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WO1994017660A1 - Tablette pesticide effervescente avec perborate de metal - Google Patents

Tablette pesticide effervescente avec perborate de metal Download PDF

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Publication number
WO1994017660A1
WO1994017660A1 PCT/US1994/000068 US9400068W WO9417660A1 WO 1994017660 A1 WO1994017660 A1 WO 1994017660A1 US 9400068 W US9400068 W US 9400068W WO 9417660 A1 WO9417660 A1 WO 9417660A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
alkyl
amino
alkoxy
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1994/000068
Other languages
English (en)
Inventor
David Allan Jackisch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to AU59636/94A priority Critical patent/AU5963694A/en
Priority to JP6518027A priority patent/JPH08506578A/ja
Priority to EP94905579A priority patent/EP0683627A1/fr
Publication of WO1994017660A1 publication Critical patent/WO1994017660A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof

Definitions

  • WO 90/00007 discloses pesticidal tablets comprising an acid and a base which react upon contact with water to produce the effervescent reaction that causes the pesticide to rapidly disperse.
  • the present tablets differ from those of
  • WO 90/00007 in several important aspects including the fact that it is the reaction of anhydrous perborate salts with water that produces the effervescent reaction.
  • This invention concerns a tablet formulation comprising, by total weight of the formulation, about 0.1% to 75% of a water-soluble pesticide which is solid at room temperature, and 25% to 99.9% of an anhydrous metal perborate salt.
  • tablette 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.
  • anhydrous metal perborate salt is meant a sodium, lithium, or potassium salt having a water content less than about 2% by weight as determined by coulometric measurement.
  • Preferred ranges of the composition are 10% to 70%, and more preferred
  • Contemplated water-soluble, solid pesticides include those selected from the following classes, including mixtures thereof: herbicides, fungicides, bactericides, and insecticides.
  • Preferred pesticides are those having a melting point of at least about 75°C and solubility in pH 7 water at 20°C of at least about 2% by weight.
  • suitable water-soluble pesticides include: insecticides such as methomyl and oxamyl; fungicides such as dodine salts, phosethyl-Al,
  • bactericides such as streptomycin and tribasic copper sulfate
  • herbicides such as sulfonylurea salts, acifluorfen salts, ammonium sulfamate, amitrole, bromoxynil salts, cacodylic acid salts, clopyralid salts, calcium salt of methylarsonic acid, dalapon salts, dazomet, dicamba salts, difenzoquat methyl sulfate, diquat, 2-methyl-4,6-dinitrophenol salts, disodium salt of methylarsonic acid, endothall, fenac, salt of fenuron and trichloroacetic acid, fluroxypyr salts, fomesafen, fosamine ammonium, glyphosate salts, haloxyfop salts, hexaflurate, imazaquin salts, imazethapyr salts,
  • Contemplated sulfonylurea salts have the formula:
  • J is selected from the group
  • R is selected from the group H and CH 3 ;
  • R 1 is selected from the group F, Cl, Br, NO 2 , C 1 -C 4 alkyl, C 1 -C 4 haloalkyl,
  • R 2 is selected from the group H, F, Cl, Br, CN, CH 3 , OCH 3 , SCH 3 , CF 3 and OCF 2 H;
  • R 3 is selected from the group Cl, NO 2 , CO 2 CH 3 , CO 2 CH 2 CH 3 ,
  • R 4 is selected from the group C 1 -C 3 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy,
  • R 5 is selected from the group H, F, Cl, Br and CH 3 ;
  • R 6 is selected from the group C 1 -C 3 alkyl, C 1 -C 2 alkoxy, C 2 -C 4
  • R 7 is selected from the group H, F, Cl, CH 3 and CF 3 ;
  • R 8 is selected from the group H, C 1 -C 3 alkyl and pyridyl;
  • R 9 is selected from the group C 1 -C 3 alkyl, C 1 -C 2 alkoxy, F, Cl, Br, NO 2 ,
  • R 10 is selected from the group H, Cl, F, Br, C 1 -C 3 alkyl and C 1 -C 2 alkoxy
  • R 11 is selected from the group H, C 1 -C 3 alkyl, C 1 -C 2 alkoxy, C 2 -C 4
  • R 12 is selected from the group allyl and propargyl and C 1 -C 3 optionally substituted by at least one member independently selected from halogen, C 1 -C 2 alkoxy and CN;
  • R 13 is selected from the group H, C 1 -C 3 alkyl and C 1 -C 2 alkoxy;
  • R 14 is C 1 -C 2 alkyl
  • R 15 is selected from the group H, C 1 -C 3 alkyl, C 1 -C 2 alkoxy, allyl and cyclopropyl;
  • R 16 is selected from the group H and C 1 -C 3 alkyl
  • R 17 is selected from the group C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, allyl and
  • R 18 is selected from the group C 1 -C 4 alkyl, C 1 -C 4 haloalkyl and C 3 -C 5 cycloalkyl optionally substituted by halogen;
  • n 0, 1 or 2;
  • M is a cation
  • R j is selected from the group H and C 1 -C 3 alkyl
  • W is selected from the group O and S;
  • X is selected from the group H, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4
  • haloalkoxy C 1 -C 4 haloalkyl, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylthio, halogen, C 2 -C 5 alkoxyalkyl, C 2 -C 5 alkoxyalkoxy, amino, C 1 -C 3 alkylamino and di( C 1 -C 3 alkyl )amino;
  • Y is selected from the group H, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4
  • alkylthioalkyl C 2 -C 5 alkylsulfinylalkyl, C 2 -C 5 alkylsulfonylalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkynyl, C 3 -C 5 cycloalkyl, azido and cyano;
  • Z is selected from the group CH and N;
  • X and Y when one or both of X and Y is C 1 haloalkoxy, then Z is CH; and ii) when X is halogen, then Z is CH and Y is OCH 3 , OCH 2 CH 3 , N(OCH 3 )CH 3 , NHCH 3 , N(CH 3 ) 2 or OCF 2 H.
  • Preferred active ingredients are salts of the following sulfonylureas:
  • Preferred salts are the sodium, potassium, calcium, magnesium, ammonium and alkylammonium salts of a sulfonylurea.
  • Most preferred sulfonylurea salts are the sodium and calcium salts of tribenuron methyl, the potassium salt of thifensulfuron methyl, the ammonium salt of chlorsulfuron and the potassium salt of metsulfuron methyl.
  • the most common method for applying pesticides is as aqueous solutions or dispersions which are sprayed onto the field or crop using ground or aerial spray rigs.
  • a tablet containing the pesticidal component is an effective form for introducing the pesticide into the water in the spray tank. It is substantially impossible to obtain rapid break-up of a tablet without the use of effervescence. Rapid break-up in water is desirable for the convenience of the growers who require quick turnaround times for the preparation of the spray solutions and dispersions.
  • Known effervescent pesticide tablets comprise a water-insoluble pesticide, an organic acid and a carbonate or bicarbonate base.
  • the acid and base react in an aqueous environment to produce carbon dioxide gas which aids in the break-up of the tablet and dispersion of the pesticide.
  • the rate of the acid-base effervescent reaction slows significantly when the tablet comprises a
  • a soft "hydrogel” is believed to form around the tablet to inhibit water from contacting the tablet and facilitating the reaction.
  • the acid in the tablet may react with the pesticide to give the water-insoluble acid form.
  • Inert ingredients up to about 74.9% of the total weight of the composition can be employed.
  • Such inert ingredients are components, complementary to the pesticide, which are known in the tablet art to improve tablet disintegration rate, dispersibility, stability during storage, and the like.
  • optional components include a manganese, copper or iron salt catalyst; a dispersant; a disintegrant; an anionic or nonionic wetting agent; a flow aid, and a desiccant.
  • the amounts and types of such ingredients will be readily determinable by one skilled in the tabletting art given the disclosure herein.
  • the effervescent reaction is due to the anhydrous metal perborate reacting with the water to liberate oxygen.
  • Any such compound which is compatible with the pesticide and liberates oxygen upon hydration is suitable for the tablets of the present invention.
  • the preferred compound is anhydrous sodium perborate (also known as sodium peroxymetaborate, NaBO 3 ).
  • Metal perborate is commonly available commercially as the monohydrate.
  • the monohydrate must be converted to its anhydrous state in order for the effervescent reaction to occur.
  • monohydrate to its anhydrous form can be accomplished by oven-drying the granules at 135°C for 24 hours in a vacuum oven with a nitrogen bleed to obtain a pressure of 1.33 x 10 3 Pascal.
  • the sodium perborate is spread in a layer less than 2 cm in thickness to facilitate drying. As a result of the drying, sodium perborate has been found to change color from white to yellow.
  • the success of the drying procedure can be tested by blending the dried sample to a homogenous mixture, and then dropping a small amount of the mixture into a beaker of water. If all the material reacts (i.e., effervesces) on the surface of the water, and no residue (i.e., monohydrate) falls to the bottom of the beaker, then the anhydrous state was achieved.
  • a metal salt can be added in catalytic amounts to decompose the monohydrate to produce oxygen and other products.
  • catalyst salts include manganese, copper or iron metal oxides or carbonates. Most preferred is iron (II) oxide.
  • Dispersants can be added to aid the initial dispersion of the particles of the active ingredient which are liberated during disintegration of the tablet.
  • Suitable dispersants include sodium, potassium and calcium salts of naphthalene sulfonic acid formaldehyde condensates; lithium, sodium, potassium, calcium, and ammonium salts of lignosulfonates such as Polyfon H ® and Lignosol TSF ® ; sodium, potassium and ammonium salts of polyacrylates and carboxylates, e.g., Tamol 731 SD ® ; sodium salts of maleic anhydride-isobutylene copolymers; and water soluble nonionic polymers such as polyvinylpyrrolidone, polyethylene oxides and cellulose derivatives.
  • Preferred dispersants include the sodium, potassium, ammonium and calcium salts of naphthalene sulfonic acid
  • Disintegrants facilitate penetration of the water into the interior of the tablet through a wicking or swelling action.
  • polyvinylpolypyrrolidone is a preferred disintegrant.
  • a wetting agent can be used to control the size of the oxygen bubbles formed during the acid-base reaction.
  • the anionic wetting agents include alkylbenzene sulfonates, alkyl and dialkylnaphthalene sulfonates, alkyl and alcohol sulfates, sulfoalkylamides, carboxylates, alpha-olefin sulfonates and dialkyl sulfosuccinates.
  • the nonionic wetting agents include acetylenic diols, ethylene oxide-propylene oxide copolymers, alkylphenol ethoxylates,
  • tristyrlphenol 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 (Monawet ® MB-100), sodium diamyl sulfosuccinate and sodium dicyclohexyl sulfosuccinate are more preferred.
  • Flow aids can be added to facilitate transfer of the dry ingredients from the feed hopper to the tablet die.
  • Suitable flow aids include silica and diatomaceous earth.
  • a dessicant is another optional component of the formulation of the
  • a tablet in a sealed container without a dessicant remains effervescent after storage.
  • a dessicant is desirable, it can be external to the tablet, or incorporated into the tablet matrix.
  • Internal desiccants can be those which "chemically bind" water in that they 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 desiccant can also be of the type which "physically adsorb" water and are 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.
  • 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.
  • Internal desiccants suitable for 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.
  • 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 ⁇ 6H 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.
  • 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.
  • lubricants 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.
  • the tablets are typically prepared in the following manner.
  • the solid water- soluble pesticide is passed through a 30 mesh screen to remove oversized particles.
  • Granular anhydrous sodium perborate prepared as described above is blended with the pesticide and, if desired, the inert ingredients.
  • the blend can be milled, e.g., in an air or hammermill, or compacted into tablet form without milling. Blends which are not milled and thereby comprise larger particle sizes are desirable for rapid tablet break-up.
  • 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, produce attractive tablets.
  • Tablets are 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 produce tablets which remain intact during storage and handling and break-up rapidly. Break-up times are determined by dropping a tablet, typically 7.5 g into 1000 mL of water. The "end point" of final dissolution is determined by the cessation of the effervescent reaction.
  • the tablets described in the following Examples were 3.5 cm in diameter, and were made with a hand-operated hydraulic press at a pressure of 525 kg/cm 2 .
  • the milled ingredients referred to hereinafter as the premixes, were blended well and aged for 3 weeks at 45°C in sealed glass jars.
  • the molecular sieves and CaSO 4 were packaged separately and added to the glass jars as external dessicants.
  • the jar containing the premix of Example 2 contained no dessicant, and the premix of Example 3 had the molecular sieves incorporated into the formulation.
  • the premixes were then cooled, and 7.5 g of each premix was tabletted. The tablets were added to water and dissolution times were measured.
  • the resulting aqueous mixtures were passed through a stack of 50, 100, and 200 mesh screens. Paniculate residue was determined by visual inspection of the screens.
  • a tablet was made from 7.5 grams of the premix. The tablet was added to water and the dissolution time was measured. The resulting aqueous mixture was passed through a stack of 50, 100, and 200 mesh screens. No residue was found upon visual inspection of the screens.
  • Tablets were made from 7.5 grams of the premixes. The tablets were added to water and the dissolution times were measured. The resulting aqueous mixtures were passed through a stack of 50, 100, and 200 mesh screens.
  • Particulate residue was determined by visual inspection of the screens.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Une formulation d'une tablette effervescente comprend environ entre 0,1 % et 75 % d'un pesticide hydrosoluble et environ 25 % à 99,9 % d'un sel de perborate de métal anhydre caractérisé par une décomposition rapide dans l'eau froide.
PCT/US1994/000068 1993-02-10 1994-01-06 Tablette pesticide effervescente avec perborate de metal Ceased WO1994017660A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU59636/94A AU5963694A (en) 1993-02-10 1994-01-06 Effervescent pesticide tablet with metal perborate
JP6518027A JPH08506578A (ja) 1993-02-10 1994-01-06 金属過ホウ酸塩を含む発泡性有害生物防除錠剤
EP94905579A EP0683627A1 (fr) 1993-02-10 1994-01-06 Tablette pesticide effervescente avec un perborate de metal

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US1575893A 1993-02-10 1993-02-10
US08/015,758 1993-02-10

Publications (1)

Publication Number Publication Date
WO1994017660A1 true WO1994017660A1 (fr) 1994-08-18

Family

ID=21773434

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/000068 Ceased WO1994017660A1 (fr) 1993-02-10 1994-01-06 Tablette pesticide effervescente avec perborate de metal

Country Status (5)

Country Link
EP (1) EP0683627A1 (fr)
JP (1) JPH08506578A (fr)
AU (1) AU5963694A (fr)
CA (1) CA2155861A1 (fr)
WO (1) WO1994017660A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999058444A3 (fr) * 1998-05-08 2000-03-09 Procter & Gamble Composant effervescent

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001247411A (ja) * 2000-03-09 2001-09-11 Tomono Agrica Co Ltd 有害生物防除剤
JP6061627B2 (ja) * 2012-02-20 2017-01-18 大日本除蟲菊株式会社 ハエ目幼虫駆除剤ならびにこれを用いたハエ目幼虫駆除方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1244815B (de) * 1962-11-17 1967-07-20 Albert Ag Chem Werke Verfahren zur Verbesserung der Loesungsgeschwindigkeit von aus Pflanzennaehrstoffen bestehenden Brechkoernern in der Bodenfluessigkeit
US3421842A (en) * 1965-09-30 1969-01-14 Fmc Corp Process for producing effervescent perborate compounds
GB1424084A (en) * 1973-06-11 1976-02-04 Holloway Ltd E R Bactericidal compositions
JPS5426988A (en) * 1977-08-03 1979-02-28 Nippon Peroxide Co Ltd Oxygen gas generating method
GB2095694A (en) * 1981-03-31 1982-10-06 Hollaway E R Ltd Tooth cleaning compositions
EP0081962A2 (fr) * 1981-12-08 1983-06-22 Warner-Lambert Company Composition pour le nettoyage des dentiers
WO1990000007A1 (fr) * 1988-06-28 1990-01-11 E.I. Du Pont De Nemours And Company Formulations de pesticides en pastilles

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1244815B (de) * 1962-11-17 1967-07-20 Albert Ag Chem Werke Verfahren zur Verbesserung der Loesungsgeschwindigkeit von aus Pflanzennaehrstoffen bestehenden Brechkoernern in der Bodenfluessigkeit
US3421842A (en) * 1965-09-30 1969-01-14 Fmc Corp Process for producing effervescent perborate compounds
GB1424084A (en) * 1973-06-11 1976-02-04 Holloway Ltd E R Bactericidal compositions
JPS5426988A (en) * 1977-08-03 1979-02-28 Nippon Peroxide Co Ltd Oxygen gas generating method
GB2095694A (en) * 1981-03-31 1982-10-06 Hollaway E R Ltd Tooth cleaning compositions
EP0081962A2 (fr) * 1981-12-08 1983-06-22 Warner-Lambert Company Composition pour le nettoyage des dentiers
WO1990000007A1 (fr) * 1988-06-28 1990-01-11 E.I. Du Pont De Nemours And Company Formulations de pesticides en pastilles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 7914, Derwent World Patents Index; AN 79-27044B [14] *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999058444A3 (fr) * 1998-05-08 2000-03-09 Procter & Gamble Composant effervescent

Also Published As

Publication number Publication date
JPH08506578A (ja) 1996-07-16
AU5963694A (en) 1994-08-29
EP0683627A1 (fr) 1995-11-29
CA2155861A1 (fr) 1994-08-18

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