Note: Descriptions are shown in the official language in which they were submitted.
1 1682~8
The present invention relates to certain new triazolyl-
propenol derivatives, to a process for their production and to their
use as plant growth regulators and fungicides.
It has already been disclosed that 4,4-dimethyl-1-phenyl-
2-triazolyl-1-penten-3-ols have a good fungicidal activity (see
DE-OS (German Published Specification) 2,838,847). However, the
action of these compounds is not always completely satisfactory,
especially when low amounts and concentrations are applied. The
plant growth-regulating action of these azole derivatives is
likewise not always completely satisfactory.
The present invention now provides, as new compounds, the
triazolylpropenol derivatives of the general formula
~ OH (I)
Rn
in which
R represents a halogen atom, an alkyl, halo-alkyl, halo-
alkoxy, alkoxy, alkylthio, halo alkylthio, alkylamino, dialkylamino,
nitro, cyano, hydroxyl or alkylcarbonyloxy radical, or represents a
phenyl, phenoxy radical or benzyloxy radical which is optionally
monosubstituted or disubstituted by identical or different
substitu~nts selected from fluorine, chlorine and methyl,
n is 0, 1, 2, 3, 4 or 5, and
X represents a cycloalkyl radical which can be monosub-
: stituted or polysubstituted by identical or different substituents
selected from methyl, ethyl, vinyl, allyl, fluorine, chlorine,
chloromethyl, trifluoromethyl, dichlorovinyl, dibromovinyl, methoxy,
1 ~824~
chlorophenyl, chlorobenzyl, dichlorophenyl, dichlorobenzyl,
trimethylene and isobutylene or represents a grouping of the
formula -CRlR2-y
where!in
Rl and R2 are identical or different and represent alkyl
radicals and
Y represents an alkyl radical with more than 1 carbon atom,
or an alkoxycarbonyl radical, or represents a phenyl radical which
is optionally substituted by Rn;
and non-phytotoxic acid addition salts and metal salt complexes
thereof wherein the metal is selected from those in main groups
II to IV and in sub-groups I, II and IV to VIII of the periodic
table.
The compound~ of the formula (I) according to the
invention occur in the geometric isomers E (trans) and Z (cis).
In the E/Z nomenclature, the substituents on the double
bond are arranged in order of decreasing priority in accordance
with the Cahn-Ingold-Prelog rule. If the preferred substituents
are on the same side of the double bond, the compound has the
Z (derived from "zusammen" (together)) configuration, and if they
are on opposite sides, the compound has the E (derived from
"entgegen" (opposite)) configuration.
Since an asymmetric carbon atom is also present, the
compounds of the formula (I) can occur in two optical isomer forms.
The present invention relates both to the individual
isomers and to the isomer mixtures.
According to the present invention ~here is further
provided a process for the production of a compound of the
,
1 1~8248
invention, characterised in that a triazolylpropenone derivative
of the general formula
~ - CH = C - CO - X (II)
Rn ~ N
N
in which
R, X and n have the abovementioned meaning,
is reduced, and the compound of the formula (I) thus obtained is
then converted, if desired, into an acid addition
~,
-2a-
1 1682
salt or ~etal salt co~plex thereof.
Finally, it has been found that the new tnazolyl-
propenol derivatives of the formula (I) and acid addition
salts and metal salt complexes thereof have powerful plant
growth-regulating and powerful fungicidal properties.
Surprisingly, the co~.pounds of the present invention,
exhibit a better growth-regulating and fungicidal action
than the 4,4-dimethyl-1-phenyl-2-triaYolyl-l-penten-3-olS,
which are known from the state of the -art and are closely
lC related compounds chemically and from the point of view of
their action. The active compounds according to the
invention thus represent an enrichment of the art.
Preferred triazolylpropenol derivatives according
to the present invention are those in which R represents
a fluorine, chlorine or bromine atom; a straight-chain or
branched alkyl, alkoxy or alkylthio radical with in each
case 1 to 4 carbon atoms; a halogenoalkyl, halogenoalkoxy
or halogenoalkylthio radical with in each case 1 or 2
carbon atoms and up to 5 identical or different halogen
atoms (such as, preferably, fluorine and chlorine atoms); an
alkylamino or dialkylamino radical with in each case 1 or 2
carbon atoms in each alkyl part; or a nitro, cyano or
hydroxyl radical, an alkylcarbonyloxy radical with 1 to 4
carbon atoms in the alkyl part; an optionally substituted
phenyl, phenoxy or benzyloxy radical (preferred substituents
which may be mentioned being: fluorine, chlorine, bromine
and alkyl with 1 or 2 carbon atoms), n is 0, 1, 2 or 3,
X represents an optionally substituted cycloalkyl radical
with 3 to 7 carbon atoms (preferred substituents which may
be mentioned being: alkyl with 1 to 4 carbon atoms,
alkenyl with 2 to 4 carbon atoms, halogenoalkyl with 1 to 4
carbon atoms and up to 5 identical or dif4erent halogen
atoms (halogen atoms which may be mentioned being fluorine,
chlorine and bromine atoms), halogenoalkenyl with 2 to 4
carbon atoms and up to 5 dentical or different halogen
. .
Le A 20 458
-
1 1~824~
atoms (halogen atoms which may be mentioned being fluorine,
chlorine and bromine atoms), halogen, alkoxy with 1 to 4
carbon ato~s and a two-membered to five-membered methylene
bridge, optionally substituted phenyl or benzyl (preferred
substituents which may be mentioned being fluorine, chlorine
and bromine atoms); or represents a grouping of the general formula
-CR1R2-Y, in which R1 and R2 are identical or different and represent a
straight-chain or branched alkyl radical with 1 to 4 carbon atoms, and
Y represents a straight-chain or branched aikyl radical with more than
1 carbon atom, an aIkoxycarbonyl radical with 1 to 4 car~on atoms in the
aIkyl part or a phenyl radical which is optionally substituted by Rn (in
which R and n have the immediately a~ove-mentioned meanings).
Particularly preferred compounds of the present
invention are those in which R repres~nts. a fluorine or
15 .chlorine atom or a methyl, isopropyl, tert.-butyl, methoxy,
methylthio, isopropoxy, trifluoromethyl, difluorochloro-
methyl, fluorodichloromethyl, trichloromethyl, 1,1,2-
trifluoro-2-chloro-ethyl, trifluoromethoxy, trifluoromethyl-
thio, 1,1,2-trifluoro-2-chloro-ethoxy and -ethylthio,
dimethylamino, nitro, cyano, hydroxyl, acetoxy or tert.-butyl-
carbonyloxy radical, or represents a phenyl, phenoxy or
benzyloxy radical which is optionally monosubstituted or
disubstituted by identical or different substituents
selected from fluorine, chlorine and methyl, n is 0, 1, 2 or
3; X represents a cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl or cycloheptyl radical, which can be monosub-
stituted or polysubstituted by identical or different
substituents selected from methyl, ethyl, vinyl, allyl,
fluorine, chlorine, chloromethyl, tri~luoromethyl, di-
chlorovinyl, dibromovinyl, methoxy, chlorophenyl, chloro-
benzyl, dichlorophenyl, dichlorobenzyl, trimethylene and
isobutylene, or represents a grouping of the general formula
-CR1R2-Y in which R1 and R2 are identical or different and
represent a methyl, ethyl, isopropyl, n-propyl or tert.-
butyl radical, and Y represents an ethyl, isopropyl, n-
propyl, isobutyl or tert.-butyl radical, a methoxy-, ethoxy-,
:Le A 20 458
1 1682~
isopropox~J-, isobutoxy- or tert.-buto~y-carbonyl radical
or a phenyl which is optionally substituted by Rn (in which
R and n have the im~ediately abo~ementioned meanlrgs).
The following ccmpounds of the general formula
~T) may be mentioned specifically, in addition to the
compounds mentioned in the Preparative Examples:
Table 1 OH
~ CH = C - CH - X
Rn ~ N ~ (I)
N ~
~n X
.
2-CF
4-SCF3 -
4-C(CH3)
4-OH
2-OH, 3,5-Cl
4-NO
4-OH, ~-OH
4 ~ C
4 ~ Cl C
4-0
4-G ~ Cl
Le ~. 20-458
.
.E~ '
1682
-- 6 --
.... ,,.,,.,Rn.,, x
. _
4-0-CH2 ~ CH3
4-0-CH2 ~Cl CH3
4-Cl
4-F
2-Cl
2, 4-C1
2,4-Cl2 ~
4-Cl ~Cl
4-F ~lCl
2-Cl ~,Cl
2,4-Cl2 ~lC
2-Cl, 4-CF3 Cl
4-Cl _<~
4-F ~>
2-Cl
2,4-Cl2 ~>
2-Cl, 4-CF3 ~
CH=CCl2
4-Cl ~CH3
CH3
Le A 20 45 8
16824
7 -
....... Rn .. . .. x
.. . . . .
~--CH=CCl2
4-F ~CH3
CH3
~CH=CCl2
2-Cl \I~CH3
CH3
~CH=CCl2 ,
2, 4-Cl2 --~CH5
CH3
~CH=CCl2
2-Cl, 4-CF3 . I~CH~
CH3
CH3
4-Cl ~1
4-F ~ Cl
CH3 ~
2-Cl ~Cl
Cl
CH3
2,4-C12 ~cC
CH3
2-Cl, 4-CF3 ~ Cl
Cl
4-Cl O
4-F ~O
2-Cl -O
2, 4-C12 ~0
L;e A 2~ 45 8
-
1 16824
-- 8 --
,,,, , Rn - - - ~
... _ .. . .
2-Cl, 4-CF3 -O
4-Cl {1
4-F -a
2-Cl -a
2, 4-C12 {~
2-Cl ~ 4-CF3 {I
4-Cl -O
4-F ~O
2-Cl {>
2 ,4-C12 -
2-Cl, 4-CF3 {~
4-F -C ( CH3 )2 ~)
2-Cl -C(CH3 )2
2, 4-Cl2 -C ( CH3 )2
4-CF3 -C(CH3 )2
2-Cl, 4-CF3 -C ( CH3 )2 ~
4-OCF3 -C(CH3 )2~)
4-Cl -C(CH3 )2 ~Cl
4-F -C ( CH3 ) 2 ~)-Cl
2,4-Cl2 -C(CH3 ~2 ~Cl
4-CF3 -C ( CH3 )2 ~Cl
2-Cl, 4-CF3 -C ( CH3 ) 2 ~Cl
4-oCF3 -C ( CH3 )3 ~-Cl
Le A 20 458
_
1 1682
R . . ... X . .
. n. . ....... .......
... . . . .
4-Cl -C(CH3 ) (C2H~ )~
4-F -C(CH3 ) (C2Hs )~
2, 4-Cl2 -C ( CH3 ) ( Cz Hs ) ~)
4-CF3 -C(CH3 )(C2Hs )~
2-Cl, 4-CF3 -C(CH3 )(C2H5 )~
4-OCF3 -C ( CH3 ) ( C2 Hs )
4-Cl -C(CH3 )2-COOCH3
4-F -C ( CH3 )2 -COOCH s
2-Cl -C(CH3 )2-COOCH3
2, 4-Cl2 -C ( CH3 )2 -COOCH3
4-CF3 -C ( CH3 )2 -COOCH3
~4-OCF3 -C(CH3 )2-COOCH3
2-Cl, 4-CF3 -C ( CH3 )2 -COOCH3
2-CF3 -C (CH3 `)2 -COOC2 Hs
4-SCF3 -C(CH3 )2-COOC2H,
4-C (CH3 )2 -C (CH3 )2 -COOC2 H~
4-OH -C (CH3 )2 -COOC2 Hs
2-OH, 3, 5-C12 -C ( CH3 )2 -COOC2 Hs
4-NO~ -C(CH3 )2-COOC2Hs
4-oH, 3-OCH3 -C(CH3 )2-COOC2Hs
4~ -C (CH3 )2 -COOC2 Hs
4~Cl -C ( CH3 )2 -COOC2 Hs
Le A 20 458
.
ll~s24a
-- 10 --
4_o ~ -C(CH3 )2 -COOC2 Hs
4-0 ~ Cl -C(CH3 )2 -COOC2 H~
4-OCH2 ~ -C(CH3 )2 -
4-O-CH2 ~ Cl -C(CH3 )2 -COOC2 H~
2-Cl -C(CH3 )2 -COOC2 Hs
2,4-Cl2 -C(CH3 )2-COOC2 Hs
4-F -C(CH3 )2 -C2 ~5
2-Cl -C(CH3 )2 -C2 Hs
2,4-Cl2 -C(CH3 )2 ~C2Hs
4-CF3 -C(CH3 )2 -
4-oCF3 -C(CH, )2 -C2 Hs
2-Cl, 4-CF3 -C(CH3 )2 -C2H~
4-F -C(CH~ ~2 -C3H7
2-Cl -C(CH3 )2 -C~ H7
2,4-Cl2 -C(CH3 ) 2 -C3 H7
4-CF3 . -C(CH3 )a -C3H7
4-OCF3 -C(cH3 )2 -C3 H7
2-Cl, 4-CF3 -C(CH3 j2 -C3 H7
4-Cl -C(CH3 )(C2 Hs )2
4-F -C(CH3 )(C2H~ )2
2-Cl -C(CH3 )(C2 Hs )2
2,4-Cl2 -C(CH~ )(C2H~ )2
4-CF3 -C(CH3 )(C2H~ )2
4-OCF3 -C(CH3 ) (C2H~ )2
2-Cl, 4-CF3 -C(CH3 )(C2Hs )2
e A 20 458
2 4 ~
If, for example, 1-(4-chlorophenyl)-4-methyl-4-
phenyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one and sodium
borohydride are used as starting substances, the course
of the reaction according to the present invention ls
illustrated by the following equation:
Cl ~ CH= -C0-~ ~ NaBH4 Cl ~ CH=C-CX-C
~ ~ N ~ ~ CH3
E/Z-isomer mixture E/Z-isomer mixture
If, for example, l-methylcycloprop-l-yl 1-(1,2,4-
triazol-l-yl)-2-(4-chlorophenyl)-ethen-1-yl ketone and
aluminium isopropylate are used as starting substances,
the course of the reaction according to the present
invention i~ illustrated by the following equation:
Cl ~ CH=~-C ~ Al( OC3 H~ -i )3~ Cl~CH~
~11 ' ~1
E/Z-isomer mixture Z-isomer
Preferred triazolylpropenone derivatives of formula
(II) requred as starting substances for the reduction
according to the invention are those in which X, R and n
have the meanings which have already been mentioned in
. connection with the description of the preferred and
particularly preferred substances according to the present
invention.
The triazolylpropenone derivatives of the formula
(II) are novel. Ho~7ever, they can be obtained in a known
manner,. by reac~ing a triazolyl-ketone of the general
Le A 20 458
1 16824~
formula
H2Ç - CO -. X
~ (III)
in which
X have the abo.ve.mentioned meaning,
with an aldehyde of the general formula
~ - CH = 0 (IV)
.Rn
in which
R and n have. the ab.oveme.ntioned meaning,
in the presence of a solvent and in the presence of a
catalyst.
Preferred possible solvents for the preparation
of the triazolylpropenone derivati~es of the for~ula (II)
are inert organic solvents. These include, as preferences.
alcohols (such as methanol and ethanol); ethers (such as
tetrahydrofuran and dioxane); aliphatic and cyclo-
aliphatic hydrocarbons (such as hexane and cyclohexane);
aromatic hydrocarbons (such as benzene, toluene and cumene);
and halogenated aliphatic and aromatic hydrocarbons (such
as methylene chloride, carbon tetrachloride, chloroform,
chlorobenzene and dichlorobenzene).
The preparation of the compounds of the formula
(II) is carried out in the presence of a catalyst. It is
possible to employ any of the acid and, in particular, basic
catalysts which can customarily be used, as well as buffer
~ixtures thereof. These catalysts incl.ude, preferably,
Lewis acids (such as boron trifluoride, boron trichloride,
tin tetrachloride or titanium tetrachloride); or~anic
bases ~such as pyridine and piperidine), and, in particular,
piperidine acetate.
Le A 20 ~58
1 168248
The reaction temperatures can be varied within a
substantia, ran~e when carrying out this process. In
general, the reaction is carried out at a temperature
between 20 and 160C, preferably at the boiling point of
the particular solvent.
In carrying out this process, 1 to 1.5 ~loles of
aldehyde of the formula (IV) and catalytic to 0.2 molar
amounts of catalyst are employed per mole of triazolyl-
ketone of the formula (III). The products of the
formula (II) are preferentially obtained as E/Z-isomer
mixtures. They can be separated into the pure isomers
in the customary manner, such as, for example, by crystal-
lisation or by chromatographic separation processes.
The, triazolylpropeno,ne derivatives of the formula
, 15 (II) are generally interesting intermediate products, for
example, for the preparation of the compounds of the
formula (I) according to, the invention. In appropriate
concentration~, the~J also exhibit growth-regulating and
fungicidal prope,rties.
Some of the triazolyl-ketones of the formula
(III) are known (see DE-OS (German Published Specification)
2,431,407 and DE-OS (German Published Specification)
2,638,470), and some of ~hem are claimed in general terms
therein without being mentioned therein by name. The
triazolyl-ketones of the general formula
H2C -` CO - X1
(V)
~,
~J
in which
x1 represents optionally substituted cyclopropyl or
optionally substituted cyclobutyl or a grouping of
the general formula -CR1R2-Y1,
wherein
R1 and R2 have the above-mentioned meaning and
y1 represents an optionally substituted phenyl
Le A 20 458
1 168248
- 14 -
.
radical or an alkoxycarbonyl radical, and
preferably has~the corresponding preferred meanin~s
of Y,
are completely new.
The triazolyl-ketones. of the formula (V) can be
obtained by generally known processes, by reacting a
halogenoketone of the general formula
Hal-CH2-C0-Xl (VI)
in which
Xl has the aboveme.ntioned meaning and
Hal represents a chlorine or bromine atom~
with 1,2,4-triazole in t,he pre.se.nce of a diluent and in the
presence of an acid-binding agent.
Preferred possible diluents for the preparation of
the triazolyl-ketones of the formula (~) are inert organic
solvents. These include, preferably, ketones (such as
acetone and methyl ethyl ketone); nitriles (such as
acetonitrile); ethers (such as tetrahydrofuran or dioxane);
aromatic hydrocarbons (such as benzene and toluene);
20. formamides (such as dimethylformamide); and halogenated
hydrocarbons.
This process i~ carried out in the presence of an
acid-binding agent. It is possible to add any of the
inorganic or organic acid-bindings agents which can cus-
tomarily be used, such as alkali metal carbonates (forexample sodium carbonate, potassium carbonate and sodium
bicarbonate); al~ali metal alcoholates (such as sodium
methylate or sodium ethylate); lower te,rtiary al~.yl-
a~ines, cycloalkylamines or aral~ylamines (such as tri-
ethylamine, dimethylbenzylamine or dimethylcyclohexylamine);or such as pyridine and an appropriate excess of 1,2,4-
triazole.
The.re,acti.on temperatures. can be. varied within a
~e A 2~ 458
.
.
1 1~8248
-- 15 -
substantial range in carry ng out this process. Ingeneral, the reaction is carried out at a temperature
between 0 and 120C, preferably between 20 and 100C.
In carrying out this process, 1 to 2 ~.oles of
5 1,2,4-triazole and 1 to 2 moles of acid-binding agent
are preferably employed per mole of the compounds of the
formula (~I). The compounds of the formula (V) are
isolated in the customary manner.
The halogenoketones of the formula (VI) are
known, or they can be obtained in a generally known manner,
by adding chlorine or bromine to a compound of the general
formula
H3C-C0-Xl (VII)
in which
xl has the abovementioned meaning,
in the pre~ence of an inert organic solvent at room
temperature; or, for example, by reacting a compound of
the formula (VII) with a chlorinating agent, such as
sulphuryl chloride, at 20 to 60C.
The aldehydes of the formula (IV) also required
as starting substances for the preparation of the tri-
azolylpropenone derivatives of the formula (II) are generally
known compounds of organic chemistry.
The reduction according to the invention is carried
out in the customary manner, for example by reaction with
complex hydrides, if appropriate in the presence of a diluent
The starting substances of the formula (II) can be employed
in the form of E/Z isomer mixtures or as pure isomers.
If complex hydrides are used, possible diluents for
the reaction according to the invention are polar organic
solvents. These include, preferably, alcohols (such as
methanol, ethanol, butanol or isopropanol), and ethers (such
as diethyl ether or tetrahydrofuran). The reaction is in
Le ~ 20 458
1 168248
- 16 -
general carried out at a temperature between -10 and +30C,
preferably at between -10 and~20C. For this reaction,
about 1 mole of a complex hydride, such as sodium boro-
hydride, calcium borohydride or lithium alanate,-are employ-
ed per mole of the ketone of the formula (II). Isolationof the compounds according tG the invention is carried out
in the customary manner, as is any separation of the E~Z
isomer mixtures which are always formed in the reduction
with complex hydrides if E/Z-isomer mixtures are used as
starting materials of the formula (II).
If aluminium isopropylate is used, preferred
possible diluents for the reaction according to the
invention are alcohols (such as isopropanol) or inert
hydrocarbons (such as benzene). The reaction temperatures
can again be varied within a substantial range; in general,
the reaction is carried out at a temperature between 20 and
120C, preferably at between 50 and 100C. For carrying
out the reaction, about 1 to 2 moles of aluminium isopropyl-
ate are employed per mole of the corresponding ketone of
the formula (II). The compounds according to the invent-
ion are isolated in the customary manner.
In the reduction with aluminium iscpropylate,
exclusively the Z-isomers are obtained.
The Hl-nuclear magnetic resonance of the two
triazole protons is an unambiguous ch~racterislng feature
of the two geometric iaomers. The difference between
the shift values of these two protons in the E-forms is
approximately twice the value of the difference in the
corresponding Z-forms.
The following acids can be used for the preparation
of physiologically acceptable acid addition salts of the
compounds of the formula (I): hydrogen halide acids (such
as hydrobromic acid and, preferably, hydrochloric acid),
phosphoric acid, nitric acid, sulphuric acid, monofunctional
and bifunctional carboxylic acids and hydroxy-carboxylic
Le A 20 458
~6824a
-- 17 --
acids (such as acetic acid, maleic acid, succinic aci`d,
fumaric acid, tartaric acld, citric acid, sal.icylic acid,
sorbic acid and lactic acid), and sulphonic acids (such as
p-toluene-sulphonic acid and 1,5-naphthalenedisulphonic
acid).
The acid addition salts of the compounds of the
formula (I) can be. obtained in a simple manner by
customary salt formation methods, for example by dissolving
a compound of the formula (I) in a suitabie inert solvent
and adding the acid, for example hydrochloric ac.id, and
they can be isolated in a known manner, for example by
filtration, and, if appropriate, purified by washing with
an inert organic solvent.
Salts. cf metals of main groups II to IV and of
.s.ub-groups I and II and IV to. VIII. can preferably be
used for the preparation of metal salt complexes of the
compounds of the formula (I), examples of metals which may
be mentioned being copper, zinc, manganese, magnesium,
tin, iron and nickel.
Possible anions of the salts are, preferably,
those which are derived from the following acids:
hydrogen halide acids (such as hydrochloric acid and
hydrobromic acid), phosphoric acid and sulphuric acid.
The metal salt co~plexes of compounds of the
formula (I) can be obtained in a simple manner by
customary Frocesses, thus, for example, by dissolving the
metal salt in alcohol, for example ethanol, and adding
the solution to the compound of the formula (I).
The metal salt complexes can be purified in a known manner,
30 for example by filtration, isolation and, if appropriate,
by recrystallisation.
Le A 20 458
1 lS~24
- 18 -
The active compounds which can be used accordingto the invention engage in the metabolism o~ the plants
and can therefore be employed as growth regùlators.
Experience to date of the ~.ode of action of
plant growth regulators has shown that an active compound
can also exert several different actions on plan~
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''int'er 'a'l'ia
of economic interest in the case of grasses, since it
i~ thereby possible to reduce the frequency of cutting
the grass in ornamental gardens, par~s and sportsgrounds,
at verges, at airports or in fruit orchards. The
inhibition of growth of herbaceous and woody plants at
verges and in the cicinity of pipelines or overland
lines or, quite generally, in areas in which heavy
additional growth of plants is undesired, is also of
importance.
The use of growth regulators to inhibit the
growth in length of cereals is also important. The
danger of lodging of the plants before harves ng is
thereby reduced or completely eliminated. Furthermore,
growth regulators can strengthen the stem of cereals,
which again counteracts lodging.
Le A 20 458
1 16824~
-- 19 -
Use of gro~th regulators for shortening and strengthening
the stem enables higher amounts of fertiliser to be applied
to increase the yield, without danger of the cereal
lodging.
In the case of many crop plarts, inhibition of
the vegetative growth makes denser planting possible, so
that greater 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 lead to increases in yield, since 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 Yegetative parts of the
plants which are harvested. Promoting the vegetative
growth can, however, also simultaneously lead to a
promotion of generative growth~ since more assimilates are
formed, so that more fruit, or larger fruit, is obtained.
Increases in yield can in some cases be achieved
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 growth
regulators. Thus it is possible, for example, to
increase the content of sugar in sugar beet, sugar can,
pineapples and citrus fruit or to increase the protein
content in soya or cereals. Using growth regulators it
is also possible, for example to inhibit the degradation
of desired constituents, such as, for example, sugar in
sugar beet or sugar can, before or after harvestin~.
Le A 20 458
. ~ =
1 1~824~
- 20 -
It is also possible favourably to influence the production
or 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 in
the cultivation of ornamertal plants, also in connection
with growth inhibition. On the other hand, however,
it is also possible to inhibit the growth of side
shoGts. There is great interest in this action, for
example, in the cultivation of tobacco or in the planting
of tomatoes-
. The 2mount of leaf on plants can be controlled,under the influence of growth regulators, so that
defoliation 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 facilitating harvesting in other crops,
such as, for example, in viticulture. Defoliation of
the plants can also be carried out to lower the trans-
piration of plants before they are transplanted.
3 The shedding of fruit can also be cor.trolled
with growth regulators. On the one hand, it is poss-
ible to prevent premature shedding of fruit. However,
Le ~ 20 458
1 16824~
- 21 -
on the ot~er hand, shedding of fruit, or even the fall
of blossom, can be promoted up to a certain degree
(thinnir.g out) in order to interrupt the al~ernance.
By alternance there is understood ~he peculiarity of some
varieties of fruit to produce very different yields from
year to year, for endogenic reason~. Finally, using
growth regulators it is possible to reduce the force
required to detach the fruit at harvest tlme 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
it isthereby possible to achieve optimum adaptation
to market requirements. Furthermore, growth regulators
can at times improve the coloration of fruit. In
addition, concentrating the ripening within a certain
period of time is also achievable with the aid of growth
regùlators. This provides the preconditions for beir.g
able to carry out completely mechanical cr manual
harvesting in only a single pass, for example in the
case of tobacco, tomatoes or coffee.
Using plant regulators, it is furtermore possible
to influence the latent period of seeds or buds of plants,
so that the plants,for example pineapple or ornamental
plants in nurseries, germinate, shoot or blossom at a
time when 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 ir.
regions where frost is 2 hazard, in order to avoid damage
by late frosts.
Finally, the resistance of plants to frost,
drought or a high salt content in the soil can be induced
with growth regulators. Cultivation of plants in regicns
.
Le A 20 458
. _
1 16824~
which are usuàlly unsùitable for this purpose thereb`y
becomes possible.
The preferred time of application of the growth
regulators depends on the climatic and vegetatlve
circumstances.
The foregoing description should not be taken as
implying that each of the compounds can exhibit all of the
described effects on plants. The effect exhibited by a
compound in 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.
~ungicidal agents in plants protection are employed
for combating P~asmod'iopho'romyc'e't'es,''Oo'myc'e't'es, Chy-
tridiom~;cetes,' Z'y~om'y'c'etes,''A's'c'om'y'cet'es,' B'as'i'~iomycetes
and ~'e'u't'e'r'o'm'y'c'e't'es.
The good toleration, by plants, of the active
compounds, at the concentratior.s 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 ~rysiphe species,
for example against the powdery mildew of barley or cereal
causative organism (Erysiphe'' ram'inis), or for combating
Podosphaera species, for example against the powdery mildew
of apple causative organis~. (Podosphaera leucotricha).
The substances according to the invention also exhibit a
broad fungicidal in vitro spectrum.
Le 'A''2'0''~'58
1 1682
23
The active compounds can be converted to the
customary formulations, such as solutions, emulsions,
suspensions, powders, ~oa~.s, pastes, gr~nules, aerosols,
very ~ine capsules in poly~.eric substances and in coating
compositions for seed, zs well as ULV formulations.
These formulations may be produced in known manner,
for example by mixing the active compounds with extenders,
that is to say liquid or liquefied gaseous or solid diluer.ts
or carriers, optionally wit~ the use of surface-active
agents, that is to say emulsifying agents and~or dispersing
agents and/or ~oam-forming agents. In the case of the
use of water as an extender, organic solvents car, for
example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents,
there are suitable in the main, aromatic hydrocarbons,
such as xyler.e, toluene or alkyl naphthalenes, chlorinated
aromatic or chlorinated aliphatic hydrocarbons, such as
chlorobenzenes, chloroethylenes or methylene chloride,
aliphatic or alicyclic hydrocarbons, such as cyclohexane
or paraffins, for example mineral oil fractions, alcohols,
such as butanol or glycol as well as their ethers and
esters, ketones, such as acetone, methyl ethyl ketone,
methyl isobutyl ketone or cyclohexanone, or strongly polar
solvents, such as dimethylformamide and dimethylsulphoxide,
as well as water.
By lique~ied gaseous diluents or carriers are meant
liquids which would be gasecus at normal temperature and
under normal pressure, for example aerosol propellants,
such as halogenated hydrocarbons as well as butane, propane,
3o nitrogen and carbon dioxide.
As solid carriers there may be used ground natural
minerals, such as kaolins, clays, talc, chalk, quartz-
attapulgite, montmorillonite or diatomaceous earth, and
ground synthetic minerals, such as highly-dispersed silicic
acid, alumina and silicates. As ~olid carriers for Eranules
. .
Le A ~0 458
1 1~82~9
- 24 -
there may be used crushed and fractionated natural
rocks such as calcite, marble, pumice, sepiolite and
dolomite, as well as synthetic granules of inorganic
and organic meals~ and granules of organic material such
as sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and~or foam-forming agents there
may be used non-ionic and anionic emulsifiers, such as
polyoxyethylene-fatty acid esters, polyoxyethylene-fatty
alcohol ethers, for example alkylaryl polyglycol ethers,
alkyl sulphonates, alkyl sulphates, aryl sulphonates
as well as albumin hydrolysis products. Dispersing agents
include, for example, lignin sulphite waste liquors and
methylcellulose.
Adhesives such as carboxymethylcellulose and natural
and synthetic polymers in the form of powders, granules
or latices, such as gum arabic, polyvinyl alcohol and
polyvinyl acetate, can be used in the formula~ions.
It is possible to use colorants such as inorganic
pigments, for example iron oxide, titanium oxide and
Prussian Blue, and organic dyestuffs, such as alizarin
dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs,
and trace nutrients, such as salts of iron, marganese,
boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to
95 per cent by weight of active compound, preferably
from 0.5 to 90 per cent by weight.
The active compounds according to the invention can
be present in the formulations as a mixture with other
active compounds, such as fungicides, insecticides,
3 acaricides and herbicides, as well as in the form of a
mixture with fertilisers and other growth regulators.
The' active compounds can be used as such or in the
form of their formulations or the use forms prepared there-
from, such as ready-to-use solutions, emulsifiable concen-
Le A 20 45~
1 16~24~
trates, emulsions, foams~ suspensions, wettable powd`ers,pastes, soluble powders, dusting agents and granules.
They are used in the customary manner, for example by
watering, spraying, atomisin~, scattering, dusting,
foaming, coating and the like. Furthermore, it is
possible to apply the active compounds in accordance with
the ultra-icw volume process or to inject the active
compound preparation or the active compound itself into
the soil. It ls also possible to treat the seeds of
plants.
When the compounds according to the invention are
used as plant growth regulators, the amounts applied can
be varied with a substantial range. In general, 0.01
to 50 kg, preferably 0.05 to 10 kg, are used per hectare
of soil surface.
The amount applied can also be varied within a
substantial range, depending on the method of application,
when the substance~ according to the invention are used
as fungicides. Thus, especially in the treatment of
parts of plants, the active compound concentrations in the
use forms can ~e in general be between 1 and 0.0001% by
weight, preferably between 0.5 and 0.001~ by weight. In
thetreatment of seed, amounts of active compound of
0.001 to 50 g per kg of seed, preferably 0.01 to 10 g,
are generally required. For the treatment of soil, ~ctive
compound concentrations of 0.00001 to 0.1% by weight,
preferably 0.0001 to 0.02%, are required at the place of
action.
The present invention also provides plart growth
regulation and fungicidal compositions containing 2S
active ingredient a compound of the present invention
in admixture with a solid or liquefied gaseous diluer.t
or carrier or in admixture with a liquid diluent or
carrier containing a surface-active agent.
Le A 20 458
.
1 16824
- 26 -
The present invention also provides a method of
co~bating fungi which comprises applying to the fungi,
~r 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 invention
in admixture with a diluent or carrier.
The present invention also provides a method of
regulating the growth of plants which comprises applying
to t~.e plants, or to a habitat thereof, a compound of
lO the present invention alone or in the form of a com- -
position containing as active ingredient a compound
of the present invention in admixture with a diluent
or carrier.
~ he present invention further provides crops protected
from damage by fungi by being grown in areas in which
i~ediately 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 present 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 the growing a compound of the present
invention was applied alone or in admixture with a diluent
or carrier.
It will be seen that the usual methods of providing
a harvested crop may be improved by the present invention.
Preparative Examples
Examples 1 and 2
OH CH3
Cl ~ CH = C - CH - C
~ N ~ CH3
Le A 20 458
1 16824~
- 27 -
~xample (1) = Z-isomer
Fxample (2) = E-isomer
16 g (0.045 mole) of 1-(4-chloropheryl)-4-methyl-
4-phenyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one as the
E/Z-iscmer mixture were dissolved in 200 ml of isopropanol,
and 0.85 g (0.0225 mole) of sodium boronate were added in
portions. The mixture was stirred at room temperature
for 15 hGurs and then poured onto water. The organic
layer was extracted wi~h ether and the combined ether
extracts were dried over sodium sulphate. After evapora-
ting off the ether, 14.7 g (92% of theory) of 1-(4-
chlorophenyl)-4-methyl-4-phenyl-2-(1,2,4-triazol-1-yl)-1-
penten-3-ol were obtained as the E/Z-isomer mixture.
The pure isomers were isolated by Craig distribution
~counter current distribution), the Z-isomer having a
melting point of 136~ and the E-isomer having a melting
point of 140C.
P'repara't'i'on'of'th'e''s't'ar't'i'n'g'mate'~i'al
~II 1) ~ CH = C - C - ~
E/Z-isomer mixture
4C g (0.175 mole) of 3-methyl-3-phenyl-1-(1,2,4-
triazol-l-yl)-butan-2-one and 24.5 g (0.175 mole) of 4-
chlorobenzaldehyde in 150 ml of toluene were heated under
reflux with 5.25 g of glacial acetic acid and 1.75 ml of
piperidine for 15 hours, and the water of reaction was
separated off azeotropically. The toluene solution was
washed with water, dried over sodium sulphate and
evaporated in vacuo. 48.6 g (79% of theory) of 1-(4-
chlorophenyl)-4-methyl-4-phenyl-2-(1,2,4-triazol-1-yl)-1-
Le A 20 458
ll6s2~a
- 28 -
penten-3-one were obtained as the E/Z-isomer mixture with
a refractive index n20 of 1.6023.
(III-l) ~ N - CH2 - C0 - ~ ~
103 g (0.525 mole) of 1-chloro-3-methyl-3-phenyl-
butan-2-one were added dropwise to a suspension of 33.4 g
(0.6 mole) of sodium methylate and 41.4 g (0.6 mole) of
1,2,4-triazole in 200 ml of acetonitrile.
me reaction mixture was heated under reflux for
18 hours and filtered when cold and the filtrate was
evaporated ln vacuo. The resulting oil was dissolved
in chloroform and the chloroform solution was washed with
water, dried over sodium sulphate and evaporated in
Vacuo. 106 g ~88% of theory) of 3-methyl-3-phenyl-1-
(1,2,4-triazol-l-yl)-butan 2-one were obtained and could be
purified by chromatography on silica gel 60 (Merck)/
chloroform: refractive index n20 = 1.5425.
CH3
Cl - CHz - C0 - C
CH3
lO ml (0.122 mole) of sulphuryl chloride were added
dropwise to a solution of 16.2 g (0.1 mole) of 3-methyl-3-
phenyl-butan-2-one in 50 ml of benzene at 40C. The
mixture was kept at 60C, until the evolution of gas had
ended, and was then distilled. 15.4 g (78.5% of theory)
of l-chloro-3-methyl-3-phenyl-butan-2-one with a boiling
point of 80 tG 85C/0.1 mm Hg and a refractive index n20
of 1.5310 were obtained.
Le A 20 458
llss2~a
- 29 -
Example 3
OH CH
Cl ~ CH - C - CH - ~ - CH2 -CH
E-isomer
2.88 g (9.5 mole) of the E-isomer of 1-(4-chloro-
phenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-hexen-3-one
were dissolved in 20 ml of isopropanol, and 180 ~g ~4.75
mmoles) ~f sodium boronate were added. After stirring
the mixture at room temperature for 15 hours, the iso-
propanol was distilled off in vacuo and the residue was
decomposed with water and glacial acetic acid. The
organic phase was separated off and dissolved in methylene
chloride and the methylene chloride solution was washed
with water, dried over sodium sulphate and evaporated.
The resulting oil was stirred with diisopropyl ether and
the crystals formed were filtered off and dried. 700 mg
(24~ of theory) of the E-isomer of 1-(4-chlorophenyl)-
4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-hexen-3-ol of melting
point 130C were obtained.
Preparation of the starting material
O CH3
Cl ~ CH = IC - e c cH2 CH3
~ N ~ CH3
N 11
E/Z-isomer mixture (II-2)
and E-isomer (II-3)
81.5 g (0.45 mole) of 3,3-dimethyl-1-(1,2,4-triazol-
l-yl)-pentan-2-one and 63.2 g (0.45 mole) of 4-chloro-
benzaldehyde in 500 ml of toluene wer~ heated under reflux
Le A 20 458
. .
~ 1682~
- 30 -
with 12.5 ml of acetic acid and 4.5 ml of piperidine for
15 hours, and the water of reaction was removed azeotro~
pically. The toluene solution was washed wlth water,
dried over sodium sulphate and evaporated ~n vacuo.
127 g (93% of theory) of 1-(4-chlorophenyl)-4~4-dimethyl-
2-(1,2,4-triazol-1-yl)-1-hexen-3-one were obtained as the
E/Z-isomer mixture of boiling point 150 to 160C/0.1 mm Hg.
After leaving the product to stand at room tem-
perature for several days, the E-isomer of l-(~-chloro-
phenyl)-4~4-dimethyl-2-(l~2~4-triazol-l-yl)-l-hexen-3-one
of melting point 90C crystallised out.
N -~ ~3
(III-2) ~ ~ - C~2 - C0 - Cl - CH2CH3
106 g (0.55 mole) of 1-bromo-3,3-dimethyl-pentan-
2-one were added dropwise to a mixture of 62.1 g (0.9 mole)
Of 1,2,4-triazole, 95.4 g (0.69 mole) of pctassium carbonate
and 600 ml of acetone at 55C. After stirring the
mixture for 15 hours, it was filtered and the filtrate was
evaporated in vacuo. The oil which remained was purified
by chromatography (siiica gel 60 (Merck)/chloroform).
85.6 g (86% of theory) of ~,3-dimethyl-1-(1,2,4-
triazol-l-yl)-penten-2-one with a refractive index n20 of
1.4805 were obtained.
CH3
Br-cH2-co-c-cH2cH3
CH3
A solution of 30.6 g (0.6 mole) of bromine in
120 ml of chloroform was added dropwise to a solution of
69 ~ (0.6 mole) of 3,3-dimethylpentan-2-one in 300 ml of
methyl alcohol at 0 to 5 C and the reaction mixture was
subsequently stirred fcr 15 rninutes. It was poured ontc
Le A 20 458
1 16824~
ice, the organic phase was separated off, washed with
water, dried over sodium sulphate and filtered arLd the
fiitrate was evaporated. The crude product was distilled
in vacuo. lOl g (87% of theory) of l-bromo-3,3-di-
methylpentan-2-one with 2 boiling point of 80 to 88C/ll
mm ~ and a refractive index n20 of 1.4685 were obtained.
Ex~mple 4 ~H l H3
Cl ~ CH = ~ - CH - C - CH2 CH3 (4)
~ N CH3
N ~ Z-isomer
30.35 g (G.l mole) of l-(4-chlorophenyl)-4,4-di-
methyl-2-(1,2,4-triazol-l-yl)-l-hexen-3-one as the E/Z-
isomer mixture (compare the preparation of the starting
material in Example 3) were reduced with sodium boronate
in a manner corresponding to that in Example 3. The
re~ulting oil (30.5 g) was chromatographed on silica ~el
60 (Merck)/chlorofo~. The fractions of melting point
100 to 108C obtained after evaporating off the
chloroform were combined, and recrystallised twice from
acetonitrile. The Z-isomer of 1-(4-chlorophenyl)-4,4-
dimethyl-2-(1,2,4-friazol-l-yl)-1-hexen-3-ol of m~ting
point 119C was obtained.
Exampl _5
r~H CH3
Cl ~ CH = C - CH ~ ( 5)
~N~N
N U E-isomer
3.5 g (12.2 mmoles) of the E-isomer of 1-(4-chloro-
phenyl)-3-(1-methyicycloprop-1-yl)-2-(1,2,4-triazol-1-
yl)-1-propen-3-one and 0.91 g (8.2 mmoles) of calcium
chloride were dissolved in lC0 ml of isopropanol, and a
solution of 0.32 g (~.5 mmoles) of sodium boronate in
Le A 20 458
1 ~6824~
- 32 -
~0 ml of water was added dropwise a~ -5C. ~fter 90
minutes, 10 ml of acetone were added d~opwise ard the
reaction mixture was evaporated''in vacuo. The residue
~las dissGl~led in methylene chloride and the solution
was washed wi~h water. The organic phase was dried over
sodium sulphate and filtered and the filtrate W2S evapor-
ated _ 'vacuo. After purification of the residue by
column chromatography, 1.7 g (48% of theory) of the E-
isomer of l-(4-chlorophenyl)-3-(1-methylcycloprop-1-yl)-
2~ 2,4-triazol-1-yl)-1-propen-3-ol of melting ~oint
110C were obtained.
Preparati-on of the''s't'ar'ting'm'aterial
CH3
(II-4) Cl- ~ - CH = C - C0
`N
- I E-isomer
This compound was obtained as described in following
Example 6.
Example 6
.
Cl ~ ~ (6)
Z-isomer
10.0 g (3.48 mmoles) of 1-(4-chlorophenyl)-3-(1-
met~.ylcycloprop-l-yl)-2-(1,2,4-triazol-1-yl)-1-propen-3-
one as the E/Z-isomer mixture and 7.1 g (3.48 mmoles) of
aluminium isopropylate in 300 ml of boiling isopropanol
were heated for 6 hours; during this procedure isopro-
panol and acetone were continuously distilled off cver a
30 cm Vigreux column, until acetone could no longer be
Le A 20' 4'58
1 168248
detected in the distillate. The solution was then
evaporated ard ice/hydrochloric acid W2S added to the
residue. After extraction with ether, the combined ether
extracts were washed with water, dried over sodium sulphate
and filtered and the filtrate was evaporated. The oil
which remained was chromatographed over silica gel 60
(Merck)/chloroform. The first fractions ga~e, after
evaporating off the solvent, 3.5 g of the E-isomer of 1-
(4-chlorophenyl)-3-(1-methyicycloprop-1-yl)-2-(1,2,4-
triazol-1-yl)-propen-3-ol of melting point 89C.
The next fractions gave, after evaporating off the
solvent, 7.8 g of the Z-isomer of 1-(4-chlorophenyl)-3-
(l-me~hylcycloprop-l-yl)-2-(1,2,4-triazol-1-yl)-1-propen-
3-ol of melting point 124C.
15' ~'~eparat10h of the startihg m'aterial
(II-5) ~ CH = ~ - C0 ~
~ ~ E/Z-isomer mixture
1-(4-Chlorophenyl)-3-(1-methylcycloprop-1-yl)-2-
(1,2,4-triazol-1-yl)-1-propen-3-one of melting point 82C
was obtained by reactin~ l-methyl-l-(1,2,4-triazol-1-yl-
acetyl)-cyclopropane with 4-chlorobenzaldehyde in a manner
corresponding to that in Example 3.
CH3
~III-3) ~ N - CH2 - C0 ~
42.5 g (0.24 mole) of l-bromoacetyl-l-methylcyclo-
propane were added dropwise to a suspension of 27.6 g (0.4
mole) of 1,2,4-triazole and 41.4 g (0.3 mole) of potassium
carbonate in 500 ml of acetone at 60C. After heating
Le A 20 458
==~= . .. .
llss2~a
- 34 -
the mixture to 60C for i5 hours, the salts were filterèd
of~ and the filtrate was evapor~ted in ~vacuo. The oil
which remained was purified by chromatography (silica gel
60 (Merck)/chloroform).
35.7 g (90% of theory) of 1-methyl-1-(1,2,4-tri-
azol-l-yl-acetyl)-cyclopropane of melting point 58C were
obtained.
CH3
Br - CH2 - C0 ~
15 ml of bromine, dissolved in 75 ml of chloroform,
were added dropwise to a solution of 29.4 g (0.3 mole) of 1-
acetyl-l-methylcyclopropane in 150 ml o methyl alcohol.
The solution was stirred at 10C until it was com-
pletely decolorised, and was poured onto ice and washed
with water. The chloroform phase was dried over sodium
sulphate and filtered, the filtrate was evaporated and the
residue was distilled
44 g (82.5% of theory) of l-bromoacetyl-l-methyl-
cyclopropane with a boiling point of 85 to 90C/ll mm Hg
and a refractive index n20 of 1.5002 were obtained.
Example 7
Cl ~ CH = C - CH - C - COOC2H~
N ~
Z-iscmer
A mixture of 63.4 g (0.1825 mole) of the Z-isomer
of 1-(4-chlorophenyl)-4-ethoxycarbonyl-4-methyl-2-(1,2,4-
triazol-l-yl)-l-penten-3-one, 37.6 ~ (0.1825 mcle) of alu-
minium isopropylate and 350 ml of isopropanol was heatedto the boiling point, and acetone was distilled off azeo-
tropically, as a mixture with isopropanol, over a Vigreux
Le A 20 458
.
1 1~82
- 3~ -
column. The solution was poured onto lce-cold dilute
hydrochloric acid and extracted by shaking with methylene
c~.loride. The or~anic phase was separated off, dried
over sodium sulphate, filtered and evaporated. ' The
oil which remained was stirred with petroleum ether and the
resulting crystals were filtered off and rinsed with di-
isopropyl ether. 22.7 g (35.6% of theory) of the Z-
isomer of 1-(4-chlorophenyl)-4-ethoxycarbonyl-4-methyl-2-
(1,2,4-triazol-1-yl)-1-penten-3-ol of melting point 90C
were obtained.
Preparat;o-n of the startin~ ~aterial
CIH3
(II-6) Cl ~ CH = IC - C0 - Cl - COOC2E~
~ N~N CH3
~J
Z-isomer
A mixture of'90 g (0.4 mole) of dimethyl-(1,2,4-
triazol-l-yl-acetyl)-acetic acid ethyl ester, 56.2 g (0.4
mole) of 4-chlorobenzaldehyde, 12 g of acetic acid and 5 ml
of 2,6-dimethylmorpholine in 300 ml of toluene was heated
under reflux for 18 hours, and the water of reaction was
separated off continuously. The cooled reaction solution
was washed with water, dried over sodium sulphate and
filtered and the filtrate was concentrated. 124 g (90%
of theory) of 1-(4-chlorophenyl)-4-ethoxycarbonyl-4-
methyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one with a re-
fractive index n20 of 1.5751 were obtained.
N ~ ICH3
(III-4) ¦ N - CH2 - C0 - C - COOC2H~
Le A 2~ 45
1 ~682~
165.9 g (0.7 mole) of bromoacetyl-dimethyl-acet`ic `
acid ethyl ester were added dropwise to a suspension of
96.7 g (1.4 moles) of 1,2,4-triazoie and l44.g g (1.05
moles) of potassium carbonate in 1,200 ml of acetone at
25 C. After stirring the mixture for 15 hours, the
salts were filtered off and the filtrate was evaporated.
The oil which remained was purified over silica gel 60
(Merck). 120.7 g (76.6% of theory) of dim~thyl-(1,2~4-
triazol-l-yl-acetyl)-acetic acid ethyl ester with a ref-
10 ractive index nD f 1.4770 were obtained.
CH3
8r-CH -CO-C-COOC2H5
CH3
95.4 ml (1.87 moles) of bromine, dissolved in 1,000
ml of chloroform, are added dropwise to a solution of
295.5 g (1.87 moles) of acetyl-dimethyl-acetic acid ethyl
ester in l,OGO ml of methyl alcohol at 0C. After
stirring the mixture at room temperature for 15 hours, it
was poured onto ice, the chloroform phase was separated off,
washed with water, dried over sodium sulphate and evapora-
ted and the residue was distilled. 780 g (88% of theory)
of bromoacetyl-dimethyl-acetic ac~d ethyl ester with a
boiling point of 90 to 115C/0.5 mm Hg and a refractive
index nD of 1.4658 were obtained.
The following compounds of the general formula (I)
were obtained in a corresponding manner:
Table 2 OH
~ CH - C - CH - X
Le A 20 458
~ 16~24~
- 37 ~
Ex- Melting
ample Rn X I point (C)
No. . .. . ..... . .... ...... ... .. . ..... .
I-8 4-Cl -C(CH3 )a~C~H7 142(Z-Isomer)
I-g 4-Cl -C(CH~ )~-C3H7 llO(E-Isomer)
I-lO 4-F -C(CH~ )2-COOC2H5 80(Z-Isomer)
-ll 2-C1,4-CF3 -C(CH3 )2 ~COOC2Hg 87(Z-Isomer)
-12 4-F ~ 124(E-Isomer)
I-13 4-F ~ 106(Z-Isomer)
I-14 2-C1 ~ 148(Z-Isomer)
I-15 2-Cl ~ 128(E-Isomer)
2,4-Cl2 ~ 148(Z-Isomer)
I-17 2 ,4-C12 ~ .126(E-Isomer)
I- ~8 4-CF3 ~ 133(Z-Isomer)
I- 19 4-CF3 ~ 120(E-Isomer)
I-202-Cl,4-CF3 ~ 141(Z-Isomer)
I-212-C1 ,4-CF3 ~ 140(h-Isomer)
I-22 4-oCF3 ~ 104(Z-Isomer)
I-23 4-OCF3 ~ 94 (E-Isomer)
I- 24 4-OCH~ ~ 126(Z-Isomer)
I- 25 4-OCH3 ~ 1 132(E-Isomer)
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Ex- MeltingO
ample Rn Xpoint ( C)
I-26 2,4-Cl -C(CH3)2-C2H5140(Z-Isomer)
I-27 2,4-Cl2 -C(CH3)2- ~ -Cl152(Z-Isomer)
I-28 2,4-Cl2 C(CH3)2 COOC2H5 100(Z-Isomer)
I-29 2,4-Cl2 ~ 126(Z-Isomer)
I-30 2,4-Cl2 -C(C~3)2- ~ -Cl158(E-Isomer)
I-31 2,3-Cl2 CH130(Z-Isomer)
I-32 3,4~Cl2 ~ 118(Z-Isomer)
I-33 3,4-Cl2 ~ 80(E-Isomer)
I-34 2,3-Cl2 ~ 126(E-Isomer)
I-35 2,4-Cl2 ~ 126(E-Isomer)
C~
I-36 3-CP3 CH3130(Z-Isomer)
I-37 3-CF3 CH395(E-Isomer)
I-38 2-CH3 ~ 146(Z-Isomer)
I-39 2-CH3 ~ 132(E-Isomer)
The following starting substances of the formula
(II) were obtained in a manner corresponding to that in
the foregoing preparative Examples: 1 to 3 and 5 to 7:
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Table 3
~ - CH = ~ - C0 - X (II)
Rn N ~
Ex- IMelting point (C)
ample R X or refractive
No. n index (n20
D
.....
II-7 4-Cl -(CH3 )2 C~ H~ 8g(E-Isomer)
II-8 4-Cl -(CH3 )2-C~H7 1.5492 (E/Z-
mixture)
II-9 2-C1,4-CF3 . -C(CH3 )2 -COOC2H5 104(Z-Isomer)
II-10 4-F ~ 74(E-Isomer)
II-11 2-Cl ~ 1. 5929 (E-
II- 1 2 2-Cl ~ Isomer)
CH~ mixture)
II-13 2, 4-Cl2 ~ 84(E-Isomer)
II-14 2,4-Cl2 ~ 1.5978 (E/Z-
CH3 mixture)
II-15 4-CF3 ~ . 1. 5142 (E-
CH3 Isomer)
II-16 4-CF3 ~ 1. 5440 (E/Z-
CH3 mixture)
II-17 4 - OCF3 ~ 1.5334 (E-
CH~ Isomer)
II-18 4-oCF3 ~ 1.5362 (E/Z-
CH mixture)
II-19 12-Cl,4-CF3 ~ 11.5232 (E-
I CH3 1Isomer)
II-20 2-C1,4-CF3 ~ 1.5334 (E/Z-
~ CH3 mixture)
II-21 4-oCH3 ~ 92 (E-Isomer)
II-22 4-oCH3 ~ 1.5g~9 (E/Z-
mixture)
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The following precursors of the .ormula (III) were '
obtained in a manner corresponding to that in the foregoing
Preparative Examples l to 3, 6 and 7:
' ~able 4 :
.
N=\
¦ ~ - CH2 - CO - X
:=N~ (III~
Example Melting point (C)
or refractive
No. index (~20)-
..... ............................. ........ D.......... .
III-5 -C(CH3)2-C3H7 1.4796
-C(CH3)2-C3H7 60C
III-7 -C(CH3)2 ~ F oil
The plant growth regulant and fungicidal activity
of the compounds of this invention is illustrated by the
1,0 following biotest Examples.
In these Examples, the compounds according to the
present invention are each identified by the number
(given in brackets) of the corresponding preparative
Example, which will be found earlier in this specification.
The known comparison compounds are identified as
follows: -
Cl OH
(A) = Cl ~ CH=C-CH-C(CH3)3
N
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Cl OH
(B) = ~ CH=C-CH-C(CH3 )3
~ N`N
'N ~
H3CO OCH3 OH
(C) = ~ -CH-~-CH-C(CH3)3
N
N ~
OH
(D) = ~ CH=~-CH-C(CH3)3
1~
N
Example A
Inhibition of growth -of grass (~estuca pratensis)
Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitane
monolaurate
To produce a suitable preparation of active compound,
1 part by weight of active compound W2S mixed with the
stated amounts of solvent and emulsifier and the mixture
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
compound until dripping wet. After 3 ueeks, the
additional grow,th was measured and the inhibition of growth
.
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in per cent of the additional growth of the control plants
was calcula~ed. 100% inhibition of growth ~eant that
growth had stopped and 0% denoted a growth corr~sponding
to that of the control plants.
In this test, active compounds (I-12) and (I-37)
exhibited a better inhibition of growth than the compounds
(A), (B), (C) and (D) known from the prior art.
Examp-le B
Inhibition of growth of c'otton
Solvent: 30 parts by weight of dimethylfor~amide
Emulsifier: l part by weight of polyoxyethylene sorbi.ta~.e
monolaurate
To produce a suitable preparation of active
compound, l part by weight of active compound was mixed with
the stated amount 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
active compound until dripping wet. After 3 weeks, the
additional ~rowth of the plants 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, active c~x~nds (I-3), (I-4), (I-6), (I-32),
(I-34), (I-35) and (I-37) exhibited a ~etter inhibition of growth than
the co~x~nds (A), (B), (c) and (D) known from the prior art.
Example C
Inhibit-ion of growth 'of's'oya'b'e'ans
Solvent:' lO parts by weight of methanol
Emulsifier: 2 parts by weight of polyoxyethylene sorbitane
monolaurate
To produce a suitable preparation of active com-
35 pound, l part by wei.ght. of active compound was mixed ~Ji.th
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the stated amounts of solvent and emulsifier and the
mixture was made up to the desired concentration with
water.
Young soya bean plants, in the stage in which
the first secondary leaves had unfolded, were sprayed with
the preparations of active compound until dripping wet.
After 2 weeks, the additional growth was measured and the
inhibition of growth in % of the additional growth of the
control plants was calculated. lOQ% meant that growth
had stopped and 0% denoted a growth corresponding to that
of the untreated control plants.
In this test, active c~x~nds (I-3), (I-6), (I-12),
(I-32), (I-34) and (I-35) exhibited a bet ~ ~ ibition of gr~h
than the c~x~nds (B), (c) and (D) known from the prior art.
Examp'l'e D
Infl'uence on growth of_sugar beet
Solvent: 30 parts by weight of dimethylformamide
Emulsifier: l part by weight of polyoxyethylene sorbitane
monolaurate
To produce a suitable preparation of active
compound, 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 concen~ration with
water.
Su~ar beet was grown in a gr~enhouse until
formation of the cotyledons was complete. In this stage,
the plants were sprayed with the preparation of active
compound until dripping wet. After 14 days, the addition-
al growth of the plants was measured and the influence on
growth in per cent of the additional growth of the control
plants was calculated. 0% influence on growth denoted a
growth which corresponded to that of the cGntrol plants.
Negative values characterised an inhibition of growth in
comparison to the control plants, whilst positive values
characterised a pro~otion of growth in comparison to the
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control plants.
In this test, compounds II-3)~ (I-4), (I-6), (I-12),
(I-13), (I-32), (I-34) and ~I-35) according to the invention
exhibited a better in~luence on growth than the compounds
(c) and (D) known from the prior art.
Exam~le E
~ormation -of ethylene
Solvent: 30 parts by weight of dimethylformamide
~mulsifier: l part by weight of polyoxyethylene sorbitane
monolaurate
To produce a suitable preparation of active
compound, 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.
Pieces of leaf of identical size were punched from
soya been leaves. These were introduced into vessels
which could be closed air-ti~ht, together with l ml of the
preparation of active compound or control solution. After
24 hours the ethylene which had co~ected in the vessels was
determined by customary methods of detection. The
evolution of ethylene from the pieces of leaf treated with
the preparations of active compound was compared with the
evolution of ethylene from the controls.
0 denoted evolution of ethylene as in the case of
the control
+ denoted slightly increased evolution of ethylene
++ denoted greatly increased evolution of ethylene
+++ denoted very greatly increased evolution of
ethylene
In this test, active compounds (I-12) and (I-i3)
caused greater formation of ethylene than the compounds
(B), (C) and (D) known from the prior art.
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Example F
- Erysiphe test ~barley)/protective
Solvent: 100 parts by weight of dimethylforma~ide
Emulsifier: 0.25 part by weight of alkylaryl polyglycol
ether
To produce a suitable preparation of active
compound, 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
concentration-
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 Er-ysiphe graminis f.sp.
hordei.
The plants were placed in a greenhouse at a
temperature of about 20C and a relative atmospheric
humidity of about 80%, in order to promote the development
of powdery mildew pustules.
Evaluation was carried out 7 days after the
inoculation.
In this test, a si~nificantly superior activity
compared with the prior art was exhibited, for example,
by the compounds (I-3), (I-4~ 6) L (I-12) a~d rI
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