Note: Descriptions are shown in the official language in which they were submitted.
~h~6~
The present invention relates to new and
valuahle ~ -azolyl sulfides and -their derivatives, ~-azolyl
sulfoxides and ~-azolyl sul~ones, and their salts and metal
complexes,processes for their production and their use as
fungicides~
It has been disclosed that imidazole deriv-
atives, e.g. l-L2/4-dichlorophenyl-~ -allylethyl ether]-imidazole
(German Laid-Open application DOS 2,063,857) have a fungicidal
action. At low application rates and concentrations, this
action is not always satisfactory. Furthermore, the fungitoxic
action is often accompanied by a high phytotoxicity; conse~
quently, at the concentration necessary for combatting rusts
the crop plants are also damaged. For these reasons, they
are not always suitable, and not in every plant species, for
use as crop protection agents for combatting fungi.
We have now found that the new ~ -azolyl sulfides,
and their derivatives consisting of ~-azolyl sulfoxides and
~-azolyl sulfones, o~ the formula
R2 (O)
Rl _ C - ~ - R3 (I),
where R denotes hydrogen, alkyl, alkoxycarbonyl, or unsub-
stituted aryl or aryl substituted by halogen, NO2, alkyl or
haloalkyl; R denotes hydrogen or alkyl, R3 denotes alkyl,
alkenyl, alkynyl, unsubstituted phenyl or phenyl substituted
by alkoxy, alkyl or halogen, or unsubstituted aralkyl or
aralkyl substituted by halogen, Az denotes imidazol-l-yl,
pyrazol-l-yl, 1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl, tetrazol-l-
yl or tetrazol-2-yl, and n denotes one of the integers 0,1 and 2,
and their salts and metal complexes of copper, tin, zinc,manga-
nese, iron, cobalt and nickel.
~h~ L7
O.Z0 32,728
Examples o~ meanings ~or R are hydrogen, methyl, ethyl,
n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl-(3),
methoxycarbonyl, phenyl, 4-nitrophenyl, 4 bromophenyl, 4-cyano-
phenyl, 2-methylphenyl, 4-tert-butylphenyl, 3-trifluoromethyl-
phenyl, 4-trifluoromethylphenyl, 4-fluorophenyl, 2-chlorophenyl,
4-chlorophenyl, 2g4-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dl-
chlorophenyl, and ~ -naphthyl~ -
Examples of meanings for R2 are hydrogen, methyl and
n-propyl.
Examples of meanings for R3 are methyl, ethyl, n-propyl,
isopropyl, n butyl, tert-butyl, n-pentyl, n~hexyl, ally~ propargyl,
phenyl, 4-methoxyphenyl, 4-tolyl,4-chlorophenyl, 3,4-dichloro-
phenyl, 2,4-dichlorophenyl, 2,3,6-trichlorophenyl, benzyl,
3-trifluoromethylbenzyl, 4-chlorobenzyl, 4-bromobenzyl, 3,4~di-
chlorobenzyl, 2,4-dichlorobenzyl, 2,3,6-trichlorobenzyl and
2~phenylethyl.
Examples o~ salts are hydrochlorides, bromides, sulfates,
nitrates, phosphates, oxalates and dodecylbenzenesulfonates. As
the action of the salts is attributable to the cationl any anion
may be selected.
The metal complexes are compounds of the formula
rMe(R1 - C - S n_ R3) ~ Xk (II),
Az
where Rl, R2, R3, Az and n have the above meanings and Me denotes
a metal, e.g. 3 copper, zinc, tin, manganese, iron, cobalt or nickel,
X denotes the anion o~ an inorganic acid, e.g., hydrochloric acid,
sul~uric acid, phosphoric acid or hydrobromic acid, m denotes one
o~ the integers 1, 2, 3 and 4, and k denotes one of the integers 1,
2, 3 and 4.
- 2 -
% ~ ~ 7
O.Z. 32,728
We have ~urther found that ~-azolyl sulfides of the
formula I (n - O) are obtained by reacting ~ -chlorosulfides o~
the ~ormula
R1 _ C - S - R3 (III),
Cl
where R1, R2 and R3 have the above meanings~ with azoles H-Az,
where Az has the above meanings, in the presence or absence of a
basa and of a diluent. Oxidation of the ~-aæolyl sulfides of the
formula I (n - O) formed gives ~ ~azolyl sulfoxides of the formula I
(n - 1) and ~-azolyl sulfones o~ the formula I (n - 2).
For the production of the ~ -azolyl sulfides of the formula I
(n = O) it is advantageous to react the ~-chlorosulfides of the
~ormula III, with or without a diluent, with about 0.5 to 2 equi-
valents of an alkali metal salt of the azole in question, or with
about 0.5 to 4 equivalents o~ the azole in question, if desired
with the addition of from 0 5 to 4 e~uivalents of a base, at tem
peratures o~ ~rom about 0 to 200C, preferably from 20 to 160C,
~; and in homogeneous or inhomogeneous phase.
Examples of diluents are methanol, ethanol, isopropanol,
n~butanol, diethyl ether, tetrahydrofuran, dioxane, acetone,
acetonitrile, dimethylformamide, dimethyl sulfoxideg chloroform~
methylene chloride and toluene. Examples of bases are organic
amines such as triethylamine and pyridine, or inorganic compounds,
e.g., potassium carbonate or sodium hydroxide.
Some of the ~-chlorosuI~ides III used as starting materials
are known Yrom the literature or may be produced by processes
known from the literature 5 e.g~
a) chlorination o~ sulfides with N-chlorosuccinimide (see,
for example, B.L. Tuleen and T.B. Stephens, J. Org. Chem., 34,
31, lg69), as follows:
-- 3 --
6~7 o. z. 32l 728
o .,
R1 _ CH - S ~ R3 ~ ~ N~Cl --
O
~2 0
R1 _ C - S R3 ~ ~ NH
Cl (III) ~
or b) reaction of aldehydes with thiols in the presence of
hydrogen chloride (see, for example, H. Bohme. H~ Fischer and
R. Frank, Liebigs Ann. Chem. 563, 54, 1~49) as follows:
1 3
R -C0 + HSR + HCl - ~ -
H
R l- C-SR3 H 20
Cl (III)
~ o produce the ~ -azolyl sulfo~ides of the formula I (n - 1),
the ~-azolyl sulfides are reacted, in the presence or absence of
.
a diluent, with about 1 equivalent of a suitable oxidant at from
about -30 to +100 5. The ~-azolyl sulfones (I, n - 2) are obtained ;~
in similar ~anner by oxidizing the ~-azolyl sulfides (I, n - 0)
with at least 2 equivalents of a suitable oxidant or by oxidizing
10 the d-azolyl sulfoxides (I, n = 1) with at least 1 equi~alent Or
an oxidant.
Examples of suitable oxidants are potassium permanganate,
hydrogen peroxide and percarboxylic acids such as peracetic acid,
perbenzoic acid and 3-chloroperbenzoic acid. Examples of diluents
are water, acetic acid, methanol, acetone, chloroform, and methylene
chloride. A preferred process for producing the sulfoxides (I~
n = 1) is the reaction of the sulfides (I, n = 0) wlth 1 equivalent
of 3-chloroperbenzoic acid in methylene chloride at from 0 to 25C.
A preferred process for producing the sulfones is the reaction of
the sulfides (I, n = 0) with 2 equivalents of 3-chloroperbenzoic
acid in methylene chloride at from 15 to 41C.
- 4
O.Z. 32,728
The compounds of the formula I (n = 03 1 or 2) are readily
soluble substances in numerous organic solvents, e.g.~ ethyl
acetate, acetone, ethanol~ methylene chloride, chloroform,
dimethyl sul~oxide, dimethylformamide and N-methylpyrrolidone.
The ~ ~azolyl sul~ides (I, n = 0) also dissolve well in toluene.
They may be converted into their salts~ e.g., hydrochlorides,
sulfates, nitrates, oxalates 3 formates, acetates and dodecyl~
benzenesulfonates, with acids.
We have also found that the metal complexes of the ~ormula II
are obtained by reacting the ~ -azolyl sulfides or their derivatives
of the formula I with metal salts of the formula
MeXk . a H20 (IV),
where Me, X and k have the above meanings and a denotes one of
the integers 0, 1, 2, 3 and 4g in the presence of a solvent. Here,
Me preferably stands for metals of subgroups I, II and IV to VIII,
and of main groups II and IV, of the Period~c Table, especially
copper, zinc, tin, manganese, iron, cobalt and nickel.
The metal salts of the formula IV are generally known and
readily accessible compounds.
For the production of the metal complexes of the ~ormula II,
2~ all water-miscible solvents are suitable, preferably methanol,
ethanol, isopropanol, acetone, tetrahydrofuran and dioxaneO The
temperatures employed ~re generally from 0 to 100~, preferably
~rom 10 to 35C.
The sulfides (I, n = 0) and sulfones (I, n = 2) contain an
asymmetric carbon akom and are therefore obtained as enantiomorphous
mixtures which may be separated into the optically active compoundsf
In the case of the sulfoxides (I, n = 1)~ diastereoisomeric mix-
tures occur as a result of the asymmetric sulfur atom adjacent
to the asy~netric carbon atom; these mixtures may be separated
into their individual cornponents in con~entional manner, e.g.,
O.Z. 32,728
crystallization or chromatography Howe~er, for use as fungicides
or agents for regulating plant growth it is normally not neces-
sary to separate the enantiomorphs and diastereoisomers.
EXAMPLE 1
tert-butyl- ~2,4-dichlorophenyl)-1,2,4-triazol-1-yl-methyl~ osul
fide (compound no. 65)
60.5 g of tert-butyl-[(2,4~dichlorophenyl~-chloromethyl3 -sul-
fide is added to a solution o~ 22.1 g of 1,2g4-triazole in 500 ml
of anhydrous acetone. After the addition of 44.2 g of finely
powderedpotassium carbonate the mixture is refluxed for 7 hours
while stirring. The insoluble components are then filtered off,
the filtrate is concentrated to dryness in vacuo, and 300 ml of
water is added to the residue, The aqueous phase is extracted
three times with methylene chloride (200 ml each time) and the
combined extracts are washed with 200 ml of water, dried and ~
concentrated in vacuo. After the addition of 100 ml o~ diiso- ~-
propyl ekher~ there is obtained ~rom the residue 3~.6 g (53%)of
colorless crystals; m.p.: 95-97C.
H-nmr (100 MHz, CDCl~ = 1.3 (s~ 9H)~ 6.95 (s~ lH),
7.0-7.4 (m. 3H, ABX), 8.0 (s, lH), 8.8 ppm (s, lH).
EXAMPLE 2
bis-<tert-butyl-[(2,4-dichlorophenyl)-1,2,4-triazol-1-yl-methyl]-sul-
fide~-copper(II) chloride
15 ml of a molar ethano]ic solution of copper(II) chloride
dihydrate is dripped into a solution o~ 9.5 g of tert-butyl-[(2,4-
dichlorophenyl)-1,2,4~triazol~1-yl-methyl]-sulfide in 100 ml of
ethanol. After this deep blue solution has stood for 2 days at
0C, there is isolated from it 9.8 g of blue crystals, which are
washed with ethanol and ether; m.p.: 130C.
-- 6 --
~$~69~7
O.Z. 32,72
EXAMPLE 3
l-pentyl Ll-(1,2,4~triazol-1-yl)-pentyl-tlj~-sulfide
(compound no. 75)
While stirring, a solution of 43.5 g of triazole in 200 ml
o~ dimethylformamide is dripped into a suspension of 13.0 g of
sodium hydride in 100 ml of dimethylformamide. Upon completion
of the hydrogen evolution, the mixture is cooled to room tem-
perature and 97~0 g of l-pentyl-[l-chloropentyl-(l)]-sulfide is
added, whereupon the mixture heats up again. It is subsequently
stirred for a further 8 hours at 80 C. It is then concentrated in
vacuo, 500 ml of water is added, and the mixture is extracted
5 times with methylene chloride. The combined and concentrated
extracts are chromatographed on silica gel (5 x 70 cm), initially
using methylene chloride as developer. After the first, brownish,
zone has passed through, increasin~ amounts (up to 10%) of acetone
are added. In this manner, 15.0 g of the desired product is isolated
as the second zone as a pale yellow oil. IR (film): 2955, 2925, 2860,
1496~ 1460, 1271, 1190, 11~3, 1008, 677 cm 1~
H-nmr (270 MHz, CDCl3): ~ = 0.9 ("tr", 6H), 1.3 (m, 8H)g
1.5 (m, 2H), 2.1 (m, 2H), 2.4 (m, 2H), 5.4 (tr, lH), 8.0
(s, lH), 8,4 ppm (s, lH)o
EXAMPLE 4
l~pentyl~ (1,2,4-triazol-1 yl)-pentyl-(l)]-sulfone
(compound no. 71)
While stirring and cooling with ice, a solution of 6.0 g o~
l-pentyl- [1-(1,2~4-triazol-1-yl)-pentyl-(1 ~sulfide is dripped into
a solution of 10.0 g of 85% strength 3-chloroperbenzoic acid in
140 ml of methyl chloride. When the heat evolution - which takes
place initially - ceases, the mixture is then stirred for 2 days
at 25C. It is then washed with sodium carbonate solution, sodium
~ 7 --
~gL%~
O.Z, 32,728
sulfite solution and water~ and the organic phase is dried. After
concentration, a pale yellow oil remains from which, upon trituration
with diisopropyl etherg there is obtained 3. 5 g of colorless crystals;
m.p.0 69-71C.
nmr (CDCl3, 100 r~z): ~- 0.9 (m, 6H), 1.4 (m~ 8H), 1.8
(m, 2H), 2.5 (m, 2H), 2.8 (l'dd"~ 2H), 5.4 (dd~ lH)~ 8.1
~s, lH), 8.5 ppm (s, lH).
EXAMPLE 5
tert-butyl-~(2-methylphenyl)-imidazol-l yl-methyl~-sulfide
(compound no. 89)
While stirring9 82 g of tert~butyl-[(2-methylphenyl)-chloro-
methyl -sulfide is dripped into a solution of 43.6 g of imidazole
in 300 ml of acetone. Arter the addition of 88 g of finely powdered
potassium carbonate, the mixture is refluxed for 5 hours. The un-
dissolved constituents are filtered off and the filtrate is con-
centrated. 300 ml of water is added to the residue, and extraction
carried out ~ith 3 x 200 ml of methylene chloride. The organic
phases are combined, washed with water~ dried and concentrated.
There is obtained 69 g of a brownish oil which i~ dissolved in
1 liter of diisopropyl ether. Dropwise addition of 90 ml o~ a
2.85 molar solution of hydrogen chloride in diisopropyl ether, while
stirring~ gives pale yellow crystals of the hydrochloride. After
recrystallization ~rom acetone, there is obtained 51 g of colorless
tert butyl- E2-methylphenyl) imidazol-1-yl-methyl~-sulfide hydro-
chloride; m.p.: 16B-170C (compound no. 110).
After an aqueous solution of 25 g of sodium bicarbonate has
been poured onto the hydrochloride, the free base is extracted
with 3 x 200 ml of ether. After drying and concentration, it is
obtained as a pale yellow oil (27 g), which gradually crystallizes
m p 93-95C~
H-nmr (ÇO MHz, CDCl3)~ 3 (s, 9H), 2.4 (s, 3H), 6.25
(s~ ~H), 6.7-7.1 (m, 6H), 7.65 ppom (dd, lH).
- 8 -
'7
O.Z. 32,728
EXAMPLE 6
4-chlorophenyl-[4'-chlorophenyl)-imidazolyl-methyl]-sul~ide
(compound no. 7)
A mixture of 60.7 g of 4-chlorophenyl-(chloromethyl~4'-chloro-
phenyO -sulfide, 27.2 g of imidazole and 55.4 g of potassium carbonate
in 400 ml of acetone is refluxed for 5 hours while stirring. The
mixture is then filteredg the ~iltrate is evaporated to dryness
and 500 ml of water is added. This mixture is extracted 3 times
with methylene chloride (200 ml each time). The combined extracts
are dried over sodium sul~ate, The solution is concentrated to
dryness in vacuo, and 26 g (38%)of colorless crystals (m.p.: 88C)
are isolated, after trituration with diisopropyl ether.
lH-nmr (60 MHzs CDCl3): ~= 6.3 (s, lH), 6.9-7.4 (m, lOH),
7.5 (broad s, lH).
EXAMPLE 7
tert butyl-[(2,6-dichlorophenyl)-pyrazolylmethy~ -sulfide
(compound no. 53)
66 g o~ triethylamine is dripped into a solution o~ 193 g of
tert-butyl-(chloromethyl-(2,6-dichlorophenyl-sulfide and 44 g o~
pyrazole in 1 liter of toluene; upon completion of the slightly
exothermic reaction, the mixture is refluxed for 1 hour. The
undissolved constituents are filtered o~f, the filtrate is con-
centrated, and 500 ml of water is added to the residue. After
extraction 3 times with methylene chloride (200 ml each time), a
solid residue is obtained upon concentration of the combined extracts
which gives, after washing with diisopropyl ether, 117 g (57%) of
colorless crystals; m.p.: g7-98c.
H-nmr (60 MHz, CDCl3): d - 1.4 ppm (s, 9H), 6.2 ("tr",
lH), 7~0-7.3 (m, 3H), 7.4 ("d", lH), 8.2 ("d", 2H).
EXAMPLE 8
2,4-dichlorobenzyl-(1,2,4-triazolylmethyl)-sulfide
(compound no~ 78)
3 A mixture of 60.4 g of chloromethyl-(2,4-dichlorobenzyl)-sulfide,
Æ Of 1,2,ll-triazole and ~ ~ o~ po~/~ered potassiu~ carbonate ln
~ 9 _
'7
0.Z. 32,728
300 ml of anhydrous acetone is refluxed a' the boil for 10 hours.
The insoluble constituents are then filtered off, the filtrate
is concentrated to dryness in vacuo, and 300 ml of water is added
to the residue. The mixture is then extracted 3 times with methylene
chloride (200 ml each time), and the combined extracts are dried
and concentrated in vacuo. 39.8 g (58%) of colorless crys~als
(m.p.: 68-70C) are obtained from the brown oil which remains, by
crystallization from diisopropyl ethertmethanol at -60C.
lH-nmr (60 MHz, CDC13: ~'= 308 (S9 2H), 5.0 (s~ 2H), 7.0-7.5
10 (m, 3H), 7.9 (s, lH), 8.2 (s, lH).
EXAMPLE 9
2,4-dichlorobenæyl-(2',4' dichlorophenyl-1,2,4-triazol-1-yl-methyl)-
sulfide (compound no. 61) and 2,4-dichlorobenzyl- [(2',4'-dichloro-
phenyl-(1,2,4-triazol-4-yl)-methyl]-sulfide (compound no. 64)
A mixture of 200 g of 2,4-dichlorobenzyl- L(2'34'-dichloro-
phenyl)-chloromethyl~-sulfide3 145 g o~ 1,2,4-triazole and 138 g
of powdered potassium carbonate in 2 liters of anhydrous acetone
is refluxed, while stirring vigorously, for 9 hours. The solid con-
stituents are then removed by filtration, the filtrate is then con-
centrated to dryness in vacuo, and 500 ml of water is added to the
20 oily residue which is then extracted 5 times with methylene chloride
(200 ml each time). The combined organic phases are dried over sodium
sulfate and concentrated to dryness in vacuo. Upon trituration of
the residue with diisopropyl ether there is obtained 157 ~ o~ color-
less crystals containing the isomeric triazolyl compounds in a
ratio of 8:2.
This mixture is extracted several times with hot hexane. The
hexane solutions are combined and, after removal of the solvent in
vacuo, there is obtained 122 g (65%) of 2,4-dichlorobenzyl- [(2'94'-di-
chlorophenyl)-1,2,4-triazol-1 yl methyl~-sulfide in the form of
3~ colorless crystals; m.pO: 120-125C.
H-nmr (220 MHz, CDC13): ~ - 3.9 ppm (broad s, 2H), 6.65
(8, lH), 7.0-7.~ (m, ~H), ~.0 (s, 1H), R.~ (s~ lH).
- 10 -
O.Z. 323728
The colorless insoluble residue from the hexane extractions
is 27 g (12%) of 2~4-dichlorobenzyl-C(2',4'-dichlorophenyl)~1~2,4-
triazol 4-yl)-methyl~-sulfide; m.p.: 132-133C.
lH-nmr (220 MHz) CDCl3): ~- 3~9 ppm (s, 2H), 6.5 (s, lH),
7.0-7.5 (m, 6H), 8.45 (s, 2H).
EXAMPLE 10
tert-butyl-[(4-chlorophenyl)-1~2,4-triazol~1-yl-meth~Jl~ -sulfide
(compound no. 30)
While stirring, 350 ml of a molar solution of lg2,4-triazolyl
sodium in dimethylformamide (DMF) (prepared from 0.35 mole of sodium
hydride and 0.35 mole o~ 1,2,4-triazole in 350 ml of DMF) is dripped
into a solu~ion of 78 g of tert-butyl-[(4~chlorophenyl)-chloro-
methy~ -sulfide in 175 ml of dry DMF. Upon completion of the slightly
exothermic reaction, the mixture is stirred for 4 hours at 80C. The
batch is then poured into 1 liter of water and extracted 3 times
with 200 ml of methylene chloride. The combined organic phases are
washed with water, dried over sodium sulfate and concentrated in
vacuo. When the residue is triturated with 150 ml of diisopropy~
ether~ there is obtained 40.0 g (46%) of colorless crystals;
m.p.: 95C.
H-nmr (60 MHzg CDCl3): ~= 1.3 ppm (s, 9H), 6.6 (s, lH),
7.2 (AA'BB', 4H)~ 8.o (S5 lH), 8.7 (S3 lH).
EXAMPLE 11
tert-butyl-((4-chlorophenyl)-1,2,l1-kriazolylmethyl)-sulfoxide
(compound no. 31)
While cooling with ice, a solutlon of 7.1 g of 85% strength
3-chloroperbenzoic acid in 70 ml of methylene chloride is dripped
into a solution of 9.7 g of tert-butyl- ~(4-chlorophenyl)-1,2,4-tri-
azolylmethyl~-sulfide in 20 ml of methylene chloride. The mixture
is stirred for 2 hours at 0 C until there is no more sulfide
(RF = 757) present according to the thin-layer chromatogram
;~ 30 (5io2, 7:3 mixture of methylene chloride and acetone), and only
the 2 diastereoisomeric sulfoxides are distinguisha~le (RF - 0.38
-- 11 --
7 o.z. 32,728
and 0.20). The solution is then washed with aqueous sodium bi-
carbonate solution until no more C02 evolves. The organic phase
is washed with water, dried and concentrated, and the solid residue
is washed with a srnall amount of ether. There is obtained 7.0 g
(67~) of colorless crystals, m.p.: 125-128C.
H-nmr (220 MHz, CDCl3): - 1.10 and 1.15 (two s, tog. 9H),
6.18 und 624 (two s~ tog. lH), 703-707) (m,4H), 8.01 and 8.07 (two s,
tog.lH), 8.41 and 8051 (two s, tog.lH).
EXAMPLE 12
tert-butyl [(4-chlorophenyl)-1,2,4-triazolylmethyl]-sulfone
(compound no. 32)
At 20C, a solution of 7.~ g of 85% strength 3-chloroperbenzoic
acid in 100 ml of methylene chloride is dripped into a solution
of 10.7 g of tert-butyl-L(4-chlorophenyl)-1,2,4-triazolylmethyl~-
sulfoxide in 50 ml of methylene chloride. According to thin-layer
chromatography, the less polar sulfoxide oxidizes more quickly;
only after stirring for a fairly long time at room temperature does
the more strongly polar sulfoxide oxidize. According to thin-layer
chromatography (SiO2, 7:3 mixture of methylene chloride and acetone),
the reaction is over after 18 hours. The sulfone (RF = o.46) is
isolated by wash mg the solution with sodiurn bicarbonate solution
and water, and drying and concentrating the organic phase. After
the residue has been washed with diisopropyl etherg there is o~tained
8.7 g (77%) of colorless crystals; m.p.: 150C,
lH-~nr ~220 MHz, CDCl3): ~- 1.3 ppm (s~ 9Hj, 6.75 (s, lH),
7.5 (AA'BB', 4H), 8.03 (s, lH), 8.84 (s~ lH).
EXAMPLE 13
4-chlorophenyl- ~4'-chlorophenyl)tetrazol 1-yl)-methyl~-sulfide
and 4 chlorophenyl-[(4~--chlorophenyl)-(tetrazol-2-yl)-methyl~-sulfide
(compound no. 15)
; At room temperature and while stirring~ }7.4 g of triethylarnine
is dripped into a mixture of 26.1 g of tetrazole and 102 g of 4~chloro-
~phenyl- L~ 4~-chlorophenyl)-chloromethyl~-sulfide in 3 5 liters of
- 12 -
'7
O.Z. 32,728
toluene. The mixture is then refluxed for 4 hours. The insoluble
material is filtered o~f, the filtrate is washed with water, and
the organic phase is dried over sodium sulfate. After removal of
the solvent in vacuo, a solid residue remains, from which, after
the addition of 50 ml of diisopropyl ether, 74.7 g (67%) of
yellowish crystals are isolated; m.p.: 104-106C.
H-nmr (60 ~z, CDCl3): ~- 6.7-7.6 ppm (m, 9H), 8.4 and 8.9
~two s~ tog. 2H).
Examples of compounds Or formula I according to the invention
are given in the following Table 1.
- 13 -
O. Z. 32,728
Table 1
Compound ) R1 R2 Az (salt j n R3 m p (C)
N~ 0 ~ 13 2-13 4
~N IR~ilm): .
2 H3C- H h~ 0 ~Cl 14,5 1ll920,
~131, 108a,
6667c~--~7 '
3 ~ H ~ 0 -CH2~ ~OoO, ~020,
127 1, 1 190,
1131, 100~, -
4 Cl~. H N ~ 0 ~ 98
Cl~ E~ N~N~ 1 ~ 151-139 )
6 Cl~ H ~ ~ 2 ~ ~15
7 Cl~ H ~? 0 ~Cl 88
.:. 8 Cl~)~ > ,~COOE132 0 ~Cl 85-~7
9 Cl~ ~ ~ 0. ~Cl 62-6~1
10 Cl~ \~ 1 ~Cl il6-ll~)
11 Cl~- H N~ 2 ~Cl 147-150
12 Cl~ }} `I 4~'Cl 136-138
)Diastereoisomeric mixture of sulfoxides
+~)The s'cructures of all the compounds l1sted have been confirmed
by lH nlnr spectra~
-- 14 --
~''; .
7 o.z. ~2,728
Compound Rl R2 Az (salt ) n R3 m.p . (C)
1~Cl~ ;`' 3J~ i ~Cl 147~)
14Cl~ }~ N~? 2 ~Cl 204
. . .
~5Cl~ H ~h N ~ ~ > Q ~Cl 104-106
. 16Cl~ ~ N ~ + N~ ~ 1 ~Cl 110-112+ 1 )
17Cl~ N N~_~N ~ 2 --~--t:l 123-125
18Cl~ ~ ~_N ~CEI3 1JO
19Cl~ H QN 1 .~CH3 147-149~ ~)
,.,
20Cl~ }~ N ~ 1 ~CH3 154-15
21C1~ ~ ~ ~l 2 ~C~3 245
22Cl~ ~ N ~ 0 ~Cl 102
:~ CI
23Cl~ X ~f~N~ 0 ~Cl 13~ 7
Cl ~ IRS~ilm):
24Cl~ ~ 0 te~ ~t.",l 2960, 1581,
: 1096, 10~ 4,
7a73'6574~
; :
) mixture of tetrazole isomers
) diastereolsomeric mixture of sulfoxides
;~ +f ) more strongly polar sulfoxide, separated from the
;~ diastereoisomeric mixture no~ 19 by crystallization
. - 15 -
7 o.z. 32,728
Compound Rl R2 Az ( salt ) nR3 m.p . ( C )
Cl~ ~ N~ o ~OC~3 116
26. Cl ~ H ~ ~ 2 ~ OCH3 198
27 Cl ~ ~ - N -CH2 ~ Cl 57-58
N IR(~ilm):
28 Cl ~ ~ N ~ O e~hy~~ 2965, ?227~,
, 1010,675cm '
29 Cl ~ H N ~ 0 294485, 22508
1127, 1084~,
1~07,67Lcm '
Cl ~ ~ N~_~ O tert,-butyl 95
31 Cl ~ .. ~ N 1 tert.-~utyl 125-128l)
32 Cl ~ ~I~N~ 2 tert~- ~tyl 150
I~( film): ::
33 Cl ~ X ~ N~ O allyl 3054~ 11480,
1007, -1
672 C~
34 Br ~ H N~_? O tert. ~ butyl 77 ~78
F ~ H N ~ o tsrt.-~utyl 102-104
36 NC ~ ~ ~N~ O terk.-~utyl 73-75
37 2~ ~ H U~ O tert.- ~tyl 76-78
.
) diastereoisomeric mixture
.,~
, . . .
- 16 - ~
. .
,i
7 O.Z. 32,728
Compound R1 R2 Az (salt ) n R3 m.p, ( C)
38 3 _~_ H N~NN~ tert .wb~tyl 94
39 H H , N~-> 0 ~Cl 47-49
<~ N N~ 0 ~ 9 ~
<~Cl N 1 ~) 70-88
4 2 (~ H U )~ 2 ~ 14 3
Cl N 0 tert.-~utg l 84
~N 1 tert.-~utyl 154-157 )
. ~ 45 ~ H N ~ 2 tert.-butyl 126
,CF3 IR t ~il~ ):
46 ~ ~? -CH24~ 127 11
,. C~ 790, o2~.
3 660 c~n .
~ ~ . (COO~d)2 0 -Ca2~Cl ~33-135
48 Cl~ ~ N~ ;~ O -CH24~Cl 101
Cl~_ H ~3 2 -CH2~;1 1.95-19 î
) diastereoisomeric mixture
~ 17 -
~7 o.z. 32~728
Compound R1 R2 Az (salt) n R3 m.p. (C)
Cl~ H ~ N -C~2~Cl g2-~4
C~ 1 -CH2~C1 104 110 )
52 Cl~ ~ 2 -CH2~1 100-105
~ Cl ~. tert.-~utyl 97-98 ~,
54 ~ H N~ 0 tert.-butyl 110-112
Cl s
8- H ~ 0 tPrt.-buoy1 112-115
; 56 ~ ~ N ~ 1 tert.-butyl 122-127 )
57 ~ ~ ~ 2 t2rt.-~utyl 1~0-la3
.. 58 Cl ~ H N > 0 ~ Cl 128
59 Cl ~ H ~N N7 ~ Cl 148-150 . ~:
Cl ~ ~-N -CH2 ~ Cl 105
:~ ) diastereoisomeric mixture
- - 18 -
'. '
O.Z. 32,728
6~L'7
Compound Rl R2 Az (~alt) n R3 m.p. (C)
61 ~ ~N~ o -C~2~-C1 120 125
62 ~l- .N\~ CH2~C1 125-131+)
63 Cl~ E~ N~ 2 -CH2~C1 163-165
64 Cl~ H ~ 0 -CH2~Cl 132-133
Cl~ H N~;,~ 0 tert.-butyl 95-97
CH3 6 6- 8 8
` 67 C1~ X N~ 0 ~ - g5-97
~ IR ~nlm) cm~1
:~ 6~ c~3 N ~ O ~> 1433~ 1250, 1~96,
1128, 994, 746,
, . 689, 672
69 n hexyl H Nl~_ 0 ~ 29845, 2C20,
1471, 127G,
;' 1132, 1o~9,
~ - 67l~8cm8~8
n-butyl ~N~ ~ 2950, 2020,
~496, 1~72,
- 1270, ~132,
:~; ' 81889872s
~ ) diastereoisomeric mixture
: -- 19 -
O.Z. 32,728
'7
Compound R1 R2 Az (salt ) nR3 m.p. ( C)
71 n-butyl ~ N ~ 2n-Pe~tyl 69-71
. ~ N o~ Cl 76~79
72 H3C- H3C- N~
ilm):
\ ~N~ ~\ 2955, 1494,
73 ~-- . H N~ 1/ 0 ~ /-Cl 1471, 1279,
~ 1130, 1050,
- . 1007, 8~5,
67} cm
: Ih~film):
74 ethyl H N~ ~ O n-propyI 1495, 1270,
1192, 11~3,
~^ o753cmQ17'
IR~ilm):
2955, 2925, ~:
n-butyl ~ N~_ ~ O n-~enty.l 1460, 1271,
~ ~ 1190, ~133,
"~ , , 670708C~
, IR(fil~):
~: 76 n-Pen~yl H ~N~ 0 n- ~xyl 2860, 1~97,
~- 1012,
6?8 cm~
77 H ~N~ 0 -CH2 ~ r 46-49
78 H~ ~N~ o -CH2 ~ Cl 68-70
79 H- H. ~ ~ -OH2 ~ 60-63
..
':
-- 20 --
O . Z . 32 1 72 8
7 :~
2 ~ O
Compound R R Az n R m~ p . ( C )
( salt )
~ ~3 H .`f~ 0 ~C} 100-10
Cl
81 ~1 \~N 1 ter~.~butyl 1~5-116+)
. C1
82 ~ H .`1~ ~ 2 tert.-b~tyl 154-165
:~ 8~ n-b~tyl ~ ~N~ 0 tert.~butyl IR(fil~)~
58, 1495,
145~, 13c4,
1272, 1190,
1158, 1134,
1010, 677
4 l-but~ O t~rt.-butyl I~
952, 28c2,
.~ . 1494, 1457,
: 1~6", 1270,
~: ~ 1189, 1157,
. . 1132~ 6757
i-butyl ~ o ~Cl 45-4
6 i-hlt~l X .~ ~ 1 ~3Cl 110-1~2
87 i-butyl H ~ 2 ~C1 140-14
''
. :
:~
- 2 1 --
Com" Rl R2 A~ n R3 m.p. (C)
pound ( salt )
3 ' O tert.-but~l 98-101
~ ~3 ' 0 tert~-but71 93-95
go3-heptyl H ~/> 0 ~ Cl (film)
1472, 126S,
1131, 1088,
I008, 6873'C~-1
; 91Cl ~ N~ 2 o 3-lnethyl- 2962, 148 ,
F 108S, 6
." 92 ~ 0 ~ Cl 105-107
93~ - H ~N~ o tert,-~ut~l 106-108
94 ~ H ~ ~ 0 tert.~ yl 4C-43
~"~ 95 ~ ~ 0 tert.-butyl 8S-87
96 ~ X N ~ ~ 0 tert~-bu~yl 1~0-112 -~
97~ - H ~ 0 tert.-~utyl ~-S5
Cl
98~ _ ~ o ethyl S9
Cl
9~~ ~ Q N 2 ethyl 102,-10
0, ~
~ L26~ -Z. 32,728
Com- Rl F~2 Az n R3 m,p. (C) : .
pound ( salt )
C1
100 ~ H ~ 0 n~ Ut'~ L~):
~_N 2958~ 2928,
14~4, ~274,
: 1132~ 1008
. ~ ` C1 748~ 678 Cm
` 101 <~ H N~ 0 n-heXJ1 IRt~i1m):
. ~N 2955~ 2923, ~r
`: 1491, 1271,
C1 ~ ~ 744~ 675 C~
102 ~ H N~N~ ~C~2~ > 96-98
:~ C1
103 ~ L_~ 2~ 13O-133 ~:
104 <~ H N~?~ -CX~-CX2~ 58-6
C1
105 ~ 2 -C~2-C~2~ 129-L3CI
, ~, 106 C l ~ ~ ,~ ,~-C 1 10 8- 110
. : 107 n X ~ o ~cl 84-87
~: : Cl
108 H ~ 3C1152-155
Cl
109 H 'd \~N 2 ~C1
/CH3
110 ~ ~ HCl 0 tert.-bu~l;yl 163-170
x ,~a dCl 0 n-.~u,,yl , 135-139
O.Z. 32,728
Com- R1 R2 Az n R3 m . p O ( C )
pound ( salt )
., _. . ... . . ~ . .
Cl
112 ~ H ~,1t . HCl 0 -C~2-C.'12~ 145-155
113 F~ H 6N~ ~Cl 90-92
114 F~3 H N~N~ 0 ~Cl 119-120
Cl
115 ~_ X 6~? 0 ~Cl cg 71
Cl
115 ~ H 1~ ijr O ~Cl 134~ 130
~Cl
-:: 117 ~ H ~ 0 tert.-?3utyl I~(1il;~):
3098, Zg50, :
~463, 1211,
. 115a, 1002,
. Cl 104~, 739~ -1
118Cl~ ~ N'N~ 2 tert.-butyl 940
119Cl~ H 6~q 1~' 2 tert.-butyl 153-156.
;: F
' >
- ~ 120(~ :~N 2 tert.-but~l 143-145
: ~ Cf~ -
121~,~~ H N~ 2 t~rt.-butyl 160-162 ~:
122(~ H ~N~ 2 t2r~.-3ltv~ ll;-llo
Cl
123 ~ H N~ 2 ~Cl l-r5-1~8
1243^heptyl H ~ 0 ~ 1472, 1 468,
1160, ~090,
1009, 817,
C%3 ~ 647 Cl;t ~
125C~3-C-C'd2- H N~? ~Cl 83 86
126CX3-C-C~2 ~ 3-C1 47- 51
127~~ ~N~ 0 _~ Cl 89 - 90
~1 t
128Cl-(~ TN~ -C~2-<~-C1 3103 15a6,
1217, 1090,
1067, 1048,
~~ 24 -- ~59 a;r~
O~Z. 32,728
The new ~-azolyl sulfides 3 ~-azolyl sulfoxides and
~-azolyl sulfones and their salts have a much "ider spectrum o~
fungicidal action and are better tolerated by crop plants than
the prior art compound 1-[2,4-dichlorophenyl-~-allylethyl ether]-
imidazole. The new active ingredients may also be uEed in the
i~ form of their salts, e.gO hydrochlorides~ oxalaltes and nitrates.
The fungicidal agents according to the invention are of
considerable interest for combatting fungus diseases in various
- crop plants, e.g., Ustilago scitaminea, Hemileia vastatrix,
10 Uromyces fabae or appendiculatus, Puccinia species, Erysiphe
graminis, Botrytis cinerea in grapes and strawberries, Uncinula
necator, Sphaerotheca fuliginea, Erysiphe cichoracearum and
Podosphaera leucotricha.
; By "crop plants" we mean in this connection especially wheat,
rye, barley, oats, rice, Indian corn~ apples, cucumbers, beans,
coffee, sugarcane, grapes, strawberries and ornamentals in horti-
culture.
The active ingredients have a systemic action, which is of
particular interest in connection with the control of internal
20 plant diseases, e.g~, rust and mildew in cereals~
The agents according to the invention may suppress the
growth of two or more of the abovementioned ~ungi at the same
time, and are well tolerated by crop plants. The application rates
necessary ~or combatting phytopathogenic fungi are from 0.05 to
2 kg of active ingredient per hectare.
The compounds of the invention can be converted into the con-
ventional formulations, e~g. solutions, emulsions, suspensions,
powders, pastes and granules. The formulations are prepared in the
conventional manner, for example by diluting the active ingredient
30 with solvents and/or carriers, with or without the addition of
emulsifiers and dispersants and, where water is used as the
diluent, with or without an organic auxiliary solvent. Suitable
- 25 -
O.Z. 32,728auxiliaries are, essentially, solvents, ~or example aromatics,
e.g. xylene and benzene, chloroaromatics, e.g. chlorobenzene,
paraffins~ e.g. petroleum fractions, alcohols, e.g. methanol and
butanol, amines, e.g. ethanolamine and dimethylformamide, and
water; carrlers, for example natural rock powders, e.g. kaolin,
alumina, talc and chalk, and synthetic rock powders, e.g. highly
disperse silica and silicates; emulsifiers, for example non-ionic -'
and anionic emulsifiers, e.g. polyoxyethylene fatty alcohol ethers,
alkylsul~onates and arylsulfonates, and dispersants, for example
li~nin, sul~ite waste liquors and methylcellulose.
The formulations in general contain from 0.1 to 95 per cent
.
by weight of active ingredient, preferably form 0.5 to 90 per cent. -~
The formulations, and the ready-to use prepara~ions obtained
therefromg e.g. solutions, emulsions, suspensionsg powders, dusts,
pastes or granules, are applied in the conventional manner, e.g by
spraying, atomizing, dustinga cattering or watering.
The above-ready-to-use preparations may contain other active
ingredients toge~her with those according to the invention, e.~.
herbicides, insecticides, growth regulators and other fungicides
or may be mixed with ~ertilizers and applied together with these.
Examples of fungicides which can be combined with the compounds
of the invention are: dithiocarbamates and their derivatives, e.g.
iron(III~ dimethyldithiocarbamate, zinc dimethyldithiocarbamate3
manganese N,N-ethylene-bis-dithiocarbamate, manganese zinc
N,N-ethylenediamine-bis-dithiocarbamate, zinc N,N-ethylene-bis~di-
thiocarhamate, tetramethylthiuram disulfide, the ammonia complex
o~ zinc N,N-ethylene-bis-dithiocarbamate and N,Nl-polyethylene- bis
(thiocarbamoyl)-disulfide, zinc N,N'-propylene-bis-dithiocarbamate,
and the ammonia complex of zinc N,N'-propylene-bis dithiocarbamate
and N-N'-polypropylenè-bis-(thiocarbamoyl)-disulfide; nitro deriv-
atives, e.g. dinitro-(1 methylheptyl)-phenyl crotonate, 2-sec~--butyl~
4,6-dinitrophenyl 3,3-dimethylacrylate and 2-sec.~butyl-4,6-di-
nitrophenyl isopropyl carbonate; heterocyclic compounds, e.g.
- 26 -
~126~7
0,Z. 32,728
N-trichloromethylthiotetrahydrophthalimide, N-trichloromethyl-
thio-phthalimide, 2-heptadecyl-2-imidazoline acetate, 2,4-di-
chloro-6-(o-chloroanilino)-s-triazine, 0,0-diethyl phthalimido-
phosphonothioate, 5-amino-1-(bis-(dimethylamino)-phosphinyl)-
3-phenyl-1,2,4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thia-
diazole, 2,3-dicyano-1,4-dithiaanthraquinone, 2-thio-1,3-dithio-
~4,5-b)-quinoxaline, methyl 1-(butylcarbamOyl)-2-benzimidazole-
carbamate, 2-methoxycarbonylamino-benzimidazole, 2-thiocyanato-
. methylthio-benzthiazole, 4-(2-chlorophenylhydrazono)-3-methyl-S-
isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline and its
copper salts, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-
4,4-dioxide, 293-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,
2-fur-2-yl-benzimidazole, piperazine-1,4-diyl-bis-(1-~2,2,2-tri-
chloroethyl)-formamide), 2-thiazol-4-yl-benzimidazole, 5-butyl-2-
dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis-(p-chlorophenyl)-
3-pyridinemethanol, 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benze~ne,
1,2-bis-(~-methoxycarbonyl-2-thioureido)-benzene and various
fungicides, e.g. dodecylguanidine acetate, 3-(2-(3,5-dimethyl-2-
hydroxycyclohexyl)-2-hydroxyethyl)-glutarimide 9 hexachlorobenzene,
N-dichlorofluoromethylthio-N',N1-dimethyl-N-phenyl-sulfuric acid
diamide, 2,5~methyl-furan 3-carboxylic acid anilide, 2,5-di-
methylfuran-3-carboxylic acid cyclohexylamide, 2-methyl-benzoic
acid anilide, 2-iodo-benzoic acid anilide, 1-(3,4-dichloroanilino)-
1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyl-
morpholine and its salts, 2,6-dimethyl-N-cyclododecyl-morpholine
and its salts, 2~3-dichloro-l~4-n~hthoquinone~ 1,4-dichloro-2,5-di
methoxybenzene, p-dimethylaminobenzene diazosodium sulfonate,
1-chloro-2-nitropropane, polychloronitrobenzenes such as penta-
chloronitrobenzene, methyl isocyanate, fungicidal antibiotics such
3 as griseofulvin or kasugamycin, tetrafluorodichloroacetone, 1-phenyl-
~thiosemicarbazide, Bordeaux mixture, nickel~containing compounds
and sul~ur.
27 -
~ OOZ. 32,728
In the following experiments demonstrating the fungicidal
action of the compounds according to the invention, the following
prior art active ingredient was used for comparison purposes
,;
Cl
~ N~V,N-CH2'fH ~ Cl (A)
;` O-CH2-CH-CH2
(disclosed in German Laid~Open Application DOS 2,063,857)
EXAMPLE 14
Action on barley mildew
Leaves of pot-grown barley seedlings of the "Firlbecks Union"
. ,
`~' variety are sprayed with aqueous emulsi'ons'consisting of 80% (by
~ weight) of active ingredient and 20% of emulsifier, and dusted, after
;-- the sprayed~on layer has dried3 with spores of barley mildew
(Rrysiphe graminis var. hordei). The plants are then placed in
a greenhouse at 20 to 22 ~ and 75 to 80% relative humidity. The
extent of mildew spread is determined after 10 days.
O - no attack~ graduated down to 5 = total attack
Compound Leaf attack after spraying with liquor
containing compound in amounts of
0.05% 0.025%
4 2
6 0 3
9 0 3
0 4
~2 0 2
14 0 2
0 3
18 3
21 0 2-3
' ~ 25 0 2
26 3
27 0 3
-- 2~ -
~' ;
O~Zr 32~728
Compound Leaf attack after spraying with liquor
containing compound in amounts o~
0~05% 0~025%
31 0 3
~1 0 2
0 2
` 50 0 3
54 0 2 3
59
64 0 2
0 3 ~`
7 0 0
0 0
0 0
92 0 0
94 0 0
104 0 0
113 0 0
114 0 0
115 0 0
116 0 0
; 125
126 ~ 0
127 0 0
128 0 0
Control (untréated) 5
- 29 o
~: ' , ' ' ' '.' :. ..
~ ,7 O.Z. 32,728
EXAMPLE 15
Action on wheat mildew
In the same manner as in Example 14, lea~es of pot-grown wheat
seedlings of the "Jubilar" variety are treated and infected with
spores of wheat mildew (Erysiphe graminis var. tritici). The
procedure is otherwise the same as in Example 14.
Compound Lea~ attack after spraying wi~h liquor
containing compounds in amounts of
0.05% 0.02~%
:
4 0 2
0 0
0 2
0 0
: 85 0 0
0 0
92 - 0 . 0
; 94 0 0
104 0
113 0
114 0
115 0 0
116 0
125
126 o 0
127 0
128 0 2
A 1 3
Control (untreated) 5
,
; . ~ 30
~'
~ O.Z. 32,728
EXAMPLE 16
Action on leaf rust of wheat
Leaves of pot~grown seedlings of the "Jubilar" variety are
; artiflcially infected~ 24 hours before being sprayed, with spores
of leaf rust (Puccinia recondita). The pots are then placed in a
high humidity chamber at from 20 to 22C. The plants are then
sprayed with aqueous emulsionsS the solids comprising 80% of
active ingredient and 20% of emulsifier. After the spray coating
has dried~ the test plants are set up in a greenhouse at from 20
to 22C and from 75 to 80% relative humidity. After 10 days, the
degree of development of the rust fungi on the leaves is determined.
10 Active ingredient Infection of the leaves after spraying with a
ingredient liquor containing 0.05% of active ingredient
4 2
12 `
27
0
7 0
0
0
9~
104
113 0
114 0
11~ o
125
126 0
127 0
A 3
Conkrol (untreated) 5
- 31 -
, .
/
O.Z. 32,728
EXAMPLE 17
90 parts by weight of compound 1 is mixed with 10 parts by
weight of N-methyl-~-pyrrolidone. A mixture is obtained which is
~; suitable ~or application in the form of very fine drops.
EXAMPLE 18
20 parts by weight of compound 2 is dissolved in a mixture
consisting of 80 parts by weight o~ xylene, 10 parts by weight
of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic
acid-N-monoethanolamide, 5 parts by weight of the calcium salt of
dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct
of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring
the solution into 1003000 parts by weight of water and uni~ormly
distributing i~ therein, an aqueous dispersion is obtained con-
taining 0.02% by weight of the actlve ingredient.
EXAMPLE lg
20 parts by weight o~ compound 3 is dissolved in a mixture
consisting o~ 40 parts by weight of cyclohexanone, 30 parts by
weight of isobutanol, 20 parts by weight of the adduct o~ 7 moles
of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight
o~ the adduct o~ 40 moles o~ ethylene oxide to 1 mole of castor
oil. By pouring the solution into 100~000 parts by weight of water
and finely distributing it therein, an aqueous dispersion is obtai~ed
containing 0.02% by weight o~ the active ingredient.
EXAMPLE 20
20 parts by weight of compound 1 is dissolved in a mixture
consisting of 25 parts by weight of cyclohexanol~ 65 parts by weight
of a mineral oil fraction having a boiling point between 210 and
280C, and 10 parts by weight of the adduct of 40 moles of ethylene
oxide to 1 mole of castor oil. By pouring the solution int`o 100,000
parts by weight o~ water and uni~ormly distributing it therein, an
aqueous dispersion is obtained containing 0.02% by weight of the
active ingredient.
- 32 -
"
/
~ '7 O.Z. 32,728
EXAMPLE 21
20 parts by weight of compound 2 is well mixed with 3 parts
by weight of the sodium salt of diisobutylnaphthalene-~-sulfonic
; acid, 17 parts by weight Or the sodium salt of a lignin-sulfonic
acid obtained from a sulfite waste liquor, and 60 parts by weight
of powdered silica gel, and trituraked in a hammer mill. By uni-
~ormly distributing the mixture in 20,000 parts by weight of water~
a spray liquid is obtained containing 0.~% by weight of the active
ingredient~
EXAMPLE 22
3 parts by weight of compound 3 is intimately mixed with 97
parts by weight of particulake kaolin. A dust is obtained con- '~
taining 3% by weight of the active ingredient.
EXAMPLE 23
30 parts by weighk of compound 4 is intimately mixed with a
mixture consisting of 92 parts by weight of powdered silica gel
and 8 parts by weight of paraffin oil whlch has been sprayed onto
the surface o~ this silica gel. A formulation of the active ingre-
; dient is obtained having good adherence.
EXAMPLE 24
40 parts by weight of compound 1 is intimately mixed with
10 parts of the sodium salt of a phenolsul~onic acid-urea form-
aldehyde condensate, 2 parts of silica gel and 48 parts of water.
A stable aqueous dispersîon is obtained. Dilution in 100,000 parts
by weight of water gives an aqueous dispersion containing o.o4wt%
of active ingredient.
EXAMPLE 25
20 parts of compound 2 is intimately mixed with 2 parts of
,.,
the calcium salt o~ dodecylbenzenesulfonic acid, 8 parts of a fatty
alcohol polyglycol ether, 2 parts of the sodium salt of a phenol-
sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraf-
finic mineral oil. A stable oily dispersion is obtained.
- 33 -
,~;
