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Патент USA US3035082

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United States Patent ()1 ice
3,035,073
Patented May 15, 1962
2
1
be run in water, with sodium hydroxide as the reagent.
,
Preferably, the inorganic sodium component is added
3,035,073
N-ALKYL-N(ALKYL-MERCURI)ALIPHATYL
to the solvent ?rst. and the sulfonamide is then added
with stirring. This sequence of ‘addition furnishes a check
on the dryness of the solvents, as hydrogen is evolved
if the solvents are wet. However, the reaction will pro
ceed satisfactorily if these components are added to the
SULFONAMIDES
Richard S.'Waritz, Wilmington, Del., assignor to E. I.
du Pont de Nemours and Company, Wilmington, Del.,
a corporation of Delaware
No Drawing. Filed Mar. 23, 1960, Ser. No. 16,955
6 Claims. (Cl. 260-431)
solvent in the reverse order.
After the sulfonamide salt has been formed, usually
This invention relates to certain N-alkyl-N(alkylmer 10 1/2 hour, the hydrocarbyl mercuri component is added and
stirring is continued until reaction is complete, generally
curi)aliphatyl sulfonamides as new compound-s and to
1/2 to 11/2 hours.
,
their use as microbiocides for plants, seeds, and soil.
The reaction is most economically run if an equimolar
More particularly, this invention is directed to com
ratio of all reactants is used. However, an excess of the
pounds of the formula
15 inorganic and the organo-mercuri components does not
(1)
R2
interfere with the reaction.
The time required for the formation of the sulfon
amide salt depends upon the reactivity of the sulfonamide
and the inorganic sodium component in the solvent used
where
20 at the particular temperature chosen. Generally, it can
be said that the reaction takes about 1/2 hour to com
R1 is a 'monovalent acyclic unsubstituted hydrocarbyl
plete. Similarly, the reaction time of the sulfonamide
radical containing from 1-4 carbon atoms,
salt with the organomercurial is dependent on tempera
R2 is R1 or a hydroxy substituted monovalent hydrocarbyl
ture and solvent. Generally, however, it is complete with
radical containing from 1-4 carbon atoms, and
in 1/2 hour.
R3 is methyl or ethyl,
In general, temperatures above 45° ‘C. are preferred
because they accelerate the reactions, but temperatures
with the proviso that R1, R2 and R3 taken together shall
from 4° C. to the boiling point of the solvent can be
used.
not contain more than 8 carbon atoms.
The monovalent hydrocarbyl radicals in the R1 and 30
If an inert solvent or an alcohol is used as a reaction
R2 positions can, for example, be such radicals as methyl,
medium, the desired product will usually be soluble in
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. butyl,
the solvent, and the by-products and unreacted starting
tert. butyl, allyl, or propargyl.
materials will not. Thus, by simply ?ltering oi the in
Preferred for use according to this invention are those
soluble material and removing the solvent from the ?ltrate
compounds in which R2 is a radical chosen from among 35 in vacuo, the desired product is obtained in an essentially
those described for R1. The superior compounds are
pure form. The product can then be puri?ed further by
those in which R1 and R2 are methyl radicals, and R3
recrystallization from a suitable solvent, such as diethyl
is methyl or ethyl.
ether, dibutylether, chlorothene, or cyclohexane.
The compounds of this invention can be prepared ac
If water is used as the reaction medium, all reaction
cording to the following equation:
products will be soluble. Isolation of the desired product
(2)
I
2
Rl-SOZNH +
can then be achieved by extraction with a water-immisci
ble solvent such as toluene or by concentration and cool
NaOH
Na°
NaH
+ RgHgX —>
1'12
45
HOE
‘rusozN-ngag + %Hi i
+ NaXJ.
BC»
ing of the reaction solution until the productprecipitates.
The product thus obtained can then be recrystallized.
Since the desired products have less solubility in water
than the sodium halide formed, the amount of water used
as a solvent can be adjusted initially so that the mixture
resulting from the reaction is supersaturated with respect
In this equation, R1, R2, and R3 have the same mean 50 to the organomercurial product and unsaturated. with re
spect to the inorganic salt product. Filtration will then
leave the desired product behind as a precipitate. This can
or bromide.
be dried and recrystallized if desired.
_
The N-substituted alkyl sulfonamides are easily pre
ing as in Formula 1, and X is an anion such as chloride
For some purposes, it is unnecessary to isolate the or
amine, as described by Baxter et al. in J. Chem. 800., p. 55 ganomercurial product from the aqueous reaction mix
pared from the corresponding sulfonyl chloride and
670 (1955). The alkyl mercuri halides can be prepared
according to the procedure of Slotta and Jacobi set forth
ture. For example, the necessary formulating adjuvants
in J. Prakt. Chem, 120, 272 (1929).
.
Reaction 2 is preferably run in an inert solvent such as
sulting composition can be used directly, or, if desired,
can be added directly to the reaction mixture'and there
all water can be removed and the resulting residue can be
benzene, toluene, or xylene. Sodium hydride, or metallic 60 formulated into a soluble powder.
sodium are preferred for the preparation of the sodium
Illustrative of the compounds within the scope of this
sulfonamide in these solvents. The reaction can also be
run in a low molecular weight liquid alcohol, such as
invention ‘are
methanol, using metallic sodium or sodium hydride to
N-rnethyl-N-methylmercurimethane sulfonamide
N-methyl-N-methylmercuriethane sulfonamide
prepare the sodium sulfonamide.
The reaction can also 65
3,035,073
4
N-methyl-N-methylrnercuripropane sulfonamide
N—methyl-N-methylmercu1iisopropane sulfonamide
N-methyl-N-methylmercuributane sulfonamide
N-methyLN-methylmercuriisobutane sulfonamide
N-methyl-N-methylmercurisec.-butane sulfonamide
N-methyl-N-methylmercuritert.-butane sulfonamide
N-methyl-N-ethylmercurymethane sulfonamide
N-methyl-N-ethylmercuripropane sulfonamide
N-methyl-N-ethylmercuriethane sul-fonamide
vents which are not toxic to plants or animals. This is
also an advantage, since more uniform coverage of a sub
strate can be achieved with a solution than with other
types of compositions, and more convenient methods of
5 application can be used.
The compounds of this invention can also be used to
control slime forming organisms in wood pulping proc
esses. They are also useful in preserving proteinaceous,
fatty, and carbohydrate materials against fungus attack.
10 Such materials as starch, animal and vegetable glues, oil
based paints, and lumber can be protected from fungus
N-2-hydroxyethyl-N-methylmercuripropane sulfonamide
attack by applying a composition of this invention.
N-2-hydroxypropyl-N-methylmercuripropane sulfonamide
N-ethyl-N-ethylmercuripropane sulfonamide
N-Z-hydroxybutyl4N-methylmercuripropane sulfonamide
The compounds of this invention can be formulated
N-( l-hydroxymethylpropyl) -N-methylmercuripropane
into a variety of compositions. They can, for example,
15 be made up as solutions ‘containing from 1 to 25% of
sulfonamide
active ingredient, or mixtures of active ingredients. The
solutions can be made up using such solvents as dimethyl
N-propyl-N-methylmercuripropane sulfonamide
N-isopropyl-N-methylmercuripropane sulfonamide
N-ethyl-N-ethylmercuriethane sulfonamide
N-ethyl-N-ethylmercuripropane sulfonamide
N-ethyl-N-ethylmercuriisopropane sulfonamide
N-ethyl-N-ethylmercuributane sulfonamide
formamide, dimethylacetamide, N-methylpyrrolidone, cy
clohexanone, ethylene glycol, ethyl Cellosolve, ethyl \al
20 cohol, isopropyl alcohol, or water. Mixtures of these
solvents are often preferred for reasons of cost, and be
cause a suitable balance of physical properties such as
N-ethyl-N-ethylmercuriisobutane sulfonamide
low ‘freezing point, high ?ash point, and extendability by
N-ethylaN-ethylmercurisec.-butane sulfo-namide
water can be obtained.
N-ethyl-N-ethylmercuritert.-butane sulfonamide
N-(Z-hydroxyethyl) -N-ethylmercuriethane sulfonamide
25 Solutions which are dilutable with water are preferred
because water is the most economical and readily avail
N-propyl-N-ethylmercuriethane sulfonamide
able carrier. The compounds of this invention are espe
N-isopropyl-N-ethylmercuriethane sulfonamide
cially suited for such formulations because they are quite
N-(Z-hydroxypropyl)-N-ethylmercuriethane sulfonamide
soluble in water, even without the use of co-solvents.
N-butyl-N-ethylmercuriethane sulfonamide
N-isobutyl-N-ethylmercuriethane sulfonamide
N-tert.-butyl-N-ethylmercuriethane sulfonamide
30
N-( l-hydroxymethy-lpropyl) -'N-ethylmercuriethane sul
fonamide
N-( l-methyl-Z-hydroxypropyl) -N-ethylmercuriethane
sulfonamide
N-allyl-N-ethylmercurimethane sulfonamide
N-propargyl-N-methylmercu.rimethane sulfonamide
N-ethyl-N-ethylmercurimethane sulfonamide
The compounds of this invention can also vbe formu
lated as solutions in oils. Such compositions have the ad
vantages of adhering to the surfaces being treated and re
sisting removal by water and abrasion. Furthermore,
such oil-base compositions tend to penetrate surfaces
35 treated and therefore destroy fungi more effectively. The
particular oil used in any given formulation must be one
which has no deleterious effect on the substance being
treated. For example, when seeds are being treated, an
oil must be used which is not ‘phytotoxic to seeds. For
The compounds of this invention possess outstanding 4O this purpose, one can use isopara?inic hydrocarbons, de
fungicidal activity. They can be used to control such
odorized kerosene, mineral oils such as diesel engine oil,
turf diseases as dollar spot (Sclerotinia homoeocarpa),
m-al
vegetable
oils such
oils as
such
whale
as linseed
oil.
oil or soybean oil, or
brown patch (Pellicularia ?lamenz‘osa), snow mold (Fu
sarium nivale), copper spot (Gleocercospora sorghi), and
Diluents, extenders, or co-solvents for the oil composi
blight caused by Helminthosporium spp. The compounds 45 tions
can also be used. These can be chosen from among
of this invention are particularly useful for the control
the common organic solvents. For example, hydrocarbon
of fungi on golf-course turf. They are also useful as soil
solvents such as benzene, xylene, or methylated naph
fungicides against such organisms as Rhizoctonia solani,
thalenes can be used. Ketones such as diacetone alcohol,
Pythium spp., and Fusarium spp. The compounds can
cyclohexanone, mesityl oxide, or isophorone can also be
be used as seed disinfectants or seed protectants for the 50
used. Also useful are such esters as ethyl acetate;
seeds of wheat, oats, cotton, barley,f?ax, sorghum, rice,
branched chain alcohols such as isopropanol or 3-hexauol;
and the like. When applied to seeds, the compounds of
ether-alcohols such ‘as 2(?3-butoxyethoxy) ethanol; ethers
this invention protect them, while germinating, from at
such as phenolic ethers or diisoamyl ether; and cyclic
tack by soil-borne pathogens such as those belonging to
nitrogen compounds such as N-methyl-Z-pyrrolidone or
the classes Pythium and Rhizoctonia. The compounds 55
pyridine.
These diluents, extenders, and co-solvents can
also disinfect seeds already infected with such seed-borne
oflten be used alone rather than in conjunction with the
fungus diseases as stinking smut of wheat (Pilletia caries),
loose smut of oats (Usz‘ilago avenue), Helminthosporium
01 s.
victoriae on oats, and anthracnose of cotton (Glomerella
gossypiiy
.
The compounds of this invention show a high degree
of fungicidal activity coupled with very low mercurial
phytotoxicity. In addition, solutions of the compounds
are unexpectedly noncorrosive to brass, which is advan
tageous since equipment currently being used to apply
such compounds for agricultural purposes usually con
tains a number of brass parts.
The compounds of this invention are volatile, which
makes them more effective as seed fungicides. Fungi
60
Aqueous emulsions, the so-called emulsi?able oil con
centrates, can be made by adding a dispersing or emulsi
fying agent to the oil solutions. Such dispersing and
emulsifying agents are listed in detail in Bulletin E-607 of
the Bureau of Entomology and Plant Quarantine of the
US. Department of Agriculture and in articles by Mc
in “Soap and Sanitary Chemicals,” December
65 Cutcheon
1957 and January, February, March, April 1958.
Suitable emulsifying agents are such polyoxyethylene
derivatives as polyoxyethylene ethers of alkylated phenols,
polyoxyethylene esters of mixed rosin and fatty acids, and
polyoxyethylene ethers of sorbitan fatty acid esters.
70 Mixtures of these nonionic emulsi?ers with anionic emul
carried on the seed, under seed hulls, and in breaks in
the seed coat are reached by the vapors of the compounds
si?ers such as sulfonated oils are also very suitable emulsi~
and destroyed. After application to seed, a compound
?er systems.
of this invention will redistribute itself over the entire
The dispersing or emulsifying agent is preferably one
seed surface, thus making the treatment more uniform.
which is soluble in the oil solution. Ordinarily, the agent
All the compounds of this invention are soluble in 501- 75 will not comprise more than 10% by weight of the emulsi~
3,035,073
5
cooled to room temperature and the salt which formed is
?ltered off. Removal of the solvent from the ?ltrate in
vacuo leaves 183 parts by weight of a viscous, yellowish
?able oil composition. 'With some materials the percent
age will be 5% or less.
The emulsi?able oil concentrates are especially suited
for dilution or extension with water. When so diluted,
the concentrates form an emulsion which is then applied
to seeds, plants, or soil. When small amounts of water are
oil. Recrystallization of this oil from dry boiling 'diethyl
ether yields pure N-methyl—N-ethylmercurirnethane sul
fonamide in the form of short white needles which melt
at 54-55 ‘’ C.
used, the emulsion can be of the water-in-oil type. When
the dilution is greater, the emulsions are usually of the
oil-in—water type. Such emulsions are especially suited
Partial concentration of the supernatant
?uid yields additional N-methyl-N-methylmercurimethane
sulfonamide as needles melting at 51-535“ C.
The procedure of this example can also be used to pre
for application to seed with slurry or misting type appli 10
pare the following compounds, by substituting a listed
cation equipment.
sulfonamide for the methylmethane sulfonamide used
Preferred emulsi?able oil concentrates contain from 8%
above.
to 40% of the active ingredient. Concentrates containing
10-30% are especially preferred.
Dust or powder compositions containing the compounds 15 Ex. N0. Name of sulionnmide Parts by
Name of product
of this invention can also be prepared. These composi
weight
tions contain the active material adsorbed on ?nely di
vided inert carriers or dusts such as natural clays, talc,
N-methylethane- ____ _.
N-methyl-N-ethylmer
N-methyl-N-ethylmer
N-methylpropane-_ . _ -
dust form. Such dusts can be converted to water-wettable
euripropane sulfon
amide.
N-methyLNethylmer
curiisopropane sul
fonamide.
N-methyl-N-ethylmer
N-methylisopro
pane.
powders by the usual expedient of including a surface
active agent of the wetting or dispersing type. These ma
terials cause the compositions to disperse easily in water 25
to give aqueous sprays.
The surface-active agents employed can be of the
anionic, cationic, or nonionic type.
73.8
curiethane sulfon
amide.
diatomaceous earth, walnut shell ?our, redwood ?our,
synthetic ?ne silica, calcium silicate, and other solid inert 20
carriers customarily used in preparing compositions in
They include, for
cuributane sulfon
amide.
N-methylisobutane-___
N-methyl-N-ethylmen
N~rnethyl-sec.
N-methyl-N-ethylmer
curiisobutane'sul
fonamide.
eurisec.-butane
sulionamide.
butaue-.
example, sodium oleate, sulfonated petroleum oils, alkyl
aryl sulfonates, sodium lauryl sulfate, polyethylene oxide
derivatives, lignin sulfonates, and other surface-active
N-methyl-tert.
agents. A detailed list of such agents is set forth in arti
N-ethylmethane- ____ __
N-ethyl~N~ethylmer
N~ethylethane- ______ -.
N—ethyl-N-ethylmer
N-ethylpr0pane-_ _ ____
N -e thyl-N-ethylmer
12 ______ _.
N-ethylis0propane-__-_
N-ethyl-N-ethylmer
13 ______ __
N-ethyl-tert.-butane-__
N-ethyLN-ethylmer
14 ______ __
N-propyhnethane_____
N -pr0pyl-N-ethylmer
15 ______ _ _
N-propylethane- ____ _ _
N~propyl-N-ethylrner
16 ______ __
N-propyl-is0pr0pane--_
N;propyl-N-ethylmer
17 ______ _ _
N-butyImethane-_ . _ _ _
N-methyl-N-ethylmer
curitert.-butane
sulfonamide.
butane-.
curimethane sulion
amide.
cles by McCutcheon in “Soap and Chemical Specialties,”
December 1957 and January, February, March, and April
1958.
Those compounds of this invention which are more
than about 10% soluble in water can be prepared as
water-soluble powders. In addition to the active ingred
ient, these powders can contain such water-soluble dilu
ents as sodium or potassium carbonate, sodium or potas 40
curiethane sulfon
amide.
euripropane sulfon
amide.
euriisopropane sul
fonamide.
curitert.-buta.ne
sulfonamide.
sium sulfate, sodium chloride, soluble phosphates, soluble
borates, and soluble nitrates. These powders can also
contain corrosion inhibitors such as sodium nitrite, wet
ting agents such as alkyl aryl sulfonates, and gums such
as methyl cellulose.
The compositions of this invention can also contain a
curimethane sul
fonamide.
euriethane sulfon
amide.
euriisopropane sul.
dye. This dye is especially useful in compositions to be
fonamide.
used in the treatment of seeds, since it provides a means
90. 6
eurimethane sul
fonamide.
for marking clearly those seeds which have been treated.
Xanthene dyes such as Rhodamine B or Rhodamine B
extra, cationic azo dyes such as Sevron Red, or oil-soluble
dyes such as Spirit Soluble Red can be used.
18 ______ __ N Aéert-butrl6
The compositions of this invention can contain almost
any percentage of the active compound. Since the exact
amount to be used will depend on such factors as the par
N -butyl-N-e thylmer
55
99. 0
bane.
N-tert.-butyl-N-ethyl
mereuriethane sul
fonamide.
EXAMPLE 19
ticular condition being treated, the substance being treated,
Preparation of N-Methyl-N-Methylmercurimethane
and climate factors, it is not possible to indicate the exact
amount to be used. Generally, however, the compositions
Twenty parts by Weight of 53% active sodium hydride
of this invention will contain not more than 95% or less
than .05% by weight of active compounds.
This invention will be better understood by referring to
the following illustrative examples.
EXAMPLE 1
Preparation of N-Methyl-N~Ethy lm ercul'im ez‘h ane
Sulfonamide
Thirty parts by weight of 53% active sodium hydride
Sulfonamide
60 mineral oil emulsion are mixed with four hundred parts
of dry toluene. This mixture is heated to 75° C. and 43.6
parts by weight of IN-methylmethane sulfonamide are
gradually added. When hydrogen is no longer evolved,
the mixture is cooled and 118 parts by weight of methyl
65 mercuribromide are added.
The mixture is then heated
to 110° C. for 1/2 hour. The resulting salt is ?ltered off
while the mixture is hot. The ?ltrate is then cooled in an
ice bath to yield 78 parts by weight of essentially pure
N-methyl-N-methylmercurimethane sulfonamide in the
emulsion in mineral oil are mixed with eight hundred
parts of dry toluene. This mixture is heated to 75° C., 70 form of short translucent parallelpipeds melting at
102-104° C.
and 65.4 parts by weight of N-methylmethane sulfonamide
The procedure of this example can also be used to pre
are added dropwise. When hydrogen evolution has
pare the following compounds, by substituting a listed sul
ceased, the reaction mixture is cooled, and 158.4 parts by
fonamide for the N-methylmethane sulfonamide used
weight of ethylmercuri chloride are added. The entire
mixture is then reheated to 75° C. for 1/2 hour. It is then 75 above.
"3,035,073
Ex. N 0.
Name of sulfonamlde
Parts by
Name of product
weight
67 ______ __ N-(2-hydr0xyethyl)
Percent
66.8
isopropane-.
68 ______ ._ N-(2-hydroxyethy1)
72.4
Ethylmercuri-N-methyl-methane -sulfonamide____ 3.91
N-(Q-hydroxyethyD
N-ethylmerenriiso
Ethanol (denatured) _______________________ __
propane sulf0u—
amide.
Water
N ethylmercuribu
I
,
69 ...... -_
N-(Z-hydroxyethyl)
'tertrbutanea
70 ______ __
N-(2-hydroxypropyl)
- methane-.
_
Rhodamine
N-(2-hydroxyetl1yl)
' N -ethylmereu.iitert.
_
61.2
10
71 ______ __
N-(fZ-hydroxypropyl)
ethane.
66.8
N-(2-hydroxypropyD
N-ethylmercuri
72 ______ ._ N-(2-hydr0xypropyl)
72.4
N-(2-hydroxypropyD
72.4
N-(2-hydroxypropyD
ethane sulfonaznide.
propane-.
isopropane-.
66.8
are often typical of overtreatment ‘with mercury com
N-(l-hydroxymethyl
propyl) -N ethylmer
20
72.4
N-(l-hydroxymethyl
66.8
N-(Z-hydroxybutyD
propyl) -N-ethylmer
.
EXAMPLE 83
euriethane sullen
amide.
76 ______ __ N-(Q-hydroxybutyD-
m hane-.
25
N-ethylmercuri‘
methane sulfon
_
77 ______ __
N-(Z-hydroxybutyD-
72.4
Percent
N‘(2-hydroxybutyl)
Dimethylformamide
N-et-hylmercurieth
ane sulionamide.
N-(l-methyl-2-hydrox—
ypropybrnethane-
79 ______ __ N-(l-methylQ-hydrox-
ypropy1)ethane-.
66.8
Rhodamine
N-(Lmethyl-Z-hydrox
y'propyD-N-ethyl
30
merenn‘methane sul
r'onarnide.
72.4
Water Extendable Liquid
Ethylmercuri-N-methyl-methane lsulfonamiden"
amide.
ethane-.
78 ______ __
pounds is noted.
This solution does not corrode brass, is stable at low
temperatures, and is dilutable with water.
curimethane sulfon
propyl)etl1ane-.
The ethylmercuri-Nmethyl-methane sulfonamide is dis
ages, no injury‘or deformation in the seedlings such as
amide.
N~(1-hydroxymethyl-
1.00
and‘the emerging ‘seedlings are observed and counted
6 days‘ after planting. In spite of the Wide range of dos
N-ethylmercuriiso
propyl) methane-.
75 ______ __
_
This formulation is applied to Triumph wheat seed in
propane sulfon
N-(l-hydroxymethyl-
a
15 ‘a Wide range of concentrations. The seed is then planted .
amide.
74 ______ _.
_____
added.
N-ethylmercuripro
N-(2-hydroxypropyl)
70.09
dye
ethylene glycol. When solution is complete, the dye is
pane sulfonamide.
73 ______ __
5.00
20.00
solved in a mixture of denatured alcohol, water,-and
butane sullonarnide.
N-(Z-hydroxypropyD
N-ethylmercnn'meth
ane sulfonamide.
-
____
tane sulfonamide.
72.4
v
___
Ethylene ; glycol
N-(2-hydroxyethy1)
butane-.
_
10
EXAMPLE 82
Water Extendable Liquid
1.00
This solution is stable,
even at low temperatures. The solution does not cor
rode brass. It can be diluted with water and used as a
ypropyD-N-ethyl
mereuriethane sul
tonamide.
dye ___________________________ ..
The solution is prepared by mixing the ingredients
until the solids are dissolved.
N-(l-methyl-Q-hydrox
3.91
______________________ __ 95.09
35 seed treatment for fuzzy cotton (a dilution of 1:2 or
1:4 with Water is desirable), for ?ax (dilute 1:2 or 1:3),
for rice (dilute 1:4 to 1:8), for rye (dilute 1:8), for
sorghum (dilute 1:5 or 1:6, approximately), for wheat
(dilute 1:16), and for oats (dilute 1:5,approximately).
EXAMPLE 80
Water Extendable Liquid
Percent
40
EXAMPLE 84
Ethylmercuri-N-methyl-methane sulfonamide_____ 7.6
Ethanol
(denatured) ________________ -aa _____ __
5.0
Rhodamme dye ____________________________ __
2.0
Ethylene glycol
__-_..
____ 65.4
Water Extendable Liquid
Percent
Methylmercuri-N-methyl-methane sulfonamide--45
Dimethylformamide ________________________ __ 20.0
Ethylene
The ethylrnercuri-N-methyl-methane sulfonamide is
dissolved in a mixture of ethyl alcohol, ethylene glycol,
3.74
Dimethylformamide _______________________ __ 26.00
glycol _____ __' ____________________ __ 50.00
Water
19.26
Rhodarnine
dye ___________________________ __
1.00
and water. When solution is complete, the dye is added.
This formulation is made up as in Example 83. It
This composition is then applied to acid-delinted cotton 50 is'similarly suitable for treatment of a Wide variety of
seed at 2.0 ?uid ounces per hundredweight. The seed is
seeds, either as is or diluted with Water. The physical
properties of this solution are also similar to those of
planted in loamy soil infected 'with a variety of soil-borne
pathogens. It will be observed that the number of emerg
ing seedlings is more than three times as great as that
obtained with untreated cotton seed used as a control.
the solution in Example 83.
55
EXAMPLE 85
Water Extendable Liquid
EXAMPLE 81
Percent
Water Extendable Liquid
Methylmercuri-N-methylmethane su1fonamide___
Methylmercuri-N - methylmethane sul
Water
fonamide
_______ __> ___________ __
_____________ __' _____ _._ _____________ __
41.23
4‘grams.
The methylmercuri-N-methylmethane 'sulfonamide is
N-methyl-Z-pyrrolidone ____________ __ To make 100 ml.
'
3.77
60 Ethylene glycol ___________________________ __ 55.00
dissolved in a mixture of water and ethylene glycol.
of solution.
This composition, sprayed to run-o? onto apple leaves
The solution is prepared by dissolving the compound 65 (Pyrus, malus) using a solution containing 0.008% of
in the solvent. This solution is then applied to Selkirk
active ingredient in water, gives 100% control of apple
Wheat seeds and to machine-delinted cotton seed by
scab ('Verzturia inaequalis).
tumbling the seed and solution together until uniform
coverage is obtained. The seeds are planted and the
wheat seed is held at 50° F. for 6 days to allow. soil 70
boi'ne pathogens to act. The cotton seed is not chilled.
The seeds are then allowed to germinate. The number of
treated seeds which germinate is signi?cantly greater
than the number of vcontrol seeds which germinate.
There is no evidence of injury due to treatment.
EXAMPLE 86
Solution
A solution is prepared by diluting 4.52 grams of ethyl
mercuri-N-methylmet'harie sulfonamide :with'enough N
methyl pyrrolidone to make 100 ml. of solution. This
75 ‘solution is applied to seeds, as follows:
3,035,073
12
(a) Trail barley: The seed is treated by tumbling it
solution in a seed treater so that the treating rate is 1.5
ounces of the concentrate per hundredweight of seed.
in the solution until uniform coverage is obtained. The
seed is then planted and held at 50° F. for several days.
EXAMPLE 91
Wettable Powder
The treated seeds show signi?cantly better germination
counts than the untreated control seeds.
(b) Vickland oats infected with Helminthosporium:
Percent
The seeds are treated as above and stored in a closed con
tainer for 4 days. The seeds are then planted in sand.
The number of healthy seedlings which emerge is sig
ni?cantly greater than the number which emerge from 10
untreated seeds.
Methylmercuri~N-n-propylisopropane sulfonamide__._ 40
Sodium salts of polymerized alkyl naphthalene sulfonic
acids
1
Sodium alkyl naphthalene sulfonate _____________ __
Sevron Red
EXAMPLE 87
Wettable Powder
2
5
Synthetic ?ne silica
52
All the ingredients are blended together, micropulver
When this powder is slurried in
Percent 15 ized, and reblended.
Ethylmercuri-N-ethylpropane sulfonamide ______ __ 60.0
water and applied to rice seed ‘at 0.2 ounce per bushel, a
Sodium alkyl naphthalene su-lfonate __________ __
2.0
good stand of rice free of fungus infection is obtained.
Sodium lignin Sulfnnate
15
Fine sihca
___.--
EXAMPLE 92
36.5
All ingredients are blended together, micropulverized,
20
Emulsi?able Oil
When this formulation is applied
Percent
to the pear tree (Pyrus communis) as a foliage spray
at a concentration of .02% of the formulation in water,
Ethylmercuri-N-allylethane sulfonamide __________ __ 25
and then reblended.
good control of scab (Venturia pyrina) is obtained.
Poly alkyl ‘aryl carboxylic acid esters plus oil-soluble
25
EXAMPLE 88
Water Soluble Powder
sulfonates
acid esters plus oil-soluble sulfonates are then added.
30
EXAMPLE 93
fonamide
25.0
Polyethylene oxide esters of tall oil acids concreted
with urea
__
Methyl cellulose ___________________________ __
Control of Turf Diseases
5.0
1.0
____ ___
61.0
‘___
2.0
Sodium nitrite
___ 70
The ethylmercuri-N-allylethane sulfonamide is dissolved
Percent
sulfate“-
__
in the cyclohexanone. The poly alkyl ‘aryl carboxylic
Methylmercuri-N - 2 - hydroxyethylpropane sul
Sodium
5
Cyclohexanone
Rhodam-ine B extra _________________________ __
Twelve ounces of the water extendable liquid formula
tion of Example 85 is diluted with water to a total volume
of 5 gallons. This is then sprayed at weekly intervals
during the growing season on. 1,000 square feet of turf
6.0
containing Kentucky bluegrass, creeping red fescue, and
Astoria colonial bent grass. Complete control is obtained
All the ingredients are ‘blended together, micropulver
ized, and reblended. This composition is dissolved in 40 of such diseases as ‘brown patch (Pellicularia ?lamentosa) ,
dollar spot (Sclerotinia homoeocarpa) copper spot (Gle
ocercospora sorghi) and Helminthosporium blight (Hel
water and is used to treat wheat seed at 0.11 ounce per
hundredweight to protect the wheat against soil-borne
and seed-home pathogens.
EXAMPLE 89
minthosporium vogans).
Control of Soil-Borne Fungi
One-half pint of the Water extendable liquid composi
Percent
Ethylmercuri-N-isobutylethane sulfonamide _____ __ 15.0
tion described in Example 85 is diluted with water to a
Alkyl aryl polyether alcohols _________________ __
7.0
Spirit Soluble Red ___________________________ __
3.0 50
Xylene
___
EXAMPLE 94
45
Emulsi?able Oil Concentrate
__ 75.0
total volume of 10 gallons. This ‘diluted preparation is
then sprayed on a band 4 inches wide over one acre of
open furrows containing cotton seed (‘approximately
12,000 linear feet of row). The spray is directed in such
The ethylmercuri-N-isobutylethane sulfonamide is dis
a way as to strike the sides of the furrow as well as the
solved in the xylene. When solution is complete, the
alkyl aryl polyether alcohols are added and dissolved. 55 seed in the bottom of the furrow. The furrow is then
For use, the formulation is diluted with Water to obtain
closed, thus completing the planting operation.
an emulsion ‘containing 0.125 pound of active ingredient
per 100 gallons. When this emulsion is applied to syca
The ‘above treatment gives essentially 100% control of
cotton seedling damage by such organisms as Rhizoctonia
solani), Fusarium spp., Pythium spp., and Sclerotinia spp.
more (Plamnus accidentalis) as a foliage ‘spray, good con
60 which abound in cotton soils.
trol of anthracnose (Gnomonia veneta) is obtained.
EXAMPLE 95
EXAMPLE 90
Water Extendable Solution
Control of Slime
Percent
65
Methylmercuri - N - 2 - hydroxyethylmethane sulfona
________________________________ .a....
8
RhodamineB ________________________________ ___
mide
2
Dimethylformamide __________________________ __ 50
Water ____
Approximately one ounce of the wettable powder for
mulation of Example 87, when added to one ton of dry
?ber equivalent, at or before the point in a wood pulping
process where slime forms, will eifectively control slime
producing organisms.
40
These organisms can also be controlled by metering
70
into the process, at or before the point Where slime forms,
The methylmercuri — N - hydroxyethylmethane sulfona
the water extendable liquid formulation of Example 85.
mide and the Rhodamine B dye are dissolved in the di
Addition is regulated so as to give a ?nal concentration
methylformamide, and the water is then added.
- Seeds can be treated with this composition by diluting
the concentrate with 8 parts of Water and applying the 75
of from 5 to 10 ounces of concentrate per ton of dry ?ber
equivalent.
1.0-.
3,035,073
13
14
EXAMPLE 96
Diplodia natalensis, Endoconia‘iophora coerulescens, and
Graphium, spp.
Preservation of Paper Coating and Wood Pulp
Paper coating stock and wood pulp can be preserved
by the addition of from 1 to 2 ounces of the wettable pow
'
The invention claimed is:
1. Compounds of the formula
5
R2
der formulation of Example 87 per ton of coating stock
or dry ?ber.
H833
EXAMPLE 97
Preservation of Carbohydrate, Protein, and Lipid
Containing Materials
where
10
Starches can be preserved by blending from .01% to
.1% of the wettable powder formulation of Example 87
into the product.
A similar concentration of the same formulation, 15
blended into vegetable and animal glues and other solid
proteinaceous materials, will stop the attack of these ma
R1 is selected from the group consisting of monovalent
acyclic unsubstituted hydrocarbyl radicals containing
from 1 to 4 carbon atoms,
R2 is selected from the group consisting of monovalent
‘acyclic unsubstituted hydrocarbyl radicals containing
from 1 to 4 carbon atoms, and hydroxy substituted
monovalent hydrocarbyl radicals containing from 1
to 4 carbon atoms, and
R3 is selected from the ‘group consisting of methyl and
terials by fungi.
ethyl,
Oil-based paints and substrates to which they are applied
can be protected from fungus attack by blending from 20 with the proviso that R1, R2, and R3 taken together shall
not contain more than a total of 8 carbon atoms.
.04% to 4% of the emulsi?able oil formulation of Ex
ample 90 into the ?nal paint or the pigment vehicle. Pro
tection can also be obtained by the [addition to the pigment
of from 0.01% to 1.0% of a compound listed in Examples
25
1 through 38.
EXAMPLE 98
2.
3.
4.
5.
6.
N-methyl-N-(methylmercuri)methane sulfonamide.
N-methyl-N-(ethylmercun‘)methane sulfonamide.
N-methyl-N-(methylmercur?butane sulfonamide.
N-ethyl-N-(ethylmercuri)ethane sulfonamide.
N-methyl-N-(methylmercu-ri)ethane sulfonamide.
References Cited in the file of this patent
UNITED STATES PATENTS
Control of Sap Stain Microorganisms in or on Wood
A dipping solution suitable ‘for the disinfection or pro
tection of freshly sawed lumber can be prepared by dilut 30 2,133,787
ing from 1/2 to 1 gallon of the water extendaible liquid
2,492,314
formulation of Example 85 to one hundred gallons with
2,571,095
water. It oak wood is to be treated, two to four pounds
2,665,234
of a caustic such as soda ash can also be added.
The solution thus prepared will give excellent control
of such organisms as the blue staining Cerotostomela spp.,
35
2,834,795
2,840,502
2,885,418
Hathaway ___________ __ Oct. 18,
Olin ________________ __ Dec. 27,
Altschul ____________ __ Oct. 16,
Goodhue _____________ __ Jan. 5,
Wendt ______________ __ May 13,
Lambrech ___________ __ June 24,
Traverso et a1 __________ __ May 5,
1938
1949
1951
1954
1958
1958
1959
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