WO2015006667A1 - Procédés et compositions de formulations de type granulés - Google Patents

Procédés et compositions de formulations de type granulés Download PDF

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Publication number
WO2015006667A1
WO2015006667A1 PCT/US2014/046308 US2014046308W WO2015006667A1 WO 2015006667 A1 WO2015006667 A1 WO 2015006667A1 US 2014046308 W US2014046308 W US 2014046308W WO 2015006667 A1 WO2015006667 A1 WO 2015006667A1
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WIPO (PCT)
Prior art keywords
granule formulation
mcp
granule
plant
group
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PCT/US2014/046308
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English (en)
Inventor
Christian Guy BECKER
Bridget Marie Stevens
Original Assignee
Agrofresh Inc.
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 to CA2917341A priority Critical patent/CA2917341A1/fr
Priority to EP14823639.1A priority patent/EP3019007A4/fr
Priority to SG11201510772UA priority patent/SG11201510772UA/en
Priority to JP2016525799A priority patent/JP6469672B2/ja
Priority to MX2016000388A priority patent/MX2016000388A/es
Priority to AU2014287025A priority patent/AU2014287025B2/en
Application filed by Agrofresh Inc. filed Critical Agrofresh Inc.
Priority to CN201480038766.7A priority patent/CN105377032B/zh
Priority to RU2016104395A priority patent/RU2016104395A/ru
Priority to KR1020167003038A priority patent/KR20160030538A/ko
Publication of WO2015006667A1 publication Critical patent/WO2015006667A1/fr
Priority to IL243331A priority patent/IL243331B/en
Priority to PH12016500053A priority patent/PH12016500053A1/en

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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
    • A01N25/12—Powders or granules
    • 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
    • A01N25/08—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 solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • 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
    • A01N27/00—Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/04—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a three-membered ring

Definitions

  • Rice is the seed of the monocot plants of the genus Oryza.
  • the term "rice” herein is used to mean either the rice seed that is harvested or the rice plant on which the seed grows or will grow.
  • Two major rice species under cultivation include Oryza sativa L. and Oryza glaberrima Steud.
  • Rice is an important crop plant. It is desired to provide a method of using cyclopropene compound that enhances the growth of rice and/or other plants while avoiding one or more of the drawbacks discussed above.
  • This invention is related to granule formulations of molecular complexes comprising a volatile compound, where no adjuvant/binder is required in such granule formulations.
  • methods of treating plant or plant parts using compositions disclosed herein are also provided.
  • a granule formulation comprising (a) a molecular complex of a volatile compound and a molecular encapsulating agent; and (b) a carrier component having moisture content between 5% and 35%.
  • the moisture content is between 7% and 15%; or between 8% and 12%. In another embodiment, the moisture content is at least 10%. In another embodiment, the moisture content is about 10%.
  • the carrier component comprises clay.
  • the carrier component comprises bentonite, limestone, or combinations thereof.
  • the carrier component comprises sodium bentonite clay.
  • the granule formulation does not comprise a binder component.
  • chemical stability of the molecular complex is improved as compared to a control formulation without the carrier component having moisture content between 5% and 35%.
  • the chemical stability of the molecular complex is improved at least two folds.
  • the chemical stability of the molecular complex is improved between two folds and five folds.
  • the chemical stability of the molecular complex is improved at room temperature, at 54 °C, or both.
  • the volatile compound comprises a cyclopropene compound of the formula:
  • R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl,
  • R is C 1-8 alkyl. In another embodiment, R is methyl.
  • the volatile compound comprises a cyclopropene compound of the formula:
  • R is a substituted or unsubstituted C1-C4 alkyl, C 1 -C 4 alkenyl, C 1 -C 4 alkynyl, C1-C4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R 2 , R 3 , and R 4 are hydrogen.
  • the cyclopropene compound comprises 1 -methylcyclopropene (1-MCP).
  • the granule formulation comprises between 0.1% and 10%; between 0.3% and 3%; or between 0.5% and 1.5% of the 1-MCP.
  • the molecular encapsulating agent is selected from the group consisting of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or combinations thereof. In another embodiment, the molecular encapsulating agent comprises alpha-cyclodextrin.
  • a method for stabilizing a molecular complex of a volatile compound and a molecular encapsulating agent comprising preparing a granule formulation using a carrier component having moisture content between 5% and 35%.
  • the moisture content is between 7% and 15%; or between 8% and 12%. In another embodiment, the moisture content is at least 10%. In another embodiment, the moisture content is about 10%.
  • the carrier component comprises clay.
  • the carrier component comprises bentonite, limestone, or combinations thereof.
  • the carrier component comprises sodium bentonite clay.
  • the granule formulation does not comprise a binder component.
  • chemical stability of the molecular complex is improved as compared to a control formulation without the carrier component having moisture content between 5% and 35%.
  • the chemical stability of the molecular complex is improved at least two folds.
  • the chemical stability of the molecular complex is improved between two folds and five folds.
  • the chemical stability of the molecular complex is improved at room temperature, at 54 °C, or both.
  • the volatile compound comprises a cyclopropene compound of the formula:
  • R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl,
  • R is C 1-8 alkyl. In another embodiment, R is methyl.
  • the volatile compound comprises a cyclopropene compound of the formula:
  • R is a substituted or unsubstituted C 1 -C 4 alkyl, C1-C4 alkenyl, C 1 -C 4 alkynyl, C1-C4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R 2 , R 3 , and R 4 are hydrogen.
  • the cyclopropene compound comprises 1 -methylcyclopropene (1-MCP).
  • the granule formulation comprises between 0.1% and 10%; between 0.3% and 3%; or between 0.5% and 1.5% of the 1-MCP.
  • the molecular encapsulating agent is selected from the group consisting of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or combinations thereof. In another embodiment, the molecular encapsulating agent comprises alpha-cyclodextrin.
  • a method for preparing the granule formulation provided herein comprises using a roller compaction process with a carrier component having moisture content between 5% and 35%.
  • no binder is used in the roller compaction process.
  • no molecular sieve is used in the roller compaction process.
  • a method of yield increase and/or yield protection of a crop plant comprising applying the granule formulation provided herein to a field cultivating the crop plant, wherein the crop plant is in a reproductive or ripening stage.
  • the crop plant is selected from the group consisting of rice plant, maize plant, wheat plant, soybean plant, canola plant, and cotton plant.
  • the granular formulation comprises 1 -methylcyclopropene (1-MCP).
  • the application rate of 1-MCP is between 10 g active ingredient (a.i.)/hectare and 100 g a.i./hectare; between 20 g a.i./hectare and 70 g a.i./hectare; or between 40 g a.i./hectare and 60 g a.i./hectare. In another embodiment, the application rate of 1-MCP is about 50 g a.i./hectare.
  • Figure 1 shows a representative roller compaction process used for the granule formulations provided herein.
  • Figure 2 shows representative results for moisture influence on degradation (curve average) at 54 °C.
  • Figures 3 shows representative results for binder influence on degradation (curve average).
  • Figure 4 shows representative 1-MCP release rate from formulations containing bentonite. Samples L, M, and N contain 0.1 % I-MCP, and Samples O and P contain 0.5% 1- MCP.
  • Figure 5 shows representative correlation between the dissolution rate of granules immersed in water, and 1-MCP %
  • Figure 6 shows representative data from headspace from 0.5% 1-MCP in sodium bentonite granules.
  • This invention is based on surprising results that no adjuvant/binder is required for granule formulations of molecular complexes comprising a volatile compound.
  • surprising that use of molecular sieve destabilizes the granule formulations provided herein, thus no molecular sieve is required.
  • Provided are methods for preparing granule formulations of a molecular complex comprising a volatile compound, and compositions comprising such granule formulations. Also provided are methods of treating plant or plant parts using compositions disclosed herein.
  • a solid particle is characterized by its particle diameter. If the particle is not spherical, its particle diameter is taken herein to be the diameter of a sphere that has the same volume as the particle.
  • Compaction is a size enlargement process that presses powdery material into sheets with or without the use of a binder. The bonding of the material is ensured by the mechanical pressure exerted on the product by the compacting equipment. The sheets are then crushed and screened to produce a granule form of the desired sized product.
  • the compaction / granulation process allows agglomeration of a wider range of materials than other processes and provides a specified and constant product size range.
  • Capacities of compaction / granulation units typically range from 50 Kg/h to 100 T/h.
  • Roll compaction is a dry granulation method, where many factors need to be considered, controlled and optimized; for example, selection of the carrier and binder, roll pressure, roll speed and the feeding rate of starting materials. These factors determine the product properties (e.g., ribbons formation), as well as the final granule properties. Important product qualities such as the density of ribbons, flowability, compressibility of granules, as well as the strength of the finished granules, are highly dependent on the parameters mentioned above.
  • moiety refers to a specific segment or functional group of a molecule. Chemical moieties are often recognized chemical entities embedded in or appended to a molecule.
  • alkyl refers to an unsubstituted or substituted, hydrocarbon group and can include straight, branched, cyclic, saturated and/or unsaturated features.
  • the alkyl moiety may be an "unsaturated alkyl” moiety, which means that it contains at least one alkene or alkyne moiety, typically, the alkyl moiety is a "saturated alkyl” group, which means that it does not contain any alkene or alkyne moieties.
  • the alkyl moiety may be a cyclic, typically the alkyl moiety is a non-cyclic group.
  • alkyl refers to an optionally substituted straight-chain, or optionally substituted branched-chain saturated hydrocarbon monoradical having from about one to about thirty carbon atoms in some embodiments, from about one to about fifteen carbon atoms in some embodiments, and from about one to about six carbon atoms in further embodiments.
  • saturated alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, 2-methyl-l -propyl, 2-methyl-2-propyl, 2-methyl-l -butyl, 3- methyl- 1 -butyl, 2-methyl-3 -butyl, 2,2-dimethyl-l -propyl, 2-methyl-l -pentyl, 3-methyl-l- pentyl, 4-methyl-l -pentyl, 2-methyl-2-pentyl, 3 -methy 1-2 -pentyl, 4-methyl-2-pentyl, 2,2- dimethyl-l -butyl, 3, 3 -dimethyl- 1 -butyl, 2-ethyl-l -butyl, butyl, isobutyl, sec-butyl, t-butyl, n- pentyl, isopentyl, neopentyl, and n-hex
  • a numerical range such as “1 to 6” refers to each integer in the given range; e.g., “1 to 6 carbon atoms” or “CW or “Ci-Ce” means that the alkyl group may consist of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, and/or 6 carbon atoms, although the present definition also covers the occurrence of the term "alkyl” where no numerical range is designated.
  • substituted alkyl refers to an alkyl group, as defined herein, in which one or more (up to about five, preferably up to about three) hydrogen atoms is replaced by a substituent independently selected from the substituent group defined herein.
  • substituted refers to groups which may be used to replace another group on a molecule.
  • alkoxy refers to the group -O-alkyl, where alkyl is as defined herein.
  • alkoxy groups include, e.g., methoxy, ethoxy, n- propoxy, iso-propoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, n-hexoxy, 1,2- dimethylbutoxy, and the like.
  • the alkoxy can be unsubstituted or substituted.
  • cyclic and “membered ring” refer to any cyclic structure, including alicyclic, heterocyclic, aromatic, heteroaromatic and polycyclic fused or non- fused ring systems as described herein.
  • the term “membered” is meant to denote the number of skeletal atoms that constitute the ring.
  • pyridine, pyran, and pyrimidine are six-membered rings and pyrrole, tetrahydrofuran, and thiophene are five- membered rings.
  • aromatic refers to a cyclic or polycyclic moiety having a conjugated unsaturated (4 ⁇ +2) ⁇ electron system (where n is a positive integer), sometimes referred to as a delocalized ⁇ electron system.
  • aryl refers to an optionally substituted, aromatic, cyclic, hydrocarbon monoradical of from six to about twenty ring atoms, preferably from six to about ten carbon atoms and includes fused (or condensed) and non-fused aromatic rings.
  • a fused aromatic ring radical contains from two to four fused rings where the ring of attachment is an aromatic ring, and the other individual rings within the fused ring may be cycloalkyl, cycloalkenyl, cycloalkynyl, heterocycloalkyl, heterocycloalkenyl,
  • heterocycloalkynyl aromatic, heteroaromatic or any combination thereof.
  • a non-limiting example of a single ring aryl group includes phenyl; a fused ring aryl group includes naphthyl, anthryl, azulenyl; and a non-fused bi-aryl group includes biphenyl.
  • substituted aryl refers to an aryl group, as defined herein, in which one or more (up to about five, preferably up to about three) hydrogen atoms is replaced by a substituent independently selected from the group defined herein, (except as otherwise constrained by the definition for the aryl substituent).
  • heteroaryl refers to an optionally substituted, aromatic, cyclic monoradical containing from about five to about twenty skeletal ring atoms, preferably from five to about ten ring atoms and includes fused (or condensed) and non-fused aromatic rings, and which have one or more (one to ten, preferably about one to about four) ring atoms selected from an atom other than carbon (i.e., a heteroatom) such as, for example, oxygen, nitrogen, sulfur, selenium, phosphorus or combinations thereof.
  • heteroaryl includes optionally substituted fused and non-fused heteroaryl radicals having at least one heteroatom.
  • a fused heteroaryl radical may contain from two to four fused rings where the ring of attachment is a heteroaromatic ring and the other individual rings within the fused ring system may be alicyclic, heterocyclic, aromatic, heteroaromatic or any combination thereof.
  • heteroaryl also includes fused and non-fused heteroaryls having from five to about twelve skeletal ring atoms, as well as those having from five to about ten skeletal ring atoms.
  • heteroaryl groups include, but are not limited to, acridinyl, benzo[l,3]dioxole, benzimidazolyl, benzindazolyl, benzoisooxazolyl, benzokisazolyl, benzofuranyl, benzofurazanyl, benzopyranyl, benzothiadiazolyl, benzothiazolyl,
  • substituted heteroaryl refers to a heteroaryl group, as defined herein, in which one or more (up to about five, preferably up to about three) hydrogen atoms is replaced by a substituent independently selected from the group defined herein.
  • leaving group refers to a group with the meaning conventionally associated with it in synthetic organic chemistry, i.e., an atom or group displaceable under substitution reaction conditions.
  • leaving groups include, but are not limited to, halogen, alkane- or arylenesulfonyloxy, such as methanesulfonyloxy, ethanesulfonyloxy, thiomethyl, benzenesulfonyloxy, tosyloxy, and thienyloxy,
  • a leaving group can be HC(0)-COOH or RC(0)-COOH, wherein R is a C ⁇ -Ce alkyl or substituted C1-C6 alkyl.
  • the compounds of the invention as described herein may be synthesized using standard synthetic techniques known to those of skill in the art or using methods known in the art in combination with methods described herein.
  • the starting materials used for the synthesis of the compounds of the invention as described herein can be obtained from commercial sources, such as Aldrich Chemical Co. (Milwaukee, Wis.), Sigma Chemical Co. (St. Louis, Mo.), or the starting materials can be synthesized.
  • the compounds described herein, and other related compounds having different substituents can be synthesized using techniques and materials known to those of skill in the art, such as described, for example, in March, Advanced Organic Chemistry 4 th Ed.
  • cyclopropene compound is any compound with the formula
  • Each L is a bivalent radical. Suitable L groups include, for example, radicals containing one or more atoms selected from H, B, C, N, O, P, S, Si, or mixtures thereof. The atoms within an L group may be connected to each other by single bonds, double bonds, triple bonds, or mixtures thereof. Each L group may be linear, branched, cyclic, or a combination thereof. In any one R group (i.e., any one of R 1 , R 2 , R 3 and R 4 ) the total number of heteroatoms (i.e., atoms that are neither H nor C) is from 0 to 6.
  • each Z is a monovalent radical.
  • Each Z is independently selected from the group consisting of hydrogen, halo, cyano, nitro, nitroso, azido, chlorate, bromate, iodate, isocyanato, isocyanido, isothiocyanato, pentafluorothio, and a chemical group G, wherein G is a 3 to 14 membered ring system.
  • the R 1 , R 2 , R 3 , and R 4 groups are independently selected from the suitable groups.
  • the groups that are suitable for use as one or more of R 1 , R 2 , R 3 , and R 4 are, for example, aliphatic groups, aliphatic-oxy groups, alkylphosphonato groups, cycloaliphatic groups, cycloalkylsulfonyl groups, cycloalkylamino groups, heterocyclic groups, aryl groups, heteroaryl groups, halogens, silyl groups, other groups, and mixtures and combinations thereof.
  • Groups that are suitable for use as one or more of R 1 , R 2 , R 3 , and R 4 may be substituted or unsubstituted.
  • R 1 , R 2 , R 3 , and R 4 groups are, for example, aliphatic groups.
  • suitable aliphatic groups include, for example, alkyl, alkenyl, and alkynyl groups.
  • Suitable aliphatic groups may be linear, branched, cyclic, or a combination thereof.
  • suitable aliphatic groups may be substituted or unsubstituted.
  • a chemical group of interest is said to be "substituted” if one or more hydrogen atoms of the chemical group of interest is replaced by a substituent.
  • R 1 , R 2 , R 3 , and R 4 groups are, for example, substituted and unsubstituted heterocyclyl groups that are connected to the cyclopropene compound through an intervening oxy group, amino group, carbonyl group, or sulfonyl group; examples of such R 1 , R 2 , R 3 , and R 4 groups are heterocyclyloxy, heterocyclylcarbonyl,
  • R 1 , R 2 , R 3 , and R 4 groups are, for example, substituted and unsubstituted heterocyclic groups that are connected to the cyclopropene compound through an intervening oxy group, amino group, carbonyl group, sulfonyl group, thioalkyl group, or aminosulfonyl group; examples of such R 1 , R 2 , R 3 , and R 4 groups are
  • R 1 , R 2 , R 3 , and R 4 groups are, for example, hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, nitroso, azido, chlorato, bromato, iodato, isocyanato, isocyanido, isothiocyanato, pentafluorothio; acetoxy, carboethoxy, cyanato, nitrato, nitrito, perchlorato, allenyl, butylmercapto, diethylphosphonato, dimethylphenylsilyl, isoquinolyl, mercapto, naphthyl, phenoxy, phenyl, piperidino, pyridyl, quinolyl, triethylsilyl, trimethylsilyl; and substituted analogs thereof.
  • the chemical group G is a 3 to 14 membered ring system.
  • Ring systems suitable as chemical group G may be substituted or unsubstituted; they may be aromatic (including, for example, phenyl and napthyl) or aliphatic (including unsaturated aliphatic, partially saturated aliphatic, or saturated aliphatic); and they may be carbocyclic or heterocyclic.
  • heterocyclic G groups some suitable heteroatoms are, for example, nitrogen, sulfur, oxygen, and combinations thereof.
  • Ring systems suitable as chemical group G may be monocyclic, bicyclic, tricyclic, polycyclic, spiro, or fused; among suitable chemical group G ring systems that are bicyclic, tricyclic, or fused, the various rings in a single chemical group G may be all the same type or may be of two or more types (for example, an aromatic ring may be fused with an aliphatic ring).
  • one or more of R 1 , R 2 , R 3 , and R 4 is hydro gen or (Ci-Cio) alkyl.
  • each of R 1 , R 2 , R 3 , and R 4 is hydrogen or (Ci-Cs) alkyl.
  • each of R 1 , R 2 , R 3 , and R 4 is hydrogen or (C1-C4) alkyl.
  • each of R 1 , R 2 , R 3 , and R 4 is hydrogen or methyl.
  • R 1 is (C1-C4) alkyl and each of R 2 , R 3 , and R 4 is hydrogen.
  • R 1 is methyl and each of R 2 , R 3 , and R 4 is hydrogen, and the cyclopropene compound is known herein as 1-methylcyclopropene or "1-MCP.”
  • the cyclopropene compound is of the formula:
  • R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl,
  • R is C 1-8 alkyl. In another embodiment, R is methyl.
  • the cyclopropene compound is of the formula:
  • R 1 is a substituted or unsubstituted C1-C4 alkyl, C 1 -C 4 alkenyl, C 1 -C 4 alkynyl, C1-C4 cylcoalkyl, cylcoalkylalkyl, phenyl, or napthyl group; and R 2 , R 3 , and R 4 are hydrogen.
  • the cyclopropene comprises 1 -methylcyclopropene (1-MCP).
  • a cyclopropene compound that has boiling point at one atmosphere pressure of 50° C. or lower; more preferred 25° C. or lower; more preferred 15° C. or lower.
  • a cyclopropene compound is used that has boiling point at one atmosphere pressure of -100° C. or higher; more preferred -50° C. or higher; more preferred -25° C. or higher; more preferred 0° C. or higher
  • the composition of the present invention includes at least one molecular encapsulating agent that encapsulates one or more cyclopropene compound or a portion of one or more cyclopropene compound.
  • a molecular complex that contains a cyclopropene compound molecule or a portion of a cyclopropene compound molecule encapsulated in a molecule of a molecular encapsulating agent is known herein as a "cyclopropene compound complex.”
  • At least one cyclopropene compound complex is present that is an inclusion complex.
  • an inclusion complex the molecular
  • encapsulating agent forms a cavity, and the cyclopropene compound or a portion of the cyclopropene compound is located within that cavity.
  • the interior of the cavity of the molecular encapsulating agent is substantially apolar or hydrophobic or both, and the cyclopropene compound (or the portion of the cyclopropene compound located within that cavity) is also substantially apolar or hydrophobic or both.
  • the present invention is not limited to any particular theory or mechanism, it is contemplated that, in such apolar cyclopropene compound complexes, van der Waals forces, or hydrophobic interactions, or both, cause the cyclopropene compound molecule or portion thereof to remain for substantial amounts of time within the cavity of the molecular encapsulating agent.
  • the amount of molecular encapsulating agent can usefully be characterized by the ratio of moles of molecular encapsulating agent to moles of cyclopropene compound.
  • the ratio of moles of molecular encapsulating agent to moles of cyclopropene compound is 0.1 or larger; more preferably 0.2 or larger; more preferably 0.5 or larger; more preferably 0.9 or larger.
  • the ratio of moles of molecular encapsulating agent to moles of cyclopropene compound is 10 or lower; more preferably 5 or lower; more preferably 2 or lower; more preferably 1.5 or lower.
  • Suitable molecular encapsulating agents include, for example, organic and inorganic molecular encapsulating agents. Preferred are organic molecular encapsulating agents, which include, for example, substituted cyclodextrins, unsubstituted cyclodextrins, and crown ethers. Suitable inorganic molecular encapsulating agents include, for example, zeolites. Mixtures of suitable molecular encapsulating agents are also suitable.
  • the encapsulating agent is alpha-cyclodextrin, beta-cyclodextrin, gamma- cyclodextrin, or a mixture thereof. In more preferred embodiments of the invention, alpha- cyclodextrin is used.
  • a granular composition is a composition that exists as solid particles under a pressure of 1 atmosphere and at all temperatures from 5° C. to 40° C.
  • a granular composition is a collection of solid particles in which 90% or more of the weight of the collection resides in particles that have particle diameter of 1 micrometer or larger and in which 90% or more of the weight of the collection resides in particles that have particle diameter of 5 centimeter or smaller.
  • Preferred are compositions in which 90% or more of the weight of the collection resides in particles that have particle diameter of 10 micrometer or larger.
  • compositions in which 90% or more of the weight of the collection resides in particles that have particle diameter of 1 centimeter or smaller.
  • a method of improving the cultivation of rice in a paddy comprising adding a granular composition to the water in said paddy, wherein said granular composition comprises one or more cyclopropene compound encapsulated in a molecular encapsulating agent.
  • Preferred granular compositions contain 0.02% or more of cyclopropene compound, by weight based on the weight of the granular composition. More preferred granular compositions contain cyclopropene compound in the amount, by weight based on the weight of the granular composition, of 0.05% or more; more preferred is 0.09% or more. Preferred granular compositions contain 5% or less of cyclopropene compound, by weight based on the weight of the granular composition. More preferred granular compositions contain cyclopropene compound in the amount, by weight based on the weight of the granular composition, of 5% or less; 3% or less; or 1% or less.
  • the particles of the granular composition may contain any material (called “inert” material) that allows the particle to remain solid and that will not inhibit the function of the cyclopropene compound.
  • Suitable materials for inclusion in the granular composition include, for example, sand (for example, feldspar sand), clay (for example, montmorillonite or attapulgite), coal dust, chipped brick, cellulosic fibers or other cellulosic materials, polymers, ground corn cobs, fertilizer, or mixtures thereof.
  • Particles of the granular composition may optionally be coated, for example with polymer, graphite, wax, or a combination thereof.
  • Rice is often grown in a paddy.
  • a paddy is a field that is flooded for some or all of the plant's growth cycle.
  • Rice may be planted in the paddy prior to flooding the paddy, and in some of such cases the rice may grow to become seedlings before the paddy is flooded.
  • the rice may be planted somewhere other than the paddy and then transplanted as seedlings into the paddy before the paddy is flooded.
  • seedlings are established in the non-flooded paddy (either by growth from seeds or by transplantation)
  • the paddy is then flooded. In many cases, the paddy remains flooded until shortly before harvest.
  • the paddy is drained for one or more short period during the growth cycle of the plants.
  • the depth of the water is preferably between 20 mm and 100 mm.
  • the paddy is flooded for more than half of the time from transplantation of seedlings until harvest.
  • the rice that is used in the practice of the present invention may be any species of the genus Oryza. Preferred is Oryza sativa L.
  • granular composition is added to the water of the paddy one or more times during the growth cycle of the plants.
  • the addition of the granular composition may be made during any time from transplantation of seedlings until harvest.
  • the growth stages of rice may be described by reference to the BBCH scale for rice (published by the Federal Biological Research Centre for Agriculture and Forestry, Berlin and Braunschweig, Germany), which may be viewed, for example, at world wide web .jki.bund.de/fileadmin/dam_uploads/_veroeff/bbch/BBCH-Skala_englisch.pdf.
  • the BBCH scale provides a code number for each step in the growth cycle of rice, from code 00 (dry seed [caryopsis]) to 99 (harvested product).
  • BBCH codes 30-32 Panicle Development
  • BBCH codes 40-45 Early Heading
  • BBCH codes 51-54 Post Anthesis
  • treatment provided is performed during boot.
  • treatment provided is perfromed during mid-boot (BBCH code 43).
  • the treatment may take place before, during, or after the exposure to high temperatures. It is preferred to treat rice prior to exposure to high temperature. This can be accomplished by identifying rice that is expected to be exposed to high temperature, either because it is being grown in a location that often experiences high temperature or because of a specific local weather forecast.
  • High night temperature occurs during a night in which the lowest temperature during that night is 23° C. or higher. It is preferred to treat rice that experiences one or more night during which the lowest temperature is 23° C. or higher; more preferred is to treat rice that experiences one or more night during which the lowest temperature is 25° C. or higher.
  • High day temperature occurs during a day in which the high temperature during that day is 32° C. or higher. It is preferred to treat rice that experiences one or more days during which the highest temperature exceeds 32° C. or higher; more preferred is to treat rice that experiences one or more days during which the highest temperature is 34° C. or higher.
  • One useful way to characterize the amount of cyclopropene compound that is used is to state the grams of cyclopropene compound (the active ingredient as “ai” or "a.L") that is applied per unit of area. This amount is reported as grams of ai per hectare (g ha).
  • Preferred embodiments employ cyclopropene compound at a rate of 1 g/ha or higher; more preferred is 2 g/ha or higher; more preferred is 5 g/ha or higher.
  • Preferred embodiments employ cyclopropene compound at a rate of 100 g/ha or lower; more preferred is 60 g/ha or lower; more preferred is 40 g/ha or lower.
  • Another characteristic of treatment methods may include the "distribution fraction" of application of granules.
  • Granules are considered to be distributed over the rice paddy randomly but consistently. That is, granules are considered to be distributed in a way that allows the randomness to be apparent if a small area (for example, 5 cm by 5 cm) is examined and that provides a consistent amount of cyclopropene compound to each large area (0.5 meter by 0.5 meter or larger).
  • Consistent amount is meant that over the entire rice paddy, if each square sized 0.5 meter by 0.5 meter were examined and the amount of cyclopropene compound were measured, the standard deviation of the distribution of those amounts would be 20% or less of the mean amount.
  • Distribution fraction is characterized by reference to application of standard granules.
  • standard granules have 0.1% cyclopropene compound by weight based on the total weight of the granules.
  • the density is said to be 100%.
  • a plot that is larger than 0.25 square meters may be divided into sub-plots that are each 0.5 meter by 0.5 meter.
  • varying the density could mimic the effect of using different-size granules or more concentrated granules.
  • transgene vector refers to a vector that contains an inserted segment of DNA, the "transgene” that is transcribed into mRNA or replicated as RNA within a host cell.
  • transgene refers not only to that portion of inserted DNA that is converted into RNA, but also those portions of the vector that are necessary for the transcription or replication of the RNA.
  • a transgene typically comprises a gene-of- interest but needs not necessarily comprise a polynucleotide sequence that contains an open reading frame capable of producing a protein.
  • Plants, or plant parts may be treated in the practice of the present invention.
  • One example is treatment of whole plants; another example is treatment of whole plants while they are planted in soil, prior to the harvesting of useful plant parts.
  • Any plants that provide useful plant parts may be treated in the practice of the present invention. Examples include plants that provide fruits, vegetables, and grains.
  • plant includes dicotyledons plants and
  • monocotyledons plants examples include tobacco, Arabidopsis, soybean, tomato, papaya, canola, sunflower, cotton, alfalfa, potato, grapevine, pigeon pea, pea, Brassica, chickpea, sugar beet, rapeseed, watermelon, melon, pepper, peanut, pumpkin, radish, spinach, squash, broccoli, cabbage, carrot, cauliflower, celery, Chinese cabbage, cucumber, eggplant, and lettuce.
  • monocotyledons plants include corn, rice, wheat, sugarcane, barley, rye, sorghum, orchids, bamboo, banana, cattails, lilies, oat, onion, millet, and triticale.
  • fruit examples include banana, pineapple, oranges, grapes, grapefruit, watermelon, melon, apples, peaches, pears, kiwifruit, mango, nectarines, guava, persimmon, avocado, lemon, fig, and berries.
  • Compaction is a multistep process in which a ribbon of compacted product is formed between wheels applying pressure on the powder to compact. The ribbon is then granulated and screened to the appropriate size.
  • the production of compacted product (for example fertilizers) is often completed by a finishing unit with polishing of granules for improved appearance, reduced amount of residual fines and easier storage.
  • a representative process provided herein is shown in Figure 1.
  • the fine created during the granulations are fully recycled in the system and re-mixed with the original powder blend. This recycling not only reduces waste but is an integral part of the process as it does enhance the compaction ability of the powder and create granules which have more strength.
  • suitable binders to increase granule integrity for the granule formulations disclosed. These suitable binders are selected based on having a low moisture content, and being chemically insert toward the active ingredient.
  • Corn Starch A dry powdery starch.
  • Lignosulfonate A dry powder sodium lignosulfonate from Borregaard
  • Potassium silicate Provided under the brand name KASIL ® SS. Powder
  • Potassium silicate is from PQ Corporation, Valley Forge, PA USA.
  • Carbowax ® 8000 Carbowax 8000 if powder polyethylene glycol with an average molecular weight of 8800. Water content is less than 0.1%. This product is from The Dow Chemical Company.
  • IGI wax 1236A is a fully refined paraffin wax with a typical melting point of 55.6°C and a specific gravity of 0.91 at 25°C. It is provided in granule form by International Group Inc. (IGI).
  • Polyset 2016A is a hard, micronized high melting point polyethylene. Softening point is around 117°C. This product was provided by International Group Inc. (IGI).
  • Feeco Clay The clay used by Feeco is unaltered Wyoming sodium bentonite clay. It is a product of Black Hills Bentonite, LLC located in WY. Moisture level is 10%. This is the clay we used in all our experiments so far. Unfortunately, we learned that this clay is not available in commercial quantities anymore.
  • Volclay powder is a naturally occurring sodium bentonite with an average particle size less than 200 mesh. Maximum moisture is 12% as shipped. This clay is from American Colloid Company, located in IL.
  • Best Bond and Probond 30 Both are activated sodium bentonite. Particle size 80% min passing 200 mesh. Moisture content is 14% maximum. They are products of Volclay Siam (Thailand), a wholly owned subsidiary of AMCOL International Company.
  • Pelbon is a high quality calcium bentonite supplied as a 150 mesh powder. Maximum moisture level is 15%. This clay is from American Colloid Company.
  • Gypsum FGD is a synthetic calcium sulfate (CAS0 4 .H 2 0) product derived from flue gas desulfurization (FGD) systems at electric power plants. This product is shipped wet. It is a product from Headwaters Resources located in West Chester, PA.
  • CaS0 4 .H 2 0 Calcium sulfate (Gypsum) can have different degrees of hydration. It is extensively used in dry walls and plaster. The anhydride is a strong desiccant.
  • KC1 Potassium chloride is also known as muriate of potash. It is a very common fertilizer. This potash with no iron addition is also called white potash.
  • K2SO4 Potassium sulfate is also known as sulfate of potash. The principal use of potassium sulfate is as a fertilizer. K2SO4 does not contain chloride, which can be harmful to some crops.
  • NaCl sodium chloride is the main component of sea salt and table salt.
  • B200 is an unmodified corn starch from yellow corn which has been dried on a belt dryer. It contains up to 1 1% moisture. This is a product from Grain Processing Company (GPC), located in Muscatine, IA.
  • GPC Grain Processing Company
  • Spress B820 Spress is a pre-gelatinized corn starch for direct compression tablets. Maximum moisture level is 14%. This is a product from GPC.
  • Pure-Dent B810 Pure-Dent is corn starch used as multifunctional excipient providing binding, carrying, lubricating and disintegrating properties for tablets. Maximum moisture level is 15%. This is a product from GPC.
  • Compaction Process is a size enlargement process that presses powdery material into sheets with or without the use of a binder. The bonding of the material is ensured by the mechanical pressure exerted on the product by the compacting equipment. The sheets are then crushed and screened to produce a granular form of the desired sized product.
  • the compaction / granulation process enables agglomeration of a wider range of materials than other processes (for example wet agglomeration ) and provides a specified and constant product size range.
  • Capacities of compaction / granulation units typically range from 50 Kg/h to 100 T/h. Advantages of compaction include reduced volume, stabilized mixtures during handling, elimination of dust problems, controlled hardness, recycle of fines, stability for moisture and/or heat-sensitive compounds.
  • Roll compaction is a dry granulation method with many factors to be considered, controlled and/or optimized; for example, selection of carrier, selection of dry binder, roll pressure, roll speed, and feeding rate of starting materials. These factors can determine various properties (e.g., ribbons formation, etc.) of the final granule products. Thus, important product qualities such as the density of ribbons, flowability, compressibility of granules, as well as the strength of the finished granules, are highly dependent on these factors.
  • Compaction is a multistep process in which a ribbon of compacted product is formed between wheels applying pressure on the powder to compact. The ribbon is then granulated and screened to the appropriate size. The production of compacted product is often completed by a finishing unit with polishing of granules for improved appearance, reduced amount of residual fines and easier storage.
  • a representative compaction process used is illustrated in Figure 1.
  • the entire fines created during the granulations can be recycled in the system and re-mixed with the original powder blend. This recycling not only reduces waste but is an integral part of the process as it does enhance the compaction ability of the powder and create granules which have more strength.
  • Raw material carriers are dried overnight in an oven in shallow pans.
  • Temperature in the compaction process used are between 40 °C and 150 °C; 60 °C and 120 °C; or 80 °C and 100 °C. Products obtained are screened to the correct size using regular sieve trays of different sizes. In some embodiment, chemical (inorganic) fertilizers can also be used as carriers.
  • Yx yield of the treated plot
  • Yu yield of the untreated plot.
  • DY of 10% means the treated plot has yield that is 10% higher than the untreated plot.
  • Negative Delta Yield means that the treated rice has lower yield than the untreated crop.
  • the granule formulations are increased in bulk by dilution with at least one inert carrier. Carriers are tested using a roller compactor in the presence of 0.1% 1-MCP equivalent of HAIP (High Active Ingredient Particles; a powder of 1-MCP complexed with alpha-cyclodextrin). The blend (before compaction) as well as both the 1 st pass and recycled materials are analyzed for chemical stability.
  • 1-MCP equivalent of HAIP High Active Ingredient Particles; a powder of 1-MCP complexed with alpha-cyclodextrin.
  • Limestone and bentonite appear to be the best carriers in term of chemical stability. However, an adjuvant may need to be added to these powders to increase the granule integrity with these carriers, which is currently poor to very poor.
  • results are unexpected and surprising where drying the clay does not increase stability because HAIP is known to be sensitive to water moisture.
  • the results show that compacted products containing clays with certain moisture contents are more stable than product containing dried clays.
  • Bentonite sodium clay can swell 8 to 10 times its weight when wetted.
  • the data suggest that the samples with more clay and less 1-MCP have a slower release rate.
  • HAIP is much quicker in contact with water and as the HAIP dissolves, more water penetrates inside the granule and in turn channels are created for the gas to escape.
  • Bentonite and limestone show the best overall chemical stability and granule strength. These granules show only minimal degradation when chemical stability is tested at 54 °C for two weeks or longer. Addition of molecular sieves to the formulation after compaction surprisingly does not help the chemical stability but unexpectedly is detrimental to the granular strength. Results are shown in Table 3.
  • Headspace analysis is performed by sampling granules into 250 ml narrow mouth bottles right after compression on the roller compactor. Bottles are approximately 1/3 filled with granules and capped with a gas tight lid having a sampling port. Samples are not re- opened once capped. The headspace analysis can be indicative to simulate how flammable the granule formulation can be after stored in an enclosure or enclosed space.
  • HAIP is sieved to remove lumps with a manual sifter. Sieve size is approximately 1 mm or 18 mesh. Sieved HAIP is then blended with Volclay (American Colloid Company, Illinois). A gentle mixing is performed in a half full glass jar rotated for 10 minutes on a Glas-Col tumbler (speed: 40% of full setting). Two concentrations of the blend are made: 0.5% 1-MCP and 1% 1-MCP. Samples prepared in this example are listed in Table 8.
  • Granule formulations of samples 7-3 and 7-4 are used to treat rice plants in open fields.
  • Typical amount of 1-MCP treated range from 10 g active ingredient (a.i.)/hectare (or 4 g a.i./acre) to 100 g a.i./hectare (or 40 g a.i./acre).
  • Optimum phonological stages of the rice plants range from maximum tillering through grain filling (for example at least one of:

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Abstract

Cette invention concerne des formulations de type granulés à base d'un complexe moléculaire comprenant un composé volatil, aucun adjuvant/liant n'étant requis dans lesdites formulations de type granulés. De plus, comme il s'est avéré de manière surprenante que l'utilisation de tamis moléculaires déstabilisait lesdits formulations de type granulés, aucun tamis moléculaire n'est requis. Cette invention concerne des procédés de préparation de formulations de type granulés à base d'un complexe moléculaire comprenant un composé volatil, et des compositions comprenant lesdites formulations de type granulés. De plus, des méthodes destinées à traiter des plantes ou des parties de plantes à l'aide des compositions ci-décrites sont en outre décrites.
PCT/US2014/046308 2013-07-11 2014-07-11 Procédés et compositions de formulations de type granulés WO2015006667A1 (fr)

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EP14823639.1A EP3019007A4 (fr) 2013-07-11 2014-07-11 Procédés et compositions de formulations de type granulés
SG11201510772UA SG11201510772UA (en) 2013-07-11 2014-07-11 Methods and compositions of granule formulations
JP2016525799A JP6469672B2 (ja) 2013-07-11 2014-07-11 粒剤の方法および組成物
MX2016000388A MX2016000388A (es) 2013-07-11 2014-07-11 Metodos y composiciones de formulaciones granuladas.
AU2014287025A AU2014287025B2 (en) 2013-07-11 2014-07-11 Methods and compositions of granule formulations
CA2917341A CA2917341A1 (fr) 2013-07-11 2014-07-11 Procedes et compositions de formulations de type granules
CN201480038766.7A CN105377032B (zh) 2013-07-11 2014-07-11 颗粒制剂的方法和组合物
RU2016104395A RU2016104395A (ru) 2013-07-11 2014-07-11 Способы получения и составы гранулированных препаратов
KR1020167003038A KR20160030538A (ko) 2013-07-11 2014-07-11 과립 제제화 방법 및 조성물
IL243331A IL243331B (en) 2013-07-11 2015-12-24 Methods and compositions of granular formulations
PH12016500053A PH12016500053A1 (en) 2013-07-11 2016-01-07 Method and compositions of granule formulations

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WO2009018069A2 (fr) * 2007-07-30 2009-02-05 Cydex Pharmaceuticals, Inc Mélanges de dérivés de cyclodextrine
WO2010000612A1 (fr) * 2008-07-01 2010-01-07 Syngenta Participations Ag Compositions fongicides
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US20060078733A1 (en) * 1999-09-17 2006-04-13 Jassan Genaro C Absorbent composition of matter for controlled release of essential oils
US20050164986A1 (en) * 2001-03-20 2005-07-28 Mosher Gerold L. Use of sulfoalkyl ether cyclodextrin as a preservative
WO2009018069A2 (fr) * 2007-07-30 2009-02-05 Cydex Pharmaceuticals, Inc Mélanges de dérivés de cyclodextrine
WO2010000612A1 (fr) * 2008-07-01 2010-01-07 Syngenta Participations Ag Compositions fongicides
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