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Патент USA US3078308

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rates
3,078,298
W
Patented Feb. 19, 1963
2
1
ClCHr-CHCk-ON + CHzOOONa —--" CHz=CCl-CN
3 078 298
s-ALKYL (sULroNYL’ANi) SULFOXYL) ACRYLIC
Acn) EsTnns AND NITRILES
Walter A. Gregory and Hein L. Klopping, ‘Wilmington,
Del., assignors to E. L du Pont deNernours and Corn
pany, Wilmington, Deb, a corporation of Delaware
No Drawing. Filed Dec. 15, 1958, der. No. 780,256
4 Claims. ((1260-4654)
This invention relates to novel chemical compounds
'XRs--oH=oH-=~oN
identi?ed as 3-alkyl(sulfonyl and sulfoxyl) acrylic acid
vderivatives, to their formulations for use as pesticides, and
to methods for the control of pests.
one 0
XR—SO——CH=CH—CN
We 0
\a
More particularly, the invention is directed to pesticidal
XR——SO2—CH=CH—ON
compositions containing at least one novel 3-alkyl(sulfonyl
The preparation of alpha-chloroacrylonitrile is described
or sulfoxyl)acrylic acid ester or nitrile characterized by 15 by Brintzinger et al., Angew. Chemie 60, 311 (1948).
the formula:
The general method for reacting this compound with
.mercaptans, and the subsequent dehydrohalogenation of
(I)
the product is described by Gundermann [Ann. 588, 174
(1954)]. The procedures for oxidizing the mercaptans
where :
‘X is hydrogen, hydroxy, nitro, cyano, or halogen such as 20 to the corresponding sulfoxides and sulfones can be gen
erally the same as discussed above for the esters of
chlorine, bromine or ?uorine;
Formula 1.
The acrylic acid derivatives of Formula 1 are useful as
R is a divalent branched or straight chain saturated hy
drocarbon radical of less than 7 carbons, namely 1
pesticidal agents, especially as anti-fungal agents, and as
through 6;
25 bactericidal and protozoicidal agents. They are of par
.n is a positive integer less than 3, namely 1 or 2; and
ticular value because of the wide spectrum of in vitro
Q is —CN or --COOR' where R’ is an alkyl radical of
activity they possess at low concentration (less than 50
less than 19 carbons, namely 1 through 18.
ppm.) against bacteria, fungi, protozoa, and algae, and
Preferably, because of effectiveness as well as economy
and ease of preparation, .preferred compounds are those 30 the expressions “pests,” “pesticidal,” etc., as used herein
is intended to embrace all of these.
wherein n is 2 and R contains less than 4 carbons.
In practicing the fungicidal methods of my invention, a
The esters and nitriles represented by Formula 1 can be
3-alkyl(sulfonyl or sulfoxyl)acrylic acid derivative of this
made by various methods. According to one exemplary
invention is applied to the material to be treated for the
procedure, the esters of Formula 1 can be prepared ac
of fungi at a dosage su?‘icient to exert fungicidal
cording to the following equations, where X, R and R’ 35 control
action. Accordingly, my compounds can be used, for
have the same signi?cance as in Formula 1:
example to treat living plants such as vegetables, orna
base
mental plants, and fruit-bearing trees. Also they may be
CHEC—CO O R’ + XRSH -—--> XRS-CH=OH—~C 00 R’
used to treat organic ?bers or fabrics and various cellu
losic materials such as paper, cardboard and wood. Like
catalysis
wise, they may be used to treat paints and lubricating oils.
One important utility appears to be in the control of
fungus diseases of agricultural crops or ornamental plants.
The dosage employed in the fungicidal methods of the
invention is largely determined by and dependent upon
The propiolic acid esters used as starting materials are 45 the particular fungicidal compound selected, and, in the
conveniently prepared by oxidation of propargyl alcohol
case of application to vegetation, the susceptibility of the
particular vegetation to the compound selected, the state
and condition of growth of the vegetation to be treated,
[cf Wolf, Ber. 86, 735 (1953)], and esteri?cation of the
resulting propiolic acid with the desired alcohol. If de
sired, the products may be separated into their cis- and
trans-isomers. This separation is conveniently accom
plished at the sul?de stage by means of fractional distilla
and the climatic conditions.
’
In general, the fungicidal compositions of my inven=
tion contain in su?icient amount to exert fungicidal ac
tion a compound of Formula 1 as an active ingredient in
admixture with a carrier material or conditioning agent
of the kind used and commonly referred to in the art as
tion at reduced pressure. Oxidation to the sulfoxide stage
is preferably carried out under mild conditions, e.g., by
using hydrogen peroxide in acetone at room temperature,
whereas oxidation to the sulfone stage is best achieved 55 a fungicide (or pest control) adjuvant. Usually from
under somewhat more rigorous conditions, e.g., by using
about 1% to 95% by weight of the fungicidal composi
peracetic acid in acetic acid. It will be understood that
tion is active ingredient.
any of a variety of oxidizing agents and methods common
The convention-a1 fungicide adjuvants are inert solids,
to the art for oxidizing sul?des to sulfoxides and sulfones
organic liquid diluents and surface-active agents. They
can be used.
The nitriles of Formula 1 can, for example, be prepared
from the esters of Formula 1 by conventional methods,
60
provide formulations adapted for ready and ef?cient appli
cation using conventional applicator equipment.
Thus,
one or more of my fungicidally-active compounds is ad
i.e., through conversion to the amides and dehydration of
mixed with a fungicide adjuvant material to provide a
these amides by means of P205 or SoCl2. In this prepara
formulation in liquid or solid form.
tion, the mercapto intermediates can conveniently be used 65
Solid compositions are preferably in the form of pow
as the starting materials, these mercapto compounds being
either mixtures of isomers or pure cis- or trans-isomers.
Another method of preparing the nitriles of Formula 1
is illustrated by the following series of equations:
ders. They are compounded to be homogeneous pow
ders that either can be used as such, diluted with inert
solids to form dusts or suspended in a suitable liquid
medium for spray application. The powders can .comé
70 prise principally the active ingredient and minor amounts
of conditioning agent. They can also be prepared by
8,078,298
3
4
admixing the active compound with large amounts of
?nely divided inert solids. Natural clays, either absorp
entire crop of 24 grams in 200 ml. absolute ethanol, add
ing 5 ml. of thionyl chloride. and allowing the mixture to
tive such as attapulgite or relatively non-absorptive such
as china clays, diatomaceous earth, Walnut shell ?our,
redwood ?our, synthetic ?ne silica, calcium silicate and
stand overnight. Upon evaporation of the alcohol and
other inert solid carriers of the kind conventionally em
drying of the colorless residual oil in a high vacuum,
there is obtained 24 grams of B-ethylsulfonylacrylic acid,
ethyl ester.
ployed in wettable powder fungicidal compositions can
be used. The active ingredient usually makes up from
Analysis.—-Calcd. for C7H12O4S: C, 43.7; H, 6.3; S,
16.7. Found: C, 43.63; H, 6.34; S, 16.34.
about 25 to 90% of these wettable powder compositions.
In a standardized tube dilution test, 3-ethylsulfonyl
Suitable diluents for conversion to dusts are talc, pyro 10 acrylic acid, ethyl ester has the following anti-microbial
phyllite, tobacco dust, volcanic ash and other dense rapid
spectrum.
settling inert solids.
organism:
Mclelililclrlglllloirghgittilil'ignrglgr‘ill.
Liquid compositions employing one or more of the
Aerobacter
aerogenes
___________________
_2S
fungicidal compounds of my invention are prepared by
Bacillus anthracis ______________________ .. 12.5
admixing the active ingredient with a suitable liquid
Bacillus subtilis ________________________ __ 12.5
diluent media. The active ingredient can be either in
solution or in suspension in the liquid media. Typical
of the liquid media commonly employed as fungicide
adjuvants are water, kerosene, Stoddard solvent, xylene,
alcohols, alkylated naphthalene, and glycols. The active
ingredient usually makes up from about 0.5 to 50% of
these liquid compositions. Some of these compositions
Brucella abortus _______________________ .. 6.3
Coryncbacterium bovis _________________ ._ 12.5
Escherichia coli _______________________ _50
are designed to be used as such, others to be extended
with large quantities of water.
Compositions in the form of wettable powders or 25
liquids in many cases also include a surface-active agent
Klebsiella pneumoniae A ________________ .._
50
Micrococcus pyogenes var. aureus _______ -_
25
Mycobacterium tuberculosis bovine _______ ..
Mycobacterium phlcii __________________ ....
50
6.3
Neisseria catarrhalis ___________________ __
Pasteurella multocida ___________________ .._
3.1
25
Proteus vulgaris _______________________ _- 12.5
of the kind sometimes referred to in the art as a wet
Salmonella gallinarum __________________ __
25
ting, dispersing or emulsifying agent. These materials
Salmonella paratyphi ___________________ -_
Salmonella pullorum ___________________ __
Salmonella typhimurium ________________ ..
25
25
50
Sarcilza lutea _________________________ ..
6.3
cause the compositions to disperse or emulsify easily in
water so as to give aqueous sprays.
30
The surface-active agents employed can be of the
anionic, cationic or nonionic type. They include, for ex
Shigella dysenteriae ___________________ _..... 12.5
Streptococcus agalactiae ________________ .._
25
ample, sodium oleate, sulfonated petroleum oils, alkyl
aryl sulfonates, sodium lauryl sulfate, polyethylene
Streptococcus pyogenes __________________ .._
50
oxides, lignin sulfonates, and other surface-active agents.
Vibrio comma _________________________ --
6.3
A detailed list of such agents is set forth in articles by
Candida albicans _____________________ _.._ 12.5
McCutcheon in “Soap and Sanitary Chemicals,” August,
Twenty parts of the 3-ethylsulfonylacrylic acid, ethyl
September and October of 1949.
With reference to the compounds of ‘Formula 1, the
ester, produced as described above, is vmixed with 25
parts of coumarone indene resin, 45 parts ethanol and 5
40
cis-isomers have been found ‘generally to be more active
parts of an alkyl aryl polyether alcohol to give a homoge
biologically than the trans-isomers. Also generally, the
neous solution. This composition when emulsi?ed in wa
nitrile compounds of Formula 1 exhibit greater activity
ter gives a formulation suitable for application as a foliar
than the esters of Formula 1.
In addition to the above, compounds of this invention
can be used as active ingredients in disinfectant com 45
positions.
The compounds of this invention are particularly ad
fungicide, particularly against Alterlzaria solam', Venturia
inacqualis, Uromyces appendiculatus, Phytophthora in
festans, Cercospora apii, Diplocarpon rosae, Botrytis
paeoniae and Plasmopara viticola.
EXAMPLE 2
vantageous in that, for example, 3-ethylsulfonylacrylo
nitrile demonstrates an outstanding stability against de
Sixteen grams of crude 3-ethylmercaptoacrylic acid
composure in aqueous solution, even at pH values as 50 ethyl ester, prepared as in Example 1, is distilled in a
high as 8.
high vacuum using a spinning band column. The follow
In order that the invention will he better understood,
ing fractions are collected:
the following speci?c illustrative examples are given in
( 1) Colorless oil, B.P. 47-49°/0.25 mm., nD25=1.5099,
addition to those already set forth above.
8.5 grams
55
EXAMPLE 1
IR spectrum: no band at 10.36 microns
UV spectrum: absorption at 277 millimicrons
To 19.6 grams (0.2 mole) of ethylpropiolate are added
This oil consists of cis-3-ethylmercaptoacrylic acid,
3 drops of triethylamine, and then 12.4 grams (0.2 mole)
ethyl ester.
of ethylmercaptan are added dropwise with stirring,
keeping the temperature of the reaction mixture below 60 (2) Colorless oil, B.P. 54-55°/0.25 mm., nD25=l.5120,
4.0 grams
38°. Stirring is continued at room temperature for 3
IR specrum: absorption at 10.36 microns
hours. The dark brown oil is distilled in a high vacuum,
UV spectrum: absorption at 287 millimicrons
and the fraction boiling at 66-70“ at 0.7 mm. Hg is col
This oil consists of trans-3-ethylmercaptoacrylic acid,
lected. The yield is 23 grams of 3-ethylmercaptoacrylic
ethyl ester.
acid, ethyl ester.
65
Twenty grams (0.125 mole) of this mercapto com
These two mercapto compounds are oxidized to the cor
pound are dissolved in 50 ml. of glacial acetic acid.
responding sulfones using the method of Example 1.
While stirring, 47.5 grams of 40% peracetic acid (0.25
There are obtained, respectively:
mole) are added dropwise. After the addition is com
plete, the mixture is stirred and heated on a steam bath 70
until the peroxide test is negative.
The solution is vacuum concentrated to an oil, weigh
ing 24 grams, which consists essentially of the desired
ester. The main impurity is 3-ethylsulfonylacrylic acid,
which is‘ converted to the desired ester by dissolving the 75
Cis-3-ethylsulfonylacrylic acid, ethyl ester.
syrup, nD25=l.4734.
Colorless
Analysis.—-Calcd. for C7H12O4S: C, 43.7; H, 6.3; S,
16.7. Found: C, 43.70; H, 6.36; S, 16.71.
Trans-3-ethylsulfonylacrylic acid, ethyl ester. Colorless
syrup, rzD25=1.4709.
3,078,298
5
d
Analysis.——~Calcd. for CqH12O4S: C, 43.7; H
16.7. Found: c, 44.34; H, 6.33; s, 16.47.
EXAMPLE 3
6.3; S,
.- '
’
O
. ,
rgamsm'
,
-
~ -
>
Mmlmé‘t?‘mgiitill‘ttii?i
gamma/m"
Aerobacter aerogenes ____________________ __ 12.5
_Ten grams (0.0625 mole)_ of 3-ethylmercaptoacry1ic
Bacillus an?zracis _______________________ __
6,3
acid, ethyl ester, prepared as in Example 1, are dissolved 5
Bacillus subn-h-S________________________ __
63
In 100 m1. of acetone, and 7.5 grams (0.071 mole) of
Brucella abort,“________________________ __
3'1
30% hydrogen peroxide are added. The mixture 18 stirred
untllithe peroxide test is negative. Evaporation of the
gorynebacterium bow-s__________________ __ 63
piplococcus pneumoniae _________________ __ 25
Solution and drying of the residual 011 yields 12.5 grams 1
of product whlch consists essentially of 3-ethylsulfonyl- 0
Escherichia to”;_______________________ __
Klebsiella pneumom-ae A ________________ __
63
63
acrylic acld» ethyl esterEXAMPLE 4
M icrococcus pyogenes var, aureus _________ __
Mycobacterium tuberculosis bovine ________ __
6.3
1.6
To 44.2 ml. of ethylmercaptan is added 1 gram of
sodium methoxide. The mixture is cooled to 5°, and 15
Myfoblfcfel‘illm'PhZEiL-e ---------------- __ 0-3
Nelsserm calarrhqlis____________________ __ 0.8
stirred. Then 70 grams (0.08 mole) of alpha-chloroacrylonitrile (prepared by the method of Brintzinger et
al., Angew Chemie 60, 311 (1948)), are added dropwise.
The temperature is allowed to rise to 40° ‘and is kept the-re
Pasteurella mulf‘oclda ----------------- _-.-__
PTotem‘ Wlgarl-Y -------------------- -_--_-Pseudomonas aeruginosa _________________ __
Salmonella galll'narutn ------------------- -_
Salmonella PamlyPhl -------------------- __
by means of external cooling. The addition requires 45 20
minutes. Stirring is continued at room temperature for
three hours.
distilled.
Salmonell? PllllQl'Mm -------------------- --
The mixture is ?ltered and the ?ltrate is
25
6.3
6.3
6-3
6-3
6.3
Salmonella lyPhlmWiHm ----------------- -- 12-5
The fraction boiling at 10‘8-—110° at 12 mm.
smjcma lute“ ----------- -- -------------- -_
(18
consists essentially of alpha-chloro-beta-ethylmerc-apto-
Shlgella dyse'lfel‘l'aé --------------------- __
3.1
25
Streptococcus agalactiae _________________ __
6.3
Twelve grams of this compound are dissolved in 50
m1. of benzene, and 25 ml. of triethylamine are added.
The mixture is refluxed for 3 hours, cooled, and ?ltered.
The ?ltrate is refluxed for another 3 hours, and a second
crop or triethylamine hydrochloride is removed by ?ltra- 3O
tion. The ?ltrate is concentrated, and the residue is distilled under reduced pressure. The fraction boiling at
ill-115° and 18 mm. consists essentially of beta-ethyl-
sl‘f‘epfococcus Pyogenes ------------------ -_
V117”? comma ------------------------- __
Candlda albl'c?ns ----------------------- __
Mycodermll lipolyiim ___________________ __
Rhodoterula sp ________________________ __
SaCchammJ/Ces Cerevl'sl'ae ---------------- _saccharomyces PllStOriamlS _______________ __
Torulopsis ml‘lfndam ____________________ __
25
3-1
12-5
12-5
12.5
12.5
6.3
25
propionitme,
mercaptoacrylonitrile(11D25=1.5290)_
TOWIOPSI'S wills ________________________ .... 12.5
Seven grams of the latter compound are dissolved in 35
210 ml. of acetic acid, and 24 grams of 40% peracetic
acid ‘are added dropwise with stirring. The solution is
'ZJ’gOSaFChaI‘OmYQQS iapo?i?lls ------------ -_ 12-5
Aspergllllls fumlgams------------------- _-. 25
Asperglllus niger _______________________ __ 25
then heated on the steam bath until the peroxide test is
negative. The solution is vacuum concentrated to an
orange oil. This oil is dissolved in about an equal volume 40
Glomerella Cinglllam_____________________ _.
Memf‘rhilillm glutinm‘ium ________________ __
PWQIZfJQWCB-Y variota ____________________ __
of chloroform and chromatographed over a column con-
Pemcllllllm cifl‘ilmm ____________________ __ 121.5
taining 15 times its weight of Alcoa alumina. The ?rst
material to leave the column is a colorless oil which
SCOPHIWI'OPSI'S brevicaulis ________________ __ 12.5
Streptomyces gl‘l'é'eus ____________________ __ 0.8
#
_
crystallizes on standing.
After recrystallization from wa-
ter, the solid melts at 44.5-45" C., and consists essen- 45
tiany of 3-ethy1su1f0ny1acrylonitr?e,
,
Amllysis.~Calcd. for C5H7N02S: N, 9.65. Found: N,
6.3
0.8
25
_
EXAMPLES 5 19
Using the methods described above, there are prepared
the compounds of Table I. The reactants, the amount of
9_36_
each employed, the number of the reference example, and
In a standardized tube dilution test, 3-ethylsulfonylthe structural formula of the resulting product are set
acrylonitrile has the following antimicrobial spectrum.
50 forth in this table.
Table 1
Reactants (Other than catalysts and oxidizing agents)
Method
of Ex-
ample
Product
No.
000
C00
000
000
000
000
C00
1
1
1
1
1
1
2
00011012115 (01111.) CzI‘IsSH (0.1m.) _____________ __
2
1
H0—OH?-oH2-s02—0H=crr—o00110511,!
OOOIlC1SI'I37(0-1H1.)SGC- C4HDSH (0.11n.) _________ _.
CHEC-—COOCH3(O.1H1.) CHsSH (0.1111.) ................. ._
1
2
sec. C4H9SO2-OH=CH—OOOIIClBIIQ'!
OH3SO—-CH=CI'I—COOCH3
3
CHsSO2——CH=CH-CN
s
nOsH7SOz——CI-I=CH—~CN
3
sec. O4HoSOz—C-H=CH—CN
3
11CdHiaSO2-—CH=CH-—CN
o OOnCEI-IU (0.1 m.) HO-OHz-—CI;Iz—-SH (0.1 m.)__
CHsSOz—GH=OH-COOC2H5
CHzSOz—CH=CH—-COOOH3
nCsH1SOz—CI-I=CH-COOC2H5
C2H5SOQ—CI-I=CH—COOI1CAHH
CzH5SOz—CH=CH——C00nCsH17
IIC41-IQSOz—OH=CH-COOCEH5
iCsH1SO—CI-I=CH~—OOOCH3
O2H5SO~CH=CH—-C001101215125
Cl
OHZ=(‘J—CN (0.1 m.) CH3SH (0.1111.) _______________________ ..
01
CHzr-(‘J-CN (0.1 m.)nCsH1SH (0.1 m.) _____________________ ..
c1
GH2=(lJ-—CN(O.1 111.)S6C.C4HOSH(O.1 m.) .................. __
o1
CH2=iC-—CN (0.1 m.) nCsH1sSH (0.1 m.) ..................... r_
3,078,298
8
Following substantially the procedures given above, the
Parts by weight
following illustrative compounds can be prepared, as will
be readily understood by one skilled in the art:
3-ethylsulfonylacrylonitrile
_________________ __
50
Alkyl naphthalene sulfonic acid, sodium salt __..__
0.5
Methyl cellulose, low viscosity _______________ .._
0.25‘
Attapulgite clay __________________________ __ 49.25
The resultant wettable powder is suitable for applica
tion as an agricultural fungicide.
An aqueous suspension
of the powder having the active ingredient present at a
concentration level of 0.2% is applied to tomato foliage.
10 The foliage is later inoculated with spores of late blight
fungus (Phylophtlzora infestans) and placed in a cham
ber where conditions of temperature and humidity suit
able for optimum infection are maintained. After suffi
cient time has elapsed for the formation of visible lesions,
15 the foliage is examined. It is found that the treated
foliage has substantially less disease than the non-treated.
Also, in place of the active ingredient in the composi
tion of this example, one can use any ester or nitrile fall
ing within the scope of Formula I. Thus, for example,
20 the compound 3~methylsulfonylacrylonitrile can be em
loyed as the active ingredient in a composition of this
example to effectively control the fungus causing black
EXAMPLE 20
A suitable fungicidal formulation of the following com
position is prepared by mixing the ingredients until a 25
homogeneous solution results.
Ingredient:
Parts by weight
Alkyl, aryl polyether alcohol (“Triton” X-155,
Parts by weight
30 3~ethylsulfonylacrylic acid, n-butyl ester _______ __
50
Synthetic calcium silicate (Micro-Cel) ________ __ 49.25
Low viscosity methyl cellulose _______________ _. 0.25
commercially available from Rohm & Haas
Co.)
____.
5
Alkylated naphthalene sodium sulfonate (commer~
Ethanol ________________________________ __ 45
This composition can be emulsi?ed in water and when
mixed with water is especially suitable as a foliar spray
A suitable wett-able powder of the following composi
tion is prepared by mixing the ingredients and passing the
mixture through a micropulverizer:
3-ethylsulfonylacrylic acid, ethyl ester _______ __ 25
Coumarone indene resin ___________________ __ 25
spot of rose (Diplocm-pon rosae).
EXAMPLE 22
35
for application by conventional spray equipment for the
protection of living plants from fungi attack.
A suspension containing 0.2% of 3-ethylsulfonylacrylic
acid, ethyl ester, is sprayed on tomato foliage. After the
deposit has dried, the foliage is inoculated with a suspen~
sion of spores of the early blight fungus (Alternaria
solani) and the foliage is then placed in a chamber where .
cial wetting agent) ______________________ ..
0.5
When made into an aqueous suspension by the addi
tion of Water, this suspension is suitable for a foliar spray.
A suspension containing 0.2 of the acrylic acid derivative
is sprayed on peony foliage. After the deposit has dried,
the foliage is inoculated with a suspension of spores of
Botrytz's paeom'ae. The foliage is then placed in a cham
ber where temperature and humidity suitable for optimum
infection are maintained.
When su?icient time has
elapsed for the formation of visible lesions, the foliage
conditions of temperature and humidity suitable for op
is examined. It is found that the treated foliage has sub
timum infection are maintained. When sul?cient time 45 stantially less disease than non-treated.
has elapsed for the formation of visible lesions the foliage
In place of the acrylic acid derivative of the above
is examined. It is found that the treated foliage has 2%
composition, the n-octyl ester can be employed in an equal
disease compared to 100% on the non-treated.
amount by weight to prepare a suitable wettable powder.
A similar composition containing the active chemical
Such a powder wets readily and forms a good dispersion
at a concentration of 0.008% is applied to apple foliage. 50 when mixed with a large quantity of water. Such a dis
The foliage is inoculated with spores of apple scab fungus
persion is effective in controlling the downy mildew of
( Venturia inaequalis) and placed in a chamber where con
grapes caused by Plasmopara vitz'cola.
ditions of temperature and humidity suitable for optimum
EXAMPLE 23
infection are maintained. The treated foliage has 7%
disease compared to 100% for non-treated.
55
A free-?owing dust is prepared by blending
In place of 3-ethylsulfonylacrylic acid, ethyl ester,
there can be used in the above formulation any of the
50 parts of 3-methylsulfonylacrylic acid, methyl ester, and
the above composition. Such a composition when mixed
with water, in an amount such that the aqueous formula
active in a ribbon blendor. The resultant free-?owing
powder is readily applicable to areas to be protected from
tion contains 0.2% of the acrylic acid derivative is sprayed
on bean foliage. After the deposit has dried, the foliage
ment.
50 parts of kaolin clay
ester-type compounds shown above. For example, the
compound 3-methylsulfonylacrylic acid, ethyl ester, can
and passing the resulting blend through a micropulverizer.
be employed in place of the compound of Example 1 in 60 This blend is then diluted with micaceous tale to 20%
is inoculated with a suspension of spores of bean rust 65
fungus (Uromyces appendiculatus) and placed in a cham
ber where conditions of temperature and humidity suit
fungi or bacteria attack by conventional dusting equip
In like manner, any other solid derivative of Formula I
can be incorporated into a powdery pesticidal formulation.
The invention claimed is:
1. A compound represented by the formula:
able for optimum infection are maintained. After sul?
cient time has elapsed for the formation of visible lesions,
X—R-—SO,,—CH==CH—Q
the foliage is examined. It is found that the treated foli 70
where:
'
age has substantially less disease than the untreated.
X
is
selected
from
the
group
consisting
of hydrogen,
EXAMPLE 21
halogen, —OH, -—N02 and —CN; R is a divalent
A suitable wettable powder of the following composi
branched or straight chain saturatedhydrocarbon of from
tion is blended, micropulverized and reblended.
75 1 to 6 carbons; n is a positive integer of from 1 to 2; and
3,078,298
10
9
Q is selected from the group consisting of -~CN and
-—-COOR' Where R’ is an aikyl radical of from 1 to 18
2,354,231
2,433,742
carbon atoms.
2. A compound as set forth in ‘claim 1 wherein n is 2
and R contains less than 4 carbons.
5
2,506,019
Goldberg et a1. ________ __ May 2, 1950
2,534,112
2,5 37,022
Edwards _____________ __ Dec. 12, 1950
3. 3-ethylsulfonylacrylonitrile.
4-. Cis-3-ethylsu1fony1acrylic acid, ethyl ester.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,181,057
'Krzikalla et a1 _________ __ Nov. 21, 1939
10
2,556,134
‘2,675,371
2,748,050
2,896,872
2,837,558
Walter ______________ __ July 25, 1944
Davis ________________ __ Dec. 30, 1947
Bartlett et a1 ____________ __ Jan. 9, 1951
Croxall et a1 ___________ __ June 5, 1951
\Coover et al ___________ __ Apr. 13,
Shearer et a1 __________ __ May 29,
Kartinos et al _________ __ Sept. 17,
Lynn ________________ __ June 3,
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