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Патент USA US3030273

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April 17, 1962
K ZEILE ET AL
3,030,263
SYNERGISTIC FUNGICIDAI.. COMPOSITIONS
Filed July 19, 1960
%.LO3:Á;|3
'IVGIOISNnd
mm
ATTORNEYS
{_Uite, States Patent _"Oìbfice
v
3,030,253
Patented Apr. 17, 1962
2
1
The attached drawing represents a graph showing the
`individual fungicidal effects of zinc >ethylene-bis-dithio
*carbamate and calcium pentasulûde, respectively, as a
3,030,263l
SYNERGISTIC FUNGICI‘DAL COMPOSITIONS
Karl Zeile, Richard Sebring, and Peter Schicke, Ingel
>function of their concentration, on the tomato seedlings
heim, Germany, assignors to C. H. Boehringer Sohn,
(inoculated with Phytophthora infestans). The dotted
Ingelheim (Rhine), Germany, a limited partnership
vlines a and b show the concentrations of the two active
ingredients which have the same fungicidal effect. These
values are summarized in Table 1. The equivalent fungi
4 Claims. (Cl. 167-14)
cidal effect for the individual concentrations of the two
This invention relates to fungicidal compositions and, ll components is indicated in the last column of Table l.
_ Filed July 19, 1960, Ser. No. 43,815 f
I Claims priority, application Germany July 23, 1959 i' i
more particularly to fungicidal compositions containing
Table 1.-`-Concentratz'on (in Percent by Weight) of Equal
Fangicidal Activity of Zinc Ethylene-Bìs-Dithiocarbam
dithiocarbamic acid salts and calcium polysulñdes as ac
tive ingredients.
ate and Calcium Pentasuljide in an Inert Carrier
It is known that thiocarbamates have excellent fungi
cidal properties and are useful in combatting numerous
phytopathogenic fungi.
However, they are not effective). '
Zinc ethyl-
Equivalent
Calcium
ene-bis-
Funglcidal
Pentasulûde
dithiocar-
Effect
l
against true mildew fungi (Erysiphaceae family). _ It is '
further known that calcium polysulíides are useful in com
bamate
batting plant diseases caused by fungi, but they are pri
marily effective against true mildew fungi. lt' is also
known .to _use barium polysulfìde to combat fungi.
Percent
0. 2
0A 1
0. 5
0.025
0.0125
A
>combination of_ barium .polysulñde with tetramethyl
thiuram-disulñde is not possible, as indicated in the Plant
Protection Summary of Bayer, page 48.
Percent
40
14
3
0.3
0.02
_ . ,v
Thiocarbamates are generally relatively'expensive com
pounds, but they exhibit a good plant compatibility. Inr »_
contrast, thereto, calcium polysulñdes Jare' substantially
cheaper, but they readilyV lead to undesirable damage’to
the plants in higher concentrations.
Percent
0. 0101
0. 0034
0. 0011
0. 0004
0.0001
» ` '
30
We have now surprisingly- found that Ya mixture con
_tainingra thiocarbarnate .and acalciumpolysuliide exhibits ,
._a considerable synergistic effect with respect to the fungi
cidal activity. In other words, the fungicidal _activity of
suchî a composition far exceeds the expected additive ef
With the aid of the values shown in Table 1 and with
the aid of the graphit is possible _to express the fungicidal
effect of calcium pentasulñde in terms of zinc ethylene
bis-dithiocarbamate equivalents and vice versa. On the
basis ofthese values it is, in turn, possible to determine v
the expected theoretical additive fungicidal effect of a
composition containing both of the components in vary
ing quantitative ratios. This shall be further explained
with .the aid of the following example: Let us say that a
composition contains 0.2% by weight calcium pentasul
ñde and 0.072% by weight zinc Äethylene-bis-dithiocar
35
?fect of the individual components. Within the general scopev of the present invention we; f bamate. From the graph it may be determined that 0.2%
have found that the combination of zinc ethylene-bis-di
calcium pentasulñde are equivalent to 0.01%A Zinc ethyl
In order to de
termine _the theoretical total fungicidal effect, the two
>to the invention was- determined-«by testsmon tomato 40 ‘values of 0.072 and 0.010 for zinc ethylene-bis-dithio
thiocarbamate and calcium pentasuliide _is particularly ef
fective. The effectiveness of _the composition according
_ ene-bis-dithiocarbamate (dotted line a).
>seedlings artiñciallyinfected with Phytophthora infestans
lcarbamate are added.
and by tests on small rye plants artificially yinfected with
Erysiphe graminis.
im»
,
v
The graph shows that a concentra
V_tion of 0.082% by weight zinc ethylene-bis-'dithiocar
~
r-bamate corresponds to an expected fungicidal effect of
Test procedure: The test plants were sprayed _with
90% _ (broken line I in the graph). However, the actual
45
aqueous 4suspensions or solutions of fungicidal composi
.fungicidal effect of such .a composition, determined by
tions according to the invention and, after drying of. the y' vexperiment, is 99%. , '
_ spray- coating, the plants were artificially infected with the l
In TableZ the theoretical fungicidal effect of composi
fungi. The infection'with .Phytophthora infestans .was
tions containing various concentrations of zinc ethylene
accomplished by means of a vspore suspension _of this
bis-dithiocarbarnate and calcium pentasulñde is compared
fungus which contained 60 to 120,000 sporesqpercubic 50 with the fungicidal effect actually found.
centimeter; the infection with-Erysiphe grantitfzisÍ was ac- ,_ _
Table 2.-Synergistic Fungìcidal Effect of a Composition
coinplished by means of dry-dusting of the testplants with
According to the Invention Against Phytophthora in
Erysiphe conidia. The tomato plants were subsequently
festans on Tomatoes, the Active Ingredient Mixture
introduced for 49 hours ,intoa climate chamber with
'steam-saturated air at _20° C.- The area of fungus attack 55
then appeared as, necrotic spots onthe leaves. The fungi
carbamate (I) and 74.4% by Weight Calcium Penta
cidal evaluationwas ,accomplished by estimating the-por
sulfide (II)
Containing 25.6% by Weight Zinc Ethylene-Bis-Dithio
.tiony of the destroyed leaf surface on the total leaf sur
face which was then compared with >the damage done to
the leaves of untreated plants. The damage doneto con 60
trol plants which had not `been ,treated with a fungicidal
agent was then given au arbitrary valueof 100.
Concentration Per-
were counted on a -leaf section 2 cm. long and-_which
-were also related to untreated control plants.
The above test'is described in theliterature by P.
Schicke, “Uber eine .einfache Versuchsanordnung der
Fungicidteste mit Phytophthora infestans” (Mont.) de
Synerglstie
Increase in
all Composition
~
incubation period with Erysiphe- graminis was 5 to 7 days.
,The fungus developed under a normal green-house _cli
mate and .after this period formed white pustules, which
Fungictdal-Effeet in Percent
»
The "
_
cent of Active
Ingredients in Over`
'
"
'
I
li‘uugicidal>
_
'
_
Effect.
-
Percent
II
_
Additive Actually
_. Expected
’
Found'
65.
'
0.072
0.036
0.1
0.0118l
0 2
0.05
0. 009
0.0045
0. 025
0 0125
90
78
»
_99
95
+17
57
v 85
+28
37
20
75
42
+38
+22
'
+9
-- _The vsynergistic increase in fungicidal effect is clear
«from-thevalues’s'hown in the last column of Table 2.
3,030,263
4
Since rthe synergistic eilect is clearly proven with the
aid of the preceding examples, the following tables merely
ner.
show the synergistic increase in fungicidal eiïect `for addi
tional varying quantitative ratios and other dithiocar
VZinc ethylene-bis-dithiocarbamate
bamates.
total composition applied, that is including the inert car
Particularly useful are the »following dithiocarbamates:
5
Manganese ethylenc-bis-dithiocarbamate
Sodium ethylene-hi's-dithiocarbamate
Table 3.-.S’yniergistic Increase in Fungicidal E?ect of
Compositions Containing Mixture of Zinc Ethylene
Bis-Dithiocarbamate (I) and Calcium Pentasulfide (II)
Zinc dimethyl-dithiocarbamate
Iron ethylene-bis-dithiocarbamate
The compositions according to the invention are em
at Various Quantitative Ratios (Phytophthora infestf
ans, Tomatoes)
10 ployed in those forms ,which are customarily used for
I. 41.8%
II. 58.2%
I. 25.6%
Il. 74.4%
I. 14.9%
II. 85.1%
Concentration
Synergistie Concentration synergistic Concentration synergistic
ctive
Ingredient
Increase in
Active
Increase in
Active
Increase in
Eiîect Aboye Ingredient Eiîect Above Ingredient Eiîect Above
Mixture,
Theory,
percent:l
Y percent
0. 344
0. 172
0. 086
0. 043
0. 002
Mixture,
Theory,
Mixture,
Theory,
Percent
percent
percent
percent
0.270
0. 135
0. 067
0. 034
0. 017
+9
+17
+28
+38
+22
0. 470
0. 235
0. 118
0. 059
0. 029
+6
+12
+19
+33
+33
.
+0. 7
+6. 2
+15. 9
+23.7
+8. 8_
Table 4.*Synergistic Increase in Fungicidal Eßect of 25 fungus control, for example as suspensions, dusting pow
Compositions Containing Disodium-Ethylene-Bis-Di
ders or solutions in inert carriers. The following exam
thiocarbamate (IV) or Zinc-Dimethyl-Dizhiocarbamate
(III) and-'Calcium Pentaswlfide» (Il) at Various Quanti
tative Ratios (Phytophthora infestants, Tomatoes)
ples will further illustrate the invention, the parts being
parts by weight.
(I) Suspension:
30
III. 28.79'
IV. 16.37
1I. 11.3%?
n. 83.1%?
7 parts kaolin
Concentration `synergistic Concentration synergistic
of active
increase in
oi active
67 parts calcium .pentasulñde
23 parts zinc, ethylene-bis-dithiocarbamate
35
increase in
ingredient
mixture,
percent
eñect >above
theory,
percent
ingredient
mixture,
percent
eiîect above
theory,
percent
0. 282
0. 141
0.071
+28
+27
+20
0.240.12
0.06
+4
+6
3 parts naphthalene; sulfonate
'I‘he individual components are intimately admirred by
milling and are then diluted rwith water to the desired
concentration of the active fungicidal components.
(2) Solution: 13 parts sodium ethylene-bis-dithiocar
bamate, 13 parts calcium pentasuliide and 4 parts naph
40 thalene sulfonate are dissolved in 70 parts water, and the
'resulting solution is diluted to the desired concentration
of the active I‘Jîu'ngicidal components.
The followingr tableY shows that not only the eiîect of
(3).' Dusting powder: 5 parts manganese ethylene-bis
the thiocar-bamates against those fungi` onk which theyV a1
dithiocarbamate and, 10 parts calcium pentasulñde are
ready exhibit a good,> eiïect is synergistically increased, 45 thoroughly admixcd with 85 parts kaolin by milling until
Ibutv also that the effect of the calcium pentasulíidel against
a homogeneous dusting powder is obtained.
true mildew fungi is*synergisticaliyv increased, which is of
particular importance in actual practice.
vWhile we have illustrated the present invention with
the aid of 'certain speciiic embodiments thereof, it will be
readily apparentto those skilled in the art that the inven
Table 5.-Synergístic Increase in Fungicidal4 Effectiveness
of Various Compositions Containing‘a Mixture'of» Cal 50 tion isnot limited -to these embodiments, and that various
changes and: modificationsV may be made without depart
cium Pentasuljîde (III) and Zinc Ethylene-Bis-Dithio
ing from the spirit of the invention or the scope of the
carbamate (I) Against Erysiphe graminison RyeY
appendedy claims.
We claim:
I. 25.517
55
1s. lFungicidalv compositions .comprising from 0.01 to
II. 74.56.'J
Concentration;
5% lay-weight of a salt of a dithiocarbamic acid selected
from the group consisting of zinc ethylene-bis-dithiocar
lbamate, manganese ethylene-bis-dithiocarbamate, sodium
synergistic
elective ingref Increase in
-dientmixture, etîect above
theory, percent
percent;
0. 136
0.A 06S"
0. 034
ethyleneebis-dithiocarbamate, zinc,y dimethyl-dithiocar
60 V-bamate and iron ethylene-bis-dithiocarbamate, and from
0:05 to 10% by weight of calcium pentasuliide. `
+26
+24
2. Fungicidal compositions comprising from 0.01 to
5%v by weight' of zinc ethylene-bis-dithiocarbamate and
0.05 to 10% by weight of calcium pentasulñde.
+42 i
The active ingredient mixture according to the present 65 Y 33.'F111'4gî.¢idall compositions comprising from 0.01 to
5%I by Weight ofzinc dimethyl-dithiocarbamate and from
exhibits the Vfollowing advantages over the dithiocarbamate
0.05 to 10% by weight of calcium pentasulñde.
or calcium polysnliìde alone:
l
4. Fungicidal compositions, comprising from 0.01 to
(1) The mixture, is more eíîectiye. tliauits individual
5% by- weight of disodium ethylenesbis-dithiocarbamate
components, so that up to 50% of the` quantity of dithio
70 and ‘fromOßS to 10% =by weight of calcium pentasulíide.
carbamate can be saved.
(2) The mixture has a greater; effective range.
References Cited‘i'n the ñle of this patent
. The active ingredient mixture according to the inven
tion preferably. comprisesbetween .0.01. and.5,% .tbyweight
0f. a, Salt 0f dithiocarbamic; acidand b_etvveetrk 0.005 and.
107i7 by Weight. of; e». wlsium nolysultids. based
lies 23,742..A
the 75 1,517,522
UNITED STATES` yPATEISITS
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