ZA200806973B

ZA200806973B - Oil formulations

Info

Publication number: ZA200806973B
Application number: ZA200806973A
Authority: ZA
Inventors: Edward Charles Kostansek
Original assignee: Rohm & Haas
Priority date: 2008-08-13
Filing date: 2008-08-13
Publication date: 2010-03-31

Description

Le vo Io,

OIL FORMULATIONS | | | I

BACKGROUND:

For the use of cyclopropenes, the cyclopropene is often in the form of a complex with a molecular encapsulating agent. Such a complex is useful, for example, for use in treating plants or plant parts by contacting the plants or plant parts with the complex in order to bring about contact between the plants or plant parts and the cyclopropene. Such treatment of plants or plant parts is often effective at desirably interrupting one or more ethylene-mediated process in the plants or plant parts. For example, such treatment of plant parts can sometimes desirably delay unwanted ripening. For another example, such treatment of crop plants prior to harvest can sometimes improve the yield of the crop.

US 6,313,068 discloses grinding and milling of dried powder of a complex of cyclodextrin and methylcyclopropene.

It is often useful to dissolve or suspend particles of such a complex in a liquid.

However, if water is the liquid, it is sometimes found that contact between the water and the particles of the complex causes release of cyclopropene from the complex earlier than desired, and some or all of the cyclopropene is thus lost to the surroundings or destroyed by a chemical reaction or a combination thereof.

Therefore, it is often desirable to suspend such particles in oil. However, in the past, attempts to suspend such particles in oil have found that such particles could not be suspended effectively in oil, often because the suspensions could not be sprayed properly, or because the suspensions had too high viscosity at reasonable concentration of particles, or because the suspensions were not stable, or because the suspensions had some combination of these problems. The object of the present invention is to provide suspensions in oil of particles containing cyclopropene complex that solve one or more of these problems.

STATEMENT OF THE INVENTION:

In one aspect of the present invention, there is provided a composition comprising an oil medium, wherein particles are suspended in said oil medium, wherein said particles comprise cyclopropene and molecular encapsulating agent, and

SE 2 wherein said particles have median size, as measured by the largest dimension, of 50 micrometer or less.

DETAILED DESCRIPTION:

The practice of the present invention involves the use of one or more cyclopropene. As used herein, "a cyclopropene" is any compound with the formula

R? Rr

R' PS Rr? where each R', R?, R* and R* is independently selected from the group consisting of H and a chemical group of the formula: (LZ where n is an integer from 0 to 12. 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', R? R® and R*) the total number of heteroatoms (i.e., atoms that ~ are neither H nor C) is from 0 to 6. Independently, in any one R group the total number of non-hydrogen atoms is 50 or less. 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, 1sothiocyanato, pentafluorothio, and a chemical group G, wherein G is a 3 to 14 membered ring system.

The R',R% R?, and R* groups are independently selected from the suitable groups. The R', R% R? and R* groups may be the same as each other, or any number of them may be different from the others. Among the groups that are suitable for use as one or more of R', R%, R3, and R* are, for example, aliphatic groups, aliphatic-oxy groups, alkylphosphonato groups, cycloaliphatic groups, cycloalkylsulfonyl groups, cycloalkylamino groups, heterocyclic groups, aryl groups, heteroaryl groups, halogens,

oo | ; 3 silyl groups, other groups, and mixtures and combinations thereof. Groups that are suitable for use as one or more of R!, R?, R?, and R* may be substituted or unsubstituted. Independently, groups that are suitable for use as one or more of R',

R? R? and R* may be connected directly to the cyclopropene ring or may be connected to the cyclopropene ring through an intervening group such as, for example, a heteroatom-containing group.

Among the suitable R', R? R?, and R* groups are, for example, aliphatic groups. Some suitable aliphatic groups include, for example, alkyl, alkenyl, and alkynyl groups. Suitable aliphatic groups may be linear, branched, cyclic, or a combination thereof. Independently, suitable aliphatic groups may be substituted or unsubstituted.

As used herein, 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. It is contemplated that such substituted groups may be made by any method, including but not limited to making the unsubstituted form of the chemical group of interest and then performing a substitution. Suitable substituents include, for example, alkyl, alkenyl, acetylamino, alkoxy, alkoxyalkoxy, alkoxycarbonyl, alkoxyimio, carboxy, halo, haloalkoxy, hydroxy, alkylsulfonyl, alkylthio, trialkylsilyl, dialkylamino, and combinations thereof. An additional suitable substituent, which, if present, may be present alone or in combination with another suitable substituent, is -Lm-Z where mis 0 to 8, and where L and Z are defined herein above. If more than one substituent is present on a single chemical group of interest, each substituent may replace a different hydrogen atom, or one substituent may be attached to another substituent, which in turn is attached to the chemical group of interest, or a combination thereof.

Among the suitable R!, R?, R3, and R* groups are, for example, substituted and unsubstituted aliphatic-oxy groups, such as, for example, alkenoxy, alkoxy, alkynoxy, and alkoxycarbonyloxy.

Also among the suitable R', R?, R?, and R* groups are, for example, substituted and unsubstituted alkylphosphonato, substituted and unsubstituted alkylphosphato, substituted and unsubstituted alkylamino, substituted and unsubstituted alkylsulfonyl, substituted and unsubstituted alkylcarbonyl, and

Co a substituted and unsubstituted alkylaminosulfonyl, including, for example, alkylphosphonato, dialkylphosphato, dialkylthiophosphato, dialkylamino, alkylcarbonyl, and dialkylaminosulfonyl.

Also among the suitable R', R?, R?, and R* groups are, for example, substituted and unsubstituted cycloalkylsulfonyl groups and cycloalkylamino groups, such as, for example, dicycloalkylaminosulfonyl and dicycloalkylamino.

Also among the suitable R!, R?, R?, and R* groups are, for example, substituted and unsubstituted heterocyclyl groups (i.e., aromatic or non-aromatic cyclic groups with at least one heteroatom in the ring).

Also among the suitable R', R* R®, and R* 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', R?, R3, and R* groups are heterocyclyloxy, heterocyclylcarbonyl, diheterocyclylamino, and diheterocyclylaminosulfonyl.

Also among the suitable R',R% R? and R* groups are, for example, substituted and unsubstituted aryl groups. Suitable substituents are those described herein above. In some embodiments, one or more substituted aryl group is used in which at least one substituent is one or more of alkenyl, alkyl, alkynyl, acetylamino, alkoxyalkoxy, alkoxy, alkoxycarbonyl, carbonyl, alkylcarbonyloxy, carboxy, arylamino, haloalkoxy, halo, hydroxy, trialkylsilyl, dialkylamino, alkylsulfonyl, sulfonylalkyl, alkylthio, thioalkyl, arylaminosulfonyl, and haloalkylthio.

Also among the suitable R!, R?, R?, and R? 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!,

R% R’, and R* groups are diheteroarylamino, heteroarylthioalkyl, and diheteroarylaminosulfonyl.

Also among the suitable R', R?, R?, and R* 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,

Co k 5 dimethylphenylsilyl, isoquinolyl, mercapto, naphthyl, phenoxy, phenyl, piperidino, pyridyl, quinolyl, triethylsilyl, trimethylsilyl; and substituted analogs thereof.

As used herein, the chemical group Gis 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. Among heterocyclic G groups, some suitable heteroatoms are, for example, nitrogen, sulfur, oxygen, and combinations thereof. Ring sysytems 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).

In some embodiments, G is a ring system that contains a saturated or unsaturated 3 membered ring, such as, for example, a substituted or unsubstituted cyclopropane, cyclopropene, epoxide, or aziridine ring.

In some embodiments, G is a ring system that contains a 4 membered heterocyclic ring; in some of such embodiments, the heterocyclic ring contains exactly one heteroatom. Independently, in some embodiments, G is a ring system that contains a heterocyclic ring with 5 or more members; in some of such embodiments, the heterocyclic ring contains 1 to 4 heteroatoms. Independently, in some embodiments, the ring in G is unsubstituted; in other embodiments, the ring system contains 1 to 5 substituents; in some of the embodiments in which G contains substituents, each substituent is independently chosen from the substituents described herein above. Also suitable are embodiments in which G is a carbocyclic ring system.

In some embodiments, each G is independently a substituted or unsubstituted phenyl, pyridyl, cyclohexyl, cyclopentyl, cycloheptyl, pyrolyl, furyl, thiophenyl, triazolyl, pyrazolyl, 1,3-dioxolanyl, or morpholinyl. Among these embodiments include those embodiments, for example, in which G is unsubstituted or substituted phenyl, cyclopentyl, cycloheptyl, or cyclohexyl. In some of these embodiments, G is cyclopentyl, cycloheptyl, cyclohexyl, phenyl, or substituted phenyl. Among embodiments in which G is substituted phenyl are

CL . | 6 embodiments, for example, in which there are 1, 2, or 3 substituents.

Independently, also among embodiments in which G is substituted phenyl are embodiments, for example, in which the substituents are independently selected from methyl, methoxy, and halo.

Also contemplated are embodiments in which R? and R* are combined into a single group, which is attached to the number 3 carbon atom of the cyclopropene ring by a double bond. Some of such compounds are described in US Patent

Publication 2005/0288189.

In some embodiments, one or more cyclopropenes are used in which one ormore of R', R%, R? and R*is hydrogen. In some embodiments, R' or R? or both

R'and R? is hydrogen. Independently, in some embodiments, R* or R* or both R® and Ris hydrogen. In some embodiments, RZ, R3, and R* are hydrogen.

In some embodiments, one or more of R!, RZ, R®, and R* is a structure that has no double bond. Independently, in some embodiments, one or more of R!, R?, R3, and

R*is a structure that has no triple bond. Independently, in some embodiments, one or more of R', R? R3 and R* is a structure that has no halogen atom substituent.

Independently, in some embodiments, one or more of R!, RZ, R?, and R* is a structure that has no substituent that is ionic.

In some embodiments, one or more of R', R%, R?, and R* is hydrogen or (C;-

Cy) alkyl. In some embodiments, each of R!, R?, R3, and R* is hydrogen or (C,-Csg) alkyl. In some embodiments, each of R!, R%, R3, and R* is hydrogen or (C,-C,) alkyl.

In some embodiments, each of R!, R?, R3, and R* is hydrogen or methyl. In some embodiments, R! is (Cy-C4) alkyl and each of R% R?, and R* is hydrogen. In some embodiments, R' is methyl and each of R%, R®, and R* is hydrogen, and the cyclopropene is known herein as "1-MCP."

In some embodiments, a cyclopropene is used that has boiling point at one atmosphere pressure of 50°C or lower; or 25°C or lower; or 15°C or lower.

Independently, in some embodiments, a cyclopropene is used that has boiling point at one atmosphere pressure of -100°C or higher; -50°C or higher; or -25°C or hi gher; or 0°Cor higher.

The cyclopropenes applicable to this invention may be prepared by any method. Some suitable methods of preparation of cyclopropenes are the processes disclosed in U.S. Patents No. 5,518,988 and 6,017,849.

cot | 7

The composition of the present invention includes at least one molecular encapsulating agent. In some embodiments, at least one molecular encapsulating agent encapsulates one or more cyclopropene or a portion of one or more cyclopropene. A complex that contains a cyclopropene molecule or a portion of a cyclopropene molecule encapsulated in a molecule of a molecular encapsulating agent is known herein as a "cyclopropene complex."

In some embodiments, at least one cyclopropene complex is present that is an inclusion complex. In such an inclusion complex, the molecular encapsulating agent forms a cavity, and the cyclopropene or a portion of the cyclopropene is located within that cavity. In some of such inclusion complexes, there is no covalent bonding between the cyclopropene and the molecular encapsulating agent. Independently, in some of such inclusion complexes, there is no ionic bonding between the cyclopropene and the molecular encapsulating complex, whether or not there is any electrostatic attraction between one or more polar moiety in the cyclopropene and one or more polar moiety in the molecular encapsulating agent.

Independently, in some of such inclusion complexes, the interior of the cavity of the molecular encapsulating agent is substantially apolar or hydrophobic or both, and the cyclopropene (or the portion of the cyclopropene located within that cavity) is : also substantially apolar or hydrophobic or both. While the present invention is not limited to any particular theory or mechanism, it is contemplated that, in such apolar cyclopropene complexes, van der Waals forces, or hydrophobic interactions, or both, cause the cyclopropene molecule or portion thereof to remain within the cavity of the molecular encapsulating agent.

The cyclopropene molecular encapsulation agent complexes can be prepared by any means. In one method of preparation, for example, such complexes are prepared by contacting the cyclopropene with a solution or slurry of the molecular encapsulation agent and then isolating the complex, using, for example, processes disclosed in U. S. Patent No. 6,017,849. For example, in one method of making a complex in which cyclopropene is encapsulated in a molecular encapsulating agent, the cyclopropene gas is bubbled through a solution of molecular encapsulation agent in water, from which the complex first precipitates and is then isolated by filtration.

In some embodiments, complexes are made by the above method and, after isolation,

Claims

. - - TE. A | & ") 29 I I We claim: See a ~

1. A composition comprising an oil medium, wherein particles are suspended in said oil medium, wherein said particles comprise cyclopropene and molecular encapsulating agent, and wherein said particles have median size, as measured by the largest dimension, of 50 micrometer or less.

2. The composition of claim 1, wherein said oil medium comprises one or more dispersant.

3. The composition of claim 1, wherein said oil medium comprises one or more nonionic surfactant.

4. The composition of claim 1, wherein said oil medium comprises one or more nonionic surfactant with HLB value of 3 to 4 and one or more nonionic surfactant with HLB value of 8 to 10.

5. The composition of claim 1, wherein said oil medium is in the form of droplets suspended in water.

: 6. The composition of claim 1, wherein said oil medium forms the continuous medium of said composition.

7. The composition of claim 1, wherein said particle have median aspect ratio of 20 or less.

8. A process for treating plants or plant parts comprising contacting the composition of claim 1 with said plants or plant parts.

9. A process for forming a composition, said process comprising making a mixture comprising cyclopropene complex, oil, and dispersant to a media mill; and milling said mixture to form particles that comprise said cyclopropene complex, wherein said particles have median size, as measured by the longest length, of 50 micrometer or less.

aris . . INE 30 . Lo ;

10. A composition comprising an oil medium substantially as herein described with reference to and as exemplified in any one of Examples 1 to 3 Dated this 13" of August 2008 BOWMAN GILFILLAN JOHN & KERNICK FOR THE APPLICANT