Note: Descriptions are shown in the official language in which they were submitted.
~5~278
The present invention relates to certain new 1-(2,4-dichlorophenyl)-
1-(2,6-dihalogenobenzylmercapto)-2-(1,2,4-triazol-1-yl)-ethanes, to a process
for their preparation and to their use as fungicides.
It has already been disclosed that certain substituted 1-
benzylmercapto-l-phenyl-2-(1,2,4-triazol-1-yl)-ethanes, for example 1-12,4-
dichlorophenyl)-1-(2,4-dichlorobenzylmercapto)-2-(1,2,4-triazol-1-yl)-ethane,
have good fungicidal properties (see our Canadian Patent No. 1,091,677 and
DE-OS (German Published Specification) 2,724,684). However, in certain fields
of indication, their action is not always completely satisfactory, especially
if small amounts and low concentrations are applied.
The present invention now provides, as new compounds, the 1-(2,4-
dichlorophenyl)-1-(2,6-dihalogenobenzylmercapto)-2-(1,2,4-triazol-1-yl)-ethanes
of the general formula
Cl ~ 1 2
X>_ ~
CH2 ~
y
in which
X and Y are identical or different and represent halogen,
and physiologically acceptable acid addition salts thereof.
The present invention also provides a process for the preparation
of a 1-(2,4-dichlorophenyl)-1-(2,6-dihalogenobenzylmercapto)-2-(1,2,4-triazol-
l-yl)-ethane of the formula (I) in which
~k
~ --1--
. .
` J
~5~78
(a) a 1-(2,4-dichlorophenyl)-1-halogeno-2-(1,2,4-
triazol-1-yl)-ethane of the general formula
,Cl
Cl ~ - CH - CH2 ~ ~ ¦ (II),
Hal
in which
Hal represents halogen,
is reacted with a mercaptan of the general formula
H - S - CH2--<~> ( I II ),
Y~
in which
X and Y have the meanings indicated above,
if appropriate in the presence of a diluent and of an
acid-binding agent, the mercaptan of the formula (III)
preferably being prepared in situ, or
(b) 1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)-ethane-
1-thiol, of the formula
fCl
r~ N
Cl ~ - fH - CH2 ~ ~N ~ (IV),
SH
is reacted with a 2,6-dihalogenobenzyl derivative of the
general formula
X
- CH2 --~
y/ (V),
in which
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-- 3 --
X and Y have the meaning indicated above and
Z represents halogen or the grouping -0-S0 -
or N(R2)(+~ 2
wherein
R1 represents alkyl or optionally substituted
phenyl and
R2 represents alkyl,
in the presence of a diluent and in the presence of a
base. An acid can then optionally be added onto the
compound of the formula ~I) obtained in process
variant (a) or (b).
It has furthermore been found that the new 1-(2,4-
dichlorophenyl)-1-(2,6-dihalogenobenzylmercapto)-2-
(1,2,4-triazol-1-yl)-ethanes have powerful fungicidal
properties. Surprisingly, the compounds according to
the invention exhibit a considerably more powerful action
than 1-(2,4-dichlorophenyl)-1-(2,4-dichlorobenzyl-
mercapto)-2-(1,2,4-triazol-1-yl)-ethane, which is known
from the state of the art and is the most closely related
compound chemically and from the point of view of its
action. The substances according to the invention thus
represent an enrichment of the art.
The formula (I) provides a general definition of
the 1-(2,4-dichlorophenyl)-1-(2,6-dihalogenobenzyl-
mercapto)-2-(1,2,4-triazol-1-yl)-ethanes according to the
invention. Preferably,in this formula, ~ and Y, which
may be identical or different, each represent chlorine
or fluorine. Examples of compounds of the present
invention which may be mentioned are: 1-(2,4-dichloro-
phenyl)-1-(2,6-dichlorobenzylmercapto)-2-(1,2,4-triazol-
1-yl)-ethane, 1-(2,4-dichlorophenyl)-1-(2-chloro-6-
fluorobenzylmercapto)-2-(1,2,4-triazol-1-yl)-ethane and
1-(2,4-dichlorophenyl)-1-(2,6-difluorobenzylmercapto)-
2-(1,2,4-triazol-1-yl)-ethane and salts thereof.
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If, for example, 1-chloro-1-(2,4-dichlorophenyl)-
2-(1,2,4-tria~ol-1-yl)-ethane and 2,6-dichlorobenzyl-
mercaptan are used as starting substances in process
variant (a), the course of the reaction can be represented
by the followin9 equation:
Cl ~ -CH-CH2-N ~ + H-S-CH2 ~ + ase >
,Cl r=N
Cl- ~ -CH-CH2-N J
I Cl
CH
C
If, for example, 1-chloro-1-(2,4-dichlorophenyl)-
2-(1,2,4-triazol-1-yl)-ethane, 2,6-dichlorobenzyl chloride
and thiourea are used as starting substances in process
variant (a), without isolation of the intermediate
product, the course of the reaction can be represented
by the following equation:
Cl ~ -CX-CH2-N~ ~ + Cl-CH2 ~ IS
- NaOH Cl ~ N
- --~ Cl~-CH-CH~ -N
- NaCl '~ I
_ o-C(NH2 )2
C~
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-- 5
If, for example, 1-(2,4-dichlorophenyl)-2-(1,2,4-
triazol-1-yl)-ethane-1-thiol and 2,6-dichlorsbenzyl
chloride are used as starting substances in process
variant (b), the course of the reactio~ can be represented
by the follo~ing equation:
Cl ~ CH-CH2-N\ ~ + Cl-CH2 ~ base
SH
S Cl
CH
C1
The formula (II~ provides a general definition of the
1-(2,4-dichlorophenyl)-1-halogeno-2-(1,2~4-triazol-1-yl)-
ethanes to be used as starting substances in carrying out
the process according to the invention. In this formula,
Hal preferably represents chlorine or bromine.
The 1-(2,4-dichlorophenyl)-1-halogeno-2-(1,2,4-
triazol-l-yl)-ethanes of the formula (II) are known (see DE-
OS (German Published Specification) 2,547,954 [Le A
16 750])- They are obtained by reacting the corresponding
known 1-(2,4-dichlorophenyl)-1-hydroxy-2-(1,2,4-triazol-1-
yl)-ethane (see DE-OS (German Published Specification)
2,431,407 [Le A 15 735]) with an agent which splits off
halogen, for example thionyl chloride, if appropriate in
the presence of a diluent, for example chloroform, at
temperatures between 20 and 100C.
The formula (III) provides a general definition of
the mercaptans also to be used as starting substances for
process variant (a). In this formula, X and Y pre~erably
have those meanings which have already been mentioned as
preferred for these substituents in connection with the
description of the substances of the formula (I).
Le A 19 794
~S~Z78
The mercaptans of the formula (III) are generally known compounds of
organic chemistry and are obtained in a generally customary manner, by heating
known 2,6-dihalogenobenzyl halides of the general formula
~ (VI),
in which
Hal, X and Y have the meanings indicated above,
with thiourea in the presence of a strong base, preferably sodium hydroxide
solution, and in the presence of a solvent, for example ethanol. The
mercaptans thereby formed can be reacted directly with the compounds of the
formula (II) in a one-pot reaction, without isolation (see also the
preparative examples).
The 1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)-ethane-1-thiol of
the formula (IV) to be used as a starting substance in carrying out process
variant (b) has been described (see Canadian Patent 1,091,677); for its
preparation, see the preparative examples.
The formula (V) provides a general definition of the 2,6-
dihalogenobenzyl derivatives also to be used as starting substances for process
variant (b). In this formula, X and Y preferably have those meanings which
have already been mentioned as preferred for these substituents in connection
with the description of the substances of the formula (I). Z preferably
represenl:s chlorine, bromine or iodine or the grouping -0-S02-Rl or -N(R2)3( ),
wherein R represents alkyl with 1 to 4 carbon atoms or phenyl which is
optionally substituted by alkyl with 1 to 2 carbon atoms, chlorine, bromine,
alkoxy with 1 to 2 carbon atoms or
nitro, and R2 represents alkyl with 1 to 2 carbon atoms.
The 2,6-dihalogenobenzyl derivati~es of the formula
(V) are generally known co;rpour.ds of organic chemistry.
Any of the physiologically acceptable acids can be used
for the preparation of acid addition salts of the compounds
of the formula (I). These include, as preferences, the
hydrogen halide acids (for example hydrobromic acid and,
in particular, hydrochloric acid), phosphoric acid, nitric
acid, sulphuric acid, monofunctional and bifunctional
carboxylic acids and hydroxycarboxylic acids (for example
acetic acid, maleic acid, succinic acid, fumaric acid,
tartaric acid, citric acid, sorbic acid and lactic acid),
and sulphonic acids (for example p-toluenesulphonic acid
and 1,5-naphthalenedisulphonic acid).
The salts of the compounds of the formula (I) can be
obtained in a simple manner by customary methods of salt
formation, for example by dissolving a compound of the
formula (I) in a suitable inert solvent and adding the
acid, for example hydrochloric acid, and they car be
isolated in a known manner, for example by filtration,
and if appropriate purified by washing with an inert
organic solvent.
Preferred diluents for the reaction in process variant
(a) are inert organic solvents or aprotic solvents. These
include, as preferences, ketones, such as diethyl ketone,
and in particular acetone and methyl ethyl ketone; alcohols,
such as ethanol or isopropanol; nitriles, such as propio-
nitrile, and in particular acetonitrile; hydrocarbons, such
as ligroin, petroleum ether, benzene, toluer.e and xylene;
3 and formamides, such as, in particular, dimethylformamide.
The reaction in process variant (a) is carried out
in the presence of an acid-binding agent. It is possible to
add any of the inorganic or organic acid-binding agents which
can customarily be used, such as alkali metal carbonates,
for example sodium carbonate, potassium carbonate and sodium
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-- 8 --
bicarbonate, or such as lower tertiary alkylamines,
cycloalkylamines or aralkylamines, for example triethyl-
amine, dimethylbenzylamine or dimethylcyclohexylamine;
or such as pyridine and diazabicyclooctane, as well as
alkali metal alcoholates, for example sodium methylate
or potassium ethylate, or such as alkali metal hydroxides,
for example sodium hydroxide and potassium hydroxide.
The reaction temperatures can be varied within a
substantial range in carrying out process variant (a~. In
general, the reaction is carried out at between 2C and
150C, preferably at the boiling point of the solvent,
for example between 60 and 100C.
In carrying out process variant (a) about 1 to 2
moles of the mercaptan of the formula (III) and about 1.5
and 2.5 moles of acid-binding agent are preferably employed
per mole of the compound of the formula (II). To isolate
the resultant compound of the formula (I), the reaction
mixture is filtered, and the filtrate is concentrated and
the residue is digested with an aqueous base~ The mixture
is then extracted by shaking with an organic solvent and
the reaction product is isolated in the customary manner.
If appropriate, the reaction products can be purified by
recrystallisation.
In a preferred embodiment of process variant (a)
f the invention, the process is carried out in a one-pot
reaction, that is to say without isolating the mercaptan
of the formula (III). In this case, 1.2 to 2 moles of
benzyl halide of the formula (IV), 1.2 to 2 moles of thio-
urea and 2 to 3 moles of base are preferably employed per
mole of the compound of the formula (II). The isolation of
the resultant compound of the formula (I) is effected in the
customary manner.
Possible diluents for the reaction in process variant
(b) are protic and aprotic solvents, especially those in
which SNl and SN2 reactions are carried out. These solvents
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g
include, for example~ water, alcohols, carboxylic acids,
acetone, acetonitrile, dimethylformamide, dimethylacetamide,
dimethylsulphoxide, tetramethylurea and aromatic hydro-
carbons, such as toluene.
The reaction in process variant (b) is carried out in
the presence of a base. These bases include any of the
organic and, in particular, inorganic bases which can
customarily be used, for example sodium hydroxide and
potassium hydroxide or sodium carbonate and potassium
carbonate.
The reaction temperatures can be varied within a
substantial range in carrying out process variant (b).
In general, the process is carried out at between 20 and
150C, preferably between 20 and 100C, or at the boiling
point of the particular solvent.
In carrying out the process variant (b)~ to 3 moles
of 2,6-dihalogenobenzyl derivative of the formula (V)
are preferably employed per mole of the compound of the
formula (IV). To isolate the end products, the reaction
mixture is freed from the solvent, and water and an organic
solvent are added to the residue. The organic phase is
separated of~ and worked up in the customary manner.
The active compounds according to the invention
exhibit a powerful microbicidal action and can be employed
in practice for combating undesired micro-organisms. The
active compounds are suitable for use as plant protection
agents.
~ ungicidal agents in plant protection are employed
for combating Plasmodiophoromycetes, Oomycetes, Chytridio-
mycetes, Zygomycetes, Ascomycetes, Basidiomycetes andDeuteromycetes.
The good toleration, by plants, of the active compounds,
at the concentrations required for combating plant diseases,
permits treatment of the above-ground parts of plants, of
vegetative propagation stock and seeds, and of the soil.
Le A 19 794
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-- 10 --
As plant protection agents, the active compounds
according to the invention can be employed with parti-
cularly good success for combating species of powdery
mildew, such as against the powdery mildew of cucumber
causative organism (Erysiphe cichoracearum) and the
powdery mildew of apple causative organism (Podosphaera
leucotricha).
The active compounds can be converted into the
customary formulations, such as solutions, emulsions,
suspensions, powders, dusting agents, foams, pastes,
soluble powders, granules, aerosols, suspension-emulsion
concentrates, seed-treatment powders, natural and synthetic
materials impregnated with active compound, very fine
capsules in polymeric substances, coating compositions
for use on seed, and formulations used with burning
equipment, such as fumigating cartridges, fumigating
cans and fumigating coils, as well as UL~ cold mist
and warm mist formulations.
These formulations may be produced in known manner,
for example by mixing the active compounds with extenders,
that is to say liquid or liquefied gaseous or solid
diluents or carriers, optionally with the use of surface-
active agents, that is to say emulsifying agents and/or
dispersing agents and/or foam-forming agents. In the
case of the use of water as an extender, organic solvents
can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents,
there are suitable in the main, aromatic hydrocarbons,
such as xylene, toluene or alkyl naphthalenes, chlorinated
3 aromatic or chlorinated aliphatic hydrocarbons, such
as chlorobenzenes, chloroethylenes or methylene chloride,
aliphatic or alicyclic hydrocarbons, such as cyclohexane
or paraffins, for example mineral oil fractions, alcohols,
such as butanol or glycol as well as their ethers and
esters, ketGnes, such as acetone, methyl ethyl ketone,
Le A 19 794
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-- 11 --
methyl isobutyl ketone or cyclohexanone, or strongly
polar solvents, such as dimethylformamide and dimethyl-
sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant
liquids which would be gaseous at normal temperature
and under normal pressure, for example aerosol propellants,
such as halogenated hydrocarbons as well as butane,
propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural
minerals, such as kaolins, clays, talc, chalk, auartz,
attapulgite, montmorillonite or diatomaceous earth,
and ground synthetic minerals, such as highly-dispersed
silicic acid, alumina and silicates. As solid carriers
for granules there may be used crushed and fractionated
natural rocks such as calcite, marble, pumice, sepiolite
and dolomite, as well as synthetic granules of inorganic
and organic meals, and granules of organic material
such as sawdust, coconut shells, maize cobs and tobacco
stalks.
As emulsifying and/or fGam-forming agents there
may be used non-ionic and anionic emulsifiers, such
as polyoxyethylene-fatty acid esters, polyoxyethylene-
fatty alcohol ethers, for example alkylaryl polyglycol
ethers, alkyl sulphonates, alkyl sulphates, aryl sul-
phonates as well as albumin hydrolysis products. Dis-
persing agents include, for example, lignin sulphite
waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural
and synthetic polymers in the form of powders, granules
or latices, such as gum arabic, poly~inyl alcohol and
polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic
pigments, for example iron oxide, titanium oxide and
Prussian ~lue, and organic dyestuffs, such as alizarin
dyestuffs, azo dyestuffs or metal phthalocyanine dye-
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- 12 -
stuffs, and trace nutrients, such as salts of iron,
manganese, boron, copper, cobalt, molybdenum and zinc.
The formu'ations in general contain from 0.1 to
95 per cent by weight of active compound, preferably
from 0.5 to 90 per cent by weight.
The active compounds according to the invention
can be present in the formulations, or in the various
use forms,as a mixture with other active compounds,
such as fungicides, bactericides, insecticides, acaricides,
nematicides, herbicides, bird repellants, growth factors,
plant nutrients and agents for improving soil structure.
The active compounds can be used as such, as
their formulations or as the use forms prepared therefrom
by further dilution, such as ready-to-use solutions,
emulsions, suspensions, powders, pastes and granules.
They may be used in the customary manner, for example
by watering, immersion, spraying, atomising, misting,
vaporising, injecting, brushing on, dusting, scattering,
dry dressing, moist dressing, wet dressing, slurry
dressing or encrusting.
Especially in the treatment of parts of plants, the
active compound concentrations in the use forms can be
varied within a substantial range. They are, in general,
from 1 to 0.0001% by weight, preferably from 0.5 to 0.001%.
In the treatment of seed, amounts of active compound
of 0.001 to 50 g, preferably 0.01 to lO g, are generally
employed per kilogram of seed.
For the treatment of soil, active compound concen-
trations of 0.00001 to 0.1% by weight, preferably 0.0001
3 to 0.02%, are generally employed at the place of action.
The present invention also provides a fungicidal
composition containing as active ingredient a compound
of the present invention in admixture with a solid
or liquefied gaseous diluent or carrier or in ad~ixture
with a liquid diluent or carrier containing a surface-
Le A 19 794
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-- 13 --
active agent.
The present invention also provides a method of
combating fungi which comprises applying to the fungi,
or to a habitat thereof, a compound of the present in-
vention alone or in the form of a composition containingas active ingredient a compound of the present invention
in admixture with a diluent or carrier.
The present invention further provides crops protected
from damage by fungi by being grown in areas in which
immediately prior to and/or during the time of the growing
a compound of the present invention was applied alone
or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing
a harvested crop may be improved by the present invention.
The fungicidal activity of the compounds of this
invention is illustrated by the following biotest Examples.
In these Examples, the compounds according to the
present invention are each identified by the number
(given in brackets) of the corresponding preparative
Example, which will be found later in this specification.
The known comparison compound is identified
as follows:
(A) = Cl ~ -CH-CH2-N\ ~
S xHN03
CH2 - ~ -C1
Cl
Example A
Erysiphe test (cucumber)/protective
Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkylaryl polyglycol
ether
Water: 95 parts by weight
3o The amount of the active co~pound required for
Le h 19 794
2~ 8
- 14 -
the desired concentration of active compound in the spray
liquid was mixed with the stated amount of solvent and
the concentrate was diluted with the stated amourAt of
water containing the stated amount of emulsifier.
Young cucumber plants with about three foliage leaves
were sprayed with the spray liquid until dripping wet.
The cucumber plants remained in a greenhouse for 24 hours
to dry. They were then, for the purpose of inoculation,
dusted with conidia of the fungus Erysiphe cichoracearum.
The plants were subsequently placed in a greenhouse at
23-24 degrees C and at a relative atmospheric humidity
of about 75%.
After 12 days, the infection of the cucumber plants
was determined. The assessment data were converted to
percent infection. 0% meant no infection, 100% meant
that the plants were totally infected.
The active compounds, the concentrations of the
active compounds and the results can be seen from the
following table:
T a b 1 e A
Erysiphe test (cucumbers)/protective
Active compound Infection in % at an
active compound con-
centration of 0.0005%
_
(A) 12
~1) 0
~xample B
Podosphaera test (apple)/protective
Solvent: 4.7 parts by weight of acetone
Emulsifier- 0.3 part by weight of alkylaryl polyglycol
ether
Water 95 parts by weight
The amount of active compound required for the desired
concentration of the active compound in the spray liquid
was mixed with the stated amount of solvent~ and the
concentrate was diluted with the stated amount of water
Le A l9 794
.
~5~278
- i5 -
which contained the stated amount of emulsifier.
Young apple seedlings in the 4 - 6 leaf stage were
sprayed with the spray liquid until dripping wet. The
plants remained in a greenhouse for 24 hours at 20 deg.C
and at a relative atmospheric humidity of 70%. They
were then inoculated by dusting the conidia of the apple
powdery mildew causative organism (Podosphaera leucotricha)
and placed in a greenhouse at a temperature of 21 -
23 deg. C and at a relative atmospheric humidity of about
70%.
10 days after the inoculation, the infection of
the seedlings was determined. The assessment data were
converted to % infection. 0% meant no infection; 100%
meant that the plants were completely infected.
15 m e active compounds, the concentrations of the
active compounds and the results can be seen from the
following table:
T a b 1 e B
_ _
Podosphaera test/protective
Active compound Infection in % at an
active compound con-
centration of 0.0001%
(A) 27
(1) 16
Preparative Examples
-
Example 1
Cl- ~ _ CH CH N~===N
C1~
Cl ~ x 2 HN03
606 g (3.1 mol) of 2,6-dichlorobenzyl chloride were
dissolved in 2.5 litres of ethanol and the solution was
added to 25~ g ~3.4 mol) of thiourea in 1,000 ml of ethanol.
The mixture was heated for 6 hours, whilst stirrir.g and
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under reflux, 1.5 litre of ethanol were distilled off, the
mixture was cooled to 45C and 173.6 g (4.34 mol) of sodium
hydroxide, dissolved in 342 g of water, were added drop-
wise in the course of 1.5 hours under a nitroger. atmosphere.
When the addition had ended, the mixture was subsequently
stirred at 45C for 30 minutes. 600 g (2.1 mol) of 1-
chloro-1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)-
ethane in 2 litres of ethanol were then added dropwise in
the course of 3 hours. The mixture was subsequently stirred
at 40C for 15 hours, 1.5 litres of ethanol were distilled
off at 50C _ vacuo, the mixture was allowed to cool and
4 litres of water were added. The reaction mixture was
extracted once with 4 litres of methylene chloride and
three times with 2 litres of methylene chloride each time;
the combined methylene chloride phases were washed twice
with 2 litres of water each time, dried over sodium sulphate
and concentrated by distilling off the solvent under a
waterpump vacuum. The oily residue was dissolved in 2.5
litres of ethanol, and 380 g of 1,5-naphthalenedisulphonic
acid in 2 litres of ethanol were added. The precipitate
formed was filtered off and stirred carefully in 3 litres
of sodium bicarbonate solution. The free base was ex-
tracted with 18 litres of methylene chloride. The organic
phase was concentrated by distilling off the methylene
chloride, the residue was dissolved in 3 litres of
chloroform and 66 ml (1.53 mol) of 96% strength nitric
acid were added dropwise, whilst cooling with ice. 1,000
ml of diethyl ether were then added and the precipitate
which had formed was filtered off and washed with 500 ml
3 of diethyl ether. 661 g (61.3% of theory) of 1-(2,4-
dichlorophenyl)-1-(2,6-dichlorobenzylmercapto)-2-(1,2,4-
triazol-l-yl)-ethane nitrate of melting point 156-158C
were obtained.
The above compound could also be prepared by reacting
1-(2,4-dichlorophenyl)-l-thiol-2-~1,2,4-triazol-1-yl)-
Le A 19 794
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- 17 -
ethane (for the preparation, see below) and 2,6-dichloro-
benzyl chloride in the presence of a diluent (for example
ethanol or acetone) and of a base (for example potassium
carbonate).
Precursor
.,
CH - CH2 N\ ~ x HCl
SEI
16.05 g (0.05 mol) of 1-bromo-1-(2,4-dichlorophenyl)-
2~(1,2,4-triazol-1-yl)-ethane and 4.2 g (0.055 mol) of thio-
urea in 50 ml of methanol were heated under reflux for 3
hours. The mixture was allowed to cool to 0C and 25 ml
of 2 N sodium hydroxide solution were added dropwise in
the course of 30 minutes under a nitrogen atmosphere.
~hereafter, the mixture was stirred at room temperature for
2 hours, 100 ml of water were added and the mixture was
extracted three times with 50 ml of methylene chloride
each time. ~he combined organic phases were dried over
sodium sulphate, and 30 ml of ethereal hydrochloric acid
were added. 13.8 g (87.6% of theory) of 1-(2,4-dichloro-
phenyl)-2-(1,2,4-triazol-1-yl)-ethane-1-thiol hydrochloride
of melting point 149-150C thereby crystallised out.
Le A 19 7~4
~5~27~3
- 18 -
The following examples of the general formula
Cl
Cl~CH-CH2-N
CH2~
could be obtained in a corresponding manner:
Example
No. X Y Physical properties
2 Cl F oil
3 F F oil
4 Cl Cl n20= 1,6158
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