WO1999039581A1 - Methomyl solvent systems - Google Patents
Methomyl solvent systems Download PDFInfo
- 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
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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
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99905747A EP1052902A1 (en) | 1998-02-06 | 1999-02-04 | Methomyl solvent systems |
CA002317127A CA2317127A1 (en) | 1998-02-06 | 1999-02-04 | Methomyl solvent systems |
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 (en) | 1999-08-12 |
Family
ID=26755131
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/002437 WO1999039581A1 (en) | 1998-02-06 | 1999-02-04 | Methomyl solvent systems |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1052902A1 (en) |
CA (1) | CA2317127A1 (en) |
WO (1) | WO1999039581A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001021687A1 (en) * | 1999-09-23 | 2001-03-29 | The Dow Chemical Company | Solvent composition |
WO2001026461A1 (en) * | 1999-10-08 | 2001-04-19 | Bayer Aktiengesellschaft | Novel liquid formulations |
WO2002017722A2 (en) * | 2000-08-31 | 2002-03-07 | 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 |
EP1695621A2 (en) | 2005-02-26 | 2006-08-30 | Bayer CropScience AG | Agrochemical formulation for increasing the effectiveness and plant tolerance of plant protective agents |
WO2016164555A1 (en) | 2015-04-09 | 2016-10-13 | Isp Investments Inc. | Synergistic preservative compositions |
GB2566700A (en) * | 2017-09-20 | 2019-03-27 | Rotam Agrochem Int Co Ltd | Pesticidal composition comprising an oxime carbamate and the use thereof |
GB2566696A (en) * | 2017-09-20 | 2019-03-27 | Rotam Agrochem Int Co Ltd | Pesticidal composition comprising an oxime carbamate and the use thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0189588A2 (en) * | 1985-01-29 | 1986-08-06 | F. Hoffmann-La Roche Ag | Herbicidal mixture |
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 |
-
1999
- 1999-02-04 CA CA002317127A patent/CA2317127A1/en not_active Withdrawn
- 1999-02-04 WO PCT/US1999/002437 patent/WO1999039581A1/en not_active Application Discontinuation
- 1999-02-04 EP EP99905747A patent/EP1052902A1/en not_active Withdrawn
Patent Citations (3)
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 (en) * | 1985-01-29 | 1986-08-06 | F. Hoffmann-La Roche Ag | Herbicidal mixture |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, vol. 112, no. 15, 9 April 1990, Columbus, Ohio, US; abstract no. 134535, XP002105064 * |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001021687A1 (en) * | 1999-09-23 | 2001-03-29 | The Dow Chemical Company | Solvent composition |
WO2001026461A1 (en) * | 1999-10-08 | 2001-04-19 | Bayer Aktiengesellschaft | Novel liquid formulations |
AU2001290541B2 (en) * | 2000-08-31 | 2007-06-14 | Huntsman Petrochemical Corporation | Water emulsifiable formulatiions |
WO2002017722A2 (en) * | 2000-08-31 | 2002-03-07 | Huntsman Petrochemical Corporation | Water emulsifiable formulations |
WO2002017722A3 (en) * | 2000-08-31 | 2002-07-04 | Huntsman Spec Chem Corp | Water emulsifiable formulations |
US6503891B1 (en) | 2000-08-31 | 2003-01-07 | Huntsman Petrochemical Corporation | Water emulsifiable formulations |
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 |
KR101302079B1 (en) * | 2005-02-26 | 2013-09-06 | 바이엘 크롭사이언스 아게 | Agrochemical formulation of plant protection active ingredients for improving the action and plant tolerance |
EP1695621A3 (en) * | 2005-02-26 | 2007-02-28 | Bayer CropScience AG | Agrochemical formulation of plant protective agents for increasing their activity and plant tolerance |
WO2006089661A1 (en) * | 2005-02-26 | 2006-08-31 | Bayer Cropscience Ag | Agrochemical formulation of plant protection active ingredients for improving the action and plant tolerance |
JP2008532940A (en) * | 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 | Agrochemical formulations of plant protective active ingredients to improve action and plant tolerance |
EA013503B1 (en) * | 2005-02-26 | 2010-06-30 | Байер Кропсайенс Аг | Formulation of a bioactive substance for plant protection, a method for producing said formulation, the use thereof for treating plants, a method for increasing the efficacy of the bioactive substance for plant protection and a method for plant protection against vermin |
EP1695621A2 (en) | 2005-02-26 | 2006-08-30 | Bayer CropScience AG | Agrochemical formulation for increasing the effectiveness and plant tolerance of plant protective agents |
EP3288380A4 (en) * | 2015-04-09 | 2018-09-19 | ISP Investments LLC | Synergistic preservative compositions |
WO2016164555A1 (en) | 2015-04-09 | 2016-10-13 | Isp Investments Inc. | Synergistic preservative compositions |
AU2016245785B2 (en) * | 2015-04-09 | 2020-07-09 | Isp Investments Llc | Synergistic preservative compositions |
GB2566700A (en) * | 2017-09-20 | 2019-03-27 | Rotam Agrochem Int Co Ltd | Pesticidal composition comprising an oxime carbamate and the use thereof |
GB2566696A (en) * | 2017-09-20 | 2019-03-27 | Rotam Agrochem Int Co Ltd | Pesticidal composition comprising an oxime carbamate and the use thereof |
WO2019057022A1 (en) * | 2017-09-20 | 2019-03-28 | Jiangsu Rotam Chemistry Co., Ltd | Pesticidal composition comprising an oxime carbamate and the use thereof |
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 (en) | 1999-08-12 |
EP1052902A1 (en) | 2000-11-22 |
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