Geometrical isomer of 1-substituted-1-triazolylstyrenes, and their production and use as fungicide, herbicide and/or plant growth regulant

The present invention relates to one of the two geometrical isomers (a compound defined as I-A isomer in the description below) of a triazole compound represented by the formula (I) or (II), ##STR1## wherein R.sub.1 is a hydrogen atom, a C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.4 alkenyl or 2-propynyl group, R.sub.2 is a C.sub.1 -C.sub.6 alkyl, cyclopropyl or 1-methylcyclopropyl group, R.sub.3, which may be the same or different, is a halogen atom, a C.sub.1 -C.sub.4 alkyl, halogen-substituted C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.4 alkoxy, phenoxy, phenyl, cyano or nitro group, n is an integer of 0 to 3, and the term, halogen, means chlorine, bromine and fluorine atoms, its salts, production thereof and a fungicide, herbicide and/or plant growth regulator for agriculture and horticulture containing said compound as an active ingredient.

The present invention relates to one of the two geometrical isomers (a 
compound defined as I-A isomer in the description below) of a triazole 
compound represented by the formula (I), 
##STR2## 
wherein R.sub.1 is a hydrogen atom, a C.sub.1 -C.sub.4 alkyl, C.sub.3 
-C.sub.4 alkenyl or 2-propynyl group, R.sub.2 is a C.sub.1 -C.sub.6 alkyl, 
cyclopropyl or 1-methylcyclopropyl group, R.sub.3, which may be the same 
or different, is a halogen atom, a C.sub.1 -C.sub.4 alkyl, 
halogen-substituted C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.4 alkoxy, 
phenoxy, phenyl, cyano or nitro group, n is an integer of 0 to 3, and the 
term, halogen, means chlorine, bromine and flourine atoms, its salts, 
production thereof and fungicide, herbicide and/or plant growth regulator 
for agriculture and horticulture containing said compound as an active 
ingredient. 
Every triazole compound of the formula (I) has two geometrical isomeric 
forms, Z-form and E-form, represented by the formulae, 
##STR3## 
It is not clear at present which of the two isomeric forms the compounds of 
the present invention belong to, and therefore the properties of the 
compounds can only be expressed conditionally. These two isomers can be 
distinguished from each other by melting point, NMR spectrum or gas 
chromatography, but the difference between them can be characterized more 
generally and clearly by their starting material, a triazole compound of 
the formula (II), 
##STR4## 
wherein R.sub.2, R.sub.3 and n are as defined above. 
The triazole compound of the formula (I) is obtained by reducing a triazole 
compound of the formula (II) to obtain a triazole compound of the formula 
(I) in which R.sub.1 is a hydrogen atom and then etherifying the resulting 
compound: 
##STR5## 
wherein R.sub.1, R.sub.2, R.sub.3 and n are as defined above. 
Hereupon, one of the two geometrical isomers of the triazole compound (II), 
of which the olefin proton appears at a higher magnetic field on the NMR 
spectrum in deutero chloroform, is defined as II-A isomer, and the other, 
of which the olefin proton appears at a lower magnetic field on the NMR 
spectrum in deutero chloroform, is defined as II-B isomer. 
Further, the compound (I) in which R.sub.1 is a hydrogen atom, produced by 
reducing II-A isomer, is defined as I'-A isomer; the compound (I) in which 
R.sub.1 is the defined substituents other than a hydrogen atom, produced 
by etherifying I'-A isomer, is defined as I"-A isomer; and I'-A isomer and 
I"-A isomer are defined generically as I-A isomer. The corresponding 
compounds derived from II-B isomer in the same manner as above are defined 
as I'-B isomer, I"-B isomer and I-B isomer, respectively. The present 
invention relates to I-A isomer and II-A isomer which is an intermediate 
for I-A isomer. 
Hitherto, there have been developed a large number of organosynthetic 
compounds which made a great contribution as agricultural chemicals to the 
stable supply of agricultural and horticultural crops by their activity 
against diseases and pests doing damage to the crops. It is however a fact 
that many problems to be improved are also still present. Such problems 
are sometimes solved, for example, by the development of new and more 
desirable pesticides, or it may be considered that they are also solved by 
investigating the conventional pesticides to establish a proper form of 
the application of agricultural chemicals. 
There are not a few organo-synthetic compounds having a possibility that 
they are also present in the form of geometrical or optical isomers. In 
fact, there are many cases in which pesticides containing these isomers 
are in practical use as agricultural chemicals. It is well known not only 
in agricultural chemicals but also in many other fields that, with many of 
active ingredients having the isomeric forms, there is observed a 
difference in biological activity between the isomers. Recently, the 
problem of environmental pollution becomes very serious in the field of 
agriculture and horticulture, and it is important to lighten this problem 
by using one of a pair of isomers which is stronger in activity. Also, 
this may be considered as bringing about a more economical effect in the 
production of the compound as well as in the practical application as 
agricultural chemicals. From this standpoint, therefore, it may be 
considered as contributing to this field to provide the isomer having a 
stronger activity. 
From this viewpoint, the inventors made a further study on the compounds 
already found by the inventors [Published Unexamined Japanese Patent 
Application No. 130661/1978, Belgian Pat. No. 870243 (Published Unexamined 
Japanese Patent Application No. 41875/1979)]. As a result, it was found 
that the present compounds defined as I-A isomer, one of the two 
geometrical isomers of a triazole compound represented by the formula (I), 
have a higher fungicidal activity on a wider range of plant pathogens as 
well as a higher herbicidal effect and a higher plant growth regulating 
action than the compounds defined as I-B isomer, in other words, they have 
excellent properties as agricultural chemicals. The inventors thus 
attained to the present invention. 
There are many other well-known triazole compounds disclosed in British 
Pat. No. 1364619, Belgian Pat. No. 845433, West German Pat. Nos. 2610022, 
2654890 and 2734426, and U.S. Pat. No. 4086351. But, the characteristic of 
the present invention is that the following new information was found: One 
of the two geometrical isomers of the triazole compound (I) characterized 
by having both of (1) a double bond (benzylidene group) and (2) a hydroxy 
group or its ethers in its structure, 
##STR6## 
has far superior properties as agricultural chemicals as compared with the 
other geometrical isomer. In this point, the present compounds have a 
different structural characteristic from that of the foregoing well-known 
compounds, and besides they have far superior properties as compared with 
the well-known compounds. Consequently, the originality of the present 
invention is such a one as to be never imaginable from the prior art. 
As diseases on which the compounds of the present invention (I-A isomer) 
can exert an excellent protective activity, there may be given rice blast 
(Pyricularia oryzae), sheath blight of rice (Pellicularia sasakii), canker 
of apple (Valsa mali), blossom blight of apple (Sclerotinia mali), powdery 
mildew of apple (Podosphaera leucotricha), apple scab (Venturia 
inaequalis), fruit spot of apple (Mycosphaerella pomi), alternaria leaf 
spot of apple (Alternaria mali), black spot of pear (Alternaria 
kikuchiana), powdery mildew of pear (Phyllactinia pyri), rust of pear 
(Gymnosporangium haraeanum), scab of pear (Venturia nashicola), melanose 
of citrus (Diaporthe citri), citrus scab (Elsinoe fawcetti), common green 
mold of citrus fruit (Penicillium digitatum), blue mold of orange 
(Penicillium italicum), brown rot of peach (Sclerotinia cinerea), 
anthracnose of grape (Elsinoe ampelina), ripe rot of grape (Glomerella 
cingulata), gray mold of grape (Botrytis cinerea), powdery mildew of grape 
(Uncinula necator), rust of grape (Phakopsora ampelopsidis), crown rust of 
oats (Puccinia coronata), powdery mildew of barley (Erysiphe graminis), 
leaf blotch of barley (Rhynchosporium secalis), stripe of barley 
(Helminthosporium gramineum), loose smut of barley (Ustilago nuda), 
covered smut of barley ( Ustilago hordei), typhula snow blight of barley 
(Typhula incarnata), stem rust of barley (Puccinia graminis), leaf rust of 
wheat (Puccinia recondita), loose smut of wheat (Ustilago tritici), bunt 
of wheat (Tilletia caries), speckled leaf blotch of wheat (Septoria 
tritici), glume blotch of wheat (Septoria nodorum), yellow rust of wheat 
(Puccinia striiformis), stem rust of wheat (Puccinia graminis), powdery 
mildew of wheat (Erysiphe graminis), powdery mildew of cucumber 
(Sphaerotheca fuliginea), gray mold of cucumber (Botrytis cinerea), gummy 
stem blight of cucumber (Mycosphaerella melonis), sclerotinia rot of 
cucumber (Sclerotinia sclerotiorum), anthracnose of cucumber 
(Colletotrichum lagenarium), leaf mold of tomato (Cladosporium fulvum), 
powdery mildew of tomato (Erysiphe cichoracearum), early blight of tomato 
(Alternaria solani), gray mold of eggplant (Botrytis cinerea), 
verticillium wilt of eggplant (Verticillium albo-atrum), powdery mildew of 
eggplant (Erysiphe cichoracearum), powdery mildew of pimento (Leveillula 
taurica), gray mold of strawberry (Botrytis cinerea), powdery mildew of 
strawberry (Sphaerotheca humuli), brown spot of tobacco (Alternaria 
longipes), powdery mildew of tobacco (Erysiphe cichoracearum), cercospora 
leaf spot of beet (Cercospora beticola), leaf spot of peanut (Cercospora 
personata), brown leaf spot of peanut (Cercospora arachidicola) and the 
like. 
By further study on the antimicrobial activity of the present compounds, 
I-A isomer, it became clear that the present compounds exhibit also an 
antimicrobial activity against Trichophyton rubrum. Thus, it was found 
that there is a possibility of the present compounds being usable as an 
antimycotic for medical purposes. 
Further, the compounds of the present invention, I-A isomer, can also be 
used as a plant growth regulator, acting to control the growth of useful 
plants. For example, they can be used for preventing the spindly growth of 
rice, wheat, turf, trees for hedge and fruit trees and for dwarfing 
horticultural plants such as potted chrysanthemum. 
In the cultivation of rice and wheat, lodging of rice and wheat caused by 
the application of more fertilizer than required or strong wind becomes 
often serious. But the application of the present compounds at a proper 
time is effective for controlling the height of rice and wheat and 
preventing lodging. 
In the cultivation of potted chrysanthemum, the application of the present 
compounds is useful to elevate the commercial value of the chrysanthemum 
because they can shorten the height of the stem with no adverse effect on 
the flower. 
The compounds of the present I-A isomer, invention have a strong herbicidal 
activity against grassy field weeds such as barnyard grass (Echinochloa 
crus-galli), large crabgrass (Digitaria sanguinalis) and green foxtail 
(Setaria viridis); broad-leaved field weeds such as Umbrella plant 
(Cyperus difformis L.), redroot pigweed (Amaranthus retroflexus), common 
lambsquarter (Chenopodium album), common purslane (Portulaca oleracea) and 
chickweed (Stellaria media); and annual weeds and perennial weeds in paddy 
field such as barnyard grass (Echinochloa crus-galli), pickerel weed 
(Monochoria viaginalis), toothcup (Rotala indica Koehne), Dopatrium 
junceum, Bulrush sp. (Scirpus juncoides var. Hotarui Ohwi) and slender 
spikerush (Eleocharis acicularis). 
When the compounds of the present invention are applied to fields, they are 
also very superior in the following points: They have a strong herbicidal 
activity against main weeds in fields; they show the activity by either of 
soil treatment before the germination of weeds or foliage treatment at the 
beginning of growth; and besides they can be applied safely without doing 
damage to main crops (e.g., rice, soybean, cotton, corn, peanut, 
sunflower, beet) as well as vegetables (e.g., lettuce, radish, tomato). 
When the compounds of the present invention are applied to paddy fields, 
they show also a strong herbicidal activity against main weeds by either 
of pre-emergence treatment or foliage treatment at the beginning of 
growth, and besides they have a high safety to rice plants. 
Further, the compounds of the present invention are very useful as 
herbicides not only for paddy rice but also for various crops, vegetables, 
orchards, turfs, pasture lands, tea gardens, mulberry farms, rubber farms, 
forest lands and non-cultivation lands. 
Further, it became clear that the compounds of the present invention have a 
high safety to mammals and fishes, and besides that they can practically 
be used without doing damage to useful crops in agriculture. 
The triazole compounds II-A, an intermediate for producing the present 
compounds I-A, have also a fungicidal activity against various pathogens 
doing damage to agriculture as well as a herbicidal and plant growth 
regulating action. It is also a fact, however, that the present compounds 
I-A have a far stronger activity against a wider range of plant pathogens 
as well as a far stronger herbicidal and plant growth regulating action 
than the compounds II-A. 
More specific methods for producing the present compounds will be given 
below: 
Method A: Reduction of the triazole compound II 
##STR7## 
wherein R.sub.2, R.sub.3 and n are as defined above. 
The I'-A isomer is produced by reducing the II-A isomer in a suitable 
solvent with a metal hydride complex (e.g. lithium aluminum hydride, 
sodium borohydride) or aluminum alkoxide (e.g. aluminum isopropoxide). The 
II-A isomer to be reduced can be obtained in a pure form, for example, by 
applying fractional crystallization or column chromatography to the 
mixture of the geometrical isomers of a triazole compound (II) produced 
according to the following reaction equation. The II-A isomer can also be 
obtained in a good yield, for example, by irradiating the mixture with 
ultraviolet rays to carry out photoisomerization. More detailed 
explanation will be given hereinafter with reference to Methods C and D. 
##STR8## 
wherein R.sub.2, R.sub.3 and n are as defined above. 
The solvent used in the reduction with a metal hydride complex includes for 
example ethers (e.g. diethyl ether, tetrahydrofuran) and alcohols (e.g. 
methanol, ethanol, isopropanol). When sodium borohydride is used as the 
metal hydride complex, the reaction is achieved by mixing 1 mole of the 
II-A isomer and 0.25 to 2 moles of sodium borohydride in a solvent. The 
reaction temperature is preferably within a range of 0.degree. C. to room 
temperature. The solvent used includes for example ethers (e.g. diethyl 
ether, tetrahydrofuran) and alcohols (e.g. methanol, ethanol, 
isopropanol). When lithium aluminum hydride is used as the metal hydride 
complex, the reaction is achieved by dissolving lithium aluminum hydride 
of 0.25 to 0.8 time by mole based on the II-A isomer in a solvent and 
adding the resulting solution to a solution of the isomer in the same 
solvent. The reaction temperature is preferably within a range of 
-60.degree. C. to 70.degree. C. The solvent used includes ethers (e.g. 
diethyl ether, tetrahydrofuran). After completion of the reaction, water 
or an aqueous dilute acid is added to the reaction solution, and after 
neutralization with an alkali if necessary, the deposited crystals are 
collected by filtration or extracted with an organic solvent sparingly 
soluble in water. The subsequent treatment is carried out by the common 
methods. 
When aluminum isopropoxide is used as reducing agent, it is preferred to 
use such solvents as alcohols (e.g. isopropanol) or aromatic hydrocarbons 
(e.g. benzene). It is a common practice to allow 1 mole of the II-A isomer 
to react with 1 to 2 moles of aluminum isopropoxide at a temperature 
between room temperature and 100.degree. C. The resulting aluminum 
compound is decomposed with a dilute sulfuric acid or an aqueous sodium 
hydroxide solution, followed by extraction with an organic solvent 
sparingly soluble in water. The subsequent treatment is carried out by the 
common methods. 
The salts of the I'-A isomer refer to those obtained with 
plant-physiologically acceptable acids such as hydrohalogenic acid (e.g. 
hydrobromic acid, hydrochloric acid, hydroiodic acid), carboxylic acids 
(e.g. acetic acid, trichloroacetic acid, maleic acid, succinic acid), 
sulfonic acids (e.g. p-toluenesulfonic acid, methanesulfonic acid), nitric 
acid, sulfuric acid and phosphoric acid. If necessary, these salts are 
produced by the conventional methods. 
Method B: Etherification of I'-A isomer 
##STR9## 
wherein R.sub.1, R.sub.2, R.sub.3 and n are as defined above. 
The present compounds, I"-A isomer, are obtained by reacting I'-A isomer 
with a reactive C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.4 alkenyl or 
2-propynyl derivative in a suitable solvent in the presence of a base. The 
reactive derivative includes for example alkyl-, alkenyl- or 
alkynyl-halides (e.g. methyl iodide, allyl bromide, propargyl bromide), 
sulfate compounds (e.g. dimethyl sulfate, diethyl sulfate) and sulfonate 
compounds (e.g. p-toluenesulfonate, naphthalenesulfonate). The solvent 
includes for example general inert organic solvents such as diethyl ether, 
tetrahydrofuran, dioxane, benzene, toluene, xylene and dimethylformamide. 
This reaction may be carried out in the presence of water using a phase 
transfer catalyst known as a reaction accelerator (e.g. 
triethylbenzylammonium chloride, trimethylbenzylammonium bromide). The 
base includes for example suitable strong bases (e.g. alkali metal 
hydrides such as sodium hydride, alkali metal amides such as sodium 
amide), carbonates (e.g. sodium carbonate, potassium carbonate) and alkali 
metal hydroxides (e.g. potassium hydroxide, sodium hydroxide). 
This reaction is achieved by mixing I'-A isomer, a reactive C.sub.1 
-C.sub.4 alkyl, C.sub.3 -C.sub.4 alkenyl or 2-propynyl derivative and a 
base, preferably in an equimolar ratio in a suitable solvent. The reaction 
is carried out within a range of 0.degree. to 100.degree. C., preferably 
20.degree. to 60.degree. C. Sometimes, it is favorable to firstly react 
I'-A isomer with a suitable strong base (e.g. alkali metal hydrides, 
alkali metal amides) in an inert solvent and then to react the resulting 
alkali metal salt with a reactive C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.4 
alkenyl or 2-propynyl derivative. 
In some cases, the following way is desirable to isolate the present 
compounds I"-A: The reaction mixture is freed from the solvent by 
evaporation, water and an organic solvent sparingly soluble in water are 
added to the residue, the organic layer after extraction is separated and 
then purification is carried out by the usual methods. 
The salts of the I"-A isomer refer to those obtained with physiologically 
acceptable acids such as hydrohalogenic acid (e.g. hydrobromic acid, 
hydrochloric acid, hydroiodic acid), carboxylic acids (e.g. acetic acid, 
trichloroacetic acid, maleic acid, succinic acid), sulfonic acids (e.g. 
p-toluenesulfonic acid, methanesulfonic acid), nitric acid, sulfuric acid 
and phosphoric acid. If necessary, these salts are produced by the 
conventional methods. 
The present invention will be illustrated in more detail with reference to 
the following examples. Unless otherwise stated, NMR spectrum in the 
examples is indicated by .delta. values with deutero chloroform as a 
solvent and tetramethylsilane as an internal standard.