WO1998058546A1 - Fungicidal and bactericidal compositions for plants containing compounds in the form of heavy metal chelates - Google Patents

Fungicidal and bactericidal compositions for plants containing compounds in the form of heavy metal chelates Download PDF

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Publication number
WO1998058546A1
WO1998058546A1 PCT/US1998/012264 US9812264W WO9858546A1 WO 1998058546 A1 WO1998058546 A1 WO 1998058546A1 US 9812264 W US9812264 W US 9812264W WO 9858546 A1 WO9858546 A1 WO 9858546A1
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Prior art keywords
heavy metal
eddha
aqueous solution
plants
metal chelate
Prior art date
Application number
PCT/US1998/012264
Other languages
French (fr)
Inventor
John B. Taylor
Original Assignee
Taylor John B
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taylor John B filed Critical Taylor John B
Priority to AU79635/98A priority Critical patent/AU743922B2/en
Priority to NZ501984A priority patent/NZ501984A/en
Publication of WO1998058546A1 publication Critical patent/WO1998058546A1/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • A01N59/20Copper
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/02Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof

Definitions

  • the present invention is broadly concerned with fungicidal and bactericidal
  • compositions, and methods of use which provide improved efficacy in controlling
  • compositions and methods of use of the invention including fungicidally and
  • Fungicides as well as bactericides, are chemical agents used to protect
  • CUTRINE Cu salt of triethanole amine is quite effective as an aquatic algaecide.
  • cupric hydroxide including for example, cupric hydroxide, tri basic copper sulfate and tank mix
  • cupric ion is extremely phytotoxic. Therefore, relatively
  • insoluble forms of inorganic copper compounds such as cupric hydroxide
  • fungicidal or bactericidal are fungicidal or bactericidal. It is known that the in vitro fungicidal activity is
  • fungicidal or bactericidal properties may be desired to for specific fungicidal or bactericidal properties.
  • the present invention address the problems outlined above, and provides an
  • an object of the present invention is to provide a fungicidal
  • composition for protection of plants against a fungal infection is provided.
  • Another object of the invention is to provide such an antifungal protection
  • Another object of the invention is to provide a method for treating plants
  • Another object of the invention is to provide an anti-fungal composition for treating plants
  • an object of the present invention is to provide a bactericide
  • composition for protection of plants against a bacterial infection is provided.
  • Another object of the invention is to provide a composition employing heavy
  • protection of plants preferably contain, as an active material, a fungicidally effective
  • anti-bacterial such as water.
  • anti-bacterial such as water.
  • compositions for the protection of plants preferably contain, as an active material, a
  • agriculturally acceptable carrier such as water.
  • agriculturally acceptable carrier such as water.
  • the fungicidal and bactericidal compositions each preferably employ a heavy
  • metal chelate selected from the group consisting of Fe-EDDHA (ethylene-diamine di
  • the amount of heavy metal is the amount of heavy metal
  • chelate is from about 0.01 to about 1.0 pounds Al per acre.
  • Fig 1 is the chemical structure for Fe EDTA (iron chelate of ethylene diamine
  • Fig 2 is the chemical structure for FE DTPA (iron chelate of diethylene-triamine
  • Fig 3 is the chemical structure for Fe EDDHA (iron chelate of ethylene
  • ferric- APC A iron chelates of ethylene bis(alpha imino-ortho-hydroxyphenylacetic
  • Fig 4 is the chemical structure for Fe pEDDHA (iron chelate of para ethylene
  • Fig 5 is the chemical structure for Fe EDDHMA (iron chelate of ethylene diamine
  • Fig 6 is the chemical structure for Cu EDDHA (copper chelate of ethylene diamine
  • Cu-EDDHA was and can be prepared using the process disclosed in U.S.
  • ferrous and ferric- APC A iron chelates of
  • the preferable method of application is foliar, either by ground or aerial
  • compositions have utility on fruit crops, and agronomic crops
  • Cu-EDDHA sodium cupric ethylene-diamine di (o-hydroxyphenylacetate).
  • KOCIDE 101 available from Griffin Corp., Valdosta, Ga.
  • perithecia spore production body of fungus
  • Treatments were allowed to dry for one hour and then placed in a commercial
  • CGA-115944 and CGA-164058 were safer than CGA115944 which was marginally unacceptable at 0.5 g ai/1.
  • PLOT SIZE Single Row X 25 ft. X 4 reps in a RCB design.
  • Second rating was 25 days after last fungicide application. Plots were
  • K-PHOS Commercially available and is sold under trademark "K-Phos" by Foliar
  • K-PHOS - (K 2 HPO 4 , 0-18-20)
  • K-Phos is a trademark of Foliar Nutrients, Inc.
  • non-metal atoms may be attached to the
  • metal ions by from one to six linkages and, thus, are called uni-, bi-, tri- dentate,
  • Heavy metals such as cobalt, copper, iron, nickel,
  • heavy metal chelate structures examples include:
  • Fe-HEEDTA hydroxy ethylenediamine triacetic acid
  • Fe-EDDHA ethylene dihydroxyphenylacetic acid
  • Phytotoxicity is also rated on an international scale of 0-10 where 0 is equal to no
  • Heavy metal chelates disclosed herein are possess water solubility acceptable
  • Sequestrene 138 Fe contains 6% Iron as metallic, or 8.5%
  • the commercial product has a moisture content of not more than
  • Fe may be applied foriarly at much reduced rates when compared to inorganic salts

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention is fungicidal and bactericidal compositions, and methods of use, which provide improved efficacy in controlling parasitic fungi and bacterial infections in plants. The compositions have fungicidally and bactericidally effective amounts of heavy metal chelates in aqueous solution. Such compositions control fungal and bacterial attacks on plants substantially nonphytotoxic.

Description

TITLE
FUNGICIDAL AND BACTERICIDAL COMPOSITIONS FOR PLANTS
CONTAINING COMPOUNDS IN THE FORM OF HEAVY METAL CHELATES
INVENTOR(S)
John B. Taylor
1420 Lemon Street
Deland, Florida 32720-4599
FIELD OF THE INVENTION
The present invention is broadly concerned with fungicidal and bactericidal
compositions, and methods of use, which provide improved efficacy in controlling
parasitic fungi and bacterial infections in plants. More particularly, the
compositions and methods of use of the invention including fungicidally and
bacterially effective amounts of copper compounds in form of heavy metal chelates,
and preferably in the form of Cu-EDDHA, cupric ethylene diamine dio-
hydroxyphenylacetate in aqueous solution).
BACKGROUND OF THE INVENTION
Fungicides, as well as bactericides, are chemical agents used to protect
agricultural crops from those pathogens which, if left uncontrolled, would result in
unacceptable economic losses.
Copper compounds that are active as fungicides and bactericides have been
in agricultural use since the advent of Bordeaux in the grape vineyards of France in
the early 1800's. Many different formulations of fungicides employing copper
compounds, such as wettable powders, water based flowables and dry flowables, are
commonly used today in modern agricultural applications. Such copper compounds, for the most part, have been inorganic in form
when applied to agricultural uses. Organic forms of the copper compounds have
been found to be generally phytotoxic, especially in foliar applications. (Certain
organic copper compounds, however, have some utility as fungicides (e.g.,
CUTRINE Cu salt of triethanole amine) is quite effective as an aquatic algaecide.)
Modern day agricultural use of inorganic copper compounds as fungicides
employ varying forms of copper compounds having relatively low water solubility,
including for example, cupric hydroxide, tri basic copper sulfate and tank mix
combinations (with heavy metal ethylene bis dithiocarbamate fungicides to enhance
the bactericidal activity against certain important agricultural bacteria such as
Xanthomonas, Pseudomonas, and Erwinia).
Water soluble copper compounds such as CuSO4, though effective to inhibit
germination of fungus spores, cannot be used in foliar applications to agricultural
crops because the cupric ion is extremely phytotoxic. Therefore, relatively
insoluble forms of inorganic copper compounds, such as cupric hydroxide, have
been found to be more effective fungicides. (Not all water insoluble Cu compounds
are fungicidal or bactericidal. It is known that the in vitro fungicidal activity is
largely dependent on its solubility in the spore exudate and in the fungal cell.)
The problem with popular copper fungicides is that, because they are largely
water insoluble, they are normally applied in relatively large volume aqueous
suspensions and, as such, are readily removed by rain. Frequent applications are
thus necessary at short intervals - an application process which is expensive and
environmentally imprudent. Therefore, the need exists for a highly water soluble Cu compound based
fungicide and bactericide that avoids the problems associated with phytotoxicity
experienced in the past with such compounds. A need also exists for such a water
soluble Cu compound based fungicide and bactericides that reduces the adverse Cu
load on the plant, thus reducing the non target impact to the environment. Further,
a need exists for such fungicidal and bactericidal compounds that permits use of
other heavy metals such as manganese, zinc, iron, copper and mixtures thereof, as
may be desired to for specific fungicidal or bactericidal properties.
SUMMARY OF THE INVENTION
The present invention address the problems outlined above, and provides an
improved anti-fungal and anti-bacterial compositions for plants that contains, as
active ingredients, fungicidally and bactericidally effective amounts of heavy metal
chelates in aqueous solution. According to the present invention, it has been
discovered that the application to the plant of the inventive composition substantially
eliminates fungus and bacteria disease, while at the same time, is substantially non-
phytotoxic.
Thus, an object of the present invention is to provide a fungicidal
composition for protection of plants against a fungal infection.
Another object of the invention is to provide such an antifungal protection
with a single product that upon application is not excessively phytotoxic.
Another object of the invention is to provide a method for treating plants and
to provide anti-fungal protection for plants against attack by fungus. 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.
Thus, an object of the present invention is to provide a bactericide
composition for protection of plants against a bacterial infection.
Another object of the invention is to provide a composition employing heavy
metal chelates that functions as both a fungicide and bactericide.
These and other objects of the invention are obtained by invention disclosed
below.
According to one aspect of the invention, anti-fungal compositions for the
protection of plants preferably contain, as an active material, a fungicidally effective
amount of a heavy metal chelate in mixture with an agriculturally acceptable carrier
such as water. According to another aspect of the invention, anti-bacterial
compositions for the protection of plants preferably contain, as an active material, a
bactericidally effective amount of a heavy metal chelate in mixture with an
agriculturally acceptable carrier, such as water.
According to another aspect of the invention, a single composition having
both fungicidal and bactericidal qualities is provided and contains fungicidally and
bactericidally effective amounts of heavy metal chelates in mixture with an
agriculturally acceptable carrier such as water.
The fungicidal and bactericidal compositions each preferably employ a heavy
metal chelate selected from the group consisting of Fe-EDDHA (ethylene-diamine di
(O-hydroxy phenylacetate)), Cu-EDDHA, Mn-EDDHA, and Zn-EDDHA and
mixtures thereof. According to another aspect of the invention, the amount of heavy metal
chelate is from about 0.01 to about 1.0 pounds Al per acre.
A DESCRIPTION OF THE DRAWINGS:
Fig 1 is the chemical structure for Fe EDTA (iron chelate of ethylene diamine
tetraacetic acid).
Fig 2 is the chemical structure for FE DTPA (iron chelate of diethylene-triamine
pentaacetic acid).
Fig 3 is the chemical structure for Fe EDDHA (iron chelate of ethylene
dihydroxyphenylacetic acid) or as listed in the U.S. Patent 2,921,847 ferrous and
ferric- APC A (iron chelates of ethylene bis(alpha imino-ortho-hydroxyphenylacetic
Acid)).
Fig 4 is the chemical structure for Fe pEDDHA (iron chelate of para ethylene
diamine dihydroxyphenylacetic acid).
Fig 5 is the chemical structure for Fe EDDHMA (iron chelate of ethylene diamine
dihydroxyphenylmethylacetic acid).
Fig 6 is the chemical structure for Cu EDDHA (copper chelate of ethylene diamine
dihydroxyphenylacetic acid).
A DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The following examples set forth preferred concentrations and techniques for
formulation thereof, as well as methods of application and use in test results,
demonstrating the efficacy of the inventive concentration in protecting plants against
attack by fungi or bacteria, or both. 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:
Cu-EDDHA was and can be prepared using the process disclosed in U.S.
Patent 2,921,847, the teachings of which are hereby incorporated herein by
reference. The '847 patent describes the process for the preparation of Fe-EDDHA,
which in the '847 patent is referred to as ferrous and ferric- APC A (iron chelates of
ethylene bis(alpha amino-ortho-hydroxyphenylacetic acid). To prepare Cu-
EDDHA, an appropriate Cu salt need merely be substituted for the iron salts
disclosed in the '847 patent. Likewise, other heavy metal chelates disclosed herein
may be prepared by substituting the desired heavy metal for Cu in the process
disclosed in the '847 patent. The chemical structure for Cu-EDDHA is illistrated in
Fig. 6. The chemical structures for other common heavy metal chelates are
illistrated in the following figures: Fig. 1 Fe-EDTA; Fig. 2, Fe-DTPA; Fig. 3, Fe-
EDDHA; Fig. 4, Fe-pEDDHA; and Fig 5, Fe-EDDHMA.
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, can also be applications depending upon specific crops and pathogens.
The inventive compositions have utility on fruit crops, and agronomic crops,
ornamentals, trees, grasses, vegetables, grains, and flori cultural crops, as well as,
some aquatic crops including rice. The fungicidal and bactericidal properties of the compounds according to the
invention are various, but are particularly interesting in the case described in the
following examples: As used in the Examples, "Ave. % infection" means percent of leaves that
exhibit fungus lesions. EXAMPLE 1
Cu-EDDHA and four commercially accepted fungicidal compositions were
applied to Valencia orange on sour orange rootstock. Applications were in 100
gallons of solution (in the concentrations indicated) per acre in mid-summer to
single-tree plots replicated six times in a randomized complete block ("RCB")
design. Seven months later the percentages of citrus greasy spot infection on five branch terminals from each tree were recorded and averaged.
CITRUS GREASY SPOT TEST
CAUKINS GROVES, INDIANTOWN, FLORIDA
RATE/100 * AVE %
TREATMENT GAL. INFECTION 2/10/88
1) FCC-455 Spray Oil (Fla. Citrus
Commission) 1 % 30.0
2) Difenconazole 50 g ai 1.56
3) Difenconazole 100 g ai 1.0
4) Cu-EDDHA 3.2% 0.2 lb ai 2.5
5) KOCIDE 101 4 lbs. 23
6) Untreated — 35
APPL. Single tree plots x 6 Reps.
* Aug. 5 terminals/tree Difenconazole: l-[2-[4-(4-chlorophenoxy)-2-chlorophenyl-(4-methyl-l, 3-dioxolan-
2-yl)-methyl]]-lH-l,2,4-triazole (available from Ciba-Geigy, Greenbough, N.C.)
Cu-EDDHA: sodium cupric ethylene-diamine di (o-hydroxyphenylacetate).
KOCIDE 101 available from Griffin Corp., Valdosta, Ga.
* % infection of citrus greasy spot (Mycosphaerella citri
EXAMPLE 2 FUNGICIDE
Cu-EDDHA, TILT (propiconzaole-Ciba-Geigy) and difenconozole were
applied in 100 gpa to single tree plots of "Valencia" oranges replicated five times in
a RCB design in mid- July.
Twenty mature leaves (from the spring flush) per replicate were harvested
approximately 4 months later and placed under greenhouse conditions and
alternately wetted and dried to simulate natural defoliation and weathering.
These conditions in turn cause the fungus to sporulate by the formation of
perithecia (spore production body of fungus) which were counted as a means of
measuring the fungicidal activity of the treatments. These data are presented below.
CITRUS GREASY SPOT
SCN NURSERY, DUNDEE, FLORIDA
RATE/100
TREATMENT GAL. #PERITHECIA
1) Cu-EDDHA 3.2% 0.2 lb ai 3.24 b
2) Cu-EDDHA 3.2% 0.4 lb ai 5.93 ab
3) TILT 3.6 EC 6 oz. Prod. 6.62 ab
4) Difenconzaole 100 g ai 5.32 ab
5) Difenconazole 200 g ai 11.57 ab
6) CONTROL inoculated 7.97 ab
7) CONTROL not 6.42 ab inoculated Function: ANOVA— 1
Date case no. 1 to 42
Without selection
One way ANOVA grouped over variable 1
TREATMENT NUMBER
with values from 1 to 7
Variable 3
NUMBER OF PERITHECIA PER 5MM FIELD AT 2.5 X -MEAN OF THREE
OBSERVATIONS
ANALYSIS OF VARIANCE TABLE
Degrees of Sum of Error Mean
Freedom Squares Square F-value Prob.
Between 6 226.6508 37.78 1.33 .270
Within 34 965.0170 28.38
Total 40 1191.6678
EXAMPLE 3 FUNGICIDE
Cu-EDDHA, Kocide (cupric hydroxide) and difenconazole were applied to
single tree plots of "Hamlin" oranges in 100 gpa (in concentration indicated) in a
RCB design replicated 4 times. Applications were made in May, June and May and
June. Ten fruit/replicate were sampled in July and percent infection of Melanose
(Diaporthe citri) was determined. See data presented below. CITRUS MELANOSE CONTROL
R.E. KEENE FRUIT COMPANY
RATE LBAI/100 % INFECTION
TREATMENT GAL. TIMING (FRUIT)
Cu-EDDHA 3.2% 0.2 May 9
Cu-EDDHA 3.2% 0.4 May 13
Cu-EDDHA 3.2% 0.8 May 21
Cu-EDDHA 3.2% 0.2 May-June 11
Cu-EDDHA 3.2% 0.4 May-June 15
Cu-EDDHA 3.2% 0.8 May-June 29
Cu-EDDHA 3.2% 0.2 June 14
KOCIDE 4.0 May 12
KOCIDE 0.4 May-June 10
DIFENCONAZOLE 0.5 June 4
Untreated — — 38
4 REPS SINGLE TREE PLOTS.
PENETRATOR (surfactant - non-ionic)@ 4 oz. ALL TREATMENTS
EXAMPLE 4 FUNGICIDE
GRAPEFRUIT (Citrus paradisi 'Marsh')
Greasy spot; Mycosphaerella citri
GREASY SPOT CONTROL ON LEAVES, 1986-87: Spray treatments
were applied dilute (applied to point of run off) by handgun in July to 10-ft-high
trees at a rate equivalent to 700 gal/acre. Treatments were replicated on 8 single¬
tree plots in a RCB design. Groups of 15 shoots on each of the east/west and east
side of each tree were tagged and the initial number of leaves was recorded. In
February, remaining leaves were counted and examined for greasy spot. All treatments except Difolatan (fungicide) reduced greasy spot-induced
defoliation and the percentage number of remaining leaves with greasy spot
symptoms. There were no significant differences in effectiveness between Tribasic
copper sulfate, spray oil, Spotless, Tilt, and Cu-EDDHA. There was too little
greasy spot rind blotch in this test to provide information on the relative efficacy of
treatments for preventing fruit infection.
% remaining leaves
Treatment and rate/100 gal defoliation with greasy spot
Tribasic copper sulfate (53 % Cu) 0.75 lb 1.9 a 20.1 a
Sunspray 7E oil 1 gal 3.1 a 27.0 a
Difolatan 80 Sprills 1.25 lb 8.9 b 49.8 b
Spotless 25W 0.8 lb 1.3 a 22.6 a
Tilt 3.6EC 8 fl oz. 1.5 a 15.9 a
Cu-EDDHA (3.2% Cu) 1.5 gal 0.8 a 12.0 a
Untreated 9.7 b 48.5 b
EXAMPLE 5 FUNGICIDE
Cu-EDDHA, TILT (propinconazole), difenconozole and MERTECT (Merck
Chem. , N.J.) (thiabendazole) were applied in 100 gpa to 2-year-old laurel oaks
(Quercus hemispherica) in 2x2 gal. pots in a RCB design replicated 4 times.
Applications were made in July approximately 3 weeks apart and rated in August a
month later. See data below.
OAK LEAF BLISTER (Taphrina caerulescens) CONTROL
TRAILRIDGE NURSERY, KEYSTONE HEIGHTS, FLORIDA
RATE/PROD ^DISEASE
TREATMENT 100 GAL, INDEX
1) Tilt 3.6 emulsifiable 8 oz 1.5
2) Difenconazole 3.6 2 oz 2.25 emulsifiable
3) Cu-EDDHA 3.2 8 oz 2.8
4) MERTECT 8 oz 1.5
5) Untreated — 4.25
ise Index: Rated 8/26/86. 1 = no disease
2 = light
3 = moderate
4 = heavy
5 = dead foliage
2 x 2 gal trees/exp. unit x 4 Reps in a RCB design
EXAMPLE 6 BACTERICIDE
Cu-EDDHA and Kocide (cupric hydroxide) were applied as foliar spray in
May to Hibiscus sinensis cuttings (100/replicate) x 4 replicates in a RCB design.
Treatments were allowed to dry for one hour and then placed in a commercial
propagation bed under intermittent mist and rated for bacterial (Erwinia
chrysanthemi) infection one week later. Data presented below.
*ERWINIA CONTROL ON HIBISCUS
NELSONS NURSERY, APOPKA, FLORIDA
RATE/CU AVG. %
TREATMENT 100 GAL. INFECTION
1) Cu-EDDHA 3.2% 0.2 lb. ai 6
2) Cu-EDDHA 3.2% 0.4 lb. ai 8
3) KOCIDE 101 2 lbs. ai 25
4) Untreated — 100
100 Cuttings/REP X 4 *ERWINIA chrysanthemi
EXAMPLE 7 BACTERICIDE
A follow-up experiment to EXAMPLE 6 was conducted on rooted cuttings
which were dipped as they were removed from the propagation bed and foliarly
sprayed 7 days later after being potted. Cu-EDDHA and Kocide were applied at the
rates specified below in a RCB design utilizing 100 plants/replicate x 4 reps. Potted
cuttings had not received any previous bactericide treatments prior to potting.
ERWINIA CONTROL ON HIBISCUS
NELSONS NURSERY-APOPKA, FLORIDA
RATE/LBAI AVE. %
TREATMENT 100 GAL. INFECTION
Cu-EDDHA 3.2% 0.2 19
Cu-EDDHA 3.2% 0.8 32
KOCIDE 2.0 22
APPLIC. DATES: 7/19 DIP, 7/26/85 SPRAY
100 PLANTS/REP. X 4
EXAMPLE 8 BACTERICIDE
Control of Bacterial Spot on Pepper Plants
With Stage II Bactericides Procedure— Early Cal Wonder variety pepper plants were treated at weekly intervals
with the following bactericides (g ai/liter): copper + mancozeb (2 + 1), Cu-
EDDHA (0.1), CGA (Ciba-Giegy of America - Bactericides)- 115944, CGA-
151731, CGA-157566, and CGA-164058 (each at 0.25 and 0.5), CGA-143268
(1.0). Treatments were applied weekly in 1000 1/ha for a total of eight
applications. The crop was artificially inoculated after the first and third
applications. Disease severity was evaluated after the fourth and eight applications.
Phytotoxicity was rated after the eight application and yields were taken continually
during the test.
Results— Disease pressure was moderate and uniform. After four applications, the
best treatments were CGA-115944, CGA-151731 , and CGA-164058. CGA-157566
was less effective than the three previously mentioned compounds but more
effective than CGA-143268 which was equal to copper plus mancozeb and Cu-
EDDHA in activity. The ranking of compounds changed when treatments were
rated 12 days after the last application. Copper plus mancozeb control has
completely broken down, which was expected because disease conditions were
severe in the final half of the test and copper should be applied on a five-day
schedule under these conditions. Cu-EDDHA at only 0.05X the rate of Kocide 101
(on a metallic copper basis) was exhibiting some control and was equal to CGA-
143268, CGA-157566, and CGA-164058. The best bactericide at the second rating
were CGA-115944 and CGA-151731. The phytotoxicity of all treatments was
assessed after eight applications had been made. The only bactericides which were
phytotoxic were CGA-115944 and CGA-164058. CGA-164058 was safer than CGA115944 which was marginally unacceptable at 0.5 g ai/1. CGA-143268 and
CGA-164058 increased yields dramatically. Yields were depressed by CGA-
0115944, CGA-151731, and CGA-157566. Cu-EDDHA had no effect on yield and
copper + mancozeb increased yields moderately. In summary, several compounds
showed excellent activity, but none had sufficient crop safety.
EXAMPLE 9 BACTERICIDE
Cu-EDDHA at 0.2 and 0.4 lbs. ai/100 gal. and Kocide 101 at 7.4 lbs. ai/A
were applied as foliar applications to croton (Codiaeum variegatum) previously
inoculated with Xanthomonas campestris a day earlier. Treatments were assigned in
a RCB design and replicated 10 times with single pots. Treatments were applied 3
times on a weekly schedule and evaluated at 7 and 14 days following the last
application. See data below.
Test 1 Codiaeum Inoculated with Xanthomonas
Number of leaves with symptoms
RATE/100 AVE. %
TREATMENT GAL. a.i. INFECTION
Water noninoculated 0 a
Water inoculated 2.6 c
Cu-EDDHA 3.2% 26 ml (.2 lb.) .6 ab
Cu-EDDHA 3.2% 52 ml (.4 lb.) 1.0 b
Kocide 101 6.8 ml. (7.4 lb.) .9 ab
ANOVA table Source Sum of squares df Mean square F Value
Treatment 37.28 4 9.319 9.177 significant at 1 % level
Error 45.7 45 1.016 Total 82.98 49
All of the copper treatments provided some control of Xanthomonas leaf spot of
Codiaeum, when compared to the inoculated control. The lower rate of Cu-
EDDHA and the Kocide 101 gave control equal to the noninoculated control
treatment.
CARROT/ ALTERNARIA FUNGICIDE TRIAL
AVG % INFECTION
RATE/100
TREATMENT GAL. 04/05/96 04/23/96
1) K-PHOS 1 % 6.9 8.2
2) PHOS-MIGHT 1 % 18.7 28.8
3) K-PHOS 0.5% 8.9 10.7 + + PHOS-MIGHT 0.5 %
4) Cu-EDDHA 0.2 lb ai 8.8 11.6
5) Fe-EDDHA 0.2 lb ai 12.7 12.9
6) Untreated 23.0 34.8
*EDDHA (ethylene-diamine di (O-hydroxy phenylacetate)
PLOT SIZE: Single Row X 25 ft. X 4 reps in a RCB design.
Application dates: 2/2, 9,15,22,3/8,14,22, and 28. Rated 4/5 and 4/23/96
NOTE: Second rating was 25 days after last fungicide application. Plots were
inoculated with Alternaria dauci
Sanford, FL
K-PHOS (Commercially available and is sold under trademark "K-Phos" by Foliar
Nutrients, Inc. , Cairo, GA 31724) (K2HPO4, 0-18-20) PHOS MIGHT (Commercially available and is sold under trademark "Phos Might"
by Foliar Nutrients, Inc., Cairo, GA 31724) (K2HPO3, 0-22-20)
EXAMPLE 15 - FUNGICIDE
CRAPE MYRTLE POWDERY MILDEW CONTROL
AVG % INFECTION TREATMENT RATE/100GAL. FL GL FOLIAGE 1) K-PHOS 1 % 12.0 22.50 2) Cu-EDDHA 0.2 lb ai 11.20 16.4 3) Fe-EDDHA 0.2 lb ai 6.4 0 4) K-PHOS 1 % 4.2 0 + Cu-EDDHA 0.2 lb ai 100 100
FL.GL. =unopended flower clusters (2/trtm X 4 reps)
Foliage (2 terminals - 10 leaves X 4 reps in RCB design).
Crape Myrtle (Lager stromia indica)
Powdery Mildrew (Erysiphe lagerstroemiae)
App. dates: 5/23, 30th and 6/6. Rated: 6/9
K-PHOS - (K2HPO4, 0-18-20) ("K-Phos" is a trademark of Foliar Nutrients, Inc. ,
Cairo, Ga.)
The above Examples demonstrate that the inventive compositions are useful in
protecting plants against attack by fungus with the application of the inventive
solution.
It will be further appreciated that foliar application of the inventive
compositions will be effective as a common agricultural practice to control bacterial
infections in plants. As used herein, the term "heavy metal chelate" is intended to refer to an
organic coordination "complexing" compound in which a metal ion is bound to
atoms of non-metals, e.g., nitrogen, carbon or oxygen, to form a hetrocylic ring
having coordinate covalent bounds. The non-metal atoms may be attached to the
metal ions by from one to six linkages and, thus, are called uni-, bi-, tri- dentate,
etc. , meaning 1-, 2-, or 3-tooth. Heavy metals, such as cobalt, copper, iron, nickel,
zinc, magnesium and platinum are metal ions that are commonly involved in chelate
structures. Examples of heavy metal chelate structures include:
Fe-HEEDTA (hydroxy ethylenediamine triacetic acid), Fe-EDTA
(ethylenediamine tetra acetic acid), Fe-DTPA (diethylene triaminepenta acetic acid),
Fe-EDDHA (ethylene dihydroxyphenylacetic acid), ethylene bis dithiocarbamates of
Mn- and Zn-, Cu-EDDHA, Mn- and Zn-EDDHA.
As used herein, unacceptably high levels of phytotoxicity is intended to mean
foliar burn, defoliation and stem die-back, or necrosis, plant stunting or death.
Phytotoxicity is also rated on an international scale of 0-10 where 0 is equal to no
phytotoxicity and 10 is complete death of the plant.
Heavy metal chelates disclosed herein are possess water solubility acceptable
for use in the inventive fungicide and bactericide.
For example, the solubility of sequestrene 138 Fe Iron Chelate in pounds per
100 gallons of water, at various temperatures (solubility weight/100 gals. HjO) is
shown in Table 1 below: Temperature (°C) Lbs.
0 69
10 70
20 75
30 81
40 84
50 88
Commercially produced Sequestrene 138 Fe contains 6% Iron as metallic, or 8.5%
iron as Fe2O3. The commercial product has a moisture content of not more than
10% .
Without being limited to this theory, it is believed that heavy metal chelation
generally increases water solubility of the heavy metal ion and the availability in
certain soil conditions of the metal ion where calcareous and high pH situations
would otherwise prevent metal ions from being available to the plant as a fungicide.
It is believed that certain heavy chelates (usually in the form of Mn, Zn, and
Fe) may be applied foriarly at much reduced rates when compared to inorganic salts
intended for fungicidal and bactericidal use.
Ranking of Fe chelates used in foliar applications are as follows: Fe-HEEDTA
- most phytotoxic; Fe-EDTA ~ intermediate phytotoxic, Fe-DTPA - less
phytotoxic, and Fe-EDDHA - least phytotoxic. Such rankings do not necessarily
apply when the chelate is EBDC fungicides in the Mn, Zn form.
It will be appreciated by those skilled in the art that beneficial effects
demonstrated in the Examples by the use of Cu-EDDHA will also be obtained when the Mn, Zn and Fe forms EDDHA and other forms of heavy metal chelates are
employed.

Claims

CLAIMSWhat is claimed is:
1. A fungicidal composition for controlling fungus disease in plants
comprising:
a fungicidally effective amount of a heavy metal chelate in aqueous solution.
2. The composition according to Claim 1, wherein the heavy metal is
selected from the group consisting of manganese, zinc, iron, and copper, and
mixture thereof.
3. The composition according to Claim 1 , wherein the amount of said
heavy metal chelate is present in aqueous solution from about 0.01 to about 1.0
pounds AI per acre.
4. A method of controlling fungus disease in plants comprising:
applying to the plant in fungicidally effective amounts a heavy metal chelate in
aqueous solution.
5. A method according to Claim 4, wherein said solution comprises an
aqueous solution, wherein said heavy metal chelate is present in solution from about
0.01 to about 1.0 pounds AI per acre.
6. A bacterial composition for controlling bacteria disease in plants comprising:
a bacterially effective amount of a heavy metal chelate in aqueous solution.
7. The composition according to Claim 6, wherein the heavy metal is
selected from the group consisting of manganese, zinc, iron, and copper.
8. The composition according to Claim 6, wherein the amount of said heavy metal chelate is present in aqueous solution from about 0.01 to about 1.0 pounds AI per acre.
9. A method of controlling bacteria disease in plants comprising:
applying to the plant in bacterially effective amounts a heavy metal chelate in aqueous solution.
10. A method according to Claim 9, wherein said solution comprises an
aqueous solution, wherein said heavy metal chelate is present in solution from about
0.01 to about 1.0 pounds AI per acre.
11. A fungicidal and bactericidal composition for controlling fungus and
bacteria disease in plants comprising:
a fungicidally and bactericidally effective amount of a heavy metal chelate in
aqueous solution.
12. The composition according to Claim 11, wherein the heavy metal is
selected from the group consisting of manganese, zinc, iron, and copper, and mixture thereof.
13. The composition according to Claim 11, wherein the amount of said
heavy metal chelate is present in aqueous solution from about 0.01 to about 1.0
pounds AI per acre.
14. A method of controlling fungus and bacterial disease in plants comprising:
applying to the plant in fungicidally and bactericidally effective amounts a
heavy metal chelate in aqueous solution.
15. A method according to Claim 14, wherein said solution comprises an
aqueous solution, wherein said heavy metal chelate is present in solution from about
0.01 to about 1.0 pounds AI per acre.
PCT/US1998/012264 1997-06-25 1998-06-12 Fungicidal and bactericidal compositions for plants containing compounds in the form of heavy metal chelates WO1998058546A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU79635/98A AU743922B2 (en) 1997-06-25 1998-06-12 Fungicidal and bactericidal compositions for plants containing compounds in the form of heavy metal chelates
NZ501984A NZ501984A (en) 1997-06-25 1998-06-12 Fungicidal and bacterial (kocide-cupric hydroxide) compositions selected from Fe-EDDHA (ethylene-diamine di-O-hydroxyphenylacetate), Cu-EDDHA, Mn-EDDHA and Zn-EDDHA

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US88196897A 1997-06-25 1997-06-25
US08/881,968 1997-06-25

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EP1363492A2 (en) * 2001-01-29 2003-11-26 Agricare Ltd. Methods and compositions for controlling plant pathogen
US9980479B2 (en) 2004-06-07 2018-05-29 Syngenta Crop Protection, Llc Method of reducing nematode damage

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WO2002056680A2 (en) * 2000-10-31 2002-07-25 Foliar Nutrients, Inc. Fungicidal and bactericidal compositions for plants containing phosphonate and phosphate salts, metal chelates, and derivatives thereof
WO2002056680A3 (en) * 2000-10-31 2002-09-19 Foliar Nutrients Inc Fungicidal and bactericidal compositions for plants containing phosphonate and phosphate salts, metal chelates, and derivatives thereof
AU2002245052B2 (en) * 2000-10-31 2005-07-21 Foliar Nutrients, Inc. Fungicidal and bactericidal compositions for plants containing phosphonate and phosphate salts, metal chelates, and derivatives thereof
EP1363492A2 (en) * 2001-01-29 2003-11-26 Agricare Ltd. Methods and compositions for controlling plant pathogen
EP1363492A4 (en) * 2001-01-29 2004-03-10 Agricare Ltd Methods and compositions for controlling plant pathogen
US9980479B2 (en) 2004-06-07 2018-05-29 Syngenta Crop Protection, Llc Method of reducing nematode damage

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AU7963598A (en) 1999-01-04
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