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WO1999039581A1 - Compositions permettant de conserver du methomyle sous forme de solution - Google Patents

Compositions permettant de conserver du methomyle sous forme de solution Download PDF

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Publication number
WO1999039581A1
WO1999039581A1 PCT/US1999/002437 US9902437W WO9939581A1 WO 1999039581 A1 WO1999039581 A1 WO 1999039581A1 US 9902437 W US9902437 W US 9902437W WO 9939581 A1 WO9939581 A1 WO 9939581A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
methomyl
glycol
carbonate
group
Prior art date
Application number
PCT/US1999/002437
Other languages
English (en)
Inventor
Edward Thomas Marquis
Howard Meyer Stridde
Original Assignee
Huntsman Petrochemical Corporation
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 Huntsman Petrochemical Corporation filed Critical Huntsman Petrochemical Corporation
Priority to CA002317127A priority Critical patent/CA2317127A1/fr
Priority to EP99905747A priority patent/EP1052902A1/fr
Publication of WO1999039581A1 publication Critical patent/WO1999039581A1/fr

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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
    • 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 the preparation and use of solutions containing dissolved insecticidal compounds for which the solubility of the insecticide in the solution is a limiting factor of the concentration at which stable solutions may be stored. More particularly, it relates to the transportation, storage, and use of solutions containing methomyl, using an alkylene carbonate in combination with at least one other oxygen- bearing organic molecule as components of liquid-phase solutions that contain dissolved methomyl.
  • Methomyl is the methyl ester of N-[(methylcarbamoyl)oxy]thioacetimidic acid. This compound has found widespread use as an insecticide since the early 1970's. Although being a very effective insecticide of relatively low toxicity, the tendency of the material to crystallize out of its solutions at low temperatures is widely known to be a nuisance to personnel involved in the storage, transportation, and use of its solutions. Since it is convenient to provide agriculturally-active compounds dissolved in suitable solvent for later dilution in the field, the tendency of a given material to crystallize out of a concentrated solution is a limiting factor of the effective concentration at which solutions of the material may be prepared for commercial transport and sale.
  • methomyl inflated amounts of solution relative to other water-emulsifyable formulations have been found necessary when proceeding according to prior art methods for preparing solutions of methomyl. This has meant that proportionately-inflated amounts of solvent or other inert ingredients must be dispersed along with the active methomyl in a given insecticidal application. 2
  • compositions disclosed herein provide methomyl solutions of higher concentrations over prior art, possessive of a decreased tendency for dissolved methomyl to crystallize out when the solution is subjected to temperatures near zero degrees centigrade for prolonged periods of time.
  • This invention provides a single-phase, liquid methomyl concentrate composition comprising methomyl and certain organic solvents that can be diluted with water for spray tank use by an end user.
  • a solvent combination according to the invention useful for dissolving methomyl and maintaining it at high concentrations in solution over a wide temperature range comprises a first component that contains at least one alkylene carbonate, and a second component (or co-solvent) that includes least one organic oxygen compound.
  • the alkylene carbonate component may be selected from propylene and butylene carbonate
  • the organic oxygen compound may be selected from classes of compounds that may include alcohols, glycols, ketones, ethers, lactones and heterocyclic compounds in which a member of the ring structure contains a keto function, such as N- methyl pyrrolidone.
  • the combination of alkylene carbonate, methomyl, and other component(s) may contain a high concentration of methomyl, preferably 20 % by weight or more with respect to the total weight of the finished solution, is not chemically 3 reactive under conditions normally encountered in storage of methomyl solutions, is easily and quickly dilutable with water to the desired spray concentration, and the applied spray does not injure the crops targeted. Additionally, the solution retains a high degree of insecticidal qualities, does not have a tendency to separate into separate liquid layers in storage, and the ingredients possess low hazard potential during and after spray applications as defined by existing local and national environmental regulations.
  • the present invention is directed at solutions comprising methomyl dissolved in a solution combination that comprises a first component containing at least one alkylene carbonate and a second component that includes an organic oxygen compound.
  • a co-solvent organic oxygen compound
  • an alkylene carbonate for example propylene carbonate
  • the co-solvent may be selected from various glycols and ethers thereof; ketones; alcohols; lactones; and alkylene carbonates.
  • a suitable solvent combination To produce a suitable solvent combination according to the invention, one mixes the components of the solvent combination under ambient or slightly elevated temperature, and agitates to produce a homogeneous solution. This typically requires between about 5 minutes and l hour of agitation, depending upon the type of vessel in which the mixing is conducted and the agitation employed. (When using laboratory-scale equipment such as a 250 ml beaker and a glass stirring rod, suitable combination is produced within one minute when vigorous stirring with a glass stirring rod is employed).
  • a solution of methomyl in accordance with this invention one preferably adds the desired amount of methomyl to the solvent combination once the solvent combination 4 has been made homogeneous, and agitates the solvent until solution is effected. This may be done with or without the assistance of added heat energy, but preferably the solution is heated to about 45 degrees Centigrade prior to the methomyl addition, to facilitate the rapid dissolution thereof.
  • compositions of several formulations useful for keeping methomyl in solution at high concentration over a wide range of temperatures have been discovered, the formulations of which are set forth in examples 1 - 12 below.
  • synergistic properties of the solvent combinations are believed responsible for their unexpected ability to maintain methomyl in solution in which no crystallization is evident even after prolonged storage at 0 degrees C.
  • the unexpectedness of the success in examples 1 - 12 is evidenced by the compositions of the samples in tables III and IV in which methomyl crystallization was evident after prolonged storage of the solutions at the same low temperatures.
  • Table II Successful solution compositions for systems retaining 28.0 and 30 % methomyl dissolved at 0 degrees C with no crystallization evident after one month.
  • the most preferred composition is that set forth in example 1. This is most preferred because of the low toxicity of the DPNB, its high flash point, its odorless character, and its relatively low cost.
  • compositions for which methomyl crystallization was evident after 30 days aging at 0 degrees C are set forth in tables III and IV below:
  • Table TV More examples of systems that displayed methomyl crystallizing out when stored at 0 degrees C for 30 days
  • These solutions are suitable for use (after appropriate dilution) in the control of pestiferous insects belonging to such orders as Lepidoptera, Homoptera, Hemiptera, Diptera, and Coleoptera, including but not limited to cotton bollworm, tobacco budworm, southern armyworm, soybean looper, beet armyworm, cotton aphid, tarnished plant bug, and white flies.
  • the insects are controlled by applying the solutions to the area to be protected, or to the pests themselves. In the case of agricultural applications, a dispersion or emulsion of the solvents are applied to the foliage to be protected.
  • Effective amounts depend upon the species to be controlled, its life stage, its size and location, the amount of rainfall, time of year, moisture, temperature. type of application and other variables, all of which are known or readily determinable by those of ordinary skill in the art. Generally, dosage levels of between about 0.0625 to 4 kilograms per hectare of methomyl are required, with levels between about 0.125 to 2.0 kilograms per hectare being sufficient in most instances.
  • the solutions of this invention may be combined with surfactants, wetting agents, dispersing agents, antifoam agents and the like, as such admixtures are typical in the agricultural field and are well-known to methomyl users having ordinary skill.
  • the formulations herein set forth may be mixed with fungicides, bacteriocides, acaricides, nematicides, or other biologically active compounds.
  • Suitable surfactants are known to those skilled in the art, and include without limitation sodium lauryl sulfate and its functional anionic, non-ionic and cationic equivalents, as such are well-known to artisans of ordinary skill.
  • concentration of methomyl relates to the amount of methomyl that is dissloved in either a neat or a mixed liquid solvent combination.
  • Methomyl is known to be soluble in various organic solvents to varying degrees; however, most solvents in which it has appreciable solubility are not approved for spray use on crops or foliage. Of those solvents that are acceptable for 9 spray use, the solubility of methomyl therein is not as high as is desired, and is typically on the order of only about 20 % by weight.
  • the term "high concentrations of methomyl” means a concentration of methomyl in solution of at least 20 % by weight based upon the total weight of the solution. According to this invention, stable solutions having methomyl concentrations as high as 30 % may be prepared, which permits one-and-a-half times as much active chemical to be transported per given volume over prior art solutions containing only 20% methomyl.
  • organic oxygen compound means a chemical compound whose molecular structure includes carbon atoms and oxygen atoms, including compounds belonging to the classes: alcohols, ethers, glycols, polyalkylene glycols, ethers of glycols, ethers of polyalkylene glycols, ketones, pyrrolidones, and lactones, including substituted analogs or derivatives of compounds within these classes, whether the substituents are straight chain, branched, aromatic, or aliphatic.
  • a typical means by which the instant invention may be employed in the destruction of unwanted pests is by diluting a composition of any one of examples 1 through 12 with a desired amount of water, either alone or with additional diluents, which may include but are not limited to dyes, oils, fungicides, bacteriocides, acaricides, nematicides, or fungicides, to produce an emulsion of desired methomyl concentration.
  • the emulsion is sprayed through a conventional atomizer, including as an example 10 illustrative and not delimitive hereof, a DeVilbiss No. 152 atomizing nozzle available from the DeVilbiss Company, Somerset, Pennsylvania 15501 using atomizing air at 12 p.s.i. onto a cotton, corn, tomato, or other food-bearing plant.
  • Non-food-bearing plants, such as tobacco may also be the target.

Landscapes

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

Abstract

L'invention concerne des compositions liquides de substances contenant l'insecticide méthomyle sous une forme concentrée pouvant être diluée sans difficultés afin d'être pulvérisée, ou appliquée d'une autre façon, sur des récoltes ou des feuillages. Ces compositions contiennent le méthomyle en concentrations plus importantes que celles de l'état actuel de la technique et le méthomyle ne se cristallise pas dans des solutions soumises à des températures de zéro degrés centigrades. L'invention permet de transporter des quantités plus élevées de méthomyle pour un volume donné de solution et de limiter la quantité de composés inertes appliqués aux récoltes, ce qui permet d'obtenir des avantages supplémentaires du point de vue de l'environnement et des coûts.
PCT/US1999/002437 1998-02-06 1999-02-04 Compositions permettant de conserver du methomyle sous forme de solution WO1999039581A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA002317127A CA2317127A1 (fr) 1998-02-06 1999-02-04 Compositions permettant de conserver du methomyle sous forme de solution
EP99905747A EP1052902A1 (fr) 1998-02-06 1999-02-04 Compositions permettant de conserver du methomyle sous forme de solution

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US7398898P 1998-02-06 1998-02-06
US60/073,988 1998-02-06
US24339499A 1999-02-01 1999-02-01
US09/243,394 1999-02-01

Publications (1)

Publication Number Publication Date
WO1999039581A1 true WO1999039581A1 (fr) 1999-08-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/002437 WO1999039581A1 (fr) 1998-02-06 1999-02-04 Compositions permettant de conserver du methomyle sous forme de solution

Country Status (3)

Country Link
EP (1) EP1052902A1 (fr)
CA (1) CA2317127A1 (fr)
WO (1) WO1999039581A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001021687A1 (fr) * 1999-09-23 2001-03-29 The Dow Chemical Company Composition de solvant
WO2001026461A1 (fr) * 1999-10-08 2001-04-19 Bayer Aktiengesellschaft Nouvelles formulations liquides
AU2001290541B8 (en) * 2000-08-31 2002-03-13 Huntsman Petrochemical Corporation Water emulsifiable formulatiions
US7030157B2 (en) 2001-07-31 2006-04-18 Pfizer Inc. Pharmaceutical compositions, kits and methods comprising combinations of estrogen agonists/antagonists, estrogens and progestins
EP1695621A2 (fr) 2005-02-26 2006-08-30 Bayer CropScience AG Formulation agrochimique contenant des agents phytosanitaires pour améliorer leur activité et la tolérance des plantes
WO2016164555A1 (fr) 2015-04-09 2016-10-13 Isp Investments Inc. Compositions de conservateurs synergiques
GB2566696A (en) * 2017-09-20 2019-03-27 Rotam Agrochem Int Co Ltd Pesticidal composition comprising an oxime carbamate and the use thereof
GB2566700A (en) * 2017-09-20 2019-03-27 Rotam Agrochem Int Co Ltd Pesticidal composition comprising an oxime carbamate and the use thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0189588A2 (fr) * 1985-01-29 1986-08-06 F. Hoffmann-La Roche Ag Mélange herbicide
AU568717B2 (en) * 1984-01-19 1988-01-07 Shell Chemical (Australia) Proprietary Limited Pesticide composition comprising a ketone, lower alkanol and dipolar aprotic solvent system
AU592970B2 (en) * 1985-01-21 1990-02-01 Basf Aktiengesellschaft Pesticide formulation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU568717B2 (en) * 1984-01-19 1988-01-07 Shell Chemical (Australia) Proprietary Limited Pesticide composition comprising a ketone, lower alkanol and dipolar aprotic solvent system
AU592970B2 (en) * 1985-01-21 1990-02-01 Basf Aktiengesellschaft Pesticide formulation
EP0189588A2 (fr) * 1985-01-29 1986-08-06 F. Hoffmann-La Roche Ag Mélange herbicide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 112, no. 15, 9 April 1990, Columbus, Ohio, US; abstract no. 134535, XP002105064 *

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001021687A1 (fr) * 1999-09-23 2001-03-29 The Dow Chemical Company Composition de solvant
WO2001026461A1 (fr) * 1999-10-08 2001-04-19 Bayer Aktiengesellschaft Nouvelles formulations liquides
AU2001290541B2 (en) * 2000-08-31 2007-06-14 Huntsman Petrochemical Corporation Water emulsifiable formulatiions
AU2001290541B8 (en) * 2000-08-31 2002-03-13 Huntsman Petrochemical Corporation Water emulsifiable formulatiions
WO2002017722A3 (fr) * 2000-08-31 2002-07-04 Huntsman Spec Chem Corp Formulations emulsionnables dans l'eau
US6503891B1 (en) 2000-08-31 2003-01-07 Huntsman Petrochemical Corporation Water emulsifiable formulations
US7030157B2 (en) 2001-07-31 2006-04-18 Pfizer Inc. Pharmaceutical compositions, kits and methods comprising combinations of estrogen agonists/antagonists, estrogens and progestins
JP2008532940A (ja) * 2005-02-26 2008-08-21 バイエル・クロツプサイエンス・アクチエンゲゼルシヤフト 作用および植物耐性を改善するための植物保護活性成分の農薬製剤
EP1695621A3 (fr) * 2005-02-26 2007-02-28 Bayer CropScience AG Formulation agrochimique contenant des agents phytosanitaires pour ameliorer leur activité et la tolerance des plantes
WO2006089661A1 (fr) * 2005-02-26 2006-08-31 Bayer Cropscience Ag Formulation agrochimique d'agents phytosanitaires permettant d'ameliorer l'efficacite et la compatibilite vis-a-vis des plantes
EP1695621A2 (fr) 2005-02-26 2006-08-30 Bayer CropScience AG Formulation agrochimique contenant des agents phytosanitaires pour améliorer leur activité et la tolérance des plantes
EA013503B1 (ru) * 2005-02-26 2010-06-30 Байер Кропсайенс Аг Препарат биологически активного вещества для защиты растений, способ его получения, его применение для обработки растений, способ повышения эффективности биологически активного вещества для защиты растений и способ защиты растений от вредителей
KR101302079B1 (ko) * 2005-02-26 2013-09-06 바이엘 크롭사이언스 아게 작용 및 식물 내성을 향상시키기 위한 식물 보호 활성성분의 농약 제제
EP3288380A4 (fr) * 2015-04-09 2018-09-19 ISP Investments LLC Compositions de conservateurs synergiques
WO2016164555A1 (fr) 2015-04-09 2016-10-13 Isp Investments Inc. Compositions de conservateurs synergiques
AU2016245785B2 (en) * 2015-04-09 2020-07-09 Isp Investments Llc Synergistic preservative compositions
GB2566696A (en) * 2017-09-20 2019-03-27 Rotam Agrochem Int Co Ltd Pesticidal composition comprising an oxime carbamate and the use thereof
GB2566700A (en) * 2017-09-20 2019-03-27 Rotam Agrochem Int Co Ltd Pesticidal composition comprising an oxime carbamate and the use thereof
WO2019057022A1 (fr) * 2017-09-20 2019-03-28 Jiangsu Rotam Chemistry Co., Ltd Composition pesticide comprenant un carbamate d'oxime et utilisation associée
GB2566696B (en) * 2017-09-20 2020-09-16 Rotam Agrochem Int Co Ltd Pesticidal composition comprising an oxime carbamate and the use thereof
GB2566700B (en) * 2017-09-20 2022-05-25 Rotam Agrochem Int Co Ltd Pesticidal composition comprising an oxime carbamate and the use thereof
US11523612B2 (en) 2017-09-20 2022-12-13 Jiangsu Rotam Chemistry Co., Ltd. Pesticidal composition comprising oxime carbamate and use thereof

Also Published As

Publication number Publication date
CA2317127A1 (fr) 1999-08-12
EP1052902A1 (fr) 2000-11-22

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