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Патент USA US3050449

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United States Patent 0
r:
ICC
1
3,050,440
Patented Aug. 21, 1962
2
liamson synthesis. A substituted phenyl mercaptan is
3,050,440
prepared which is reacted with an alkali metal hydroxide,
such as potassium ‘hydroxide, to form an alkali metal salt
of the mercaptan. This latter intermediate product is
reacted with a substituted phenyl halide, such as a sub
NEW FUNGICIDAL COMPOSITIONS OF MATTER
Sidney B. Richter, Chicago, 11]., assignor to Velsicol
Chemical Corporation, Chicago, 11]., a corporation of
Illinois
stituted phenyl bromide, to yield the desired polychloro
nitrodiphenyl-sul?de. For example, 2,3,4-trichloro-6-ni
No Drawing. Filed Oct. 13, 1960, Ser. No. 62,318
2 Claims. (Cl. 167-30)
trophenyl 2,3,5,6-tetrachlorophenyl sul?de can be pre
This invention relates to new polychloronitrodiphenyl
pared by the above process ‘from the reactants 2,3,4-tri
compounds and more particularly to polychloronitrodi 10 chloro-6-nitrophenyl mercaptan and 2,3,5',6-tetrachloro
phenyl ether, sul?de, sulfone, and sulfoxide compounds
possessing properties which provide superior protection
against fungus growths.
phenyl bromide.
The sul?de compounds described herein can also be
prepared by the interaction of an alkali metal salt of a
The new novel compounds of the present invention
substituted phenyl mercaptan, described in the previous
15 method, with a substituted diazonium chloride.
have the following structure:
Symmetrical polychloronitrodiphenyl sul?des of this
(H),
(at.
invention can also be prepared by the thermal decomposi
/
CI a
( )
tion of a lead salt of a polychloronitrophenyl mercaptan.
35..
(Noni.
CI
(Noni )d
Alternatively, the symmetrical sul?de compounds can be
20 prepared by the oxidation of the said class of mercaptans
Structure I
wherein Y is selected from the group consisting of O, S,
SO and 502; a is an integer from 1 to 4, b is an integer
with ‘chromic acid or in ammoniacal solution by contact
with air.
‘from 1 to 3; c is an integer from 0 to 2, the sum of b and 0 25
trichloro-3-nitrophenyl 2,4,6etrichloro-3-nitrophenyl sul
?de; 2,3,4-trichloro-5-nitrophenyl 2,3,4-trichloro-5-nitro
phenyl sul?de; 3,4,S-trichloro-Z-nitrophenyl 3,4,5-trichlo
ro~2~nitrophenyl sul?de; 2,3,4,5-tetrachloro-6-nitrophenyl
2,3,4,S-tetrachloro-6-nitrophenyl sul?de; and 2,3,4,6-tetra
chloro-S-nitrophenyl 2,3,4,6-tetrachloro-5-nitrophenyl sul
Examples of symmetrical sul?des of this invention
which can be prepared by the above methods are: 2,4,6
being a maximum of 3; d is an integer from 2 to 5, the
sum of a and d being larger than 5; and e and f are inte
gers from 0 to 3, the sums of a, b and f, and c, d, and e
each being 5.
It is one object of the present invention to provide new 30
polychlorinated nitrodiphenyl derivatives, which are use
ful in the control of fungus growths.
Another object of the present invention is to provide
fungicides of low phytotoxicity suitable for use in agri
?de.
Although sulfoxides, such as diphenyl sulfoxide, can be
prepared by ‘the reaction of an aromatic compound, such
as benzene, and thionyl chloride in the presence of alumi
35 num chloride, such procedure is not preferred for the
culture.
These and other objects of the present invention will be
preparation of the sulfoxide compounds of the present in
readily apparent from the ensuing description.
vention due to the formation of by-products. It is pre
The ether compounds of the present invention can be
‘ferred to prepare the sulfoxides of this invention by par
prepared by one or more of the condensation, chlorina
tial oxidation of the corresponding sul?de or by partial re
40
tion and nitration procedures known to the art. The
duction of the corresponding sulfone.
ether compounds of the present invention which have sym
In the preferred method, the sul?de of this invention is
metrical phenyl rings, save of a nitro group, can readily be
partially oxidized to the sulfoxide by the aid of a mild oxi
prepared by reacting corresponding substituted anisole or
dizing agent, such as nitric acid, hydrogen peroxide in
phenetole with fuming nitric acid and recovering the di
acetic acid solution, or nitric oxide. Thus, 2,3,5-tri
45
phenyl ether compound thereform. By means of this
chloro-4-nitrophenyl 2,3,5,6-tetrachlorophenyl sulfoxide
procedure an zahnost symmetrical diphenyl ether is formed
can be prepared by gently boiling 2,3,5-trichloro-4-nitro
with a newly substituted nitro group in a position on one
phenyl 2,3,5,6-tetrachlorophenyl sul?de with ?ve times
of the rings according to the directing in?uence of those
its Weight of 3 N nitric acid for ?fteen hours, separating
groups already attached to the ring.
50 the sulfoxide compound by pouring the reaction mixture
The ether compounds of the present invention can also
into ice-water, and recovering the product by ?ltration
be readily prepared by a process analogous to the William
son synthesis. By this method, a substituted potassium
phenolate is reacted with a substituted halobenzene. For
therefrom. Similarly, 2,3,6-trichloro-4-nitrophenyl 2,3,5,
6-tetrachloro-4-nitrophenyl sulfoxide can be prepared by
contacting 2,3,6-trichloro-4-nitrophenyl 2',3’,5’,6’-tetra
example, the reaction of potassium 2-chloro-4-nitropheno
chloro-4-nitrophenyl sul?de with hydrogen peroxide in
late with 2,3,4,5,6-pentachlorobromobenzene yields 2 55 acetic acid solution at room temperature.
chloro-4-nitrophenyl 2,3,4,5,6-pentachlorophenyl ether.
The polychloronitrodiphenyl sultones of the present
It should be noted that the nitro group may be present in
either the phenolate or the halobenzene reactant, or both,
invention can be readily prepared by oxidation of the cor
responding sul?de or sulfoxide. Suitable oxidizing agents
for said oxidation are fuming nitric acid, potassium per
depending upon the particular product desired.
manganate, hypochlorous acid, sodium hypochlorite,
When neither reactant contains a ‘nitro radical, and the
chromic acid, and hydrogen peroxide.
latter is to be added by a subsequent substitution reaction,
The new hexachloronitrodiphenyl ether compounds of
a catalyst should be utilized to accelerate the coupling re
the present invention represented by the structure I,
, action. Copper is a suitable catalytic material, especially
in the form of copper-bronze.
65 wherein Y is O, b is 1, c is Zero, the sum of a and d is 6,
and the sum of e and f is 3, include:
Another procedure useful in preparing the ether com
pounds of this invention is to prepare a lower chloro
3-nitro-4-chlorophenyl 2,3,4,5,6-pentachlor'ophenyl ether;
and/or nitro-substituted diphenyl ether compound and
successively chlorinate and/ or nitrate until the desired
compound is prepared.
The sul?de compounds of the present invention can also
readily be prepared by a procedure analogous to the Wil
70
2-chloro4-nitrophenyl 2,3,4,5,6-pentachlorophenyl ether;
2,3-dichloro-4-nitrophenyl 2,3,5,6-tetrachlorophenyl ether;
2,6-dichloro-4-nitrophenyl 2,3,5,6-tetrachlorophenyl ether;
2,4-dichloro-S-nitrophenyl 2,3,4,6-tetrachlorophenyl ether;
3,4-dichloro-6-nitrophenyl 2,3,4,6-tetrachlorophenyl ether;
3,050,440
3
at
2,3,4-trichloro-6-nitrophenyl 2,3,4-trichlorophenyl ether;
2,3,6-trichloro-4-nitrophenyl 2,3,5-trichlorophenyl ether;
2,3,6-trichloro-S-nitrophenyl 2,3,6-trichlorophenyl ether;
3,4,S-trichloro-Z-nitrophenyl 3,4,5-trichlorophenyl ether;
2,3,4,6-tetrachloro-5-nitrophenyl 2,3-dichloropheny1 ether;
2,3,5 ,6-tetrachloro-4-nitrophe-nyl 2,4-dichlorophenyl ether;
2,3,4,6-tetrachloro~5-nitrophenyl 2,5-dichlorophenyl ether;
‘above. One example of an octachloronitrodiphenyl ether
having structure I, wherein Y is O, b is 1, c is Zero, the sum
of a and dis 8, and the sum of e and f is 1, is: 2,3,6-tri
chloro~4~nitrophenyl 2,3,4,5,6-pentachlorophenyl ether.
Included among the new nonachloronitrodiphenyl sul
fones, represented by structure I, where Y is S02; a is
4; d is 5; b is 1; and c, e, and f are zero, are: 2,3,5,6
and 2,3,5,6-tetrachloro-4-nitrophenyl 3,4-dichlorophenyl
tetrachloro - 4 - nitrophenyl
2,3,4,5,6-pentachlorophenyl
ether.
sulfone; 2,3,4,6-tetrachloro-5-nitrophenyl 2,3,4,5,6-penta
It is understood that the above diphenyl con?gurations 10 chlorophenyl sulfone; and 2,3,4,S-tetrachloro-G-nitro
phenyl 2,3,4,5,6-pentachlorophenyl sulfone. Likewise
apply equally to the corresponding sul?des, sulfoxides and
the new nonachloronitrodiphenyl ethers, sul?des, and sul
sulfones, by the substitution of S, SO, ‘and S02, respec
foxides may be represented by structure I, wherein Y is
tively, for Y in the said con?gurations. For example, a
O, S, and SO, respectively; a is 4; b is 1; d is 5; and c, e,
hexachloronitrodiphenyl sulfoxide having the- structure
and f are zero.
I, wherein Y is SO, b: is 1, c is Zero, the sum of a and d
is 6, and the sum of e‘ and J‘ is 3, is: 3-nitro-4-chloro
Examples of the new hexachlorodinitrodiphenyl ether
compounds of the present invention represented by struc
phenyl 2,3,4,5,6-pentachlorophenyl sulfoxide.
ture I, wherein Y is O, the sum of a and d is 6, the sum
Among the heptachloronitrodiphenyl sul?de com
pounds of this invention represented by structure I,
of b and c is 2, and the sum of e and f is 2, are:
wherein Y is S, b is 1, c is zero, the sum of a and d is 7, 20
and the sum of e and J‘ is 2, are:
3,5-dichloro~4-nitrophenyl 2,3,5,6~tetrachloro-4~nitrophen
yl ether;
2,6-dichloro-4-nitrophenyl 2,3,4,5,6-pentachlorophenyl
2,3-dichlono-4~nitr0phenyl 2,3,5,6~tetrachloro-4-nitrophen
sul?de;
2,4-dichloro-3-nitrophenyl 2,3,4,5,6-pentachlorophenyl
sul?de;
3,S-dichloro-Z-nitrophenyl 2,3,4,5,6-pentachlor0phenyl
2,4-dichloro-5-nitropheny1 2,3,4,6-tetrachloro-5-nitrophen_
yl ether;
yl ether;
2,6-dichl0ro-4-nitrophenyl 2,3,4,S-tetrachloro-5-nitrophen
yl ether;
sul?de;
2,3,4-trichloro-6-nitrophenyl 2,3,5,6—tetrachlorophenyl
sul?de;
2,3,6-trichloro-4-nitrophenyl 2,3,4,6-tetrachlorophenyl
30
2,6-dichloro-4-nitrophenyl 2,3,4,S-tetrachloro-6-nitrophen
yl ether;
2,3,4-trichlor0-6-nitropheny1 2,3,4~trichloro~6-nitrophenyl
ether;
sul?de;
2,4,6-trichloro-5-nitrophenyl 2,3,5-trichloro-4-nitrophen
yl ether;
2,4,5-trichloro-6-nitrophenyl 2,3,6-trichloro-4-nitrophenyl
sul?de;
3,4,5-trichloro-2~nitrophenyl 3,4,S-trichloro-Z-nitrophenyl
sul?de;
3,5-dichloro-2,4-dinitrophenyl
2,3,5-trichloro-4-nitrophenyl 2,3,4,5-tetrachlorophenyl
sul?de;
3,4,S-trichloro-Z-nitrophenyl 2,3,4,5-tetrachlorophenyl
ether;
2,3,4,6-tetrachlor0-5-nitrophenyl 2,3,4-trichlorophenyl
ether;
2,3,4,5-tetrachloro-6-nitrophenyl 2,3,6-trichlor0phenyl
3,5,‘6-trich1oro-2A - dinitrophenyl 2,3,5 - trichlorophenyl
2,3,4,6-tetrachlor0-S-nitrophenyl 2,3,5-trichlorophenyl
ether.
sul?de; and
2,3,5,6-tetrachloro-4-nitrophenyl 3,4,5-trichlorophenyl
It is understood that the above con?gurations apply
equally to the corresponding sul?des, sulfoxides, and sul
sul?de.
fones, by the substitution of S, SO, and S02, respectively,
for Y in the above examples. 3,5~dichloro-4-nitrophenyl
2,3,5,6-tetrachl0ro-4-nitrophenyl sulfone is an example of
a hexachlorodinitrophenyl sulfone having the structure I,
Similarly, the corresponding ethers, sulfoxides, and
sulfones, may have the same con?guration as the above
compounds by the substitution of 0, SO, and 80;, re
spectively, for Y in the said con?gurations.
For ex
wherein Y is S02, the sum of a and d is 6, the ‘sum of
b and c is 2, and the sum of e and fis 2.
ample, a heptachloronitrodiphenyl sulfone having the
structure I, wherein Y is S02, b is 1, c is zero, the sum
of a- and d is 7, and the sum of e and f is 2, is: 2,3,4-tri
The new sulfoxide compounds of the present inven
tion include heptachlorodinitrodiphenyl sulfoxide com
pounds represented by the structure I, wherein Y is SO,
chloro-6-nitrophenyl 2,3,5,6-tetrachlorophenyl ether.
Examples of the new octachloronitrodiphenyl sulfoxide
a is 3, the sum of b and c is 2, c is 4, and the sum of
compounds represented by structure I, wherein Y is SO,
e and f is 1, such as: 2,3,4-trichloro~6-nitrophenyl 2,35,6
b is 1, c is zero, the sum of a and d is 8, and the sum. of e
and f is 1, are:
2,3,6-trichloro-4-nitrophenyl 2,3,4,5,6-pentachlor0pheny1
sulfoxide;
2,3,5-trichloro-4-nitrophenyl 2,3,4,5,6-phentachloro
phenyl sulfoxide;
3,4,5-trichloro-2- nitrophenyl 2,3,4,5,6-pentachloro
phenyl sulfoxide;
60
tetrachloro-4-nitrophenyl sulfoxide; 2,3,6-trichloro-4-ni
trophenyl 2,3,4,6-tetrachloro-S-nitrophenyl sulfoxide;
2,4,6-trichlor0-3-nitrophenyl 2,3,4,6-tetrachloro-5-nitro
phenyl sulfoxide; 3,4,S-trichloro-Z-nitrophenyl 2,3,4,5-tet
rachloro-6-nitrophenyl sulfoxide; 2,3,4-trichloro-5-nitr0
phenyl 2,3,4,6-tetrachloro-5-nitrophenyl sulfoxide; 2,3,5
trich'loro-4,:6-dinitrophenyl 2,3,4,6-tetrachlorophenyl sulf
oxide; and octachlorodinitrodiphenyl sulfoxide com
pounds represented by structure I, wherein Y is SO, a
1
2,3,4,6-tetrachloro-S-nitrophenyl 2,3,5,6-tetrachloro
phenyl sulfoxide;
2,3,5,6-tetrachloro-4-nitrophenyl 2,3,5,6-tetrachloro
phenyl sulfoxide;
2,3,4,5-tetrachloro-6-nitrophenyl 2,3,4,6-tetrachloro
2,3,4, ?-tetrachlorophenyl
ether; and
sul?de;
65 and d are each 4, b and c are each 1, and e and f are
phenyl sulfoxide; and
2,3,4,5-tetrachloro-6-nitrophenyl 2,3,4,5~tetrachloro
‘both zero, such as:
2,3,4,6-tetrachloro~5-nitrophenyl
2,3,5,6-tetrachlor0-4-nitrophenyl sul‘foxide; 2,3,5,6-tetra
chloro-4-nitrophenyl 2,3,5,6 - tetrachloro - 4-nitrophenyl
sulfoxide; and 2,3,4,5-tetrachlor0-6-nitrophenyl 2,3,4,6~
70 tetrachloro-S-nitrophenyl sul-foxide. \
phenyl sulfoxide.
Similarly, the new ether, sul?de, and sul?one com
pounds of the present invention may have the above con
These con?gurations apply equally to the ether, sul
?gurations by substituting O, S, and S02, respectively, for
?de, and sulfone compounds of this invention, which may
have the same con?guration by the substitution of O, S,
Y in the above con?gurations. For example, 2,4,6-tri
and S02, respectively, for Y in the structure described 75
chloro-3-nitrophenyl 2,3,4,:6—tetrachloro - 5 - nitrophenyl
‘3,050,440
ether is a heptachlorodinitrodiphenyl ether having struc
ture I, ‘wherein Y is O, a is 3, b, c, and f are each 1, c iS
chloro-1,3-dinitrobenzene (271.5 g.; 1 mol), which can
be prepared as described by Jackson and Wing, Am. Chem.
4, and e is zero.
1., 9, p. 353 (1887), is added to the ?ask and the contents
are heated, with stirring, by means of a heating mantle.
The mixture is re?uxed until the precipitation of potas
Among the hexachlorotrinitrodiphenyl sul?de com
pounds of the present invention are those represented by
structure I, where Y is S, a and d are each 3, b is 1, c is
2, e is zero, and f is 1, such as: 2,3,4-trichloro-6-nitro
sium chloride ceases.
The reaction mixture is poured into ice-water (1 liter).
The Water mixture is ?ltered and the precipitate is ?ltered
phenyl 2,3,5-trichloro-4,6-dinitrophenyl sul?de; 2,3,5-tri
chl0ro-4-nitrophenyl 2,4,6-trichloro-3,S-dinitrophenyl sul
?de; and 3,4,5etrichloro-2-nitrophenyl 2,4,6-trichloro-3,5
from the wash water, washed with water, and dried in a
The product therefrom is crude 2,6
dinitrophenyl sul?de; those represented by structure I,
10 vacuum oven.
dinitro - 3,5 - dichlorophenyl 2,3,4,5,6-pentachlorophenyl
where Y is S, a is 4, b is 1, c and d are each 2, e is 1,
‘and 7‘ is Zero, such as: 2,3,4,16-tetrachloro-S-nitrophenyl
2,3-dichloro-4,6- dinitrophenyl sul?de; 2,3,5,6-tetrachloro
4‘nitrophenyl 2,4-dichloro-3,S-dinitrophenyl sul?de; 2,3,
4,5-tetrachloro-6-nitrophenyl 3,5-dichloro-2,4-dinitrophen
ether.
The crude product can be used as such or can be
puri?ed ‘by recrystallizing from a suitable solvent.
EXAMPLE 2
15
yl sul?de; and 2,3,5,6~tetrachloro-4-nitrophenyl 3,5-di
chloro-2,'6-dinitr0phenyl sul?de; and those represented by
Preparation of 4-Chl0r0-2-Nitr0phenyl 2,3,4,5,6-Penta
chlo-rophenyl Sul?de
Pentachloroaniline (265.5 g., 1 mol), which can be
structure I, wherein Y is S, a is 2, b is 3, c and f are each
prepared as described by Willegerodt and Wilcke, Ber.
zero, 0! is 4, and e is 1, such as: 3,5-dichloro-2,4,6-tri~ 20 43, p. 2754 (1910), is suspended in concentrated hydro
nitrophenyl 2,3,5,6-tetrachlorophenyl sul?de.
chloric acid (100 cc.) in a 1-liter three-necked round
The above con?gurations apply equally to the ethers,
bottom ?ask equipped with a mechanical stirrer, ther
sulfoxides, and sulfones, of this invention and may be
mometer, and Dry-Ice-acetone cooling bath. The contents
represented by structure I wherein Y is 0, SO, and S02,
of the ?ask are cooled to 0° C. andya, cold aqueous 5%
respectively, the sum of a and d is 6, the sum of b ‘and c 25
solution of sodium nitrite (69 g., 1 mol) is ‘added with
is 3, and the sum of e and f is 1. _An example of a sul
stirring at a rate such that the temperature does not rise
tone ‘of structure I, wherein Y is S02, a and d are each
above 5° C., 4-chloro-2-nitrothiophenol (189.5 g., 1 mol)
3, b is 1, c is 2, e is zero, and f is 1, is: 3,4,5-trichloro
is dissolved in an aqueous solution (100‘ cc.) of sodium
Z-nitrophenyl 2,4,6-trichloro-3,S-dinitrophenyl sulfone;
hydroxide (40 g., 1 mol). This solution is cooled to
while an example of an ether of structure I, wherein Y 30 about 0° C. and slowly added with stirring to the cold
is O, a is 4, b is 1, c and d are each 2, e is 1, and f is
solution in the ?ask. The mixture is stirred and the
zero, is:
2,3,4-trichloro~6-nitrophenyl 2,3,4-trichloro
5,6-dinitrophenyl ether.
temperature is gradually increased, to 60° C., during
which time nitrogen is evolved from the mixture. When
Examples of the new heptachlorotrinitrodiphenyl ether
compounds of the present invention represented by struc 35 the evolution of nitrogen has ceased, the reaction mixture
is cooled, and the precipitate ?ltered therefrom. The pre
ture I, wherein Y is O, a is 4, b is 1, c is 2, d is 3, and
cipitate is dried in a vacuum oven. The precipi
e and f are each zero, are: ‘2,3,4,6-tetrachlioro~5-nitro
tate is the crude product 4-chloro-2-nitrophenyl 2,3,4,5,6
phenyl 2,3,4-trichloro-5,6-dinitrophenyl ether; 2,3,4,5
pentachlorophenyl sul?de. The crude product can be
tetrachloro-6-nitrophenyl 2,3,5-trichloro-4,‘6-dinitrophenyl
used as such, or can bepuri?ed by recrystallizing from
ether; and 2,3,5,6-tetrachloro-4-nitrophenyl 2,4,6-trich10
40 a suitable solvent.
ro-3,5-dinitrophenyl ether.
EXAMPLE 3
Similarly, the new sul?de, sulfoxide, and sulfone com
pounds of the present invention may have the above con
?gurations by substituting S, SO, and S02, respectively,
Preparation of 4-Chl0r0~2-Nitr0phenyl 2,3,4,5,6-Penta
chlorophenyl Sulfoxide
‘for Y in the above con?guration. For example, 2,3,5,6—
tetrachloro-4-nitrophenyl 2,3,4-trichloro-5,6-dinitnophenyl 45 Puri?ed product of Example 2 (12 g., 0.03 mol) is
added dropwise to nitric acid (50 cc. of 1.35-1.42 speci?c
su‘lfoxide is a heptachlorotrinitrodiphenyl sulfoxide hav
gravity) and the solution is stirred for one hour at room
ing structure I, wherein Y is $0, a is 4, b is 2, c is 3,
temperature. The solution is poured into water (approxi
and d and e are each zero.
The new heptachloronitrodiphenyl ether compounds of 50 mately one-liter) and the precipitate is ?ltered therefrom,
and dried in a vacuum oven for about 6 hours at a
the present invention also include those represented by
medium temperature (about 50° C.). The precipitate
structure I, wherein Y is O, a is 2, b is 3, c, e, and f are
each zero, and d is 5, such as: 3,S-dichloro-2,4,6-trinitro
is the product 4-ch1oro-2-nitrophenyl 2,3,4,5,6-penta
phenyl 2,3,4,5,6-pentachlorophenyl ether. Similarly, the
chlorophenyl sulfoxide, and can be used as such, or can
sul?de, sulfoxide and sulfone compounds of this inven 55 be puri?ed by recrystallizing from a suitable solvent.
tion may also have this con?guration 'by substituting S,
EXAMPLE 4
SO, S02, respectively, for Y in structure I, wherein a, b
:
c, d, e and f are as speci?ed.
The following examples are presented by way of il
lustration of the preparation of the compounds of the
Preparation of 4-Chl0r0-2-Nitr0phenyl 2,3,4,5,6-Penta
chlorophenyl Sulfone
Puri?ed product of Example 2 (25 g., 0.06 mol) is
present invention and are not intended to limit the scope 60 placed into ‘a 200 cc. three-necked round-bottom ?ask
of this invention:
EXAMPLE 1
Preparation of 2,6-Dinirro-3,5-Dichlarophenyl 2,3,4,5,6
Pentachlorophenyl Ether
equipped with mechanical stirrer and re?ux condense-r.
Glacial acetic acid is added in small portions until the
product of Example 2 just dissolves. Hydrogen peroxide
65 (50 cc. ‘of a 30% solution in water) is added and the
?ask is heated on a steam bath for four hours. The ?ask
is cooled to room temperature and its contents are poured
Pentachlorophenol (266.5 g.; 1 mol), which ‘can be
into ‘water (3 liters). The precipitate is ?ltered ?rom the
prepared as described by Fichter and Glantzstein, Ber.,
aqueous ?ltrate, washed with water (100 cc.), re?ltered,
49, p. 2480 (1916), is dissolved in ethanol (1 liter). The 70 and dried in a vacuum oven for about 6 hours at a
solution is placed in a 2-liter three-necked round-bottom
medium temperature (about 50° C.). The precipitate is
?ask equipped with mechanical stirrer, re?ux condenser,
the product 4-chloro-2-nitrophenyl 2,3,4,5,6-pentachloro~
and thermometer. A concentrated ‘solution (50% by
phenyl sulfone and can be used as such, or can be puri?ed
weight) of potassium hydroxide (56 g.; 1 mol) in water
by recrystallizing from a suitable solvent.
is ‘added to form the potassium phenolate. 2,4,6-tri 75 The compounds of the present invention are import
3,050,440
8
ant and valuable because of their pesticidal character
istics, especially those relating to the killing of and inhi
lations are diluted with water or solid diluents and sprayed
or dusted on the plants to be protected. Alternatively,
bition of growth of a wide variety of fungi:
The need for ef?cient and economical fungicidal and
fungistatal compositions in the ?elds of agriculture, paper
making, clothing, adhesives, leather goods, etc., is very
great and while various organic fungicides and fungistats
the soil in which the plant is growing may be treated with
excellent results.
Articles other than plants which are to be treated,
such as leather goods, clothing, wood products, and the
like, may be sprayed or dusted, and in addition thereto
are known and utilized, such materials are generally de
?cient in the various concomitant characteristics neces
may also be dipped in aqueous or organic solutions of
the compounds of the present invention.
I claim:
1. A fungicidal composition comprising an inert carrier
sary for satisfactory, economic commercial usage.
The use of fungicides in agriculture is very important.
The destruction of various food crops by fungus growths
and a fungicidal toxic amount of a compound of the
can be measured in the millions of dollars annually.
formula
Since fungi ‘are themselves a low order of plant life, it
(H):
(11)‘.
is not unusual nor surprising that a material which will 15
control the growth of, or kill fungi will also adversely
affect the growing or stored crops which are the host
O] a
(00d
plants. A fungicide which destroys the crop at the same
( )
(N090
(N 02) I:
time that it destroys the fungus has no value for such
use even though its fungicidal activity is very great. It is 20 wherein Y is selected from the group consisting of O,
therefore important that agricultural fungicides exhibit
S, SO and S02; a is an integer ‘from 1 to 4, b is an in
little or no phytotoxicity under the conditions utilized for
teger from 1 to 3; c is an integer from 0 to 2; the sum
of b and 0 being a maximum of 3; d is an integer from
fungus control, and such is the case with the present
compounds.
2 to 5, the sum of a and d being larger than 5; and e and
The active fungicidal material of this invention is ad 25 f are integers from 0 to 3, the sums of a, b and f, and c,
vantageously utilized ‘with a suitable carrier or diluent
d and e each being 5.
to provide compositions in the form of aqueous disper
sions or emulsions, water dispersible powders, dusts, or
2. The method of controlling fungus growths which
comprises applying to fungi and their places of growth
ganic spraying solutions, ‘and the like. Aqueous disper
a fungicidal toxic amount of a compound of the formula
sions and emulsions of the compounds of this invention
are readily prepared by dissolving the fungicidal com
pounds in a suitable inert liquid solvent, such as acetone,
‘and then diluting with water to the desired concentra
tion. ‘The dry formulations, i.e., dust bases or concen
trates, wettable powders, and granular formulations, of
the compounds of the present invention are prepared by
blending the compounds described herein with any of
the solid carriers and diluents commonly known to the
(H):
(line
(N02) b
(N02) 0
(01)»
35
(CD11
wherein Y is selected from the group consisting of O,
S, SO and S02; a is an integer from 1 to 4, b is an integer
from 1 to 3; c is an integer from 0 to 2; the sum of b
art of pesticide formulations, and exempli?ed by clays,
40 and 0 being a maximum of 3; d is an integer from 2 to 5,
diatomaceous earths, tales, chalks, and the like.
the sum of a and at being larger than 5; and e and f are
Typical concentrates for aqueous dispersions and emul
integers from 0 to 3, the sums of a, b and f, and c, d and e
sions will contain from about 0.5% to about 15% by
weight of fungicidally toxic compound based on the total
weight of the solution. Dustbases or concentrates will
typically contain from about 1.0% to about 70% of toxic
compound based on the total weight of dry blend and
may contain suitable quantities of wetting agents, dis
persing agents, and synergists. Similarly, wettable pow
ders will also contain from about 10% to about 70% by
weight of fungicidal material. Granular formulations
typically contain from about 2% to about 40% active
fungicidal ingredient by weight. These fungicide formu
each being 5.
References Cited in the ?le of this patent
UNITED STATES PATENTS
1,835,394
2,812,281
Hentrich et al. _________ .._ Dec. 8, 1931
Meltzer ______________ __ Nov. 5, 1951
OTHER REFERENCES
Groves et al.: J. Chem. Soc. 1929, 512-524.
Speckling et al.: Comp. Read. 231, 228-9 (1950).
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3uO50E44O
August 21, 1962
Sidney Bo Richter
It is hereby certified that error appears in the above ‘numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Column 39
line‘ 52' for "ether‘" read —- sulfone --= ;
59 and 60, for "phentachlorophenyl‘" read ——=
lines
pentachlorophenyl
-—-; column 4y line 26v for "Q?A?-tetrachloro" read
f“ 2,3¢4,6—tetrachl0r0 --g column 5, line 57, after "SOY"
insert
-~---
and
-——..
Signed and sealed this 14th day of May 1963.
(SEAL)
Attest:
ERNEST w. SWIDER
DAVID L- LADD
Attesting Officer
Commissioner of Patents
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