COMPOSITION AND METHOD OF TREATING PLANTS AND PLANT PARTS WITH VOLATILE SPOILAGE ORGANISM CONTROLLING ACTIVES

Abstract

The present disclosure provides compositions and methods to promote improved delivery of volatile compounds to produce. As a result, the present disclosure provides more efficient and uniform delivery of volatile compounds and more effective control of spoilage organisms located on or near the stored produce.

Claims

1. A method of applying a volatile compound to a target produce, said method comprising the steps of: A. delivering a formulation comprising the volatile compound to a first location, and thereafter B. redistributing the volatile compound from the first location to a second location.

2. The method of claim 1, wherein the second location is on a surface of the target produce.

3. The method of claim 1, wherein the first location is on a first surface of the target produce and wherein the second location is on a second surface of the target produce.

4. The method of claim 1, wherein the step of delivering is selected from the group consisting of spraying, misting, thermal or non-thermal fogging, drenching, dipping, submersing, and combinations thereof.

5. The method of claim 1, wherein the step of delivering comprises spraying.

6. The method of claim 5, wherein the spraying is selected from the group consisting of electrostatic spraying, electrospraying, pneumatic air spraying, compressed air spraying, ultrasonic air spraying, air assisted ultrasonic air spraying, and combinations thereof.

7. The method of claim 1, wherein the step of delivering comprises fogging.

8. The method of claim 7, wherein the fogging is selected from the group consisting of thermo fogging, thermal fogging, cold fogging, nebulizing, misting, air brushing, and combinations thereof.

9. The method of claim 1, wherein the step of delivering comprises a continuous liquid application selected from the group consisting of a drench, a dip, a submersion, a flooding, a curtain shower, and combinations thereof.

10. The method of claim 1, wherein the first location is a composition located within about 1 meter of the target produce.

11. The method of claim 1, wherein the first location is selected from the group consisting of a package, a container, a pallet, a bin, a bag, a case, a clamshell, and a composition located near the target produce.

12. The method of claim 1, wherein the second location is selected from the group consisting of a storage room, a package, a container, a pallet, a bin, a bag, a case, a clamshell, and a composition located near the target produce.

13. The method of claim 1, wherein the step of delivering provides the volatile compound to a first percentage of available surface area coverage and the step of redistributing provides the volatile compound to a second percentage of available surface area coverage that is greater than the first percentage of available surface area coverage.

14. The method of claim 1, wherein the formulation comprises the volatile compound at a vapor pressure of about 10.sup.−5 torr at 1 atm/25° C. to about 10.sup.−3 torr at 1 atm/25° C.

15. The method of claim 1, wherein the volatile compound is a benzoxaborole.

16. The method of claim 1, wherein the volatile compound has a structure of ##STR00072##

17. The method of claim 1, wherein the volatile compound is more uniformly distributed after the step of redistribution.

18. The method of claim 17, wherein the uniform distribution is on a surface of the target produce.

19. The method of claim 1, wherein the volatile component comprises a first concentration at the first location and a second concentration at the second location, wherein the second concentration is lower than the first concentration.

20. The method of claim 1, wherein the step of delivering provides the volatile component at a first mass transfer rate and the step of redistributing provides the volatile component at a second mass transfer rate, wherein the second mass transfer rate is slower than the first mass transfer rate.

Description

DETAILED DESCRIPTION

[0368] Various embodiments of the invention are described herein as follows. In one embodiment described herein, a method of applying a volatile compound to a target produce is provided. The method comprises the steps of delivering a formulation comprising the volatile compound to a first location, and thereafter redistributing the volatile compound from the first location to a second location.

[0369] In another embodiment, a second method of applying a volatile compound to a target produce is provided. The method comprises the steps of delivering a formulation comprising the volatile compound to a first location, and thereafter redistributing the volatile compound from the first location to a second location, wherein the second location is on a surface of the target produce.

[0370] In yet another embodiment, a third method of applying a volatile compound to a target produce is provided. The method comprises the steps of delivering a formulation comprising the volatile compound to a first location, wherein the first location is on a first surface of the target produce and thereafter redistributing the volatile compound from the first location to a second location, wherein the second location is on a second surface of the target produce.

[0371] In another embodiment, an agricultural formulation is provided. The agricultural formulation comprises a volatile compound, wherein the volatile compound has at a vapor pressure of about 10.sup.−6 torr at 1 atm/25° C. to about 1 torr at 1 atm/25° C.

[0372] In a first aspect described herein, a method of applying a volatile compound to a target produce comprises the steps of delivering a formulation comprising the volatile compound to a first location, and thereafter redistributing the volatile compound from the first location to a second location.

[0373] In the various embodiments, the volatile compound refers to a chemical compound that is capable of being volatized. For example, the term “volatile compound” can refer to a chemical compound having a particular vapor pressure at which the chemical compound is volatile.

[0374] In some embodiments, the formulation comprises the volatile compound at a vapor pressure of about 10.sup.−6 torr at 1 atm/25° C. to about 1 torr at 1 atm/25° C. In other embodiments, the formulation comprises the volatile compound at a vapor pressure of about 10-6 torr at 1 atm/25° C. to about 10.sup.−1 torr at 1 atm/25° C. In yet other embodiments, the formulation comprises the volatile compound at a vapor pressure of about 10.sup.−6 torr at 1 atm/25° C. to about 10.sup.−2 torr at 1 atm/25° C. In some embodiments, the formulation comprises the volatile compound at a vapor pressure of about 10.sup.−6 torr at 1 atm/25° C. to about 10.sup.−3 torr at 1 atm/25° C. In other embodiments, the formulation comprises the volatile compound at a vapor pressure of about 10.sup.−5 torr at 1 atm/25° C. to about 10.sup.−3 torr at 1 atm/25° C. In yet other embodiments, the formulation comprises the volatile compound at a vapor pressure of about 10.sup.−5 torr at 1 atm/25° C. to about 10.sup.−4 torr at 1 atm/25° C. In some embodiments, the formulation comprises the volatile compound at a vapor pressure of about 10.sup.−4 torr at 1 atm/25° C. to about 10.sup.−3 torr at 1 atm/25° C. In other embodiments, the formulation comprises the volatile compound at a vapor pressure of about 10.sup.−6 torr at 1 atm/25° C. to about 10.sup.−5 torr at 1 atm/25° C. In yet other embodiments, the formulation comprises the volatile compound at a vapor pressure of about 10.sup.−3 torr at 1 atm/25° C. In some embodiments, the formulation comprises the volatile compound at a vapor pressure of about 10.sup.−4 torr at 1 atm/25° C. In other embodiments, the formulation comprises the volatile compound at a vapor pressure of about 10.sup.−5 torr at 1 atm/25° C. In yet other embodiments, the formulation comprises the volatile compound at a vapor pressure of about 1.65×10.sup.−6 torr at 1 atm/25° C. In some embodiments, the formulation comprises the volatile compound at a vapor pressure of about 10.sup.−6 torr at 1 atm/25° C. In other embodiments, wherein the formulation comprises the volatile compound at a vapor pressure of about 3.25×10.sup.−3 torr at 1 atm/25° C. In yet other embodiments, wherein the formulation comprises the volatile compound at a vapor pressure of about 3×10.sup.−3 torr at 1 atm/25° C.

[0375] In certain embodiments, the step of delivering is selected from the group consisting of spraying, misting, thermal or non-thermal fogging, drenching, dipping, submersing, and combinations thereof. In some embodiments, the step of delivering comprises spraying. In certain aspects, the spraying is selected from the group consisting of electrospraying, pneumatic air spraying, compressed air spraying, ultrasonic air spraying, air assisted ultrasonic air spraying, and combinations thereof.

[0376] In one embodiment, the spraying produces a droplet size of the formulation between about 0.01 μm to about 1 cm. In another embodiment, the spraying produces a droplet size of the formulation between about 0.01 μm to about 1000 μm. In one embodiment, the spraying produces a droplet size of the formulation between about 0.01 μm to about 100 μm. In another embodiment, the spraying produces a droplet size of the formulation between about 0.1 μm to about 1000 μm. In yet another embodiment, the spraying produces a droplet size of the formulation between about 0.1 μm to about 100 μm. In one embodiment, the spraying produces a droplet size of the formulation between about 1 μm to about 1000 μm. In another embodiment, the spraying produces a droplet size of the formulation between about 1 μm to about 100 μm. In yet another embodiment, the spraying produces a droplet size of the formulation between about 1 μm to about 10 μm.

[0377] In some embodiments, the step of delivering comprises fogging. In certain aspects, the fogging is selected from the group consisting of thermo fogging, thermal fogging, cold fogging, nebulizing, misting, air brushing, and combinations thereof.

[0378] In one embodiment, the fogging produces a droplet size of the formulation between about 0.01 μm to about 1000 μm. In another embodiment, the spraying produces a droplet size of the formulation between about 0.01 μm to about 100 μm. In yet another embodiment, the spraying produces a droplet size of the formulation between about 0.1 μm to about 1000 μm. In one embodiment, the spraying produces a droplet size of the formulation between about 0.1 μm to about 100 μm. In another embodiment, the spraying produces a droplet size of the formulation between about 1 μm to about 1000 m. In yet another embodiment, the spraying produces a droplet size of the formulation between about 1 μm to about 100 μm. In one embodiment, the spraying produces a droplet size of the formulation between about 1 μm to about 10 μm.

[0379] For instance, an exemplary formulation can comprise a volatile compound (e.g., an active ingredient) in a form of solid particulates with a typical median diameter (e.g., from about 0.1 μm to about 20 μm, from about 0.5 μm to about 15 μm, or from about 1 μm to about 10 μm). The solid particulates of active ingredient can be suspended or dispersed in liquid carriers (e.g., water) to form a consistent mixture useful for spray, drench, flood, or dip applications.

[0380] In some embodiments, the step of delivering comprises a continuous liquid application. In certain aspects, the continuous liquid application is selected from the group consisting of a drench, a dip, a submersion, a flooding, a curtain shower, and combinations thereof.

[0381] In certain embodiments, the volatile compound comprises a volatile antimicrobial compound against pathogens affecting meats, plants, or plant parts. The term “antimicrobial” is well known in the art, including concepts such as “anti-decay” and “anti-spoiling.”

[0382] In various aspects, the volatile compound is applied to a target produce wherein the target produce is a plant or a plant part. The term “plant(s)” and “plant parts” include, but not limited to, plant tissues, such as leaves, calli, stems, roots, flowers, fruits, vegetables, pollen, and seeds. A class of plants that may be used in the present invention is generally as broad as the class of higher and lower plants including, but not limited to, dicotyledonous plants, monocotyledonous plants, and plant crops, including, but not limited to, vegetable crops, fruit crops, ornamental crops, and meats.

[0383] “Vegetable crops” include, but are not limited to, asparagus, beet (e.g., sugar beet and fodder beet), beans, broccoli, cabbage, carrot, cassava, cauliflower, celery, cucumber, eggplant, garlic, gherkin, leafy greens (lettuce, kale, spinach, and other leafy greens), leek, lentils, mushroom, onion, peas, pepper (e.g., sweet peppers, bell peppers, and hot peppers), potato, pumpkin, sweet potato, snap bean, squash, tomato, and turnip.

[0384] “Fruit crops” include, but are not limited to, apple, avocado, banana, soft fruits, such as, strawberry, blueberry, raspberry, blackberry, cranberry, currents and other types of soft fruit berries, carambola, cherry, citrus (e.g., oranges, lemon, lime, mandarin, grapefruit, and other citrus), coconut, fig, grapes, guava, kiwifruit, mango, nectarine, melons (including cantaloupe, muskmelon, watermelon, and other melons), olive, papaya, passionfruit, peach, pear, persimmon, pineapple, plum, and pomegranate. More specifically, horticultural crops of the present disclosure include, but are not limited to, soft fruits (e.g., grape, apple, pear, and persimmon) and berries (e.g., strawberries, blackberries, blueberries, and raspberries).

[0385] “Ornamental crops” include, but are not limited to, baby's breath, carnation, dahlia, daffodil, geranium, gerbera, lily, orchid, peony, Queen Anne's lace, rose, snapdragon, or other cut-flowers or ornamental flowers, potted flowers, flower bulbs, shrub, and deciduous or coniferous tree.

[0386] “Meat” or “Meats” include, but are not limited to beef, bison, chicken, deer, goat, turkey, pork, sheep, fish, shellfish, mollusks, or dry-cured meat products.

[0387] The methods provided by the present disclosure are premised on delivering a formulation comprising the volatile compound to a first location, and thereafter redistributing the volatile compound from the first location to a second location. As described herein, the “first location” and the “second location” can be specified to be as various sites.

[0388] In various embodiments, the first location is a post-harvest processing facility. In some embodiments, the post-harvest processing facility is a storage room. In other embodiments, the post-harvest processing facility is a packing house. In yet other embodiments, the post-harvest processing facility is a packing or sorting line. In some embodiments, the post-harvest processing facility is a transit center. In other embodiments, the post-harvest processing facility is a distribution center. In yet other embodiments, the post-harvest processing facility is a field packing area.

[0389] For instance, a storage room can be a long term cold storage room. The storage room can be present with or without a controlled atmosphere, with or without ventilation, and with or without air scrubbing/cleaning mechanisms.

[0390] For instance, a post-harvest processing facility can be a space or an enclosure such as holding room, cooling room, degreening room, and the like.

[0391] For instance, a post-harvest processing facility can be a transport enclosure such as a container, a pallet wrap, a pallet cover, and the like.

[0392] For instance, a produce packaging enclosure can be utilized according to the present disclosure. The produce packaging enclosure can be, for example, a box, a liner bag, a retail bag, a clamshell, a punnet, a perforated managed atmosphere package (MAP), a microperforated MAP, a perforated modified atmosphere package, a microperforated modified atmosphere package, and the like.

[0393] In some embodiments, the first location is a composition located near the target produce. In various aspects, the composition located near the target produce is within about 1 meter of the target produce.

[0394] In various embodiments, the first location is selected from the group consisting of a storage room, a package, a container, a pallet, a bin, a bag, a case, a clamshell, and a composition located near the target produce.

[0395] In one embodiment, the first location is a storage room. In another embodiment, the first location is a package. In yet another embodiment, the first location is a bin. In one embodiment, the first location is a bag. In another embodiment, the first location is a case. In yet another embodiment, the first location is a clamshell.

[0396] In some embodiments, the second location is an enclosed space or a partially enclosed space. In various embodiments, the second location is selected from the group consisting of a storage room, a package, a container, a pallet, a bin, a bag, a case, a clamshell, and a composition located near the target produce.

[0397] In one embodiment, the second location is a storage room. In another embodiment, the second location is a package. In yet another embodiment, the second location is a bin. In one embodiment, the second location is a bag. In another embodiment, the second location is a case. In yet another embodiment, the second location is a clamshell.

[0398] In some embodiments, the second location is a composition located near the target produce. In various aspects, the composition located near the target produce is within about 1 meter of the target produce.

[0399] In various aspects, wherein the step of delivering provides the volatile compound to a first percentage of available surface area coverage and the step of redistributing provides the volatile compound to a second percentage of available surface area coverage that is greater than the first percentage of available surface area coverage.

[0400] In some embodiments, the partially enclosed space is between about 50% to 100% enclosed from an outside environment. In some embodiments, the partially enclosed space is between about 60% to 100% enclosed from an outside environment. In other embodiments, the partially enclosed space is between about 70% to 100% enclosed from an outside environment. In yet other embodiments, the partially enclosed space is between about 70% to 90% enclosed from an outside environment.

[0401] In certain aspects, the formulation is a non-aqueous soluble liquid. In other aspects, the formulation is an aqueous soluble liquid. In yet other aspects, the formulation is a suspension or dispersion of the volatile compound in liquid media.

[0402] In some embodiments, the distance between the first location and the second location is between about 0.001 meter to about 1 meter. In other embodiments, the distance between the first location and the second location is between about 0.01 meter to about 1 meter.

[0403] In yet other embodiments, the distance between the first location and the second location is between about 0.1 meter to about 1 meter.

[0404] In certain aspects, the volatile compound is a benzoxaborole. In some embodiments, the volatile compound of the invention has a structure of formula (I), (II), or (III):

##STR00021##

[0405] wherein q1 and q2 are independently 1, 2, or 3;

[0406] q3=0, 1, 2, 3, or 4;

[0407] M is hydrogen, halogen, —OCH.sub.3, or —CH.sub.2—O—CH.sub.2—O—CH.sub.3;

[0408] M.sup.1 is halogen, —CH.sub.2OH, or —OCH.sub.3;

[0409] X is O, S, or NR.sup.1c, wherein R.sup.1c is hydrogen, substituted alkyl, or unsubstituted alkyl;

[0410] R.sup.1, R.sup.1a, R.sup.1b, R.sup.2, and R.sup.5 are independently hydrogen, OH, NH.sub.2, SH, CN, NO.sub.2, SO.sub.2, OSO.sub.2OH, OSO.sub.2NH.sub.2, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; R* is substituted or unsubstituted aryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroarylalkyl, or substituted or unsubstituted vinyl;

[0411] with a proviso that when M is F, R* is not a member selected from:

##STR00022##

[0412] and with a proviso that when M is Cl, R* is not a member selected from:

##STR00023##

[0413] and with a proviso that when M is hydrogen, R* is not a member selected from:

##STR00024##

[0414] wherein s=1 or 2; and R.sup.3 and R.sup.4 are independently methyl or ethyl;

[0415] and with a provision that when M is OCH.sub.3, R* is not a member selected from:

##STR00025##

[0416] and with a provision that when M.sup.1 is F, R* is not a member selected from:

##STR00026##

and pharmaceutically acceptable salts thereof.

[0417] In one embodiment, the R* has a structure selected from:

##STR00027##

[0418] wherein X is a member selected from CH═CH, N═CH, NR.sup.14, O and S;

[0419] wherein R.sup.14 is a member selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl and substituted or unsubstituted arylalkyl;

[0420] Y is a member selected from CH and N;

[0421] R.sup.17 and R.sup.18 are members independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted arylalkyl, (CH.sub.2).sub.vOH, (CH.sub.2).sub.wNR.sup.15R.sup.16, CO.sub.2H, C.sub.2-alkyl, CONH.sub.2, S-alkyl, S-aryl, SO-alkyl, SO-aryl, SO.sub.2-alkyl, SO.sub.2-aryl, SO.sub.2H, SCF.sub.2, CN, halogen, CF.sub.3 and NO.sub.2;

[0422] wherein R.sup.15 and R.sup.16 are members independently selected from hydrogen, substituted or unsubstituted alkyl and substituted or unsubstituted alkanoyl;

[0423] v=1, 2, or 3; and

[0424] w=0, 1, 2, or 3.

[0425] In another embodiment, the R* has the following structure:

##STR00028##

[0426] wherein R.sup.17, R.sup.18, R.sup.19, R.sup.20, and R.sup.21 are independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted alkyloxy, substituted or unsubstituted aryloxy, substituted or unsubstituted oxazolidin-2-yl, (CH.sub.2).sub.tOH, CO.sub.2H, CO.sub.2-alkyl, CONH.sub.2, CONH-alkyl, CON(alkyl).sub.2, OH, SH, S-alkyl, S-aryl, SO-alkyl, SO-aryl, SO.sub.2-alkyl, SO.sub.2-aryl, SO.sub.2H, SCF.sub.3, CN, halogen, CF.sub.3, NO.sub.2, (CH.sub.2).sub.uNR.sup.22R.sup.23, SO.sub.2NH.sub.2, OCH.sub.2CH.sub.2NH.sub.2, OCH.sub.2CH.sub.2NH-alkyl and OCH.sub.2CH.sub.2N(alkyl).sub.2;

[0427] wherein t=1, 2 or 3;

[0428] u=0, 1, or 2;

[0429] R.sup.22 and R.sup.23 are independently selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted alkanoyl.

[0430] In another embodiment, the R* has the following structure:

##STR00029##

[0431] wherein R.sup.17, R.sup.18, R.sup.19, R.sup.20, and R.sup.21 are independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted alkyloxy, substituted or unsubstituted aryloxy, substituted or unsubstituted oxazolidin-2-yl, (CH.sub.2).sub.tOH, CO.sub.2H, CO.sub.2-alkyl, CONH.sub.2, CONH-alkyl, CON(alkyl).sub.2, OH, SH, S-alkyl, S-aryl, SO-alkyl, SO-aryl, SO.sub.2-alkyl, SO.sub.2-aryl, SO.sub.2H, SCF.sub.3, CN, halogen, CF.sub.3, NO.sub.2, (CH.sub.2).sub.uNR.sup.22R.sup.23, SO.sub.2NH.sub.2, OCH.sub.2CH.sub.2NH.sub.2, OCH.sub.2CH.sub.2NH-alkyl and OCH.sub.2CH.sub.2N(alkyl).sub.2;

[0432] wherein t=1, 2 or 3;

[0433] u=0, 1, or 2;

[0434] R.sup.22 and R.sup.23 are independently selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted alkanoyl;

[0435] R.sup.24 and R.sup.25 are independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted alkyloxy, substituted or unsubstituted aryloxy, substituted or unsubstituted oxazolidin-2-yl, (CH.sub.2), OH, CO.sub.2H, CO.sub.2-alkyl, CONH.sub.2, CONH-alkyl, CON(alkyl).sub.2, OH, SH, S-alkyl, S-aryl, SO-alkyl, SO-aryl, SO.sub.2-alkyl, SO.sub.2-aryl, SO.sub.3H, SCF.sub.3, CN, halogen, CF.sub.3, NO.sub.2, (CH.sub.2).sub.uNR.sup.22R.sup.23, SO.sub.2NH.sub.2, OCH.sub.2CH.sub.2NH.sub.2, OCH.sub.2CH.sub.2NH-alkyl and OCH.sub.2CH.sub.2N(alkyl).sub.2;

[0436] Z=1, 2, 3, 4, 5, or 6.

[0437] Additional volatile compounds are also disclosed previously in U.S. Pat. No. 8,106,031, and International Patent Application WO 2007/131072A2, the contents of which are hereby incorporated by reference in their entireties.

[0438] In some embodiments, the volatile compound of the invention has the structure of formula (IV):

##STR00030##

[0439] wherein A and D together with the carbon atoms to which they are attached form a 5-6- or 7-membered fused ring which may be substituted by C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, hydroxy, halogen, nitro, nitrile, amino, amino substituted by one or more C.sub.1-C.sub.6-alkyl groups, carboxy, acyl, aryloxy, carbonamido, carbonamido substituted by C.sub.1-C.sub.6-alkyl, sulfonamido or trifluoromethyl or the fused ring may link two oxaborole rings;

[0440] X is a group —CR.sup.7R.sup.8 wherein R.sup.7 and R.sup.8 are each independently hydrogen, C.sub.1-C.sub.6-alkyl, nitrile. nitro, aryl, arylalkyl or R.sup.7 and R.sup.8 together with the carbon atom to which they are attached form an alicyclic ring; and

[0441] R.sup.6 is hydrogen, C.sub.1-C.sub.18-alkyl, C.sub.1-C.sub.18-alkyl substituted by C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6 alkylthio, hydroxy, amino, amino substituted by C.sub.1-C.sub.18-alkyl, carboxy, aryl, aryloxy, carbonamido, carbonamido substituted by C.sub.1-C.sub.6-alkyl, aryl or arylalkyl, arylalkyl, aryl, heteroaryl, cycloalkyl, C.sub.1-C.sub.18-alkyleneamino, C.sub.1-C.sub.18-alkyleneamino substituted by phenyl, C.sub.1-C.sub.6-alkoxy or C.sub.1-C.sub.6-alkylthio, carbonyl alkyleneamino or a radical of formula (V):

##STR00031##

[0442] wherein A, D and X are as defined herein before except for boronophthalide;

[0443] and pharmaceutically acceptable salts thereof.

[0444] In one embodiment, the volatile compound of the invention has the structure of formula (IX):

##STR00032##

[0445] wherein A, D, and X are defined as above;

[0446] Y is a divalent alkylene linking group containing up to 18 carbon atoms or a divalent alkylene linking group containing up to 18 carbon atoms which is substituted by phenyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6-alkylthio; carbonyl alkylene amino; and

[0447] R.sup.3 and R.sup.4 are each, independently, hydrogen, C.sub.1-C.sub.18-alkyl or phenyl or R.sup.3 together with Y or part of Y forms a 5-, 6- or 7-membered ring containing the nitrogen atom.

[0448] In another embodiment, the volatile compound of the invention has the structure of formula (X):

##STR00033##

[0449] wherein A, D, and X are defined as above;

[0450] n is 1, 2, or 3;

[0451] R.sup.3 is hydrogen, C.sub.1-C.sub.18-alkyl or phenyl; and

[0452] R.sup.5 and R.sup.6 are each, independently, hydrogen, alkyl containing up to a total of 16 carbon atoms or phenyl.

[0453] Additional volatile compounds are also disclosed previously in U.S. Pat. No. 5,880,188, the content of which is hereby incorporated by reference in its entirety.

[0454] In another aspect, the volatile compound of the invention has the structure of formula (VI):

##STR00034##

[0455] wherein each R is independently hydrogen, alkyl, alkene, alkyne, haloalkyl, haloalkene, haloalkyne, alkoxy, alkeneoxy, haloalkoxy, aryl, heteroaryl, arylalkyl, arylalkene, arylalkyne, heteroarylalkyl, heteroarylalkene, heteroarylalkyne, halogen, hydroxyl, nitrile, amine, ester, carboxylic acid, ketone, alcohol, sulfide, sulfoxide, sulfone, sulfoximine, sulfilimine, sulfonamide, sulfate, sulfonate, nitroalkyl, amide, oxime, imine, hydroxylamine, hydrazine, hydrazone, carbamate, thiocarbamate, urea, thiourea, carbonate, aryloxy, or heteroaryloxy;

[0456] n=1, 2, 3, or 4;

[0457] B is boron;

[0458] X═(CR.sub.2).sub.m where m=1, 2, 3, or 4;

[0459] Y is alkyl, alkene, alkyne, haloalkyl, haloalkene, haloalkyne, alkoxy, alkeneoxy, haloalkoxy, aryl, heteroaryl, arylalkyl, arylalkene, arylalkyne, heteroarylalkyl, heteroarylalkene, heteroarylalkyne, hydroxyl, nitrile, amine, ester, carboxylic acid, ketone, alcohol, sulfide, sulfoxide, sulfone, sulfoximine, sulfilimine, sulfonamide, sulfate, sulfonate, nitroalkyl, amide, oxime, imine, hydroxylamine, hydrazine, hydrazone, carbamate, thiocarbamate, urea, thiourea, carbonate, aryloxy, or heteroaryloxy;

[0460] with a proviso that R is not aryloxy or heteroaryloxy when Y is hydroxyl;

[0461] and pharmaceutically acceptable salts thereof.

[0462] In one embodiment, the volatile compound has a structure of formula (VII):

##STR00035##

[0463] wherein W═(CH.sub.2).sub.q where q is 1, 2, or 3.

[0464] In another embodiment, the volatile compound has a structure of

##STR00036##

[0465] In another embodiment, the volatile compound of the invention has the structure of formula (VIII):

##STR00037##

wherein R.sup.a is CN, C(O)NR.sup.9R.sup.10, or C(O)OR.sup.11 wherein R.sup.11 is hydrogen, substituted alkyl, or unsubstituted alkyl,

[0466] X is N, CH and CR.sup.b;

[0467] R.sup.b is halogen, substituted or unsubstituted alkyl, C(O)R.sup.2, C(O)OR.sup.12, OR.sup.12, NR.sup.12R.sup.13, wherein R.sup.9, R.sup.10, R.sup.12, and R.sup.13 are independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0468] with a proviso that R.sup.9 and R.sup.10, together with the atoms to which they are attached, are optionally combined to form a 4- to 8-membered substituted or unsubstituted heterocycloalkyl ring;

[0469] and with a proviso that R.sup.12 and R.sup.13, together with the atoms to which they are attached, are optionally combined to form a 4- to 8-membered substituted or unsubstituted heterocycloalkyl ring;

[0470] and pharmaceutically acceptable salts thereof.

[0471] In one embodiment, the volatile compound of the invention has the structure of formula (XI):

##STR00038##

[0472] In another embodiment, the volatile compound of the invention is selected from:

##STR00039##

[0473] In another embodiment, the volatile compound of the invention is selected from:

##STR00040##

[0474] In another embodiment, the volatile compound of the invention is selected from:

##STR00041##

[0475] In one embodiment, the volatile compound of the invention has the structure of formula (XII):

##STR00042##

[0476] In another embodiment, the volatile compound of the invention is selected from:

##STR00043##

[0477] wherein R.sup.3 is hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted heteroalkyl.

[0478] In another embodiment, the volatile compound of the invention is selected from:

##STR00044##

[0479] wherein R.sup.3 is hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted heteroalkyl.

[0480] In another embodiment, the volatile compound of the invention is selected from:

##STR00045##

[0481] wherein R.sup.3 is hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted heteroalkyl.

[0482] In one embodiment, the volatile compound of the invention has the structure of formula (XIII):

##STR00046##

[0483] wherein each of R.sup.1 and R.sup.2 is independently hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted heteroalkyl.

[0484] In another embodiment, the volatile compound of the invention is selected from:

##STR00047##

[0485] In another embodiment, the volatile compound of the invention is selected from:

##STR00048##

[0486] wherein each of R.sup.1 and R.sup.2 is independently hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted heteroalkyl.

[0487] In another embodiment, the volatile compound of the invention is selected from:

##STR00049##

[0488] wherein each of R.sup.1 and R.sup.2 is independently hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted heteroalkyl.

[0489] In one embodiment, R.sup.b is selected from fluorine and chlorine. In another embodiment, R.sup.b is selected from OR.sup.26 and NR.sup.27R.sup.28. In another embodiment when R.sup.b is OR.sup.26, R.sup.26 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl. In another embodiment when R.sup.b is OR.sup.26, R.sup.26 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl and substituted or unsubstituted cycloalkyl. In another embodiment when R.sup.b is OR.sup.26, R.sup.26 is unsubstituted C.sub.1-C.sub.6 alkyl. In another embodiment when R.sup.b is OR.sup.26, R.sup.26 is unsubstituted cycloalkyl. In another embodiment when R.sup.b is OR.sup.26, R.sup.26 is alkyl, substituted with a member selected from substituted or unsubstituted C.sub.1-C.sub.6 alkoxy. In another embodiment when R.sup.b is OR.sup.26, R.sup.26 is alkyl, substituted with at least one halogen. In another embodiment when R.sup.b is OR.sup.26, R.sup.26 is alkyl, substituted with at least one oxo moiety.

[0490] In another embodiment when R.sup.b is OR.sup.26, R.sup.26 is a member selected from —CH.sub.3, —CH.sub.2CH.sub.3, —(CH.sub.2).sub.2CH.sub.3, —CH(CH.sub.3).sub.2, —CH.sub.2CF.sub.3, —CH.sub.2CHF.sub.2, —CH.sub.2CH.sub.2(OH), —CH.sub.2CH.sub.2(OCH.sub.3), —CH.sub.2CH.sub.2(OC(CH.sub.3).sub.2), —C(O)CH.sub.3, —CH.sub.2CH.sub.2OC(O)CH.sub.3, —CH.sub.2C(O)OCH.sub.2CH.sub.3, —CH.sub.2C(O)OC(CH.sub.3).sub.3, —(CH.sub.2).sub.3C(O)CH.sub.3, —CH.sub.2C(O)OC(CH.sub.3).sub.3, cyclopentyl, cyclohexyl,

##STR00050##

[0491] In another embodiment when R.sup.b is NR.sup.27R.sup.28, R.sup.27 and R.sup.28 are members independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl. In another embodiment when R.sup.b is NR.sup.27R.sup.28, R.sup.27 is H or unsubstituted alkyl; and R.sup.28 is unsubstituted alkyl or alkyl substituted with a member selected from hydroxyl, phenyl, unsubstituted alkoxy and alkoxy substituted with a phenyl. In a further embodiment when R.sup.b is NR.sup.27R.sup.28, R.sup.27 is H or CH.sub.3.

[0492] In another embodiment when R.sup.b is NR.sup.27R.sup.28, R.sup.27 and R.sup.28 are independently selected from substituted or unsubstituted alkyl. In another embodiment when R.sup.b is NR.sup.27R.sup.28, R.sup.27 is unsubstituted alkyl; and R.sup.28 is substituted or unsubstituted alkyl. In another embodiment when R.sup.b is NR.sup.27R.sup.28, R.sup.27 is unsubstituted alkyl; and R.sup.28 is alkyl, substituted with a member selected from substituted or unsubstituted alkoxy and hydroxyl. In another embodiment when R.sup.b is NR.sup.27R.sup.28, R.sup.27 is unsubstituted alkyl; and R.sup.28 is alkyl, substituted with unsubstituted alkoxy. In another embodiment when R.sup.b is NR.sup.27R.sup.28, R.sup.27 is unsubstituted alkyl; and R.sup.28 is alkyl, substituted with alkoxy, substituted with phenyl. In another embodiment when R.sup.b is NR.sup.27R.sup.28, R.sup.27 is unsubstituted alkyl; and R.sup.28 is alkyl, substituted with unsubstituted alkoxy. In another embodiment when R.sup.b is NR.sup.27R.sup.28, R.sup.27 and R.sup.28 together with the nitrogen to which they are attached, are combined to form a 4- to 8-membered substituted or unsubstituted heterocycloalkyl ring. In another embodiment when R is NR.sup.27R.sup.28, R.sup.27 and R.sup.28 together with the nitrogen to which they are attached, are combined to form a 5- or 6-membered substituted or unsubstituted heterocycloalkyl ring.

[0493] In another embodiment, R.sup.b is selected from N(CH.sub.3).sub.2, N(CH.sub.3)(CH.sub.2CH.sub.2(OCH.sub.3)), N(CH.sub.3)(CH.sub.2CH.sub.2OH), NH.sub.2, NHCH.sub.3, NH(CH.sub.2CH.sub.2(OCH.sub.3)), NH(CH.sub.2CH.sub.2(OCH.sub.2Ph), NH(CH.sub.2Ph), NH(C(CH.sub.3).sub.3) and NH(CH.sub.2CH.sub.2OH). In another embodiment, R.sup.b is selected from

##STR00051##

[0494] Additional volatile compounds are also disclosed previously in U.S. Pat. No. 8,039,450, and patent application publication US 2009/0291917, the contents of which are hereby incorporated by reference in their entireties.

[0495] In one aspect, the volatile compound of the invention has the structure of formula (A):

R.sup.A-L.sup.A-G-L.sup.B-R.sup.B  (A),

wherein

[0496] each of R.sup.A and R.sup.B is independently a radical comprising an oxaborole moiety;

[0497] each of L.sup.A and L.sup.B is independently —O— or

##STR00052##

[0498] each of R and R′ is independently hydrogen, unsubstituted or substituted C.sub.1-18-alkyl, arylalkyl, aryl, or heterocyclic moiety; and

[0499] G is a substituted or unsubstituted C.sub.1-18-alkylene, arylalkylene, arylene, or heterocyclic moiety; and pharmaceutically acceptable salts thereof.

[0500] In one embodiment, the volatile compound has use against pathogens affecting meats, plants, or plant parts, comprising contacting the meats, plants, or plant parts. In another embodiment, the -L.sup.A-G-L.sup.B- portion of formula (A) is derived from a diol or diamine compound. In a further embodiment, the diol compound is selected from the group consisting of 1,2-ethylene glycol; 1,2-propylene glycol; 1,3-propylene glycol; 1,1,2,2-tetramethyl-1,2-ethylene glycol; 2,2-dimethyl-1,3-propylene glycol; 1,6-hexanediol; 1,10-decanediol; and combinations thereof. In another embodiment, the diamine compound is 1,2-ethylene diamine; 1,3-propylene diamine; or combinations thereof. In another embodiment, L.sup.A and L.sup.B are identical. In another embodiment, L.sup.A and L.sup.B are different. In another embodiment, each of L.sup.A and L.sup.B is independently —O— or —NH—. In another embodiment, L.sup.A and L.sup.B are identical. In another embodiment, L.sup.A and L.sup.B are different.

[0501] In another embodiment, the -L.sup.A-G-L.sup.B- portion of formula (A) comprises asymmetrical functional groups (i.e., asymmetrical bridges). In a further embodiment, the -L.sup.A-G-L.sup.B- portion of formula (A) comprises one hydroxyl group and one amine group. In a further embodiment, the -L.sup.A-G-L.sup.B- portion of formula (A) comprises an amino alcohol. In another embodiment, G is a substituted or unsubstituted C.sub.1_8-alkylene. In a further embodiment, G is a substituted or unsubstituted C.sub.1-4-alkylene. In a further embodiment, G is selected from —CH.sub.2—, —CH.sub.2—CH.sub.2—, and —CH.sub.2—CH.sub.2—CH.sub.2—.

[0502] In another embodiment, each of R.sup.A and R.sup.B is independently derived from the group consisting of 5-fluoro-1,3-dihydro-1-hydroxy-2,1-benzoxaborole; 5-chloro-1,3-dihydro-1-hydroxy-2,1-benzoxaborole; 1,3-dihydro-1-hydroxy-2,1-benzoxaborole; and combinations thereof. In another embodiment, R.sup.A and R.sup.B are identical. In another embodiment, R.sup.A and R.sup.B are different.

[0503] In another embodiment, at least one of R.sup.A and R.sup.B is selected from formula (B), (C), or (D):

##STR00053##

[0504] wherein q1 and q2 are independently 1, 2, or 3;

[0505] q3=0, 1, 2, 3, or 4;

[0506] B is boron;

[0507] M is hydrogen, halogen, —OCH.sub.3, or —CH.sub.2—O—CH.sub.2—O—CH.sub.3;

[0508] M.sup.1 is halogen, —CH.sub.2OH, or —OCH.sub.3;

[0509] X is O, S, or NR.sup.1c, wherein R.sup.1c is hydrogen, substituted alkyl, or unsubstituted alkyl; R.sup.1, R.sup.1a, R.sup.1b, R.sup.2, and R.sup.5 are independently hydrogen, OH, NH.sub.2, SH, CN, NO.sub.2, SO.sub.2, OSO.sub.2OH, OSO.sub.2NH.sub.2, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0510] and pharmaceutically acceptable salts thereof.

[0511] Additional oxaborole moieties are also disclosed previously in U.S. Pat. No. 8,106,031, and International Patent Application WO 2007/131072A2, the contents of which are hereby incorporated by reference in their entireties.

[0512] In another embodiment, at least one of R.sup.A and R.sup.B has a structure of formula (F):

##STR00054##

[0513] wherein A and D together with the carbon atoms to which they are attached form a 5, 6, or 7-membered fused ring which may be substituted by C.sub.1-6-alkyl, C.sub.1-6-alkoxy, hydroxy, halogen, nitro, nitrile, amino, amino substituted by one or more C.sub.1-6-alkyl groups, carboxy, acyl, aryloxy, carbonamido, carbonamido substituted by C.sub.1-6-alkyl, sulphonamido or trifluoromethyl or the fused ring may link two oxaborole rings; B is boron;

[0514] X.sup.1 is a group —CR.sup.7R.sup.8 wherein R.sup.7 and R.sup.8 are each independently hydrogen, C.sub.1-6-alkyl, nitrile, nitro, aryl, aralkyl or R.sup.7 and R.sup.8 together with the carbon atom to which they are attached form an alicyclic ring; and

[0515] and pharmaceutically acceptable salts thereof.

[0516] Additional oxaborole moieties are also disclosed previously in U.S. Pat. No. 5,880,188, the content of which is hereby incorporated by reference in its entirety.

[0517] In another embodiment, at least one of R.sup.A and R.sup.B is selected from formula (E) or (G):

##STR00055##

[0518] wherein each R.sup.6 is independently hydrogen, alkyl, alkene, alkyne, haloalkyl, haloalkene, haloalkyne, alkoxy, alkeneoxy, haloalkoxy, aryl, heteroaryl, arylalkyl, arylalkene, arylalkyne, heteroarylalkyl, heteroarylalkene, heteroarylalkyne, halogen, hydroxyl, nitrile, amine, ester, carboxylic acid, ketone, alcohol, sulfide, sulfoxide, sulfone, sulfoximine, sulfilimine, sulfonamide, sulfate, sulfonate, nitroalkyl, amide, oxime, imine, hydroxylamine, hydrazine, hydrazone, carbamate, thiocarbamate, urea, thiourea, carbonate, aryloxy, or heteroaryloxy;

[0519] n=1, 2, 3, or 4;

[0520] B is boron;

[0521] X.sup.2═(CR.sup.6.sub.2).sub.m where m=1, 2, 3, or 4; or

##STR00056##

[0522] wherein R.sup.9 is CN, C(O)NR.sup.11R.sup.12, or C(O)OR.sup.3 wherein R.sup.3 is hydrogen, substituted alkyl, or unsubstituted alkyl,

[0523] X.sup.3 is N, CH and CR.sup.10;

[0524] R.sup.10 is halogen, substituted or unsubstituted alkyl, C(O)R.sup.14, C(O)OR.sup.14, OR.sup.14, NR.sup.14R.sup.15, wherein each of R.sup.11, R.sup.12, R.sup.14, and R.sup.15 is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0525] and pharmaceutically acceptable salts thereof.

[0526] In a further embodiment when at least one of R.sup.A and R.sup.B has a structure of formula (G), R.sup.9 is CN and R.sup.10 is R.sup.b.

[0527] In another embodiment, at least one of R.sup.A and R.sup.B has a structure selected from:

##STR00057##

[0528] In another embodiment, at least one of R.sup.A and R.sup.B has a structure selected from:

##STR00058##

[0529] In another embodiment, at least one of R.sup.A and R.sup.B has a structure selected from:

##STR00059##

[0530] In another embodiment when at least one of R.sup.A and R.sup.B has a structure of formula (G), R.sup.9 is —COOR.sup.3 and R.sup.10 is R.sup.b.

[0531] In another embodiment, at least one of R.sup.A and R.sup.B has a structure selected from:

##STR00060##

[0532] In another embodiment, at least one of R.sup.A and R.sup.B has a structure selected from:

##STR00061##

[0533] In another embodiment, at least one of R.sup.A and R.sup.B has a structure selected from:

##STR00062##

[0534] In another embodiment when at least one of R.sup.A and R.sup.B has a structure of formula (G), R.sup.9 is —CONR.sup.1R.sup.2 and R.sup.10 is R.sup.b.

[0535] In another embodiment, each of R.sup.A and R.sup.B is independently selected from formula (B), (C), (D), (E), (F), or (G).

[0536] In another embodiment, the volatile compound of the invention is selected from:

##STR00063##

[0537] In another embodiment, the volatile compound of the invention is selected from:

##STR00064##

[0538] In another embodiment, the volatile compound of the invention is selected from:

##STR00065##

[0539] In one embodiment, R.sup.b is selected from fluorine and chlorine. In another embodiment, R.sup.b is selected from OR.sup.20 and NR.sup.21R.sup.22. In another embodiment when R.sup.b is OR.sup.20, R.sup.20 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl. In another embodiment when R.sup.b is OR.sup.20, R.sup.20 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl and substituted or unsubstituted cycloalkyl. In another embodiment when R.sup.b is OR.sup.20, R.sup.20 is unsubstituted C.sub.1-6 alkyl. In another embodiment when R.sup.b is OR.sup.20, R.sup.20 is unsubstituted cycloalkyl. In another embodiment when R.sup.b is OR.sup.20, R.sup.20 is alkyl, substituted with a member selected from substituted or unsubstituted C.sub.1-6 alkoxy. In another embodiment when R.sup.b is OR.sup.20, R.sup.20 is alkyl, substituted with at least one halogen. In another embodiment when R.sup.b OR.sup.20, R.sup.20 is alkyl, substituted with at least one oxo moiety.

[0540] In another embodiment when R.sup.b is OR.sup.20, R.sup.20 is a member selected from —CH.sub.3, —CH.sub.2CH.sub.3, —(CH.sub.2).sub.2CH.sub.3, —CH(CH.sub.3).sub.2, —CH.sub.2CF.sub.3, —CH.sub.2CHF.sub.2, —CH.sub.2CH.sub.2(OH), —CH.sub.2CH.sub.2(OCH.sub.3), —CH.sub.2CH.sub.2(OC(CH.sub.3).sub.2), —C(O)CH.sub.3, —CH.sub.2CH.sub.2OC(O)CH.sub.3, —CH.sub.2C(O)OCH.sub.2CH.sub.3, —CH.sub.2C(O)OC(CH.sub.3).sub.3, —(CH.sub.2).sub.3C(O)CH.sub.3, —CH.sub.2C(O)OC(CH).sub.3, cyclopentyl, cyclohexyl,

##STR00066##

[0541] In another embodiment when R.sup.b is NR.sup.21R.sup.22, R.sup.21 and R.sup.22 are members independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl. In another embodiment when R.sup.b is NR.sup.21R.sup.22, R.sup.21 is H or unsubstituted alkyl; and R.sup.22 is unsubstituted alkyl or alkyl substituted with a member selected from hydroxyl, phenyl, unsubstituted alkoxy and alkoxy substituted with a phenyl. In a further embodiment when R.sup.b is NR.sup.21R.sup.22, R.sup.21 is H or CH.sub.3.

[0542] In another embodiment when R.sup.b is NR.sup.21R.sup.22, R.sup.21 and R.sup.22 are independently selected from substituted or unsubstituted alkyl. In another embodiment when R.sup.b is NR.sup.21R.sup.22, R.sup.21 is unsubstituted alkyl; and R.sup.22 is substituted or unsubstituted alkyl. In another embodiment when R.sup.b is NR.sup.21R.sup.22, R.sup.21 is unsubstituted alkyl; and R.sup.22 is alkyl, substituted with a member selected from substituted or unsubstituted alkoxy and hydroxyl. In another embodiment when R.sup.b is NR.sup.21R.sup.22, R.sup.21 is unsubstituted alkyl; and R.sup.22 is alkyl, substituted with unsubstituted alkoxy. In another embodiment when R.sup.b is NR.sup.21R.sup.22, R.sup.21 is unsubstituted alkyl; and R.sup.22 is alkyl, substituted with alkoxy, substituted with phenyl. In another embodiment when R.sup.b is NR.sup.21R.sup.22, R.sup.21 is unsubstituted alkyl; and R.sup.22 is alkyl, substituted with unsubstituted alkoxy. In another embodiment when R.sup.b is NR.sup.21R.sup.22, R.sup.21 and R.sup.22 together with the nitrogen to which they are attached, are combined to form a 4- to 8-membered substituted or unsubstituted heterocycloalkyl ring. In another embodiment when R.sup.b is NR.sup.21R.sup.22, R.sup.21 and R.sup.22 together with the nitrogen to which they are attached, are combined to form a 5- or 6-membered substituted or unsubstituted heterocycloalkyl ring.

[0543] In another embodiment, R.sup.b is selected from N(CH.sub.3).sub.2, N(CH.sub.3)(CH.sub.2CH.sub.2(OCH.sub.3)), N(CH.sub.3)(CH.sub.2CH.sub.2OH), NH.sub.2, NHCH.sub.3, NH(CH.sub.2CH.sub.2(OCH.sub.3)), NH(CH.sub.2CH.sub.2(OCH.sub.2Ph), NH(CH.sub.2Ph), NH(C(CH.sub.3).sub.3) and NH(CH.sub.2CH.sub.2OH). In another embodiment, R.sup.b is selected from

##STR00067##

[0544] Additional oxaborole moieties are also disclosed previously in U.S. Pat. No. 8,039,450, and patent application publication US 2009/0291917, the contents of which are hereby incorporated by reference in their entireties.

[0545] In another embodiment, the volatile compound provided has a structure of formula (A1) or (A2):

##STR00068##

[0546] wherein each of A.sup.1, A.sup.2, D.sup.1, and D.sup.2 is independently hydrogen, substituted or unsubstituted C.sub.1-18-alkyl, arylalkyl, aryl, or heterocyclic; or A.sup.1 and D.sup.1, or A.sup.2 and D.sup.2 together form a 5, 6, or 7-membered fused ring which is substituted or unsubstituted;

[0547] each of R.sup.13, R.sup.16, R.sup.17, R.sup.18, and R.sup.19 is independently hydrogen, substituted or unsubstituted C.sub.1_6-alkyl, nitrile, nitro, aryl or aryl alkyl; or R.sup.16 and R.sup.17, or R.sup.18 and R.sup.19 together form an alicyclic ring which is substituted or unsubstituted;

[0548] B is boron; and

[0549] G is a substituted or unsubstituted C.sub.1-18-alkylene, arylalkylene, arylene, or heterocyclic moiety.

[0550] In another embodiment, each of R.sup.A and R.sup.B is independently

##STR00069##

wherein X.sup.2═(CR.sup.6.sub.2).sub.m and m=1, 2, 3, or 4.

[0551] In another embodiment, each of R.sup.A and R.sup.B is independently

##STR00070##

[0552] In another embodiment, the volatile compound provided has the structure of

##STR00071##

[0553] Additional oxaborole moieties are also disclosed previously in U.S. Pat. No. 5,880,188, the content of which is hereby incorporated by reference in its entirety.

[0554] In some embodiments, the volatile compound is present in the formulation at a concentration of about 0.001% to about 1%. In other embodiments, the volatile compound is present in the formulation at a concentration of about 0.01% to about 0.1%. In yet other embodiments, the volatile compound is present in the formulation at a concentration of about 0.02% to about 0.1%. In other embodiments, the volatile compound is present in the formulation at a concentration of about 1% to about 10%. In yet other embodiments, the volatile compound is present in the formulation at a concentration of about 10% to about 30%. In other embodiments, the volatile compound is present in the formulation at a concentration of about 10% to about 60%. In yet other embodiments, the volatile compound is present in the formulation at a concentration of about 30% to about 60%.

[0555] In various aspects, the formulation comprises one or more solvents, liquid carriers, liquid media, or any combination thereof. In some embodiments, the one or more solvents, liquid carriers, and liquid media is an alcohol. In other embodiments, the one or more solvents, liquid carriers, and liquid media are selected from the group consisting of a glycol, a polyglycol, or combinations thereof. In yet other embodiments, the one or more solvents, liquid carriers, and liquid media are selected from the group consisting of glycerin, polyols, sugars, water, and any combination thereof.

[0556] For instance, an exemplary formulation can comprise about 15% w/w or higher of one or more volatile solvents (e.g., volatile solvents with boiling points of 280° C. or less under normal ambient conditions). The exemplary formulation can be useful for applications involving thermal fogging or thermal atomization processes.

[0557] In some instances, the exemplary formulation comprises volatile compound (e.g., an active ingredient) dissolved in one or more water insoluble solvents. The exemplary formulation can comprise surfactants or emulsifiers. The exemplary formulation can be useful to form an emulsion or dispersion upon dilution in water suitable for spray, drench, flood, or dip applications.

[0558] In other aspects, the formulation comprises one or more enhancing agents. In some embodiments, the enhancing agents are selected from the group consisting of a spreading agent, an adhesion agent, a surfactant, a stabilizer, a surface tension reducing agent, a dynamic surface tension reducing agent, a rheology modifying agent, and any combination thereof.

[0559] In certain aspects, the formulation comprises one or more release modifiers. In some embodiments, the release modifiers are selected from the group consisting of a thickener, a gellant, a polymer, and combinations thereof.

[0560] For instance, an exemplary formulation can comprise i) a volatile compound (e.g., an active ingredient) from about 0.01% to about 50%; ii) one or more solvents and carriers (e.g., water, alcohols, esters, amides, glycols, ethers, glycerin, glycol ethers, their polymers, oligomers, other derivatives, and mixtures thereof); iii) optionally, other general functional ingredients to improve the delivery or use characteristics of the formulation (e.g., stabilizers, pH control agents, surfactants (for wetting, dispersing, spreading, emulsifying, adjuvancy, and the like), rheology control agents, biocides, antifoams, and other ingredients known to the skilled artisan. The exemplary formulation can be in the forms of a solution, or n emulsion, or a suspension, or a dispersion, or any combination thereof.

[0561] In some instances, the exemplary formulation comprises volatile compound (e.g., an active ingredient) in the form of water soluble salt which can be formed by an acidic active ingredient neutralized by a base such as alkaline metal or alkaline earth metal hydroxides, or carbonate, or bicarbonate, or other metal hydroxides, or carbonate, or bicarbonate, or organic amines, or ammonium hydroxide, or choline hydroxide, or histidine, or arginine, or lysine, or any combinations thereof. Such volatile compound could be formed by basic active ingredients neutralized by an acid such as inorganic acids including but not limited hydrochloride acid, nitric acid, sulfuric acid, or organic acids including but not limited to citric acid, acetic acid, or other carboxylic acid containing molecules. The exemplary formulation can be useful for direct application or for application after further dilution in a form of spray, drench, flood, or dip.

[0562] According to certain aspects of the present disclosure, the volatile compound is more uniformly distributed after the step of redistribution. For instance, delivery of the formulation comprising the volatile compound to a first location can result in a non-uniform distribution of the volatile compound at the first location. The volatile compound may thereafter undergo redistribution from the first location to a second location, thus resulting in a more uniform distribution of the volatile compound at the second location. In some embodiments, the uniform distribution is on a surface of the target produce.

[0563] Evaluation of the “uniform distribution” can be accomplished according to practices known in the art. In other embodiments, the uniform distribution is identified via residue analysis of the volatile compound.

[0564] In certain aspects, delivery of the volatile compound to a first location can result in a concentration of the volatile compound at the first location, referred to as a “first concentration.” Upon redistribution of the volatile compound from the first location to a second location, a “second concentration” of the volatile compound can be present at the second location. In some embodiments, the second concentration is lower than the first concentration.

[0565] In various aspects, the step of delivering the volatile compound provides the volatile component at a first mass transfer rate and the step of redistributing provides the volatile component at a second mass transfer rate. In some embodiments, the second mass transfer rate is slower than the first mass transfer rate.

[0566] In a second aspect described herein, a method of applying a volatile compound to a target produce comprises the steps of delivering a formulation comprising the volatile compound to a first location, and thereafter redistributing the volatile compound from the first location to a second location, wherein the second location is on a surface of the target produce. The previously described embodiments of the first method of applying a volatile compound to a target produce are applicable to the second method of applying a volatile compound to a target produce described herein.

[0567] In the second aspect, the volatile compound is redistributed from the first location to a second location, wherein the second location is on a surface of the target produce. Any spot or a plurality of spots located on the surface of the target can comprise the second location in this described method.

[0568] In a third aspect described herein, a method of applying a volatile compound to a target produce comprises the steps of delivering a formulation comprising the volatile compound to a first location, wherein the first location is on a first surface of the target produce and thereafter redistributing the volatile compound from the first location to a second location, wherein the second location is on a second surface of the target produce. The previously described embodiments of the first method of applying a volatile compound to a target produce and of the second method of applying a volatile compound to a target produce are applicable to the third method of applying a volatile compound to a target produce described herein.

[0569] In the third aspect, the volatile compound is delivered to a first location, wherein the first location is on a first surface of the target produce. Any spot or a plurality of spots located on the surface of the target can comprise the first surface of the first location in this described method. Thereafter, the volatile compound is redistributed from the first location to a second location, wherein the second location is on a second surface of the target produce. Likewise, any spot or a plurality of spots located on the surface of the target can comprise the second location in this described method as long as it is different than the first location.

EXAMPLES

[0570] The various embodiments of the present disclosure can be evaluated according to the following exemplary factorial design. The instant example can evaluate methods of applying a volatile compound to a target produce, including the steps of delivering a formulation comprising the volatile compound to a first location, and thereafter, and thereafter redistributing the volatile compound from the first location to a second location, wherein the second location is an enclosed space or a partially enclosed space.

[0571] A negative control formulation (e.g., an untreated substrate and/or a blank treatment formulation) can be tested for comparison to the evaluated formulations of the present disclosure. In addition, one or more positive control formulations (e.g., using similar experimentation but including commercially available active ingredients such as Fludioxonil, Pyrimethanil, Thiabendazole, or Imazalil) can be tested for comparison to the evaluated formulations of the present disclosure.

[0572] Input Parameters

[0573] The input parameters for evaluation of the embodiments can include varying the delivery mechanism and the redistribution mechanism of the formulation to be tested. Various substrates can be evaluated, as well as various volatile compounds at differing percentages in the formulation. In addition, other co-ingredients for the formulations can be tested.

[0574] Input parameters for exemplary formulations of the present disclosure can be found in the following tables:

TABLE-US-00001 TABLE 1 Exemplary Formulation 1 Primary Room fog (e.g., ActiMist) delivery Secondary Within bag or case redistribution Substrate Grape and/or package Volatile Benzoxaborole compound % of volatile 10-30% compound Formulation Non-aqueous soluble liquid Co-ingredients Basic (glycol/alcohol) + Enhancers (spreading agents, adhesion agents, atomizing surfactants, etc.) + Release modifiers (thickeners, gellants, polymers, etc.) + Stabi- lizers (alpha-hydroxy carboxylic acids, anti-oxidizers, etc.)

TABLE-US-00002 TABLE 2 Exemplary Formulation 2 Primary Room fog (e.g., ActiMist) delivery Secondary Within bin redistribution Substrate Apple and/or crate Volatile Benzoxaborole compound % of volatile 10-30% compound Formulation Non-aqueous soluble liquid Co-ingredients Basic (glycol/alcohol) + Enhancers (spreading agents, adhesion agents, atomizing surfactants, etc.) + Release modifiers (thickeners, gellants, polymers, etc.) + Stabi- lizers (alpha-hydroxy carboxylic acids, anti-oxidizers, etc.)

TABLE-US-00003 TABLE 3 Exemplary Formulation 3 Primary Room fog (e.g., ActiMist) delivery Secondary Within case and/or clamshell redistribution Substrate Blueberry, strawberry, and/or package Volatile Benzoxaborole compound % of volatile 10-30% compound Formulation Non-aqueous soluble liquid Co-ingredients Basic (glycol/alcohol) + Enhancers (spreading agents, adhesion agents, atomizing surfactants, etc.) + Release modifiers (thickeners, gellants, polymers, etc.) + Stabi- lizers (alpha-hydroxy carboxylic acids, anti-oxidizers, etc.)

TABLE-US-00004 TABLE 4 Exemplary Formulation 4 Primary Room fog (e.g., ActiMist) delivery Secondary Within case and/or pallet redistribution Substrate Citrus fruit and/or package Volatile Benzoxaborole compound % of volatile 10-30% compound Formulation Non-aqueous soluble liquid Co-ingredients Basic (glycol/alcohol) + Enhancers (spreading agents, adhesion agents, atomizing surfactants, etc.) + Release modifiers (thickeners, gellants, polymers, etc.) + Stabi- lizers (alpha-hydroxy carboxylic acids, anti-oxidizers, etc.)

TABLE-US-00005 TABLE 5 Exemplary Formulation 5 Primary In-line spray or fog tunnel delivery Secondary Within bag and/or case redistribution Substrate Grape and/or package Volatile Benzoxaborole compound % of volatile 0.1-10% compound Formulation Non-aqueous soluble liquid or Aqueous soluble liquid Co-ingredients Basic (glycol/alcohol) + Enhancers (spreading agents, adhesion agents, atomizing surfactants, etc.) + Release modifiers (thickeners, gellants, polymers, etc.) + Stabi- lizers (alpha-hydroxy carboxylic acids, anti-oxidizers, etc.)

TABLE-US-00006 TABLE 6 Exemplary Formulation 6 Primary In-line spray or fog tunnel delivery Secondary Within case and/or clamshell redistribution Substrate Blueberry and/or package Volatile Benzoxaborole compound % of volatile 0.1-10% compound Formulation Non-aqueous soluble liquid or Aqueous soluble liquid Co-ingredients Basic (glycol/alcohol) + Enhancers (spreading agents, adhesion agents, atomizing surfactants, etc.) + Release modifiers (thickeners, gellants, polymers, etc.) + Stabi- lizers (alpha-hydroxy carboxylic acids, anti-oxidizers, etc.)

TABLE-US-00007 TABLE 7 Exemplary Formulation 7 Primary In-line spray or fog tunnel delivery Secondary Within package redistribution Substrate Citrus fruit, pome, and/or package Volatile Benzoxaborole compound % of volatile 0.1-10% compound Formulation Non-aqueous soluble liquid or Aqueous soluble liquid Co-ingredients Basic (glycol/alcohol) + Enhancers (spreading agents, adhesion agents, atomizing surfactants, etc.) + Release modifiers (thickeners, gellants, polymers, etc.) + Stabi- lizers (alpha-hydroxy carboxylic acids, anti-oxidizers, etc.)

TABLE-US-00008 TABLE 8 Exemplary Formulation 8 Primary Drench, dip, and/or flood delivery Secondary Within pallet, bin, and/or case redistribution Substrate Citrus fruit, pome, and/or package Volatile Benzoxaborole compound % of volatile 0.01-0.2% compound Formulation Aqueous soluble liquid Co-ingredients Basic (glycol/alcohol) + Enhancers (spreading agents, adhesion agents, atomizing surfactants, etc.) + Release modifiers (thickeners, gellants, polymers, etc.) + Stabi- lizers (alpha-hydroxy carboxylic acids, anti-oxidizers, etc.)

TABLE-US-00009 TABLE 9 Exemplary Formulation 9 Primary Drench, dip, and/or flood delivery Secondary Within bag and/or case redistribution Substrate Cherry and/or package Volatile Benzoxaborole compound % of volatile 0.02-0.1% compound Formulation Aqueous soluble liquid Co-ingredients Basic (glycol/alcohol) + Enhancers (spreading agents, adhesion agents, atomizing surfactants, etc.) + Release modifiers (thickeners, gellants, polymers, etc.) + Stabi- lizers (alpha-hydroxy carboxylic acids, anti-oxidizers, etc.)

TABLE-US-00010 TABLE 10 Exemplary Formulation 10 Primary Pallet fog delivery Secondary Within pallet and/or case redistribution Substrate Cherry, grape, berry fruit, and/or package Volatile Benzoxaborole compound % of volatile 10-30% compound Formulation Non-aqueous soluble liquid Co-ingredients Basic (glycol/alcohol) + Enhancers (spreading agents, adhesion agents, atomizing surfactants, etc.) + Release modifiers (thickeners, gellants, polymers, etc.) + Stabi- lizers (alpha-hydroxy carboxylic acids, anti-oxidizers, etc.)

[0575] Output Parameters

[0576] The output parameters for evaluation of the embodiments can include testing of: [0577] i) Initial atomization of the volatile compound upon primary delivery; [0578] ii) Initial deposition of the volatile compound upon primary delivery; [0579] iii) Initial coverage uniformity of the volatile compound upon primary delivery; [0580] iv) Rate and/or mobility of the volatile compound via redistribution from a first location to a second location; [0581] v) Endpoint coverage uniformity of the volatile compound following redistribution; [0582] vi) Endpoint coverage of the volatile compound within a package or enclosure following redistribution; and [0583] vii) Percentage of decay of the volatile compound over time.

[0584] The output parameters can be evaluated according to the following means or by a method known to the skilled artisan:

TABLE-US-00011 TABLE 11 Initial Sympatec drop size distribution atomization Initial Microscopic visualization, or visual evaluation using deposition dye Initial coverage Produce surfaces, pedicels, locations via color uniformity indicator or residue analysis of volatile compound Rate and/or Rate of residue loss or gain of the volatile com- mobility of the pound over time volatile compound via redistribution Endpoint coverage Residue variation of the volatile compound across uniformity plants or plant parts Endpoint coverage Residue variation of the volatile compound across within a package plants or plant parts within the package or enclosure or enclosure % decay of the Decay rating of the volatile compound across plants volatile compound or plant parts over time

Example 1

Exemplary Preparation Process

[0585] The formulation or composition comprising the volatile compound can be prepared, amongst other methods, according to the following exemplary example.

[0586] First, one or more solvents or liquid carriers, with optionally functional ingredients, can be combined to achieve a consistent mixture followed by combination with one or more active ingredients. Thereafter, the prepared combination can be mixed, or dissolved, or agitated, or homogenized, or milled to a desired consistency.

[0587] In addition, the active ingredients may be dissolved in the liquid carriers to form a clear solution. For instance, the active ingredients may be suspended or dispersed in the liquid carriers to form a consistent dispersion. In some embodiments, the active ingredients may be neutralized and dissolved in an aqueous carrier to form a clear solution. In some embodiments, the active ingredient may be dissolved in one or more hydrophobic solvents and then added into aqueous phase to form a consistent oil in water emulsion.

[0588] A person skilled in the art can first prepare a concentrated composition comprising an active ingredient at higher concentration (e.g., from 1-50% by weight, or from 5-50% by weight, or from 10-40% by weight, etc.) with a remaining balance of solvents and other functional ingredients. Such concentrated composition can optionally be further diluted by the end user before applying to the intended crops, or can be directly applied depending on the desired use rates, user practices, or conventions known to those skilled in the art.

Example 2

Thermal Fogging Treatment of Red Delicious Apples

[0589] The instant example utilizes 5-fluoro-1-hydroxy-3H-2,1-benzoxaborole (CAS #174671-46-6) as the exemplary volatile compound.

[0590] The instant example was conducted by 1) setting up a 4 m.sup.3 rectangular plastic tent, 2) placing about 500 lbs of red delicious apples in stacked plastic boxes, 3) preparing a foggable formulation by dissolving the volatile compound into a solvent mixture containing 50% w/w propylene glycol, 49.8% w/w isopropyl alcohol, and 0.2% of citric acid to achieve about 30% w/w volatile compound, 4) applying the formulation through a thermal fogger with set temperature at 200° C. and flow rate of about 70 ml/min, 5) storing the apples under refrigerated condition of about 40° F. or 4.4° C. after treatment for observation and residue analysis.

[0591] The residue analysis was performed by 1) homogenizing apples with a blender or food processor into a puree, 2) taking 15 g of puree and adding 15 ml ethyl acetate and QuEChERS Salt (Agilent), 3) thoroughly mixing and agitating the mixture, 4) centrifuging the mixture to allow separation of the supernatant or the extract from the fruit puree or matrix, 5) analyzing the extract for volatile compound residue with a LCMS (6470A Triple Quadrupole LC/MS from Agilent).

TABLE-US-00012 TABLE 12 Volatile compound residue over time during storage Residue found on the Average untreated apples mixed with the Time residue treated apples during storage (days) (mg/kg) (mg/kg) 0 2.971 N/A 9 1.745 N/A 52 1.887 0.166 94 1.205 0.452

[0592] The untreated apples were added to the treated apple storage at 40 days after treatment. As shown in Table 12, the untreated apples received volatile compound and accumulate during storage over time, which indicated the fruits that might not be treated or lack of sufficient treatment due to imperfect applications would be protected or receive better protection due to the secondary redistributions of the volatile compound.

Example 3

Thermal Fogging Treatment of Blueberries

[0593] The instant example utilizes 5-fluoro-1-hydroxy-3H-2,1-benzoxaborole (CAS #174671-46-6) as the exemplary volatile compound.

[0594] The experiment was conducted by 1) setting up a 4.3 m.sup.3 rectangular plastic tent, 2) placing blueberries in open clamshells in the tent, 3) preparing a foggable formulation by dissolving volatile compound into a solvent mixture containing 50% w/w propylene glycol, 47.8% w/w isopropyl alcohol, 2% w/w sorbitan mono-oleate, and 0.2% of citric acid to achieve about 10% w/w volatile compound, 4) inoculating the blueberries before treatment, 5) applying the formulation through a thermal fogger with set temperature at 200° C. and flow rate of about 70 ml/min, and target use rate of 10 mg active ingredient per kg of blueberries, and 6) storing the blueberries under refrigerated condition of about 4° C. after treatment, and at room temperature to incubate for observation of disease infections.

TABLE-US-00013 TABLE 13 B. cinerea infection assessment for blueberries Untreated blueberries Untreated blueberries placed adjacent to isolated in storage treated blueberries Time B. cinerea B. cinerea B. cinerea B. cinerea (days) incidence severity incidence severity 4 12.6% 3.1% 2.6% 0.2% 13 35.6% 17.1% 19.2% 10.6%

[0595] B. cinerea (Botrytis cinerea or Gray mold) infection was assessed at 4 and 13 days incubation time for both untreated blueberries in isolation and untreated blueberries placed adjacent to the treated blueberries one day after the treatment. As shown in Table 13, the untreated blueberries placed adjacent to the treated blueberries have lower disease incidence and severity than those untreated blueberries placed in isolation, which indicated the blueberries that received insufficient or no treatment of volatile compound during the applications can be protected by the secondary redistribution approach described herein.

Example 4

Thermal Fogging Treatment of Blueberries

[0596] The instant example utilizes 5-fluoro-1-hydroxy-3H-2,1-benzoxaborole (CAS #174671-46-6) as the exemplary volatile compound.

[0597] The experiment was conducted by 1) setting up a 4.3 m.sup.3 rectangular plastic tent, 2) placing blueberries in open clamshells in the tent, 3) preparing a foggable formulation by dissolving volatile compound into a solvent mixture containing 50% w/w propylene glycol, 47.8% w/w isopropyl alcohol, 2% w/w sorbitan mono-oleate, and 0.2% of citric acid to achieve about 10% w/w volatile compound, 4) inoculating the blueberries before treatment, 5) applying the formulation through a thermal fogger with set temperature at 200° C. and flow rate of about 70 ml/min, and target use rate of 10 mg active ingredient per kg of blueberries, and 6) storing the blueberries under refrigerated condition of about 4° C. after treatment, and at room temperature to incubate for observation of disease infections.

TABLE-US-00014 TABLE 14 B. cinerea infection assessment for blueberries Untreated blueberries Untreated placed adjacent to blueberries treated blueberries 6 isolated in storage days after treatment Treated blueberries Time B. cinerea B. cinerea B. cinerea B. cinerea B. cinerea B. cinerea (days) incidence severity incidence severity incidence severity 13 23.4% 10.8% 16.7%  4.7% 2.8% 1.1% 16 25.0% 13.8% 23.0%  6.2% 2.8% 1.1% 24 31.3% 25.2% 33.3% 15.0% 5.6% 3.3%

[0598] B. cinerea infection was assessed at 13, 16, and 24 days incubation time under room temperature shelf life conditions for both untreated blueberry in isolation, untreated blueberry placed adjacent to the treated blueberry six days after the treatment, and the treated blueberries. As shown in Table 14, the untreated blueberries placed adjacent to the treated blueberries have lower disease incidence and severity than those untreated blueberries placed in isolation, which indicated the blueberries that received insufficient or no treatment during the applications can be protected by the secondary redistribution approach described herein.

Example 5

Dipping Treatment of Strawberries

[0599] The instant example utilizes 5-fluoro-1-hydroxy-3H-2,1-benzoxaborole (CAS #174671-46-6) as the exemplary volatile compound.

[0600] The experiment was conducted by 1) preparing a dipping treatment solution by dissolving volatile compound into 20% v/v isopropanol water solution to achieve 10 ppm concentration, 2) pre-inoculate all the strawberries before treatment, 3) dipping strawberries in the prepared solution for 30 seconds, 4) storing the strawberries under refrigerated conditions and at room temperature to incubate for disease observations.

TABLE-US-00015 TABLE 15 B. cinerea infection assessment for strawberries Untreated Untreated strawberries strawberries placed adjacent isolated to treated Treated in storage strawberries strawberries Time B. cinerea B. cinerea B. cinerea (days) severity severity severity 3 17.3% 5.4% 0.0% 5 94.0% 43.8% 0.0%

[0601] B. cinerea infection was assessed at 3 and 5 days incubation time for both untreated strawberries in isolation and untreated strawberries placed adjacent to the treated strawberries. As shown in Table 15, the untreated strawberries placed adjacent to the treated strawberries have lower disease severity than those untreated but placed in isolation, which indicated the strawberries that received insufficient or no treatment of volatile compound during the applications can be protected by the secondary redistribution approach described herein.

Example 6

Dipping Treatment of Mandarins

[0602] The instant example utilizes 5-fluoro-1-hydroxy-3H-2,1-benzoxaborole (CAS #174671-46-6) as the exemplary volatile compound.

[0603] The experiment was conducted by 1) preparing a dipping treatment solution by diluting 360 ml concentrated formulation containing 10% w/w volatile compound, 45% w/w propylene glycol, 43.02% w/w isopropanol, 1.8% w/w sorbitan mono-oleate, 0.18% w/w citric acid into 60 L water, 2) dipping a box of mandarins into the treatment solution bath for about 60 seconds, 3) after air drying of the mandarins, preparing a box of mandarins containing 50% untreated mandarins and 50% treated mandarins, 4) storing the mandarins under 3-5° C. refrigerated conditions for 7 days, and then storing at room temperature with high humidity to incubate for disease observations.

TABLE-US-00016 TABLE 16 Penicillium Digitatum (Green mold) and Penicillium italicum (Blue mold) infection assessment for mandarins Untreated mandarins Equally mixed mandarins isolated in storage of untreated and treated Time Green and Gray molds Green and Gray (days) incidence molds incidence 10 6.4% 4.1%

[0604] Penicillium digitatum (Green mold) and Penicillium italicum (Blue mold) infection incidence of the mandarins was assessed at 10 days incubation time under room temperature shelf life conditions for both untreated mandarins in isolation and equally mixed untreated and treated mandarins to simulate uneven drench or dip treatment applications. As shown in Table 16, the box of equally mixed mandarins demonstrated lower overall mold incidence than those untreated mandarins placed in isolation, which indicated the mandarins that received insufficient or no treatment during the applications can be protected by the secondary redistribution approach described herein.

[0605] The residues of volatile compound was also analyzed for the mandarins of initial untreated and treated fruits as well as the untreated fruits mixed with the treated fruits during cold storage to simulate insufficient coverage of initial dipping or drenching treatment applications. As shown in Table 17, the untreated mandarins received volatile compound during the cold storage over time, which indicated the mandarins that might not be treated or lack of sufficient treatment due to imperfect applications would be protected or better protected due to the secondary redistributions of the active ingredient.

TABLE-US-00017 TABLE 17 Volatile compound residue over time during cold storage Residue on Residue on Time untreated untreated Residue on in cold mandarins in mandarins mixed with treated storage isolation treated mandarins mandarins (days) (mg/kg) (mg/kg) (mg/kg) 0 Non-detectable Non-detectable 0.877 3 Not analyzed 0.400 1.168 7 Not analyzed 0.403 1.182

Example 7

Spray Treatment of Mandarins

[0606] The instant example utilizes 5-fluoro-1-hydroxy-3H-2,1-benzoxaborole (CAS #174671-46-6) as the exemplary volatile compound.

[0607] The experiment was conducted by 1) preparing a spray treatment solution by diluting 6 nil concentrated formulation containing 10% w/w volatile compound, 45% w/w propylene glycol, 43.02% w/w isopropanol, 1.8% w/w sorbitan mono-oleate, 0.18% w/w citric acid into 1 L water, 2) spraying a box of mandarins with the use rate of 60 ml treatment solution per box, 3) after air drying of the mandarins, preparing a box of mandarins containing 50% untreated mandarins and 50% treated mandarins, 4) storing the mandarins under 3-5° C. refrigerated conditions for 7 days, and then storing at room temperature with high humidity to incubate for disease observations.

TABLE-US-00018 TABLE 18 Penicillium Digitatum (Green mold) and Penicillium italicum (Blue mold) infection assessment for mandarins Untreated mandarins Equally mixed mandarins isolated in storage of untreated and treated Time Green and Gray molds Green and Gray (days) incidence molds incidence 10 0.97% 0.64%

[0608] Penicillium Digitatum (Green mold) and Penicillium italicum (Blue mold) infection incidence of the mandarins was assessed at 10 days incubation time under room temperature shelf life conditions for both untreated mandarins in isolation and equally mixed untreated and treated mandarins to simulate uneven spray treatment applications. As shown in Table 18, the box of equally mixed mandarins demonstrated lower overall mold incidence than those untreated mandarins placed in isolation, which indicated the mandarins that received insufficient or no treatment during the applications can be protected by the secondary redistribution approach described herein.

[0609] The residues of volatile compound was also analyzed for the mandarins of initial untreated and treated fruits as well as the untreated fruits mixed with the treated fruits during cold storage to simulate insufficient coverage of initial spray treatment applications. As shown in Table 19, the untreated mandarins received volatile compound during the cold storage over time, which indicated the mandarins that might not be treated or lack of sufficient treatment due to imperfect spray applications would be protected or better protected due to the secondary redistributions of the active ingredient.

TABLE-US-00019 TABLE 19 Volatile compound residue over time during cold storage Residue on Relative Residue on untreated standard Time untreated mandarins mixed Residue on deviation in cold mandarins in with treated treated of residue storage isolation mandarins mandarins, on treated (days) (mg/kg) (mg/kg) mg/kg mandarin, % 0 Non-detectable Non- 0.649 40.9% detectable 3 Not analyzed 0.239 0.505 11.2% 7 Not analyzed 0.190 0.278 18.1%