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EP0683627A1 - Tablette pesticide effervescente avec un perborate de metal - Google Patents

Tablette pesticide effervescente avec un perborate de metal

Info

Publication number
EP0683627A1
EP0683627A1 EP94905579A EP94905579A EP0683627A1 EP 0683627 A1 EP0683627 A1 EP 0683627A1 EP 94905579 A EP94905579 A EP 94905579A EP 94905579 A EP94905579 A EP 94905579A EP 0683627 A1 EP0683627 A1 EP 0683627A1
Authority
EP
European Patent Office
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
EP94905579A
Other languages
German (de)
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
Publication of EP0683627A1 publication Critical patent/EP0683627A1/fr
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

  • Contemplated sulfonylurea salts have the formula:
  • J is selected from the group
  • R is selected from the group H and CH3;
  • R 1 is selected from the group F, Cl, Br, NO 2 , C1-C4 alkyl, C j -C ⁇ 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 , 1
  • SO 2 N(CH 3 ) 2 , SO 2 CH 3 , SO 2 CH 2 CH 3 , OCH 3 , and OCH 2 CH 3 R 4 is selected from the group C1-C3 alkyl, C ⁇ -C 2 haloalkyl, C j -C 2 alkoxy,
  • R 5 is selected from the group H, F, Cl, Br and CH3
  • R 6 is selected from the group C C3 alkyl, Cj-C 2 alkoxy, C2-C4 haloalkenyl, F, Cl, Br, CO 2 R 12 , C(O)NR 1 3R14 ? SO 2 NR15R16 ;
  • R 7 is selected from the group H, F, Cl, CH3 and CF3
  • R 8 is selected from the group H, C1-C3 alkyl and pyridyl
  • R 9 is selected from the group 0 ⁇ 3 alkyl, C r C 2 alkoxy, F, Cl, Br, NO 2 ,
  • R 12 is selected from the group H, Cl, F, Br, C 1 -C3 alkyl and C j -C 2 alkoxy
  • R 11 is selected from the group H, C1-C3 alkyl, C ⁇ -C 2 alkoxy, C -C4 haloalkenyl, F, Cl, Br, CO 2 R 12 , C ⁇ NR ⁇ R 14 , S0 2 NR 15 R 16 ,
  • R 12 is selected from the group allyl and propargyl and 0 ⁇ 3 optionally substituted by at least one member independently selected from halogen, Cj-C 2 alkoxy and CN;
  • R 13 is selected from the group H, C1-C3 alkyl and C ⁇ -C 2 alkoxy;
  • R 14 is C r C 2 alkyl;
  • R 15 is selected from the group H, C 1 -C3 alkyl, C ⁇ -C 2 alkoxy, allyl and cyclopropyl;
  • R 16 is selected from the group H and C1-C3 alkyl;
  • R 17 is selected from the group C1-C3 alkyl, C1-C3 haloalkyl, allyl and propargyl;
  • R 18 is selected from the group Cj-C4 alkyl, C j -C4 haloalkyl and C3-C5 cycloalkyl optionally substituted by halogen;
  • n is 0, 1
  • M is a cation
  • Rj is selected from the group H and C1-C3 alkyl
  • W is selected from the group O and S;
  • X is selected from the group H, C1-C4 alkyl, C1-C4 alkoxy, C j -C4 haloalkoxy, 0 ⁇ 4 haloalkyl, C1-C4 haloalkylthio, C1-C4 alkylthio, halogen, C 2 -C 5 alkoxyalkyl, C2-C5 alkoxyalkoxy, amino, C1-C3 alkylamino and di(Cj-C3 alkyl )amino;
  • Y is selected from the group H, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, Cj-04 alkylthio, 0 ⁇ 0 haloalkylthio, C 2 -C5 alkoxyalkyl, C -C5 alkoxyalkoxy, amino, C1-C3 alkylamino, di(C j -C3 alkyl)amino, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C 2 -C5 alkylthioalkyl, C 2 -C 5 alkylsulfinylalkyl, C 2 -C 5 alkylsulfonylalkyl, C1-C4 haloalkyl, C -C4 alkynyl, C3-C5 cycloalkyl, azido and cyano; and Z is selected from the group CH and N; provided that i) when one or
  • Preferred active ingredients are salts of the following sulfonylureas: chlorsulfuron; sulfometuron; chlorimuron ethyl; metsulfiiron methyl; methyl 2- [[[[(4,6-dimethoxy-2-pyrimidinyl)-amino]carbonyl]-amino]sulfonyl]-6- 1 (trifluoromethyl)-3-pyridrnecarboxylate; ethametsulfuron methyl; triasulfuron; ethyl 5-[[[[[(4,6-dimethoxy-2-pyrm ⁇ idinyl)amino]carbonyl]-amino]s ⁇ lfonyl]-l- methyl- lH-pyrazole-4-carboxylate; N-[[(4,6-dimethoxy-2- pyrimidinylamino]carbonyl]-3-(ethylsulfonyl)-2-pyr
  • Preferred salts are the sodium, potassium, calcium, magnesium, ammonium 'I 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 water-soluble pesticide.
  • 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.
  • 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.
  • a manganese, copper or iron salt catalyst e.g., a manganese, copper or iron salt catalyst
  • a dispersant e.g., a dispersant
  • a disintegrant e.g., sodium bicarbonate
  • an anionic or nonionic wetting agent e.g., sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate
  • 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, NaBO3).
  • 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.
  • the conversion of the metal perborate 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.
  • Monohydrate which is not destroyed by a catalyst will not effervesce when contacted with water, but it does dissolve within the time necessary for disintegration of the tablet (i.e., less than 10 minutes).
  • Preferred 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 formaldehyde condensates, with the ammonium salts, specifically Lomar PWA®, more preferred.
  • Disintegrants facilitate penetration of the water into the interior of the tablet through a wicking or swelling action.
  • Water-insoluble cross-linked 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 invention. As indicated in Example 2 below, a tablet in a sealed container without a dessicant remains effervescent after storage. However, if 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) . 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. Combinations of these desiccants with those that form hydroxides and hydrates can be used. Kirk-Othmer's Encyclopedia 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 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 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.
  • 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 3.43xl0 7 to 6.86xl0 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 CaSO4 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.
  • EXAMPLE 5 The following ingredients were blended without a milling step.
  • 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.

Landscapes

  • 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.
EP94905579A 1993-02-10 1994-01-06 Tablette pesticide effervescente avec un perborate de metal Ceased EP0683627A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US15758 1987-04-10
US1575893A 1993-02-10 1993-02-10
PCT/US1994/000068 WO1994017660A1 (fr) 1993-02-10 1994-01-06 Tablette pesticide effervescente avec perborate de metal

Publications (1)

Publication Number Publication Date
EP0683627A1 true EP0683627A1 (fr) 1995-11-29

Family

ID=21773434

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94905579A Ceased EP0683627A1 (fr) 1993-02-10 1994-01-06 Tablette pesticide effervescente avec un 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)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2337055A (en) * 1998-05-08 1999-11-10 Procter & Gamble Effervescent particle
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

Family Cites Families (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
JPS6034482B2 (ja) * 1977-08-03 1985-08-09 日本パ−オキサイド株式会社 酸素ガス発生方法
GB2095694B (en) * 1981-03-31 1984-08-01 Hollaway E R Ltd Tooth cleaning compositions
ZA828968B (en) * 1981-12-08 1983-11-30 Warner Lambert Co Denture cleanser
GEP19971018B (en) * 1988-06-28 1997-04-06 E I Du Pont De Nemours & Company Tablet formulations

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9417660A1 *

Also Published As

Publication number Publication date
CA2155861A1 (fr) 1994-08-18
AU5963694A (en) 1994-08-29
JPH08506578A (ja) 1996-07-16
WO1994017660A1 (fr) 1994-08-18

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