WO2014047021A1 - Formulations de cinnamaldéhyde et de disulfure de diallyle et procédés d'utilisation - Google Patents

Formulations de cinnamaldéhyde et de disulfure de diallyle et procédés d'utilisation Download PDF

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Publication number
WO2014047021A1
WO2014047021A1 PCT/US2013/060037 US2013060037W WO2014047021A1 WO 2014047021 A1 WO2014047021 A1 WO 2014047021A1 US 2013060037 W US2013060037 W US 2013060037W WO 2014047021 A1 WO2014047021 A1 WO 2014047021A1
Authority
WO
WIPO (PCT)
Prior art keywords
formulation
cinnamaldehyde
emulsion
diallyl disulfide
disulfide
Prior art date
Application number
PCT/US2013/060037
Other languages
English (en)
Inventor
Benjamin A. Belkind
Bassam Shammo
Rebecca Dickenson
Linda A. Rehberger
Daniel F. Heiman
Original Assignee
Valent Biosciences 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
Priority claimed from US13/624,315 external-priority patent/US8808762B2/en
Application filed by Valent Biosciences Corporation filed Critical Valent Biosciences Corporation
Publication of WO2014047021A1 publication Critical patent/WO2014047021A1/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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom not containing sulfur-to-oxygen bonds, e.g. polysulfides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/11—Aldehydes

Definitions

  • the present invention relates to stable emulsions containing cinnamaldehyde and diallyl disulfide.
  • the stable emulsions utilize Emulsogen ® EH and S rfonic ® CO 36 to form .a superior emulsion stability system.
  • Emulsions generally refer to heterogeneous systems that comprise two immiscible liquids.
  • emulsions provide formulation vehicles fo deliver)' of herbicides, insecticides, fungicides, bactericides, and fertilizers,
  • Emulsions are inherently unstable, meaning that once they are formed, the immiscible liquids tend to revert or separate.
  • Emulsifying agents such as surface- active agents, can be used to increase the stability of the emulsions.
  • stable or “stability” means that the droplet particles of one liquid are uniformly distributed into another liquid and that this status is maintained for a desirable amount of time.
  • Emulsions are especially useful in the field of agriculture wherein numerous lipophilic active ingredients must be dissolved and suspended into water prior to application to the plants.
  • An oil-in- water emulsion (O/W emulsion) is an emulsion wherein liquid oil droplets are finely dispersed in water. Preparing stable O/W emulsions in very difficult and frequently involves extensive experimentation to determine formulations that provide stable concentrated products for end-use diluted emulsions.
  • the emulsion system plays an essential role in providing stable emulsions, but identification of a proper system is complex and not easy to identify because of the required optimization of many different formulation characteristics, such as interfacial tension, viscosity, relative density, and temperature.
  • Calsogen ⁇ EH (available from Clariant) is an emulsifier, specifically, an iso-Cl ' 2 alkyl benzene sulphonate calcium salt.
  • Surfonic ® CO 36 (available from Huntsman., Inc.) is a surfactant and it contains poiyglycol esters of castor oil.
  • Cinnamaldehyde is a naturally occurring organic compound that can be derived from the bark of trees of the genus Cinnamomu . Cinnamaldehyde is a viscous oil that has low solubility in water. Cinnamaldehyde does not present any known risk to humans or the environment and is considered to have a minimal safety risk. For this reason, it is not regulated by the Environmental Protection Agency ("EPA") because it is exempt from the Federal Insecticide, Fungicide, and Rodenticide Act (“FiFRA"). See 40 C.F.R. 152.25(f).
  • EPA Environmental Protection Agency
  • Cinnamaldehyde is known to have pesticidal activity.
  • cinnamaldehyde- is effective against nematodes. See, for example, U.S. Patent No. 6,251,951 Bl.
  • Diallyl. disulfide (4,5-dithia- 1 ,7-octadiene) is a naturally occurring organosulfi.tr compound that can be derived from garlic and plants of the genus Allium, Diallyl disulfide is an oil that has low solubility in water. Diallyl disulfide does not present any known risk to humans or the environment and is considered to have a minimal safety risk. For this reason, it is not regulated by the Environmental Protection Agency ("EPA") because it is exempt from the Federal Insecticide, Fungicide, and Rodenticide Act (“FIFRA"). See 40 C.F.R. ⁇ 152.25(f).
  • EPA Environmental Protection Agency
  • an. emulsion system comprising Emulsogen ® EH and Sulfonic ® CO 36 provided excellent emulsion stability for cinnamaldehyde and diallyl disulfide formulations.
  • the invention is directed to improved and stable formulations containing cinnamaldehyde and diallyl disulfide with the emulsion system of Emulsogen ® EH and Surfonie ® CO 36.
  • the invention is directed to a specific agricultural formulation comprising about 61.0 % cinnamaldehyde about 6.0 to about 8,5 % diallyl disulfide, from about 13.0 to about 15.5 % soybean oil, about 7.0 % Calsogen ® EH, and about 10.5 % Surfonie ® CO 36.
  • the invention is directed to methods for suppressing plant damage by plant pathogens comprising applying the formulations of the invention to the locus, soii or seeds of plants in need of said treatment.
  • the invention is directed to agricultural formulations comprising a synergistic amount of cinnamaldehyde and diallyl disulfide.
  • the invention is an agricultural formulation comprising cinnamaldehyde, diallyl disulfide, Surfonic ® CO 36, and an iso-C12 aikylbenzene sulphonate calcium salt,
  • the iso-C12 alkyl benzene sulphonate calcium salt is Calsogen ® EH.
  • the formulation may contain from about 5 to about 9 % by weight of the iso-C12 alkyl benzene sulphonate calcium salt or Calsogen ® EH, preferably from, about. 6.0 to about 8.(3 %, and most preferably about 7.0 % of the iso-C12 alkyl benzene sulphonate calcium salt or Calsogen ® EH.
  • the formulation may contain a lipophilic solvent.
  • the lipophilic solvent is soybean oil.
  • the formulation may contain from about. 10.0 to about 2.0.0 % by weight, preferably from about 12.0 to 16.0 %, and most preferably from about 13.0 to about 15.5 % of the lipophilic solvent or soybea oil.
  • the formulation may contain from about 50 to about 70 % by weight of cinnamaldehyde. preferably from about 58 to about 63 % of cinnamaldehyde, and most preferably about 61 % ⁇ cinnamaldehyde.
  • the formulation may contain from about 5 to about 10 % by weight of diallyl disulfide, preferably from about 5.5 to about 9.0 3 ⁇ 4, and most preferably about from about 6.0 to about 8.5 % of diallyl disulfide.
  • the formulation may contain from about 8 to about 12 % of Surfonic ® CO 36 by weight in one embodiment.
  • the formulation contains from about 9.0 to about 11.0 % of Surfonic ® CO 36, and more preferably, about 10.5 % of Surfonic ® CO 36.
  • the invention is directed to an agricultural formulation comprising: from about 59.5 to about 61.5 % cinnamaldehyde; from about 6.0 to about 8.5 % diallyl disulfide; from about 1.3.0 to about 15.5 % soybean oil; about 7.0 % Calsogen ® EH; and about 10,5 % Surfonic CO 36.
  • the formulation contains about 61.0 % cinnamaldehyde.
  • An alternative embodiment is directed to methods for suppressing plant damage by plant pathogens comprising applying the formulation of the present invention to the locus, soil or seeds of plants in need of said treatment, in a preferred embodiment, the plant pathogens are nematodes.
  • the emulsifying system utilized in formulations of the present invention is a unique eombination of two emulsifiers, Caisogen ® EH and Surfonic ® CO 36.
  • This system can be used in the formulation with a total % weight from about 10 to about 30 % of the formulation, preferably from about 15 to about 19 % of the formulation, and most preferably at about 17.5 % of the formulation.
  • formulations of the present invention may contain lipophilic solvents.
  • the preferred solvent is soybean oil, however, other solvents may be used as long as the solvents are "environmentally safe,” meaning that they are exempt from volatile organic compound ("VOC") regulation by the EPA.
  • VOC volatile organic compound
  • the following solvents may be used: methyl oleate, ethyl lactate, and .methyl soyate.
  • the agricultural formulations of the present, invention explicitly exclude organic solvents which are considered to have unsatisfactory VOC levels as defined by California Environmental Protection Agency.
  • the agricultural formulations of the present invention explicitly exclude ingredients which are. considered by the state of California to cause cancer or reproductive toxicity under the The Safe Drinking Water and Toxic Enforcement Act of 1986 (see Health and Safety Code Section 25249.8(b)).
  • Formulations of the present invention contain an iso-C ' 12 alkyl benzene sulfonate calcium salt.
  • Caisogen ® EH is preferred.
  • other iso-C 12 alkyl benzene sulfonate calcium salts known by those of skill in the art may be used, in formulations of the invention, such as Phenylsulfonat CA or Phenylsulfonat CA 62 (both available from Clariant).
  • a cinnamaldehyde and diallyl disulfide emulsion concentrate was prepared. The following components, in the amounts indicated below (in weight % of the component/total weight % of the formulation), were added in the order listed. The formulation was then mixed well with a magnetic stirrer until a homogeneous emulsion was formed.
  • diallyl disulfide added will vary depending upon the purity of the technical grade diallyl disulfide. Soybean oil may be used in varying amounts to accommodate the strength of the technical grade diallyl disulfide.
  • Example 1 The Formulation of Example 1 was compared with 16 other formulations containing the same amount of cinnamaldehyde, diallyl disulfide, and solvent but with different emulsifying systems.
  • the 16 comparative emulsion concentrate formulations were prepared in a manner similai- to the manner in which the Formulation of Example 1 was prepared as described above.
  • Example 1 had superior stability, even after 24 hours.
  • the Formulation of Example 1 quickly produced an emulsion.
  • the Formulation of Example 1 remained uniform, and thick without separating. All of the other emulsion systems failed to produce satisfactory results. Achieving excellent stability after 24 hours is extremely rare in emulsion concentrate dilutions.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Agronomy & Crop Science (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne des concentrés agricoles en émulsion formant des émulsions huile dans l'eau stables lors de leur dilution dans l'eau. En particulier, l'invention concerne des émulsions huile dans l'eau stables contenant du cinnamaldéhyde et du disulfure de diallyle avec un système d'émulsion Calsogen® BH et Surfonic® CO 36. La stabilité accrue de l'émulsion permet de mélanger efficacement les ingrédients de l'émulsion et de stocker et d'appliquer efficacement le cinnamaldéhyde et le disulfure de diallyle sur des zones devant être protégées ou traitées contre les nématodes.
PCT/US2013/060037 2012-09-21 2013-09-17 Formulations de cinnamaldéhyde et de disulfure de diallyle et procédés d'utilisation WO2014047021A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/624,315 US8808762B2 (en) 2008-10-17 2012-09-21 Cinnamaldehyde and diallyl disulfide formulations and methods of use
US13/624,315 2012-09-21

Publications (1)

Publication Number Publication Date
WO2014047021A1 true WO2014047021A1 (fr) 2014-03-27

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Family Applications (1)

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PCT/US2013/060037 WO2014047021A1 (fr) 2012-09-21 2013-09-17 Formulations de cinnamaldéhyde et de disulfure de diallyle et procédés d'utilisation

Country Status (2)

Country Link
AR (1) AR092639A1 (fr)
WO (1) WO2014047021A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022064434A1 (fr) * 2020-09-24 2022-03-31 Upl Limited Composition fongicide

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999056544A1 (fr) * 1998-05-01 1999-11-11 Summus Group, Ltd. Compositions herbicides
US6348434B1 (en) * 1999-07-01 2002-02-19 Basf Aktiengesellschaft Herbicidal emulsifiable concentrate
US20080193387A1 (en) * 2007-02-14 2008-08-14 Ricki De Wolff Essential oil compositions for killing or repelling ectoparasites and pests and methods for use thereof
US20100098787A1 (en) * 2008-10-17 2010-04-22 Belkind Benjamin A Compositions Comprising Cinnamon Oil (and/or its Component Cinnamaldehyde) and Diallyl Disulfide, Their Formulations, and Methods of Use
WO2012123408A1 (fr) * 2011-03-14 2012-09-20 Bayer Cropscience Ag Préparations herbicides liquides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999056544A1 (fr) * 1998-05-01 1999-11-11 Summus Group, Ltd. Compositions herbicides
US6348434B1 (en) * 1999-07-01 2002-02-19 Basf Aktiengesellschaft Herbicidal emulsifiable concentrate
US20080193387A1 (en) * 2007-02-14 2008-08-14 Ricki De Wolff Essential oil compositions for killing or repelling ectoparasites and pests and methods for use thereof
US20100098787A1 (en) * 2008-10-17 2010-04-22 Belkind Benjamin A Compositions Comprising Cinnamon Oil (and/or its Component Cinnamaldehyde) and Diallyl Disulfide, Their Formulations, and Methods of Use
WO2012123408A1 (fr) * 2011-03-14 2012-09-20 Bayer Cropscience Ag Préparations herbicides liquides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022064434A1 (fr) * 2020-09-24 2022-03-31 Upl Limited Composition fongicide

Also Published As

Publication number Publication date
AR092639A1 (es) 2015-04-29

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