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WO1986005950A1 - Carbamates de bis alkylthio-alkylimino-n-alkyle stabilises thermiquement - Google Patents

Carbamates de bis alkylthio-alkylimino-n-alkyle stabilises thermiquement Download PDF

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Publication number
WO1986005950A1
WO1986005950A1 PCT/US1986/000776 US8600776W WO8605950A1 WO 1986005950 A1 WO1986005950 A1 WO 1986005950A1 US 8600776 W US8600776 W US 8600776W WO 8605950 A1 WO8605950 A1 WO 8605950A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
weight
pesticidal composition
composition according
carbon atoms
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/US1986/000776
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English (en)
Inventor
David Lucas Miles
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.)
Union Carbide Corp
Original Assignee
Union Carbide Corp
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 Union Carbide Corp filed Critical Union Carbide Corp
Priority to KR1019860700896A priority Critical patent/KR930008436B1/ko
Priority to BR8606630A priority patent/BR8606630A/pt
Publication of WO1986005950A1 publication Critical patent/WO1986005950A1/fr
Priority to MYPI87002828A priority patent/MY101393A/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • A01N25/22—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 containing ingredients stabilising the active ingredients
    • 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof

Definitions

  • This invention relates to thermal stabilization of alkylthio-alkylimino carbamate pesticides. More particularly, it relates to the retardation or prevention of thermal decomposition of sulfur-linked bis alkylthio-alkylimino carbamates by incorporation of multioxygen inorganic compounds into formulations containing these pesticides.
  • Active compounds exhibit a very high level of pesticidal activity and substantially reduced mammalian toxicity and phytotoxicity when compared to other pesticidal compounds having a comparable spectrum of activity against the above mentioned pests.
  • the principal object of this invention to provide a method to inhibit or retard the thermal decomposition processes that may occur in bulk quantities of sulfur-linked bis alkylthio-alkylamino-N-alkyl pesticides when they are dried at elevated temperatures or stored for extended periods of time, especially in warmer climates. It is a further object to provide stable wettable powders and dispersible granular formulations of these pesticides.
  • This invention provides a method of retarding or inhibiting thermal decomposition of pesticides of the formula
  • R 1 is alkyl containing from one to five carbon atoms
  • R 2 is alkyl, alkylthio, alkoxy, alkanoyl or alkoxycarbonyl, all of which may contain from one to five carbon atoms and which may be unsubstituted or aliphatically substituted in any combination with one or more cyano, nitro, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxy or
  • R4R 5 -NCO- groups or R 2 is phenyl
  • R 4 R 5 -NCO- or R 6 CON(R 4 ), wherein R 4 and
  • R 5 are individually hydrogen or alkyl, R 6 is hydrogen, alkyl or alkoxy; and R 3 is hydrogen, cyano, alkyl or alkylthio containing from one to five carbon atoms; provided that the total number of carbon atoms in R 2 and R 3 may not exceed eight and provided further that when R 2 is alkyl substituted with alkylthio, R 3 is alkyl, the inhibition or retardation of thermal decomposition of this compound being achieved by mixing the pesticide with from about 0.01% to about 95% by weight of a substantially non-alkaline inorganic compound containing at least two oxygen atoms bound to a multivalent cationic atom.
  • This invention also provides a pesticidal composition which comprises:
  • powder or granular composition embraces all solid formulations which range in size from fine dusts (e.g., those which pass through U.S. Sieve screens No. 400 up to No. 100) to substantial particles as large as 5 mm in their largest dimension (e.g. those which pass through a No. 4 U.S. Sieve screen).
  • a “substantially non-alkaline inorganic compound” is one which, when dissolved or dispersed in water in an amount useful to this invention, does not create a pH greater than 9 or which can be buffered to a pH less than 9.
  • Thiodicarb is the generic name of a pesticide having the formula set forth below:
  • compositions encompasses additives that permit different pesticides to be combined in a single liquid formulation. Such agents may be incorporated into solid or liquid compositions containing one or all of the pesticides to be combined.
  • the organic compounds of this invention are alkylthio-alkylimino-N-alkyl carbamates. They are widely used to control a variety of insect pests. They may be prepared by well known methods, such as those set forth in U.S. Patents No. 4,004,031 and 4,382,957.
  • R 1 and R 3 or alkyl and R 2 is alkyl or alkylthio.
  • the compound thiodicarb is especially preferred for the practice of this invention.
  • Typical decomposition times for thiocarb in the presence of a variety of contaminants are shown in Table I. These data were collected using the following procedure. A one-gram sample of thiodicarb was intimately mixed with the indicated weight percent of contaminant. The solid was placed in a test tube that was then covered with a rubber septum cap and immersed in a constant temperature bath maintained at 100°C. An uncontaminated standard was run under similar conditions. Decomposition was manifested in a variety of forms. Some samples exhibited a rapid change from solid to dark liquid; dense yellow smoke was usually observed. Others underwent gradual discoloration and moistening. In these experiments the time of decomposition was the point when the sample was a dark-brown semi-solid. Reported values were averages of several repetitions for each sample.
  • Thiodicarb is stable at low concentrations (1% by weight or less) of one of its principal decomposition products, methomyl. However, as the concentration of methomyl is raised, the rate of decomposition increases significantly. Likewise, the effect of methomyl oxime is also substantial. As amounts of other decomposition products, such as dimethyltrisulfide and dimethyldisulfide increase, the rate of decomposition is substantially accelerated.
  • Section C of Table I results of studies using contaminants that might be introduced during the preparation or storage of the pesticidal substance.
  • heavy metal ions particularly copper and iron, are especially deleterious.
  • Use of manufacturing equipment or storage containers made of these metals in forms that can corrode to produce deleterious salts should be avoided if at all possible.
  • the other organic materials are included to demonstrate the effects that such compounds might have on the product if they should be present, e.g. because they are found in the solvents that are used in the manufacturing process.
  • thermocouple test conducted as follows.
  • a test mixture was prepared by intimately mixing the pesticide standard and the desired quantity of stabilizer.
  • the pesticide standard was thiodicarb containing sulfur as a synthesis impurity; no additional contaminants were added.
  • a thermocouple was placed into two grams of dried sample in a measuring vial.
  • a second thermocouple was placed in the vial one inch above the surface of the mixture.
  • the vial was then placed in a heating block and heated as quickly as possible to 160°C; the rate of heating was not important as long as it was reproducible and the mixture reached 160°C before the exotherm occurred for untreated pesticide.
  • the time to exotherm for the mixture was compared to that for an untreated standard, i.e. one containing pesticide alone. Measurements for a single mixture of additive and pesticide were usually taken five to ten times to assure reproducibility. In all cases the pesticide was taken from the same batch to avoid differences in contamination levels that are often observed from one batch to the next. The time to exotherm was directly proportional to the thermal stability of the mixture.
  • substantially non-alkaline inorganic compounds containing at least two oxygen atoms bound to a multivalent cationic atom are surprisingly effective at retarding or inhibiting the occurrence of the exotherm in sulfur-linked carbamate pesticides such as thiodicarb.
  • sulfur-linked carbamate pesticides such as thiodicarb.
  • Included in this group are the phosphorous acids; alkali metal monobasic phosphates, metaphosphates, sulfites or bisulfites; alkali metal or alkaline earth aluminosilicates (zeolites or molecular sieves); alkali metal bicarbonates; and silicon dioxide in the form of silicas and silicates.
  • the compounds that are especially effective at retarding the exotherm are sodium or potassium monobasic phosphate, sulfite or bisulfite; hexametaphosphate; and phosphoric acid. Mixtures of these compounds are also effective.
  • the abilities of several of the preferred stabilizers to retard the exotherm in thiodicarb as measured in the dual thermcouple test described above are apparent from the results shown in Table III. These results indicate that potassium monobasic phosphate is an especially preferred stabilizer for thiodicarb.
  • Stabilization of sulfur-linked bis alkylthio-alkylamino-N-alkyl carbamates may be achieved by incorporating the stabilizers of this invention in amounts ranging from 0.01 to 95 percent by weight of total mixture.
  • concentration of a particular inorganic stabilizer must be evaluated empirically, as a general rule preferred concentrations range from about 0.01 to about 10% by weight in solid formulations and from 0.0001% to about 6% by weight in liquid formulations.
  • concentration of a particular inorganic stabilizer must be evaluated empirically, as a general rule preferred concentrations range from about 0.01 to about 10% by weight in solid formulations and from 0.0001% to about 6% by weight in liquid formulations.
  • stabilization will be observed with as little as 0.01 to 2% by weight.
  • Sulfite stabilizers are effective in the range of 0.1 to 5% by weight.
  • compositions of this invention may be applied as solids or as liquid dispersions or solutions to both field and turf to control pests. Application is by methods readily known to those skilled in the art. Effective amounts range from about 0.05 to about 20 lbs. per acre of active pesticide.
  • Formulations useful in the practice of this invention are solids, as wettable powders or dispersible granulars, and liquids, as solutions or dispersions.
  • the preferred wettable powders and dispersible granular formulations comprise: (a) from about 1% to about 98% by weight of a bis alkylthio-alkylamino-N-alkyl carbamate pesticide; (b) from about 0.01% to about 10% by weight of a substantially non-alkaline inorganic compound containing at least two oxygen atoms bound to a multivalent cationic atom; (c) from about 0.01% to about 20% by weight of wetting agent; and (d) from about 1% to about 12% by weight dispersant.
  • Preferred liquid formulations comprise:
  • Suitable carriers include water, unsubstituted aliphatic and aromatic hydrocarbons or analogues containing, for example, alkyl, halo or hydroxy substltuents, fatty acids, and oils, such as linseed and cottonseed oil, derived from natural extracts.
  • the preferred compound is thiodicarb.
  • the preferred oxygen-containing inorganic compounds are phosphoric acid and sodium or potassium monobasic phosphate, metaphosphate, sulfite or bisulfite.
  • wetting agents anionic, cationic or nonionic are available for these formulations.
  • Illustrative wetting agents are alkali metal salts of fatty alkyl or alkenyl sulfates or sulfonates containing eight to twenty carbon atoms; alkali metal salts of alkylbenzyl or alkylnaphthyl sulfonates wherein the alkyl chain contains eight to twelve carbon atoms; ethoxylated alkylphenols wherein the alkyl groups contain eight to twelve carbon atoms; dialkylesters of sodium sulfonsuccinic acids wherein the dialkyl groups contain five to ten carbon atoms; or polyalkylene oxide modified dimethypolysiloxane in which the alkylene groups are ethylene or propylene or a mixture of both.
  • Other suitable wetting agents may also be used.
  • Dispersants are materials which interact with solid ingredients in the formulations and the liquid medium that is used to suspend those solids for purposes of application. They must be soluble in that liquid phase and they usually behave as a binder for the solid powder or granular.
  • Representative dispersants useful in the practice of this invention include starches, alkali metal or alkaline earth salts of lignin sulfonates; and condensates of alkali metal alkylnaphthalene sulfonates and organic compounds containing one to three carbon atoms and at least one oxygen atom, such as the condensate of formaldehyde and sodium naphthalene sulfonic acid.
  • An additional component particularly useful in the formulations of this invention is an antifoaming agent. It prevents or reduces foam during the preparation of the powder or granulars and during dispersion and application of the composition. It also stabilizes the resulting dispersion and permits more rapid redispersion if coagulation of solids occurs in a dispersion.
  • An especially useful antifoamer is a dialkylpolysiloxane. Particularly effective are dimethylpolysiloxanes formulated as emulsions or pastes. Such additives do not act as stabilizers for the pesticides.
  • Pesticidal formulations containing multiple pesticides are popular for the obvious reason of convenience--only one application is necessary to deposit all of the actives. While many multiple formulations are easily prepared simply by mixing all of the active ingredients, the formulations of this invention may require the presence of a compatability agent that prevents flocculation in the final solution or dispersion that is applied to the target plants. The presence of an additional, chemically unrelated pesticide such as parathion may destabilize a dispersion prepared for spray application.
  • the preferred compatability agents for these compositions are condensates of alkylene oxide and hydrophobic bases made by condensing an alkylene oxide with an. alkylene glycol wherein all aklyl substltuents contain from two to four carbon atoms.
  • a particularly effective agent is a paste condensate of ethylene oxide with hydrophobic bases formed by condensing propylene oxide with propylene glycol.
  • a number of other well known ingredients can be incorporated into the wettable powders and dispersible granulars of this invention as the need arises, provided, of course, that they do not affect the ability of the inorganic compound to stabilize the pesticide or the stability and dispersibility or wettability of the powder or granular.
  • additives might include buffers, carriers or diluents, dyes, fragrances, humectants, thickeners, biocides and anti-evaporative agents.
  • the solid compositions of this invention can be prepared by various methods well known in the art, such as pan granulation, fluidized bed mixing and drying, spray drying, intensive mixing agglomeration, extrusion, compaction or pelletizing.
  • pan granulation and fluidized bed processes a mixture of dry ingredients is prepared and transferred into the mixing/drying chamber that contains water and any liquid ingredients; the slurry is thoroughly mixed and then dried. Particles are then ground to a desired size. If a spray drying process is used, grinding of the mixture of dry ingredients or of the slurry is preferred.
  • the various processes yield solids containing a spectrum of particle sizes and moisture contents.
  • a useful product is one which meets the particle size requirements for a particular application, which contains less than 5% by weight water, and preferably less than 2%, and which disperses well in water or oil.
  • good dispersibility is obtained with particles retained on a U.S. Screen No. 100 (149 microns), and optimum particle stability is obtained with less than 2% moisture. Any particles that are too small, too large or too wet can be returned to the manufacturing or drying apparatus and recyled.
  • Preparation of the liquid compositions of this invention may be accomplished by methods known in the art.
  • Useful dispersion formulations will not separate into liquid and solid phases during extended storage at ambient temperatures.
  • size of dispersed particles may be reduced by techniques, such as air and wet milling, known in the art.
  • Formulation B can be stored for much longer times at elevated temperatures (approximately 45-55°C) than Formulation A, and Formulation B is much less likely to decompose during drying than is Formulation A.
  • EXAMPLE 2 A dispersible granular stabilized with silica was prepared by mixing 86.5% by weight thiodicarb containing approximately 3% silica and 3% sulfur; dispersants (1.5% by weight starch, 6.8% by weight sodium salt of sulfonated naththalene formaldehyde condensate, and 3.0% by weight polyalkylene glycol ether); wetting agent (1.0% by weight dioctyl ester of sodium sulfosuccinic acid); antifoamer (1.0% by weight magnesium stearate); and buffer (0.2% by weight citric acid).
  • stabilizer (i.e., silica) content was approximately 2.6% by weight.
  • the mixture was ground to a powder of average particle size less than 10 microns and then transferred to a fluidized bed chamber for mixing with water and subsequent drying.
  • EXAMPLE 3 A very stable sample containing two stabilizers was prepared by slurrying, in water, the following ingredients (all weight percents are based on added weights of the ingredients except water): 86.1% thiodicarb containing 5% sulfur and 1.0% silica; 10.1% dispersant (sodium salt of sulfonated naphthalene formaldehyde condensate); 2.5% wetting agent (sodium salt of a sulfonated lauryl acid); 0.6% antifoaming emulsifier (dimethylpolysiloxane emulsion); and 0.7% thermal stabilizer (KH 2 PO 4 ).
  • the slurry is wet ground to pass through a No. 325 screen (U.S. Sieve size) and spray dried to a moisture content of less than 2%. Approximately 95% of the resulting granular has a particle size distribution spanning the narrow range of -14 to +100 mesh (U.S. Sieve size).
  • the granular within this particle size range exhibits the following characteristics: CIPAC suspendibility 90% Time to exotherm >120 minutes

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Des pesticides de carbamate bis-alkythio-alkylimino-n-alkyle à liaison soufre peuvent être stabilisés contre la décomposition thermique provoquée et accélérée par une variété d'impuretés en incorporant un composé inorganique sensiblement non-alcalin, contenant au moins deux atomes d'oxygène liés à un atome cationique polyvalent. Il est possible de préparer de la poudre mouillable ainsi que des formulations granulaires et liquides dispersibles thermiquement stables de ces pesticides.
PCT/US1986/000776 1985-04-18 1986-04-17 Carbamates de bis alkylthio-alkylimino-n-alkyle stabilises thermiquement Ceased WO1986005950A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1019860700896A KR930008436B1 (ko) 1985-04-18 1986-04-17 열에 안정한 비스 알킬티오-알킬이미노-n-알킬 카바메이트
BR8606630A BR8606630A (pt) 1985-04-18 1986-04-17 Carbamatos de bis alquiltio-alquilamino-n-alquila termicamente estabilizados
MYPI87002828A MY101393A (en) 1985-04-18 1987-10-01 Thermally stabilized bis alkylthio-alkylamino-n-alkyl carbamates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US72455685A 1985-04-18 1985-04-18
US724,556 1985-04-18

Publications (1)

Publication Number Publication Date
WO1986005950A1 true WO1986005950A1 (fr) 1986-10-23

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1986/000776 Ceased WO1986005950A1 (fr) 1985-04-18 1986-04-17 Carbamates de bis alkylthio-alkylimino-n-alkyle stabilises thermiquement

Country Status (14)

Country Link
EP (1) EP0218698A1 (fr)
JP (1) JPS62502542A (fr)
KR (1) KR930008436B1 (fr)
AU (1) AU594053B2 (fr)
BR (1) BR8606630A (fr)
CA (1) CA1305050C (fr)
ES (1) ES8707650A1 (fr)
GR (1) GR861005B (fr)
IL (1) IL78508A0 (fr)
MX (1) MX162186A (fr)
MY (1) MY101393A (fr)
TR (1) TR23438A (fr)
WO (1) WO1986005950A1 (fr)
ZA (1) ZA862900B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992002491A1 (fr) * 1990-08-06 1992-02-20 E.I. Du Pont De Nemours And Company Nouveaux derives de (chlorure d'hydroximidoyl)-bis utilises comme fongicides agricoles
WO2006089058A1 (fr) * 2005-02-14 2006-08-24 E.I. Dupont De Nemours And Company Procede d'elimination des insectes nuisibles sur des vegetaux

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2005140A (en) * 1977-09-28 1979-04-19 Du Pont Insecticidal compositions and use thereof
US4297370A (en) * 1979-11-27 1981-10-27 E. I. Du Pont De Nemours And Company Insecticidal compositions
GB2079154A (en) * 1980-07-03 1982-01-20 Du Pont Substituted Carbamates for Tick Control
EP0056739A2 (fr) * 1981-01-21 1982-07-28 Union Carbide Corporation Concentré non-rhéopectique de pesticides contenant des bis-carbamates symétriques

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2085369A (en) * 1980-07-17 1982-04-28 Turner David Robin Cargo support means

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2005140A (en) * 1977-09-28 1979-04-19 Du Pont Insecticidal compositions and use thereof
US4297370A (en) * 1979-11-27 1981-10-27 E. I. Du Pont De Nemours And Company Insecticidal compositions
GB2079154A (en) * 1980-07-03 1982-01-20 Du Pont Substituted Carbamates for Tick Control
EP0056739A2 (fr) * 1981-01-21 1982-07-28 Union Carbide Corporation Concentré non-rhéopectique de pesticides contenant des bis-carbamates symétriques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Journal of Agricultural and Food Chemistry Vol. 27, No. 5, September/October 1979, American Chemical Society, (Washington D.C., US) M. CHIBA: "Use of Ammonium or Potassium Dihydrogen Phosphate to Protect Pesticides in Spray Mixtures Prepared with Alkaline Waters", pages 1023-1026 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992002491A1 (fr) * 1990-08-06 1992-02-20 E.I. Du Pont De Nemours And Company Nouveaux derives de (chlorure d'hydroximidoyl)-bis utilises comme fongicides agricoles
WO2006089058A1 (fr) * 2005-02-14 2006-08-24 E.I. Dupont De Nemours And Company Procede d'elimination des insectes nuisibles sur des vegetaux

Also Published As

Publication number Publication date
GR861005B (en) 1986-08-12
KR930008436B1 (ko) 1993-09-04
JPH0523241B2 (fr) 1993-04-02
AU5696486A (en) 1986-11-05
TR23438A (tr) 1989-12-29
MX162186A (es) 1991-04-08
BR8606630A (pt) 1987-08-04
CA1305050C (fr) 1992-07-14
EP0218698A1 (fr) 1987-04-22
IL78508A0 (en) 1986-08-31
MY101393A (en) 1991-10-23
JPS62502542A (ja) 1987-10-01
AU594053B2 (en) 1990-03-01
ZA862900B (en) 1986-12-30
KR870700290A (ko) 1987-12-28
ES554105A0 (es) 1987-08-16
ES8707650A1 (es) 1987-08-16

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