Mixture of 1-amino-1-cyclopropanecarboxylic acid and methyl jasmonate and its use

Abstract

The present invention relates to an agricultural mixture comprising 1-amino-1-cyclopropanecarboxylic acid, a hydrate thereof, a polymorph thereof, or a salt thereof, and methyl jasmonate. The present invention further relates to a method for enhancing apple coloration, comprising applying the mixture of the present invention to apples.

Description

[Technical Field]

[0001] The present invention relates to an agricultural mixture comprising 1-amino-1-cyclopropanecarboxylic acid, a hydrate thereof, a polymorph thereof, or a salt thereof, and methyl jasmonate. The present invention further relates to a method for enhancing apple coloration, comprising applying the mixture of the present invention to apples. [Background technology]

[0002] 1-Amino-1-cyclopropanecarboxylic acid ("ACC") is synthesized by ACC synthase in plants and serves as a precursor for the biosynthesis of ethylene. Ethylene has been shown to be involved in several plant responses, including stress, fruit set, leaf abscission, and flowering. Because of its role as an ethylene precursor, ACC has been used in agriculture to induce ethylene response events.

[0003] Methyl jasmonate is a plant hormone derived from cyclic fatty acids that regulates plant defenses against pests and also regulates developmental processes. Methyl jasmonate has been well studied and has further been found to be involved in root growth, reproductive organ growth, and plant senescence.

[0004] Apple color is very important for marketability and is associated with increased nutritional value. However, many growers struggle to achieve the 50-60% color that retailers require, especially with certain varieties such as Gala. Therefore, there is a need in the art for compositions that can enhance apple color. Summary of the Invention

[0005] In one aspect, the present invention relates to an agricultural mixture comprising 1-amino-1-cyclopropanecarboxylic acid ("ACC"), a hydrate thereof, a polymorph thereof, or a salt thereof, and methyl jasmonate.

[0006] In another aspect, the present invention relates to a method for enhancing apple coloration, comprising applying to apples an effective amount of a mixture comprising ACC, a hydrate thereof, a polymorph thereof, or a salt thereof, and methyl jasmonate.

[0007] Detailed Description of the Invention Applicants have discovered that a mixture of 1-amino-1-cyclopropanecarboxylic acid ("ACC") and methyl jasmonate is unexpectedly superior in enhancing apple coloration compared to the application of either compound alone.

[0008] In one embodiment, the present invention relates to an agricultural mixture comprising 1-amino-1-cyclopropanecarboxylic acid ("ACC"), a hydrate thereof, a polymorph thereof, or a salt thereof, and methyl jasmonate.

[0009] ACC can be used in the form of salts derived from inorganic or organic acids or bases. The acid addition salts of the active ingredients of the present invention can be prepared in situ during the final isolation and purification of the compounds of the present invention, or can be prepared separately by reacting the free base function with a suitable organic acid. Representative acid addition salts include, but are not limited to, acetate, adipate, alginate, aspartate, benzoate, benzenesulfonate, bisulfate, butyrate, camphorate, camphorsulfonate, digluconate, glycerophosphate, hemisulfate, heptanoate, hexanoate, fumarate, hydrochloride, hydrobromide, hydroiodide, 2-hydroxyethanesulfonate (isothionate), lactate, maleate, methanesulfonate, nicotinate, 2-naphthalenesulfonate, oxalate, palmitate, pectinate, persulfate, 3-phenylpropionate, picrate, pivalate, propionate, succinate, tartrate, thiocyanate, phosphate, glutamate, bicarbonate, p-toluenesulfonate, and undecanoate salts. Basic nitrogen-containing groups can be quaternized with agents such as lower alkyl halides, such as methyl, ethyl, propyl, and butyl chlorides, and methyl, ethyl, propyl, and butyl bromides, and methyl, ethyl, propyl, and butyl iodides; dialkyl sulfates (such as dimethyl, diethyl, dibutyl, and diamyl sulfate); long-chain halides, such as decyl, lauryl, myristyl, and stearyl chlorides, and decyl, lauryl, myristyl, and stearyl bromides; aryl alkyl halides (such as benzyl and phenethyl bromides), and others. This results in water- or oil-soluble or dispersible products. Examples of acids that can be employed to form acid addition salts include inorganic acids such as hydrochloric acid, hydrobromic acid, hyaluronic acid, and phosphoric acid, and organic acids such as oxalic acid, maleic acid, methanesulfonic acid, and succinic acid.Base addition salts can be prepared in situ during the final isolation and purification of the compounds of this invention by reacting the carboxylic acid-containing moiety with a suitable base, such as a hydroxide, carbonate, or bicarbonate of a pharmaceutically acceptable metal cation, or with ammonia, an organic primary, secondary, or tertiary amine. Salts include, but are not limited to, cations based on alkali or alkaline earth metals, such as lithium, sodium, potassium, calcium, magnesium, and aluminum salts, and non-toxic quaternary ammonia and amine cations, including ammonium, tetramethylammonium, tetraethylammonium, methylammonium, dimethylammonium, trimethylammonium, triethylammonium, diethylammonium, and ethylammonium. Other representative organic amines useful for the formation of base addition salts include ethylenediamine, ethanolamine, diethanolamine, piperidine, piperazine, and the like.

[0010] Hydrates of ACC suitable for use in the present invention include ACC trihydrate and ACC anhydrate.

[0011] In a preferred embodiment, the concentration ratio of ACC, its hydrate, its polymorph, or a salt thereof to methyl jasmonate is about 1,000:1 to about 1:1,000, more preferably about 100:1 to 1:100, even more preferably about 10:1 to about 1:10, even more preferably about 6:1 to about 1:6, and most preferably about 6:1, 1:1, or 1:6.

[0012] The present invention further relates to a composition comprising a mixture of ACC, a hydrate thereof, a polymorph thereof, or a salt thereof, and methyl jasmonate.

[0013] In preferred embodiments, ACC is present in the compositions of the present invention at a concentration of from about 1 to about 1,000 parts per million ("ppm"), more preferably from about 10 to about 500 ppm, even more preferably from about 50 to about 300 ppm, and most preferably from about 50 ppm to about 300 ppm.

[0014] In a preferred embodiment, methyl jasmonate is present in the composition of the present invention at a concentration of about 1 to about 1,000 ppm, more preferably about 10 to about 500 ppm, even more preferably about 50 to about 300 ppm, and most preferably about 50 ppm to about 300 ppm.

[0015] In a preferred embodiment, the compositions of the present invention may further comprise one or more excipients selected from the group consisting of solvents, anti-caking agents, stabilizers, anti-foaming agents, slip agents, wetting agents, dispersing agents, humectants, thickeners, emulsifiers, penetrating agents, adjuvants, synergists, polymers, propellants and preservatives.

[0016] In another aspect, the present invention relates to a method for enhancing apple coloration, comprising applying to apples an effective amount of a mixture of ACC, a hydrate thereof, a polymorph thereof, or a salt thereof, and methyl jasmonate.

[0017] In a preferred embodiment, ACC, its hydrate, its polymorph, or its salt is applied at a rate of about 1 to about 1,000 grams per hectare ("g / HA"), more preferably at a rate of about 10 to about 500 g / HA, even more preferably at a rate of about 50 to about 300 g / HA, and most preferably at a rate of about 50 or about 300 g / HA.

[0018] In another preferred embodiment, methyl jasmonate is applied at a rate of about 1 to about 1,000 grams per hectare ("g / HA"), more preferably at a rate of about 10 to about 500 g / HA, even more preferably at a rate of about 50 to about 300 g / HA, and most preferably at a rate of about 50 or about 300 g / HA.

[0019] The mixture of the present invention can be applied by any convenient means. Those skilled in the art are familiar with application methods, including foliar application such as spraying, dusting, granular application, and soil application such as spraying, in-furrow treatment, or side dressing. In a preferred embodiment, the mixture of the present invention is applied to plants and / or their fruits as a spray, more preferably as a foliar or space spray.

[0020] As used herein, all numerical values ​​relating to amounts, weight percent, and the like are defined as "about" or "approximately" each specified value, i.e., ±10%. For example, the phrase "about 5,000 parts per million" should be understood as "4,500 to 5,500 parts per million." Thus, amounts within 10% of a specified value are encompassed within the specified range.

[0021] As used herein, a "composition" refers to one or more active ingredients in a carrier. The carrier may be liquid, semi-solid, solid, or gaseous, and may contain additional ingredients. For example, a fermentation broth is a suitable carrier for the present invention.

[0022] The term "effective amount" refers to the amount of formulation that controls the targeted pest. The "effective amount" varies depending on the concentration of the mixture, the type of pest being treated, the severity of the pest infestation, the desired results, and the life stage of the pest being treated. Therefore, it is not always possible to specify an exact "effective amount." However, the appropriate "effective amount" for each individual case can be determined by those skilled in the art.

[0023] Throughout this application, the singular forms "a", "an" and "the" include the plural forms unless the context clearly indicates otherwise.

[0024] The present invention is demonstrated by the following representative examples, which are offered by way of illustration only and not by way of limitation. [Example]

[0025] Example 1 - Coloration of Imperial Gala apples method Ten sets of unripe Imperial Gala apples, harvested three weeks before the normal harvest date, were each sprayed with a foliar application of either 1) 0.05% Regulaid® (control), 2) 50 ppm methyl jasmonate, 3) 300 ppm methyl jasmonate, 4) 50 ppm ACC, 5) 300 ppm ACC, 6) a mixture of 50 ppm methyl jasmonate and 50 ppm ACC, or 7) a mixture of 300 ppm methyl jasmonate and 300 ppm ACC. The percentage of red pixel area (shading) was measured 34 hours after spray application. The percentage of red pixel area is an indicator of apple coloration.

[0026] To determine whether a mixture produced unexpected results, the observed combined efficacy ("OCE") was divided by the expected combined efficacy ("ECE"), where ECE is calculated by the Abbott method: ECE=A+B-(AB / 100) [Where ECE is the expected combined efficacy, and A and B are the fold changes from the control imparted by the single active ingredients.] When the ratio of OCE of the mixture to ECE of the mixture is greater than 1, there is more interaction than expected in the mixture. (Gisi, Synergistic Interaction of Fungicides in Mixtures, The American Phytopathological Society, 86:11, 1273-1279,1996) The results are shown in Table 1 below. [Table 1] result Application of a mixture of methyl jasmonate and ACC had a greater than additive effect on the color development of Imperial Gala apples, as evidenced in Table 1. Specifically, the mixture application resulted in an OCE / ECE ratio of 1.02 for the average % red pixel area compared to the control when methyl jasmonate and ACC were each applied at 300 ppm.

[0027] Example 2 - Coloration of Ultima Gala apples method Ten sets of unripe Ultima Gala apples, harvested three weeks before the normal harvest date, were each sprayed with a foliar spray of either: 1) 0.05% Regulaid® (control); 2) 50 ppm methyl jasmonate; 3) 300 ppm methyl jasmonate; 4) 50 ppm ACC; 5) 300 ppm ACC; 6) a mixture of 50 ppm methyl jasmonate and 50 ppm ACC; or 7) a mixture of 300 ppm methyl jasmonate and 300 ppm ACC. The percentage of red pixel area (shade) was measured 34 hours after spray application. The percentage of red pixel area is an indicator of apple fruit coloration. The results are shown in Table 2 below. [Table 2] result Application of a mixture of methyl jasmonate and ACC had a greater than additive effect on coloration of Ultima Gala apples, as evidenced in Table 1. Specifically, application of the mixture resulted in an OCE / ECE ratio of 1.06 for the average % red pixel area when methyl jasmonate and ACC were each applied at 300 ppm compared to the control.

Claims

1. An agricultural mixture comprising 1-amino-1-cyclopropanecarboxylic acid, a hydrate thereof, a polymorph thereof, or a salt thereof, and methyl jasmonate.

2. 2. The mixture of claim 1, wherein 1-amino-1-cyclopropanecarboxylic acid, a hydrate thereof, a polymorph thereof, or a salt thereof and methyl jasmonate are present in a concentration ratio of about 1,000:1 to about 1:1,000.

3. 3. The mixture of claim 2, wherein 1-amino-1-cyclopropanecarboxylic acid, a hydrate thereof, a polymorph thereof, or a salt thereof and methyl jasmonate are present in a concentration ratio of about 100:1 to about 1:

100.

4. 4. The mixture of claim 3, wherein 1-amino-1-cyclopropanecarboxylic acid, a hydrate thereof, a polymorph thereof, or a salt thereof and methyl jasmonate are present in a concentration ratio of about 10:1 to about 1:

10.

5. 5. The mixture of claim 4, wherein 1-amino-1-cyclopropanecarboxylic acid, a hydrate thereof, a polymorph thereof, or a salt thereof and methyl jasmonate are present in a concentration ratio of about 1:

1.

6. A composition comprising the mixture of claim 1.

7. 7. The composition of claim 6, wherein the concentration of 1-amino-1-cyclopropanecarboxylic acid, its hydrate, its polymorph, or its salt is from about 1 to about 1,000 parts per million.

8. 8. The composition of claim 7, wherein the concentration of 1-amino-1-cyclopropanecarboxylic acid, its hydrate, its polymorph, or its salt is from about 10 to about 500 ppm.

9. 9. The composition of claim 8, wherein the concentration of 1-amino-1-cyclopropanecarboxylic acid, its hydrate, its polymorph, or its salt is from about 50 to about 300 ppm.

10. 7. The composition of claim 6, wherein the concentration of methyl jasmonate is from about 1 to about 1,000 parts per million.

11. 11. The composition of claim 10, wherein the concentration of methyl jasmonate is from about 10 to about 500 ppm.

12. 12. The composition of claim 11, wherein the concentration of methyl jasmonate is from about 50 to about 300 ppm.

13. 10. The composition of claim 1, further comprising one or more excipients selected from the group consisting of solvents, anti-caking agents, stabilizers, anti-foaming agents, slip agents, wetting agents, dispersing agents, humectants, thickeners, emulsifiers, penetrants, adjuvants, synergists, polymers, propellants, and preservatives.

14. 1. A method for enhancing the color development of apples, comprising applying to apples an effective amount of a mixture of 1-amino-1-cyclopropanecarboxylic acid, a hydrate thereof, a polymorph thereof, or a salt thereof, and methyl jasmonate.

15. 15. The method of claim 14, wherein the 1-amino-1-cyclopropanecarboxylic acid, its hydrate, its polymorph, or its salt is applied at a rate of about 1 to about 1,000 grams per hectare.

16. 16. The method of claim 15, wherein the 1-amino-1-cyclopropanecarboxylic acid, its hydrate, its polymorph, or its salt is applied at a rate of about 10 to about 500 grams per hectare.

17. 17. The method of claim 16, wherein the 1-amino-1-cyclopropanecarboxylic acid, its hydrate, its polymorph, or its salt is applied at a rate of about 50 to about 300 grams per hectare.

18. 15. The method of claim 14, wherein the methyl jasmonate is applied at a rate of about 1 to about 1,000 grams per hectare.

19. 20. The method of claim 18, wherein the methyl jasmonate is applied at a rate of about 10 to about 500 grams per hectare.

20. 20. The method of claim 19, wherein the methyl jasmonate is applied at a rate of about 50 to about 300 grams per hectare.

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