U.S. patent application number 14/288797 was filed with the patent office on 2014-09-18 for compounds and methods for controlling fungi.
The applicant listed for this patent is DOW AGROSCIENCES LLC. Invention is credited to George E. Davis, William C. Lo, James M. Renga, Francis Tisdell, JR., Maurice C.H. Yap, David H. Young.
Application Number | 20140275123 14/288797 |
Document ID | / |
Family ID | 42315653 |
Filed Date | 2014-09-18 |
United States Patent
Application |
20140275123 |
Kind Code |
A1 |
Tisdell, JR.; Francis ; et
al. |
September 18, 2014 |
COMPOUNDS AND METHODS FOR CONTROLLING FUNGI
Abstract
Various aspects disclosed herein relate to aryl substituted
aminopyrimidines according to Formula 1: ##STR00001## wherein,
X.sub.1 is N or C--R.sub.3; X.sub.2 is N or C--R.sub.4 provided
that X.sub.1 and X.sub.2 are not both N; R.sub.1-R.sub.7 are H, CN,
CHO, --SCN, NO.sub.2, F, Cl, Br, I, substituted or unsubstituted
C1-C4-alkyl, substituted or unsubstituted halo-C1-C4-alkyl,
substituted or unsubstituted C1-C4-alkoxy, substituted or
unsubstituted halo-C1-C4-alkoxy, substituted or unsubstituted
C1-C4-thioalkyl, substituted or unsubstituted halo-C1-C4-thioalkyl,
substituted or unsubstituted C3-C-7-cycloalkyl, substituted or
unsubstituted C2-C4-alkenyl, C2-C4-alkynyl, substituted or
unsubstituted C1-C4-acylalkyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl,
C1-C4-alkoxy-amino, C1-C4-alkyl-S(O).dbd.NH, substituted or
unsubstituted aryl, substituted or unsubstituted heterocycle,
wherein the substituents are one or more of the following F, Cl,
Br, OH, CN, NO.sub.2, CHO, --SCN, S(O)n-C1-C4-alkyl (where n=0-2),
C1-C4-alkyl, halo-C1-C4-alkyl, C1-C4-alkylamine, C1-C4-alkoxy,
halo-C1-C4-alkoxy, C1-C4-thioalkyl, halo-C1-C4-thioalkyl,
C1-C4-alkylacyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl,
C1-C4-alkoxy-imino, hydroxy-imino; C-C4-alkyl-S(O).dbd.NH; and Q is
a substituted or unsubstituted aryl, substituted or unsubstituted
heterocycle wherein the substituents of Q are taken from
R.sub.1-R.sub.7
Inventors: |
Tisdell, JR.; Francis;
(Carmel, IN) ; Renga; James M.; (Indianapolis,
IN) ; Young; David H.; (Carmel, IN) ; Davis;
George E.; (Carmel, IN) ; Lo; William C.;
(Fishers, IN) ; Yap; Maurice C.H.; (Zionsville,
IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DOW AGROSCIENCES LLC |
Indianapolis |
IN |
US |
|
|
Family ID: |
42315653 |
Appl. No.: |
14/288797 |
Filed: |
May 28, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12772248 |
May 3, 2010 |
8759356 |
|
|
14288797 |
|
|
|
|
61179402 |
May 19, 2009 |
|
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Current U.S.
Class: |
514/256 ;
544/326 |
Current CPC
Class: |
A01N 43/54 20130101;
A61K 31/505 20130101; C07D 239/30 20130101 |
Class at
Publication: |
514/256 ;
544/326 |
International
Class: |
A01N 43/54 20060101
A01N043/54 |
Claims
1-8. (canceled)
9. A compound of Formula 1: ##STR00012## wherein: X.sub.1 is N or
C--R.sub.3; X.sub.2 is N or C--R.sub.4 provided that exactly one of
X.sub.1 and X.sub.2 is N; R.sub.1 is selected from H, CN, CHO,
--SCN, NO.sub.2, F, Cl, Br, I, substituted or unsubstituted
halo-C1-C4-alkyl, substituted or unsubstituted C1-C4-alkoxy,
substituted or unsubstituted halo-C1-C4-alkoxy, substituted or
unsubstituted C1-C4-thioalkyl, substituted or unsubstituted
halo-C1-C4-thioalkyl, substituted or unsubstituted
C3-C-7-cycloalkyl, substituted or unsubstituted C2-C4-alkenyl,
C2-C4-alkynyl, substituted or unsubstituted C1-C4-acylalkyl,
C1-C4-acyloxy, C1-C4 alkoxycarbonyl, C1-C4-alkoxy-amino,
C1-C4-alkyl-S(O).dbd.NH, substituted or unsubstituted aryl,
substituted or unsubstituted heterocycle, wherein the substituents
are one or more of the following F, Cl, Br, OH, CN, NO.sub.2, CHO,
--SCN, S(O)n-C1-C4-alkyl (where n=0-2), C1-C4-alkyl,
halo-C1-C4-alkyl, C1-C4-alkylamine, C1-C4-alkoxy,
halo-C1-C4-alkoxy, C1-C4-thioalkyl, halo-C1-C4-thioalkyl,
C1-C4-alkylacyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl,
C1-C4-alkoxy-imino, hydroxy-imino; C1-C4-alkyl-S(O).dbd.NH; R.sub.2
is selected from H, CN, CHO, --SCN, NO.sub.2, F, Br, I, substituted
C3-C4-alkyl, unsubstituted C1 alkyl, substituted or unsubstituted
halo-C1-C4-alkyl, substituted or unsubstituted C1-C4-alkoxy,
substituted or unsubstituted halo-C1-C4-alkoxy, substituted or
unsubstituted C1-C4-thioalkyl, substituted or unsubstituted
halo-C1-C4-thioalkyl, substituted or unsubstituted
C3-C-7-cycloalkyl, substituted or unsubstituted C2-C4-alkenyl,
C2-C4-alkynyl, substituted or unsubstituted C1-C4-acylalkyl,
C1-C4-acyloxy, C1-C4-alkoxy-amino, C1-C4-alkyl-S(O).dbd.NH,
substituted heterocycle, wherein the substituents are one or more
of the following F, Cl, Br, OH, CN, NO.sub.2, CHO, --SCN,
S(O)n-C1-C4-alkyl (where n=0-2), C1-C4-alkyl, halo-C1-C4-alkyl,
C1-C4-alkylamine, C1-C4-alkoxy, halo-C1-C4-alkoxy, C1-C4-thioalkyl,
halo-C1-C4-thioalkyl, C1-C4-alkylacyl, C1-C4-acyloxy, C1-C4
alkoxycarbonyl, C1-C4-alkoxy-imino, hydroxy-imino;
C1-C4-alkyl-S(O).dbd.NH; R.sub.3and R.sub.4 are independently
selected from CHO, --SCN, NO.sub.2, F, Cl, Br, I, substituted or
unsubstituted halo-C1-C4-alkyl, substituted or unsubstituted
C1-C4-alkoxy, substituted or unsubstituted halo-C1-C4-alkoxy,
substituted or unsubstituted C1-C4-thioalkyl, substituted or
unsubstituted halo-C1-C4-thioalkyl, substituted or unsubstituted
C3-C-7-cycloalkyl, substituted or unsubstituted C2-C4-alkenyl,
C2-C4-alkynyl, substituted or unsubstituted C1-C4-acylalkyl,
C1-C4-acyloxy, C1-C4 alkoxycarbonyl, C1-C4-alkoxy-amino,
C1-C4-alkyl-S(O).dbd.NH, unsubstituted aryl, substituted or
unsubstituted heterocycle, wherein the substituents are one or more
of the following F, Cl, Br, OH, CN, NO.sub.2, CHO, --SCN,
S(O)n-C1-C4-alkyl (where n=0-2), C1-C4-alkyl, halo-C1-C4-alkyl,
C1-C4-alkylamine, C1-C4-alkoxy, halo-C1-C4-alkoxy, C1-C4-thioalkyl,
halo-C1-C4-thioalkyl, C1-C4-alkylacyl, C1-C4-acyloxy, C1-C4
alkoxycarbonyl, C1-C4-alkoxy-imino, hydroxy-imino;
C1-C4-alkyl-S(O).dbd.NH; R.sub.5-R.sub.7 are independently selected
from H, CN, CHO, --SCN, NO.sub.2, F, Cl, Br, I, substituted or
unsubstituted C1-C4-alkyl, substituted or unsubstituted
halo-C1-C4-alkyl, substituted or unsubstituted C1-C4-alkoxy,
substituted or unsubstituted halo-C1-C4-alkoxy, substituted or
unsubstituted C1-C4-thioalkyl, substituted or unsubstituted
halo-C1-C4-thioalkyl, substituted or unsubstituted
C3-C-7-cycloalkyl, substituted or unsubstituted C2-C4-alkenyl,
C2-C4-alkynyl, substituted or unsubstituted C1-C4-acylalkyl,
C1-C4-acyloxy, C1-C4 alkoxycarbonyl, C1-C4-alkoxy-amino,
C1-C4-alkyl-S(O).dbd.NH, substituted or unsubstituted aryl,
substituted or unsubstituted heterocycle, wherein the substituents
are one or more of the following F, Cl, Br, OH, CN, NO.sub.2, CHO,
--SCN, S(O)n-C1-C4-alkyl (where n=0-2), C1-C4-alkyl, halo-C
1-C4-alkyl, C1-C4-alkylamine, C1-C4-alkoxy, halo-C1-C4-alkoxy,
C1-C4-thioalkyl, halo-C1-C4-thioalkyl, C1-C4-alkylacyl,
C1-C4-acyloxy, C1-C4 alkoxycarbonyl, C1-C4-alkoxy-imino,
hydroxy-imino; C1-C4-alkyl-S(O).dbd.NH; and Q is a substituted or
unsubstituted aryl, or unsubstituted heterocyle wherein the
substituents of Q are taken from H, CN, CHO, --SCN, NO.sub.2, F,
Cl, Br, I, substituted or unsubstituted C1-C4-alkyl, substituted or
unsubstituted halo-C1-C4-alkyl, substituted or unsubstituted
C1-C4-alkoxy, substituted or unsubstituted halo-C1-C4-alkoxy,
substituted or unsubstituted C1-C4-thioalkyl, substituted or
unsubstituted halo-C1-C4-thioalkyl, substituted or unsubstituted
C3-C-7-cycloalkyl, substituted or unsubstituted C2-C4-alkenyl,
C2-C4-alkynyl, substituted or unsubstituted C1-C4-acylalkyl,
C1-C4-acyloxy, C1-C4 alkoxycarbonyl, C1-C4-alkoxy-amino,
C1-C4-alkyl-S(O).dbd.NH, substituted or unsubstituted aryl,
substituted or unsubstituted heterocycle, wherein the substituents
are one or more of the following F, Cl, Br, OH, CN, NO.sub.2, CHO,
--SCN, S(O)n-C1-C4-alkyl (where n=0-2), C1-C4-alkyl, halo-C
1-C4-alkyl, C1-C4-alkylamine, C1-C4-alkoxy, halo-C1-C4-alkoxy,
C1-C4-thioalkyl, halo-C1-C4-thioalkyl, C1-C4-alkylacyl,
C1-C4-acyloxy, C1-C4 alkoxycarbonyl, hydroxy-imino;
C1-C4-alkyl-S(O).dbd.NH .sub.7.
10. The compound according to claim 9, wherein R.sub.1 is H.
11. The compound according to claim 9, wherein R.sub.2 is H.
12. The compound according to claim 9, wherein each R.sub.5,
R.sub.6, R.sub.7 is H.
13. The compound according to claim 9, wherein X.sub.1 is N and
X.sub.2 is C--R.sub.4.
14. The compound according to claim 13, wherein R.sub.4 is selected
from F, Cl, Br, or I.
15. The compound according to claim 13, wherein R.sub.4 is
16. The compound according to claim 9, wherein X.sub.1 is
C--R.sub.3 and X.sub.2 is N.
17. The compound according to claim 16, wherein R.sub.3 is selected
from F, Cl, Br, or I.
18. The compound according to claim 16, wherein R.sub.3 is
19. The compound of claim 9, wherein Q is unsubstituted aryl.
20. The compound of claim 9, wherein Q is substituted aryl, wherein
the substituents are selected from the group consisting of F, Cl,
unsubstituted C.sub.1-C.sub.4 alkyl, and unsubstituted
C.sub.1-C.sub.4 alkoxy.
21. A fungicidal composition, comprising at least one compound
according to claim 9, and a phytologically acceptable carrier.
22. The composition according to claim 21, further including at
least one additional compound selected from the group consisting
of: insecticides, fungicides, and herbicides.
23. A method of controlling a fungal infestation, comprising the
steps of: providing at least one compound according to claim 9; and
applying the compound to a surface adjacent to a fungal
infestation.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This Application claims the benefit of U.S. Provisional
Application 61/179,402 filed on May 19, 2009, which is expressly
incorporated by reference herein.
FIELD OF THE INVENTION
[0002] This invention relates to the synthesis of aryl substituted
aminopyrimidines and methods of using theses compounds to control
various fungi including some plant pathogens.
BACKGROUND
[0003] Fungi comprise one of the largest and perhaps most diverse
kingdoms of eukaryotic life. Taxonomists have already characterized
some 70,000 different species and estimate that the entire kingdom
may encompass some one and a half million different species. A
number of these organisms are a source of food such as mushrooms
and some are the source of useful chemicals such as some
antibiotics. The primary role of most fungi in the ecosystem is to
recycle organic matter and many fungi are involved in the process
of decaying plant matter. Unfortunately, a large number of fungi
are known to grow at the expense of useful materials and perhaps
more importantly commercially important plants that are essential
to human survival.
[0004] Given their diversity and impact on industries such as
agriculture, compounds and methods for controlling fungi receive a
lot of attention. Currently, a number of fungicides have been
identified and synthesized and are currently used to protect both
ornamental plants and food crops from pathogenic fungi. And while
many safe and effective fungicides are currently in use, the
evolution of pathogenic fungi and the ever increasing pressures to
use lower levels of fungicides in part to reduce costs continues to
create the need for new fungicides and/or effective means of using
existing fungicides. It is one object of this instant disclosure to
address this on-going need.
SUMMARY
[0005] One embodiment is an aryl substituted aminopyrimidine
according to Formula 1:
##STR00002##
wherein, X.sub.1 is N or C--R.sub.3; X.sub.2 is N or C--R.sub.4
provided that X.sub.1 and X.sub.2 are not both N; R.sub.1-R.sub.7
are H, CN, CHO, --SCN, NO.sub.2, F, Cl, Br, I, substituted or
unsubstituted C1-C4-alkyl, substituted or unsubstituted
halo-C1-C4-alkyl, substituted or unsubstituted C1-C4-alkoxy,
substituted or unsubstituted halo-C1-C4-alkoxy, substituted or
unsubstituted C1-C4-thioalkyl, substituted or unsubstituted
halo-C1-C4-thioalkyl, substituted or unsubstituted
C3-C-7-cycloalkyl, substituted or unsubstituted C2-C4-alkenyl,
C2-C4-alkynyl, substituted or unsubstituted C1-C4-acylalkyl,
C1-C4-acyloxy, C1-C4 alkoxycarbonyl, C1-C4-alkoxy-amino,
C1-C4-alkyl-S(O).dbd.NH, substituted or unsubstituted aryl,
substituted or unsubstituted heterocycle, wherein the substituents
are one or more of the following F, Cl, Br, OH, CN, NO.sub.2, CHO,
--SCN, S(O)n-C1-C4-alkyl (where n=0-2), C1-C4-alkyl,
halo-C1-C4-alkyl, C1-C4-alkylamine, C1-C4-alkoxy,
halo-C1-C4-alkoxy, C1-C4-thioalkyl, halo-C1-C4-thioalkyl,
C1-C4-alkylacyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl,
C1-C4-alkoxy-imino, hydroxy-imino; C1-C4-alkyl-S(O).dbd.NH; and Q
is a substituted or unsubstituted aryl, substituted or
unsubstituted heterocycle wherein the substituents of Q are taken
from R.sub.1-R.sub.7
[0006] Another embodiment is an a fungicidal composition,
comprising at least one compound according to Formula 1 and a
phytologically acceptable carrier.
[0007] In still another embodiment the antifungal formulation
further includes at least one additional compound selected from the
group consisting of: insecticides, and herbicides.
[0008] Another embodiment is a method for controlling a fungal
infestation, comprising the steps of providing at least one
compound according to claim 1; and applying the compound to a
surface adjacent to a fungal infestation.
[0009] Still another embodiment is a compound selected from the
group of aryl substituted aminopyrimidines consisting of:
##STR00003##
[0010] Still another embodiment is an anti-fungicidal composition,
comprising at least one compound according to the above aryl
substituted aminopyrimidines and a phytologically acceptable
carrier.
[0011] In still another embodiment, the composition includes at
least one additional compound selected from the group consisting
of: insecticides, fungicides, and herbicides.
[0012] Another embodiment is a method of controlling a fungal
infestation, comprising the steps of: providing at least one
compound according to the group of aryl substituted
aminopyrimidines illustrated herein; and applying the compound to a
surface adjacent to a fungal infestation.
[0013] Another embodiment is a method of controlling fungal
infestation, comprising the steps of: providing at least one
compound according to Formula 1; and applying the compound to a
surface adjacent to a fungal infestation.
DESCRIPTION
[0014] For the purposes of promoting an understanding of the
principles of the novel technology, reference will now be made to
the various exemplary embodiments thereof, and specific language
will be used to describe the same. It will nevertheless be
understood that no limitation of the scope of the novel technology
is thereby intended, such alterations, modifications, and further
applications of the principles of the novel technology being
contemplated as would normally occur to one skilled in the art to
which the novel technology relates.
EXAMPLE 1
##STR00004##
[0016] Briefly, 2,5-dichloro-4-cyclopropylaminopyrimidine (1 mmol.,
204 mg) was dissolved in dimethoxyethane (8 ml) and 4-chlorophenyl
boronic acid (1.5 mmol, 234 mg), sodium carbonate (2 mmol., 2 ml of
a 1 molar aqueous solution), and tetrakis (triphenylphosphine)
palladium (0.05 mmol, 60 mg) was added. The reaction was heated to
reflux for 4 hours and stirred overnight at 25.degree. C. Next the
reaction mixture was filtered through silica gel using ethyl
acetate; then concentrated and chromatographed using 15% ethyl
acetate in hexane to afford the product as a white solid. wgt. 138
mg. 49% yield MP 103-105.degree. C. GC/MS 279; H.sup.1 NMR (CDCI3)
ppm 8.36 (d,2H, J=0.03 Hz); 8.26 (s, 1H); 7.42 (d, 2H, J-0.03 Hz);
5.55 (sb, 1H); 2.98 (m, 1H); 0.98 (m, 1H); 0.68 (m, 1H).
Method of Testing the Fungicidal Activity of Various Compounds
Disclosed Herein.
[0017] The compounds of the present invention have been found to
have significant fungicidal effect, particularly for agricultural
use. Many of the compounds are particularly effective for use with
agricultural crops and horticultural plants. In particular, the
compounds have the potential to effectively control a variety of
undesirable fungi that infect useful plant crops as illustrated by
the examples herein. Activity has been demonstrated for fungi,
including for example the following representative fungi species:
brown rust of wheat (Puccinia recondita tritici--PUCCRT); septoria
blotch of wheat (Septoria tritici--SEPTTR).
[0018] Referring now to Table 1, some of the exemplary compounds
were tested in order to measure their ability to either prevent or
cure fungal infections. A given compound's preventative properties
were determined by treating a susceptible test plant with the
exemplary compound and then exposing the plant to fungal spores. A
given compound's curative properties were determined by first
exposing a susceptible plant to an infective fungus and then
applying the exemplary fungicidal compounds.
[0019] It will be understood by those in the art that the efficacy
of the compounds against the foregoing fungi establishes the
general utility of the compounds as fungicides. The activity of the
compounds as effective fungicides was determined by applying the
compounds to plants and observing control of fungal disease. The
compounds were formulated at rates of 50 ppm and 200 ppm in 10 vol.
% acetone plus 90 vol. % Triton X water (deionized water 99.99 wt
%+0.01 wt % Triton X100), giving a "formulated test compound."
Formulated test compounds were applied to plants using a turntable
sprayer fitted with two opposing air atomization nozzles which
delivered approximately 1500 L/ha of spray volume.
[0020] Again referring to Table 1, tests were carried out to
determine a given exemplary compound's ability to prevent or at
least limit a fungal infection as follows. All plants in the study
were inoculated with spores of the fungus in this case either
PUCCRT or SEPTTR) the day after treatment with the putative
fungicide. Next, the plants were incubated in an environment
conducive to disease development. Disease severity was evaluated 7
to 25 days later, depending on the speed of disease development.
The following experiments were performed in the laboratory to
determine the fungicidal efficacy of the compounds of the
invention.
Measuring the Protective Effect of Various Compounds Against Leaf
Rust of Wheat (Causal Agent Bayer Code PUCCRT).
[0021] Wheat plants (variety `Yuma`) were grown from seed in a
soil-less peat-based potting mixture (Metromix) until the seedlings
had a fully expanded first leaf. Each pot contained 3-8 seedlings.
These plants were sprayed until wet with the formulated test
compounds. On the following day, the leaves were inoculated with an
aqueous spore suspension of Puccinia recondita tritici and the
plants were kept in high humidity overnight to permit the spores to
germinate and to infect the leaf. The plants were then transferred
to a greenhouse until disease developed on untreated control
plants. These tests were carried out using two different levels of
the compound, 50 ppm and 200 ppm, see Table 1.
Measuring the Preventative Effect of Various Compounds Against
Septoria Blotch of Wheat (Causal Agent Bayer Code SEPTTR).
[0022] Wheat plants (variety `Yuma`) were grown from seed in a 50%
pasteurized soil/50% soil-less mix until the seedlings had a fully
expanded first leaf. Each pot contained 3-10 seedlings. These
plants were sprayed until wet with the formulated test compound. On
the following day, the leaves were inoculated with an aqueous spore
suspension of Septoria tritici and the plants were kept in high
humidity (one day in a dark dew chamber followed by three days in a
lighted dew chamber) to permit the spores to germinate and to
infect the leaf. The plants were then transferred to a greenhouse
until disease developed on untreated control plants. These tests
were carried out using two different levels of the compound, 50 ppm
and 200 ppm, see Table 1.
Measuring the Curative Effect of Various Compounds Against Septoria
Blotch of Wheat (Causal Agent Bayer Code SEPTTR).
[0023] Wheat plants (variety `Yuma`) were grown from seed in a
mixture of about 50% pasteurized soil/50% soil-less mix until the
seedlings had a fully expanded first leaf. Each pot contained 3-10
seedlings. These plants were inoculated with an aqueous spore
suspension of Septoria tritici and the plants were kept in high
humidity (one day in a dark dew chamber followed by two days in a
lighted dew chamber) to permit the spores to germinate and to
infect the leaf. The plants were then removed form the dew chamber
and allowed to dry. After drying, the inoculated plants were
sprayed until wet with the formulated test compound. On the
following day, the plants were transferred to a greenhouse until
disease developed on untreated control plants. These tests were
carried out using two different levels of the compound, 50 ppm and
200 ppm, see Table 1.
[0024] Disease control was determined by visually estimating the
percent disease severity in treated and untreated pots 7 to 24 days
after inoculation, depending on speed of disease development.
Evaluations were typically made 7 or 8 days after inoculation for
PUCCRT and 18 to 22 days after inoculation for SEPTTR. Percent
disease control (% DC) was calculated by: % DC=(1-% Disease
severity treated/% disease severity untreated)*100.
[0025] The compounds of this invention may be preferably applied in
the form of a composition comprising one or more of the compounds
of Formula 1 with a phytologically-acceptable carrier. The
compositions include, for example, concentrated formulations which
are dispersed in water or another liquid for application, or are
dust or granular formulations which are applied without further
treatment. The compositions may be prepared according to procedures
which are conventional in the agricultural chemical art, but which
are novel and important because of the presence therein of the
compounds disclosed herein.
TABLE-US-00001 TABLE 1 Representative aryl substituted
aminopyrmidines and their curative and protective activity measured
at 50 and 200 ppm-against the pathological fungi Septoria tritici
(SEPTTR) and Puccinia recondita (PUCCRT) Percent Disease Control
Three Day One Day Protectant Curative [ppm]: Reference 50 200 50
200 50 200 Molecular Structure Number SEPTTR PUCCRT SEPTTR
##STR00005## 1 90 97 93 97 0 0 ##STR00006## 2 0 35 0 0 62 72
##STR00007## 3 74 85 99 97 0 0 ##STR00008## 4 38 86 50 99 0 18
##STR00009## 5 38 90 99 99 0 0 ##STR00010## 6 65 95 97 99 0 27
##STR00011## 7 91 61 53 0 50 50
[0026] The dispersions in which the compounds are applied are most
often aqueous suspensions or emulsions prepared from concentrated
formulations of the compounds. Such water-soluble, water
suspendable, or emulsifiable formulations are either solids,
usually known as wettable powers, or liquids, usually known as
emulsifiable concentrates, or aqueous suspensions. The present
invention contemplates all vehicles by which the compounds of this
invention can be formulated for delivery for use as a fungicide. As
will be readily appreciated, any material to which these compounds
can be added may be used, provided they yield the desired utility
without significantly interfering with the fungicidal activity of
the compounds of this invention.
[0027] Wettable powders, which may be compacted to form water
dispersible granules, comprise an intimate mixture of the active
compound, an inert carrier, and surfactants. The concentration of
the active compound is usually from about 10 percent weight/weight
(% w/w) to about 90% % w/w, and more preferably about 25% to about
75% w/w. In the preparation of wettable powder compositions, the
active ingredients can be compounded with any of the finely divided
solids, such as prophyllite, talc, chalk, gypsum, Fuller's earth,
bentonite, attapulgite, starch, casein, gluten, montmorillonite
clays, diatomaceous earths, purified silicantes or the like. In
such operations, the finely divided carrier is ground or mixed with
the toxicant in a volatile organic solvent. Effective surfactants,
comprising from about 0.5% to about 10% of the wettable powder,
that can be used in combination with the inventive compounds,
include sulfonated lignins, naphthalenesulfonates,
alkylbenzenesulfonates, alyl sulfates, and non-ionic surfactants
such as ethylene oxide adducts of alkyl phenols.
[0028] Emulsifiable concentrates of the compounds of this invention
comprise a convenient concentration, such as from about 10% to
about 50% w/w, in a suitable liquid. Briefly, one method for
creating these emulsions includes the step of dissolving the
compound in an inert carrier (either a water miscible solvent or a
mixture of water-immiscible organic solvents and emulsifiers). The
concentrates may be diluted with water and oil to form spray
mixtures in the form of oil-in-water emulsions. Useful organic
solvents that can be used to practice the invention, include
aromatics, especially the high-boiling naphthalenic and olefini
portions of petroleum such as heavy aromatic naphtha and the like.
Other organic solvents may also be used such as, for example,
terpenic solvents including rosin derivatives, aliphatic ketones,
such as cyclohexanone, and complex alcohols such as
1-ethoxyethanol.
[0029] Emulsifiers which can be advantageously employed herein can
be readily determined by those skilled in the art and include
various non-ionic, anionic, cationic, and amphoteric emulsifiers,
or a blend of two or more emulsifiers. Examples of non-ionic
emulsifiers useful in preparing the emulsifiable concentrates
include, for example, the polyalkylene glycol ethers and
condensation products of alkyl and aryl phenols, aliphatic
alcohols, aliphatic amines, or fatty acids with ethylene oxide,
propylene oxides such as the ethoxylated alkyl phenols, and
carboxylic esters solubilised with polyol or polyoxyalkylene.
Cationic emulsifiers include quaternary ammonium compounds and
fatty amine salts. Anionic emulsifiers include the oil-soluble
salts (e.g., calcium) of alkylaryl sulfonic acids, oil-soluble
salts of sulphated polyglycol ethers, and appropriate salts of
phosphated polyglycol ether.
[0030] Representative organic liquids which can be employed in
preparing the emulsifiable concentrates of the present invention
include aromatic liquids such as zylene, propyl benzene fractions
or mixed naphtlalene fractions, mineral oils, substituted aromatic
organic liquids such as dioctyl phthalate, kerosene, and dialkyl
amides of various fatty acids; particularly the dimethyl amides of
fatty glycols and glycol derivatives such as the n-butyl ether,
ethyl ether, or methyl ether of triethylene blycol. Mixtures of two
or more organic liquids are also often suitably employed in the
preparation of the emulsifiable concentrate. The preferred organic
liquids are xylene and propyl enzene fractions, with xylene being
most preferred. The surface active dispersing agents are usually
employed in liquid compositions and in the amount of from about 0.1
weight % (wt. %) to about 20 (wt. %) of the combined weight of the
dispersing agent and active compound. The active compositions can
also contain other compatible additives, for example, plant growth
regulators and other biologically active compounds used in
agriculture.
[0031] Aqueous suspensions may comprise suspensions of
water-insoluble compounds of this invention, dispersed in an
aqueous vehicle at a concentration in the range of from about 5% to
about 50% w/w. In one embodiment, suspensions are prepared by
finely grinding the compound and vigorously mixing it into a
vehicle comprised of water and surfactants chosen from the type of
surfactants as discussed above. Inert ingredients, such as
inorganic salts and synthetic or natural gums, may also be added to
increase the density and viscosity of the aqueous vehicle. It is
often most effective to grind and mix the compound at the same time
by preparing the aqueous mixture and homogenizing it in an
implement such as a sand mill, ball mill, or piston-type
homogenizer.
[0032] The compounds may also be applied as granular compositions
which are particularly useful when applying the composition to the
soil. Granular compositions may include from about 0.5% w/w of to
about 10% w/w of the compound dispersed in an inert carrier
comprising entirely or in large part of a coarsely divided
attapulgite, bentonite, diatomite, clay, or a similar inexpensive
substance. Such compositions are usually prepared by dissolving the
compound in a suitable solvent and applying it to a granular
carrier which has been preformed to the appropriate particle size,
in the range of from about 0.5 to about 3 mm. Such compositions may
also be formulated by making a dough or paste of the carrier and
compound, and crushing, and drying to obtain the desired granular
particle.
[0033] Dusts including the compounds may be prepared by intimately
mixing the compound in powdered form with a suitable dusty
agricultural carrier such as, for example, kaolin clay, ground
volcanic rock, and the like. Many such dusts can suitably include
from about 1% w/w to about 10% w/w of the compound.
[0034] The active compositions may contain adjuvant surfactants to
enhance properties such as deposition, wetting, and penetration of
the compositions onto the target crop and organism. These adjuvant
surfactants may optionally be employed as a component of the
formulation or as part of a tank mix. The amount of adjuvant
surfactant may vary from about 0.01 percent volume/volume of (%v/v)
percent to 1.0% v/v based on a spray-volume of water, preferably
0.05 to 0.5 percent. Suitable adjuvant surfactants include
ethoxylated nonyl phenols, ethoxylated synthetic or natural
alcohols, salts of the esters of sulphosuccinic acids, ethoxylated
organosilicones, ethoxylated fatty amines, and blends of
surfactants with mineral or vegetable oils.
[0035] The compositions may optionally include combinations which
comprise at least 1% of one or more of the compounds of this
invention with another agriculturally active ingredient (Al). Such
additional Al may include for example fungicides, insecticides,
nematocides, miticides, arthropodicides, bactericides, herbicidal,
or combinations thereof that are compatible with the compounds of
the present invention in the medium selected for application, and
not antagonistic to the activity of the present compounds.
Accordingly, in such embodiments, the other Al is employed as a
supplemental Al for the same or for a different use with plants
than the inventive compounds. The compounds in combination can
generally be present in a ratio of from about 1:10 to about
100:1.
[0036] The present invention includes within its scope methods for
the control or prevention of fungal attack. These methods comprise
applying the active compounds to the locus of the fungus, or to a
locus in which the infestation is to be prevented (for example
applying it to a cereal or grape plant. The compounds are suitable
for treatment of various plants at fungicidal levels while
exhibiting low phytotoxicity. The compounds are useful in a
protectant or eradicant fashion. The compounds of this invention
are applied by any of a variety of known techniques, either as the
compounds or as compositions including the compounds. For example,
the compounds may be applied to the roots, seeds, or foliage of
plants for the control of various fungi without damaging the
commercial value of the plants. The materials are applied in the
form of any of the generally used formulation types, for example,
as solutions, dusts, wettable powders, flowable concentrates, or
emulsifiable concentrates. These materials are conveniently applied
in various known fashions.
[0037] The compounds of this invention have been found to have
significant fungicidal effect, particularly for agricultural use.
Many of the compounds are particularly effective for use with
agricultural crops and horticultural plants, or with wood, paint,
leather, or carpet backing.
[0038] In particular, the compounds effectively control a variety
of undesirable fungi which infect useful plant crops. In addition
to the fungi tested, these compounds will likely have activity
against a variety of fungi, including, for example, the following
representative fungi species: downy mildew of grape (Plasmopara
viticola--PLASVI), late blight of tomato (Phytophthora
infestants--PHYTIN), apple scab (Venturia inaequalis--VENTIN),
brown rust of wheat (Puccinia recondite--PUCCRT), stripe rust of
wheat (Puccinia striiformis--PUCCST), rice blast (Pyricularia
oryzae--PYRIOR), Cercospora leaf spot of beet (Cercospora
beticola--CERCBE), powdery mildew of wheat (Erysiphe
graminis--ERYSGT), leaf blotch of wheat (Septoria tritici--SEPTTR),
sheath blight of rice (Rhizoctonia solani--RHIZSO), eyespot of
wheat (Pseudocercosporella herpotrichoides--PSDCHE), brown rot of
peach (Monilinia fructicola--MONIFC), and glume blotch of wheat
(Leptosphaeria nodorum--LEPTNO). It will be understood by those in
the art that the efficacy of the compounds of this invention for
the foregoing fungi establishes the general utility of the
compounds as fungicides.
[0039] The compounds of this invention have broad ranges of
efficacy as fungicides. The exact amount of the active material to
be applied is dependent not only on the specific active material
being applied, but also on the particular action desired. The
fungal species to be controlled and the stage of growth thereof, as
well as the part of the plant or other product to be contacted with
the toxic active ingredient. Thus, all the active ingredients of
the compounds of this invention, and compositions containing the
same, may not be equally effective at similar concentrations or
against the same fungal species. The compounds of this invention
and compositions are effective in use with plants in a disease
inhibiting and phytologically acceptable amounts.
[0040] While the novel technology has been illustrated and
described in detail in the figures and foregoing description, the
same is to be considered as illustrative and not restrictive in
character, it being understood that only the preferred embodiments
have been shown and described and that all changes and
modifications that come within the spirit of the novel technology
are desired to be protected. As well, while the novel technology
was illustrated using specific examples, theoretical arguments,
accounts, and illustrations, these illustrations and the
accompanying discussion should by no means be interpreted as
limiting the technology. All patents, patent applications, and
references to texts, scientific treatises, publications, and the
like referenced in this application are incorporated herein by
reference in their entirety.
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