH 3 , Cl. F. OCF 2 H or SCF 2 H; Y is CH 3 , OCH 3 , OC 2 H 5 , CH 2 OCH 3 , ΝH 2 , NHCH 3 , N(CH 3 ) 2 , CH(OCH 3 ) 2 , CH(OCH 2 CH 3 ) 2 , C 2 H 5 , CF 3 , CH 2 =CHCH 2 O, CH≡CCH 2 O. CF 3 CH 2 O, OCH 2 CH 2 Cl, OCH 2 CH 2 Br, OCH 2 CH 2 F, CN, CH 2 OCH 2 CH 3 , OCH 2 CH 2 OCH 3 or GCF 2 T wherein G is O or S and T is H, CHC1F, CHBrF, CF 2 H or CHFCF 3 ; Z is CH, N, CCH 3 , CC 2 H 5 , CC1 or CBr; Y j is O or CH 2 ; X j is CH 3 , OCH 3 , OC 2 H 5 or OCF 2 H; X 2 is CH 3 , C 2 H 5 or CH 2 CF 3 ; Y 2 is C 2 H 5 , CH 3 , OCH 3 , OC 2 H 5 , SCH 3 or SC 2 H 5 ; and X 3 is CH 3 or OCH 3 . EXAMPLE 26 The pesticide, described in more detail in U.S. 4,547,215, is a compound of the formula: wherein R is C 2 H 5 or CH(CH 3 ) 2 ; and their agriculturally suitable salts. EXAMPLE 27 The pesticide, described in more detail in U.S. 4,548,638, is a compound of the formula: wherein R is CO 2 CH 3 , CO 2 CH 2 CH 3 , CO 2 CH 2 CH 2 CH 3 , CO 2 CH 2 CH=CH 2 , CO 2 CH(CH 3 ), CO 2 CH 2 CH 2 Cl, SO 2 N(CH 3 ) 2 or OSO 2 CH 3 . EXAMPLE 28 The pesticide, described in more detail in U.S. 4,479,821, is a compound of the formula: (X-A) m, wherein A is a C j -Cg alkyl radical which is substituted by Cι-C alkoxy, Cj-C alkylthio, Cχ-C 4 alkylsulfinyl or C 1 -C 4 alkylsulfonyl; X is oxygen, sulfur, a sulfinyl or sulfonyl bridge; Z is oxygen or sulfur; m is 1 or 2; R 2 is hydrogen, halogen, C 1 -C 5 alkyl, C 2 -C5 alkenyl, Cι-C haloalkyl, or a radical -Y-R 5 , -COORg, -NO 2 or -CO-NR 7 R 8 ; R 3 and R , each independendy of die otiier, are hydrogen, C t -C 4 alkyl, C | -C alkoxy, Cι-C 4 alkylthio, Cι-C haloalkyl, halogen or alkoxy- alkyl of at most 4 carbon atoms; R 5 andRg, each independendy of the other, are C^^ alkyl, C 2 -C5 alkenyl or C 2 -Cg alkynyl; R 7 and Rg, each independendy of the other, are hydrogen, C r C 5 alkyl, Q2-C5 alkenyl or C 2 -Cg alkynyl; and Y is oxygen, sulfur, a sulfinyl or sulfonyl bridge, and salts of these compounds. EXAMPLE 29 The pesticide, described in more detail in U.S. 4,566,898, is a compound of the formula: CH 3 EXAMPLE 30 The pesticide, described in more detail in U.S. 4,435,206, is a compound of the formula: wherein R is R t is H, Cl, Br, F, C r C 4 alkyl, C r C 4 alkoxy, C r C 4 alkylthio, NO 2 , CF 3 , COOR 5 or SO 2 NR 6 R 7 ; R 2 is H, Cl, Br or CH 3 ; R 3 and R are independendy H or CH 3 ; R 5 is C r C 6 alkyl, C 3 -C 6 alkenyl, CH 2 CH 2 OCH 3 , CH 2 CH 2 OCH 2 CH 3 , CH 2 CH 2 CH 2 OCH 3 or CH 2 CH 2 C1; Rg and R 7 are independently CH 3 or CH 3 CH 2 ; W is oxygen or sulfur; X is CH 3 -OCH 3 or -OCH 2 CH 3 ; Y is H, Cl, CH 3 , CF 3 , -NHCH 3 , -N(CH 3 ) 2 -, -CH 2 OR 8 , -CH 2 CH 2 OR 8 , -OCH 2 CF 3 or NR 6 ; Z is CH or Ν; N is oxygen or sulfur; R 8 is CH 3 , CH 3 CH 2 -, CH 2 CO 2 R 8? -CH 2 CH 2 OR 6 , C(CH 3 )HCO 2 R 8 or CH 2 CH 2 CO 2 R 8 ; Y x is H, CH 3 or OCH 3 ; and X j is H, Cl,.-OCH 3 , -OCH 2 CH 3 or CH 3 ; and agricultural salts thereof. EXAMPLE 31 The pesticide, described in more detail in U.S.4,514,212, is a compound of the formula: and die salts thereof with amines, alkali metal or alkaline earth metal bases or with quaternary ammonium bases wherein: Q is fluorine, fluoromethyl, chloromethyl, trichloromethyl, 1,2-dichloro- ethyl, 1,2-dibromoemyI, 1,2-dichloropropyl, 1,2-dibromopropyl, 1,2-dibromoisobutyl, 1,2-dichloro-l-methyl-ethyl or 1,2-dibromo- 1-methylethyl; X is oxygen, sulfur, a sulfinyl or sulfonyl bridge; Z is oxygen or sulfur; R 2 is hydrogen, halogen, Ci-C 5 alkyl, C -C 5 alkenyl, C 1 -C 4 haloalkyl, or a radical -Y-R 5 , -COORg, -NO 2 or -CO-NR 7 -R 8 ; R 3 and R 4 , each independendy of d e other, are hydrogen, C j -C 4 alkyl, t -C 4 alkoxy, C^-C 4 alkylthio, C1-C4 haloalkyl, halogen or alkoxyalkyl of at most 4 carbon atoms; R5 and Rg, each independently of d e other, are C1-C5 alkyl, C 2 -C5 alkenyl or C 2 -C 6 alkynyl; R 7 andRg, each independendy of die other, are hydrogen, C 1 -C5 alkyl, C 2 -C 5 alkenyl or C 2 -Cg alkynyl; and Y is oxygen, sulfur, a sulfinyl or sulfonyl bridge. EXAMPLE 32 The pesticide, described in more detail in U.S.4,478,635, is a compound of ie formula: wherein X is a radical of the formula: Y is C r C 3 alkyl, C r C 3 haloalkyl, C r C 3 alkoxy, C r C 3 haloalkoxy, C 2 -C 3 alkoxyalkyl, -C 3 alkylthio, halogen or -NR 16 R 17 ; Z is oxygen or sulfur; Ri is hydrogen, halogen, cyano, nitro, C1-C4 haloalkyl, C t -C 4 alkyl, C j - . alkoxy, -CO-R 6 , -NR 7 R 8 , -S(O) m -C r C 4 alkyl or -SO 2 R 9 ; R 2 is hydrogen, fluorine, chlorine, bromine, nitro, trifluoromethyl, -NR 20 R 21 , methyl, ethyl, methoxy, ethoxy or -S(O) m -C!-C4 alkyl; R 3 is hydrogen, fluorine, chlorine, bromine, amino, nitro or methoxy; Rg is hydrogen, Cj-C alkyl, Cι-C 3 alkenyloxy, C 3 -C 5 alkynyloxy, C j -C 4 haloalkyl, Cι-C ζ alkylthio, phenoxy, benzyloxy, -NR 10 Rn or C j -C 5 alkoxy which is unsubstituted or substimted by 1 to 3 halogen atoms or Cj-C 3 alkoxy; R 7 is hydrogen, methoxy, ethoxy, C j -C 4 alkyl or -CO-R 12 ; Rg is hydrogen or -CO-R 12 ; R 9 is an -O-R 13 or -NR 14 R i5 group; R^l is C j -C 4 alkyl which is unsubstituted or substimted by 1 to 3 halogen atoms, or is phenyl or benzyl; R 12 is hydrogen, C r C 4 alkyl or C r C alkoxy; and m is 0, 1 or 2; and R 4 has the same meaning as R 2 ; R 5 has die same meaning as Rj; R lls R 14 and R 2 o each have the same meaning as R 7 ; and R^. R15- R 16 , R 17 and R 21 each have die same meaning as Rg. EXAMPLE 33 The pesticide, described in more detail in U.S. 4,634,465, is a compound of the formula: wherein Z is oxygen or sulfur; E is nitrogen or =C-; Ri is hydrogen, halogen, nitro, C r C 4 alkyl, C^ . haloalkyl, C r C 4 alkoxy, C j -C haloalkoxy, C r C 4 alkoxycarbonyl, Cι-C 4 alkylthio, Cι-C 4 alkylsulfinyl, C1-C4 alkylsulfonyl or C 2 -C 5 alkoxyalkoxy; R 2 is hydrogen, C r C 4 alkyl or C r C 3 alkoxy; R 3 and R 4 , each independendy of die other, are hydrogen, Cι-C 4 alkyl, C 1 -C 4 alkoxy, Cχ-C haloalkoxy, C x -C haloalkylthio, C r C 4 alkylthio, halogen, C 2 -C5 alkoxyalkyl, C 2 -C5 alkoxyalkoxy or -NR 5 Rg, wherein R 5 and R 4 are hydrogen or Ci -C 4 alkyl; and A is an unsubstimted or substimted bridge of 3 or 4 atoms which contains 1 or 2 oxygen, sulfur or nitrogen atoms and, together with die linking carbon atom, forms a non-aromatic 5- or 6-membered heterocyclic ring system, with die proviso that two oxygen atoms are separated by at least one carbon atom and that oxygen and sulfur atoms are only linked to each other if the sulfur atom takes the form of the -SO- or -SO 2 - group. EXAMPLE 34 The pesticide, described in more detail in EPA-202,830, is: 2-[[N-(4-medιoxy-6-medιyl-l,3 ,5-triazin-2-yl)-N-methylamino- carbonyl]aminosulfonyl]benzoic acid, metiiyl ester. EXAMPLE 35 The pesticide, described in more detail in EPA-237,292, is a compound of the formula: wherein J is O II J-3 J-4 R is H or CH 3 ; R j is H or C r C 3 alkyl; R 2 is C!-C 3 alkyl or Cj-C2 alkoxy; or R j and R2 may be taken together to form -(CH 2 )n-, wherein n is 2, 3 or 4; R 3 is H, Cl, F, Br, CH 3 , CF 3 , OCH 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 . EXAMPLE 36 The pesticide, described in more detail in EPA-87,780, is a compound of the formula: wherein A represents a hydrogen atom, a C r Cg alkyl group or a phenyl group which may be substituted with C^-Cg alkyl groups, halogen atoms or nitro groups; B and C represent independendy hydrogen atoms, halogen atoms, mtro groups, C^-Cg alkyl groups, arylalkyl groups, C j -Cg alkoxy groups; haloalkyl groups, -CO2R [where R is a hydrogen atom, a C j -Cg alkyl group, an allyl group or a propargyl group), -CONR 1 R (where R is a hydrogen atom, a C^Cg alkyl group or a phenyl group, R 2 is a hydrogen atom or a C j -Cg alkyl group, or R j and R2 taken togedier may represent -(CH2) m - (m is 4, 5 or 6), -CH 2 CH 2 OCH 2 CH 2 -, or -CH 2 CH 2 N(CH 3 )CH 2 CH 2 -], -S(O)uR 3 (where R 3 is a C^C alkyl group, a phenyl group or an arylalkyl group and n is 0, 1 or 2), -SO 2 NR 4 R 5 [where R 4 is a C j -Cg alkyl group, R 5 is a hydrogen atom or a C^-Cg alkyl group, or R and R 5 taken togedier may represent -(CH 2 ) p - (~ι is 4, 5 or 6), ' -CH2CH2OCH2CH2- or -CH 2 CH 2 N(CH 3 )CH 2 CH 2 -] or a phenyl group which may be substimted witii C^Cg alkyl groups, halogen atoms or nitro groups, D represents a hydrogen atom or a C j -Cg alkyl group; X and Y represent independendy hydrogen atoms, halogen atoms, C^-Cg alkyl groups, C -C alkoxy groups, C -Cg alkoxyalkyl groups, -CF 3 groups, C r Cg haloalkoxy groups, alkylamino R / groups, dialkylamino groups, -OCHCO 2 R 7 (where Rg and R 7 each represent hydrogen atoms or C t -Cg 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 Rg represents a hydrogen atom, a haloalkyl group or may form a five -membered ring containing an oxygen atom together with X or Y). EXAMPLE 37 The pesticide, described in more detail in U.S. 4,710,221, is a compound of the formula: wherein R is H or CH 3 ; R j is C r C 3 alkyl, C 3 -C alkoxyalkyl, C 2 -C haloalkyl, C 3 -C alkenyl or C 3 -C 4 alkynyl; R 2 is C 2 -C 6 alkoxy, C -Cg cycloalkoxy, C 4 -C 6 cycloalkylalkoxy, Cj-Cg haloalkoxy, C 2 -Cg alkenyloxy, C 2 -C 6 haloalkenyloxy, C 3 -Cg alkynyloxy, C 3 -Cg haloalkynyloxy, C 2 -C alkoxyalkoxy, C 2 -C 4 haloalkoxy alkoxy, C 2 -C 4 alkylthioalkoxy, C 2 -C 4 haloalkylthio- alkoxy, C2- alkylsulfinylalkoxy, C2-C 4 haloalkylsulfinylalkoxy, C 2 -C 4 alkylsulfonylalkoxy, C 2 -C 4 haloalkylsulfonylalkoxy, C -C 4 cyanoalkoxy, OCH 2 C(O)CH 3 , OCH 2 CH 2 C(O)CH 3 , C 2 -C 4 aminoalkoxy, C r C 8 alkylthio, C 3 -C 6 cycloalkylthio, C 4 -C 6 cycloalkylalkylthio, Cι-C 8 haloalkylthio, C2-Cg alkenylthio, C2-C 6 haloalkenyldiio, C -Cg alkynyldύo, C 3 -C 6 haloalkynyldiio, C 2 -C 4 alkoxy alkylthio, C 2 -C haloalkoxyalkylthio, C 2 -C 4 alkylthio- alkyldiio, C2-C 4 haloalkylthioalkylthio, C2-C4 cyanoalkylthio, SCH 2 C(O)CH 3 , SCH 2 CH 2 C(O)CH 3 , C 2 -C 4 aminoalkylthio, SCgH 5 , SCH 2 C 6 H 5 , C r Cg alkylsulfinyl, C 3 -C 6 cycloalkylsulfmyl, C 4 -C 6 cycloalkylalkylsulfinyl, Cj-Cg haloalkylsulfinyl, C2-C alkenyl- sulfinyl, C2-Cg haloalkenylsulfinyl, C 3 -Cg alkynylsulfinyl, C 3 -Cg haloalkynylsulfinyl, C2~C 4 alkoxyalkylsulfϊnyl, C2-C 4 haloalkoxy- alkylsulfinyl, C 2 -C 4 cyanoalkylsulfinyl, S(O)CH 2 C(O)CH 3 , S(O)CH 2 CH 2 C(O)CH 3 , C 2 -C 4 aminoalkylsulfinyl, C 2 -C 8 alkylsulfonyl, C 3 -Cg cycloalkylsulfonyl, C 4 -C 6 cycloalkylalkyl- sulfonyl, C j -Cg haloalkylsulfonyl, C 2 -Cg alkenylsulfonyl, C 2 -Cg haloalkenylsulfonyl, C 3 -C 6 alkynylsulfonyl, C 3 -Cg haloalkynyl- sulfonyl, C 2 -C 4 alkoxyalkylsulfonyl, C 2 -C haloalkoxyalkylsulfonyl, C 2 -C 4 cyanoalkylsulfonyl, SO 2 CH 2 C(O)CH 3 , SO 2 CH 2 CH 2 C(O)CH 3 , C 2 -C 4 a inoalkylsulfonyl, CH 2 F, CH 2 C1, CHC1 2 , CH 2 Br, CHBr 2 , C 2 -C 6 alkyl substimted with 1-3 atoms of F, Q or Br, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C-.-CH, C r C 6 haloalkynyl, OC(O)C r C alkyl, CH 2 C(O)NR a R b , NHCH 3 , NR b R c or C j -C 4 alkyl substimted with Cj- . alkoxy, C 3 -C 4 cycloalkoxy, cyclopropylmethoxy, C r C 4 haloalkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 haloalkenyloxy, C 3 -C 4 alkynyloxy, C 3 -C 4 haloalkynyloxy, C 2 -C 4 alkoxyalkoxy, C 2 -C 4 aminoalkoxy, Cι-C 4 alkylcarbonyloxy, Cj-C 4 haloalkylcarbonyloxy, Cι-C 4 carbamoyloxy, C1-C4 alkoxy- carbonyloxy, OH, OP(O)(OC r C 2 alkyl) 2 , C r C 4 alkylsulfonyloxy, C r C 2 haloalkylsulfonyloxy. OSi(CH 3 ) 3 , OSi(CH 3 ) 2 C(CH 3 ) 3 , C r C 4 alkylthio, C 3 -C 4 cycloalkylthio, cyclopropylmethyl iio, Ci-C 4 haloalkyldiio, C 2 -C 4 alkenylthio, C 2 -C 4 haloalkenylthio, C 3 -C alkynyltiiio, C 3 -C 4 haloalkynylthio, C 2 -C 4 alkoxy alkylthio, C 2 -C 4 aminoalkyltiiio, SH, SP(O)(OC 1 -C 2 alkyl) 2 , C r C 4 alkylsulfinyl, C 3 -C 4 cycloalkylsulfonyl, cyclopropylmediylsulfinyl, C 1 -C 4 haloalkylsulfinyl, C 2 -C 4 alkenylsulfinyl, C 2 -C 4 haloalkenylsulfinyl, C 3 -C 4 alkynylsulfinyl, C 3 -C 4 haloalkynylsulfinyl, C 2 -C 4 alkoxyalkylsulfinyl, C 2 -C aminoalkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 3 -C 4 cycloalkylsulfonyl, cyclopropylmediylsulfonyl, Ci -C 4 haloalkylsulfonyl, C 2 -C alkenylsulfonyl, C 2 -C 4 haloalkenylsulfonyl, C -C 4 alkynylsulfonyl, C -C 4 haloalkynylsulfonyl, C 2 -C 4 alkoxyalkylsulfonyl or C 2 -C 4 aminoalkylsulfonyl; R a and R b are independendy H or C1-C3 alkyl; R c is C 2 -C alkyl, cyclopropylmethyl, C2-C cyanoalkyl, CH 2 C(O)CH 3 , CH 2 CH 2 C(O)CH 3 , C 10 -C 4 haloalkyl, C 3 -C 4 alkenyl, C 3 -C 4 haloalkenyl, C 3 -C 4 alkynyl, C 3 -C 4 haloalkynyl, C j -C 4 alkyl substimted widi C 1 -C 4 alkoxy, C r C 4 alkylthio, C!-C 4 alkylsulfinyl, C r C 4 alkylsulfonyl, OH, NH 2 , NHCH 3 or N(CH 3 ) 2 ; X is CH 3 , OCH 3 , OC 2 H 5 , Cl orBr; Y is C r C 2 alkyl, C r C 2 alkoxy, OCH 2 CH 2 F, OCH 2 CHF 2 , OCH 2 CF 3 , NHCH 3 orN(CH 3 ) 2 ;and Z is CH or N; and tiieir agriculturally suitable salts.

Claims: CLAIMS What is claimed is: L 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 OB) one or a mixture of desiccants diat physically adsorb water; 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 mixture thereof, and die 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! in die form of a tablet. 5- A tablet formulation according to Claim2 in die form of a tablet. 6. A tablet formulation according to Claim3 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 metiiyl, chlorimuron etiiyl, metsulfuron methyl, ediametsulfuron methyl, d ifensulfuron methyl, tribenuron etiiyl. bensulfuron metiiyl, primisulfuron, methyl 2-[[[[(4,6-dimedιoxy-2-pyrimidinyl)amino]- carbonyl]ammo]sulfonyl]-6-(triiluoro-methyl)-3-pyridinecarboxylate, 2-(2- chloroethoxy)-N-[[(4-methoxy-6-memyl-l,3,5-triazin-2-yl)amino]carbonyl]- benzenesulfonamide, ethyl 5-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]- amino]sulfonyl]-l-methyl-lH-pyrazole-4-carboxylate, N-[[(4,6-dimethoxy-2- pyrimidmylamino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide, 2-[[[[(4,6- dimethoxy-2-pyr-imidmyl)ammo]carbonyl]ammo]sulfonyl]-NN-dimethyl-3- pyridinecarboxamide, and metiiyl 2-[[[[[4-(dimethylamino)-6-(2,2,2-trifluoro- ethoxy)-l,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 thifensulfuron methyl, tribenuron ethyl, and bensulfuron metiiyl.

Inventors: JACKISCH DAVID ALLAN, JACKISCH, DAVID, ALLAN
Applicants: DU PONT, E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1992
Main classification: A01N25
IPC codes: A01N25, A01N47