Note: Descriptions are shown in the official language in which they were submitted.
Le A 21 385-C~
The present invention re]a-tes to cer-tain new azolyl-
alkenones and -ols, to a process for -their produc-tion, and to
-their use as plant-growth reguiatc)rs and fungicides.
It has already been disclosed tha-t cer-tain 6,6-disub-
stituted 2,2-dimethyl-4-(1,2,4--triazol-1-yl)-hex-5-en-3-ones and
-ols possess good plant growth-regulating and fungicidal properties
(see DE-OS (German Published Specification) 2,905,981). However,
the action of these compounds is no-t always comp:l.etely satisfac-tory,
in particular when low amounts and concentrations are used.
The present invent.ion now provides, as new compounds,
the azolyl-alkenones and -ols of -the general formula
R - X - CH - CH = CH - R
~ N~
N l I
in which Rl represents an alkyl radical, a halogenoalkyl radical
or a phenyl radical, which phenyl radical is op-tionally monosub-
stituted or polysubstituted by identical or different substituent(s)
selected from halogen, alkyl having 1 to 4 carbon a-toms, alkoxy
and alkylthio, each having 1 to 4 carbon atoms, alkylamino and
dialkylamino, each having 1 -to 4 carbon a-toms in each alkyl part,
and also halogenoalkyl, halogenoal]coxy and halogenoalkyl-thio, each
having 1 or 2 carbon atoms and 1 -to 5 identical or different halo-
gen atoms, phenyl and phenoxy, it being possible for -the -two las-t-
mentioned radicals in turn to be substituted by halogen and/or
alkyl having 1 or 2 carbon atoms; R2 represents an alkyl radical,
a phenyl radical, which phenyl radical is optionally monosubsti-
tuted or polysubstituted by iden-tical or different substi-tuen-ts
selected from halogen, alkyl having 1 to 4 carbon atomsl alkoxy
23189-5447 ~ b
and alkylthio, each having 1 to 4 carbon atoms, alkylamlno and
dialkylamino, each having 1 to 4 carbon a-toms in each alkyl part,
and also halogenoalkyl, halogenoalkoxy and halogenoalkylthio, each
having 1 or 2 carbon atoms and 1 to 5 identical or difEerent halo-
gen atoms, phenyl and phenoxy, it being possible -for the two last-
mentioned radicals in turn to be substituted by halogen and/or
alkyl having 1 or 2 carbon atoms, a cycloalkyl radical, which
cycloalkyl radical is optionally substituted by halogen and/or
alkyl having 1 to 4 carbon atoms or a cycloalkylalkyl radical,
which cycloalkylalkyl radical is optionally substitu-ted by halogen
and/or alkyl having 1 to 4 carbon atoms; X represents a CO or
CH(OH) group; and Y represen-ts a nitrogen atom or a CH group; and
the acid addition salts and metal salt complexes thereof.
The compounds according to the invention, of the formula
I, occur as the geometric isomers E(trans) and Z.(cis). In the
E,Z nomenclature, the substituents located at the double bond are
: placed in order of decreasing priority, according to the Cahn-
Ingold Prelog rule. If the preferred substituents are located
on the same side of the doubl.e bond, the configuration Z (derived
from "zusammen" (together)) is present, and if they are located
~ - la -
-- 2 --
on opposite sides, the configuration E (derived From
"entgegen" (opposed)~ is present.
In addition, when X=CH(OH), the compounds according
to the invention, of the formula (I), possess two
asymmetric carbon atoms; they can then be present as
the two geometric isomers (threo form and erythro form),
which may be obtained in varying proportions. In both
cases, -they are present as optical isomers.
The invention also provides a process for the
production of a compound of the present inven-tion,
characterised in that a compound of the general formula
R1 _ CO - f = CH - CH2 - R2 (II)
~N~y
N
in which
R1, R2 and Y have the meanings given above,
is heated in the presence of a diluent and, if appropriate,
in the presence of a catalyst or in the presence of alu-
minium oxide,
and, if a compound in which X represents a CH(OH) group is
required, the resulting azolyl-alkenones according to the
invention, of the general formula
R1 _ CO - CH- CH = CH - R2
¦ (Ia)
N~y
I!
: in which
R1, R2 and Y have the meaning given above,
is reduced;
and, if desired, an acid or a metal salt is added onto the
compound of the present invention produced by the foregoing
process.
Finally, it has been found that the new azolyl-
Le A 21 385
~, _
,
~ r~
alkenones and -ols of the formula (I), and their acid
addition salts and metal salt complexes, possess powerful
plant growth-regulating properties and powerful fungicida:L
properties.
In addition, the new azolyl-alkenones and -ols of
the formula (I) are interesting intermediate products ~or
the preparation of further plant protection ager1ts.
In the keto derivatives, the keto group can be reduced
not only to a -CH(OH~ group (according to the invention)
but also to a -CR(OH) group. 8y appropriate reactions,
it is also possible to obtain functional derivatives of
the keto group, such as oximes and oxirne ethers, hydrazones
and ketals. The hydroxyl group of the carbinol derivatives
can be converted into -the corresponding ethers in a cus-
tomary manner. Furthermore, acyl derivatives of carbamoylderivatives of the compounds of the formula (I) can be
obtained by reaction with, for example, acyl halides or
carbamoyl chlorides, in a manner which is known in principle.
Surprisingly, the compounds according to the
2n invention poe,sess a better plant growth-regulating and
fungicidal action than the 6,6-disubstituted 2,2-dimethyl-
4-(1,2,~-triazol-1-yl)-hex-5-en-3-ones and -ols which are
known from the prior art and are similar compounds chemic-
~; ~ ally and with regard to their action. The active com-
pounds according to the invention thus represent an enrich-
ment of the art.
Preferred compounds according to the present
invention are those
in which
R1 represents a grouping of the general formula
~CH2Z
-C-CH3
CH2Z2
wherein
Le A ~1 38
-- 4
z1 and z2 are identical or different and rPpresen-t
a hydrogen or halogen atom or an alkyl radical
having l to 4 carbon atoms; ~
R1 represents a phenyl radical which is optionally
monosubstituted or polysubstituted (the substlt-
uent(s) thereon preferably being selected from
halogen, alkyl having l to 4 carbon atoms, alkoxy
and alkylthio, each having l to 4 carbon atoms,
alkylamino and dialkylamino, each having 1 to ~
carbon atoms in each alkyl part, and also halo-
genoalkyl, halogenoalkoxy and halogenoalkylthio,
each having l or 2 carbon atoms and l to 5 iden-
tical or dlFferent halogen atoms, such as fluorine
atoms and chlorine atoms, and phenoxy and phenyl
: 1S optionally substituted by halogen and/or alkyl
having l or 2 carbon atoms);
. ~ R2 represents a straight-chain or branched alkyl
radical having l to 12 carbon atoms; phenyl which
is optionally monosubstituted or polysubstitited
2~ by identical or different substituents (the
substituent(s) thereon preferably being selected
from halogen, alkyl having l to 4 carbon atoms,
: alkoxy and alkylthio, each having l to 4 carbon
atoms, alkylamino and dialkylamino, each having
l to 4 carbon atoms in each alkyl part, and also
halogenoalkyl, halogenoalkoxy and halogenoalkylthio,
each having l or 2 carbon atoms and l to 5 identical
or different halogen atoms, such as fluorine atoms
; ~ and chlorine atoms, and phenoxy and phenyl option-
` 30 ally substituted by halogen and/or alkyl having l
or 2 carbon atoms);
and furthermore
: R2 preferably represents a cycloalkyl or cyclo-
alkylalkyl radical which is optionally monos~lb-
stituted or polysubstituted by identical or different
~: :
Le A 21 ~85
:
substituents and each of which has 3 to 7 carbon
atoms in the cycloalkyl part and l or 2 carbon
atoms in each alkyl part (the following being
mentionPd as preferred substituents: alkyl having
l to 4 carbon atoms and halogen)S
X represents a CO or CH(OH) ~roup and
Y represents a nitrogen atom or a CH group.
Particularly preferred compounds of the present
: invention are those
in which
R1 represents a grouping of the general formula
~CH2Z
-C-CH3 ,
wherein
z1 and z2 are identical or different and repre-
~: l5 sent a hydrogen, fluorine, chlorine or bromine
atom or a methyl, ethyl, propyl or butyl; or
Rl represen-ts a phenyl radical which is optionally
; monosubstituted to trisubstituted by iden-tical or
.~ different substituents selected from fluorine7
chlorine, methyl, isopropyl, tert.-butyl, methoxy,
methylthio, isopropoxy, trifluoromethyl, tri-
~` fluoromethoxy, trifluoromethylthio, methylamino,
dimethylamino, and phenoxy or phenyl optionally
substituted by fluorine, chlorine or methyl;
R2 represents a straight-chain or branched alkyl
: radical having 1 to 8 carbon atoms, or a phenyl
which is optionally monosubstituted to trisub-
stituted by identical or different substituents
selected from fluorine, chlorine, methyl, isopropyl,
tert.-butyl, methoxy, methylthio, isopropoxy,
trifluoromethyl, trifluoromethoxy, trifluoromethyl-
thio, methylamino, dimethylamino, and phenoxy or
Le A Z1 }E: 5
v~
phenyl optlonally substituted by fluorine,
chlorine or methyl; and
R2 furthermore represents a cyclopropyl, cyclo-
butyl J cyclopentyl, cyclohexyl, cyclopropylmethyl,
cyclobutylme-thyl, cyclopentylmethyl or cyclo-
hexylmethyl radical, each of which is optionally
substituted by methyl~ ethyl 9 isopropyl, fluorine
or chlorine;
X represents a CO or CH(OH) group and
Y represents a nitrogen atom or the CH group.
In addition to the co~pounds mentioned in the
preparative Examples, the following compounds of the gen-
eral formula (I) may be men-tioned individually (wherein
X represents the CO or the CH(OH) group and Y represents
~ 15 a nitrogen atom or the CH group):
I Table l
R1 - X - CH - CH = CH - R2
~N~y (I)
N !l
. ~
::~ R1 R2
CH2F
H3C- C- -CH2-CH(CH3)2
CH2F
~:
:` CH2Cl
: H3C-C- -CH2-CH(C~I3)2
C~12Cl
(CH3)3C- -CH
(CH3)3C- -CH~
:~
~ ~ Le A ~1 385
-- 7
Table 1 (~on-tinuation)
~1 R . . -
(CH3)3C- -CH
(CH3)3c- -CH2 ~
(C~3)3c- -CH2-cH(cH3)c2Hs
(CH3)3C- -CH2-CH(CH3)C3H7
(CH3)3c- -CH2-CH(CH3)C4Hs
(CH3)3c_ -CH2-C(CH3)3
(CH3)3C- -CH2-CH(C2Hs)2
(CH3)3C_ -CH2-CH(C3H7)2
CH3
(CH3)3C- -CH
CH3
(CH3)3C- -CH
CH3
(CH3)3c- -CH2 ~
( CH3 ) 3C- -CH2\~3
~ (CH3)3c_ -CH(CH3)-CH(CH3)~
: : (CH3)3C- -C(CH3)2-CH(CH3)2
; (CH3)3c_ ~ OCF3
(CH3)3C- - ~ OSCF3
(CH3)3C- ~ OCH3
(CH3)3C- ~ Cl
CH3
Le A 21.:.385
-- 8
Tabl.c l (continuation)
.~
Rl R2 , . . .
~,., . " .
(CH3)3C- ~ Cl
Cl
H3C~_~
(CH3)3C- H3 ~ CH3
(CH3)3C_ ~ C(CH3)3
(CH3)3C- ~ CF3
(cH3)3c- ~
(CH3)3C- ~ N(CH3)2
(CH3)3c_ Cl SCH3
(CH3)3C_
CH3
(C~13)3C- - ~ Cl
~CH3
(CH3)3c_ Cl CH3
Preferred compounds according to the invention, of
course, also include addition products of acids on those
azolyl-alkenones and -ols of the formula (I) in which R1,
R , X and Y have the respective meanings which have already
been menkioned in respect of preferred and particularly
preferred compound of the invention.
Le.A 21 385
-
- 9
The acids which can be used to form adducts
include, as preference, hydrohalic acids (such as
hydrobromic ac.id and9 especially, hydrochloric acid),
phosphoric acid, nitric acid, sulphuric acid, monofunctional
and bifunctional carboxylic acids and hydroxycarboxylic
acids (such as acetic acid 9 maleic acid, succinic acid,
fumaric acid, tartaric acid, citric acid, salicylic acid,
sorbic acid and lactic acid) and sulphonic acids (such
as p-toluenesulphonic acid and naphthalene-1,5-disulphonic
1~ acid)~
Prcferred compounds according to the inv~ntion also
include addition products of salts of metals of main groups
II to IV and of subgroups I and II as well as IV to VIII,
with those azolyl-alkenones and ols of the formula (I)
in which Rl, R2, X and Y ha~e the respective meanings which
have already been mentioned in the description of preferred
and particularly preferred compounds of the invention.
Arnongst these salts, salts of copper, zinc,
manganese, ma~nesium, tin, iron and nickel are particularly
preferred Suitable anions of these salts are those
which are derived from those acids which produce physiologic-
ally tolerated addition products. Particularly pre-
ferred acids of this type, in this connection, are hydro-
halic acids (such as hydrochlic acid and hydrobromic acid),
and also phosphoric acid, nitri.c acid and sulphuric acid.
If, for example, 6-cyclohexyl-2,2-dimethyl-4-
(1,2,4-triazol-1-yl)-hex-4-en-3-one is used as the starting
material, aluminium oxide is used as a reactant and methanol
i8 used as the diluent, the course of the reaction according
to the process of the invention can be represented by the
following equation:
Le A 21 ~85
- 10 -
Al2o3/cH3oH
(CH3)3C-CO-C-cH-cH2 ~ ~~ ~~~ >
Nl N (CH3)3C-CO-CH-CH=CH
~ N
If, for example, 6-cyclohexyl-2,2-dimethyl-4-
(1~2,4-triazol-1-yl)-hex-5-en-3-one is used as -the starting
material and sodium borohydride is used as the reducing
agent, the course of the reaction according to the process
- of the invention can be represented by the following
equation:
NaBH4
(CH3)3C-CO-CH-CH=CH ~ -- - 73
`N (CH3)3C-C~ CH-CH=CH
N ~
~; ~
Preferred compounds of formula (II) required as
starting materials in carrying out the process according to
: the invention are those in which R1, R2 and Y have those
:~: meanings which have already been mentioned for these sub-
: : stituents in connection with the description of the
~; preferred and particularly preferred compounds according
to the invention.
The compounds of the formula (II) are known or
can be prepared in a simple manner, according to pro-
cesses which are known in principle (see DE-OS (German
: Published Specification) 3,000~643 and the literature
q~oted therein). Thus a campound of the formula (II)
is ottained by reacting a keto-enamine of the general
formula
:~ Le A.21 385
.
.
~ ~5~
/ R3
R1 _ CO - C = CH - N (III)
'N`y \ R4
N ¦¦
in which
R and Y have the meaning given above and
R3 and R4 are identical or different and represent
an alkyl radical having l to 4 carbon atoms,
especially a methyl radical,
with an organo-magnesium compound of the general formula
Hal - Mg - R2 (IV)
in which
: 10 R2 has the meaning given above and
Hal represents a halogen atom,
in the presence of an iner-t organic solvent (such as
ether), and, if appropriate, in the presence of an inert
gas (such as nitrogen), at a temperature between -20 and
120C (in this context, see also DE-05 (German Published
Specification~ 3,000,643 and th~ preparative Examples).
~ The keto-enamines of the formula (III) are known
: ~ or can be prepared in a simple manner, according to pro~
cesses which are known in principle (see DE-OS (German
Published Specification) 3,000,643). Thus, a keto-
amine of the formula (III) is obtained by reacting, at the
boil, an azolyl-ketone oF the general formula
R1 - C0 - CH2 - N ~ N (V)
in which
~ ~5R1 and Y have the meaning given above,
: with an amide acetal or aminal ester of the general Formula
Le A 21, 385
- 12 -
CH-N (VIa)
R50 \ R4
or
NR3R4
R50-C~ / (VIb)
\ NR3R4
in which
R3 and R4 have the meaning given above, and
R5 represents an alkyl radical having 1 to 4
carbon atoms,
in a manner which is in itself known, in the presence of
an inert organic solvent, such as an aromatic hydrocarbon
and such as, especially, an amide acetal or aminal ester,
of the formula (VIa) or (VIb), employed in excess (in this
10 context, see also Chem. 8er. 101, 41-50 (1968); J. Org.
Chem. 43, 4,248-50 (1978), and the preparative Examples).
The azolyl-ketones of the formula (V) are known (see,
for example, I)E-OS (German Published Specification)
25431,407 and DE-OS (German Published Specification)
15 2,610,022 and DE-OS (German Published Specification)
2,638,470); or they can be prepared according to customary
methods, by reacting the corresponding halogeno-ketones
with 1,2,4-triazole or imidazole, in the presence of an
acid-binding agent.
The amide acetals or aminal esters of the formulae
(VIa) or (VIb) are generally known compounds of organic
~hemistry (see, for example, Chem. Ber. 101, 41-50 (1968)
` and J. Org. Chem. 43, 4,248-50 (1978)).
; The organo~magnesium compounds of the formula (IV)
25 are generally known compounds of organic chemistry.
Suitable diluents for the process, according to
the invention, for the preparation of the azolyl-alkenones
of the formula (Ia) are organic solvents which are inert
Le A 21 385
'' `-' .
. .
"
under the reaction conditions. These include, as
preferences, ketones (such as acetone and methyl ethyl
ketone), alcohols (such as methanol, ethanol or isopropanol),
aliphatic and aromatic hydrocarbons (such as benzene,
toluene or xylene) J and halogenated hydrocarbons (such as
methylene chloride, carbon tetrachloride, chloroform or
chlorooenzene).
The process, according to th~ invention, for the
i preparation of the azolyl-alkenones of the formula (Ia)
is carried out, if appropriate, in the presence of a base
; as a catalyst. ThesP include, as preferences, organic
nitrogen bases, such as morpholine, pyridine, triethylamine
and N,N-dimethylbenzylamine.
In the process, according to the invention, for
the preparation of the azolyl-alkenones of the formula (~a)
the reaction temperatures can be varied within a rela-
tively wide range. In general, the reaction is carried
out at a temperature bétween 30 and 150C, preferably
between 50 and 120C.
The process, according to the invention, for the
preparation of the azolyl-alkenones of the formula (Ia)
is carried o~t either completely thermally, by heating
the compounds of the formula (II), or as a base-catalysed
reaction, O.l to l mol of base being employed per mol of
; 25 the compounds of the formula (II), or in the presence of
aluminium oxide. The compounds according to the inven-
tion are isolated in a customary manner in all cases.
~ The reduction, according to the invention, for
; the preparation of the azolyl-alkenols of the formula (I)
is effected in a customary manner, for example by reacting
the azolyl-alkenone of the formula (Ia) with a complex
hydride, if appropriate in the presence of a diluent, or
by reacting the azolyl-alkenone of the formula (Ia) with
aluminium isopropylate in the presence of a diluent.
3S If complex hydrides are used, suitable diluents
Le A 21 ~as
14 -
for this reaction according to the invenkion are polar
organic solvents. These include, as preferences, alcohols
(such as methanol, ethanol,butanol or isopropanol) and
ethers (such as diethyl ether or tetrahydrofuran). The
reaction is carried out in general at a temperature from
0 to 3ûC, preferably at from 0 to 20C. For this
purpose, about l reaction equivalent of a complex hydride
(such as sodium borohydride or lithium alanate) is employed
per mol of the ketone of the formula (Ia). To isolate
10 the reduced compounds cf thP formula (I), the residue is
taken up in dilute hydrochloric acid, and the solution is
then rendered alkaline and extracted with an organic solvent.
The further working-up is effected in a customary manner.
If aluminium isopropylate is used, preferred
15 diluents for this reaction a~cording to the invention
are alcohols (such as isopropanol), or inert hydrocarbons
(such as benzene). The reaction temperatwres can again
be varied within a relatively wide range; in general, the
reaction is carried out at a temperature between 20 and
20 120C, preferably at from 50 to 100C. To carry out
~; the reaction, about l to 2 mnl of aluminium isopropylate
are employed per mol of the ketone of the formula (Ia).
To isolate the reduced compounds of the formula (I)~ the
excess solvent is removed by distillation ln vacuo, and
25 the aluminium compound formed is decomposed with dilute
sulphuric acid or sodium hydroxide solution. The further
working-up is effected in a customary manner.
Prefarred acids for the preparation of acid
addition alts of the azolyl-alkenones and -ols of the
30 -formula (I) are those which have already been mentioned
in connection with the description of the acid addition
salts according to the inv~ntion as being preferred acids.
The acid addition salts of the compounds of the
formula (I) can be obtained in a simple manner according
35 to customary methods of salt formation, for example by
Lz A 21 385
~5~3~3
- 15 -
dissolving a compound of the formula (I) in a suitable
inert solvent and adding the acid, for example hydro-
chloric acid, ~nd can be isolated in a known manner, for
example by Filtration, and can be purified, if appropriate,
by washing with an inert organic solvent.
Preferred salts for the preparation of metal salt
complexe~ of azolyl-alkenones and -ols of the formula (I)
are salts of those anions and cations which have already
been mentioned in connection with the description of the
metal salt complexes according to the invention as being
preferred.
The metal salt complexes of compounds of the for-
mula (I) can be obtained in a simple manner according to
customary processes, thus, for example, by dissolving the
metal salt in an alcohol (such as ethanol), and adding
the solution to the compound of the formula (I). The
metal salt complexes can be isolated in a known manner,
for example by filtration, and if appropriate purified by
recrystallisation.
2û The active compounds according to the invention
engage in the metabolism of the plants and can therefore
be employed as growth regulators.
Experience to date of the mode of action of plant
growth regulators has shown that an active compound can
also exert several differen-t actions on plants. The
actions of the compounds depend essentially on the point
in time at which they are used, relative to the stage of
development of the plant, and on -the amounts of active
compound applied to the plants or their environment and
the way in which the compounds are applied. In every
case, growth regulators are intended to influence the
crop plants in the particular manner desired.
Plant growth-regulating compounds can be employed,
for example, to inhibit vegetative growth of the plants.
Such inhibition of growth is inter alia of economic inter-
Lel~ 2~ 385
~ ~S~$~
- 16 -
est in the case of gra~ses, since it is thereby possible
to reduce the frequency of cutting the grass in ornamental
gardens, parks and sportsgrounds, at verges, at airports
or in fruit orchards. The inhibition of growth of
herbaceous and woody plants at verges and in the vicinity
of pipelines or overland lines or, quite generally, in
areas in which heavy additional growth of plants is un-
desired, is also of importance.
The use of growth regulators to inhibit the growth
ln length of cereals is also important. The danger of
lodging of the plants before harvesting is thereby reduced
or completely eliminated. Furthermore, growth regulators
can strengthen the stem of cereals, which again counter-
acts lodging. Use of growth regulators for shortening
and strengthening the stem enables higher amounts of fer-
tiliser to be applied to increase the yield, without
danger of the cereal lodging.
In the case of many crop plants, inhibition of
the vegetative growth makes denser planting possible, so
that grea-ter yields per area of ground can be achieved.
;~ An advantage of the smaller plants thus produced is also
that the crop can be worked and harvested more easily.
Inhibition of the vegetative growth of plants
can also leacl to increases in yield, sinca the nutrients
and assimilates benefit blossoming and fruit formation to
a greater extent than they benefit the vegetative parts
of plants.
Promotion of vegetative growth can also frequently
be achieved with growth regulators. This is oF great
utility if it is the vegetative parts of the plants which
are harvested. Promoting the vegetative growth can, how-
ever, also simultaneously lead to a promotion of gener-
ative growth, since more assimilates are formed, so that
more fruit, or larger fruit, is obtained.
Increases in yield can in some cases be achieved
Le A 21 385
~ ~ ~15~
- 17 -
by affecting the plant metabolism, without noticeable
changes in vegetative growth. A change in the composition
of plants, which in turn can lead to a better quality of
the harvested products, can furthermore be achieved with
grow-th regwlators. Thus it is possible, for example, to
increase the content of sugar in sugar beet, sugar cane,
pineapples and citrus fruit or to increase the protein
content in soya o~ cereals. Using growth regulators it
is also possible, for example, to inhibit the degradation
1û of desired constituents, such as sugar in sugar beet or
sugar cane, before or after harvesting. It is also
possible favourably to influence the production of the
efflux of secondary plant constituents. The stimulation
of latex flux in rubber trees may be mentioned as an
example.
Parthenocarpous fruit can be formed under the
; influence of growth regulators. Furthermore, the gender
of the flowers can be influenced. Sterility of the
pollen can also be produced, which is of great importance
in the breeding and preparation of hybrid seed.
Branching of plants can be controlled by using
growth regulators. On the one hand, by breaking the
apical dominance the development of side shoots can be
promoted, which can be very desirable, especially i.n the
cultivation of ornamental plants, also in connection with
growth inhibition. Qn the other hand, however, it is
also possible to inhibit the growth of side shoots. There
is great interest in this action, for example, in the culti-
vation of tobacco or in the planting o~ tomatoes.
The amount oF leaf on plants can be controlled,
; under the influence of growth regulators, so that defoli-
ation of the plants at a desired point in time is achieved.
Such defoliation is of great importance in the mechanical
harvesting of cotton~ but is also of interest for facili-
tating harvesting in other crops, such as in viticulture.
Le A 2~1 ~85
Defoliation of the plants can also be carried out to lowerthe transpiration of plants before they are transplanted.
The shedding of fruit can also be controlled with
growth regulators. On the one hand~ it is possible to
prevent premature shedding of fruit. However, on the
other hand, shedding of fruit, or even the fall of blossom~
can be promoted up to a certain degree (thinning out)
in order to interrupt the alternance. ~y alternance there
is understood the peculiarity of some varieties of fruit
to produce very different yields from year to year, for
endogenir reasons. Finally, using growth regulators it
is possible to reduce the force required to detach the
fruit at harvest time so as to permit mechanical harvesting
or facilitate manual harvesting.
Using growth regulators, it is furthermore possible
~ to achieve an acceleration or retardation of ripening
- ` of the harvest product, before or after harvesting. This
~ is of particular advantage, since i-t is thereby possible
; to achieve op-timum adaptation to market requirements.
Furthermore, growth regulators can at timss improve the
coloration of fruit. In addition, concentrating the
ripening within a certain period of time is also achievable
with the aid of growth regulators. This provides the
preconditions for being able to carry out complete
mechanical or manual harvesting in only a single pass,
for example in the case of tobacco, tomatoes or coffee.
Using growth regulatorq, it is furthermore possible
to influence the latent period of seeds or buds of plants,
so that the plants, such as, for example, pineapple or
ornamental plants in nurseries, germinate, shoot or blossom
at a time at which they normally show no readiness to do so.
Retarding the shooting of buds or the germination of
seeds with the aid of growth regulators can be desirable in
regions where frost is a hazard, in order to avoid damage
by late frosts.
:
Le A 21 ,385 .
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Finally, the resistance of plan-ts ta frost, drought
or a high salt content in the soil can be induced with
growth regulators. Cultivation of plants in regions which
are usually ~n~uita~le for this purpose thereby becomes
possible.
The preferred time of application of the growth
regulators depends on the climatic and vegetative circum-
stances.
The foregoing description should not be taken as
implying that each of the compounds can exhibit all of the
describsd effects on plants. The effect exhibited by a
compound ln any particular set of circumstances must be
determined empirically.
The active compounds according to the invention
also 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.
Fungicidal agents in plant protection are employed
for combatinS~ Plasmodiophoromycetes, Oomycetes, Chytridio-
; mycetes, Zygomycetes, Ascomycetes, Basidiomycetes and
Deuteromycetes.
The good toleration, by plants, of the active com-
pound~, at the concentrations required -for combating plant
diseases, permits treatment of above-ground parts of
plants, of vegetative propagation stock and seeds, and of
the soil.
As plant protection agents, the active compounds
according to the invention can be used with particularly
good success for combating those fungi which cause powdery
mildew diseases, thus, For combating Erysiphe species,
such as, for example, against the powdery mlldew of barley
or of cereal causative oryanism (Erysiphe graminis)~ for
combating stripe disease of barley (Drechsiera graminea),
for combatin~ Venturia species~ such as, for example,
Le A 21 335
- 20 -
against the apple scab causative organism (Venturia
inaeq~alis), or for combating rice diseases, such as, ~or
example, Pyricularia oryzae and Pellicularia sasakii.
The active compounds can be converted into the
customary formulations, such as solutions, emulsions, sus-
pensions, po~ders, foams, pastes, granules, aerosols, very
fine capsules in polymeric substances and in coating
compositions for seed, as well as ULV ~ormulations.
These formulations may be produced in known manner,
for example by mixing the active compounds with extenders,
tha-t 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 sol~ents can, -For example,
also be used as auxiliary solvents.
As liquid diluents or carriers, especially
solvents, there are suitable in the main, aromatic hydro-
carbons, such as xylene, toluene or alkyl naphthalenes,
chlorinated aromatic or chlorinated aliphatic hydrocarbons,
such as chlorobenzenes, chloroethylenes or methylene chlor-
ide, aliphatic or alicyclic hydrocarbons, such as cyclo-
hexane 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 ketone or cyclohexanone, or strongly
polar solvents, such as dimethylformamide and dimethyl-
sulphoxide, as well as water.
By liquefied gaseou~ 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, chalk3 quartz,
Ls A 21 385
- 21 --
attapolgite, montmorillonite or diatomaceous earth, and
ground synthetic minerals, such as highly-dispersed
silicic acid, alumina and silicates. As olid 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 organlc material such
as sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there may
10 be used non-ionic and anionic emulsifiers, such as polyoxy-
ethylene-fat~y acid esters, polyoxyethylene-fatty alcohol
ethers, for example alkylaryl polyglycol ethers, alkyl
~ulphonates, alkyl sulphates, aryl sulphonates as well as
albumin hydrolysis products. Dispersing agents include,
15 for example, lignin sulphite waste liquors and methyl-
~ cellulose.
; Adhesives such as carboxymethylcellulose and nat-
ural and synthetic polynlers in the form of powders,
granules or latices, such as gum arabic, polyvinyl alcohol
20 and polyvinyl acetate, can be used in the Formulations.
It is possible to use colorants such as inorganic
pigments, for example iron oxida, titanium oxide and
Prussian 31ue, and organic dyest~ffs~ such as alizarin
dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs,
25 and trace nutrients, such as salts of iron, manganese,
boron, copper, cobalt, molybdenum and ~inc.
The formulations in yeneral 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 as a mixture with other
known ac~ive compo~nds, such as fungicides, insecticides,
acaricides and herbicides, and also as mixtures with fer-
tilisers and other growth regulators.
The active compounds can be used as such, in the
Le A 21 ~85
-
- 22 -
form of their formulations or as the use forms prepared
therefrom, such as ready-to-use solutions, emulsifiable
concentrates, emulsions,foams, suspensions, wettable
powders, pas~es, soluble powders, dusting agents and
granules. rhey are used in the customary manner, for
example by watering, spraying, atomising, scattering,
- dusting, foaming or coating. Furthermore, it is
possible to apply the active compounds in accordance with
the ultra~low volume process or to inject the active
compound preparation or the active compound itself into
the soil. It is also possible to treat the seed of
plants.
When the compounds according to the invention
are employed as plant growth regulators, the amoun-ts
applied can be varied within a relatively wide range.
In general, O.Ol to 5û kg, preferably 0.05 to lO kg, are
employed per hectare of soil surface.
When the substances according to the invention
are employed as fungicides, also, the amount applied can
be varied within a relatively wide range, depending on
the type Df application.
Thus, especially in the treatment of parts of
plants, the active compound concentrations in the use
forms are in general between l and 0. 000lo by weight
25 preferably between 0.5 and O.OOlJo by weight.
In the treatment of seed, amounts of active compound
oF O.OOl to 50 9 per kg of seed, preferably O.Ol to lû 9,
are generally required.
In the treatment of soil, active compound
concentrations of O.OOOOl to 0.16 by weight, preferably
û.OOOl to 0.02o~ are generally required at the place of
action~
The present invention also provides plant growth
regulating or fungicidal composition containing as active
ingredient a compound of the present invention in admixture
Le A.21..385
.:
'
with a solid or liquefied gaseous diluen-t or carrier or
in adrnixture with a liquid diluent or carrier containing a
surface-active agent.
The present invention also pro~ides a method of com-
bating fungi which comprises applying to the fungi, or toa habitat thereof, a compound of the present invention
alone or in the form of a composition containing as active
ingredient a compound of the present invention in admixture
with a diluent or carrier.
The present invention also provides a method of
rogulating the growth of plants which cornprises applying to
the plants, or to a habitat thereof, a compound of the
present invention alone or in the form of a composition
containing as active ingredient a compound of the present
in~ention in admixture with a diluent or carrier.
The present invention further provides crops
protected from damage by fungi by being grown in area~ 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.
The prssent invention further provides plants, the
growth of which has been regulated by their being grown in
areas in which immediately prior to and/or during the time
of tho growing a compound of tha presant invention was
applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing
a harYested crop may be improved by the present inven-tion.
The Example: which follow illustrate the prepar-
ation of the substqnces according to the present invention.
3n Preparative E_amples
Example l
~ N (l)
N
Le,A 21,~85
... . .. _ _
a~
- 2~ -
20 g (0.073 mol) of 6-cyclohexyl-2,2-dimethyl-4-
(1,2~4-triazol-1-yl)-hex-4-en-3-one and 2~ 9 of aluminium
oxide in 300 ml of methanol were heated under ~eflux for
24 hours. The reaction mixture was ~llowed to cool and
was Filtered under suction over kieselguhr, and the fil-
; trate was concentrated. 19~9 9 (99O of theory) of 6-
cyclohexyl-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-hex-5-en-
3-one of refractive index nD = 1~4890 were obtained.
Preparation of the starting material
________________________~___________
r-~
a) (CH3)3C - C0 - C = CH - CH
~ N~N
44.4 9 (0.2 mol) of 2,2-dimsthyl-5-dimethylamino-
~ 4-(1,2,4-triazol-1-yl)-pent-4-en-3-one were dissolved in
; 600 ml oF ether, and a solution of 48.2 9 (0.24 mol) of
- cyclohexylmethyl-magnesium bromide in 200 ml of ether was
added at -20C. Stirring was continued for 1.5 hours, the
reaction mixture was adjusted to a pH value of from 7 to
8 with dilute hydrochloric acid. Thereafter, the organic
phase was separated off, washed twice with water, dried
; over sodium sulphate and concentrated. 27.4 9 (49.8~ of
theory) of 6-cyclohexyl-2,2-dimethyl-4-(1,2,4-triazol-1-
;~ yl)-hex-4-en-3-one of reFractive index nD = 1.4910 were
obtained.
-(CH3)3C - C0 - C = CH - N(CH3)2
b) ~ N`N
N LJ
250.8 9 (1.5 mol) of 2,2-dimethyl-4-(1,2,4-triazol-
1-yl)-butan-3~one were heated under reflux with 196 9
(1.65 mol) oF dimethylformamide di~ethylacetal for 5 hours~
Le A 21 -385
i
.
- 25 -
Thereafter, the excess acetal was distilled off. 306 g
(92~o of theory) of 2,2-dimethyl-5-dimethylamino-4~(192,4-
triazol-l-yl)-pent-4-en-3 one of refractive index nD =
1.531 were obtained.
c) (CH3)3C - CO - C~2 - N ~
138 g (2 mol) of 1,2,4-triazole were added in
portions to 276.4 g (2 mol~ of ground potassium carbonate
and 296.2 g (2 mol) of ~-chloropinacolin in 500 ml of
acetone at room temperature, the internal temperature
increasing to the boiling point. The mixture was stirred
- under reflux for 5 hours and was then cooled to room tem-
perature. The reaction mixture was filtered, and the fil-
trate was concentrated by distilling off the solvent in
vacuo. The oily residue crystallised after the addition
of naphtha. 240.8 g (72% of theory) of 2,2-dimethyl-4-
(1,2,4-triaæo:L-l-yl)-butan~3-one^of melting point 62 to
64C were obtained.
Example 2
OH
CH - CH = CH ~ (2)
N ~
10.~ g (0.038 mol) of 6-cyclohexyl-2,2-dimethyl-
4-(1,2,4-kriazol-1-yl)-hex-5-en-3-one (obtained as described
in Example 1) were dissolved in 100 ml of methanol, and a
; solution of 0.38 g (0.01 mol) of scdium borohydride in 5
ml of ice-~ater was added dropwise at -10C. Stirring
was continued for a further 2 hoursl and the reaction
mixture was then ad~ustecl to a pH value of from 6 to 7
with dilute hydrochloric acid. The reaction mixture was
Le ~ 21 385
:
- 26 -
concentrated by distilling off the solvent in vacuo.
The residue was taken up in methylene chloride, and the
solution was washed with water, dried over sodium sulphate
and concentrated. 8.9 g (86% of theory) of S-cyclohexyl-
5 2,2-dimethyl-4-(1,294-triazol-1-yl)-hex-5-en-3 ol of
refractive index nD = 1.4920 were obtained.
The following compounds of the formula (I) were
obtained in a corresponding manner and according to the
processes given:
Table 2
R 1 _ X - CH - CH = CH - R;~
~N~y (I)
N 1¦
Melting point
Example 1 2 (C), refract-
No. R X Y R ive index n~
( 3)3 C0 N C6H13 1.5388
( 3)3 C0 7 15 1.4778
( 3)3 C0 3 7 1.4880
Cl
6 (CH3)3c- C0 N ~ Cl 105-108
7 (CH3)3c- C0 N ~ Cl 1.5512
8 (CH3)3c- C0 N -i-C3H7 1.4871
( 3)3 C0 2 3 7 8
(CH3)3c- C0 N - ~ F 1.5434
~ C 1
11 (CH3)3C-- C0 N ~ -Cl 138-140
Cl~
12 (CH3)3c- C0 N ~ 1.5624
Cl/
13 (CH3)3C- C0 N -CH(C2H5)2 1.4885
Le A 21 385
`: -
- 27 -
Table 2 (continuation) r~lelting point
Examp le 220
No.Rl X Y. R. . .i.ve. in.dex. nD
14ClCH2C(CH3)2- CO N -CH2-i-C3H7 1.4969
15FCH2C(CH3)~- CO N -CH2-i C3 7 1.4777
16(CH3)3c- CH(OH) N - ~ ~ Cl viscous oil
17(CH3)3c- CH(OH) N -C3H7 1.4898
18(CH3)3c- CH(OH) N C6H13 1.4798
19(CH3)3c- CH(OH) N ~ Cl 1.5633
203)3 CH(OH) N -i-C3H7 1.4841
21( 3)3 CH(OH) N -CH2-i-C3H7 1.4857
22(CH3)3c- CH(OH) N -C7H15 1.4807
23(CH3)3c- CH(OH) M ~ F 112-124
Cl
243)3 CH(OH) N - ~ Cl (A form)
25(CH3)3c- CH(OH) N ~ Cl 46-48
26(CH3)3c- CH(OH) N ~ 180 (A form)
Cl
27(CH3)3c- CH(OH) N -CH(C2H5)C4H9 1.4832
28( 3)3 CH(OH) N -CH(C2H5)C4H9 1.4832
29ClCH2C(CH3)2- CH(OH) N -CH2-i-C3H7 1.500].
30 FCH2C(CH3)2- CH(OH) N -CH2-i C3H7 1.4852
31 Cl- ~ CH(OH) N ~ 50-60
32 (CH3)3C- CO CH -C3H7 1.4915
Le A 21 385
.
28 -
Table 2 (continuaticnj Melting point
Example (C), refractive
No. Rl X Y R2 index n20
3)3 CO C6H13 1.4773
34 (CH3)3C- CO CH -C7H13 1.4808
( 3)3 CO CH C8H17 1.4742
36 (CH3)3C- CO CH -C9Hl9 1.4770
7 ( 3)3 CO C~ -C5Hll 1.4890
Cl
38 ( 3)3 CO CH ~ ,-Cl viscous oil
39 - (CH3)3C- CO CH - ~ 1.5018
(CH3)3C- CO 5 11 1.4892
Cl
41 (CH3)3c- CH(OH) CH - ~ Cl 92-96
42 (CH3)3C- CH(OH) CH ~C6Hl3 1.4742
43 (CH3)3C- CH(OH) CH ~ 1.5050
44 Br- ~ r CO N @` 46
Br ~ ~ CO N ~ 107-111
( X CUC 12 )
:: :
46 C3H7-C(CH3)2- CH(OH) N -CH2-i-C3H7 1.4849
A form and B form ~ the two possible geometric isomers
47 CH30-~ ~ CH(OH) N C2H5 1.5320 (A
48 (CH3)3C- CO N -CH2-C(CH3)3 1.4828
49 (C~I3)3C- CO N -CH2 ~ 1.4884
5 (CH3)3C- CH(OH) N -CH2 ~ 1.4887
51 (CH3)3C- CH(OH) N -CH2-C(CH3)3 62
52 C1- ~ CH(OH) N -CH2-i-C H 49
53 CH30 ~ CH(OH) N C2H5 Lio (B form)
: ` ~
54 Cl ~ CH(OH) N C2H5 67
Le A 21 385
:`
.
- 29 -
Table ~ (conti.nuation) Melting point
(C), rer~c-tive
Example 1 2 20
No. R X Y R index nD
C3H7-C (CH3) 2- CO N -CH2-C3E~7-i 1 . 4819
56 (CH3) 3C- CO 2 ( 3) 2H5
3 ) 3 CH ( OH ) N -CH2-CH (C~13) -C2H5 1 4 81 9
~: 58 Cl~O~ CO N CH3 1 . 5996
The plant growth regulating and fungici.dal 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 correspon~ing preparative Example.
~ he known comparison compounds are identified as
ollows:
OH / CH3
(A) = (CH3)3C-~H-CH-CH=C
:~ 0
; ~ (CH3)3C-CH-CH-CH
(B) = ~ N~N
: : N l¦
OH ,CH3
(C) = (CH3)3C-CI - IH-CH=C~
OH
(D) (CH3)3C-CH-~H-CH= ~
N ~ x H2SO4
`; :
(E) - (CH3)3C-CO-CH-CH= ~
N~N CH3
N l¦
Le ~ 21 385
_ , . ... . . ... . ..... . . . . . . . . . . .
- 30 -
Example A
Inhibition of growth o~ soya ~eans
Solvent: 30 parts by weight of dimethylformamide
~mulsifier: 1 part by weight of polyoxyethylene sorbitane
monolaurate
To produce a suitable preparation of active com-
pound, 1 part by weight of active compound was mixed with
the stated amounts of solvent and ernulsifier and the mix-
ture was made up to the desired concentration with water.
Soya bean plants were grown in a greenhouse until
the first secondary leaf had unfolded completely. In
this stage, the plants were sprayed with the preparations
of active compound until dripping wet. After 3 weeks,
the additional growth was measured on all the plants and
the inhibition of growth in per cent of the additional
growth of the control plants was calculated. 100~ inhi-
bition of growth meant that growth had stopped and 0%
denoted a growth corresponding to that of the control
plants.
In this test, the active compounds (21) and (19)
according to the in~ention showed a better inhibition of
growth than the compound (~) which is known from the prior
art.
Example B
Inhibition of growth of grass (Festuca pratensis)
Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of polyoxyethylene sorbitane
monolaurate
~o produce a suitable preparation of active com-
3 pound, 1 part by weight of active compound was mixed withthe stated amounts of solvent and emulsifier and the mix-
ture was made up to the desired concentration with water.
Grass (Festuca pratensis) was grown in a green~
house up to a height in growth of 5 cm. In this stage,
the plants were sprayed with the preparations of active
Le A 21 385
5~
- 31 --
compound until dripping wet. After 3 weeks, the additional
growth was measured and the inhibition of growth in per
cent of the additional growth of the control plants was
calculated. 100% inhibition of growth meant that growth
had stopped and 0% denoted a growth corresponding to that
of the control plants.
In this test, the active compound (21) according
to the invention showed a substantially better inhibition
of growth than the compounds (A) and (B) which are known
from the prior art.
Example C
Influence on_growth of sugar beet
Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of polyoxyethylene sorbitane
monolaurate
To produce a suitable preparation of active com-
pound, 1 part by weight of active compound was mixed with
the stated amounts of solvent and emulsifier and the
mixture was ~.ade up to the desired concentration with
water.
Sugar beet was grown in a greenhouse until f`orm-
ation of the cotyledons was complete. In this stage, the
plants were sprayed with the preparation of active com-
pound until dripping wet. After 14 days, the additional
growth of the plants was measured and the influence on
growth in per cent of the additional growth of the con-
trol plants was calculated. 0% influence on growth
denoted a growth which corresponded to that of the control
plants. Negative values characterised an inhibition of
growth in comparison to the control plants, whilst
positive values characterised a promotion of growth in
comparison to the control plants.
In this test, the active compounds (16), (1&), (19),
(21), (26), (36) and (41) according to the invention had
a greater influence on growth than the compounds (C) and (D)
1e_A 21 385
G`.~
- 32
known from the prior art.
Exam
In~ibition of growth of cotton
Solvent: 30 parts by weight of dimethylformamide
Emulsifier: l part by weight of polyoxyethylene sorbitane
monolaurate
To produce a suitable preparation of active com-
pound, 1 part by weight of active compound was mixed with
the stated amounts of solvent and emulsifier and the
mixture was made up to the desired concentration with
water.
Cotton plants were grown in a greenhouse until the
5th secondary leaf had unfolded completely. In this
stage, the plants were sprayed with the preparations of act-
ive compound until dripping wet. After 3 weeks, theadditional growth of the plants was measured and the
inhibition of growth in per cent of the additional growth
of the control was calculated. 100% inhibition of growth
meant that growth had stopped and 0% denoted a growth
corresponding to that of the control plants.
~ In this test, the active compounds (1~, (6), (10),
; (11), (16) and (25) according to the invention show a
better inhibition of growth than the compounds (A), (B)
and (E) known ~rom the prior art.
Example E
2 in soya beans
Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of polyoxyethylene sorbitane
monolaurate
To produce a suitable preparation of active com-
pound, l part by weight of active compound was mixed with
the stated amounts of solvent and emulsifier and the
mixture was made up to the desired concentration with
water.
Soya bean plants were grown in a greenhouse until
:
Le A 21 385
,
the first secondary leaf had completely unfolded. At
this stage, the plants were sprayed with the preparations
of active compound until dripping wet. In the further
course of the experiment, the fixation of C02 in the
plants was determined by customary methods. The values
were compared with those of the control plants which had
not been tr-eated with the active compounds.
The figures of merit had the following meanings:
denoted inhibition of the fixation of C02
0 denoted fixation of C02 as in the case of the
control
+ denoted low stimulation of the fixation of C02
~+ denoted powerful stimulation of the fixation of C02
~++ denoted very powerful stimulation of the fixation
f C2
In this test, the active compounds (1) a~ld (22)
according to the invention showed stimulation of the fixat-
ion of C02~ in contrast to the compounds (A), (B) and (E)
known from the prior art.
ExamPle F
_ _
Erysiphe test ~
Solvent: 100 parts by weight of dimethylformamide
Emulsifier: 0.25 part by weight of alkylaryl polyglycol
ether
To produce a suitable preparation of active com-
pound, 1 part by weight of active compound was mixed with
the stated amounts of solvent and emulsifier, and the
concentrate was diluted with water to the desired conc-
; entration.
To test for protective activity, young plants were
; sprayed with the preparation of active compound until dew-
moist. After the spray coating had dried on, the plants
were dusted with spores of Erysiphe graminis f.sp. hordei.
The plants were placed in a greenhouse at a temper-
ature of about 20C and a relative atmospheric humidity of
I.e A 21 385
- 34 -
about 80%, in order to promote the development of powdery
mildew pustules.
~val~ation was carried out 7 days after the
inoculation.
In this test, a clearly superior activity com-
pared with the compound (E) known ~rom the prior art was
shown, for example, by the compounds (5), (32), (34)7 (35),
(36), (4G), (42), (38), (~), (17), (18) 3 ( 19), (20), (21),
(22)~ (10), (11), (25) and (12).
10 ~
Drechslera graminea test (barley)/seed treatment
(syn. Helminthosporium gramineum)
The active compounds were used as dry dressings.
These were prepared by extending the particular active com-
pound with a ground mineral to give a finely pulverulent
mixture, which ensured uniform distribution on the seed
surface.
To apply the dressing, the infected seed was shaken
with the dressing in a closed glass flask for 3 minutes.
The seed was embedded in sieved, moist standard
soil and was exposed to a temperature of 40C in closed
Petri dishes in a refrigerator for 10 days. Germination
of the barley, and possibly also of the fungus spores,
was thereby initiated. 2 batches of 50 grains of the
pregerminated barley were subsequently sown 3 cm deep in
standard soil and were cultivated in a greenhouse at a
temperature of about 18C in seedboxes which were exposed to
light for 15 hours daily.
About 3 weeks after sowing, the plants were evaluated
3 for symptoms of stripe disease.
In this test, a clearly superior activity compared
with the compound (B) known from the prior art was shown,
for example, by the compounds (17) and (21).
Le A 21 385
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