WO1999015017A1

WO1999015017A1 - Fungicidal compositions for plants containing phosphonate and phosphate salts, and derivatives thereof

Info

Publication number: WO1999015017A1
Application number: PCT/US1997/016997
Authority: WO
Inventors: John B. Taylor
Original assignee: Foliar Nutrients, Inc.
Priority date: 1997-09-19
Filing date: 1997-09-19
Publication date: 1999-04-01
Also published as: AU741341B2; AU4495397A

Abstract

A fungicidal composition for plants containing phosphonate and phosphate salts, and derivatives thereof is disclosed. The composition provides a single product which may be employed to control parasitic fungi in plants through mitigation of pathological acerbation of certain fungi.

Description

FUNGICIDAL COMPOSITIONS FOR PLANTS CONTAINING PHOSPHONATE AND PHOSPHATE SALTS, AND DERIVATIVES

THEREOF

Background of the invention

The present invention is broadly concerned with fungicidal compositions, and methods of use, which provide improved efficacy in controlling parasitic fungi in plants. More particularly, the compositions and methods of use of the invention include fungicidally effective amounts of both phosphate, preferably in the form of either mono or dipotassium phosphate (KH₂PO₄, K₂HPO₄) and phosphonate, preferably in the form of either mono or dipotassium phosphonate (KH₂PO₃, K₂HPO₃), in aqueous

solution.

Phosphorus is an essential major element in plant nutrition because it governs the energy producing reactions, including those that are oxidative, and photophosphorylative and the production of adenosine diphosphate (ADP) and adenosine triphosphate (ATP). Energy-rich phosphate bonds of ADP and ATP provide the energy for many of the physiological reactions that occur in plants.

The element phosphorous appears in two general forms that concern the present invention — phosphonate and phosphate. The term "phosphonate," sometimes also referred to as "phosphite," means the salts (organic or inorganic) of either phosphonic acid or phosphorous acid. Phosphonic and phosphorous acids have the formula H₃PO₃ and a molecular weight of 82.00. Their structures from the International Union of Pure and Applied Chemistry are shown below: OH OH

H — P = O HO — P

OH OH

Phosphonic Acid Phosphorous Acid

CA: 13598-36-2 CA: 10294-56-1

The term "phosphate" means the salts (organic or inorganic) of phosphoric acid having the formula H₃PO₄, molecular weight of 98, and has the following structure:

O

II HO — P — OH

I

OH

Phosphoric Acid CA: 7664-38-2

In the past, various phosphonate compounds have been proposed as useful in fungicidal and fertilizer compositions for application to plants. See, e.g. U.S. Patent

Nos. 4,075,324 and 4,119,724 to Thizy, describing phosphorous acid, its inorganic and organic salts, as a plant fungicide; U.S. Patent No. 4,139,616 to Dueret, describing fungicidal compositions based on phosphorous acid esters and salts thereof;

U.S. Patent No. 4,542,023 to Lacroix et al., describing organophosphorous derivatives as possessing systemic and contact fungistatic and fungicidal activity; U.S.

Patent Nos. 4,698,334 and 4,806,445 and 5,169,646 to Horriere et al., describing fungicidal compositions based on alkyl phosphonates; U.S. Patent Nos. 4,935,410 and 5,070,083 to Barlet, describing fungicidal aluminum tris-alkyl-phosphonate compositions; and U.S. Patent No. 5,514,200 to Lovatt, describing formulations of phosphorous-containing acid fertilizer for plants. (The teachings ofthe proceeding U.S. Patents are hereby incorporated by reference.) The above references disclose phosphonate compositions have been found to be effective for protecting plants, and particularly grape vines, citrus and fruit trees and tropical plants, against fungal attack.

Once assimilated, phosphonates have been shown to enhance the phytoimmune system. The phosphonate induced stimulation of the phytoimmune system is triggered by the induction of ethylene production, followed by a rapid accumulation of phytoalexins at the site of infection. Phosphonates have also been shown to have detrimental effect on the growth of Phycomycetes. See, Pegg, K.G. and deBoer, R.F., "Proceedings of the Phosphonic (Phosphorous) Acid Work Shop, "Australiasian Plant

Pathology, Vol. 19 (4) 1990.

In accordance with this development of the present invention, however, it has recently been discovered that phosphonates exacerbate the non-target Ascomycete fungi, producing an eiphytotic outbreak of much greater magnitude than the infections occurring without phosphonate treatment. This phenomenon is known as pathological acerbation.

In the past, phosphates were not viewed as a solution to pathological acerbation of Ascomycete fungal infections. This is because phosphates are viewed primarily as a fertilizer with only limited, or even detrimental, fungical properties. For example, U.S. Patent 5,514,200 teaches that phosphate fertilizers inhibit beneficial symbiosis between plant roots and mycorrhizal fungi, and further promote bacterial and fungical growth in the rhizosphere, including the growth of pathogenic fungi and other small soil-borne organisms. (Col. 2, lines 18-28). Phosphates have also been considered to be a competitive inhibitor for phosphonate assimilation, thus inhibiting the ability of phosphonates to protect against fungus attack. See, Pegg, K.G. and deBoer, R.F., "Proceedings of the Phosphonic (Phosphorous) Acid Work Shop," Australiasian Plant Pathology, Vol. 19 (4), pp. 117 and 144, 1990. Yet further, phosphonates and phosphates were believed to be "biological strangers," with the presence of phosphonates or its esters, exerting little or no influence on enzyme reactions involving phosphates. Robertson, H.E. and Boyer, P.D., "The Biological Inactivity of Glucose 6 — phosphonate, Inorganic Phosphites and Other Phosphites," Archives of

Biochemistry and Biophysics, 62 pp. 380-395 (1956).

Accordingly, the requirements for a successful phosphonate-based fungicide depend on the elimination of the phosphonate-induced pathological ascerbation of Ascomycete fungical infections. Summary of the Invention

The present invention addresses the problems outlined above, and provides an improved anti-fungicidal composition for plants that contains, as active ingredients, fungicidally effective amounts of both phosphonates and phosphates. According to the present invention, it has been discovered that the application to a plant of the inventive phosphonate/phosphate composition substantially eliminates pathological acerbation of Ascomycete fungi, while at the same time, provides a means to control Phycomycetes and Ascomycetes with a single product. Thus, an object of present invention is to provide a fungicidal composition for protection for plants against fungal infection, especially Phycomycetes and Ascomycetes.

Another object of the invention is to provide such anti-fungal protection with a single product that upon application does not cause pathological acerbation of Ascomycetes infections.

A further object of the invention is to provide a method of treating plants and to provide anti-fungical protection in plants against attack by Phycomycete and Ascomycete fungi.

A yet further object of the invention is to provide an anti-fungal composition for treating plants that is environmentally safe, inexpensive to use and has low mammalian toxicity.

These and other objects of the invention are attained by the invention disclosed below. According to the invention, anti-fungicidal compositions for the protection of plants, especially citrus and fruit trees and vines against fungus attack, preferably contain as an active material a fungicidally effective amount of at least a first salt formula selected from the group consisting of KH₂PO₃, K₂HPO₃, and K₃PO₃, and at least a second salt selected from the group consisting of KH₂PO₄, K₂HPO₄ and K₃PO₄, in a mixture with an agriculturally acceptable carrier.

The composition preferably comprises an aqueous solution wherein each salt is present in solution from about 20 millimole to about 5% vol. /vol.. According to another aspect of the invention, the amount of the first salt is one part by weight and the amount of the second salt is between 0.001 and 1,000 parts by weight.

Phosphonate salts useful in the practice of the invention also include those

organic and inorganic salts taught by U.S. Patent Nos. 4,075,324 and 4,119,724 to Thizy et al., (see, e.g., col. 1, In. 51-69 through col. 2, In. 1-4). A Detailed Description of the Preferred Embodiment.

The following examples set for preferred concentrations and techniques for formulation thereof, as well as methods of application and use and test results

demonstrating the efficacy of the inventive concentration in protecting plants against attack by Ascomycete and Phycomycete fungi. It is to be understood, however, that these Examples are presented by way of illustration only and nothing therein shall be

taken as a limitation upon the overall scope of the invention. The specific components tested in the Examples were prepared and applied as follows. Method of Preparation

A. Potassium Phosphonate (KH₂PO₃1 Aqueous Solution. H₃PO₃ is produced by the hydrolysis of phosphorus trichloride according to the reaction: PC1₃ + 3H₂0 > H₃PO₃ + 3HC1. The HCI is removed by stripping under reduced pressure and the

phosphonic acid (H₃PO₃) is sold as a 70% acid solution.

The phosphonic acid is then neutralized in aqueous solution by potassium hydroxide according to the reaction: H₃PO₃ + KOH > KH₂PO₃ + H₂0 to about pH 6.5 and to produce a 0-22-20 liquid weighing 11.15 lbs. /gal. This solution is commercially available and is sold under the trademark "Phos-Might" by Foliar Nutrients, Inc., Cairo, GA 31728.

B. Potassium Phosphate (K HPO^ Aqueous Solution. Mono potassium phosphate (0-51.5-34) is reacted with 45% potassium hydroxide in aqueous solution to produce dipotassium phosphate by the following reaction: This solution is commercially available and is sold under trademark "K-Phos" by Foliar Nutrients, Inc., Cairo, GA 31724

KH₂PO₄ + KOH > K₂HP0₄ + H₂0 with a product density of 1.394 at 20°C and a solution pH of 7.6 producing a 0-18-20 analysis.

C. ΪQ POj/KjHPO,, Solution. Varying amounts of each compound (K₂HPO₃;KH₂PO₃; K₂HPO₄; or KH₂PO₄) in aqueous solution are combined at rates ranging from 20 millimole to 5% vol./ vol., depending on crop host and the pathogen complex and level of infection.

Method of Application

The preferable method of application is foliar, either by ground or aerial equipment, but is not limited to that method alone. Injection or soil applications, for example, could also be efficacious depending on specific crops and pathogens.

The inventive compositions have utility on fruit crops, agronomic crops, ornamentals, trees, grasses, vegetables, grains, and floricultural crops, as well as, some aquatic crops including water cress.

The fungicidal properties of the compounds according to the invention are various, but are particularly interesting in the case described in the following examples: Examples 1-5 exemplify a portion of these applications. In Examples 1-4, fungicidal treatments were applied to ornamentals, citrus and vegetables. In each of Examples 1-4, treatments were applied as a one gallon solution by a back pack sprayer, maintained at about 60 psi, in sufficient quantities of water to achieve thorough coverage.

All treatments were applied to the appropriate number of experimental units assigned in a randomized complete block (RCB) design replicated four times. Example #5 was a pre-harvest fungicidal spray evaluation on "Nova" tangelos.

As used in the examples, "percent infection" means percent of leaves that exhibit fungus lesions. "Phytotoxicity" means number crop injury to leaves that fell off the plant following the application of the solution.

The Ascomycete fungi were the subjects of testing in Examples 1 through 5 and are all members of the Ascomycete family.

EXAMPLE NO. 1

Dogwood\Powdery Mildew Fungicide Trial Trail Ridge Nursery, Keystone Hts., Florida

The compounds according to the invention are studied for the effect on the powdery mildew (Oidium Spp.), which is responsible for foliar infections in dogwood.

Potassium phosphonate and potassium phosphate solutions were applied in compositions as set forth in Table 1 below. An average of 5 six-inch pots per experimental unit with 4 repetitions in a randomized complete block ("RCB") design were considered. The solutions were applied to Dogwood (Cornis Florida Var. "Weaver"). The application of the compositions were made in April 25, 1996, May 8, 1996, and May 23, 1996. The effects of the various compositions were rated on May 30, 1996.

Table 1 shows that when a potassium phosphonate solution (containing no appreciable amount of phosphate) is applied to dogwood, pathological acerbation of the Ascomycete fungus occurs in 100 percent of the dogwood leaves, in contrast to the

control, which exhibited only 30 percent infection. The inventive composition that combine potassium phosphate and potassium phosphonate showed a complete

elimination of the pathological acerbation phenomenon, and in fact, dropped the

amount of infection by about 20 percent.

TREATMENT RATE/100 gal. *%INFECTION PHYTOTOXICiTY

1) POTASSIUM PH0S- 1 % 100 0 PHONATE SOLUTION

2) POTASSIUM PHOS- 1 % 0 0 PHATE SOLUTION

3) POTASSIUM PHOS- 1 % 10 PHONATE SOLUTION

+ +

POTASSIUM PHOS- 1 % 0 PHATE SOLUTION

4) POTASSIUM PHOS2% 0 0 PHATE SOLUTION

5) CONTROL 30 0 EXAMPLE NO. 2

Shumard Oak/Powdery Mildew Fungicide Trial Trail Ridge Nursery, Keystone Hts., Florida

In Example No. 2, the inventive compositions were tested for effectiveness against the powdery mildew (Phyllactinia corylea) that infects shumard oak (Quercus

shumardii). In Example No. 2, an average of ten 3-gallon plots per experimental unit

with 4 repetitions in a randomized complete block design were examined.

When only potassium phosphonate solution was applied, the percentage of

infection increased to 40 percent, compared to a 20 percent infection in the control, indicating a pathological acerbation of the Ascomycete fungi. When the inventive composition including potassium phosphonate and potassium phosphate was applied, the infection was completely eliminated.

TABLE 2 TREATMENT RATE/100 gal, *%INFECTION PHYTOTQXICnT

1) POTASSIUM PHOS- 1 % 40 0 PHONATE SOLUTION

2) POTASSIUM PHOS- 1 % 0 0 PHATE SOLUTION

3) POTASSIUM PHOS- 1 % 0 0 PHONATE SOLUTION

+ +

POTASSIUM PHOS- 1 % PHATE SOLUTION

4) POTASSIUM PHOS2% 0 PHATE SOLUTION

5) CONTROL 20 0 EXAMPLE NO. 3

Citrus Alternaria Fungicide Trial Kerr Center, Vero Beach, Florida

In Example No. 3, the inventive composition was tested for effectiveness in

citrus trees (Alternaria citrϊ) that were infected with the fungi.

As used in Table No. 3 below, "% Y.L.D. " means percent young leaf drop, and " % Y.F.D." means percent young fruit drop. % Y.L.D. and % Y.F.D. were determined by exanώiing 4 terminals/tree with 4 repetitions in a randomized complete

block design. The date on which the compositions were applied were March 21, 1996. The compositions were rated on April 2, 1996. When only potassium phosphonate solutions were applied, % Y.L.D. and % Y.F.D. increased from 6.2 and 1.5 to 23.9 and 37.9, respectively, indicating pathological acerbation of the Ascomycete fungi. Application of the inventive composition not only eliminated the acerbation, but

showed an improvement in Y.L.D. and Y.F.D.

TABLE 3

TREATMENT RATE/100 gal %Y,L,D- % Y , F , D ,

PHYTOTOXICITY

1) POTASSIUM PHOS- 0.5% 5.2 3.8 0 PHATE SOLUTION

2) POTASSIUM PHOS- 1 % 2.5 2.5 0 PHATE SOLUTION

3) POTASSIUM PHOS- 2 % 1.5 1.0 0 PHATE SOLUTION

4) POTASSIUM PHOS- 1 % 23.9 37.5 0 PHONATE SOLUTION

5) POTASSIUM PHOS- 0.5% 2.2 3.7 0 PHATE SOLUTION

+ +

POTASSIUM PHOS- 0.5% PHONATE SOLUTION

6) CONTROL - 6.2 1.5 0

EXAMPLE NO.4

Carrot/ Alternaria Fungicide Trial

In Example No. 4, carrot plots were inoculated with Alternaria dauci fungi. The plot sizes were single rows X 25 feet X 4 repetitions in a RCB design. The dates that compositions were applied were February 2, 9, 15, 22, and March 8, 14, 22, and 28, 1996. The fungi infections were rated on April 5 and April 23, 1996. The second rating was 25 days after the last fungicide application. The test took place at Sanford, Florida.

Application of the inventive solutions including potassium phosphonate and potassium phosphate improved the extent of infection from that otherwise occurring in the control carrots. Although the solution making use of only potassium phosphonate caused a slight improvement from the infection occurring in the control, it was substantially less than that associated with the inventive composition.

Also shown in Example No. 4 is a comparison of the effectiveness of the inventive composition to other fungicides, including Cu-Alexin and Fe-Alexin. This test demonstrates that the inventive composition is as effective as other well known fungicides, but without being as environmentally toxic. TABLE 4

TREATMENT RATE/100 GAL. AVG% INFECTION

4/5/96

4/23/96

1) POTASSIUM PHOS1 % 6.9 8.2 PHATE SOLUTION

2) POTASSIUM PHOS- 1 % 18.7 28.8 PHONATE SOLUTION

3) POTASSIUM PHOS- 0.5 % 8.9 10.7 PHATE SOLUTION

+ +

POTASSIUM PHOS- 0.5%

PHONATE SOLUTION

4) Cu-ALEXIN 0.2 lb ai 8.8 11.6

5) Fe-ALEXIN 0.2 lb ai 12.7 12.9

6) CONTROL 23.0 34.8

EXAMPLE NO. 5

Citrus Preharvest Spray Trials Kerr Center, Vero Beach, Florida

In Example No. 5, twenty-two fruits, each from five nova tangelo trees, were randomly selected and marked. The fruits were scuffed with an emery board and then sprayed with the compositions set forth below in Table 5, with five treatments on the

same day. Seven days later, the fruit was picked and stored for two weeks in sealed white plastic bags, then examined for penicillium mold.

The degree of infection was rated using following scores: 0 = no infection, 1 = light infection (less than 30% coverage), 2 = severe infection (100% coverage).

The degree of infection is the mean of scores from 22 fruit. TABLE 5

DEGREE OF TREATMENT RATE INFECTION #ROTTEN FRUTT

PHYTOTOXICITY

1) POTASSIUM 1 %

PHOSPHONATE

SOLUTION

2) POTASSIUM 2% 0.91 12 0

PHOSPHONATE

SOLUTION

3) POTASSIUM 1 % 0 0 0

PHOSPHATE

SOLUTION

4) POTASSIUM 0.5% 0.27 0

PHOSPHATE

SOLUTION

+ +

POTASSIUM 0.5%

PHOSPHONATE

SOLUTION

5) CONTROL _ 1.41 12 0

The above Examples demonstrate that the inventive compositions are useful in protecting plants against attack by both Phycomycete and Ascomycete with the application of one solution.

It will also be appreciated that compositions for controlling Phycomycete and Ascomycete fungi diseases in plants may also contain phosphate and phosphonate compounds comprising a fungicidally effective amount of at least a first salt having the following formula: R²

I _ n+

R, — O — P — O Me

O

And a second sa"lt having the following forjnula:

O

II R, — O — P — OH

I o

I

R₃

Where R, is selected from group consisting of H, K, an alkyl radical containing from 1 to 4 carbon atoms, halogen-substituted alkyl or mtro-substituted alkyl radical, an alkenyl, halogen-substituted alkenyl, alkinyl, halogen-substituted alkinyl, alkoxy- substituted alkyl radical, ammonium substituted by alkyl and hydroxy alkyl radicals;

R₂ and R₃ are selected from a group consisting of H and K;

Me is selected from a group consisting of K, alkaline earth metal cations,

aluminum atom; ammonium cation; and n is a whole number from 1 to 3, equal to the valence of Me.

It will be appreciated that foliar applications of the inventive compositions will

be effective as a common agricultural practice to control root pathogens caused by

Phytophthoran, Phythium, and foliar infections caused by Plasmopara.

It will also be appreciated that the inventive compositions will have biocidal and arthropod pest control activity, and also have fertilizer effects, in plants. (See e.g., U.S. Pat. Nos. 5,206,228, 5,133,891 and 5,514,200).

The disclosures in all references cited herein are incorporated by reference.

Claims

What is Claimed is:

1. A fungicidal composition for controlling fungus disease in plants

comprising: a fungicidally effective amount of at least a first salt selected from a group consisting of K₂HPO, KH₂PO₃ and K₃PO₃; and a second salt selected from a group consisting of K₂HPO₄, KH₂PO₄ and K₃PO₄.

2. The composition according to claim 1 wherein said composition

comprises an aqueous solution, wherein each said first and second salt being present in solution from about 20 millimole to about 5% vol. /vol.

3. The composition according to claim 1 wherein the amount of said first said salt is one part by weight and the amount of said second salt is between 0.001 and 1 ,000 parts by weight.

4. A method of controlling fungus disease in plants comprising: applying to the plants in fungicidally effective amounts at least a first salt selected from a group consisting of K₂HPO₃, KH₂PO₃ and K₃PO₃; and a second salt selected from a group consisting of K₂HPO₄, KH₂PO₄ and K₃PO₄

5. The method according to claim 4 wherein said composition comprises an aqueous solution, wherein each said first and second salt being present in solution

from about 20 millimole to about 5% vol. /vol.

6. The method according to claim 4 wherein the amount of said first said salt is one part by weight and the amount of said second salt is between 0.001 and 1,000 parts by weight.

7. A fungicidal composition for controlling fungus in plants comprising: a fungicidally effective amount of at least a first salt having the following formula:

R² n+

R, ΓÇö O ΓÇö P ΓÇö O Me

O

And a second salt having the following formula:

O

II R, ΓÇö O ΓÇö P ΓÇö OH

I o

I

R₃

Where R, is selected from group consisting of H, K, an alkyl radical containing from 1 to 4 carbon atoms, halogen-substituted alkyl or nitro-substituted alkyl radical, an alkenyl, halogen-substituted alkenyl, alkinyl, halogen-substituted alkinyl, alkoxy- substituted alkyl radical, ammonium substituted by alkyl or hydroxy alkyl radicals;

R₂ and R₃ are selected from a group consisting of H and K;

Me is selected from a group consisting of K, alkaline earth metal cations, or aluminum atom; ammonium cation; and n is a whole number from 1 to 3, equal to the valence of Me.

8. The composition according to claim 7 wherein said composition comprises an aqueous solution, wherein each said first and second salt being present in solution from about 20 millimole to about 5% vol. /vol.

9. The composition according to claim 7 wherein the amount of said first said salt is one part by weight and the amount of said second salt is between 0.001 and 1,000 parts by weight.