Note: Descriptions are shown in the official language in which they were submitted.
- 1 - T~pe IIa
The present invantion relates to the u~e of certain
hydroxyalkyl-triazole~ as fungicides.
It has already been di~closad khat l-phenyl-2-
triazol-l-yl-ethanols substituted in the phenyl part have
good fungicidal properties (Qee DE-OS (German Published
Specification) 2,431,407 [Le A 15 735]). However, their
activity is not always completely satisfactory,
especially when small amounts and low concentrations are
applied.
It has now been found that the hydroxyalkyl-triazoles
of the general formula
Rl
OH
R2~3 C - ( CH2 ) m ~ R ( I )
R3n
Az
in which
Az represents triazolyl,
R represents an optionally substituted phenyl,
naphthyl or tetrahydronaphthyl radical,
Rl represents an optionally slubstituted phenyl or
cycloalkyl radical and
R2 represants hydrogen,or
Rl and R2 together, in an o-position relati~e
to one another, reprPsent an optionally eubQtituted,
multi-membsred methylene bridge, or together with the
phenyl ring represent naphthyl,
R3 represents halogen, alkyl, alkoxy or halogeno- :
alkyl,
n rapresents 0, 1, 2 or 3~ the substituants R3 being
selected independently when n i8 2 or 3, and
: m represents 0 or 1,
and physiologically acceptable acid-addition salta there-
of have good fungicidal properties.
Le A 19 636
~5~253
-- 2 --
Accorclingly 9 the present invention provideQ a
fiungicidal composition containing as active ingredient
a compound of the formula (I), or a physiologically
acceptable acid-addition salt thereof, in admixture with
a solid or liquafied gaseous diluent or csrrier or in
admixturo with a liquid diluent or carrier containing a
surface-active agent.
The invention also providas a method of combating
fungi which compri~es applying to the fungi, or to a
habitat thereof~ a compound of the formula (I), or a
physiologically acceptable acid-addition Ralt thereof,
alone or in the form of a composition containing as
active ingredient such a compound or qalt, in admixture
with a diluent or carrier.
Surprisingly, th~ hydroxyalkyl-triazoles of thc
formula (I) which can be used according to the invention
exhibit a b~tter fungicidal activity than the substitut-
ed l-phenyl-2-triazol-1-yl-ethanols known from the state
of the art, which are closely related compounds chem-
cally and from the point of view of their action. The
substances which can be used according to the inYention
thus represent an enrichment of the art.
Preferred hydroxyalkyl-triazoles of the formula
(I) which can be used according to the invention are thoee
in which
Az repr~santq 1,2,4-triazol-1-yl or 1,2,4-triazol-4-yl,
R reprosents optionally substituted phenyl, n2phthyl
or tetrahydronaphthyl, the or each substituent
being selected from halcgen (especially fluorine,
chlorine and bromine), straight-chain or branchad
alkyl and alkoxy with in either caqe 1 to 4 carbon
ato~s and halogenoalkyl with 1 to 4 carbon atoms and
up to 5 halogen atoms (e~pecially with 1 or 2 carbon
atoms and up to 3 identical or different hslogen
atome, preferred halogens being fluorine and chlorin~,
Le A 19 636
~L4~ii3
and trifluoromsthyl being mentioned as an example),
R r~presents optionally substituted phenyl or
cycloalkyl with 3 to 7 carbon atoms, the or each
substituent being selected from halogen (especially
fluorine, chlorine or bromine), alkyl with 1 to 4
(aspecially with 1 to 2) carbon atoms and alkonyl
with 2 to 4 carbon atoms, and
R2 r2prssents hydrogen9 or Rl and R~ together, in an
ortho-position ralativa to one another, represent
an optionally mono~ubstituted or polysubstitutcd
methylene bridge with 3 to 5 methy~ene groups, the
or each substituent being selected from halogen
(especially fluorine7 chlorine or bromine) and alkyl
with 1 to 4 (especially with 1 to 2) carbon atome,or
together with the phenyl ring represent naphthyl,
R3 represents halogen (especially fluorine, chlorine
or bromine), straight-chain or branched alkyl or
alkoxy with in aither case 1 to 4 carbon atoms, or
halogenoalkyl with 1 to 4 carbon atoms and up to
5 halogen atomR (especially with 1 or 2 carbon atoms
and up to 3 identical or different halogen atoms,
preferr~d halogens being fluorine and chlorine, and
trifluoromethyl being mentioned as an example),
n represents 0, 1 or 2 and
m represents n or 1.
Very particularly preferred compounde of the formula
(I) are thos~ in which Az has the preferrsd meaning
indicated above,
R represents phenyl which is optionally mono-
substitutsd or disubstituted, by identical or
differ~nt substituents, by chlorine, fluorine or
methyl, or naphthyl or tetrahydronaphthyl;
Rl repreqents phenyl, cyclopentyl or cyclohexyl,
and thcse radicals can optionally be monosubstituted
or disubstituted by chlorine9 bromine, fluorine,
mothyl, ethyl, isopropyl or isopropenyl; and
Le A 19 636
~5~53
-- 4 --
R2 represents hydrogen; or R and R~ together, in
anortht,-position relative to one another, reprasent
a tri-, tetra- or penta-methylene bridge, which is
optionally substituted by chlorine or methyl, or
togethar with the phenyl ring represent naphthyl;
R3 represents chlorine, fluorine or methyl; n represent~
O or l; and m represents 0 or 1.
The following compounds of tha general formula (I)
(Az in each case representing 1,2,4- or 1,3,4-triazol-1-yl)
may be mentioned specifically, in addition to the compounds
mention~d later in the proparative examples:
CHz
n ~z
R R1 R2 R3 m
Cl
~Cl 4~) H - O
~Cl 4- <~ H - O
4-~ H - O
4-~ H - O
Cl
4-@ H - O
Cl~ 4-~ H -- O
Le A 19 636
53
-- 5 --
f~ Rl R2 R3 m
n
~Cl 4-~ H - O
F Cl 3,4-(CH2)3- - O
~3 4~-CH3 H - O
Cl, Cl
-OE) 4~ H - O
F~ Cl
-~ 4-:~ H - 0
~ 4~CH3 H - 0
Cl~ 4~0CH3 H - 0
C1 4~!C(CH3 )3 H - O
Cl
~F 4~-Cl H - 0
_~ Cl H - O
~Cl 3,4-(CH2 )~- -
4~Cl H - 0
~Cl 4~-Cl H - 0
4~ H - 0
,Cl Cl
4~-C1 4~ H - O
Cl Cl
~-Cl 4~> H - O
L~ A 19 636
,.
`
~5~53
R Rl F~2 R3 m
_ _ _ n
,~ 4~ H - O
4~ H ~ O
Cl
~-Cl 4- ~ H - O
Cl 3,4-(CH2 ~ O
Cl~ 3,4-(CH2 ),~, - O
~Cl 4-~ H - O
~-F 4~)-F H - O
~F 4- (~> H - O
Cl 4~ H - O
~F 4~ H - O
Cl
~Cl 4~Cl H - Q
C~-F 4~> H - O
~})-Cl 4- <~ H - 1
~ 4 ~) H - 1
Cl,
Cl~ ~ H ~ 1
-~ 4-@ H - 1
Cl
Le A 19 636
- 7 -
R Rl R2 R3n m
Cl 4- ~ H
-~ 4-~ H - 1
4~ C~I3 H
~' 4~C2 Hg H - 1
F` 4~C3 H7 -i H
Fc~l~ 4~) C~CH2 H - 1
-~ 4~)-CH3 H
Cl~ 4~C2 H5 H
Cl~ 4-~C3 H7~ -i H
Cl~ 4~> C~ H - 1
~3-C1 4-
~-Cl 3,4-(CH2 )3- _
~Cl 3,4-(CH2 )~
~ 4~-Cl H
j~F 4~ H - 1 :
~3 4~Cl H
Le A 19 636
~5'~3
- a
R ~1 R2 R3n m
Cl~F 4~oc~
~Cl 4~C H - 1
4~-C1 4~ H
Cl
4~> 4~ H - 1
Cl
~-Cl 4~Cl H - 1
F 4C~) H
~)-F 4~)-Cl H - 1
Cl Cl
~-Cl 4~ H
Cl Cl
~)-Cl 4~ H - 1
Cl Cl
~ 4~ H
Cl Cl
~) 4~-Cl H
Cl'
Cl
-$~Cl 4-~Cl H
4~Cl H - 1
~) 4 3 H - 1
,~ 4-~ H - 1
L~ A 19 636
.
53~
Rl R2 R3ll m
Cl
_ ~ Cl 4- ~ 3-l - 1
Cl
3,4-(CH2)4-
Cl
-~) 3,4-(CH2)3-
Cl
Cl~
- ~ Cl 4 ~ H
; _ ~ F 4 ~ F H
- ~ F 4 ~ H
The active compounds of the :Eormula (I~ and acid addition salts
thereof have not hitherto been described in the literature. I-lowever, the sub-
stances, their preparations and medicinal use are the subject of our Canadian
Patent Applications 340~546 LLe A 19 272] ~nd 340,547 ILe A 19 273] both of
23.11.1979. They can be prepared by the processes described in these applica-
tions, by
~a) reacting triazolylmethyl phenyl ketones of the general formula
R ~ ,_ 0
R3
in which Az, Rl, R2, R3 and n have the meanings ~ndicated above,
"-'
.' ,
.
;i3
- 10 -
with a Grignard compound of the general formula
R ~ (CH~ ~m ~ Mg - X ( III),
in which
R and m have the meanings indicated above and
X reprsssnt~ halogen, e~pecially chlorine or
bromine,
in the prcsence of a sGlvent customary for a Grignard
reaction, praferably an ether, at a tsmperature between
30 and 80C, or
(b) reacting l-halogeno~alkyl alcohols of the general
formula
R~ OH
R2 ~ C - (CH2)~ - R (IV),
R3n l H2
y
in which
R, Rl, R2, R3, n and m have the meanings indicated
above and
Y represents halogen, e~pecially chlorine or bromine,
with triazole, if appropriate in the presence of an acid-
binding ag~nt, for example an exce~ of triazole, and if
appropriatc in ths presence of an inert organic aolvent ~
fo~ sxample acetonitrile, at temperature~ betweon 30n and
200C, preferably at the boiling point of tho colvent.
In some cases, it proves advantageous to employ the
triazoles in the form of their alkali metal ~alts, such
as the 30dium salt or potaa~ium salt.
The actiYa compounds to be used according to the
invention in which the index m rapre~cnts 0 can al~o be
obtained by a furthar process, which, however~ has al80
Le A 19 636
, . , - : . .
i%53
been described in published European Patent Application Serial No. 0,017,080, by
(c) reacting oxiranes of the general formula
Rl
~ ~ R V
in which R, Rl, R2, R3 and n have the meanings indicated above, with triazole
in the presence of an alkali metal alcoholate, for example sodium methylate,
and in the presence of an inert organic solvent, for example dimethylformamide,
at temperatures between 30 and 100C.
The triazolylmethyl phenyl ketones of the formula II have not
hitherto been described in the literature. However, they can be prepared in a
generally customary and known manner by reacting corresponding phenacyl halides
~that is to say ~-halogenoacetophenone derivatives) with triazole in the
presence of a diluent, for example dimethylformamide, and in the presence of an
acid-binding agent, especially an excess of triazole, at temperatures between
20 and 80C.
The Grignard compounds of the formula III are generally known com-
pounds of organic chemistry.
The l-halogeno-alkyl alcohols of the formula IV have not yet been
described in the literature. However, they can be prepared in a generally
customary and known manner, by reacting corresponding phenacyl halides with
Grignard compounds of the formula III according to process (a) above.
The oxiranes of the formula V have not yet been described in the
literature. They are also the subject of the abovementioned European Patent
Application No. 0,017,080, and can be
obtained by reacting corresponding ketonea eith~r with
dimethyloxosulphonium methylide in a manr.er which is
in itself known in tha presence of a diluent, for examplo
dimethylsulphoxide, at temperatures betwaen 20 and 80C,
or with trimethylsulphonium mathyl sulphate in a manner
which is in itself known in the presence of a two-phase
system and if appropriate in tha presencs of a phase
transfer catalyst, at temperatures between O and 100C.
Any of the physiologically acceptable acids can be
used for the preparation of acid addition salt~ of th~
compounds of the fDrmula (I). These acids include, as
preferences, hydrogen halide acids tfor example
hydrobromic acid and in particular hydrochloric acid),
phosphoric acid, nitric acid, sulphuric acid, mono-
functional and bifunctional carboxylic acids and hydroxy-
carboxyl:ic acids(for example acetic acid, maleic acid,
succinic acid, fumaric acid, tartaric acid, citric acid,
salicylic acid, sorbic acid and lactic acid) and
sulphanic acid~ (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 salt forma-
tion methcds, for example by dissolving a compound of the
formula (I) in a suitable inert solvent and adding the
2~ acid, for examplc hydrogen chloride, and they can be iso-
lated in a known manner, for example by filtration, and
if appropriate purified by washing with an inert organic
solvent.
The active compound~ to be used according to the
invention exhibit a powerful microbicidal action end can
be employed in practice for combating undesired micro-
organisms. The active compounda are suitable for use as
plant protection agents.
Fungicidal agents in plant protection ars cmployed
for combating Pla~modioohoromycet~, Ocmycete3,
Le A 19 636
~5~i3
- 13 -
Chy~ridi~rnycetes, Zygomycetsq9 Ascumycstes,
and D~utcromyc~t~s.
The good toleration, by plants, of the active compoun~s,
at thc ~oncentrations requi~2d for combati~g plant
di~ea~s, p~rmits treatment of above-ground parts o~
plants, of vegstativ~ propagation tock and ~eeds, and
of the soil.
As plant protcction agents, the active compounds
according to th~ invention can be u~ed with particularly
good succ~ss for combating Podosphaera, Uromycc~ and
Erysiphe sp~cies, such as the powdery mildcw of apple
causative organism (_odosphaera l~ucotricha), the bean
rust causative organism (Uromyce~ phaseoli) and the
powdery mild~w of cucumber causative organism (EryQiphe
cichoracearum). Good successes are also achieved in
combating cereal diseases, such as powdery mildew of
cereal and cereal rust.
When certain amounts are applied, the active com-
pounds according to the inv~ntion al~o exhibit a growth-
regulation action.
The active compounds can be converted into thecustomary formulations, such as solutions, emulsions,
suspensions, powders, dusting agent~, 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 ULV 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 carriers9 optionally with the use of surface-active
Le A 19 636
53
- 14 -
agents, that is to say emulsifying agents and/or dispersing
agents and/or foam-forming agents. In the case Or the
use of water as an extenderg 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
aromatic or chlorinated aliphatic hydrocarbons J 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, ketones, such as acetone~ methyl ethyl ketone,
methyl isobutyl ~etone or cyclohexanone, or strongly
polar solvents, such as dimethylformamide and dimethyl-
sulphoxide~ as well as water.
By lique.fied 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, quartz,
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 foam-forming agents there
may be used non-ionic and anionic emulsifiers, such
as polyoxyethylene-fatty acid esters, polyoxyethylene-
Le A 19 636
~L5'~i3
fatty alcohol ethers 3 ~or example alkylaryl polyglycolethers, alkyl sulphonates b alkyl sulphates, aryl sul-
phonates as well as albumin hydrolysis products. Dis-
persing agents include9 for example9 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, polyvinyl 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 Blue, and organic dyestuffs, such as alizari~
dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs,
and trace nutrients, such as salts of iron, manganese,
boron, copper, cobalt, molybdenum and zinc.
The formulations 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 9 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 ~urther dilution~ such as ready-to-use solutions,
emulsionsl suspensions, powders, pastes and granules.
m ey may be used in the customary manner, for example
3o by watering, immersion, spraying, atomi~ing, misting,
vaporising, injecting9 brushing on3 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
~ `:
` Le A 19 636
5~3
- 16 -
varied within a substantial range. They are, in general,
from 1 to 0.0001~ by weight3 preferably from 0.5 to
O . 001 % .
In the treatment of seed, amounts of active compound
of in general 0.001 to 50 g~ preferably 0.01 to 10 g3 are
employed per kilogram of seed.
For the treatment of soil; active compound concen-
trations of in general 0.00001 to 0.1% by weight, preferably
0.0001 to 0.02%, are employed at the place of action.
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 i~vention.
The fungicidal activity of the compounds of this
invention is lllustrated 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 compounds are identified as
follows:
(A) ~ CH-CH2-N~
(B) Cl ~ CH-CHz-~
(C) Br ~ CH-CH2~N
(D) Cl- ~ CH-CH2-N
Le A 19 636
.
~5~3
- 17 -
(E) H3C ~ CH-CH2-N\ J
(F) Cl ~ CH-CH~-~ J x 1/2
Cl SO~H
Example A
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 oP solvent, and the con-
centrate was diluted with the stated amount of water
which contained the stated amount of emulsifier.
Young apple seedlings in the 4 - 6 leaf ~tage were
sprayed with the spray liquid until dripping wet. m e
plants remained in a greenhouse f~or 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 ( ~ leuaatriaha) and
placed in a greenhouse at a temperature o~ 21 23 deg.
C and at a relative atmospheric humidity of about 70~.
lO days after the inoculation, the infection of the
seedlings was determined. The assessment data were con-
verted to % infection. 0% meant no infection; lO0~ meant
that the plants were completely infected.
In this test 3 for example, the following compounds
; showed a very good action which was significantly superior
to that of the compounds (A) and (B) known from the prior
art: compounds (l) and (3)~
: : '
Le A l9 636
:
.
~5~53
- 18 -
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
The amount of the active compound required ~or the
desired concentration of active compound in the spray
liquid was mixed with the stated amount of solYent and
the concentrate was diluted with the stated amount o~
water containing the stated amount of emulsi~ier.
Young cucumber plants with about three foliage leaves
were sprayed with khe spray liquid until dripping wet.
The cucumber plants remained in a greenhouse for 24 hours
to dry. They were then3 for the purpose of inoculationJ
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 infectlon. 0% meant no infection; 100% meant
that the plants were totally infected.
In this test, for example, the following compound~
showed a very good action which was superior to that of the
compounds (C) and (D) known from the prior art: compounds
(1), (7), (10), (12), (14) and (5).
Example C
~ test (bean rust)~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 ~or the desired
concentration of active compound in the spray liquor
Le A 19 636
. ~...... .
5~53
- 19 -
was mixed with the stated amount of the solvent and the
concentrate was diluted with the stated amount of water
which contained the stated amount of emulsifier.
The young bean plants, which were in the 2-leaf
stage; were sprayed with the spray liquor until dripping
wet. The plants remained in a greenhouse for 24 hours
at 20-22 deg.C and a relative atmospheric humidity of
70~ in order to dry. They were then inoculated with an
aqueous uredospore suspension of the causative organism
of bean rust ( ~ phaseoli) and incubated for 24
hours in a dark humidity chamber at 20 - 22 deg.C and
100% relative atmospheric humidity.
The plants were then set up in a greenhouse under
intensive illumination for 9 days at 20 - 22 deg.C and
a relative atmospheric humidity of 70-80%.
10 days after the inoculation, the infection of
the plants was determined. The assessment data were
converted to % infection. 0% denoted no infection and
100% denoted that the plants were completely infected.
In this test, for example, the following compounds
showed a very good action which was significantly superior
to that of the compound (E) know~ from the prior art:
(12),(14) and (5).
~e~
Shoot treatment test/powdery mildew of cereals
(leaf-destructive mycosis)/protective
To produce a suitable preparation of active compound~
0.25 part by weight of active compound was taken up in
25 parts by weight of dimethylformamide and 0.06 part
3 by weight of alkylaryl polyglycol etherg 975 parts by
weight o~ water were then added. The concentrate was
diluted with water to the desired final concentration
of the spray liquor.
To test for protective activity3 single-leaved
young barley plants of the Amsel variety were sprayed
Le A 19 636
~S~53
- 20 -
with the preparation of active compound until dew-moist.
After drying, the barley plants were dusted with spores
of ~ ~ var. hordei.
After 6 days' dwell time of the plants at a tempera-
ture of 21-22 deg.C and 80-90~ atmospheric humidity the
occurrence of mildew pustules on the plants was evaluated.
The degree of infection was expressed as a percentage
of the infection of the untreated control plants. 0%
denoted no infection and 100% denoted the same degree
of infection as in the case of the untreated control.
The active compound was the more active, the lower was
the degree of mildew infection.
In this test, for example, the following compound~
showed a very good action which was significantly superior
to that of the compounds (D) and (F) known from the prior
art: (1), (~), (7), (10), (12), (14) and (5).
Exa~ e E
Shoot treatment test/cereal rust
(leaf-destructive mycosis)/protective
To produce a suita~le preparation of active compound,
0.25 part by weight of active compound was taken up in
25 parts by weight of dimethylformamide and 0.06 part
by weight of alkylaryl polyglycol ether and then 975
parts by weight of water were added. The concentrate
was diluted with water to the desired final concentration
of the spray liquor.
To test the protective activity, one-leaved young
wheat plants of the Michigan Amber variety were inoculated
with a uredospore suspension o~ Puc ~econdita in
0.1% strength aqueous agar. After the spore suspension
had dried on, the wheat plants were sprayed with the
preparation of active compound until dew-moist and were
placed, for incubation, in a greenhouse for 24 hours
at about 20 deg.C and 100% relativa atmospheric humidity.
After 10 daysl dwell time of the plants at a tempera-
Le A 19 636
53
- 21 -
ture of 20 deg.C ~nd 80-90% atmospherio humidity, the
occurrence o~ ru~t pustules on the plant was evaluated.
m e degree of infection wa~ expre~sed a~ a percentage
of the infection of the untreated control plants. 0~
denoted no infection and 100% denoted the same degree
of infection as in the case of the untreated control.
The active compound was the more active, the lower wa~
the ~egree of rust infection.
In this test, for example, the following compounds
showed a very good action which was significantly superior
to that of the compound (D) known from the prior art:
(8), (12)J (14) and (5).
Example 1 and 2
~-C -CH 2 ~-Cl
~ N
Az = - ~ ¦ = Example l
/==N
Az - -N\= ¦ ~ Example 2
N
Process (b)
7.6 9 (0.11 mol) of 1,2,4-triazola were added to a
901ution of 3.5 9 (0.065 mol) of sodium methylate in
18 ml of methyl alcohol; a solution of 19.5 9 $0.05 mol)
2n of 2-(4-biphenylyl)-3-chloro-1-(2,4-dichlorophonyl)-
propan-2-ol in 38 ml of dimethylformamid~ was then add~d
dropwis~ and the mixture was heated to 70C for 90 minutos.
The solvents were removed in v;acu~-in a rotary avaporator
and the r~aidue was stirrad with water. Th~ resulting
Le A 19 636
~5~53
22
crystals were waahed with diethyl ether and r~crystalli~d
from acetonitrile. 2.2 9 of 2-(4-biphenylyl)~ 2,4-
dichlorophsnyl)-3-(1,2,4-triazol-4-yl)-propan-2-ol of
mclting point 260C were obtained.
Ths acetonitrile solution (mother liquor) was
evaporated and the re~ulting crystals were wa~hed with
diathyl ether and ethyl acetate. 6.5 g of ~-(4-
biphonylyl)-1-(2,4~dichlorophenyl)-3-(1,2,4-triazol-1-
yl)-propan-2-ol of melting point 124C were obtained.
Preparation of the startinq mstorial
~ C-C~2-~-Cl
Cl
69.3 9 (0.3 mol) of 4-phenylphenacyl chloride were
added in portions to a solution of 0.6 mol of 2,4-
dichlorobenzyl-magneaium chloride, obtained from 15.9 9
~0.65 mol) of magnesium and 117.3 g (0.6 mol) of 2,4-
dichlorobenzyl chloride in 300 ml of ether. The reaction
mixture was then poured onto aqueous ammonium chloride
solution and the ~ther phase was separated off, washed
with water, dried over sodium sulphate and evaporated.
The oil which remainad wa~ extracted with petroleum eth~r
and the petroleum ethar solution waa evaporated. Th~
crystals were filtered off and dried. 62 g (53~ of
theory) of 2-(4-biphenylyl)-3-chloro-1-(2,4-dichloro-
phenyl)-propan-2-ol of m21ting poi'nt 84C w~re obtained.
~ 4
~-C-C~2~
AZ
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f~5~
- 23 -
f~N
A2 ~ Example 3
'N=J '
~ N
AZ = -N I = Example 4
~=:N
Process (b)
,
38.3 9 (0.56 mol) of 1,2,4-triazole were added to a
solution of 17.9 9 (0.33 mol) of sodium methylate in
90 ml of methyl alcohol; a solution of 82 9 (0.254 mol~
of 2-(4-biphenylyl)-3-chloro-1-phenyl-propan-2-ol in
191 ml of dimethylformamide wae then addsd dropwise and
the mixture was heated to 60C for 90 minutes. The sol-
vents wer~ removed in vacuo in a rotary evaporator; ther~siduo was dissolved in methylene chloride and the methy-
lane chloride solution was washed with water. The
methylene chloride solution wa~ dried o~er sodium sulphat~
and filtered and the filtrate was concentrated in vacuo.
The resulting oil was separated by chromatography.
13.8 9 of 2-(4-biphenylyl)-1-phe~nyl-3-(1,2,4-triazol-1-yl~-
propan-2-ol of melting point 124C and 2.7 9 of 2-(4-
biphenylyl)-l-phenyl-3-(1,2,~-triazol-4-yl)-propan-2-ol
of molting point 246C wero obt~lined.
Preparation of the startinq mat~rial
~ ~ -C-CH2
CH2
Cl
115.3 9 (0.5 mol) of 4-phonylph~n~cyl chlnrido w~re
~dded in portions to a solution of benzyl-megne~ium
chlorid~, obtainod from 24.3 9 (1 mol) of magn~ium ~nd
115 ml (1 mol) of b~nzyl chloride in 150 ml of diethyl
~ther. The reaction mixture was warmsd und~r reflux
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L~ 5 3
_ 24 _
for 90 minut~s and then poured onto aqueouc ammonium
chloride solution. The ether phase was separatad off,
washed with water, dried over sodium sulphata snd con-
centratsd. The oil which remained was made to cryetQl-
lise by stirring with petroleum ether. 50 9 (31o of
thaory) o~ 2-(4-biphenylyl)-3-chloro-1-phenyl-propan-2-
ol of melting point 96C wera obtained.
~e.~
~ ~ -C-<~-Cl
~1 C~2
,N~
N
Proc0ss ~b)
14.96 9 (0.22 mol) of triazole were added to a
solution of 7.02 9 (0.13 mol) oF sodium methylate in
36 ml of methyl alcohol. A solution of 40 9 tO.1 mol)
of 1-(2'-chloro-4-biphenylyl)-2-chloro-1-~4-chloro-
phenyl)-ethanol in 75 ml of dimethylformamide wa~ then
added dropwise and the reaction rnixture was heated to 70C
for 3 hours. It was concentrated by distilling off th0
solvents in vacuo, and the re~idue was stirred with water7
The crystals which remained were washed with ac~tonitrile
and recrystallieed. 16.2 9 (400D of theory) of 1-(2'-
chloro-4-biphenylyl)-1-t4-chlorophenyl)-2-(1,2,4-tri~ol-
l-yl)-ethanol of melting point 1~0C were obtained.
PreparatiDn of tho ~tarting mat~rial
~ ~ O ~
75 g of 1-(2'-chloro-4-biphenylyl)-2-chloro-1-
(4-chlorophenyl)-ethanol were obtained from 10.69 9
(0.44 mol~ of magneQium, 76.6 9 (0.4 mol) of 4-bromo-
Le A 19 636
~5~25~
- 25 .
ehlorobsnzane and 53 9 (0.2 mol) of 4-(2-ehlorophenyl)-
phenaeyl ehlorido analogou~ly to Example 1.
~ - COCH2 Cl
29~.7 9 (2.2 mol) of aluminium chloride wsre
introdueed in portions into a solution of 377 9 (2 mol)
of 2-ehlorobiphenyl in 160 ml (2 mol) of ehloroaeetyl
ehloride and 1,000 ml of methylene ehloride. After 18
hours, the reaction mixture was poured onto iee and hydro-
ehloric acid. The organic phas0 was separated off,
washed, dried over sodium ~ulphate and concentrated in
vaeuo by distilling off tha solvant. The oil whieh
r~mained was purifiad by di~tillation. 478.7 g (90OD of
theory) of 4-(2-chlorophenyl)-phenacyl ehloride of melt-
ing point 47C were obtained.
The follnwing eompounds of the general formula
R~ OH
R2 ~ C (Cll2)m - R (I)
R3n l H2
Az
eould be obtained analogously to Examples 1 to 5:
Le A 19 636
- 26 _
Meltin~
point( C)
Example R Rl R R3n Az m tive index
No .
~ . _ , _ .
r=~N
6 ~ Cl 4 ~ H ~ 1 250
f==N
7 ~ -Cl 4 ~ \N _1 1 104
8 ~ -Cl 4 ~ -Cl H - -N I 1 144
Cl~_ ,- N
9 ~ -Cl 4~2i H - N I 1 175
~ Cl 4 ~ ,~ N 1 nD:1.5992
11 ~ Cl 4~ ~ -Cl H --N~ I 1 160
r==N
12 ~ Cl 4 ~ -Cl H - -N ~ 0 189
13 ~ -F 4 ~ Cl H _-N I 0 217
Cl ~ 4 ~ Cl H _ -N I 0 144
- ~ 4 ~ H - -N ~ 0 164
F , - N
16 ~ 4 ~ H - -N I 0 170
1 7 ~> 4 - ~ H -- N~ ~J O 1 6 0
Cl ~N
18 _~ 4_~ H - -N 1 0 220
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