1-(2-PHENYLETHYL)-TRIAZOLIUM SALTS AND THEIR USE AS FUNGICIDES

TRADUCTION NON-DISPONIBLE

English Abstract

ABSTRACT OF THE DISCLOSURE
The present invention relates to certain new fungicidal 1-(2-
phenylethyl)-triazolium salts of the formula
<IMG>
in which the phenyl and triazole rings may be substituted, in which R'
is -O-R2, -S(O)m-R3 or -O-CO-R4 wherein R2, R3 and R4 are optional sub-
stituted hydrocarbon substituents and m is 0, 1 or 2, and in which Z?
is an equivalent of an anion of a non-phytotoxic acid. The compounds
are prepared by reaction of a 1-phenyl-2-triazolyl-ethyl derivative with
a halide in the presence of a diluent, and the halide in the resulting
triazolium halide is optionally replaced by another anion in a manner
which is in itself known. As plant protection agents, the active compounds
according to the invention can be employed particularly successfully for
combating species of Venturia, for combating powdery mildew fungi, and
powdery mildew of cereals.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A 1-(2-phenyl-2-substituted-ethyl)-substituted triazolium salt
of the formula
<IMG> (I)
in which
R each independently is halogen, alkyl, alkoxy, alkylthio, alkyl-
sulphonyl, halogenoalkyl, nitro, cyano, or phenyl or phenoxy,
either of which may optionally carry one or more substituents
selected independently from halogen, cyano, nitro and halogeno-
alkyl with up to 2 carbon atoms and up to 3 identical or differ-
ent halogen atoms;
R1 -O-R2,-S(O)m-R3 or -O-CO-R4;
R2 is alkyl, alkenyl, alkynyl, cycloalkyl, or aryl, arylalkyl or
arylalkenyl, the three last-mentioned groups being optionally
substituted in the aryl nucleus by halogen, cyano, nitro, amino,
alkyl with 1 to 4 carbon atoms, halogenoalkyl with up to 2 carbon
atoms and up to 3 identical or different halogen atoms, or
phenoxy which is itself optionally substituted by halogen;
R3 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl,
arylalkyl or arylalkenyl, the three last-mentioned groups being
optionally substituted in the aryl nucleus by halogen, cyano,
nitro, amino, alkyl with 1 to 4 carbon atoms, halogenoalkyl with
up to 2 carbon atoms and up to 3 identical or different halogen
atoms, or phenoxy which is itself optionally substituted by
halogen;
R4 is alkyl, alkenyl, alkynyl, cycloalkyl, or aryl, arylalkyl or
arylalkenyl, the three last mentioned groups being optionally
substituted in the aryl nucleus by halogen, cyano, nitro, amino,
alkyl with 1 to 4 carbon atoms, halogenoalkyl with up to 2 car-

bon atoms and up to 3 identical or different halogen atoms, or
phenoxy which is itself optionally substituted by halogen; or
R4 represents halogenoalkyl, phenoxyalkyl which is optionally
substituted in the phenyl part by halogen, amino, cyano, nitro
or alkyl with 1 or 2 carbon atoms, or R4 represents amino, alkyl-
amino, dialkylamino or alkyl-alkylcarbonylamino, or phenylamino
which is optionally substituted in the phenyl part by halogen,
nitro or cyano;
R5 is alkyl optionally substituted by alkylcarbonyl with 1 to 4
carbon atoms in the alkyl part, phenyl or benzoyl, the phenyl or
benzoyl themselves being optionally substituted by nitro, cyano,
alkyl with 1 to 4 carbon atoms, halogen, alkylsulphonyl with 1
to 4 carbon atoms, alkoxy with 1 or 2 carbon atoms, alkylthio
with 1 or 2 carbon atoms, halogenoalkyl with up to 4 carbon atoms
and up to 5 halogen atoms, or phenyl or phenoxy, either of which
may optionally carry one or more substituents selected independ-
ently from halogen, cyano, nitro and halogenoalkyl with up to 2
carbon atoms and up to 3 identical or different halogen atoms;
n is 0, 1, 2, 3, 4 or 5;
m is 0, 1 or 2; and
Z is an equivalent of an anion of a non-phytotoxic acid.
41

2. A compound according to claim 1, in which
R each independently is halogen, nitro, cyano alkyl
with 1 to 4 carbon atoms, alkylsulphonyl with 1 to
4 carbon atoms, alkoxy with 1 or 2 carbon atoms,
alkylthio with 1 or 2 carbon atoms, halogenoalkyl with up
to 4 carbon atoms and up to 5 halogen atoms, phenyl,
phenoxy, or phenyl or phenoxy carrying at least
one substituent selected from halogen, cyano, nitro,
and halogenoalkyl with up to 2 carbon atoms and up
to 3 independent halogen atoms:
R2 is alkyl, alkenyl or alkynyl each with up to 4
carbon atoms; cycloalkyl with 5 to 7 carbon atoms;
or aryl with 6 to 10 carbon atoms, or arylalkyl or
arylalkenyl with 6 to 10 carbon atoms in the aryl
part and up to 4 carbon atoms in the alkyl or
alkenyl part, the aryl, arylalkyl or arylalkenyl
groups being optionally substituted by halogen,
cyano, nitro, amino, alkyl with 1 to 4 carbon atoms,
halogenalkyl with up to 2 carbon atoms and up to
3 independent halogen atoms, phenoxy or halophenoxy;
R3 is hydrogen; alkyl, alkenyl or alkynyl each with
up to 4 carbon atoms; cycloalkyl with 5 to 7 carbon
atoms; or aryl with 6 to 10 carbon atoms, or
arylalkyl or arylalkenyl with 6 to 10 carbon atoms
in the aryl part and up to 4 carbon atoms in the
alkyl or alkenyl part, the aryl, arylalkyl or
arylalkenyl groups being optionally substituted
Le A 18 115 42

by halogen, cyano, nitro, amino, alkyl with 1 to
4 carbon atoms, halogenoalkyl with up to 2 carbon
atoms and up to 3 independent halogen atoms, phenoxy
or halophenoxy;
R4 is alkyl, alkenyl or alkynyl each with up to
4 carbon atoms; cycloalkyl with 5 to 7 carbon
atoms; aryl with 6 to 10 carbon atoms, or arylalkyl
or arylalkenyl with 6 to 10 carbon atoms in the
aryl part and up to 4 carbon atoms in the alkyl
or alkenyl part, the aryl, arylalkyl or arylalkenyl
groups being optionally substituted by halogen,
cyano, nitro, amino, alkyl with 1 to 4 carbon atoms,
halogenoalkyl with up to 2 carbon atoms and up to
3 independent halogen atoms, phenoxy or halophenoxy;
halogenoalkyl with 1 to 2 carbon atoms and 1 to 5
halogen atoms; phenoxyalkyl with 1 or 2 carbon
atoms; phenoxyalkyl with 1 or 2 carbon atoms in
the alkyl part and optionally substituted in the
phenyl part by halogen, amino, cyano, nitro or alkyl
with 1 or 2 carbon atoms; amino; alkylamino, di-
alkylamino or alkyl-alkylcarbonylamino with 1 to
4 carbon atoms in each alkyl part; phenylamino; or
phenylamino substituted by halogen, nitro or cyano;
R5 is alkyl with 1 to 6 carbon atoms optionally sub-
stituted by alkylcarbonyl with 1 to 4 carbon atoms
in the alkyl part, phenyl or benzoyl, the phenyl
or benzoyl themselves being optionally substituted
by nitro, cyano, alkyl with 1 to 4 carbon atoms,
Le A 18 115 43

halogen, alkylsulphonyl with 1 to 4 carbon atoms, alkoxy with 1
or 2 carbon atoms, alkylthio with 1 or 2 carbon atoms, halogeno-
alkyl with up to 4 carbon atoms and up to 5 halogen atoms, or
phenyl or phenoxy either of which may optionally carry one or
more substituents selected independently from halogen, cyano,
nitro and halogenoalkyl with up to 2 carbon atoms and up to 3
independent halogen atoms;
n is 0, 1, 2 or 3; and
Z is an equivalent of a fluoride, chloride,bromide, iodide,
nitrate, sulphate, phosphate, acetate, propionate, glycollate,
lactate, malonate, succinate, maleate, fumarate, tartrate,
citrate, benzoate, methylsulphonate, ethylsulphonate, p-toluene-
sulphonate, benzenesulphonate or salicylate anion.
3. A 1-[2-(2,4-dichlorobenzoyloxy)-2-(2,4-dichlorophenyl)ethyl]-
tert.-butyl-carbonylmethyl-1,2,4-triazolium halide of the formula
<IMG>
4. A 1-[2-(2,6-dichlorobenzyloxy)-2-(2,4-dichlorophenyl)ethyl]-2,4-
dichlorobenzoylmethyl-1,2,4-triazolium halide of the formula
<IMG>
5. A 1-[2-(allyloxy)-2-(2,4-dichlorophenyl)ethyl]-4-chlorobenzoyl-
44

methyl-1,2,4-triazolium halide of the formula
<IMG>
6. A 1-[2-(allyloxy)-2-(2,4-dichlorophenyl)ethyl]-2,4-dichlorobenzoyl-
methyl-1,2,4-triazolium halide of the formula
<IMG>
7. A 1-[2-(acetoxy)-2-(2,4-dichlorophenyl)ethyl]-2,4-dichlorobenzoyl-
methyl-1,2,4-triazolium halide of the formula
<IMG>

8. A method of combating fungi which comprises applying to the fungi or
to a habitat thereof, a fungicidally effective amount of a compound according
to claim 1.
9. A method according to claim 83 wherein the compound is applied in
the form of a composition comprising said compound as active ingredient in
admixture with a diluent or carrier.
10. A method according to claim 9, wherein the composition comprises
0.00001 to 0.1% by weight of said active ingredient.
11. A method according to claim 9, wherein the composition comprises
0.0001 to 0.05% by weight of said active ingredient.
12. A method according to claim 8, in which the compound is applied to
soil in an amount of 1 to 1000 g per cubic metre of soil.
13. A method according to claim 12, in which the compound is applied in
an amount of 10 to 200 g per cubic metre of soil.
14. A method according to claim 8, in which the compound is applied to
seed in an amount of 0.001 to 50 g per kg of seed.
15. A method according to claim 14, in which the compound is applied in
an amount of 0.01 to 10 g per kg of seed.
16. A method according to claim 8 or 11, wherein the compound is a
compound as defined according to claim 2.
17. A method for combating fungi which comprises applying to the fungi
or to a habitat thereof, a fungicidally effective amount of a compound ac-
cording to claim 3, 4 or 5.
18. A method for combating fungi which comprises applying to the fungi
46

or to a habitat thereof, a fungicidally effective amount of a compound ac-
cording to claim 6 or 7.
47

Description

The present invention relates to c0rtain new 1-(2-phenylethyl)-
triazolium salts, to a process for their preparation and to their use as
fungicides.
It has already been disclosed that certain l-[~-aryl-~-(R-oxy)-
ethyl]-imidazoles, for example l-[~-butoxy-~-(4'-chlorophenyl)-ethyl]-imid- ~`:
azole, and certain l-E~-aryl-~-(R-oxy)-ethyl] triazoles, for example l-L~
allyloxy-~-~4'-chlorophenyl)-ethyl]-1,2,4-triazole, have a good fungicidal
activity (see German Offenlegungsschriften ~German Published Speci-fications)
2,063,857 and 2,640,823). However, in certain fields of indication their
action is not always completely satisfactory, in particular when low amounts
and concentrations are used. Furthermore, it has been generally known for a
relatively long time that zinc ethylene-1,2-bis-dithiocarbamidate is a good
agent for combating fungal plant diseases (see Phytopathology 33, 1,113
(1963)). However, its use as a seed dressing is only possible to a limited
extent since it is not very active when low amounts and concentrations are
used.
The present invention provides, as new compounds, the 1-(2-phenyl-
ethyl)-triazolium salts of the general formula
n ~ _ C~ - CH2 - N ~ ~ R5 ~ (I)
in which
R each independently is halogen, alkyl, alkoxy, alkylthio, alkyl-
sulphonyl, halogenoalkyl~ nitro, cyano, or phenoxy, either of
which may optionally carry one or more substituents selected
independently from halogen, cyano, nitro and halogenoalkyl with
up to 2 carbon atoms and up to 3 identical or different halogen
atoms;
R is -o-R2, -S(0) -R or -0-CO-R ;
R2 is alkyl, alkenyl, alkynyl, cycloalkyl, or aryl, arylalkyl
or arylalkenyl, the three last-mentioned groups being optionally
substi~uted in the aryl nucleus by halogen, cyano, nitro,
- 2 -

q~7Ei
amino, alkyl with 1 to 4 carbon atoms~ halogenoalkyl with up
to 2 carbon atoms and up to 3 identical or different halogen
atoms, or phenoxy which is itself optionally substituted by -
halogen; -~
R3 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl,
arylalkyl or arylalkenyl, the three last-mentioned groups being
optionally substituted in the aryl nucleus by halogen, cyano,
nitro, amino, alkyl with 1 to 4 carbon atoms, halogenoalkyl
with up to 2 carbon atoms and up to 3 identical or different
halogen atoms, or phenoxy which is itself optionally substituted :
by halogen;
R4 is alkyl, alkenyl, alkynyl, cycloalkyl, or aryl, aralkyl or
arylalkenyl, the *hree last-mentioned groups being optionally
substituted in the aryl nucleus by halogen, cyano, nitro, amino,
alkyl with 1 to 4 carbon atoms, halogenoalkyl with up to 2
: carbon atoms and up to 3 identical or different halogen atoms,
or phenoxy which is itself optionally substituted by halogen;
or R4 represents halogenoalkyl, phenoxyalkyl which is optionally
substituted in the phenyl part by halogen, amino, cyano, nitro
or alkyl with 1 or 2carbona~ms,or R4 rerresents~Mno, alkylamino-
dialkylamino or alkyl-alkylcarbonylamino, or phenylamino which
is opti.onally substituted in the phenyl part by halogen, nitro
or cyano;
R5 is alkyl optionally substituted by alkylcarbonyl with 1 to 4
carbon atoms in the alkyl part, phenyl or benzoyl, the phenyl or
benzoyl themselves being optionally substituted by nitro, cyano,
alkyl with 1 to 4 carbon atoms, halogen, alkylsulphonyl with 1 :~
to 4 carbon atoms, alkoxy with 1 or 2 carbon atoms, alkylthio
with 1 or 2 carbon atoms, halogenoalkyl with up to 4 carbon atoms
and up to S halogen atoms, or phenyl or phenoxy, either of which
may optionally carry one or more substituents selected inde-
pendently from halogen, cyano, nitro and halogenoalkyl with
_ ~:

7~
i
up to 2 carbon atoms and up to 3 identical or different
halogen atoms;
n is 0, 1, 2, 3, 4 or 5; ; ~:~
m is 0, 1, or 2; and
Z is an equivalent of an anion of a non-phytotoxic acid.
The compounds of this invention have powerful fungicidal proper-
ties.
Preferably, R represents halogen ~especially fluorine, chlorine or
bromine), nitro, cyano, alkyl with 1 to 4 carbon atoms, alkylsulphonyl with
1 to 4 carbon atoms, alkoxy with 1 or 2 carbon atoms, alkylthio with 1 or 2
carbon atoms, halogenoalkyl with up to 4 carbon atoms and up to 5 halogen
~,, . '

376
atoms (especially with up to 2 carbon atoms and up to 3
identical or di~ferent halogen atom~ 9 preferred halogen
atoms be;ng fluorine and chlorine, and trifluoromethyl
being an example of such halogenoalkyl)~ or phenyl or
phenoxy, eîther of which may optionally carry one or more
sub~tituentæ selec~ed independently from halogen (especially
fluorine, chlorine and bromine) J CyaIlO~ nitro and halogeno-
alkyl with up to 2 carbon atoms and up to 3 identical or
different halogen atoms (pre~erred halogens being fluorine
and chlorine, and tri~luoromethyl be;ng an example o~ such
halogenoalkyl~,
n represenks 0, l, 2 or 33
Rl repre~ents a grouping -o-R2, -S(o)~-R3 or o-co-R4;
R represents alkyll alkenyl or alkynyl with up to
4 carbon atoms in each case, cycloalkyl) with 5 to 7
carbon atoms, especially cyclohexyl, or aryl with 6 to
lO carbon atoms, or arylalkyl or arylalkenyl with 6 to lO
carbon atoms in the aryl part and up to 4 carbon atoms in
the alkyl or alkenyl part (~or example phenyl 9 naphthyl,
benzyl, naphthylmethyl and styryl), the three last-mentioned
groups being optionally substituted by halogen (especially
fluorine, chlorine or bromine), cyano, nitro, amino, alkyl
with l to 4 carbon atoms, halogenoalkyl with up to 2 carbon
atoms and up to 3 identical or difrerent halogen a~oms
(pre~erred halogen atoms being fluorine and chlorine, as in,
for example, trifluoromethyl) or phenoxy which is :itself
optionally substituted by halogen (especially fluorine or
chlorine),
R3 represents hydrogen, alkyl, alkenyl or alkynyl with
up to 4 carbon atoms in each case, cycloalkyl with 5 to 7
carbon atoms, especially cyclohexyl, or aryl with 6
to 10 carbon atoms~ or arylalkyl or arylalkenyl with 6 to
Le A 18 115 -4-
-. . . ~ . ....

10 carbon atoms in the aryl part and up to 4 carbon atom~
in the alkyl or alkenyl part (ror example phenyl, naphthyl,
benzyl, naphthylmethyl and styryl) J ~he three last-mentioned
groups being optional~ substituted by halogen (especially
~luorine, chlorine or ~romine), cyano, nitro, amino, alkyl
with 1 to 4 carbon atoms, halogenoalkyl with up to 2 carbon
atoms and up to 3 ident;cal or different halogen atoms
(pre~erred halogen atoms being fluorine and chlorine, as
in, for example ~rifluoromethyl) or phenoxy which is itself
optionally substituted by halogen (especially ~luorine or
chlorine);
R4 represents alkyl, alkenyl or alkynyl with up to 4
carbon atoms in each case, cycloalkyl with 5 to 7 carbon
atomsl ~specially cyclohexyl, or aryl with 6 to 10
carbon atoms, or arylalkyl or arylalkenyl with 6 ~o 10
carbon atoms in the aryl part and up to 4 carbon ~toms in
the alkyl or alkenyl part (~or example phenyl, naphthyl,
ben~yl, naphthylmethyl and styryl)~ the three last-mentioned
groups being optionally sub~tituted by halogen (especially
fluorine, chlorine or bromine), cyano, nitro9 amino, alkyl
with 1 to 4 carbon atoms, halogenoalkyl with up to 2 carbon
atoms and up to 3 identioal or di~erent halogen atoms
(preferred halogen atoms being fluorine and chlorine, as
in, for example, trifluoromethyl) or phenoxy which :is itsel~
optionally ~ub~tituted by halogen (e~pecially f~uor:ine or
chlorine), or R4 represents halogenoalkyl with 1 to 2 carbon
atoms and 1 to 5 halogen atoms (preferred halogen at;oms bein~
fluorine and chlorine, as in, ~or example, tri~luoromethyl,
dichloromethyl and chloromethyl)~ or phenoxyalkyl wi.th 1 or
2 car~on atoms in the alkyl part and which is optionally
substituted in the phenyl part by halogen (especially
Le A 18 115 - 5 ~

76
fluorine or chlorine)~ amino~ cyano~ nitro or alkyl with 1
or 2 carbon atoms, or R4 represents amino 3 alkylamino 3
dialkylamino or alkyl-alkylcarbonylamino each with 1 to 4
(especially 1 or ~) carbon atoms in each al~yl part or
phenylamino ~hich is optionally substituted by halo~en
(especially fluorine or chlorine), nitro and cyano,
R5 represents straight-chain or branched alkyl with
1 to 6 carbon atoms which is optionally substituted by
alkyl~arbonyl with 1 to 4 carbon atoms in the alkyl part,
phenyl or benzoyl, the phenyl or benzoyl themselves being
optionally substituted by halogen (especially fluorine,
chlorine or bromine), nitro, cyano, alkyl with 1 to 4
carbon atoms, alkylsulphonyl with 1 to 4 carbon atoms,
alkoxy wi~h 1 or 2 carbon atoms, alkylthio with 1 or 2
carbon atoms, halogenoalkyl with up to 4 carbon atoms and
up to 5 halogen atoms (especially with up to 2 carbon atoms
and up to 3 identical or different halogen atoms, preferred
halo~en atoms being fluorine and chlorine, and trifluoro-
methyl being an example o~ such halogenoalkyl), or phenyl
or phenoxy, either o~ which may optionally carry one or more
substituents selected independantly from halogen (especially
fluorine, chlorine and bromine), cyano, nitro and halogeno-
alkyl with up to 2 carbon atoms and up to 3 identical or
different halogen atoms (preferred halogens being fluorine
and chlorine, and trifluoromethyl being an example of such
halogenoalkyl); and
Z represents an equivalent o~ 2 fluoride, chloride,
bromide, iodide, nitrate, sulphate, phosphate, acetate,
propionate, ~lycollate, lactate, malonate 9 succinate 9
maleate, fumarate, tartrate, citrate, benzoate, met}lyl-
Le A 18 115 - 6 -

7G
sulphonate, ethylsulphonate, ~-toluenesulphonate, benzene-
sulphonate or salicylate anion.
The invention also provides ~ process for the pre-
paration of a 1-~2-phenylethyl)-triazolium salt of the
formula (I), in which a l-phenyl-2-~riazolyl--ethyl
~erivative o~ the general formula
Rn ~ CH - CH
in which
Rs Rl and n have the meanings stated above,
is reacted with a halide o~ the general formula
R5 - X (III)~
in which
R5 has the meaning stated above and
X represents halogen,
in the presence of a diluent, and the halide in the re-
sulting triazolium halide is optionally replaced by another
anion in a manner which is in itself known.
In some cases it proves advantageous to employ~ instead
of the halides of the formula (III), corresponding reactive
esters, which are obtained by reacting the appropriate
alcohols with the appropriate acids.
Surprisingly~ the l-t2-phenylethyl)-triazolium salts
according to the invention exhibit a considerably higher
fungicidal activity, in particular against species of rust
2g and powdery mildew, than the l~ aryl-~-(R-oxy)-e~hyl]-
Le A 18 115 - 7 -

9~
imidazoles and -triazoles~ for example l-C~-butoxy-~-
(4'~chlorophenyl)-ethyl]-imidazole, which are known from
the state o~ the art and are closely related 3ubstances
chemically and from the point of view of their action, and
than zinc ethylene-l,2-bi~-dithiocarbamadate, which is a
known substance of the same type o~ action. ~he active
compounds according to the invention thus represent an
enrichment of the art.
If l-(2a4~dichlorophenyl)-2-(l,2,4-triazol-l-yl)-ethyl
2~4-dichloroben~yl ether and monochloropinacoline are used
as starting materials, the course of the reaction can be
represented by the following equation:
Cl
Cl- ~ -CH-CH2- ~ N ~ ClCN~-C0-C(CN~
CH2~ ~ -Cl
~1
~1 /N.~/ CH2 CO-C ( ~I3 )3
Cl- ~ -CH-CH2-N
O
C~2 - ~ -Cl Cl
Cl
In this type of reaction, the alkyl part pre~erentially
joins on to the nitrogen atom 4 of the 192,4-triazc)l-l-yl
radical, a3 can be seen from the nuclear magnetic resonance
data; however, depending on the reactivity of the alkyl
halide and o~ the starting material of the formula (II), it
iæ also possible for alkylation to take place on the nitrogen
atom l of the l52,4-triazo~ yl radical. Both ty~es o~
. 1e A 18 115 - 8 -

97i6
compound and the mixtures obtained during this alkylation
are intended to be represented by the formula tI).
Some of the starting materials of the formula (II) are
krlOWII rrom DT~OS (Germarl Published Speci~ication) 2 ,547 j953
and D~OS (German Published Specification) 2,640,823, and
some of them are the subject o~ German Patent Applications
P26 28 419.5 ~Le A 17 198] o~ 24.6.1976 and P 26 45 496.6
~Le A 17 4563 of 8. lû. 1976. Starting materials of the
formula (II) which ha~e not yet been described in the
literature can be obtaîned by the processes described
therein, for example by
(a) reacting alkanolates of l-hydroxy-l-phenyl-2-triazolyl-
ethane derivatives of the general formula
¦ ~==N ~IV)
~ OM
in which
R and n have the meanings stated above and
M represents an alkali metal, pre~erably lithium,
sodium or potassium, or a quaternary ammonium or
phosphonium ~roup~
with a halide o~ the general ~ormula
Hal _ Rl (V),
.in which
Rl has the meaning stated above and
Hal represents chlorine or bromine,
in the presence of an organic solvent J such as, for example,
dioxan or chloroform3 at temperatures between 20 and 120C.
In order to isolate the end products, the reaction mixture
Le A 18 115 - 9 -

976
i9 freed ~rom the solvent, and water and an organic solvent
are added to the residue. The organic phase is separated
off, worked up in the customary manner and purified.
In a preferred embodiment, the procedure is approprlakeo
ly to use a 1-hydroxy-1-phenyl-2-triazoly~ethane derivative
as the starting material, to convert this into the a]kali
metal alcoholate of the formula (IV) in a suitable inert
solvent by means o~ an alkali metal hydride or alkali metal
amide and to react the alcoholate immediately, without
isolation~ with a ~alide o~ the ~ormula (V), the compound
of the formula (II) being obtained in one operation ~ith
the elimination of alkali metal halide.
According to a further preferred embodiment, the
preparation of the alkanolates of the formula (IV) and the
1$ reaction with the halide of the formula (V) are appropriately
carried out in a two-phase system, for example aqueou
sodium hydroxide solution or potassium hydroxide ~olution/
toluene or methylene chloride, a phase transfer catalyst,
for example an ammonium or phosphonium compound, being addedl
The starting materials of the formula (II) can also be
obtained when
(b) the 1 hydroxy-1-phenyl-2-triazolyl-ethanes on which the
alkanolates o~ the formula (IV) are based
are reacted with appropriate acid anhydrides by known methods~
for example in equimolar amounts in the presence of an inert
organic solvent, for example acetone, or with an ex~ess of
acid anhydride and in the presence of an acid or basic
catalyst, for example sodium acetate, at temperatures
between 0 and 150C, and t~.e compounds of the formlla (II)
are i~olated in the customary manner, ox the said l-hydroxy-
Le A 18 115 - 10 -

~a~s7~
l-phenyl-2-triazolyl-ethanes are reacted with appropri.ate
isocyan~tes by known methods~ for example in equimolar
amounts in the presence of an inert organic solvent, I'cr
example benzene~ and in the presence o~ a catalyst, fc,r
example dibutyl-tin dilaurate, at temperatures between 0
and 100C, and the compounds o~ ~he ~ormula (II) are
isolated in the customary manner~ or
tc) l-halogeno-l-phenyl-2 triazolyl-ethanffl of the general
formula
,~-- CH - CH2 - ~ ¦
in which
R and n have the meanings stated above and
X represents halogen,
are reacted with mercaptans of the general formula
H ~ S - R3 (VII),
in which
R3 has the meaning stated above~
in a known manner in the presence of an inert organic
solvent, for example acetone, and in the presence o~ an
acid-binding agent, for example potassium carb.onate, at
temperatures between 60 and 100C, and the thioethers
thereby obtained are optionally oxidised in a manner which
is in itself known at temperatures between -30 and 80C
using inorganic or organic oxidising agents, for example
m-chloroperbenzoic acid or potassium permanganate. The
compounds of the rormula (II) are isolated in the customary
Le A 18 115 - 11 -
., ; - . ~ , .,

manner~
The 1 hydroxy-1-phenyl 2-triazolyl-ethane derivat:ives
on which the alkanolates of the formula (IV) are based are
known (see DT-OS ~German Published Specification) 2~43:L,407
and DT-OS (German Published Specification) 235479953~,
~he l-halogeno-l-phenyl-2-triazolyl-ethane derivatives
of the formula ~VI) are also known (see DT-OS (German
Published Specification) 2,547,954).
Examples o~ the l-phenyl-2-triazolyl-ethyl derivative~
of the ~ormula (II) to be used according to the invention
as starting materials are given in the ~ollowing Tables
1, 2 and 3:
T a b 1 e
- CH2 - ~ ( IIa)
R~ O
R2
R 2 Melting point (C) or
n R -refractive index
~ ,~ ~
2,4-Cl2 -CH2- ~ -Cl 84
2,4-Cl2 -CH2-CH=CH~ n2~ 545
2,4-C12 -CH2~C-CH 130~decomposition)
4-Cl -CH2- ~ ~Cl 7~
4-Cl -CHz- ~ -Cl 111
2,4-Cl2 Cl ~ 120
4~C~ Cl ~ 118
4- ~ -Cl -CH~-CH=CH2 225 ~decomposition)
(x~ NDS)
Le A 18- 115 - 12 -
, . . . .. .. ~ .

71~
F~n }~2 . Meltin~; point (C~
o~ refracti~ie index
C~2~CH-CH2 n2D 1,570
4-0-~-Cl -CHZ~ C1 20t) (x~ NDS)
4 0~ -Cl -CH2 ~OE:=CH2 213 (~ ~DS )
2~4-CL2 ~-N2 174 (decomposition~
~,4-~12 ~) 124 ~dec mposition)
4 0~) CH2 1~ Cl 145 (de~COmpOSition)
2,4-C12 CH3 143-46 (x HCl)
4-Br -CH2-CH=CH2 193 (x~ NI)S)
4-~ -Cl CH2~ Cl 237 ~ NDS)
4_o~ C~2~)-Cl go
4~)~ -CH2 ~ 124
4-0~ Cl t::H~ 211 (de~omposition)
4_o~ CH2 -C~CH 158 (de~omposition)
4-~r -C~ Cl 76
4-Cl -C~-C~=~2 140 (x HC:l~
4~0 ~-Br CH~c~ cl Yiscous oil
4 0-~-Br -CH2-CH=CH2 visoous oil
4-0~-Br ~2-~; Cl 1~5
Le A 18 115 - 13 -
. .

Rn R2 Melting point (C)
__ _~x
2 D 4~C18 --C~ ) 10~3
2,4~ 2 C~,H, viscous oil
2~4-C18 -CH2-~-C:l 89 91
2 9 4-Cl~ ~ N02
4 F C1~3 138
4-0~ Br Cl~ 189 (x HCl)
4-Br _C~I2-~3-Cl 102
4-~-Cl Cl;~ 165
2, 4-Cl~ -CH~ Cl 107
2~4-C15~ C=C~ visQc>u3 oil
4-~ -C1 -C~I2 - ~)-Cl 103
4 o-~ 3-Cl -CH~ Cl 136
4~0-~-Cl -CH2 ~) 98
4-0-~-Cl -CN2-C=CH2 185 (d~COmpOSition)
4-0-~g3-Cl ~ C-CH vi~cous oil
4-0-~-C~ ; CH2~ 212 (x ~ ND'3~
4 0-~-Cl -CHa-~-Cl 212 (x ~ ND,~)
4~0-~-Cl ~ 203
~tO~
Le A 18 115 - 14 -

7~i
R~2 ~elting point (C)
- n. . . or r.e*.r.ac.t.i.ve. .~de x
4_0 ~ 302 -CH2~ CH~ 135
2, 4-Cl2 -CH -~ -C~ 92
2,4~ 12 -CH2- ~ ~ viscous oil
4_0-~-Cl -CH~-~ 216 (x ~ NDS)
4~0~ l CH2 ~) -CH~ 214 (x~ NDS)
NOTE:
__ .
NDS = 1 ,5-naphthalenedisulphonic acid
T a b 1 e 2
CH - CH~ - N~¦ (IIb)
C0 - R~
Rn R4 Melting point (C)
2,4-Cl2 C(~!l )3 149-51 (x ~IN0!~ )
2, 4-Cl2 CH~ 92~96
2, 4-Cl2 -NEICHI 204
2,4-~l2 -N(CH3 ~2 140
Z,4-Cl2 C2H, 156 tx ~ NDS)
2,4-t:}2 CH2 Cl 227 (x ~ NDS)
4-~-Cl ~ 3
2,4-Cl2 ~Cl 174 ~X ~
4~ 3DC~ ~H3~ 150 (~: HN0~ )
2t4-Cl2 ~ 3 14
Le A 18 115 ~ 15 -
. , , . . .. ~.; .- . . ,. . ~

Rn .R4 .... Meltin~ point (C)
2,4~ 120
OCH~
4-~Cl -NHCE~ 18C)
2,4-C1,E _~ C~ 205 (~ ~ ~DS~
2 9 4-~12 NH2 164
2, 4-Cl2 ~ Cl 125
4~ Cl C(CH~ )~ 121
4-~-Cl -NH-~ ~70 (~econ~po~tion)
4-Cl CH~ 90-92
4-Cl C(CH.. ~ )3 1~5-136
4-Cl ~ C~ 177-180
4-~-Cl -N~I~ 116-1~6
4-Cl -N-CH~
COC~ 155 158 (x HCl)
2,~oC12 <~> 170-175 (x HCl)
2, 4-Cl~ ~H~l2 128-1~0
4-Cl ~ Cl 18û-~85
T a b 1 e 3
~ C:H CH2 ~ N =¦ (IIc)
Rn S(~m \~N
R3
Le A 18 11~ ~ 16 -
. . , ~ , . ~ . ~.. .

7~
Rn R3 m.. Mel~in~ point
.. ... ............. .. ..... ,. "~.. ~.
4~ ~ Cl posit~on ) ( x
4~ 1 1 HN03 )
4~ Cl ~ Cl ~
2 j4-Cl~ ~ Cl ~ 158 (d~com-
,~ position) (x
2 ~ 4-Cl2_~ ~ -Cl 1 HN03 )
294-C12 ~ 1 2
4-0-~-Cl -~ Cl ~ 135 ~deCom-
positlon) tx
4-0-~-Cl ~-Cl 1 HN03 )
4-0~ Cl 2
2~ 2 ~ ~ 210 (x ~ NDS)
2,4-C12 C ~ 182 (~ H~
2~4-Cl~ ~ ~ 14~ 15~
The starting materials o~ the rormula (III) are gener
ally known compounds of organic chemistry, or they can be
obtained in a manner which i~ generally known and cu~tomary.
Example~ which may be mentioned are: methyl fluoride~ methyl
chloride~ methyl bromide, methyl iodide, ethyl bromi.de~ ethyl
iodide, chloroacetone, bromoacetone, ~luoroacetone, ethyl
~hloromethyl ketone~ rluoropinacoline~ chloropinacoline, bromo-
2Q pinacoline5 benzyl chloride~ a~ biphenylyl) benzyl chloride~
~-bromoaeet~phenone~-chloroacetophenone~ ~-chloro-(4~chloro-
Le A 18 115- 17 -

7~
acetophenone), ~-bromo-(4-Ghloroacetophenone), ~-chloro-
(2,4-dichloroacetophenone), ~-bromo-(2,4~dichloroacetophenone)~
4-chlorobenzylmethy1 bromide, 2,4-dichlorobenzy1 chlo:ride~
2- ( 4- chlorophenylcarb onyl ) -ethyl ch~oride and 2- ( 4-ch:Loro
phenylcarbonyl)-ethyl bromide.
Pre~erred diluen~s for the reac~ion according to the
invention are polar organic solvents~ especially nitriles,
such a~ acetonitrile; sulphoxides, such as dimethyl-
sulphoxide; formamidesD ~uch as dimethylformamide; ket;one~,
such as acetone9 ethers, such as diethyl ether and tet;ra-
hydro~uran; and chlorohydrocarbons, ~ucA as methylene
chloride and chloroform.
The reaction temperature~ in the process according to
the invention can be varied within a relatively wide range.
In general~ the reaction is carried out at ~rom 0 to 120C,
preferably at from 20 to 90C, or at the boiling point of
the particular so lvent .
Equimolar amounts o~ the starting materials are pre-
~erably used in carrying out the proce~æ according to the
invention. The compound~ o~ the formula (I) are isolated
in the customary manner.
The anion replacement reaction, which may optionally
be ef~ected in the process accordin~ to the invention~ may
be carried out in a generally known manner (see German
Offenle~ungsschri~t (German Published Speci~ication)
2~504,114),by converting the 1-~2-phenylethyl~-triazclium
halide of the formula (I) into the corresponding triazolium
hydroxide9 for example by means o~ a ba~e or an anion
exchange resin, and khen to react the hydroxide with an
appropriate acid.
Le A 18 115 ~ 18 -

)9~6
The active compounds according to the inventiorl
exhibit a powerful flm~gitoxio action. They do not ~amage
crop plant3 in the concentrations required for combating
~ungi. For these reason3, they are suitable for u~e
a~ plant protection a~ en~ ~or ~ombatin~; fungi . Fungitoxi~
agents are employed in plant protection rOr combating
, ~ , ~ and ~ 5
The aotive compounds according to the invention
have a broad spectrum of action and can be u~ed again~t
parasitic fungi which attack above ~round parts o~ plant~
or which attack the plants through the soil, as well
a~ a~ainst seed-borne pathogens.
As plant protection agent~,the active compound~ accord-
ing to the invention can be employed particularly succe~s-
fully for combating specie3 of Venturia, such as against
the pathogen of apple ~cab (Fusicladium dendriticum), for
combating powdery mildew fungi~ for example ~or combating
powdery mildew of appl~ (~ leucotrioha) and
powdery mildew of Gereals, and al~o ~gainst other cereal
diceases .
The partially ~ystemic action of the compounds ~hould
be sis~gled out particularly. Thu~3 it proves possible to
protect plants against fungal infection by supplyi~g the
active compound to the above;~round parts o~ the plant
through the soil and ths root.
As p}ant protection agents, the compounds according
to the invention can be u~ed ~or the treatment o~ soil,
for the treatment of seed and ~or the 'creagment o~ aboYe-
ground parts o~ plant~.
Le A 18 1~:5 - 19 -

The active compounds can be converted into
the cu~tomary rormulations~, such as solution , emul~ion~,
wettab le powder~, su~pension ~, powders, dusting agent~,
~oams~ paBte~ soluble powder~, granules, aerosols, sus-
pen~ion-emul~ion cQncentrates3 ~eed-treatment powders,
natural and ~ynthetic mat@rials impre~;nated with active
compound, very ~ine capsule~ in polymeric substances 9
coating compo~itions ~or use on ~eed, and ~ormulation~
u~ed with burning eguipment~ such as ~umigatin~ cartridge~,
fumagatin~ can~ and fumigating coilsD as well a~ UL~ cold
mist and warm mist ~ormulations.
These ~ormulations may be produced in known manner,
for example by mixing the active compounds with extenders,
that is to ~ay liquid or lique~ied Ka~eous or solid diluents
or carriers, optionally with the u~e o~ surface-active
agents, that i8 to say emulsifyin~ agents and/or dispersing
agents and/or roam-~orming agents. In the ~ase of the
use o~ water a~ an extender~ organic so}vents can, rOr
example~ alqo be used as auxiliary ~olvents.
2a As liquid ~olvent~ diluents or carriers, espeoially
solvents, there are suitable in the main, aro~atic hydro-
carbons, such as xylene, toluene or alkyl naphthalenes,
chlorinated aromatic or chlorinated aliphati~ hydrocarbons,
such a~ chlorobenzenes~ chloroethylenes or methylene
chloride~ aliphatic or alicyclic hydrocarbons, such as
cyclohexane or pararfin~, ~or example mineral oil ~r~ctions9
alcohol~, ~uch as butanol or glycol as well a~ their ethers
and e~ter~, ketones, such as acetone, methyl ethyl ketone,
methyl isobutyl ketone or cyclohexanone, or strongly polar
solvents, such as dimethylro~mamide and dimethylsulphoxide,
Le A 18 155 - 20 -

76
as well as water.
By liguefied gaseous diluents or carriers are meant
liquids which would be gaseous at normal temperature and
under normal pre~sure, rOr example aerosol propellants"
such as halogenated hydrocarbons as well as butane~ propane3
nitro~en and carbon dioxideO
As solid carriers there may be uæed ground natural
minerals, such as kaolins9 clays~ talc, chalk3 quartz~
attapul~ite, montmorillonite or diatomaceous earth, and
ground 9ynthetic mineral~ such as highly-disp~rsed silicic
acid, alumina and silicates. As solid carriers for granule~
there may be used crushed and fractionated natural rocks
such as calcite, marble, pumice, sepiolite and dolomite~
as well a~ synthetic granules o~ inorganic and organic
meals, and granules of organic material such as sawdust,
coconut shells, maize cobs and tobacco s~alks.
As emulsifying and/or foam-~orming agents there may
be used non-ionic and anionic emulsi~iers~ such as polyoxy-
ethylene~-fa~ty acid esters, polyoxyethylene-fatty alcohol
ethers~ for example alkylaryl polyglycol ethers~ alkyl
sulphonates, al~yl su~phate~ aryl sulphonates as well
as albumin hydrolysis products. D;spers;ng agents include,
for example ~ lignin sulphite wast~ liquors and methyl-
cellulose~
The active compounds according to the invention
can be present in the formulations as a mixture with other
active compounds~ such as fungicides, insecticides, acaricides3 ..
nematicides, herbicides, bird repellants9 growth factors,
plant nutrients and agents for improving soil structureO
The formulations in general contain from 0.1 to
Le A 18 115 - 21 -
- : ., . , . ;, . ., ~- . ~ . "- , , .

76
95 per cent by weight Or active compound, pre~erably from
0.5 to 90 per cent.
The active compounds can be used as such, as their
formulations or as the use forms prepared thererrom by
~urther dilution9 such as ready-to~use solutions, emulsions~
suspension~, pow~ers, past~s and granules. They may be
used in the customary manner, for example by watering,
~praying, atomi~ing~ du~ting~ ~cattering~ dry dressing~
moist dressing, wet dressing, slurry dressing or encrusting.
Especially wllen used as leaf fungicideæ9 the acti-ve
compound concentrations in the use forms can be varied
within a fairly wide range. They are, in general, ~rom
O.lto 0.00001 per cent by weight, pre~erably from O.C5 to
0.0001 per cent.
For the treatment of seed, amounts of active compound
of 0.001 to 50 gg preferably 0.01 to 10 g~ are generally
employed per kilo~ram of seed.
~or the treatment of soil, amounts o~ active compound
of 1 to lC00 g, preferably lO to 200 g, are generally
employed per cubic metre of soil.
The preRent 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 admixture with
a liquid diluent or carrier containing a surface-active
agent.
The present invention also provides a method of
combating f~ngi which comprises applying to the ~ungi,
or to a habitat thereof~ a compound of the present invention
alone or in the form o~ a compo~ition containin~ as active
Le A 18 115 ~ 22 -

in~redient a compound o~ the present invention in admixture
with a diluent or carrierO
The pr~3ent invention further provides crop~ protected
from damage by fungi by being grown in areas in which
immediately prior to and/or ~urin~ the time of the growing
a compound o~ the present invention was applied alone
or in admixture with a diluent or carrier.
It will be ~een that the usual method~ of providing
a harvested crop may be improved by the present invention.
~he fun~icidal activity o~ the compounds of this
invention i~ illustrated by the following biotest Example~.
In these Examples, the compounds according to the
pre ent 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
~ollows:
(A) = ~~ ~ CH-CH~- ~ O~H
~4~g X1!2~
0
(B) - ~H~-
C ) ~ O
CH~-CHzCH~ x HCl
Le A 18 115 - 23 -

te~t (apple~/protective
Solvent. 4.7 parts by weight o~ acetone
Emulsifier: O. 3 part by weight of alkylaryl polyglycol
ether
Water: 95 parts by weight
The amount of active compound required for the desired
concentration o~ the active compound in the spray liquid
was mixed with the stated amount of solvent, and the con-
centrate was diluted with the stated amount of water
which contained the stated amount of emulsifier.
Youn~ apple æeedlings 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 atmo~pheric humidity of 70~. They were
then inoculated by duRting the conidia of the apple powdery
mildew causative organism (Podo~phaera leuootrich~) and
placed in a greenhouse at a temperature of 21 - 23 deg.
C and at a relative atmospheric humidi~y of about 70%~
10 day after the inoculation, the infection Or the
seedlings was determined. The assessment data were con
verted to % infection. 0% meant no infection; 100~ meant
that the plants were completely infected.
The active compounds~ the concentration~ of the
active compounds and the results can be seen from the
following table:
Le A 18 115 ~ 24 -
. . ,. ~ .

37~i
T a b 1 e A
Podosphaera test (apple)/protective
Active compound In~ection in % at an
active compound con-
centration Or O.G025%
(A) 48
(5) 5
~6) 4
(7)
(8)
(9) 41
~1) o
(10) 31
Fusiclad;um te~t (apple)/protective
Solvent: 4.7 parts by weight of acetone5 Emul~ifier: 0.3 part by wei~ht of alkylaryl poly~lycol
ether
Water: 95 parts by weight
The amoun~ o~ active compound re~uired for the desired
eoncentration ~f the active compound in the spray liqui~
was mixed with the stated amount of solvent, and the
concentrate wa~ diluted with the ~tated amount o~ ~ater
which contained the 3tated amount of emulsifier.
Young apple seedlings in the 4 - 6 leaf stage were
~prayed with the spray liquid until dripping wet. The
~5 plants remained in a greenhouse for 24 hour~ at 20 degrees
C and at ~ relative atmo~pheric humîdity of 70%. I'hey
were then inoculated with an aqueous ~onidium su~pension
Le A 18 115 - 25 -

976i
o~ the apple scab causative organism (Fusioladium ~en-
d~i ) and incubated for 18 hour~ in a humidity chamber
at 18-20 degrees C and at a relative atmospheric humi~ity
of 100,~.
The plants were then brough~ into a greenhouse agai
~or 14 days.
15 days a~ter inoculation, the infection o~ the
~eedlings wa~ determined. The a3Aes~ment data were con-
verted to percent inf~ction. 0% meant no infection;
100~ meant that the plants were totally in~ected.
The active compounds, the concentrations of the active
c~mpounds and the result~ can be seen from the followin~
table:
T a b 1 e B
__
Fusicladium test (apple)/protective
Active compound Infection in % at an active
compound concentration of
0.00~5%
(A)51
~2)
(6)39
(1) 7
Example C
Shoot treatment test/powdery mildew of cereals
(leaf-destructive mycoæis)/protective
~o produce a suitable preparation of active compound,
0.25 part by weight of active compound was taken up in
25 parts by weight o~ dimethyl~ormamide and 0.06 part
by weight of alkylaryl polyglycol ether~ 975 parts by
weight o~ water were then added. The concentrate wa~
Le A 18 115 - 26 ~ ~i
~7 ~'~ 561~

76
diluted with ~ater to the desired ~inal concentration
of ~he spray liquor.
To test for protective activityJ single-leaved young
barley plants of the Amsel variety were sprayed with t;he
preparation of active compound until dew-moist. After
drying, the barley plants were dusted with spores of
E~ var. hordei,
A~ter 6 days' dwell time o~ the plants at a temperature
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 in~ection
o~ the untreated control plantR. 0% denoted no infection
and 100~ denoted the same degree o~ infection as in the
oase of the untreated control. The active compound was
the more active, the lower was the degree of mildew in-
~ec~ion.
The active compounds, active compound concentrations
in the spray liquor and degrees of infection can be seen
from the table which follows:
T a b 1 e C
Shook treatment test/powdery mildew of
cereals/protective
Active Active compound Infection in %
compounds concentration in of the untreated
the spray liquor control
in % bY wei~ht
untreated - 100
25(B) 0,025 100
(4) 0.025 25.0
(2) 0.025 16.3
(5) 0.02~ 42.5
(6) 0.025 0.0
Le A 18 115 - 27

976
T a b 1 e C (continued)
Shoot treatment test~powdery mildew o~
cereals/protective
Active Active compound Tnfection in %
compounds concentration in o~ the untreated
the spray liquor control
(7) 0.025 0,0
(8) 0.025 0.0
(9) 0.025 12,5
Powdery mil~ew o~ barley ( ~ ~ var. hordei)
(~ungal disea~e Or cereal shoot~/systemic
The active compound was u~ed as a pulverulent seed
treatment agent. This was prepared by extending the
particular active compound with a mixture of equal parts
by weight of talc and kie~elguhr to give a finely pulverulent
mixture of the de ired concentration o~ active compound.
For the treatment of seed~ barley seed was shaken
with the extended active compound in a closed glas~ bottle.
me seed was sown at the rate of 3 x 12 grains in flowerpots,
2 cm deep in a mixture o~ one part by volume o~ Fruh~torrer
standard soil and one part by volume o~ quartz sand.
The germination and emergence took plac~ under favourable
conditions in a greenhouse. 7 days a~ter sowing, when
the barley plants had developed their ~irst leaf, they
~er0 dusted with fresh spores of ~ ~ var.
hordei and grown on at 21-22 deg.C and 80-90% relative
atmo~pheric humidity and 16 hour~' exposure to light.
The typical mildew pustule~ ~ormed on the leaves over :~.
the course of 6 days.
Le A 18 115 - 28 -

The degree of in~ection was expressed as a percentage
of the infection of the untreated control plants. Thus~
0% denoted no infection and 100% denoted the same degree
of in~ection as in the case of the untreated control.
The active compound was the more active9 the lower wa~
the degree of mildew infection,
The active compounds and concentrations o~ active
compound in the seed treatment agent 9 as well as the
amount used o~ the latter~ and the percentage infection
with mildew can be seen from the table which follows:
T a b 1 e D
Powdery mildew of barley test (
~raminis var. hordei), systemic
Active Active com- Amount of Infection in
compounds pound con- dressing % of the un-
centration used in treated con-
in the g/kg of trol
dressing in seed
no dressing - - 100
(B) 25 10 100
(8) 25 10 16.3
le E
Mycellum growth test
Nutrient medium used:
20 parts by weight o~ agar-agar
200 parts by weight of potato decoction
5 parts by weight Or malt
15 parts by weight of dextrose
5 parts by weight of peptone
2 parts by weight o~ disodium hy~rogen phosphate
0.3 part by weight o~ calcium nitrate
Le A 18 115 - 29 -

Ratio of solvent mixture to nutrient medium:
2 parts by weight of solvent mixture
100 parts by weight o~ agar nutrient medium
Compo~ition of the solvent mixture:
0.19 part by weight of acetone or DMF
0.01 part by weight of emulsi~ier (alkylaryl polyglycol
ether)
1~80 parts by weight o~ water
The amount of Pctive compound required for the desired
active compound concentration in the nutrient medium
was mixed with the stated amount of solvent mixture.
The concentrate was thoroughly mixed, in the stated proport-
ion, with the liquid nutrient medium (which had been
cooled to 42 degOC) and was then poured into Petri dishes
of 9 cm diameter. ~ontrol plates to which the preparation
had not been added were also set up.
When the nutrient medium had cooled and solidified~
the plates were inoculated with the species oP organi~ms
stated in the table and incubat~d at about 21 deg~C,
Evaluation was carried ou~ after 4-10 days, dependent
upon the speed of growth of the organisms. When evalu-
ation was carried out the radial growth o~ the organism
on the treated nutrient media was compared with the growth
on the control nutrient medium. In the evaluation of
the orga~ism growth~ the ~ollowing characteristic values
were used: ` `
1 no growth
up to 3 very strong inhibition of growth
up to 5 medium inhibition of growth
30up to 7 slight inhibition of growth
Le A 18 115 - 30 ~

9 growth equal to that of untreated control.
The active compounds, the active compound concen-
tration and the results can be seen from the following
tab le:
Le A 18 115 - 31 -
. .. , ... ..... - ... ~ -. . ~ .. .

976
b~
~ pC~
~ ~' 'O~ O~
a~ O s~ O
a~
.,, ~; ~ ~ o o o
o~ ~
.,, C~
C~
¢
Le A 18 115 - 32 --

976
Pre~arativ _exameles
EXample 1
~ .
,Cl ' ~N ~ CH2 - C0 - C(CH333
CH - CH2 - N ~ ~
CH2 ~ ~ - Cl C1 ~3
(1)
Cl'
20.7 g (0 05 mol) of 1-~2~4-dichlorophenyl)-2 (1~2p4-
triazol-l-yl)-ethyl 2,4-dichlorobenzyl ekher and 6.7 g
~0.05 mol) o~ monochloropinacoline were heated under reflux
in 50 ml o~ acetonitrile for 12 hours. m ereafter~ the
mixture was allowed to cool and the solid which had pre-
cipitated waæ ~iltered off~ rin~ed with acetone and dried.
This gave 10.9 g (40g of theory) o~ 2-(2,4-dichloro-
benzyloxy)-2-(2, 4-dichlorophenyl ) -ethyl]-tert~obutyl
carbonylmethyl-1,2,4-triàzolium chloride o~ meltin~ point
216-218C.
~ CH - CH2 - N
CH2 ~ ~ _ Cl
Cl~
25.8 g (0.1 mol) of 1-hydroxy-1-(2,4-dichlorophenyl)-
2~ 2,4-triazol l-yl)-ethane were dissolved in 125 ml of
dioxan and the solution was added dropwise to a mixture of
4 g of 80% pure sodium hydride and 100 ml of dioxan~ whilst
stirrin~. ~herea~ter, the mixture was heated under re~lux
for one hour. A~ter cooling, 20 g ~0.1 mol) of 2t4-
Le A 18 115 ~ 33 -

76
dichlorobenzyl chloride were added dropwise at room
temperature to the sodium salt obtained. The mixtur@
was then heated under reflux ~or several hours, allowed to
cool and concentrated by distilling off the solvent. Water
and methylene chloride were added to the residue and the
organic phase was separated of~9 dried over sodium 3ul-
phate and concentrated. The solid residue was recrystalli~ed
from ligroin. This gave 29 g (70% o~ theory) of 1-(2,4-
dichlorophenyl)-2~ 2,4-triazol-1-yl) ethyl 2,4-dichloro-
benzyl ether oP melting point 84C.
OH
25.6 ~ (0.1 mol~ of ~ 2~4-~riazol-1-yl~-2,4-
dichloroacetophenone were dissolved in 300 ml o~ methanol~
and 4 g (0.1 mol) of sodium borohydride were added in
portions at 5 to 10C~ whilst stirring. The mixture was
then stirred ror a further hour at room temperature and
heat0d to the boil for one hour. Afker distilling orf the
solv~nt, the residue wa3 heated ~or a short tim~ with 200
ml of water and 40 ml of concentrated hydrochloric acid.
After the reaction mixture had been rendered alkaline with
sodium hydroxide solution, th~ solid reaction product could
be filtered of r. Recry tallisation from 1 igroin/iso ~
propanol ~ave 21.3 g ~82% Or theory) o~ 1-hydroxy-1-(2,4-
dichlorophenyl)-2~ 2 3 4-triazol-1-yl)-ethane of melting
poi~t 90C.
Le A 18 115 ~ 34 -

971~i
, Cl N
Cl ~ 0 - CH2 ~ 1
26g g ~1 mol) o~ romo-2 J,4-dichloroacetophenone were
dissolved in 250 ml of acetonitrile. This solution was
added dropwi~e to a suspensiQn" boiling under reflux9 3f
69 g (1 mol) of 1,2,4-triazole and 150 g of potassium
carbonate in 2 litres of acetonitrile. After heating
under reflux for 20 hourR, the cooled suspen~ion was
filtered, the filtrate was ~reed ~rom the ~olvent, the
residue wa~ ta~en up in ethyl acetate and ~he ethyl acetate
solution was washed with water, dried over sodium sulphate
and ~reed from the solvent. On adding isopropa~ol, the
ethyl acetate residue cryskallised out. Recrystallisation
from li~roin/isopropanol gave 154 g (60% of theory) of
~-tl92,4-triazol-1-yl)~2,4-dichloroacetophenone of meltin~
l point 117C.
OEI2 - C0 - ~ - Cl
Cl - ~ CH - CH2 ~ ~ Cl '
CH2 - ~ ~r ~3 (2)
Cl
20.7 g (0.05 mol) o~ 1-(2,4-dichlorophenyl)-2-tl~2,4-
triazol-l-yl)-ethyl 2~6-dichlorobenzyl ether and 13.4 g (0.05
mol~ sf 2,4-dichlorobenzoylmethyl bromide were heated under
Le A 18 115 - 35 -
- - , . ~ . . . . ....... ..... . .... . .
.

7Ç~ :
reflux in 250 ml of chloro~orm for 15 hours. ~he mixture
was allowed to cool and was concentrated by distilling off
the ~olvent in vacuo The residue was boiled up briefly
with acetone. A~ter coolin~ the crystalline residue was
filtered ofr, washed with acetone and dried. Thi~ gav0
5.6 g ~16.5~ of theory) of 1-[2-(2,6-~ichlorobenzyloxy)-
2-(~,4-dichlorophenyl) ethyl~-2,4-dichlorobenzoylmethyl-
192~4~triazolium bromide of melting poin~ 202C.
, Ci / CH
0 ~1
CH
Cl'
20.7 g (0.05 mol) o~ 1-(2,4-dichlorophenyl)-2-(1,2?4-
triazol-l-yl)-ethyl 2,6-dichlorobenzyl ether and 7.1 g
~0.05 mol) o~ methyl iodide were heated under reflux in
100 ml of acetonitrile for 12 hours. Therea~ter, the
mixture was allowed ~o cool and the solid which had pre-
cipitated was ~iltered of~, rinsed with acetone and dried.
This gave 26.7 g (96.7% Or theory) of 1-~2-(2,6-dichloro-
benzyloxy)-2-(2,4-dichlorophenyl)-ethyl]-methyl-1,294-
triazolium iodide vf melting point 228-230C (decompo3ition).
The followin~ compounds in Table 4 were obtained in
an analogous manner.
Le A 18 115 - 36 -

o
J~
_~ Q.
~3 ~ ~D N rl oD ~ N
u~ (D
m
t~ C~
E~ 7
o o o o ~ o o
a~ ~ ;~
~; ~ 0 ~
Le A 18 115 - 37 -

76
ou
_
bO
c ~ æ
~ ~ ~) ~q H H sr~ V
Lr~p; ~ ~U ~
~ ~ ~ $
~P: $ o ~ O 0
rl rl
~æ ,~ D P
~3
Le A 18 115 - 38 -

9~7~
The ~ollowing compounds of the general formula (I) could
be prepared in the corresponding manner:
T a b l e 5
___
Rn Rl R5
Cl~
9 4-Cl2 ~S-CH~ -CH2 -CO~-Cl Br
2 4 Cla -S C2 H~ CO-~Cl :Br
Cl
2, 4-Cl2 S-aC4 H9 -CH2 -CO-~Cl Br
Cl
2,4 Cl2 -S-CH2-CH=CH2 -CH2-CO-~Cl Br
C
2,4-Cl~ -S-CRk~-Cl -CR2-CO-~-Cl Br
2 4-Cl ~ CH2 ~3 -CH2 -C~ Cl Br
Le A 1~ 115 - 39 ~
.Y