CA1329995C - Influencing plant growth by means of azolylmethyloxiranes - Google Patents
Influencing plant growth by means of azolylmethyloxiranesInfo
- Publication number
- CA1329995C CA1329995C CA000582228A CA582228A CA1329995C CA 1329995 C CA1329995 C CA 1329995C CA 000582228 A CA000582228 A CA 000582228A CA 582228 A CA582228 A CA 582228A CA 1329995 C CA1329995 C CA 1329995C
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- phenyl
- cis
- chlorophenyl
- fluorophenyl
- plants
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Health & Medical Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
- Luminescent Compositions (AREA)
- Pyrrole Compounds (AREA)
- Cultivation Of Plants (AREA)
- Epoxy Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE: A method of influencing the growth of plants, wherein the soil, the seeds and/or the plants are treated with an azolyl-methyloxirane of the formula
Description
; ' 13291q5 - 1 - o.z. OOS0/39557 Influencing plant growth by means of azolylmethyloxiranes The present invention relates to a method for influencing plant gro~th by treating the soil, the seed and/or the plants with an azolylmethyloxirane of the general formula I
( I ) ~N`Z
~ L~
where A and B are identical or different and are each C1-C4-alkyl, phenyl~ naphthyl or diphenyl or are each phenyl which is substituted by one radical, or two or three identical or different radicals, from the group consis-ting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-halo-alkyl, nitro and phenoxy, and Z is CH or nitrogen, or its metal salts or acid addition salts, and plant growth regu-lators containing a bioregulatory amount of an azolylmethyl-oxirane I.
EP-A-94 564 discloses the azolylmethyloxiranes of the general for1ula I; they are recommended for use as drugs, particularly as antimycotics, and as crop protec tion agents, especially as fun~icides. No other uses of these compounds are known.
It is an object of the present invention to pro-vide the azolylmethyloxiranes for novel fields of use.
~ e have found that this object is achieved and that the azolylmethyloxiranes I defined at the outset are suitable for r~gulating plant growth.
The substituents in formula I have the following specific meanings:
A and ~ independently of one another are each straight-chain or branched C1-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl~ isobutyl, sec-butyl or tert-butyl~
phenyl, ~ ,.
t 3~9~q~
( I ) ~N`Z
~ L~
where A and B are identical or different and are each C1-C4-alkyl, phenyl~ naphthyl or diphenyl or are each phenyl which is substituted by one radical, or two or three identical or different radicals, from the group consis-ting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-halo-alkyl, nitro and phenoxy, and Z is CH or nitrogen, or its metal salts or acid addition salts, and plant growth regu-lators containing a bioregulatory amount of an azolylmethyl-oxirane I.
EP-A-94 564 discloses the azolylmethyloxiranes of the general for1ula I; they are recommended for use as drugs, particularly as antimycotics, and as crop protec tion agents, especially as fun~icides. No other uses of these compounds are known.
It is an object of the present invention to pro-vide the azolylmethyloxiranes for novel fields of use.
~ e have found that this object is achieved and that the azolylmethyloxiranes I defined at the outset are suitable for r~gulating plant growth.
The substituents in formula I have the following specific meanings:
A and ~ independently of one another are each straight-chain or branched C1-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl~ isobutyl, sec-butyl or tert-butyl~
phenyl, ~ ,.
t 3~9~q~
- 2 - O.Z. 0050/39557 naphthyl, such as 1-naphthyl or 2-naphthyl, preferably 2-naphthyl, diphenyl, such as o-diphenyl, m-diphenyl or p-diphenyl, phenyl which is substituted by one, two or three halogen S atoms, such as 2-fluorophenyl, 3-fluorophenyl, 4-fluoro-phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, Z-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2,3-d;-fluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluoro-10 phenyl, 2,3-difluorophenyl, Z,4-dichlorophenyl, 2,5~ -dichlorophenyl, 296-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2,3-dibromophenyl, 2,4-di-bromophenyl, 2,5-dibromophenyl, 2,6-dibro0ophenyl, 3,4-dibromophenyl, 3,5-dibromophenyl, 2-chloro-3-fluorophen-yl, 3-chloro-2-fluorophenyl, 2-chloro-4-~luorophenyl, 4-chloro-2-fluorophenyl, 2-chloro-S-fluorophenyl, 5-chloro-2-fluorophenyl, 2-chloro-6-fluorophenyl, 3-chloro-4-fluorophenyl, 4-chloro-3-fluorophenyl, 3-chloro-5-fluorophenyl, 2-bromo-3-fluorophenyl, 3-bromo-2-fluoro-phenyl, 2-bromo-4-fluorophenyl, 4-bromo-2-fluorophenyl, 2-bromo-5-fluorophenyl, 5-bro~o-2-fluorophenyl, 2-bromo-6-fluorophenyl, 3-bromo-4-fluorophenyl, 4-bromo-3-fluoro-phenyl, 3-bromo-5-~luorophenyl, 2-bromo-3-chlorophenyl~
3-bromo-2-chlorophenyl, 2-bromo-4 chlorophenyl, 4-bromo-2-chlorophenyl, 2-bromo-5-fluorophenyl, 5-bromo-2-chloro-phenyl, 4-bromo-6-chlorophenyl, 3-bromo-4-chlorophenyl, 4-bromo-3-chlorophenyl or 3-bromo-5-chlorophenyl, phenyl wh;ch is substituted by one, two or three C1-C4-alkyl groups, phenyl ~hich is substituted by one, two or three C~-C4-alkoxy groups, phenyl which is substituted by one, two or three C1-C4-haloalkyl groups, phenyl which is substituted by one or two nitro groups, phenyl which is substituted by one, two or three pheno~y groups, phenyl which is disubstituted or trisubstituted by 1 32',~qq5 - 3 - o.Z. 0050/39557 halogen and C1-C4-alkyl, phenyl which is disubstituted or trisubstituted by halo-gen and C1-C4-alkoxy, pheny-l ~hich is disubstituted or trisubstituted by halo-gen and C1-C4-haloaLkyl, phenyl ~hich is disubstituted or trisubstituted by halo-gen and nitro, phenyl which is disubsti~uted or trisubstituted by halo-gen and phenoxy, phenyl which is disubstituted or trisubstituted by C1-C4-alkyl and C1-C4-alkoxy, phenyl which is disubstituted or trisubstituted by C1-C4-alkyl and C1-C4-haloalkyl, phenyl which is disubstituted or trisubstituted by C1-C4-alkyl and nitro,phenyl which is disubstituted or trisubstituted by C1-C4-alkyl and phenoxy, phenyl which is disubstituted or trisubstituted by C1-C4-alkoxy and C1-C4-haloalkyl, Z0 phenyl which is disubstituted or trisubstituted by C1-C4-alkoxy and nitro, phenyl which is disubstituted or trisubstituted by C1-C4-alkoxy and phenoxy, phenyl which is disubstituted or trisubstituted by C1-C4-haloalkyl and nitro,phenyl ~hich is disubstituted or trisubstituted by C1-C4-haloalkyl and phenoxy, phenyl which is disubstituted or trisubstituted by nitro and phenoxy, phenyl which is trisubstituted by halogen, C1-C4-alkyl and C1-C4-alkoxy, phenyl which is trisubstituted by halogen, C1-C4-alkyl and C1-C4-haloalkyl, phenyl which is trisubstituted by halogen, C1-C4-alkyl and nitro, phenyl which is trisubstituted by halogen, C1-C4-alkyl and phenoxy 1 32~q95 ~ O.ZO 0050/39557 phenyl which is trisubstituted by halogen, C1-C4-aLkoxy and C1-C4-haloalkyl, phenyl wh;ch is trisubstituted by halogen, C1-C4-alkoxy ancl n-itro, phenyl which is trisubstituted by halogen, C1-C4-alkoxy and phenoxy, phenyl which is trisubstituted by halogen, C1-C4-halo-alkyl and nitro, phenyl which is trisubstituted by halogen, C1-C4-halo-alkyl and phenoxy,phenyl which is trisubstituted by halogen~ nitro and phen-oxy,phenyl which ;s trisubstituted by C1-C4-alkyl, C1-C4-alkoxy and C1-C4-haloalkyl, phenyl which is trisubstituted by C1-C4-alkyl, C1-C4-alkoxy and nitro, phenyl which is trisubstituted by C1-C4-alkyl, C1-C4-alkoxy and phenoxy, phenyl which is trisubstituted by C1-C4-alkyl, C1-C4-haloalkyl and nitro,phenyl which is trisubstituted by C1-C4-alkyl, C1-C4-haloalkyl and phenoxy, phenyl which is trisubstituted by C1-C4-alkyl, nitro and phenoxy, phenyl which is trisubstituted by C1-C4-alkoxy, C1-C4-haloalkyl and nitro, phenyl which is trisubstituted by C1-C4-alkoxy, C1-C4-haloaLkyl and phenoxy and phenyl ~hich is trisubstituted by C1-C4-haloalkyl, nitro and phenoxy.
Particularly preferred a~olylmethyloxiranes I are those in which A is 4-fluorophenyl or 4-chlorophenyl, B
is trifluoromethylphenyl and Z is nitrogen.
Suitable acids for the formation of salts of the compounds I are, preferably, halohydric acids, such as hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, ~hich forms particularly readily 1 3 2 ~ q 9 ~
3-bromo-2-chlorophenyl, 2-bromo-4 chlorophenyl, 4-bromo-2-chlorophenyl, 2-bromo-5-fluorophenyl, 5-bromo-2-chloro-phenyl, 4-bromo-6-chlorophenyl, 3-bromo-4-chlorophenyl, 4-bromo-3-chlorophenyl or 3-bromo-5-chlorophenyl, phenyl wh;ch is substituted by one, two or three C1-C4-alkyl groups, phenyl ~hich is substituted by one, two or three C~-C4-alkoxy groups, phenyl which is substituted by one, two or three C1-C4-haloalkyl groups, phenyl which is substituted by one or two nitro groups, phenyl which is substituted by one, two or three pheno~y groups, phenyl which is disubstituted or trisubstituted by 1 32',~qq5 - 3 - o.Z. 0050/39557 halogen and C1-C4-alkyl, phenyl which is disubstituted or trisubstituted by halo-gen and C1-C4-alkoxy, pheny-l ~hich is disubstituted or trisubstituted by halo-gen and C1-C4-haloaLkyl, phenyl ~hich is disubstituted or trisubstituted by halo-gen and nitro, phenyl which is disubsti~uted or trisubstituted by halo-gen and phenoxy, phenyl which is disubstituted or trisubstituted by C1-C4-alkyl and C1-C4-alkoxy, phenyl which is disubstituted or trisubstituted by C1-C4-alkyl and C1-C4-haloalkyl, phenyl which is disubstituted or trisubstituted by C1-C4-alkyl and nitro,phenyl which is disubstituted or trisubstituted by C1-C4-alkyl and phenoxy, phenyl which is disubstituted or trisubstituted by C1-C4-alkoxy and C1-C4-haloalkyl, Z0 phenyl which is disubstituted or trisubstituted by C1-C4-alkoxy and nitro, phenyl which is disubstituted or trisubstituted by C1-C4-alkoxy and phenoxy, phenyl which is disubstituted or trisubstituted by C1-C4-haloalkyl and nitro,phenyl ~hich is disubstituted or trisubstituted by C1-C4-haloalkyl and phenoxy, phenyl which is disubstituted or trisubstituted by nitro and phenoxy, phenyl which is trisubstituted by halogen, C1-C4-alkyl and C1-C4-alkoxy, phenyl which is trisubstituted by halogen, C1-C4-alkyl and C1-C4-haloalkyl, phenyl which is trisubstituted by halogen, C1-C4-alkyl and nitro, phenyl which is trisubstituted by halogen, C1-C4-alkyl and phenoxy 1 32~q95 ~ O.ZO 0050/39557 phenyl which is trisubstituted by halogen, C1-C4-aLkoxy and C1-C4-haloalkyl, phenyl wh;ch is trisubstituted by halogen, C1-C4-alkoxy ancl n-itro, phenyl which is trisubstituted by halogen, C1-C4-alkoxy and phenoxy, phenyl which is trisubstituted by halogen, C1-C4-halo-alkyl and nitro, phenyl which is trisubstituted by halogen, C1-C4-halo-alkyl and phenoxy,phenyl which is trisubstituted by halogen~ nitro and phen-oxy,phenyl which ;s trisubstituted by C1-C4-alkyl, C1-C4-alkoxy and C1-C4-haloalkyl, phenyl which is trisubstituted by C1-C4-alkyl, C1-C4-alkoxy and nitro, phenyl which is trisubstituted by C1-C4-alkyl, C1-C4-alkoxy and phenoxy, phenyl which is trisubstituted by C1-C4-alkyl, C1-C4-haloalkyl and nitro,phenyl which is trisubstituted by C1-C4-alkyl, C1-C4-haloalkyl and phenoxy, phenyl which is trisubstituted by C1-C4-alkyl, nitro and phenoxy, phenyl which is trisubstituted by C1-C4-alkoxy, C1-C4-haloalkyl and nitro, phenyl which is trisubstituted by C1-C4-alkoxy, C1-C4-haloaLkyl and phenoxy and phenyl ~hich is trisubstituted by C1-C4-haloalkyl, nitro and phenoxy.
Particularly preferred a~olylmethyloxiranes I are those in which A is 4-fluorophenyl or 4-chlorophenyl, B
is trifluoromethylphenyl and Z is nitrogen.
Suitable acids for the formation of salts of the compounds I are, preferably, halohydric acids, such as hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, ~hich forms particularly readily 1 3 2 ~ q 9 ~
- 5 - - o.Z. 0050/39557 crystallizing salts ~ith the co~pounds I; other suitable acids are phosphoric acid, nitric acid, sulfuric acid, monofunct;onal and b;functional carbo~ylic acids and hydroxycarboxylic acids, such as acetic acid, oxalic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and sulfonic acids, such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid.
Acid addition salts are, for e~ample, the chlor-ides, bromides, sulfates, nitrates, phosphates, oxalates or dodecylbenzenesulfonates. The activity of the salts is due to the cation, so that any anion may be chosen.
Metal comple~es of the compounds I are compounds of the general formula la M r ~2 1 X
L I ~ q (Ia) ~IZ n N
where M is a meta~, eg. copper, zinc, tin, manganese, iron, cobalt or nickel, preferably copper, X is the an-ion of an inorganic acid, eg. chloride, sulfate, phos-phate or bromide, preferably chloride~ and n and q are each 1, 2, 3 or 4, preferably 1 and 2.
The a~olylmethyloxiranes of the general formula I
can be prepared by the methods described in EP-A-94 564.
The compounds I contain 2 chiral centers and are generally obtained in the form of diastereomer mixtures.
These can be separated into the pure diastereomeric enan-tiomer pairs on the basis o~ their different physical properties, for example by recrystallization or column chromatography, including HPLC. The said enan~iomer pairs can be converted into pure enantiomeric compounds I
by kno~n methods for resolving racemates, for example by reaction ~ith a chira( auxiliary componen~, separation of the resulting diastereomers by one of the abovementioned methods and subsequent elimination of the auxi~iary , , . ~
~ 1 32~995 6 O.Z. 0050/3q557 component, or by column chromatography, including HPLC, over chiral col-umns packed with, for example, silica gel doped with a solid chiral aux-iliary which cannot be washed out.
5 The azolylmethyloxiranes of the formula I may have a variety of influences on practically all plant development stages, and may therefore be used as growth regulators. The diversity of action of growth regulators depends especially on a) the type and variety of plant;
10 b) the time applied, with reference to the development stage of the plant and the time of the year;
c) the place and method of application (seed treatment, soil treatment, or foliage application);
d) climatic factors, e.g., temperature, amount of precipitate, day length and light intensity;
e) soil conditions (including fertilization);
f) the formulation of the active ingredient; and g) the concentration at which the active ingredient is applied.
20 A description of some of the various possibilities of using the growth regulators according to the invention in agriculture and horticulture is given below.
A. Vegetative plant growth can be inhibited to a considerable extent, a fact which is manifested particularly in a reduction in plant height.
The treated plants thus have a compact habit; furthermore, the leaf color is darker.
Of advantage in practice is for example the reduction in grass growth on roadsides, hedges, canal embankments and on areas such as parks, sportsgrounds, fruit orchards, lawns and airfields, thus reducing e~pensive and time-consuming mowing.
A further feature of economic interest is the increase in the rigor of crops which tend to lodge, such as cereals, Indian corn, sunflowers and soybeans. The shortening and strengthening of the stem thus caused reduces or eliminates the danger of lodging under un~avorable weather conditions.
The use of growth regulators is also important for inhibiting plant height and changing the time of ripening in cotton. It is thus pos-sible for this important crop to be harvested completely mechanically.
1 32~9'~5 7 O.Z. 0050/39557 Growth regulators may also increase or inhibit lateral branching. This is of interest when, for instance in tobacco plants, it is desired to inhibit the formation of lateral shoots (suckers) in favor of leaf devetopment.
With the compounds of the formula I, it is possible for instance in winter rape to considerably increase the resistance to freeze injury.
On the one hand, upward growth and the development of a too luxuriant (and thus particularly frost-susceptible) leaf or plant mass are inhibited; on the other, the young rape plants are kept, in spite of favorable growth conditions, in the vege$ative development stage before winter frosts begin. The danger of freeze injury is thus eliminated in plants which tend to lose prematurely their inhibition to bloom and pass into the generative phase. In other crops, too, e.g., winter cereals, it is advantageous if the plants are well tillered in the fall as a result of treatment with the compounds according to the invention, but enter winter with not too lush a growth. This is a preventive measure against increased susceptibility to freeze injury and - because of the relatively low leaf or plant mass - attack by various (especially fungus) diseases. The inhibition of vegetative growth also makes closer planting possible in numerous crops, which mears an increase in yield, based on the area cropped.
B. Better yields both of plant parts and plant materials may be obtained with the active ingredients according to the invention. It is thus for instance possible to induce increased formation of buds, blossom, leaves, fruit, seed grains, roots and tubers, to increase the sugar content of sugarbeets, sugarcane and citrus fruit, to raise the protein content of cereals and soybeans, and to stimulate the increased formation of latex in rubber trees.
The azolylmethyloxiranes of the formula I may raise the yield by influencing plant metabolism or by promoting or inhibiting vegetative and/or generative plant growth.
3~ -C. It is also possible with the azolylmethyloxiranes I to shorten or lengthen growth stages and to accelerate or retard the ripening process in plant parts either before or after harvesting.
A factor of economic interest is for example the facilitation of har-vesting made possible by a chemical, temporally concentrated loosening (abscission) of the adherence of sta1ks to the branches of citrus fruit, olive trees, and other kinds of pomes, drupes and indehiscent fruit. The same mechanism, i.e., promotion of the formation of separ-ation layers between fruit or leaf and stem of the plant, is also essential for a readily controllable defoliation of crop plants, e.g., cotton.
1 32q9q5 8 o.Z. 0050/39557 D. Further, transpiration in crop plants may be reduced with growth regulators. This is particularly important for plants growing in agricultural areas which are expensive to irrigate, e.g., in arid or semi-arid areas. Irrigation frequency can be reduced by using the compounds according to the invention, making for lower costs. AS a result of the use of growth regulators, the water available can be better utilizsd, because, inter alia, - the size of the stomata opening is reduced;
- a thicker epidermis and cuticle are formed;
- penetration of the soil by the roots is improved;
- the micro-climate in the stand is favorably influenced by the more compact growth.
15 The active ingredients to be used in accordance with the invention may be applied not only to the seed (as a disinfectant), but also to the soil, i.e., via the roots, and to the foliage.
As a result of the good crop plant tolerance, the application rate may 20 vary considerably. When seed is treated, active ingredient amounts of from 0.001 to 50, and preferably from 0.01 to 1, g per kg of seed are generally needed. When the soil or foliage is treated, rates of from 0.01 to 10, and preferably from 0.01 to 5, kg per hectare are generally considered to be sufficient.
The agents based on the azolylmethyloxiranes I can be employed in the form of conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes for which they are intended; they should at all events 30 ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for examp1e by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable 35 auxiliaries for this purpose are solvents such as aromatics (e.g., xylenes, toluene, benzene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., crude oil fractions), alcohols ~e.g., methanol, butanol), amines ~eg., ethanolamine) N,N-dimethylformamide, and water; solid carriers such as ground natural minerals (e.g., kaolins, aluminas, talc 40 and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose. It is preferred ~` 1 329995 9 O.Z. 0050/39557 to apply the active ingredients according to the invention in aqueous solution, if desired with the addition of water-miscible organic solvents such as methanol or other lower alcohols, acetone, N, N-dimethylformamide or N-methylpyrrolidone.
The fungicides generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt% of active ingredient.
The formulations, or the ready-to-use preparations prepared therefrom, 10 such as solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied ir. known manner, for example preemergence, post-emerg~nce, or as seed disinfectants.
Examples of formulations are given below.
I. 20 parts by weight of compound no. 8 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-~sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica 20 gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.
II. 3 parts by weight of compound no. 131 is intimately mixed with 25 97 parts by weight of particulate kaolin. A dust is obtained containing 3Y0 by weight of the active ingredient.
, .
III. 30 parts by weight of compound no. 38 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 30 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
IV. 40 parts by weight of compound no. 43 is intimately mixed with 10 35 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution in 100,000 parts by-weight of water gives an aqueous dispersion containing 0.04% by weight of active ingredient.
40 V. 20 parts of compound no. 43 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acidl 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A
stable oily dispersion is obtained.
1 32q99'~
0.7. 0050/39557 VI. 90 parts by weight of compound no. 49 is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
5 VII. 20 parts by weight of compound no. 19 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 mol~s of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene 10 oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dis-persion is obtained containing 0.02% by weight of the active ingredient.
VIII. 20 parts by weight of compound no. 8 is dissolved in a mixture 15 consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,0~0 parts by weight of water and finely distributing it 20 therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
IX. 20 parts by weight of compound no. ~ is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a 25 mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it $herein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
In these application forms, the agents based on the azolylmethyloxiranes I
may also be present together with other active ingredients, for example herbicides, insecticides, other growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with 35 other growth regulator mixtures gives synergistic effects, i.e., the action of the combination product is greater than the added actions of its components.
Examples of fungicides which may be combined with the novel compounds are:
40 sulfur, dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate, zinc dimethyldithiocarbamate, 1 329~'~5 11 O.Z. 0050/39557 zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiura~ disulfides, 5 ammonia complex of zinc N,N'-ethylenebisdithiocarbamate, ammonia complex of zinc N,N'-propylenebisdithiocarbamate, zinc N,N'-propylenebisdithioccarbamate and N,N'-polypropylenebis(thiocarbamyl) disulfide;
nitro derivatives, such as 10 dinitro(1-methylheptyl)-phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-but~1-4,6-dinitrophenyl isopropylcarbonate and diisopropyl 5-nitroisophthalate;
heterocyclic substances, such as 15 2-heptadecylimidazol-2-yl acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethyl phthalimidophosphonothioate, 5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2~ 2-thio-1,3-dithio[4,5 b]quinoxaline, methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 2-(fur-2-yl)-benzimidazole, 2-(thiazol-4-yl)benzimidazole, 2~ N-(1,1,2,2-tetrachloroethylthio~-tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsul~uric acid dlamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 30 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, 2-thiopyridine l-oxide, 8-hydroxyquinoline and its copper salt, 35 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 40 2,4,5-trimethylfuran-3-carboxanilide, 2,5-dimethyl-N-cyclohexylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, 1 32q~qS
Acid addition salts are, for e~ample, the chlor-ides, bromides, sulfates, nitrates, phosphates, oxalates or dodecylbenzenesulfonates. The activity of the salts is due to the cation, so that any anion may be chosen.
Metal comple~es of the compounds I are compounds of the general formula la M r ~2 1 X
L I ~ q (Ia) ~IZ n N
where M is a meta~, eg. copper, zinc, tin, manganese, iron, cobalt or nickel, preferably copper, X is the an-ion of an inorganic acid, eg. chloride, sulfate, phos-phate or bromide, preferably chloride~ and n and q are each 1, 2, 3 or 4, preferably 1 and 2.
The a~olylmethyloxiranes of the general formula I
can be prepared by the methods described in EP-A-94 564.
The compounds I contain 2 chiral centers and are generally obtained in the form of diastereomer mixtures.
These can be separated into the pure diastereomeric enan-tiomer pairs on the basis o~ their different physical properties, for example by recrystallization or column chromatography, including HPLC. The said enan~iomer pairs can be converted into pure enantiomeric compounds I
by kno~n methods for resolving racemates, for example by reaction ~ith a chira( auxiliary componen~, separation of the resulting diastereomers by one of the abovementioned methods and subsequent elimination of the auxi~iary , , . ~
~ 1 32~995 6 O.Z. 0050/3q557 component, or by column chromatography, including HPLC, over chiral col-umns packed with, for example, silica gel doped with a solid chiral aux-iliary which cannot be washed out.
5 The azolylmethyloxiranes of the formula I may have a variety of influences on practically all plant development stages, and may therefore be used as growth regulators. The diversity of action of growth regulators depends especially on a) the type and variety of plant;
10 b) the time applied, with reference to the development stage of the plant and the time of the year;
c) the place and method of application (seed treatment, soil treatment, or foliage application);
d) climatic factors, e.g., temperature, amount of precipitate, day length and light intensity;
e) soil conditions (including fertilization);
f) the formulation of the active ingredient; and g) the concentration at which the active ingredient is applied.
20 A description of some of the various possibilities of using the growth regulators according to the invention in agriculture and horticulture is given below.
A. Vegetative plant growth can be inhibited to a considerable extent, a fact which is manifested particularly in a reduction in plant height.
The treated plants thus have a compact habit; furthermore, the leaf color is darker.
Of advantage in practice is for example the reduction in grass growth on roadsides, hedges, canal embankments and on areas such as parks, sportsgrounds, fruit orchards, lawns and airfields, thus reducing e~pensive and time-consuming mowing.
A further feature of economic interest is the increase in the rigor of crops which tend to lodge, such as cereals, Indian corn, sunflowers and soybeans. The shortening and strengthening of the stem thus caused reduces or eliminates the danger of lodging under un~avorable weather conditions.
The use of growth regulators is also important for inhibiting plant height and changing the time of ripening in cotton. It is thus pos-sible for this important crop to be harvested completely mechanically.
1 32~9'~5 7 O.Z. 0050/39557 Growth regulators may also increase or inhibit lateral branching. This is of interest when, for instance in tobacco plants, it is desired to inhibit the formation of lateral shoots (suckers) in favor of leaf devetopment.
With the compounds of the formula I, it is possible for instance in winter rape to considerably increase the resistance to freeze injury.
On the one hand, upward growth and the development of a too luxuriant (and thus particularly frost-susceptible) leaf or plant mass are inhibited; on the other, the young rape plants are kept, in spite of favorable growth conditions, in the vege$ative development stage before winter frosts begin. The danger of freeze injury is thus eliminated in plants which tend to lose prematurely their inhibition to bloom and pass into the generative phase. In other crops, too, e.g., winter cereals, it is advantageous if the plants are well tillered in the fall as a result of treatment with the compounds according to the invention, but enter winter with not too lush a growth. This is a preventive measure against increased susceptibility to freeze injury and - because of the relatively low leaf or plant mass - attack by various (especially fungus) diseases. The inhibition of vegetative growth also makes closer planting possible in numerous crops, which mears an increase in yield, based on the area cropped.
B. Better yields both of plant parts and plant materials may be obtained with the active ingredients according to the invention. It is thus for instance possible to induce increased formation of buds, blossom, leaves, fruit, seed grains, roots and tubers, to increase the sugar content of sugarbeets, sugarcane and citrus fruit, to raise the protein content of cereals and soybeans, and to stimulate the increased formation of latex in rubber trees.
The azolylmethyloxiranes of the formula I may raise the yield by influencing plant metabolism or by promoting or inhibiting vegetative and/or generative plant growth.
3~ -C. It is also possible with the azolylmethyloxiranes I to shorten or lengthen growth stages and to accelerate or retard the ripening process in plant parts either before or after harvesting.
A factor of economic interest is for example the facilitation of har-vesting made possible by a chemical, temporally concentrated loosening (abscission) of the adherence of sta1ks to the branches of citrus fruit, olive trees, and other kinds of pomes, drupes and indehiscent fruit. The same mechanism, i.e., promotion of the formation of separ-ation layers between fruit or leaf and stem of the plant, is also essential for a readily controllable defoliation of crop plants, e.g., cotton.
1 32q9q5 8 o.Z. 0050/39557 D. Further, transpiration in crop plants may be reduced with growth regulators. This is particularly important for plants growing in agricultural areas which are expensive to irrigate, e.g., in arid or semi-arid areas. Irrigation frequency can be reduced by using the compounds according to the invention, making for lower costs. AS a result of the use of growth regulators, the water available can be better utilizsd, because, inter alia, - the size of the stomata opening is reduced;
- a thicker epidermis and cuticle are formed;
- penetration of the soil by the roots is improved;
- the micro-climate in the stand is favorably influenced by the more compact growth.
15 The active ingredients to be used in accordance with the invention may be applied not only to the seed (as a disinfectant), but also to the soil, i.e., via the roots, and to the foliage.
As a result of the good crop plant tolerance, the application rate may 20 vary considerably. When seed is treated, active ingredient amounts of from 0.001 to 50, and preferably from 0.01 to 1, g per kg of seed are generally needed. When the soil or foliage is treated, rates of from 0.01 to 10, and preferably from 0.01 to 5, kg per hectare are generally considered to be sufficient.
The agents based on the azolylmethyloxiranes I can be employed in the form of conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes for which they are intended; they should at all events 30 ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for examp1e by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable 35 auxiliaries for this purpose are solvents such as aromatics (e.g., xylenes, toluene, benzene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., crude oil fractions), alcohols ~e.g., methanol, butanol), amines ~eg., ethanolamine) N,N-dimethylformamide, and water; solid carriers such as ground natural minerals (e.g., kaolins, aluminas, talc 40 and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose. It is preferred ~` 1 329995 9 O.Z. 0050/39557 to apply the active ingredients according to the invention in aqueous solution, if desired with the addition of water-miscible organic solvents such as methanol or other lower alcohols, acetone, N, N-dimethylformamide or N-methylpyrrolidone.
The fungicides generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt% of active ingredient.
The formulations, or the ready-to-use preparations prepared therefrom, 10 such as solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied ir. known manner, for example preemergence, post-emerg~nce, or as seed disinfectants.
Examples of formulations are given below.
I. 20 parts by weight of compound no. 8 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-~sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica 20 gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.
II. 3 parts by weight of compound no. 131 is intimately mixed with 25 97 parts by weight of particulate kaolin. A dust is obtained containing 3Y0 by weight of the active ingredient.
, .
III. 30 parts by weight of compound no. 38 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 30 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
IV. 40 parts by weight of compound no. 43 is intimately mixed with 10 35 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution in 100,000 parts by-weight of water gives an aqueous dispersion containing 0.04% by weight of active ingredient.
40 V. 20 parts of compound no. 43 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acidl 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A
stable oily dispersion is obtained.
1 32q99'~
0.7. 0050/39557 VI. 90 parts by weight of compound no. 49 is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
5 VII. 20 parts by weight of compound no. 19 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 mol~s of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene 10 oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dis-persion is obtained containing 0.02% by weight of the active ingredient.
VIII. 20 parts by weight of compound no. 8 is dissolved in a mixture 15 consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,0~0 parts by weight of water and finely distributing it 20 therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
IX. 20 parts by weight of compound no. ~ is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a 25 mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it $herein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
In these application forms, the agents based on the azolylmethyloxiranes I
may also be present together with other active ingredients, for example herbicides, insecticides, other growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with 35 other growth regulator mixtures gives synergistic effects, i.e., the action of the combination product is greater than the added actions of its components.
Examples of fungicides which may be combined with the novel compounds are:
40 sulfur, dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate, zinc dimethyldithiocarbamate, 1 329~'~5 11 O.Z. 0050/39557 zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiura~ disulfides, 5 ammonia complex of zinc N,N'-ethylenebisdithiocarbamate, ammonia complex of zinc N,N'-propylenebisdithiocarbamate, zinc N,N'-propylenebisdithioccarbamate and N,N'-polypropylenebis(thiocarbamyl) disulfide;
nitro derivatives, such as 10 dinitro(1-methylheptyl)-phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-but~1-4,6-dinitrophenyl isopropylcarbonate and diisopropyl 5-nitroisophthalate;
heterocyclic substances, such as 15 2-heptadecylimidazol-2-yl acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethyl phthalimidophosphonothioate, 5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2~ 2-thio-1,3-dithio[4,5 b]quinoxaline, methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 2-(fur-2-yl)-benzimidazole, 2-(thiazol-4-yl)benzimidazole, 2~ N-(1,1,2,2-tetrachloroethylthio~-tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsul~uric acid dlamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 30 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, 2-thiopyridine l-oxide, 8-hydroxyquinoline and its copper salt, 35 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 40 2,4,5-trimethylfuran-3-carboxanilide, 2,5-dimethyl-N-cyclohexylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, 1 32q~qS
12 O.Z. 0050/39557 N-formyl-N-morpholine-2,2,2-trichloroethylacetal, piperazine-1,4-diylbis-(1-~2,2,2-trichloroethyl)-formamide), 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine and its salts, 5 2,6-dimethyl-N-cyclododecylmorpholine and its salts, N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine, N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine, 1-[2-(2,4-dichlorophenyl~-4-ethyl-1,3-dioxolan 2-ylethyl]-lH-1,2,4--triazole, 10 1-~2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1~1-1,2,~--triazole, N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl-urea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1r2,4-triazol-1-yl)-butan-2-one, 1~(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-butan-2-ol, 15 1-(4-phenylphenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-2-butanol, ~-(2-chlorophsnyl)-~-(4-chlorophenyl)-5-pyrimidinemethanol, 5-butyl-(2-dimethylamino-4-hydroxy-6-methytpyrimidine, bis-(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene, 20 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene, and various fungicides, such as dodecylguanidine acetate, 3-t3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide, hexachlorobenzene, 25 DL-methyl-N-(2,6-dimethylphenyl~-N-fur-2-yl alanate, methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl~-alanate, N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone, methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine, 30 3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione, 3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin, N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano-[N-(ethylaminocarbonyl)-2-methoximino~-acetamide, 1-[2-(2,4-dichlorophenyl)-pentyl]-lH-1,2,4-triazole, 35 2,4-difluoro--(lH-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol.
Manufacturing example I. Manufacture of the precursors 2-Bromomethyl-2-phenyl-3-(2-chlorophenyl)-oxirane 30 g of 1-(2-chlorophenyl)-2-phenyl-3-bromoprop-1-ene was refluxed with 23 g of 3-chloroperoxybenzoic acid in 500 ml of chloroform. Upon 1 32~Q95 13 o.Z. 0050/39557 completion of the reaction, the chloroform phase was washed free of acid with aqueous sodium bicarbonate solution and water, dried over sodium sutfate and evaporated down under reduced pressure. From the residue there was obtained 41.3 g (70.2%) of 2-bromomethyl-2-phenyl-3-(2-chlorophenyl)-oxirane, which was then processed further.
I I . Manufacture of the end products 2-(l~2~4-Triazol-l-ylmethyl)-2-phenyl-3-(2-chlorophenyl)-oxirane At room temperature, a solution of 32 g of 2-bromomethyl-2-phenyl-3-(2-chlorophenyl)-oxirane in 150 ml of N,N-dimethylformamide was added to a suspension of 23 g of 1,2,4-triazole and 5 9 of sodium hydride (80% dispersion in mineral oil) in 150 ml of N,N-dimethylformamide.
After 8 hours, the reaction solution was poured into water and extracted with ethyl acetate. The organic phase was washed with water and dried over sodium sulfate, and the solvent was stripped off under reduced pressure. The diastereomer mixture which formed was subjected to incipient crystallization from methyl tert-butyl ether to give 15 g of cis-2-(1,2,4-triazolyl-1-ylmethyl)-2-~phenyl)-3-(2-chlorophenyl)-oxirane of melting point 150C. From the mother liquors there was obtained 6.3 9 of trans-2-~1,2,4-triazolyl-1-ylmethyl)-2-(phenyl)-3-(2-chlorophenyl)-oxirane of melting point 117C.
25 The compounds I listed in the table below may be readily obtained from appropriate starting materials in accordance with the above manufacturing example; their action is expected to be similar. The nomenclature "cis" or "trans" isomer relates to the position of the azole to the radical B with regard to the C-C bond of the oxirane ring.
~0 ' ~ 1 329995 14 O.Z. 0050/39557 Table B ~ 2 (I) ~N~Z
11~ ~
N
Compound A B Z Isomer mp ~C]
5 No.
1 phenyl 2-chlorophenyl N cis 159 2 4-chlorophenyl 2-chlorophenyl N cis 166 3 4-diphenyl 2-chlorophenyl N cis 191 10 4 2,4-dichlorophenyl 2-chlorophenyl N cis resin 5 2-chlorophenyl 2-chlorophenyl N cis 6 2-fluorophenyl 2-chlorophenyl N cis 145-147 7 4-tolyl 2-chlorophenyl N cis 140 8 4-fluorophenyl 2-chlorophenyl N cis 136 15 9 3-bromo-4-fluorophenyl 2-chlorophenyl N cis 129-130 10 4-bromophenyl 2-chlorophenyl N cis 11 3,4-dichlorophenyl 2-chlorophenyl N cis 12 4-tert.-butylphenyl 2-chlorophenyl N cis 122 13 3-chlorophenyl 2-chlorophenyl N cis 20 14 3,5-dichlorophenyl 2-chlorophenyl N cis 15 4-phenoxyphenyl 2-chlorophenyl N cis 16 4-tert.-butylphenyl 2-chlorophenyl CH cis 123 17 4-fluorophenyl 2-chlorophenyl CH cis 119-122 18 4-fluorophenyl 2-chlorophenyl CH trans resin 25 19 4-fluorophenyl 2-chlorophenyl N trans resin 20 2-fluorophenyl 2-chlorophenyl CH cis 87 21 4-chlorophenyl 2-chlorophenyl CH cis 90- 92 22 phenyl 2-chlorophenyl CH cis 85- 87 23 4-chlorophenyl 2-fluorophenyl N cis 140 30 24 phenyl 2-fluorophenyl N cis 139 25 2-fluorophenyl 2-fluorophenyl N cis 128 26 2,4-dichlorophenyl 2-fluorophenyl N cis resin 27 4-fluorophenyl 2-trifluoromethylphenyl N cis 110-112 28 phenyl 4-fluorophenyl N cis 73 35 29 4-fluorophenyl 2-trifluoromethylphenyl CH cis 133-135 30 4-fluorophenyl 2,4-dichlorophenyl N cis 127 31 4-fluorophenyl 3-chlorophenyl N cîs resin 32 4-fluorophenyl 3-chlorophenyl CH cis resin .
.
1 3~9995 O.Z. 0050/39557 Compound A B Z Isomer mp ~C]
No.
33 4-chlorophenyl 2-chloro-4-fluorophenyl CH cis 132 34 4-chlorophenyl 2-chloro-4-fluorophenyl N cis 143-145 35 phenyl 2-chloro-4-fluorophenyl CH cis 117 36 phenyl 2-chloro-4-fluorophenyl N cis 123 37 4-fluorophenyl 2-chloro-4-fluorophenyl CH cis 135 38 4-fluorophenyl 2-chloro-4-fluorophenyl N cis 139 10 39 4-fluorophenyl phenyl N cis 89- 92 40 2-fluorophenyl 2-fluorophenyl CH cis 79- 82 41 phenyl 4-trifluoromethylphenyl CH cis 106 42 phenyl 4-trifluoromethylphenyl N cis 132 43 4-chlorophenyl 4-trifluoromethylphenyl N cis 135 44 4-chlorophenyl 4-trifluoromethylphenyl CH cis 123 45 2,4-dichlorophenyl 3-fluorophenyl CH cis 125 46 4-fluorophenyl 4-bromophenyl N cis t19 47 4-fluorophenyl 3-fluorophenyl N cis 99 48 4-fluorophenyl 4-fluorophenyl N cis 69 49 4-chlorophenyl 2-chloro-6-fluorophenyl N cis 150 50 phenyl 4-bromophenyl N cis 122 51 phenyl 2-chloro-6-fluorophenyl N cis 158 52 4-tolyl 2-fluorophenyl N cis 127 53 4-fluorophenyl 2-fluorophenyl N cis 114 25 54 3~bromo-4-fluorophenyl2-fluorophenyl N cis 106 55 4-diphenyl 2-fluorophenyl N cis 56 2-chlorophenyl 2-fluorophenyl N cis 57 4-bromophenyl 2-fluorophenyl N cis 58 3,4-dichlorophenyl 2-fluorophenyl N cis 30 59 4-tert.-butylphenyl 2-fluorophenyl N cis 60 3-chlorophenyl 2-fluorophenyl N cis 61 3,5-dichlorophenyl 2-fluorophenyl N cis 62 4-phenoxyphenyl 2-fluorophenyl N cis 63 phenyl 2-bromophenyl N c;s 153 3~ 64 4-bromophenyl phenyl CH cis 152-153 65 4-bromophenyl 4-chlorophenyl CH cis 143-144 66 phenyl 2,4-dichlorophenyl CH cis 103 67 4-bromophenyl 2,4-dichlorophenyl CH cis 107-108 68 2,4-dichlorophenyl 4-chlorophenyl CH cis 135 ' 1 32~q~5 16 o.z. 0050/39557 Compound A B ~ Salt Isomer mp ~C]
No.
69 4-chlorophenyl phenyl CH cis 138 70 4-bromophenyl 2,4-dichlorophenyl N cis 133-134 71 methyl 2,4-dichlorophenyl CH cis 113-117.5 72 methyl 2,4-dichlorophenyl CH tr~ns 98-104 73 tert.-butyl 4-chlorophenyl N cis79- 86 74 tert.-butyl 4-chlorophenyl CH HCI cis214-216 75 tert.-butyl phenyl N HCI cis 148 76 tert.-butyl phenyl CH cis 75 77 tert.-butyl 2,4-dichlorophenyl N cis 124 78 tert.-butyl 2,4-dichlorophenyl CH cis 95 79 4-chlorophenyl 4-tert.-butylphenyl CH trans 160-162 80 4-chlorophenyl 4-tert.-butylphenyl N cis 176-177 81 2,4-dichlorophenyl 4-tert.-butylphenyl CH cis 132-134 82 methyl 2,4-dichlorophenyl N cis 105-108 83 methyl 2,4-dichlorophenyl N trans 80- 85 84 methyl 2,4-dichlorophenyl N cis/trans 70- 81 =1:1 85 4-tert.-butylphenyl 4-chlorophenyl CH cis100-102 86 4-tert.-butylphenyl 4-chlorophenyl N cis105-107 87 4-tert.-butylphenyl 2,4-dichlorophenyl CH cis 101-113 88 4-tert.-butylphenyl 2,4-dichlorophenyl N cis 108-111 89 4-chlorophenyl 3-methoxyphenyl CH HCI cis 173 90 4-chlorophenyl 3-methoxyphenyl N cis 77 91 phenyl 2,4-dichlorophenyl N cis 159-161 92 4-chlorophenyl 3-trifluoromethylphenyl C~l cis 101-104 93 4-chlorophenyl 3-trifluoromethylphenyl N cis 107-109 30 94 phenyl 3-trifluoromethylphenyl CH cis 77-78.5 95 phenyl 3-trifluoromethylphenyl N HCI cis 131-133 96 phenyl phenyl CH cis108-110 97 4-chlorophenyl 4-fluorophenyl CH cis130-132 98 phenyl 4-chlorophenyl CH cis105-106 35 99 phenyl phenyl N cis116-118 100 phenyl 4-chlorophenyl N cis 114-115 101 4-chlorophenyl phenyl N cis 106-110 102 4-diphenyl 4-chlorophenyl N cis 163-165 103 4-bromophenyl phenyl N cis 115-120 40 104 4-bromophenyl 4-chlorophenyl N cis115-120 105 4-chlorophenyl 4-fluorophenyl N cis112-117 106 4-chlorophenyl 4-bromophenyl N c i s 115-119 107 4-chlorophenyl 4-bromophenyl CH cis114-116 ~ 329995 17 O.Z. 0050/39557 Compound A B Z Salt Isomer mp [C~
No.
108 4-chlorophenyl 4-bromophenyl CH trans 179-181 5 109 2,4-dichlorophenyl 4-bromophenyl CH cis 135-139 110 4-chlorophenyl 4-fluorophenyl N trans 219-223 111 4-chlorophenyl 4-bromophenyl N trans 210-213 112 2,4-dichlorophenyl 4-bromophenyl N cis 108-110 113 2,4-dichlorophenyl phenyl CH cis resin 10 114 2,4-dichlorophenyl phenyl CH trans 118-121 115 2,4-dichlorophenyl phenyl N cis resin 116 4-benzenesulfonyl- 4-chlorophenyl CH cis 193-195 phenyl 117 4-benzenesulfonyl- 4-chlorophenyl CH trans 204-205 phenyl -` 18 1 329q95 ~, U~ ,~ o Co~ ~ ~ $
o ._ ~ ~ _, ~ ~ ~
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s s I I s s s c a) L C S
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1 32~q95 19 o.Z. 0050/39557 Use examples To determine the growth-regulating properties of the candidate compounds, a culture medium was supplied with sufficient nutrients, and test plants 5 were grown therein in plastic pots approx. 12.5 cm in diameter and having a volume of about 500 ml.
In the preemergence treatment, the candidate compounds were poured onto the seedbed as aqueous formulations on the day of sowing. In the post-10 emergence treatment, the candidate compounds were sprayed onto the plantsas aqueous formulations.
The growth-regulating action observed was confirmed at the end of the experiment by height measurements. The figures obtained were compared with 15 those for untreated plants.
Not only was growth height reduced - the leaves also took on a more intense color. The increased chlorophyll content is indicative of a higher rate of photosynthesis, making for bigger yields.
The substance used for comparison purposes was 2-chloroethyltrimet~lyl-ammonium chloride (CCC).
Table 1 Spring barley, ~Aramirll variety; preemergence (soil) treatment Compound Concentration in mg Relative No. of compound/vessel _ growth height 30 untreated - 100 CCC 6 86.1 27 6 25.7 43 6 43.1 35 Table 2 Lawnseed ~Tiergarten Mischung~; postemergence (leaf) treatment Compound Concentration in mg Relative 40 No. of_compound/vessel growth height untreated - 100 CCC 1.5 104.1 6 104.1 43 1.5 65.8 6 38.~
~ 1 329995 O.Z. 0050/39557 Table 3 Sunflowers "Sorex" variety; postemergence (leaf) treatment 5 Compound Concentration in mg Relative No. of compound/vessel growth height _ untreated - 100 CCC 6 84.7 8 6 63.5 19 6 77.6 43 6 64.0 131 6 71.8 Table 4 Spring rape "Petranova" variety; postemergence tleaf) treatment Compound Concentration in mg Relative No. of compound/vessel growth height 2~ untreated - 100 CCC 6 89.3 4 6 69.1 7 6 76.0 8 6 70.6 27 6 69.1 6 81.7 34 6 72.2 43 6 80.2 49 6 72.2 30 131 6 71.9 2. Rice seedling test Young rice seedlings tBahia variety) were cultivated in a nutrient 35 solution containing the active ingredients in various concentrations.
After cultivation for six days at 25C in permanent light the active : ingredient concentration was determined at which the length of the second sheath is decreased by 50 % 1= kI50).
40 tW. Rademacher and J. Jung, Berichte aus dem Fachgebiet Herbologie ("Reports from the herbology field"), vol. 24, pp 127-134, University of Hohenheim, 1983).
., .
'-` 1 32~qq5 21 o.Z. 0050/39557 Compound ~I50 (molar) No .
CCC } . 5 X 10-~
7 1.8 ~ 10-5 8 1.3 x 10~6 17 6.5 x 10-6 19 6.0 x 10-5 6.4 x 10-6 33 8.9 x 10-6 10 34 2.8 x 10-6 3.2 x 10-5 36 7.3 x 10-6 37 1.5 x 10-5 38 1.2 x 10-6 15 47 1.1 x 10-6 48 8.1 x 10-7 3.0 x 10-6 3. Improving the yield in barley Spring barley of the Aura variety was grown in 5 liter Mitscherlich vessels in a sandy loam to which sufficient nutrients had been added. Each vessel contained 14 plants. All the plants had been treated several times with fungicides to prevent fungal infection and thus substantially 25 eliminate falsification of the results. The plants were cultivated in the open, protection merely being given against inclement weather conditions.
At a growth height of approx. 38 cm, the plants were sprayed uniformly with an aqueous formulation of an azolylmethyloxirane I (3.1 ml/vessel).
30 The yields are given in the Table below and show that for example compound no. 8 results in a significant increase in yield. It can be concluded from the way in which this experiment was carried out that the increase in yield is not attributable to a fungicidal action of the candidate com-pounds or to the avoidance of lodging.
Compound Appln. rate Yield [%~
No. ~mg of compound/vessel) _ (Control =_100%) .:
Manufacturing example I. Manufacture of the precursors 2-Bromomethyl-2-phenyl-3-(2-chlorophenyl)-oxirane 30 g of 1-(2-chlorophenyl)-2-phenyl-3-bromoprop-1-ene was refluxed with 23 g of 3-chloroperoxybenzoic acid in 500 ml of chloroform. Upon 1 32~Q95 13 o.Z. 0050/39557 completion of the reaction, the chloroform phase was washed free of acid with aqueous sodium bicarbonate solution and water, dried over sodium sutfate and evaporated down under reduced pressure. From the residue there was obtained 41.3 g (70.2%) of 2-bromomethyl-2-phenyl-3-(2-chlorophenyl)-oxirane, which was then processed further.
I I . Manufacture of the end products 2-(l~2~4-Triazol-l-ylmethyl)-2-phenyl-3-(2-chlorophenyl)-oxirane At room temperature, a solution of 32 g of 2-bromomethyl-2-phenyl-3-(2-chlorophenyl)-oxirane in 150 ml of N,N-dimethylformamide was added to a suspension of 23 g of 1,2,4-triazole and 5 9 of sodium hydride (80% dispersion in mineral oil) in 150 ml of N,N-dimethylformamide.
After 8 hours, the reaction solution was poured into water and extracted with ethyl acetate. The organic phase was washed with water and dried over sodium sulfate, and the solvent was stripped off under reduced pressure. The diastereomer mixture which formed was subjected to incipient crystallization from methyl tert-butyl ether to give 15 g of cis-2-(1,2,4-triazolyl-1-ylmethyl)-2-~phenyl)-3-(2-chlorophenyl)-oxirane of melting point 150C. From the mother liquors there was obtained 6.3 9 of trans-2-~1,2,4-triazolyl-1-ylmethyl)-2-(phenyl)-3-(2-chlorophenyl)-oxirane of melting point 117C.
25 The compounds I listed in the table below may be readily obtained from appropriate starting materials in accordance with the above manufacturing example; their action is expected to be similar. The nomenclature "cis" or "trans" isomer relates to the position of the azole to the radical B with regard to the C-C bond of the oxirane ring.
~0 ' ~ 1 329995 14 O.Z. 0050/39557 Table B ~ 2 (I) ~N~Z
11~ ~
N
Compound A B Z Isomer mp ~C]
5 No.
1 phenyl 2-chlorophenyl N cis 159 2 4-chlorophenyl 2-chlorophenyl N cis 166 3 4-diphenyl 2-chlorophenyl N cis 191 10 4 2,4-dichlorophenyl 2-chlorophenyl N cis resin 5 2-chlorophenyl 2-chlorophenyl N cis 6 2-fluorophenyl 2-chlorophenyl N cis 145-147 7 4-tolyl 2-chlorophenyl N cis 140 8 4-fluorophenyl 2-chlorophenyl N cis 136 15 9 3-bromo-4-fluorophenyl 2-chlorophenyl N cis 129-130 10 4-bromophenyl 2-chlorophenyl N cis 11 3,4-dichlorophenyl 2-chlorophenyl N cis 12 4-tert.-butylphenyl 2-chlorophenyl N cis 122 13 3-chlorophenyl 2-chlorophenyl N cis 20 14 3,5-dichlorophenyl 2-chlorophenyl N cis 15 4-phenoxyphenyl 2-chlorophenyl N cis 16 4-tert.-butylphenyl 2-chlorophenyl CH cis 123 17 4-fluorophenyl 2-chlorophenyl CH cis 119-122 18 4-fluorophenyl 2-chlorophenyl CH trans resin 25 19 4-fluorophenyl 2-chlorophenyl N trans resin 20 2-fluorophenyl 2-chlorophenyl CH cis 87 21 4-chlorophenyl 2-chlorophenyl CH cis 90- 92 22 phenyl 2-chlorophenyl CH cis 85- 87 23 4-chlorophenyl 2-fluorophenyl N cis 140 30 24 phenyl 2-fluorophenyl N cis 139 25 2-fluorophenyl 2-fluorophenyl N cis 128 26 2,4-dichlorophenyl 2-fluorophenyl N cis resin 27 4-fluorophenyl 2-trifluoromethylphenyl N cis 110-112 28 phenyl 4-fluorophenyl N cis 73 35 29 4-fluorophenyl 2-trifluoromethylphenyl CH cis 133-135 30 4-fluorophenyl 2,4-dichlorophenyl N cis 127 31 4-fluorophenyl 3-chlorophenyl N cîs resin 32 4-fluorophenyl 3-chlorophenyl CH cis resin .
.
1 3~9995 O.Z. 0050/39557 Compound A B Z Isomer mp ~C]
No.
33 4-chlorophenyl 2-chloro-4-fluorophenyl CH cis 132 34 4-chlorophenyl 2-chloro-4-fluorophenyl N cis 143-145 35 phenyl 2-chloro-4-fluorophenyl CH cis 117 36 phenyl 2-chloro-4-fluorophenyl N cis 123 37 4-fluorophenyl 2-chloro-4-fluorophenyl CH cis 135 38 4-fluorophenyl 2-chloro-4-fluorophenyl N cis 139 10 39 4-fluorophenyl phenyl N cis 89- 92 40 2-fluorophenyl 2-fluorophenyl CH cis 79- 82 41 phenyl 4-trifluoromethylphenyl CH cis 106 42 phenyl 4-trifluoromethylphenyl N cis 132 43 4-chlorophenyl 4-trifluoromethylphenyl N cis 135 44 4-chlorophenyl 4-trifluoromethylphenyl CH cis 123 45 2,4-dichlorophenyl 3-fluorophenyl CH cis 125 46 4-fluorophenyl 4-bromophenyl N cis t19 47 4-fluorophenyl 3-fluorophenyl N cis 99 48 4-fluorophenyl 4-fluorophenyl N cis 69 49 4-chlorophenyl 2-chloro-6-fluorophenyl N cis 150 50 phenyl 4-bromophenyl N cis 122 51 phenyl 2-chloro-6-fluorophenyl N cis 158 52 4-tolyl 2-fluorophenyl N cis 127 53 4-fluorophenyl 2-fluorophenyl N cis 114 25 54 3~bromo-4-fluorophenyl2-fluorophenyl N cis 106 55 4-diphenyl 2-fluorophenyl N cis 56 2-chlorophenyl 2-fluorophenyl N cis 57 4-bromophenyl 2-fluorophenyl N cis 58 3,4-dichlorophenyl 2-fluorophenyl N cis 30 59 4-tert.-butylphenyl 2-fluorophenyl N cis 60 3-chlorophenyl 2-fluorophenyl N cis 61 3,5-dichlorophenyl 2-fluorophenyl N cis 62 4-phenoxyphenyl 2-fluorophenyl N cis 63 phenyl 2-bromophenyl N c;s 153 3~ 64 4-bromophenyl phenyl CH cis 152-153 65 4-bromophenyl 4-chlorophenyl CH cis 143-144 66 phenyl 2,4-dichlorophenyl CH cis 103 67 4-bromophenyl 2,4-dichlorophenyl CH cis 107-108 68 2,4-dichlorophenyl 4-chlorophenyl CH cis 135 ' 1 32~q~5 16 o.z. 0050/39557 Compound A B ~ Salt Isomer mp ~C]
No.
69 4-chlorophenyl phenyl CH cis 138 70 4-bromophenyl 2,4-dichlorophenyl N cis 133-134 71 methyl 2,4-dichlorophenyl CH cis 113-117.5 72 methyl 2,4-dichlorophenyl CH tr~ns 98-104 73 tert.-butyl 4-chlorophenyl N cis79- 86 74 tert.-butyl 4-chlorophenyl CH HCI cis214-216 75 tert.-butyl phenyl N HCI cis 148 76 tert.-butyl phenyl CH cis 75 77 tert.-butyl 2,4-dichlorophenyl N cis 124 78 tert.-butyl 2,4-dichlorophenyl CH cis 95 79 4-chlorophenyl 4-tert.-butylphenyl CH trans 160-162 80 4-chlorophenyl 4-tert.-butylphenyl N cis 176-177 81 2,4-dichlorophenyl 4-tert.-butylphenyl CH cis 132-134 82 methyl 2,4-dichlorophenyl N cis 105-108 83 methyl 2,4-dichlorophenyl N trans 80- 85 84 methyl 2,4-dichlorophenyl N cis/trans 70- 81 =1:1 85 4-tert.-butylphenyl 4-chlorophenyl CH cis100-102 86 4-tert.-butylphenyl 4-chlorophenyl N cis105-107 87 4-tert.-butylphenyl 2,4-dichlorophenyl CH cis 101-113 88 4-tert.-butylphenyl 2,4-dichlorophenyl N cis 108-111 89 4-chlorophenyl 3-methoxyphenyl CH HCI cis 173 90 4-chlorophenyl 3-methoxyphenyl N cis 77 91 phenyl 2,4-dichlorophenyl N cis 159-161 92 4-chlorophenyl 3-trifluoromethylphenyl C~l cis 101-104 93 4-chlorophenyl 3-trifluoromethylphenyl N cis 107-109 30 94 phenyl 3-trifluoromethylphenyl CH cis 77-78.5 95 phenyl 3-trifluoromethylphenyl N HCI cis 131-133 96 phenyl phenyl CH cis108-110 97 4-chlorophenyl 4-fluorophenyl CH cis130-132 98 phenyl 4-chlorophenyl CH cis105-106 35 99 phenyl phenyl N cis116-118 100 phenyl 4-chlorophenyl N cis 114-115 101 4-chlorophenyl phenyl N cis 106-110 102 4-diphenyl 4-chlorophenyl N cis 163-165 103 4-bromophenyl phenyl N cis 115-120 40 104 4-bromophenyl 4-chlorophenyl N cis115-120 105 4-chlorophenyl 4-fluorophenyl N cis112-117 106 4-chlorophenyl 4-bromophenyl N c i s 115-119 107 4-chlorophenyl 4-bromophenyl CH cis114-116 ~ 329995 17 O.Z. 0050/39557 Compound A B Z Salt Isomer mp [C~
No.
108 4-chlorophenyl 4-bromophenyl CH trans 179-181 5 109 2,4-dichlorophenyl 4-bromophenyl CH cis 135-139 110 4-chlorophenyl 4-fluorophenyl N trans 219-223 111 4-chlorophenyl 4-bromophenyl N trans 210-213 112 2,4-dichlorophenyl 4-bromophenyl N cis 108-110 113 2,4-dichlorophenyl phenyl CH cis resin 10 114 2,4-dichlorophenyl phenyl CH trans 118-121 115 2,4-dichlorophenyl phenyl N cis resin 116 4-benzenesulfonyl- 4-chlorophenyl CH cis 193-195 phenyl 117 4-benzenesulfonyl- 4-chlorophenyl CH trans 204-205 phenyl -` 18 1 329q95 ~, U~ ,~ o Co~ ~ ~ $
o ._ ~ ~ _, ~ ~ ~
~_ ~ ~ U~ ~ o l_ ~ o ~ ~ o I~ ~ Ln _ o ~ o ;t ~ a~
L ~ ~
r` E .r L ~ L ._ ._ ._ ._ ._ ._ U~ ~
~ ~ ~ ~ ~ ~ .
O X C~
~0 ~ a~ 3 3 ~ 3 ~
o ~ ~.
., ~
I Z I Z I Z I Z ~) z 2 Z Z
. ~
~7 c' a~
a~ c -- C S
CCOOC~:CC~ =~C~
~J L L a~ <D ~ ~ ~ C ~ ~ ~) ~
c o O S S S S .R S S S C Q
OOC~~OOOOIt~ OOOO
L L ~J C~ o O O O ~ E O O O O
s s I I s s s c a) L C S
m ~ Y ~ ~` I I I I I ~ ~ I I I I
C ~
s n. ~ ~ .
~, ~ C C
O O r~ ~~ S S ~ --' ~
~ ~ ~ CC~ OL L e- ~1) ~1) ID
V~ S C ~~ r 4 0 0 0 S S S
J L L ~ S O 5~ O O O
~1 1~1 S S O O C S r` _ E O O O -C ~ ~ ~ ~ ,~ ~ y OL .~ ~
~ n n ~
O ~ ~ ~ ') ~ ~ ~ ~ Q
E 0 cn O ~ ~1 ~'1 ~ li~ ~ 1-- CO C~ O
O O ~ ~ 1 ~I t`J (~ ~J ~ "~
~ O ~ O U~
1 32~q95 19 o.Z. 0050/39557 Use examples To determine the growth-regulating properties of the candidate compounds, a culture medium was supplied with sufficient nutrients, and test plants 5 were grown therein in plastic pots approx. 12.5 cm in diameter and having a volume of about 500 ml.
In the preemergence treatment, the candidate compounds were poured onto the seedbed as aqueous formulations on the day of sowing. In the post-10 emergence treatment, the candidate compounds were sprayed onto the plantsas aqueous formulations.
The growth-regulating action observed was confirmed at the end of the experiment by height measurements. The figures obtained were compared with 15 those for untreated plants.
Not only was growth height reduced - the leaves also took on a more intense color. The increased chlorophyll content is indicative of a higher rate of photosynthesis, making for bigger yields.
The substance used for comparison purposes was 2-chloroethyltrimet~lyl-ammonium chloride (CCC).
Table 1 Spring barley, ~Aramirll variety; preemergence (soil) treatment Compound Concentration in mg Relative No. of compound/vessel _ growth height 30 untreated - 100 CCC 6 86.1 27 6 25.7 43 6 43.1 35 Table 2 Lawnseed ~Tiergarten Mischung~; postemergence (leaf) treatment Compound Concentration in mg Relative 40 No. of_compound/vessel growth height untreated - 100 CCC 1.5 104.1 6 104.1 43 1.5 65.8 6 38.~
~ 1 329995 O.Z. 0050/39557 Table 3 Sunflowers "Sorex" variety; postemergence (leaf) treatment 5 Compound Concentration in mg Relative No. of compound/vessel growth height _ untreated - 100 CCC 6 84.7 8 6 63.5 19 6 77.6 43 6 64.0 131 6 71.8 Table 4 Spring rape "Petranova" variety; postemergence tleaf) treatment Compound Concentration in mg Relative No. of compound/vessel growth height 2~ untreated - 100 CCC 6 89.3 4 6 69.1 7 6 76.0 8 6 70.6 27 6 69.1 6 81.7 34 6 72.2 43 6 80.2 49 6 72.2 30 131 6 71.9 2. Rice seedling test Young rice seedlings tBahia variety) were cultivated in a nutrient 35 solution containing the active ingredients in various concentrations.
After cultivation for six days at 25C in permanent light the active : ingredient concentration was determined at which the length of the second sheath is decreased by 50 % 1= kI50).
40 tW. Rademacher and J. Jung, Berichte aus dem Fachgebiet Herbologie ("Reports from the herbology field"), vol. 24, pp 127-134, University of Hohenheim, 1983).
., .
'-` 1 32~qq5 21 o.Z. 0050/39557 Compound ~I50 (molar) No .
CCC } . 5 X 10-~
7 1.8 ~ 10-5 8 1.3 x 10~6 17 6.5 x 10-6 19 6.0 x 10-5 6.4 x 10-6 33 8.9 x 10-6 10 34 2.8 x 10-6 3.2 x 10-5 36 7.3 x 10-6 37 1.5 x 10-5 38 1.2 x 10-6 15 47 1.1 x 10-6 48 8.1 x 10-7 3.0 x 10-6 3. Improving the yield in barley Spring barley of the Aura variety was grown in 5 liter Mitscherlich vessels in a sandy loam to which sufficient nutrients had been added. Each vessel contained 14 plants. All the plants had been treated several times with fungicides to prevent fungal infection and thus substantially 25 eliminate falsification of the results. The plants were cultivated in the open, protection merely being given against inclement weather conditions.
At a growth height of approx. 38 cm, the plants were sprayed uniformly with an aqueous formulation of an azolylmethyloxirane I (3.1 ml/vessel).
30 The yields are given in the Table below and show that for example compound no. 8 results in a significant increase in yield. It can be concluded from the way in which this experiment was carried out that the increase in yield is not attributable to a fungicidal action of the candidate com-pounds or to the avoidance of lodging.
Compound Appln. rate Yield [%~
No. ~mg of compound/vessel) _ (Control =_100%) .:
Claims (9)
1. A process for influencing the growth of plants, wherein the soil, the seeds or the plants are treated with an azolylmethyloxirane of the general formula I
(I), where A and B are each C1-C4-alkyl, phenyl, naphthyl, diphenyl or phenyl bearing from one to three substituents selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, nitro or phenoxy, and Z is CH or nitrogen, or a metal salt or acid addition salt thereof.
(I), where A and B are each C1-C4-alkyl, phenyl, naphthyl, diphenyl or phenyl bearing from one to three substituents selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, nitro or phenoxy, and Z is CH or nitrogen, or a metal salt or acid addition salt thereof.
2. A process for influencing the growth of plants as set forth in claim 1, wherein the soil, the seeds or the plants are treated with from 0.1 to 95wt% of an azolylmethyloxirane of the formula I, together with conventional carriers.
3. The use of azolylmethyloxiranes of the general formula I as set forth in claim 1 for influencing plant growth.
4. A process for influencing the growth of plants, wherein the soil, the seeds or the plants are treated with an azolylmethyloxirane of the general formula I as set forth in claim 1, where A is 4-fluorophenyl, B is 2-trifluoromethylphenyl and Z is nitrogen.
5. A process for influencing the growth of plants, wherein the soil, the seeds or the plants are treated with an azolylmethyloxirane of the general formula I as set forth in claim 1, where A is 4-chlorophenyl, B is 4-trifluoromethylphenyl and Z is nitrogen.
6. A composition for influencing plant growth, containing an effective amount of at least one azolylmethyloxi-rane of the formula I
(I), where A and B are each C1-C4-alkyl, phenyl, naphtyl, diphenyl or phenyl bearing from one to three substituents selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, nitro or phenoxy, and Z is CH or nitrogen, or a metal salt or acid addition salt thereof, and at least one solid or liquid carrier.
(I), where A and B are each C1-C4-alkyl, phenyl, naphtyl, diphenyl or phenyl bearing from one to three substituents selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, nitro or phenoxy, and Z is CH or nitrogen, or a metal salt or acid addition salt thereof, and at least one solid or liquid carrier.
7. A composition as set forth in claim 6, wherein A is 4-fluorophenyl, B is 2-trifluoromethylphenyl and Z
is nitrogen.
is nitrogen.
8. A composition as set forth in claim 6, containing an effective amount of an azolylmethyloxirane of the general formula I as set forth in claim 1, wherein A
is 4-chlorophenyl, B is 4-triofluoromethylphenyl and Z is nitrogen.
is 4-chlorophenyl, B is 4-triofluoromethylphenyl and Z is nitrogen.
9. A composition as set forth in claim 6, further containing at least one surfactant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873737888 DE3737888A1 (en) | 1987-11-07 | 1987-11-07 | PROCESS FOR INFLUENCING PLANT GROWTH THROUGH AZOLYL METHYLOXIRANE |
| DEP3737888.0 | 1987-11-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1329995C true CA1329995C (en) | 1994-06-07 |
Family
ID=6340039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000582228A Expired - Fee Related CA1329995C (en) | 1987-11-07 | 1988-11-04 | Influencing plant growth by means of azolylmethyloxiranes |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0315850B1 (en) |
| JP (1) | JP2765878B2 (en) |
| KR (1) | KR960007690B1 (en) |
| AT (1) | ATE78131T1 (en) |
| CA (1) | CA1329995C (en) |
| DD (1) | DD283322A5 (en) |
| DE (2) | DE3737888A1 (en) |
| FI (1) | FI89854C (en) |
| HU (1) | HU203832B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7368464B2 (en) | 2002-06-24 | 2008-05-06 | Basf Aktiengesellschaft | Preparation for the production of 1,2,4-triazolylmethyl-oxiranes |
| US7569699B2 (en) | 2004-11-30 | 2009-08-04 | Sumitomo Chemical Company, Limited | Process for producing epoxytriazole derivative |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3907729A1 (en) * | 1989-03-10 | 1990-09-13 | Basf Ag | TRIFLUORMETHYLPHENYLAZOLYLMETHYLOXIRANE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PLANT PROTECTANT |
| EP0388871B1 (en) * | 1989-03-21 | 1993-01-13 | BASF Aktiengesellschaft | Herbicidal and plant growth regulating azolylmethyloxiranes |
| DE3936824A1 (en) * | 1989-11-04 | 1991-05-08 | Basf Ag | N-OXO-AZOLYL METHYLOXIRANES AND FUNGICIDES AND BIOREGULATORS CONTAINING THEM |
| ES2142828T3 (en) * | 1991-08-01 | 2000-05-01 | Hickson Int Plc | PRESERVATIVES FOR WOOD AND OTHER CELLULOSIC MATERIALS. |
| GB9116672D0 (en) * | 1991-08-01 | 1991-09-18 | Hickson Int Plc | Preservatives for wood and other cellulosic materials |
| EP0994650B1 (en) | 1997-06-30 | 2004-02-25 | Monsanto Technology LLC | Microparticles containing agricultural active ingredients |
| WO2005056548A1 (en) * | 2003-12-11 | 2005-06-23 | Cheminova A/S | Enantiomerically pure epoxiconazole and its use as crop protection agent |
| UA91078C2 (en) * | 2005-10-07 | 2010-06-25 | Басф Сэ | Fungicidal and bioregulatory miuxture, method for controlling phytopathogenous fungi, method for regulating plant growth, seeds, fungicidal and bioregulatory agents |
| WO2007088116A2 (en) * | 2006-01-31 | 2007-08-09 | Basf Se | Fungicidal mixtures containing epoxiconazole and metiram |
| AU2007263091B2 (en) * | 2006-06-21 | 2012-03-08 | Basf Se | Azolylmethyloxiranes, their use for controlling phytopathogenic fungi and compositions comprising them |
| JP2009541250A (en) * | 2006-06-23 | 2009-11-26 | ビーエーエスエフ ソシエタス・ヨーロピア | Azolylmethyloxirane, its use for controlling phytopathogenic fungi, and compositions containing it |
| ATE495170T1 (en) * | 2006-06-23 | 2011-01-15 | Basf Se | AZOLYLMETHYLOXIRANES, THEIR USE FOR CONTROLLING PLANT PATHOGENIC FUNGI AND AGENTS CONTAINING THEM |
| JP2009541430A (en) * | 2006-07-05 | 2009-11-26 | ビーエーエスエフ ソシエタス・ヨーロピア | Azolylmethyloxirane, its use for controlling phytopathogenic fungi, and drugs containing it |
| BRPI0713450A2 (en) * | 2006-07-05 | 2012-01-31 | Basf Se | compounds, use of compounds, crop protection composition, seed, and process to combat phytopathogenic fungi |
| CN101495473A (en) * | 2006-07-24 | 2009-07-29 | 巴斯夫欧洲公司 | Azolylmethyloxiranes, use thereof for controlling plant pathogenic fungi, and agents containing the same |
| CN101490043A (en) * | 2006-07-25 | 2009-07-22 | 巴斯夫欧洲公司 | Azolylmethyloxiranes, use thereof for controlling plant pathogenic fungi, and agents containing the same |
| KR20100093127A (en) * | 2007-12-19 | 2010-08-24 | 바스프 에스이 | Azolylmethyloxiranes, use thereof and agents containing the same |
| US20100273651A1 (en) * | 2007-12-19 | 2010-10-28 | Basf Se | Azolylmethyloxiranes, use Thereof and Agents Containing the Same |
| EP2224812A2 (en) * | 2007-12-19 | 2010-09-08 | Basf Se | Azolylmethyloxiranes, use thereof and agents containing the same |
| EP2746275A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | New substituted triazoles and imidazoles and their use as fungicides |
| WO2014095555A1 (en) | 2012-12-19 | 2014-06-26 | Basf Se | New substituted triazoles and imidazoles and their use as fungicides |
| EP2746276A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | New substituted triazoles and imidazoles and their use as fungicides |
| EP2746277A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | Fungicidal imidazolyl and triazolyl compounds |
| CA3038401A1 (en) | 2016-09-29 | 2018-04-05 | Bayer Cropscience Aktiengesellschaft | 5-substituted imidazolylmethyloxirane derivatives as fungicides |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3111238A1 (en) * | 1981-03-21 | 1982-10-07 | Bayer Ag, 5090 Leverkusen | SUBSTITUTED TRIAZOLYL METHYL OXIRANES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INTERMEDIATE PRODUCTS |
| IL68433A (en) * | 1982-05-14 | 1986-04-29 | Basf Ag | Azolylmethyloxiranes,their manufacture and their use as fungicides and in pharmaceutical compositions |
| DE3537817A1 (en) * | 1985-10-24 | 1987-04-30 | Bayer Ag | METHOD FOR PRODUCING OXIRANES |
-
1987
- 1987-11-07 DE DE19873737888 patent/DE3737888A1/en not_active Withdrawn
-
1988
- 1988-10-31 DE DE8888118076T patent/DE3872831D1/en not_active Expired - Lifetime
- 1988-10-31 AT AT88118076T patent/ATE78131T1/en not_active IP Right Cessation
- 1988-10-31 EP EP88118076A patent/EP0315850B1/en not_active Expired - Lifetime
- 1988-11-04 HU HU885709A patent/HU203832B/en not_active IP Right Cessation
- 1988-11-04 CA CA000582228A patent/CA1329995C/en not_active Expired - Fee Related
- 1988-11-04 FI FI885097A patent/FI89854C/en not_active IP Right Cessation
- 1988-11-04 DD DD88321477A patent/DD283322A5/en unknown
- 1988-11-07 JP JP63279549A patent/JP2765878B2/en not_active Expired - Fee Related
- 1988-11-07 KR KR1019880014638A patent/KR960007690B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7368464B2 (en) | 2002-06-24 | 2008-05-06 | Basf Aktiengesellschaft | Preparation for the production of 1,2,4-triazolylmethyl-oxiranes |
| US7569699B2 (en) | 2004-11-30 | 2009-08-04 | Sumitomo Chemical Company, Limited | Process for producing epoxytriazole derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01157905A (en) | 1989-06-21 |
| JP2765878B2 (en) | 1998-06-18 |
| DD283322A5 (en) | 1990-10-10 |
| EP0315850A2 (en) | 1989-05-17 |
| HU203832B (en) | 1991-10-28 |
| DE3872831D1 (en) | 1992-08-20 |
| KR890007641A (en) | 1989-07-05 |
| FI885097A0 (en) | 1988-11-04 |
| HUT49460A (en) | 1989-10-30 |
| ATE78131T1 (en) | 1992-08-15 |
| FI885097A (en) | 1989-05-08 |
| DE3737888A1 (en) | 1989-05-18 |
| EP0315850B1 (en) | 1992-07-15 |
| FI89854C (en) | 1993-12-10 |
| KR960007690B1 (en) | 1996-06-08 |
| EP0315850A3 (en) | 1990-01-24 |
| FI89854B (en) | 1993-08-31 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |