JPH0526789B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides triazole and imidazole compounds useful as fungicides, methods for producing the compounds, fungicidal compositions containing the compounds, and the use of these compounds to exterminate fungi, particularly to prevent fungal infections of plants, and to This invention relates to a method for regulating the growth of. According to the invention, the following formula (I): (wherein W is -CH= or =N-; Q is an optionally substituted aryl, especially phenyl, halophenyl, alkylphenyl, alkoxyphenyl,
haloalkyl phenyl or phenyl group substituted with both halogen and alkyl group; R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and are hydrogen, C _1-4 alkyl or trifluoromethyl group; R ⁷ and R ⁸ may be the same or different,
hydrogen, C _1-4 alkyl or phenyl group; R ⁷
and R ⁸ is hydrogen, alkyl, or an optionally substituted phenyl group) and stereoisomers thereof; and acid addition salts and metal complexes thereof. The compounds of the invention contain at least one asymmetric center. Such compounds are generally obtained in the form of racemic mixtures. However, these and other mixtures can be separated into individual isomers by methods known in the art, and the present invention encompasses such isomers. Examples of Q are phenyl, 2-, 3- or 4-chlorophenyl, 2,4- or 2,6-dichlorophenyl, 2,4- or 2,6-difluorophenyl,
2-,3- or 4-fluorophenyl, 2-,3
- or 4-bromophenyl, 2-, 3- or 4-
Methoxyphenyl, 2,4-dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-
Fluoro-4-chlorophenyl, 2-chloro-4
-fluorophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethyl-phenyl, 2-, 3- or 4-trifluoromethylphenyl, 2-chloro-4-methylphenyl and −
It is fluoro-4-methylphenyl, 4-isopropylphenyl, 2-methyl-4-chlorophenyl or 2-methyl-4-fluorophenyl group. It is preferred that the W moiety is =N-, ie the preferred compound is a triazole. Said salts can be salts with inorganic or organic acids, such as with hydrochloric acid, nitric acid, sulfuric acid, acetic acid, 4-toluenesulfonic acid or oxalic acid. Suitably, the metal complex is a complex containing copper, zinc, manganese or iron as the metal. The metal complex has the following formula: [In the formula, W, Q, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷
and R ⁸ have the above meaning, M is a metal,
A is an anion (e.g. chloride ion, bromide ion,
iodine ion, nitrate ion, nitrate ion or phosphate ion), n is 2 or 4, and y
is O or an integer from 1 to 12, and m is an integer corresponding to the valence. Examples of compounds of the invention are shown in Table I below.

【table】

【table】

【table】 *Mixtures of dilatational isomers (note, not shown in table)
Other mixtures of left-handed isomers exist, such as
The contrast ratios reflect the different proportions of left-handed isomers.
have different melting points). A Bilateral isomer A B Bilateral isomer B The following formula (I): (In the formula, Q, R¹,R²,R³,R^Four,R^Five,R⁶,R⁷，
R⁸and W has the above meaning)
The light compound has the following formula (): [In the formula, Q, R¹,R²,R³,R^Four,R^Five,R⁶,R⁷as well as
R⁸has the above meaning, and A is halogen (preferably
(bromine, chlorine or iodine)
of 1,2,4-triazole or imidazole
either in the presence of an acid binder or its alkaline
A form of potassium metal salt, dimethylform
in a convenient solvent such as amide or acetonitrile
processing at a convenient temperature such as 60-160°C
It can be manufactured by The halide of the above formula () is an acid such as pyridine.
in a suitable solution such as dichloromethane in the presence of a binder.
By treatment with halogen in the agent, the following formula
(): (In the formula, Q, R¹,R²,R³,R^Four,R^Five,R⁶,R⁷as well as
R⁸has the above meaning)
[e.g., J.Med.Chem.,
16, 403 (1973); J.Org.Chem., 39, 1042 (1974)
reference〕. R¹and R²In the above formula () where both are hydrogen,
Olefin alcohol is diethyl ether or
is hydrogen in a suitable solvent such as tetrahydrofuran.
Treat with a reducing agent such as lithium aluminum chloride
By the following formula (): (R in the formula³,R^Four,R^Five,R⁶,R⁷,R⁸and Q are as above
has the significance of R⁹is alkyl, alkenyl, a
ruquinyl, optionally substituted phenyl or aralkyl
prepared from an olefinic ester of
obtain. R¹and R²The above formula where is the same but not hydrogen
The olefinic alcohol in () is diethyl ethyl
a suitable solvent such as ether or tetrahydrofuran.
The olefinic ester of the above formula () is expressed by the following formula:
(): R¹-Mg-A () (R in the formula¹and A has the meaning given above)
It can be prepared by treatment with Linard reagent.
Ru. The Grignard reagent of the above formula () is found in the chemical literature.
It can be prepared by standard methods as described in . Alternatively, the olefinic alcohol of formula ()
The call is the following formula(): (R in the formula²,R³,R^Four,R^Five,R⁶,R⁷,R⁸and Q are
carbonyl compound having the above meaning)
By treatment with Grignard reagent of formula ()
It can be prepared as follows. R²Carbonylation of the above formula () where is hydrogen
The compound is usually treated at low temperature with a suitable solution such as diethyl ether.
For example, diisobutylaluminum water in a suitable solvent.
Olefin-based esters of the above formula () can be prepared using chemical compounds.
It can be prepared by selective reduction of tel. Alternatively R²is hydrogen in the above formula ()
Rubonyl compounds can be dissolved in a suitable solvent such as dichloromethane.
In the agent, the above formula () (where R¹and R²is hydrogen
), for example, pyridinyl alcohol.
Prepared by selective oxidation with dichromate
(e.g. Tetrahedron Letters 399 (1979))
reference). R²Carbonylation of the above formula () where is not hydrogen
Among the many oxidation methods described in the chemical literature,
The above formula () (where R¹is hydrogen
R, R²is not hydrogen)
can be prepared by oxidation. The olefinic ester of the above formula () is
Tylsulfoxide, diethyl ether or tetra
For example, alkylene in a suitable solvent such as hydrofuran.
The following formula using redentrifhenylphosphorane
(VII): (R in the formula³,R^Four,R^Five,R⁶,R⁹and Q have the above meanings.
olefinization of γ-ketoester of
[For example, J.Org.
See Chem. 28, 1128 (1963)]. R³γ-ketoes of the above formula (VII), where is hydrogen
Tel is dimethylformamide or dioxane.
cyanide in a suitable solvent such as or in the absence of a solvent.
or in the presence of a thiazolium salt
(VIII): Q-CHO (VIII) Aldehyde (wherein Q has the above meaning)
The following formula (): (R in the formula^Four,R^Five,R⁶and R⁹has the above meaning
react with α,β-unsaturated ketoester of
[For example, Angew.Chem.Int.
See Edn. English, 15, 639 (1976)]. The aldehyde of the formula (VIII) and the formula ()
The α,β-unsaturated esters of
It can be prepared by the following method. Alternatively, a carbonyl compound of the formula ()
is the following formula (X): (R in the formula²,R³,R^Four,R^Five,R⁶,R⁷,R⁸and Q are
having the above meaning, R^Tenand R¹¹is alkyl, a
alkenyl or alkynyl group or are linked together
acetal/digit of ) which together form one ring
can be prepared by acid-promoted hydrolysis of
Ru. The acetal/ketal of formula (X) is
Tylsulfoxide, diethyl ether or tetra
in a suitable solvent such as hydrofuran.
Next using alkylidene triphenylphosphorane
Formula (XI): (R in the formula²,R³,R^Four,R^Five,R⁶,R^Ten,R¹¹and Q
has the above meaning) to olefinize the ketone of
It can be prepared by [for example, J.Org.
See Chem. 28, 1128 (1963)]. The ketone of formula (XI) is dimethylformamide.
using e.g. pyridinium dichromate in a
Formula (XII): (R in the formula²,R³,R^Four,R^Five,R⁶,R^Ten,R¹¹and Q
has the above meaning)
[e.g. Tetrahedron]
See detters399 (1979)]. The alcohol of formula (XII) is diethyl ether.
in a suitable solvent such as ester or tetrahydrofuran.
The aldehyde of the above formula (VIII) is converted to the following formula (XIII): (A, R in the formula²,R³,R^Four,R^Five,R⁶,R^Tenand R¹¹
has the meaning given above) and the Grignard reagent.
It can be prepared by reacting. The Grignard reagent of formula (XIII) above is found in the chemical literature.
According to the standard method described in the following formula (XIV): (A, R in the formula²,R³,R^Four,R^Five,R⁶,R^Tenand R¹¹
can be prepared from the halides of
Ru. The halide of formula (XIV) is described in the chemical literature.
It can be prepared by the method described [eg J.
Pharm.Sci., 60, 1250 (1971); J.Org.Chem.41,
560 (1976); Bull.Chem.Soc.Japan54, 505 (1981)
reference〕. Alternatively, the ketone of formula (XI) may be
suitable such as thyl ether or tetrahydrofuran
Grignard reagent of formula (XIII) above in a suitable solvent.
The following formula (XV): Q-CN (XV) (in the formula, Q has the above-mentioned meaning) and a nitrile of
react, followed by hydrolysis and selection if desired
can be prepared by reacetalization. Furthermore, the ketone of formula (XI) is diethyl
A suitable solution such as ether or tetrahydrofuran
Grignard of the above formula (XIII), often at low temperature in a
The reagent has the following formula (XVI): (in the formula, Q and A have the above meanings)
It can be prepared by reacting with a compound [e.g.
See Bull.Chem.Soc.Japan, 54, 505 (1981)]. Nitrile of the above formula (XV) and the above formula (XVI)
Acid halides are prepared by standard methods described in the chemical literature.
It can be prepared by According to another production method, having the formula (I)
The compounds of the present invention have a large number of compounds described in the chemical literature.
One of the methods yields the following equation (XVII): (R in the formula¹,R²,R³,R^Four,R^Five,R⁶,R⁷,R⁸，
1,4-geo (Q and W have the above meanings)
can be produced by dehydrating the
[For example, “Methoden der Organischen Chemie”
(Houken-Weyl), Band VI/3, 528 (1965)
reference〕. R¹and R²The above formula (XVII) where both are hydrogen
The diol is diethyl ether or tetrahydride.
Lithium hydride in a suitable solvent such as Lofuran
Using a suitable reducing agent such as aluminum, the formula
(XVIII): (R in the formula³,R^Four,R^Five,R⁶,R⁷,R⁸, Q and W are
lactone of the above meaning) or the formula
(XIX): (R in the formula³,R^Four,R^Five,R⁶,R⁷,R⁸,R⁹, Q and
W has the above-mentioned meaning)
It can be prepared by reduction. The above formula (XVII) (where R¹and R²Isn't it the same?
(but not hydrogen) is diethyl ether.
in a suitable solvent such as ester or tetrahydrofuran.
a lactone of the above formula (XVIII) or the above formula
Any of the esters of (XIX) to the group of formula (V)
It can be prepared by treatment with Linard reagent.
Ru. The ester of formula (XIX) above is suitable under acidic conditions.
in a suitable solvent or with excess alcohol as a solvent.
Using the lactone of the above formula (XVIII), the following formula R⁹OH
(R in the formula⁹has the meaning given above)
It can be prepared by processing. The lactone of the above formula (XVIII) is the following formula (XX): (R in the formula³,R^Four,R^Five,R⁶,R⁷,R⁸,R⁹and Q are
1, 2, 4 epoxides (having the above meaning)
- either a triazole or an imidazole,
each in the presence of an acid binder or an alkali metal salt thereof
in one form of dimethylformamide or
in a convenient solvent such as acetonitrile and from 60 to
By processing at an appropriate temperature such as 160℃.
It can be manufactured. The above formula (XX) (where R⁷and R₈are both hydrogen atoms
The epoxides (which are children) have been described in the chemical literature.
The γ-ketoester of formula (VII)
dimethylsulfonium, methylide (J.Amer.
Chem.Soc.84, 3782 (1962)) or dimethyloxo
Sulfonium methylide (J.Amer.Chem.Soc.,
87, 1353 (1965).
It can be prepared. Alternatively, the epoxide of formula (XX) is
in a suitable solvent by methods described in the chemical literature.
For example, the olefin of formula (IV) can be prepared using a peracid.
can be prepared by oxidizing esters. In addition to the method described above, γ- of the formula (VII)
The ketoester has the following formula (XXI): (In the formula, Q, R³,R^Four,R^Fiveand R⁶has the above meaning
acid) The following formula: R⁹OH (R in the formula⁹has the above meaning)
prepared by esterification with alcohol of
obtain. Formula (XXI) (where Q is an optionally substituted atom)
aryl group) is an acid such as aluminum chloride.
The chemical QH in the presence of a Lewis acid such as
Q is an optionally substituted aryl group) and the following formula
(XXII): (R in the formula³,R^Four,R^Fiveand R⁶has the above meaning
can be prepared by reaction between succinic anhydride and succinic anhydride.
(e.g. J.Amer.Chem.Soc., 60, 170 (1938)
reference〕. The succinic anhydride of the formula (XXII) is described in the chemical literature.
It can be prepared by standard methods as described. In another production method, the formula (I) (wherein R³,R^Four，
R^Fiveand R⁶are all hydrogen atoms)
The chemical compound is prepared using a suitable catalyst such as palladium on charcoal.
By hydrogenation in the presence of the following formula (XXIII): (In the formula, R¹,R²,R⁷,R⁸, Q and W are the above
Manufactured from acetylene diol (with significance)
can be done. The desired compound (I) loses water
The cyclizations to obtain can be carried out simultaneously under the same reaction conditions.
[For example, “Acetylenic Compounds in
Organic Synthesis” pp171-2 (1955)],
or among the numerous methods described in the chemical literature.
The cyclization can be carried out in a subsequent step by one of the following steps [e.g.
“Methoden der Organischen Chemie”
See Band VI/3, 528 (1965)]. The acetylene diol of the above formula (XXIII) is as follows:
Formula (XXIV): (R in the formula¹,R²,R⁷,R⁸and Q have the above meaning
epoxide of the following formula (XXV): (R in the formula¹,R²,R⁷,R⁸, Q and A have the above meanings.
1,2,4-t-halohydrin
Either lyazole or imidazole, each acid
in the presence of a binder or in its alkali metal salts
in one form of dimethylformamide or acetate
in a convenient solvent such as nitrile and at a convenient temperature.
It can be prepared by treatment at Epoxide of the above formula (XXIV) or the above formula
(XXV) halohydrin or epoxide
(XXIV) and halohydrin (XXV).
A suitable mixture such as tetrahydrofuran
The following formula (XXVI) in a solvent: (R in the formula⁷,R⁸and A has the above meaning)
The ketone is expressed by the following formula (XXVII): [R in the formula¹and R²has the above meaning and M is metal
atoms or one or more metal atoms
Hybrids with halogen atoms such as lithium or magnet
Si-A (where A has the above meaning)
by treatment with metalated acetylene
It can be prepared. The metalated acetylene of the above formula (XXVII) is
According to the standard method described in academic literature, the following formula
(XXVIII): (R in the formula¹and R²has the above meaning)
It can be prepared by metalation of acetylene. The above formula
Acetylene of (XXVIII) and the above formula (XXVI)
Ketones are prepared by standard methods described in the chemical literature
It is possible. In a related manner, the halide of the formula ()
in the presence of a suitable catalyst such as palladium on charcoal
by hydrogenation of the diol of formula (XXV) above.
Can be prepared. Same reaction conditions for cyclization while losing water
(e.g. “Acetylenic”)
Compounds in Organic Synthesis”pp171〜
2 (1955)] or described in the chemical literature.
cyclized in a subsequent step by one of a number of methods.
(e.g. “Methoden der
Organischen Chemie”Band VI/3,528
(1965)]. According to another method of preparation, the olefin of the formula ()
In-based alcohols are diethyl ether or tetyl ether.
In a suitable solvent such as lahydrofuran, the formula
(XXIX): (R in the formula¹and R²has the above meaning)
A dehyde or ketone with the following formula (XXX): (R in the formula³,R^Four,R^Five,R⁶,R⁷,R⁸, A and Q are
treated with Grignard reagent (with the meaning given above)
It can be prepared by The Grignard reagent of the above formula (XXX) is a chemical
According to standard methods described in the literature, the following equation
(XXXI): (R in the formula³,R^Four,R^Five,R⁶,R⁷,R⁸, A and Q are
prepared from the corresponding halide (with the meaning given above)
It is possible. The halide of formula (XXXI) above is described in the chemical literature.
According to the standard method listed below, the following formula (XXXII): (R in the formula³,R^Four,R^Five,R⁶,R⁷,R⁸and Q are as above
prepared from homoallylic alcohol (having the significance of
It can be manufactured. before using methods described in the chemical literature.
Homoallylic alcohol of the notation (XXXII) [e.g.
Tet. Letts21, 1815 (1980); J.Org.Chem., 33,
1156 (1967); J.Amer.Chem.Soc.94, 4298
(1972); see Tet. Letts, 4115 (1973)] and above.
Aldehydes or ketones of formula (XXIX) may be prepared.
Ru. Furthermore, the olefinic alcohol of the formula ()
is dimethyl sulfoxide, diethyl ether
or in a suitable solvent such as tetrahydrofuran.
For example, using alkylidene triphenylphosphorane
The following formula (XXXIII): (R in the formula¹,R²,R³,R^Four,R^Five,R⁶and Q are as above
olefinization of ketones (having the significance of
[For example, J.Org.Chem.28,
1128 (1963)]. The ketone of formula (XXXIII) above is described in the chemical literature.
Under standard conditions as listed, the following formula (XXXIV): (R in the formula¹,R²,R³,R^Four,R^Five,R⁶,R^Ten,R¹¹Reach
and Q have the above-mentioned meanings) are stimulated with acid.
It can be prepared by subjecting it to advanced hydrolysis.
Ru. The ketal of the above formula (XXXIV) is diethyl ethyl ether.
a suitable solvent such as ether or tetrahydrofuran.
In which the aldehyde or ketone of the formula (XXIX) is
The following formula (XXXV): (R in the formula³,R^Four,R^Five,R⁶,R^Ten,R¹¹, Q and A
is treated with Grignard reagent (having the above meaning)
It can be prepared by processing. The Grignard reagent of the above formula (XXXV) is
The following formula (XXXVI) can be obtained using a standard method: (R in the formula³,R^Four,R^Five,R⁶,R^Ten,R¹¹, A and Q
has the above meaning) from the corresponding halide of the form
It can be accomplished. The halide of formula (XXXVI) above is under acidic conditions.
The following formula (XXXVII): (R in the formula³,R^Four,R^Five,R⁶, Q and A have the above meanings.
) with the following formula: R^TenOH Arco
alcohols or diols (especially ethylene glycol or
propane-1,3-diol)
It can be prepared by The ketone of formula (XXXVII) is described in the chemical literature.
It can be prepared by standard methods as described. For example, the above
Formula (XXXVII) (where Q is an optionally substituted Fe)
The ketone (which is a nyl ring) is a
Under the compound QH and the following formula (XXXVIII): (R in the formula³,R^Four,R^Five,R⁶and A has the above meaning.
and X is a halogen atom, especially a chlorine or bromine atom
can be prepared by reaction between acid halides of
Ru. The acid halide of the above formula (XXXVIII) is prepared using the standard method.
It can be prepared by In another manufacturing method, R^Fouris a hydrogen atom
The compound of the present invention of formula (I) has the following formula (XXXIX): (R in the formula¹,R²,R³,R^Five,R⁶,R⁷,R⁸, Q and
W has the above meaning)
by subjecting the polymer to an acid-promoted cyclization reaction.
can be formed. Similarly, the formula (I) [where R¹is base −CHR¹²
R¹³(R in the formula¹²and R¹³may be the same or different;
H, alkyl, cycloalkyl or aralkyl group
The compound with the following formula (XXXX): (R in the formula²,R³,R^Four,R^Five,R⁶,R⁷,R⁸,R¹²，
R¹³, W and Q have the meanings given above).
The acid-promoted cyclization reaction of alcohols
It can be formed by Similarly, the above formula () (where R^Fouris a hydrogen atom
or R¹is base −CHR¹²R¹³(equal to)
are the following formulas (XXXXI): (R in the formula¹,R²,R³,R^Five,R⁶,R⁷,R⁸,A and
Q has the above meaning)
or the following formula (XXXXII): (R in the formula²,R³,R^Four,R^Five,R⁶,R⁷,R⁸,R¹²，
R¹³, Q and A have the meanings given above)
The acid-promoted cyclization reaction of alcohols
It can be formed by Olefinic alcohols promoted with similar acids
An example of the cyclization reaction is “Methoden der Organischen
Chemie” Band VI/3, 539 (1965)
ing. Ru. In another form of preparation, olefinic compounds of the formula ()
The ester has the following formula (XXXXIII): (R in the formula^Five,R⁶,R⁷,R⁸, and Q have the above meanings
The allyl alcohol of
(XXXXIV): (R in the formula³,R^Fourand R⁹has the above meaning, but
R⁹is preferably a methyl or ethyl group)
prepared by heating with the orthoester of
[e.g. J.Amer.Chem.Soc.92, 741]
(1970); see Org.Synth.54, 74 (1975)]. The allyl alcohol of the above formula (XXXXIII) is
It can be obtained by a similar method [for example, J.Amer.Chem.
See Soc. 99, 5526 (1977)]. Many of the intermediates described here [e.g. formula (),
(), (VII), (XI), (XVIII), (XIX), (XX
),
Intermediate with (XXI), (XXII) and (XXXIII)
body] can be found in chemical literature [e.g. J.Amer.Chem.Soc.85,
2178 (1963)].
For example, a base such as lithium diisopropylamide
and the following formula: R¹A,R²A,R³A,R^FourA,R^FiveA or R⁶
A (in the formula R¹,R²,R³,R^Four,R^Five,R⁶and A is the above
with the meaning of ) and alkyl
It can be produced by For example, the above formula () (where
ShiR³is hydrogen) in these methods.
The above formula () (where R³is archi
can be converted into a compound (which is a radical). The compounds, salts and metal complexes of the invention are effective carcicides.
A fungicidal agent that is particularly effective against the following diseases:
is an agent: Piricularia oryzae of rice, Piricularia oryzae of wheat
Rust (Puccinia recondita), (Puccinia
striiformis) and other rusts, barley rust
(Puccinia hordei), (Puccinia striifomis) and
Other rusts and other host plants, such as coffee,
Rust on apples, vegetables and ornamental plants, on grapes
Downy mildew (Plasmoparaviticola) of barley and wheat
Powdery mildew (Erysiphegraminis) and various infestations
Other powdery mildew diseases on main plants, such as gourd
Powdery mildew (Sphaerotheca)
fuliginea), apple powdery mildew (Podosphaera
leucotricha) and powdery mildew of grapes
(Uncinula necator), helminth spot of grains
Helminthosporium spp and Rhynchos
Rhynchosporium spp, peanut mosquito
Tuppan disease (Cercospora arachidicola) and examples
Other cutlet diseases of sugar beets, bananas and soybeans
(Cercospora), Ashes of tomatoes, strawberries, grapes and other host plants
Botrytis cinerea, Apple scab (Venturia inaequalis). Some of the compounds of the invention may also be used in molds in vitro.
It showed a wide range of activity against. These compounds are
Various diseases after fruit harvest [e.g. orange green disease]
Mildew disease (Penicillium digitatum) and blue mold disease
(Penicillium italicum) and banana tanso disease
(Gloeosporium musarum)]
do. Additionally, some of the compounds of the present invention may be used in cereals.
Yeast disease (Fusarium spp), Hakama Hanten's disease
(Septoria spp), Tilletia spp.
spp) (i.e. wheat smut, a seed-borne disease)
Harm), (Ustilago spp), (Helminthosporium
spp), cotton white silk disease (Rhizoctonia solanl) and
A shield against rice sheath blight (Cortici-um sasakii).
It is effective as a dressing agent. The compounds of the present invention can be used in plant tissues from the bottom to the tip.
can move vertically in the direction. Furthermore, the compounds of the present invention
is effective against molds on plants in the gas phase.
can be quite volatile. The compounds of the invention are also useful for treating candidiasis and human skin.
It is also useful in treating infections caused by dermatophytes. The compounds of the invention and the above-mentioned derivatives thereof may also be used in plants.
It also has biological growth regulating activity. The plant growth regulating effect of the compounds of the present invention is, for example,
Development of material plants and grassy monocots and dicots
As an inhibitory or inhibiting effect on the growth of parts.
shown. Such suppression or inhibition may include, for example,
Reducing the height of the stem strengthens, thickens and shortens the stem.
reduction, internodal shortening, increased protruding root formation and more straight
along with other beneficial effects such as upright stem and leaf orientation.
can reduce the risk of lodging with or without these effects.
peanuts, cereals such as wheat and barley, nata if
Oilseed rape, outdoor legumes, sunflowers,
Useful for potatoes and soybeans and also increases fertilizer
It can be applied in amounts. For example, make the leaves of wheat and barley plants more upright
Compounds that are particularly useful for leaf orientation are No. 1 in Table I above.
6, 24, 25, 32, 49 and 62. Main material
Suppression of the growth of quality plants is caused by undergrowth under power lines, etc.
useful for controlling induce suppression or inhibition
The compound also alters sugarcane stalk growth.
This is useful and allows sugarcane sand to be removed during harvesting.
Can increase sugar concentration;
Budding and maturation can be regulated by application of said compounds.
Ru. Stunting of groundnuts can aid harvest. Grass
Growth retardation can help maintain the lawn. suitable grasses
An example of St. Augustine grass (Stenotaphrum
secundatum), Sinothrus cristatus
(Cynosurus cristatus), Lolium multiflora
Lamb (Lolium muitiflorum) and perennial tares
(Lolium perenne), Agrostis tenuis
(Agrostis tenuis), Bamiyuda grass (Cynodon
dactylon), Dactylis glomereta
(Dactylis glomerata), Huestuca sp.
(Festuca) [e.g. Festuca rubra]
(Festuca rubra)] and boa species (poa) [e.g.
Poa pratense]. Main departure
Akira's compounds have significant phytotoxic (phytotoxic) effects.
without any effects and harmful to the appearance (especially color) of the grass.
It is possible to suppress the growth of grass without causing
;This compound is used in ornamental lawns and meadow greenery.
This makes it attractive for use in the above
Compounds also play a role in the flowering of flower heads in grasses, for example.
may have an impact. The compounds of the invention may also be found in grasses.
May suppress the growth of existing weeds;
Examples of grasses are amazing [such as Cyperus species and
and dicotyledonous weeds (such as daisies, plantains, and dicots)
willow, black-and-white, thistle, scumbo and wildflower
borogiku). non-crop plants (e.g. weeds or
It slows down the growth of plants (plants and trees that grow all over the place).
and thus the maintenance of farm crops and field crops.
This is to help. Erosion of the orchard, especially the soil
In the orchards receiving the
The presence of grass is important. However, excessive grass
growth requires substantial maintenance. Embodiment of the present invention
compounds may be useful in this situation. Because it is applicable
The compound controls the growth of plants without killing them.
This is because plant death can lead to soil erosion.
): At the same time, nutrients and water from grass
The degree of competition is reduced and this increases fruit yield.
It can occur. In some cases, one species of grass is mixed with another.
This selectivity is desirable.
By preferentially suppressing the growth of plant species that are
is useful for improving the properties of grass, for example.
obtain. The above growth inhibition is used for ornamental plants, indoor plants, and garden plants.
Garden plants and nursery plants (e.g.
Chrysanthemums, chrysanthemums, carnations, tulips and rats
It may also be useful for miniaturizing daffodils).
Ru. As mentioned above, the compound of the present invention can be used to improve wood quality.
May inhibit plant growth. Arrange using this characteristic.
Adjust the shape of the hedge or grow fruit trees (e.g. apple, western
Shape pears, cherries, peaches, grapes, etc.)
That is, the need for pruning can be reduced. Slightly
coniferous trees are significantly affected by the compounds of the present invention.
Growth is not inhibited and therefore desirable in conifer nurseries.
Compounds of the invention can be used to regulate the growth of plants that are not healthy.
can be useful. As mentioned above, the plant growth regulating effect increases crop yield.
may manifest itself in large; or orchard or other
The effects of
This can be manifested in the ability to increase yield. Regarding potatoes, adjustment of vines in the field and
Suppression of germination in storage may be possible. Other plant growth conditions caused by the compounds of the present invention
Nodal effects include changes in leaf angle and changes in leaf morphology (this
Both can increase ray intercept and utilization.
) and promotion of tillering in monocots. improvement
The rays are intercepted by all major crops around the world.
For example, wheat, barley, rice, corn, soybeans, marten
Rhinoceros, potatoes, plantation crops and orchard production
have value in things. For example, the leaf angle changing effect is
Useful, for example, to change the leaf orientation of potato crops.
This allows the potatoes to be exposed to light rays.
This causes an increase in photosynthesis and an increase in tuber weight.
It is something that Tillering of monocot crops (e.g. rice)
By increasing the amount of flowering per unit area,
This increases the number of buds produced.
It increases the total grain yield of such crops.
be. Furthermore, better regulation of the association of plant classification stages
and modification of wheat, barley, rice and corn, among others.
Cereals such as grass, monocotyledonous and dicotyledonous crops
It is possible both in the long stage and in the multiplication stage, and in this
Therefore, the number of flowering buds per unit area is increased.
The grain size distribution within the ear can be adjusted to improve the yield.
can be modified in such a way as to increase
Ru. In the treatment of rice plants or rice crops, the compounds of the invention
The product can be used, for example, as a fine granule or granular composition, e.g.
As a release type granule, nursery, rice field water and other similar
It can be applied to various cultivation locations and media. On the lawn, especially
In lawns that provide comfort, the increase in tillering is more
This can give you a denser lawn, which is less abrasive.
The elasticity can be increased; and the lintel can be increased.
Greater yield and better quality e.g. improved digestibility
and can give good taste. When plants are treated with compounds of the invention, they become greener and greener.
It can provide colored leaves. soybean and cotton
In dicotyledonous plants such as flowers, promotion of lateral buds is possible.
Ru. The compound of the present invention inhibits sugar beet flowering or
At least it can be delayed (this allows sand
sugar yield) or otherwise
It can alter the flowering pattern of many other crops. Said
The compound also significantly reduced sugar yield.
It is possible to reduce the size of sugar beets without
This can lead to an increase in cultivation density.
Similarly, other root vegetables (e.g. capra, swede)
(swede), mangold, American bower, te
Cultivation density will also be increased in
It can be made bigger. The compounds of the invention restrict the growth of developing parts of cotton.
It can be useful to make cotton
This causes an increase in flower yield. crop yield
is the yield index by changing the dry matter distribution.
(i.e. harvested as a percentage of total dry matter produced)
This can be increased by improving the yield (yield). This is all
All of the above root, pod crops, cereals, trees, plantations and fruit trees.
Applied to garden crops. The compounds of the present invention can help plants respond to external stimuli.
It can be useful for making people resistant to cancer. because
The compound retards the germination of plants grown from seeds.
can shorten stem height and delay flowering.
This is because; these characteristics are uniform throughout the winter.
In regions covered with snow, it is useful for preventing frost damage.
It can be used for This is because treated plants have a low temperature.
during the weather, it stays under a blanket of snow.
be. In addition, the compounds may exhibit early blight resistance or
can cause cold damage resistance. When applied as a seed treatment at low rates,
The compounds may have a growth-promoting effect on plants. In carrying out the plant growth regulation method of the present invention,
The amount of compound applied to regulate the growth of
It depends on a number of factors, such as the
Specific compounds and types of plants whose growth should be regulated
Determined according to. However, generally 1 hectare
Application of 0.1 to 15 Kg, preferably 0.1 to 5 Kg per roll
Use rate. Slow release type of biodegradable polymer
1 to 10 g per hectare using fine grains of
However, with electrokinetic spray technology
It can also be developed at lower application rates. however,
Application rates even within these ranges may be desirable for some plants.
It ends up giving an undesirable toxic effect. any specific purpose
to determine the best application rate of a particular compound for
Steady-state testing may be necessary. The compounds of the present invention may be used for fungicidal purposes or for regulating plant growth.
Although it can be used as is for this purpose,
is more conveniently formulated into a composition. That is, the original
The compound represented by general formula (I) as described above or this
salt or metal complex and optionally a carrier or diluent.
Also provided is a fungicidal or plant growth regulating composition comprising:
This is what we provide. The present invention also relates to compounds such as those mentioned above or
Salts, metal complexes, or compositions containing them
Application to plants, plant seeds or the location of plants or seeds
We provide a method of exterminating mold that consists of
It is something that The present invention also provides a compound as described above or a salt thereof,
or a metal complex, or a composition containing the same.
applied to plants, plant seeds, or the location of plants or seeds.
The present invention provides a method for regulating plant growth by
It is. In the above method, the following compounds of Table I are particularly useful:
Compound No.s, 3, 4, 5, 6, 8, 13,
14, 17, 18, 24, 25, 30, 32, 49, 61, 62, 63,
69, 70 and 72. These compounds have the following chemical names:
do: 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-3-prop
-1-yltetrahydrofuran (compound No. 3); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-4-prop
-1-yltetrahydrofuran (compound No. 4); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-3-ethyl
Tetrahydrofuran (compound No. 5); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-5,5-di
Methyltetrahydrofuran (compound No. 6); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-4-ethyl
Tetrahydrofuran (compound No. 8); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-4-methyl
Tetrahydrofuran (Compound No. 13); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-3-methyl
Tetrahydrofuran (Compound No. 14); 2-(2,4-dichlorophenyl)-2-(1,
2,4-triazol-1-yl)methyl-4-
Prop-1-yltetrahydrofuran (Compound No.
17); 2-(2,4-dichlorophenyl)-2-(1,
2,4-triazol-1-yl)methyltetra
Hydrofuran (compound No. 18); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-5-methyl
Tetrahydrofuran, dilatational isomer A (compound no.
twenty four); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-5-methyl
Tetrahydrofuran, dilatational isomer B (compound no.
twenty five); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-5-methyl
-5-prop-1-yltetrahydrofuran, partial
Left-right isomer B (compound No. 30); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-5-methyl
-5-but-1-yltetrahydrofuran, left-sided
Right isomer B (compound No. 32); 2-(2-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-5-methyl
Tetrahydrofuran, dilatational isomer A (compound no.
49); 2-(2,4-dichlorophenyl)-2-(1,
2,4-triazol-1-yl)methyltetra
Hydrofuran (compound No. 61); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-4,4-di
Methyltetrahydrofuran (Compound No. 62); 2-(2,4-dichlorophenyl)-2-(1,
2,4-triazol-1-yl)methyl-5,
5-Dimethyltetrahydrofuran (Compound No.
63); 2-(4-isopropylphenyl)-2-(1,
2,4-triazol-1-yl)methyl-5,
5-Dimethyltetrihydrofuran (Compound No.
69); 2-(4-methylphenyl)-2-(1,2,4
-triazol-1-yl)-methyl-5,5-
Dimethyltetrahydrofuran (Compound No. 70); as well as 2-(4-methoxyphenyl)-2-(1,2,
4-triazol-1-yl)methyl-5,5-
Dimethyltetrahydrofuran (Compound No. 72); Compounds, salts, metal complexes, ethers and
Esters can be applied in a number of ways, e.g.
For example, directly on the leaves of the plant in formulated or unformulated form.
May be applied to trees, trees, seeds or
A plant, plant or tree is growing or about to be planted.
The compound may be applied to other media, or the compound may be
spraying substances, salts, metal complexes, ethers and esters
spray, spray or cream preparation or paste.
Can be applied as a spray formulation or
Can be applied as a vapor. or slow release
Can be applied as mold granules. plant, tree or tree
can be applied to any part of the body, e.g. leaves,
Can be applied to stems, branches or roots;
can be applied to soil surrounding or
It can be applied to the seeds before sowing;
Rui is generally applied to soil, rice fields or hydroponic systems.
can be done. The compounds of the invention can be applied to plants or trees.
Can be injected and sprayed onto plants using electric spray technology
can. As used herein, the term "plant" refers to seedlings, cane trees, etc.
and trees. Furthermore, the fungicidal method of the present invention
Preventive treatment, preventive protection treatment, preventive treatment and eradication eradication
Includes processing. The compounds of the invention can be used in compositions for agricultural and garden purposes.
Preferably used for artistic purposes. Used in any case
The type of composition that is used depends on the specific purpose being met.
It is decided. The composition of the present invention comprises an active ingredient and a solid diluent or
carriers, e.g. kaolin, bentonite, silica
Earth (Kieselguhr), dolomite, calcium carbonate
mu, talc, powdered magnesia, fuller's earth, gypsum,
Hewitt earth, diatomaceous earth
earth) and fillers such as china clay.
Or it can be in the form of granules. Such details
The grains can be applied to the soil without subsequent treatment.
It can be any suitable preformed granules. These fine grains
Impregnating filler pellets with active ingredients
or a mixture of active ingredient and powder filler.
It can be formed by pelletizing. seeded
The composition for dressing may be applied to seeds, for example.
Contains agents (e.g. mineral oil) that help the
Alternatively, organic solvents (e.g. N
-methylpyrrolidone or dimethylformamide)
to process active ingredients for seed dressing purposes.
You can do it either way. The compositions of the invention also include powders or particles that are
Dispersible powders containing wetting agents to facilitate dispersion
It can be in the form of powder, granules or particles. Kayo
The eel powder or particles also contain fillers and suspending agents.
be able to. one or more wetting agents, dispersing agents or emulsifying agents
one or more in an organic solvent that may contain
and then dissolve the active ingredient in the mixture thus obtained.
as well as one or more wetting agents, dispersing agents or
is added to water, which may contain emulsifiers, to reduce the aqueous content.
Dispersions or emulsions can be prepared. Appropriate
The solvent is ethylene dichloride and isopropyl acetate.
alcohol, propylene glycol, diacetone
alcohol, toluene, kerosene, methylnaphthalene
xylene, trichloroethylene, furfurin
alcohol, tetrahydrofurfuryl alcohol
and glycol ethers (e.g. 2-ethoxy
ethanol and 2-butoxyethanol).
Ru. The composition of the invention to be used as a spray liquid
propellants, such as fluorotrichloromethane or dichloromethane;
Preparation under pressure in the presence of chlorodifluoromethane
can also be in the form of an aerosol in a container.
Ru. The compounds of the invention can be mixed with pyrotechnic mixtures in the dry state.
Smoke containing active ingredient compounds in a closed space
to form a composition suitable for generating
can. Alternatively, compounds of the invention can be used in microcapsules.
It can be used in the form of a cell. the compound
The product can also be formulated into biodegradable polymeric formulations.
The ingredients can be released in a slow controlled manner.
Ru. Suitable additives, e.g. dispersion, adhesion and treatment tables
Contains additives to improve surface rain resistance
This allows different compositions to be used in different applications.
Can fit well. The compounds of the invention can be used in fertilizers (e.g. nitrogen-containing fertilizers, potassium fertilizers).
Used as a mixture with phosphorus-containing fertilizers or phosphorus-containing fertilizers)
I can be there. Formulated with the compound of the present invention,
For example, it consists only of fine fertilizer particles coated with the compound.
Compositions are preferred. Such fine grains contain up to 25% by weight.
It is suitable to contain the active ingredient compound.
Therefore, the present invention also provides compounds of the general formula (I)
or fertilizers containing salts or metal complexes thereof.
It provides a product. The compositions of the invention can also be used as dip or spray liquids.
These are generally
one or more surfactants such as wetting agents,
Containing the active ingredient in the presence of powders, emulsifying agents or suspending agents
an aqueous dispersion or emulsion; or an electric spray technique.
It is a spray formulation of the type suitable for use in surgical procedures. Up
The drugs listed below may be cationic, anionic or non-ionic.
It can be a sexual drug. Suitable cationic drugs are
Quaternary ammonium compounds, such as cetyltribromide
It is methylammonium. Suitable anionic agents include soap, sulfuric acid, fat
Salts of group monoesters (e.g. sodium lauryl sulfate)
salts of sulfonated aromatic compounds (e.g.
Sodium dodecylbenzenesulfonate, ligno
Sodium, calcium or ammonia sulfonate
um, butylnaphthalene sulfonate, and diiso
Propyl- and triisopropyl-naphthalene
mixture of sodium salts of sulfonic acids). A suitable non-ionic agent is oleyl alcohol
or fatty alcohols such as cetyl alcohol.
Condensation product with tyrene oxide or octyl
Phenol or nonylphenol and octylc
Alkylphenols and ethylene phenols such as resols
It is a condensation product with oxide. Other non-ionic drugs
The agent is derived from long chain fatty acids and hexitol anhydride.
derived partial ester, ethylene oxide and said
Condensation products with partial esters and lecithin
Ru. Suitable suspending agents include hydrocolloids (e.g.
Vinylpyrrolidone and sodium carboxyme
cellulose), and vegetable gums (e.g. arabic)
rubber gum and gum tragacanth). The composition used as an aqueous dispersion or emulsion may contain 1
Concentrates containing a high percentage of one or more active ingredients
Generally supplied in liquid form. The above concentrated liquid should be used before use.
diluted with water. These concentrates last for a long time
It is often necessary to withstand storage, but
Ordinary and electric after dilution with water after storage
These can be applied using a spray device.
form an aqueous solution that is homogeneous for sufficient time to
It is necessary to be able to Concentrated liquid is 95 weight
may contain up to % of one or more active ingredients.
It is convenient to contain 10 to 85% by weight, e.g.
It may contain 25-60% by weight of active ingredient. These dark
Thick liquids contain organic acids (e.g. xylene sulfonic acid or
Alkaryl or alkaryl such as decylbenzenesulfonic acid
It is suitable to contain arylsulfonic acid).
Ru. This is because the presence of such organic acids
One that is soluble in polar solvents that are often used in liquids or
It is possible to further increase the solubility of the active ingredient.
Because you can. The concentrated liquid has a high proportion of surface activity.
It is also suitable to contain a sex agent, so it can be emulsified with water.
A sufficiently stable emulsion is obtained. diluted and aqueous
After making the solvent, such liquids should not be used for the intended purpose.
one or more active agents in varying amounts depending on the purpose
It may contain ingredients, but 0.0005% to 10% by weight or
One or more effective 0.01% to 10% by weight
Aqueous solutions containing the ingredients may be used. The compositions of the present invention also have biologically active properties.
one or more compounds, e.g. similar or complementary
Compounds with complete fungicidal or plant growth activity
substance or plant growth regulating activity, herbicidal activity or insecticidal activity
It can also contain active compounds. The other fungicidal compounds include, for example, Septoria,
Grains such as Gibberella and Helminthosporium spp.
diseases of crops (e.g. wheat), grape seeds and
and soil-borne diseases and downy mildew and powdery mildew.
It can exterminate powdery mildew, scab, etc. on apples.
Can be a compound. These fungicide mixtures
The compound has a wider range of properties than the compound of general formula (I) alone.
may have the activity of
The fungicide is compatible with the fungicidal activity of the compound of general formula (I).
It can have a multiplicative effect. Examples of the other fungicidal compounds are
imazalil, benomyl, carbendazim, thiof
Enate-methyl, captafol, captan, sulfur
yellow, triphorine, dodemorph, tridemorph, pi
Lazofos, Fralaxyl, Ethyrimol, Tecna
Zen, dimethylimole, bupirimate, chlorota
Ronil, pinklozolin, procymidone, ipro
Dione, metalaxyl, forcetyl-aluminum
Mu, Carboxin, Oxycarboxin, Fuena
Rimor, Nuarimor, Fuenflam, Metfu
Roxane, nitrotal-isopropyl, thoria
Dimefone, Thiabendazole, Ethuridiazo
triadimenol, viloxazole, dithia
Non, binapacryl, chinomethionate, guadi
Chin, Dojin, Fuentin Acetate, Fuentin
ion, hydroxide, dinocap, fluorpetu
g, dichlofluanid, ditarimphos, kitaji
cycloheximide, diclobuturazole, di
Thiocarbamate, copper compound, mercury compound, 1-
(2-cyano-2-methoxyiminoacetyl)-3
−Ethyl, urea, fenaponyl, ofurase, platinum
Ropiconazole, Etaconazole and Fuenpro
It's a pemorph. The compound of general formula (I) can be used to treat seed-borne diseases,
Plants are protected from soil-borne diseases or leaf mold diseases.
soil, charcoal or other rooting medium to protect the plant
Can be mixed with Suitable insecticides include pyrimol, clonetone, and dime.
with toate, metacystochus and formothion.
be. The other plant growth regulating compound may be a weed or a seed.
Controlling head formation, plants of compounds of general formula (I)
Improve the degree of growth regulating activity or shelf life, and
Selective growth of undesirable plants (e.g. grasses)
control or control the compound of general formula (I) on plant life.
Acting more quickly or more slowly as a long-term regulator
It can be something that can be done. These other plant growth regulations
Some of the agents are herbicides. It is used by showing a synergistic effect when mixed with the compound of the present invention.
An example of a suitable plant growth regulating compound is gibberellin.
(For example, GA₃,GA_Four, or GA₇), auxin (e.g.
For example, indole acetic acid, indole butyric acid, naphtoki
cyaacetic acid or naphthylacetic acid), cytokinin (e.g.
Kinetin, diphenyl urea, benzimidazole
Benzyl adenine or benzylaminopurine
), phenoxyacetic acid (e.g. 2,4-D or
MCPA), substituted benzoic acids (e.g. triiodobenzoic acid)
aromatic acid), morphactin (e.g. chlorfluoride), morphactin (e.g.
Cole), maleic hydrazide, glyphosate,
glyphosine, long chain fatty alcohols and fatty acids,
Dikegratsk, fluoridamide, mefluidide,
Substituted quaternary ammonium and phosphonium compounds
(e.g. chlormequat_*, chlorphonium or metal
picote chloride_*), ethephon, karbetami
Do, methyl-3,6-dichloroanisate, Dami
nojid_*, aslam, abscissic acid (abscissic
acid), isopyrimole, 1-(4-chlorophenylene)
)-4,6-dimethyl-2-oxo-1,2-
dihydropyridine-3-carboxylic acid, hydroxy
Benzonitrile (e.g. bromoxynil), diphenyl
enzo coat_*, benzoylpropeethyl 3,
6-dichloropicolinic acid and technazene.
The synergistic effect is that quaternary ammonium compounds are
Use the compound and the compound marked with an asterisk (*).
most likely to occur. A compound of general formula (I) in combination with gibberellin
use reduces the plant growth regulating effect of the compound.
can be useful if it is desirable to
(e.g. use the compound as a fungicide)
). The compound is added to the soil surrounding the plant.
When applying to soil or plant roots, apply
The plant growth-regulating effects of compounds may also be attributed to certain phenolics.
Using xybenzoic acid and their derivatives
In some cases, it may be lower. The invention is illustrated by the following example, in which the temperature
It is given in °C. Example 1 This example shows 2-(4-chlorophenyl)-2-
(1,2,4-triazol-1-yl)methyl
-5-prop-1-yl-tetrahydrofuran
(Compounds No. 15 and 16 of Table I)
It is. in dry dimethylformamide (DMF: 100ml)
Dissolved 4-chlorobenzaldehyde (23.4g)
The solution was dried with sodium cyanide (4.0g).
Add to stirred mixture with DMF (200 ml) over 10 min.
Add. Dissolved in dry DMF (100ml) after 5 minutes.
solution of methyl acrylate (10.75 g) over 20 minutes.
and add to the reaction mixture. During the two additions
The temperature of the reaction mixture was maintained at 35°C and then for an additional 3
After maintaining the time, soak it in water and add diethyl ethyl ether.
Extract with ether. Add the extract to water (several times), dilute sulfuric acid,
Wash sequentially with aqueous sodium bicarbonate solution and water.
dried over magnesium sulfate and dried under reduced pressure.
When concentrated to methyl 3-(4-
Chlorobenzoyl)-propanoate (24.4g, 86
%). Dry dimethyl sulfoxide (DMSO: 50ml)
A suspension of sodium hydride (1.8g) in
Allow to stir at 60 °C for 2.5 h under nitrogen atmosphere.
The resulting clear solution was cooled in an ice-water bath and allowed to dry.
Methyltripheni dissolved in dry DMSO (100ml)
A solution of phosphonium bromide (26.8g)
and the resulting dark yellow ylide solution
Warm to room temperature for 10 minutes. drying
Methyl 3-(4-chloro) dissolved in DMSO (50ml)
Solution of lobenzoyl)-propanoate (11.4g)
is added and the reaction mixture is stirred at room temperature for 2.5 hours.
Soak this in water and extract with diethyl ether.
Ru. Wash the extract with water and dry over magnesium sulfate.
and concentrated under reduced pressure to give a red oily solid.
(20g). Dichloromethane as eluent
Chromatography on a silica gel column using
When applied to -, methyl 4-
(4-chlorophenyl)pent-4-enoate
(6.6g, 62%).¹Hnmr(CDCl₃): δ5.1(1H,
wide singlet) and 5.3 (1H, singlet), = CH₂. methi dissolved in dry diethyl ether (20ml)
4-(4-chlorophenyl)pent-4-eno
A solution of ate (5.5 g) was placed on ice under an atmosphere of nitrogen.
Cooled in a water bath, dry diethyl ether (130
Lithium aluminum hydride suspended in ml)
(1.9 g) dropwise over 10 minutes.
I can do it. Following this addition, the cooling bath was removed and the reaction
The mixture was stirred at room temperature for 1 hour and then treated with ammonium chloride.
dilute with aqueous solution of umum. Add this mixture to diethyl ethyl ether
The extract was washed with water and extracted with magnesium sulfate.
After drying on a wafer and concentrating under reduced pressure, a pale yellow color is obtained.
4-(4-chlorophenyl)pent-4 as oil
-en-1-ol (4.5g, 93%) obtained, IR
(Film): 3400cm^-1. 4-(4-k) in dichloromethane (50ml)
rolophenyl) pent-4-en-1-ol
(5.5g) and pyridinium dichromate (14.62g)
Stir the mixture at room temperature for 24 hours. this mixture
dilute with diethyl ether and remove the solid material
Ru. Wash the solution with water and dry over magnesium sulfate.
and concentrated under reduced pressure to obtain 4-(chloro) as a yellow oil.
lofuenyl) pent-4-enal (2.6g, 48
%).¹H nmr (CDCl₃): 9.75 (1H, wide one
Doublet, CHO), IR (film): 1720cm^-1. 4- dissolved in dry diethyl ether (25 ml)
(4-chlorophenyl)pent-4-enal
(2.0 g) solution in a nitrogen atmosphere, dry diethyl
Propyl iodide mug dissolved in ether (50ml)
nesium [1-iodopropane (2.72g) and mug
Stirring solution of nesium shavings (0.48g)
(exothermic reaction). After stirring for 1 hour,
Pour the reaction mixture into a mixture of ice and dilute sulfuric acid, then
and extract with ether. Wash the extract with water, add sulfuric acid
Dry over magnesium and concentrate under reduced pressure.
2-(4-chlorophenyl)-5-hyperoxygenate as a yellow oil
Obtained droxyoct-1-ene (1.9g, 77%)
Ru. Bromine dissolved in dichloromethane (25ml)
(1.28g) in dichloromethane (25ml).
2-(4-chlorophenyl)-5-hydroxy
Cyocto-1-ene (1.9g) and pyridine (0.63g)
Dropwise over 15 minutes at 0-5℃ into a stirred solution of
Add (bromine decolorization and mild exotherm). Take the cooling bath
leave, stir the mixture for an additional 30 minutes, then
Concatenate with water, dilute hydrochloric acid, aqueous sodium bicarbonate solution and water.
Continuously washed and concentrated under reduced pressure as a red oil.
2-(4-chlorophenyl)-2-bromomethyl-
5-prop-1-yltetrahydrofuran
(2.6g) obtained,¹H nmr (CDCl₃): δ3.9 (2H, single
Term, CH₂Br). 2-(4-chloro) dissolved in dry DMF (25 ml)
phenyl)-2-promomethyl-5-prop-1
- A solution of yltetrahydrofuran (2.54 g) was
Na dissolved in dry DMF (25 ml) under normal atmosphere.
Thorium triazole [1,2,4-triazo
(1.11g) and sodium hydride (0.38g)
to the stirred solution of
Heat to 160℃ for a while. Soak the reaction mixture in water,
Extract with diethyl ether. Wash the extract with water,
Dry over magnesium sulfate and reduce under reduced pressure.
Boil to obtain red oil (1.5g). Diesel as eluent
Chromate on a silica gel column using methyl ether.
When subjected to matography, there are two obvious deviations.
The title compound is obtained as the isomer A, 185 mg.
[2-(4-chlorophenyl)-5-hydroxyo
8% from ct-1-ene] slightly viscous solid
body, m.p.55-61℃,¹H nmr (CDCl₃): δ3.90 (1H,
multiplet, CHO) and two doublets, each J14Hz,
δ4.33(CH₂Rf (silica gel) with center at N)
diethyl ether above) 0.3; Isomer B, 390 mg
[2-(4-chlorophenyl)-5-hydroxyo
16% from ct-1-ene] pale yellow solid, m.p.66
~67℃,¹H nmr (CDCl₃): 3.85 (1H, multiplet,
HCO) and two doublets, each J14Hz, δ4.37
(CH₂N), centered at Rf (on silica gel)
diethyl ether) 0.2. Example 2 This example shows 2-(4-chlorophenyl)-2-
(1,2,4-triazol-1-yl)methyl
-5,5-dimethyl-tetrahydrofuran (Table I
The production of compound No. 6) will be explained. methi dissolved in dry diethyl ether (25 ml)
4-(4-chlorophenyl)pent-4-e
Noate (5.8 g, prepared as described in Example 1)
) in dry diethyl ether (50ml).
Dissolved methylmagnesium iodide
(8.52g) and magnesium shavings (1.7g)
Add to the stirred solution of (exothermic reaction). room
After 1 hour at room temperature, the reaction mixture was mixed with ice and dilute sulfuric acid.
and then extract with diethyl ether.
Ru. Wash the extract with water and dry over magnesium sulfate.
and concentrated under reduced pressure to obtain 2-(4) as a yellow oil.
-chlorophenyl)-5-hydroxy-5-methy
Obtain 5.8 g of ruhex-1-ene, quantitative).¹H
nmr (CDCl₃): δ1.22 (6H, singlet, CH₃×2). 2-(4-chlorophenyl)-2-bromomethyl
-Preparation of 5-prop-1-yltetrahydrofuran
by the cyclization method described for the preparation (see Example 1).
2-(4-) in dichloromethane (60 ml)
chlorophenyl)-5-hydroxy-5-methyl
Hex-1-ene (5.3g), bromine (3.8g) and pyril
2-(4-chloride) as red oil from gin (1.9g)
lophenyl) 2-bromomethyl-5,5-dimethy
Obtain Lutetrahydrofuran (7.6g),¹H nmr
(CDCl₃): δ1.2 (3H, singlet) and 1.4 (3H, singlet
term), 2×CH₃, 3.5 (2H, singlet, CH₂Br). 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)-methyl-5-pro
Describes p-1-yltetrahydrofuran.
By the substitution method (see Example 1), dry dimethyl
2-(4-chloro) in formamide (40 ml)
phenyl)-2-bromomethyl-5,5-dimethy
Lutetrahydrofuran (3.5g) and 1,2,4-t
Riazole (1.24g) and sodium hydride
(0.43g) of the title compound as a white solid.
[1.32g, methyl 4-(4-chlorophenyl)pe
39%] obtained from ant-4-enoate, m.p.79
~80℃,¹H nmr (CDCl₃): δ1.13 (3H, singlet)
and 1.20 (3H, singlet), 2×CH₃:(Actual measurement value:
C, 61.94; H, 6.16; N, 14.38%, C₁₅H₁₈ClN₃
Theoretical value of O: C, 61.75; H, 6.17; N, 14.41
%). Example 3 This example shows 2-(4-chlorophenyl)-2-
(1,2,4-triazol-1-yl)methyl
-3-ethyltetrahydrofuran (compounds of Table I)
The production of No. 5) will be explained. Methyl 3-(4-chlorobenzoyl)propa
The method described for the preparation of noate (Example 1
(see) in dry dimethylformamide
4-chlorobenzal in (DMF: 250ml)
Dehyde (22.48g) and methyl pent-2-enoe
salt (13.65g) and sodium cyanide (3.92g)
followed by dichloromethane as eluent.
silica using 40~60° petroleum fraction (1:2)
column chromatography on gel
methyl 3-(4-chlorobenzene) as a yellow oil.
(6.5g, 21%)
Ru. The reaction mixture was stirred at room temperature for 1 hour and at 50°C for 1 hour.
Methyl 4-(4-chlorophenyl) except
The preparation of pent-4-enoate is described
According to the method (see Example 1), dry dimethyl sulfur
Methyl 3-(4-chloride) in phoxide (150ml)
lolobenzoyl) pentanoate (5.9g) and methi
Lutriphenylphosphonium bromide
(12.5g) and sodium hydride (0.84g)
Methyl 3-ethyl-4-(4-chloro) as a colored oil.
lofuenyl) pent-4-enoate (2.0g, 34
%),¹H nmr (CDCl₃): δ5.03 (1H, wide
singlet) and 5.22 (1H, singlet), =CH₂. 4-(4-chlorophenyl)pent-4-ene
The method described for the preparation of -1-ol (performed)
(see Example 1) with dry diethyl ether (50
methyl 3-ethyl-4-(4-k) in
Rolophenyl) pent-4-enoate (1.50g)
and lithium aluminum hydride (0.57g)
3-Ethyl-4-(4-chlorofluoride) as a pale yellow oil.
enyl)pent-4-en-1-ol (1.40g,
quantitative). 2-(4-chlorophenyl)-2-bromomethyl
-Preparation of 5-prop-1-yltetrahydrofuran
by the cyclization method described for the preparation (see Example 1).
3-ethyl-4- in dichloromethane
(4-chlorophenyl)pent-4-ene-1-
All (1.20g), bromine (0.86g) and pyridine
(0.43g) as a red oil.
enyl)-2-bromo-methyl-3-ethyltetate
Obtain lahydrofuran (1.60g). 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)-methyl-5-pro
Regarding the production of p-1-yltetrahydrofuran
Drying by the described displacement method (see Example 1)
2-(4-chlorophenyl) in DMF (35ml)
-2-bromomethyl-2-ethyltetrahydrof
Ran (1.40g) and 1,2,4-triazole
(0.62g) and sodium hydride (0.22g)
The title compound (0.35 g, methyl 3-
Ethyl-4-(4-chlorophenyl)pent-4
-27%) from enoate (approximately 19:1 left-sided
mixture of right isomers), m.p.100-105℃,¹H nmr
(CDCl₃): δ4.52 (2H, singlet, CH₂N). (actual measurement
Values: C, 61.59; H, 6.15; N, 13.85%. C₁₅H₁₈
ClN₃Theoretical value of O: C, 61.75; H, 6.17; N,
14.41%). Example 4 In this example, 2-(2,4-dichlorophenyl)-
2-(1,2,4-triazol-1-yl)methyl
Tyl-4-prop-1-yltetrahydrofuran
The production of (Compound No. 17 in Table I) will be explained. Dissolved in dry tetrahydrofuran (THF: 100ml)
2,4-Dichlorobenzaldehyde
(21.0 g) of 2-
(2-chloroethyl)-1,3-dioxane
(18.0g) and magnesium shavings (3.9g)
Grigna dissolved in fresh and dry THF (100ml)
Add slowly to the stirred solution of the reagent. 1 at room temperature
After an hour the reaction mixture was poured with ice and ammonium chloride.
into the mixture and then dilute it with diethyl ether.
Extract with Wash the extract with water and add magnesium sulfate.
Dry above and concentrate under reduced pressure as a yellow oil.
2-[3-hydroxy-3-(2,4-dichloroph)
enyl)prop-1-yl]-1,3-dioxa
(36.5g, quantitative), IR (film):
3420cm^-1. in dry dimethylformamide (DMF: 20ml)
The added 2-[3-hydroxy-3-(2,4-dimethyl)
rolophenyl)prop-1-yl]-1,3-di
Oxane (2.91g) and pyridinium dichromate
(6.96 g) was stirred at room temperature for 7 hours. anti
The reaction mixture was diluted with water (100ml) and diluted with diethyl ether.
Extract with tell. Wash the extract with water and add magnesium sulfate to it.
Dry over a vacuum and concentrate under reduced pressure to an orange oil.
and 2-[2-(2,4-dichlorobenzoyl)ethyl
Chil]-1,3-dioxane (2.7g, 93%) was obtained.
IR (Film); 1700cm^-1. The reaction mixture was stirred for 1 hour at room temperature and 1 hour at 50°C.
Except for stirring, methyl 4-(4-chlorophenylene)
Describes the preparation of pent-4-enoate
Dry dimethyl
2-[2-(2,
4-dichlorobenzoyl)ethyl]-1,3-di
Oxane (15.0g) and methyltriphenylphos
Honium bromide (25.0g) and sodium hydride
2-[3-(2,
4-dichlorophenyl)-but-3-ene-1-
]-1,3-dioxane (9.3g, 62%) was obtained.
Ru,¹H nmr (CDCl₃): δ5.02 (1H, singlet) and
5.30 (1H, wide singlet), =CH₂. 2-[3-(2,4-dichloride) in water (100 ml)
rolophenyl)but-3-en-1-yl]-1,
3-dioxane (13.5g) and oxalic acid (8.0g)
Add the mixture to the steam inlet and the splash-proof still head.
heated in a flask equipped with a capacitor and a condenser.
Ru. The reaction flask contains mostly immiscible oily spherules.
Distillate the collected distillate until no residue remains.
Extract with ether. Sodium bicarbonate extract
Wash with aqueous solution of sodium chloride and aqueous solution of sulfuric acid.
Dry over magnesium acid and concentrate under reduced pressure.
Contains trace amounts of reactants as a pale yellow oil with
4-(2,4-dichlorophenyl)pent-4-
Obtain Enal (9.21g, 86%),¹H nmr
(CDCl₃): δ9.84 (1H, tJ.2Hz, CHO). 4-(2,4-dichloroph) dissolved in hexane
(enyl) pent-4-enal (10.66g)
Dean and solution of thylamine (4.08g)
Reflux for 4 hours under Stark condenser conditions
Then, the hexane and excess amine are stripped under reduced pressure.
When pulled, the crude imine is obtained as a yellow oil;
The infrared spectrum of this shows absorption of carbonyl groups.
Sazu 1670cm^-1showed a peak. Dry this imine
The solution in dry tetrahydrofuran was placed in a nitrogen atmosphere.
Iodide salt dissolved in tetrahydrofuran under an atmosphere
Lopylmagnesium [1-iodopropane
(7.92g) and magnesium shavings (1.12g)
formation] and the mixture was heated for 3 hours.
Heat reflux. Add 1-iodopropane (7.92g) and react
The mixture is heated to reflux for a further 14 hours. excess 10% salt
Acid was added and the reaction mixture was refluxed for 2 hours, then
Extract with diethyl ether. Extract with bicarbonate
Washed with aqueous sodium solution and placed on magnesium sulfate.
dried, concentrated under reduced pressure, and diluted with dichloromethane as eluent.
Lolomethane: using 40-60° petroleum fraction (1:1)
chromatograph on a silica gel column
and 4-formyl-2-(2,4-di
Chlorophenyl)hept-1-ene (1.71g, 20
%),¹H nmr (CDCl₃): δ0.84 (3H, tJ7Hz,
CH₃), 973 (1H, dJ3Hz, CHO). 4-(4-chlorophenyl)pent-4-ene
The method described for the preparation of -1-ol (performed)
(see Example 1) with dry diethyl ether (30
4-formyl-2-(2,4-dichloride) in
rolophenyl)hept-1-ene (1.7g) and hydrogen
Lithium aluminum chloride (0.5g) and colorless oil
and 4-(hydroxymethyl)-2-(2,4-di
Chlorophenyl)hept-1-ene (1.55g, 91
%),¹H nmr (CDCl₃): δ3.52 (2H, dJ6
Hz, CH₂OH). 2-(4-chlorophenyl)-2-bromomethyl
-5-prop-1-yl-tetrahydrofuran
According to the method described for the preparation (see Example 1)
4- in dry dichloromethane (30 ml)
(Hydroxymethyl)-2-(2,4-dichloroph)
enyl)hept-1-ene (1.5g) and bromine
(0.88g) and pyridine (0.43g) to produce pale yellow oil.
and 2-(2,4-dichlorophenyl)-2-pro
Momethyl-4-prop-1-yltetrahydrof
Orchid (1.9 g, 98%) is obtained. 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)-methyl-5-pro
Regarding the production of p-1-yltetrahydrofuran
The described substitution method (see Example 1)
2-(2,
4-dichlorophenyl)-2-bromomethyl-4
-Prop-1-yltetrahydrofuran (1.8g)
and hydrogenated with 1,2,4-triazole (1.04g)
Sodium (0.36g) and labeled as yellow oil
The compound (1.12g, 60%) is obtained (of dilatational isomer).
3:1 mixture), 1H nmr (CDCl₃): δ3.39 and
4.07 (each 1H, pseudotriplet, J8Hz, major dilatation
CH of the body₂O). Example 5 This example shows 2-(4-chlorophenyl)-2-
(1,2,4-triazol-1-yl)methyl
-4,4-dimethyltetrahydrofuran (from Table I)
The production of compound No. 62) will be explained. Add acetic chloride to 2,2-dimethylsuccinic acid (25g).
Add chill (35ml). Stir this mixture and
Heat to reflux for 3 hours, then cool to room temperature. small amount
of dry ether and store the resulting solution in the refrigerator.
Leave it overnight. A solid precipitates out and is removed with a small amount of cold air.
and then dried in vacuo. collection
Amount: 14.9g. This 2,2-dimethylsuccinic anhydride
Used without further purification. Finely powdered aluminum chloride (29.35g) and 2,2
-Dimethylsuccinic anhydride (13.9g) and chloroben
(45ml) and then stirred for 1.5 hours.
Heat over a boiling water bath. Bring the resulting mixture to room temperature
Cool and then mix with ice and water containing a small amount of hydrochloric acid.
Soaking in the mixture. Extract the resulting mixture with ether
do. This ether layer was mixed with 2N sodium hydroxide.
Shake together and wash the resulting aqueous layer with ether.
acidified with concentrated hydrochloric acid and extracted with ether.
Ru. Wash this ether layer with water and canned water and finally
Dry over magnesium sulfate. melt in vacuum
When the agent is removed, 13.9g of 3-(4-chlorobenzoin) is removed.
)-2,2-dimethylpropionic acid is obtained. I.
R. (Nuzhiormal): 1680cm^-1(s)，1590cm^-1(s). 3-(4-chlorobenzoyl)-2,2-dimethy
Lupropionic acid (13.7g) was saturated with hydrogen chloride gas.
Dissolve in ethanol (100ml). child
The solution is refluxed for 8 hours. Distill the solvent and
Replace with tell. Add this ether solution to sodium bicarbonate.
saturated solution, then washed with water and washed with sulfuric acid mug.
Dry over nesium and concentrate in vacuo to an oil.
14.5g of ethyl 3-(4-chlorobenzoi)
)-2,2-dimethylpropionate is obtained. I.R. (Film): 1720cm^-1(s)，1685cm^-1(s)，1590cm
^-1(s). ¹H n.m.r. (CDCl₃): δ1.2 (3H, t), 1.3 (6H,
s), 3.2 (2H, s) 4.1 (2H, s), 7, 2-
8.0 (4H, m). By the method described in the example above,
Converts the stellate to the title compound: white solid, m.p.86~7℃, I.R.: 1490cm^-1
(m), 3140cm^-1(w)．¹H n.m.r. ¹H n.m.r. (CDCl₃): δ0.8 (3H, s), 0.9 (3H,
s), 2.2 (2H, dd), 3.5 (2H, dd), 4.3 (2H,
dd), 7.3 (4H, s), 7.8 (1H, s), 8.0 (1H,
s). Example 6 In this example, 4-(4-chlorophenyl)-γ-
(1,2,4-triazol-1-yl)methyl
-The production of γ-butyrolactone (A) will be explained. Ethyl 3-(4-chlorobenzoyl)propyl
Noate (25.0g, 83%) was added to the corresponding method of Example 1.
by the method described for the preparation of methyl esters.
and dimethylformamide (DMF: 300ml).
4-chlorobenzaldehyde (23.4g) and a
Ethyl acrylate (12.5g) and sodium cyanide
(4.0g). Dry dimethyl sulfoxide (DMSO: 10ml)
A suspension of sodium hydride (0.48g) in
Stir the solution at 50°C for 2.5 hours. Clear ash obtained
The color solution was allowed to cool and then diluted with tetrahydrofuran.
(THF: 30ml) and cooled in an ice-salt bath.
Ru. Trimeiodide dissolved in dry DMSO (20ml)
A solution of thylsulfonium (4.08g) and THF (20g)
ethyl 3-(4-chlorobenzo
solution of propanoate (4.0 g) at 0°C.
continuously added to the reaction mixture for 10 min at 0 °C and
Allow to stir at room temperature for 1 hour before adding water. The mixture
Extract the compound with diethyl ether and wash the extract with water.
and MgSO_FourAfter drying and concentrating, ethyl
4-(4-chlorophenyl)-4,5-epoxype
A red oil (2.54 g) containing ntanoate is obtained. This crude epoxy dissolved in dry DMF (100ml)
A solution of siester was dissolved in DMF (15 ml).
Thorium triazole [1,2,4-triazo
(1.4g) and sodium hydride (0.45g)
] and the resulting mixture was brought to room temperature.
Stir at room temperature for 45 minutes and at 55°C for 3.5 hours. this
The mixture was allowed to cool, then poured into water and diluted with ether.
Extract. Wash the extract with water and add MgSO_Fourdry on
Separate and concentrate to obtain a viscous red oil (1.2 g). melt
Silica gel column using ethyl acetate as synerte
When chromatographed above, a viscous yellow oil appears.
Obtain a small amount of the title compound as Rf(EtDAc)
0.2: IR (film): 1780cm^-1;1H n.m.r. ¹H n.m.r. (CDCl₃): δ2.2−2.8 (4H, m), 4.85
(2H, s), 7.34 (4H, solid AB quadruple
term, almost one singlet), 7.90 (1H, s),
8.10 (1H, s); m/e279and277 (M⁺That's it
0.9% and 1.1%); 197and195 (M-CH₂・
C₂H₂N₃, 33.9% and 100%, respectively). Example 7 This example shows 2-(4-chlorophenyl)-2-
[1-(1,2,4-triazol-1-yl)et
]-5,5-dimethyltetrahydrofuran
(Compound No. 60 in Table I)
Ru. Dry dimethyl sulfoxide (DMSO: 50ml)
A suspension of sodium hydride (1.44g) in
The solution is allowed to stir at 60° C. for 2.5 hours under nitrogen atmosphere.
The resulting clear solution was cooled in an ice-water bath and dried.
Ethyltriphenylpho dissolved in DMSO (50ml)
Add a solution of sulfonium bromide (23.0g)
the resulting bright orange-red ylide solution for 10 min.
Allow to warm to room temperature. Dry DMSO (50
methyl 3-(4-chlorobenzoylene) dissolved in
) propanoate (9.0 g; as described in Example 1)
(prepared) and bring the reaction mixture to 60~
Heat to 70°C for 2 hours. The mixture was allowed to cool and then poured into water.
Then, extract with diethyl ether. extract liquid
Wash with water, dry over magnesium sulfate and concentrate.
A dark red oil (12.5g) is obtained. Syringe as eluent
Chloromethane: petroleum distillate (1:1) at 40-60℃
Chromatography on silica gel column using
When poured, methyl 4-(4-chloro) turns into an orange oil.
Lofenyl) hexa-4-enoate (3.65g,
38%), (3:2 mixture of geometric isomers). ¹H n.m.r. (CDCl₃): δ1.53 and 1.81 (respectively d,
J 7Hz, CHCH₃), 5.48−5.86 (m, :
CHCH₃) IR (film): 1740cm^-1. methi dissolved in dry diethyl ether (20ml)
4-(4-chlorophenyl)hex-4-e
A solution of noate (3.50 g) was added under nitrogen atmosphere.
Iodide dissolved in dry diethyl ether (30ml)
Methylmagnesium [methyl iodide (4.8g) and magnesium]
A stirred solution of ] formed from gnesium (0.9g)
Add dropwise. The reaction mixture was kept at room temperature for 1 hour.
Stir and pour into a mixture of ice and dilute sulfuric acid, then
Extract with diethyl ether. Wash the extract with water,
Dry over magnesium sulfate and concentrate to orange color.
2-Methyl-5-(4-chlorophenyl) as oil
hept-5-en-2-ol (3.3g, 95%),
A 3:2 mixture of geometric isomers is obtained. IR (Film
): 3400cm^-1. 2-(4-chlorophenyl)-2-bromomethyl
-Preparation of 5-prop-1-yltetrahydrofuran
Dry the product using the method described in Example 1.
2-Methyl-5 in dichloromethane (40ml)
-(4-chlorophenyl)hept-5-ene-2
-ol (3.2g), bromine (2.35g) and pyridine
(1.18g) and 2-(4-chlorochlorofluoride) as an orange oil.
enyl-2-(1-bromoethyl)-5,5-dime
Chiltetrahydrofuran (4.4g, 94%), bilateral
A mixture of isomers is obtained.¹ H n.m.r (CDCl₃): δ4.06~4.40 (1H, m.CH₃
CHBr). in dry dimethylformamide (DMF: 10ml)
A portion (2.0 g) of this crude bromide was dissolved.
Sodium solution dissolved in dry DMF (20ml)
Triazole [1,2,4-triazole
(0.69g) and sodium hydride (0.24g)
under nitrogen atmosphere to a stirred solution of
Ru. The mixture was heated to reflux for 7 hours, then water
Leave to cool and extract with ether. Wash the extract with water
and dried over magnesium sulfate and concentrated.
Obtain a yellow oil (1.33g). This crude product is protonated.
Analysis by n.m.r. spectroscopy shows that this is 2-(4-
(chlorophenyl)-2-vinyl-5,5-dimethy
It is shown that it is mainly composed of lutetrahydrofuran.
did. However, diethyl ether as an eluent
Chromatograph on a silica gel column using
A small amount of the title compound appears as a colorless oil when applied to a feed.
can be isolated, a 3:1 mixture of stereoisomers,
Ta. ¹H n.m.r. (CDCl₃):¹δ1.11−1.18 (6H, 3 pieces
singlet, THF-ring methyl group), 1.31-1.78 (5H,
m, CH₃CHN and two THF-ring protons),
2.11−2.84 (2H, m, THF-ring proton), 4.45
−4.79 (1H, two overlapping quartets, J7Hz,
CH₃CHN), 7.41 and 7.48 (4H, two singlets,
phenyl ring proton), 8.04, 8.09, 8.19 and 8.32
(2H, 4 singlets, triazole proton),
MS (electron ionization): 308 and 306 (1.2% each
and 2.6%, MH⁺), 211 and 209 (28.6% each
and 83.5%, M-CH₃CH.C.₂H₂N₃), 141 and 139
(33.9% and 100% respectively, CO.C.₆H_FourCl); (chemistry
Ionization: Isoptane): 308 and 306 (35 each
% and 100%, MH⁺). Example 8 Mix the following ingredients until all ingredients are dissolved
An emulsion is formed by stirring the mixture. Compound of Example 2 10% Ethylene dichloride 40% Calcium dodecylbenzenesulfonate 5% “Rubro” L 10% "Aromazol" H 35% Example 9 Compositions in the form of particles readily dispersible in liquids such as water
The first three components listed above are mixed together in the presence of added water.
and then mixed with sodium acetate.
Manufactured by Dry the resulting mixture
Pass through standard mesh sieve, size 44-100 to obtain desired grains
Get child dimensions. Compound of Example 2 50% "Dispersol" T 25% “Lubro” APN5 1.5% Sodium acetate 23.5% Example 10 Grind all of the following ingredients together for easy dispersion into liquid.
A powder composition is prepared. Compound of Example 2 45% "Dispersol" T 5% "Rizapol" NX 0.5% “Celophus” B600 2% Sodium acetate 47.5% Example 11 The active ingredient is dissolved in a solvent and the resulting liquid is made into china clay.
Spray onto the granules. Then the solvent is evaporated and the particles are
A composition is prepared. Compound of Example 2 5% Fine clay 95% Example 12 Groups suitable for use as seed dressings
The product is manufactured by mixing the following three components.
Ru. Compound of Example 2 50% Mineral oil 2% Pottery clay 48% Example 13 powder by mixing the active ingredient with talc
Manufacture. Compound of Example 2 5% Talc 95% Example 14 The ingredients listed below are crushed in a pole mill and then
separation by forming an aqueous suspension with the grinding mixture.
A Col composition is produced. Compound of Example 2 40% "Dispersol" T 10% “Rubro” APN5 1% water Example 15 Mix the ingredients listed below with each other and then
grinding the mixture until thoroughly mixed;
A dispersible powder composition is produced. Compound of Example 2 25% "Aerosol" OT/B 2% "Dispersol" A.C. 5% Pottery clay 28% Silica 40% Example 16 This example describes the production of a dispersible powder composition. various
Mix the ingredients and then grind the mixture in a pulverizing mill
do. Compound of Example 2 25% "Perminal" BX 1% "Dispersol" T 5% Polyvinylpyrrolidone 10% Silica 25% Pottery clay 34% Example 17 Mix the ingredients listed below and then grind to meet the requirements.
Formulate the ingredients into a dispersible powder. Compound of Example 2 25% "Aerosol" OT/B 2% “Dispersol” A 5% Pottery clay 68% In Examples 9-17, the proportions of the given ingredients are by weight.
%. The remaining compounds in Table I above are formulated similarly. Represented by the various trade names and product names mentioned above.
A description of the compositions or materials used is given below. Luprole L: nonylphenol (1 mol) and ether
Condensate with tyrene oxide (13 mol) Aromazole H: Solvent mixture of alkylbenzenes
thing Dispersol T&AC: Sodium sulfate and hol
Mialdehyde and sodium naphthalene sulfonate
mixture with condensate with um Luprole APN5: Nonylphenol (1 mol)
condensation of with naphthalene oxide (5.5 mol)
thing Cellophas B600: Sodium carboxymethyl
cellulose thickener Rizapol NX: nonylphenol (1 mol) and
Condensate with ethylene oxide (8 mol) Aerosol OT/B: Dioctyl sulfosuccinate
sodium Perminal BX] Alkylnaphthalene sulfonic acid
sodium. Example 18 The compound of the present invention is used to parasitize mainly the leaves of plants.
Tests against diseases caused by various fungi. use
The technology used is as follows. Testing against gray mold (Botrytia cinerea)
For all tests except for
John Innes flower pot compost in a small flower pot.
The plants were grown in fertilizer (No. 1 or 2). dicotyledonous plants
Place a layer of fine sand on the bottom of the pot to protect the plant.
Promote uptake of test compound by roots. Trial version
The compound was mixed with Dispersol T aqueous solution.
Can it be formulated by grinding both in a bead mill?
Alternatively, test compounds can be added to acetone or acetone/ethyl alcohol.
After dissolving it in tanol, add it to the required concentration just before use.
Test compounds were formulated as solutions that were diluted frequently.
For leaf diseases, the active ingredient content is 100ppm.
Solutions and suspensions are sprayed onto the leaves and via the soil.
Apply to the roots of plants. gray mold of grapes
(Botrytis cinerea)
Dough berries are sprayed with the test compound. Easy to spray leaves
Apply to the maximum retention power of the
The final concentration will be equivalent to approximately 40 ppm per dry soil.
Soak the sea urchin. When applying spray liquid to grains,
Tween to give a final concentration of 0.05%
(Tween)20 was added. For most tests, plants are inoculated with the disease.
1 or 2 days before applying the test compound to the soil and roots.
This is a preventive protection test applied to leaves. However, barley
Powdery mildew (Erysiphe graminis hordei) and
Tests against gray mold (Botrytis cinerea)
In some cases, the treatment is an eradication eradication test, and it may be inoculated or
The test compound was applied one day later. Grapes in Botrytis cinerea test
To inoculate the berries, incise the fruit twice and then remove the fruit.
This is done by immersion in a suspension of disease spores.
Disease damage to remaining leaves is caused by suspending spores on the leaves of the test plants.
It was applied as a liquid by spraying. After inoculating the plants with the disease, place them in an appropriate environment.
to allow infection to occur and assess disease damage.
I was infected until I became sick. Disease evaluation from disease inoculation
The period until evaluation depends on the type of disease and environment.
The period was varied between 4 and 14 days. Disease control rates were recorded using the following grading: 4=No disease outbreak 3=Contains about 5% of untreated plants
disease 2 = 6-25% disease on untreated plants 1 = 26-59% disease on untreated plants 0 = 60-100% disease on untreated plants The results obtained are shown in the table below.

【table】

[Table] It means that it is about.
Example 19 This example reveals the plant growth regulating properties of compounds of the invention. The test compound is applied as a total spray of emulsion diluted to give the concentration indicated in the table. Plants are grown in 7.62 cm pots with peat compost and sprayed at the two-leaf stage. The plant growth regulating effect is evaluated 13 or 19 days after application of the test compound. The growth inhibition rate is recorded by a grade of 1 to 3: 1 = 0 to 30% inhibition rate 2 = 31 to 75% inhibition rate 3 = 75% inhibition rate or higher No grade of 1 to 3 indicates no effect. . The associated plant growth regulating effects are shown as follows: G = Darker green color of leaves A = Tip growth effect T = Tillering effect The results are shown in the table. If no numerical value is given, the test compound is substantially inactive as an inhibitor.

【table】

[Table] Example 20 This example demonstrates the plant growth regulating properties of Compound No. 6 in barley. Compound No. 6 is 95% water and 95% cyclohexanone and "Simperonik" NPE1800
5% mixture of 3.3% and "Tween" 85 1.7%
and applied to barley plants at a field equivalent rate of 4 Kg per hectare (at a volume equivalent of 1000 per hectare). Barley was grown in 10.16 cm pots of John Innes No. 1 Potting Compost at a ratio of 3 barley plants per pot, with 1 to 1.5 barley plants per pot.
Ten consecutive pots are treated at the leaf stage (13 days after sowing). On the 14th day, the plant growth regulating effect is recorded on untreated plants according to a grade of 1 to 3: 1 = 1 to 30% plant growth regulating effect 2 = 31 to 75% 〃 〃 3 = >75% 〃 〃 Absence of grades 1 to 3 indicates no effect. Plant toxicity (phytotoxicity) is recorded on a scale of 0 to 5. Repeated record drug damage 1 Y2D2L/
2 However: Y = Decrease in overall plant size 2 Y2D2B/G/L/ 2 3 Y2D2B/L/ 2 4 Y/D/ 1 D = Decrease in leaf size or area 5 Y/D/L2 2 6 Y/ D/L/ 2 L = shorter internodes 7 Y/E/B/L2G/ 2 8 Y2D2L2 2 B = reduced number of leaves 9 Y2D2B/L2 3 10 Y2D2B/L/ 2 G = darker green color of leaves Compound All barley plants treated with No. 6 were observed to have strong erect stems and erect leaves. Plants that were not treated fell over when not supported. On day 36, plants were evaluated for height from the soil surface to the apical lamina. Average height (mm) Plants treated with compound No. 6 69.9 Untreated control 132.4 This represents a 47% reduction in height. On the 84th day, 3 pots of treated plants and 3 pots of untreated plants are extracted and the height to the apical leaf lamina, leaf area, new weight, dry weight, and number of spikelets are measured. . The results are shown below for average data.

Table 1 The compounds therefore retard the growth of plants without adversely affecting their growth. Example 21 This example illustrates the synergistic effect exhibited by a mixture of compound No. 6 of Table I and a substance having the internationally recognized common name chlormequat chloride (CCC). Spring wheat (cv. Timmo) and spring barley (cv.
Sundance) is grown in John Innes No. 1 potting compost in 10 cm diameter pots at a rate of 4 wheat plants per pot. At the 2-3 leaf stage, the test compound (Compound No. 6 in Table I) and CCC ('Allotecus'
5C) in multiple combinations and at multiple application rates. A complete processing list is given below.
The term "Allotex" is the trade name for a commercial preparation containing chlormequat chloride.

【table】

[Table] Compound No. 6 is 95% water and cyclohexane
It is formulated as an emulsion consisting of 5% of a preparation containing 95%, "Sinperonik" NPE 1800 3.33% and "Tween" 85 1.65%. "Allotex" 5C
and by adding a solution containing “Aglar” 90.
Make a final concentration of 0.1%. As is clear from the table of results below, not all application rates shown were used in all tests.

[Table] The numbers in parentheses are the suppression rate of plant height growth.
(%).

[Table] The numbers in parentheses are the suppression rate of plant height growth.
(%).
The following table lists the compounds of Table I only for height inhibition.
This clearly demonstrates the synergy between No. 6 and chlormequat chloride. The data on tillering (algae development) is shown below.

【table】

[Table] The results shown in the table and in the table show that the tillering effect produced by using a mixture of the test compound and curmecoat chloride is greater than the tillering effect achieved when the test compound is used by itself. There is clear evidence of augmentation (and synergy). Example 22 This example illustrates the ability of Compound No. 6 of Table I to inhibit the growth of rice plants. Rice plants were grown in pots with two high ridges (i.e. small clumps) placed in each pot and grown at two times: 14 days after transplanting ( _T1 ) and 39 days after transplanting. After a day (T ₂ ), it is treated with compound No. 6 of Table I. The test compound was 0.1, 0.4, 1.0, 4.0Kg/ha at 1000/ha using a 5% preparation* system of the test solution.
Apply with. The final height measurement will be made after transplantation.
Do this after 103 days. The results are shown in the table below.

[Table] Compound No. 6 is formulated as an aqueous emulsion consisting of 95% water and 5% of a mixture containing 95% cyclohexane, 3.33% "Simperonik" NPE 1800 and 1.67% "Tween" 85. The above results show that the height of the rice plants is Compound No. in Table I.
6; and that application early in the rice growth stage produces the greatest suppressive effect. Example 23 This example illustrates the plant growth regulating properties of Compound No. 6 of Table I in dicotyledonous plants. At a pressure of 30 p.si on young apple and grape trees with approximately 4 to 5 leaves,
The test compound formulated as an emulsion was applied at three application rates.
Spray to a volume equivalent of 1000/ha. The plant is a Jion Innes No. 1 pot with a diameter of 10 to accommodate compost.
cm pots and maintained in a warm greenhouse with 14 hours of sunlight per day at a temperature of 25°C during the day and 20°C at night, where the natural sunlight was extended by high-pressure mercury vapor lamps (model MBFR). let Three weeks after treatment, the height of the young plants from the soil surface to the apical bud is evaluated. The results are given in Table X below. Particularly strong control was observed for both apples and grapes at application rates of 0.4 and 1.0 Kg/ha.

[Table] The apple and grape saplings used in this experiment were grown from small seeds of Retsudo delicias (apple) and small seeds of Ohanezu (grape). Example 24 This example illustrates the plant growth regulating properties of compounds of the invention in cereals. John Innes Potted Compost No.
Wheat (Amada species) in a 10cm diameter pot containing 2.
and seeds of barley (Sonya variety) that have undergone vernalization and have germinated. The compound is formulated as an emulsion*, which is applied to 1 leaf at the 2-leaf stage using a track sprayer.
Spray at 30 p.si to a volume equivalent of 1000/ha on barley and wheat quintuple pots containing 3 plants per pot. The plants were then arranged in a heterogeneous pattern and maintained with a minimum nighttime temperature of 11°C and a minimum daytime temperature of 14°C during a 14-h daylight period, with natural light supplemented by high-pressure mercury vapor lamps (model MBFR). extend it. Irrigate the plants underground. The height of the apical tongue is measured 5 weeks after treatment. The results are shown in the table below
Shown in XI. These results indicate that the tested compounds are capable of producing inhibition and therefore controlling grain lodging. *Test compound 5% Dispensing aid ⁺ 95% + Mixture of cyclohexanone 95%, "Simperonik" NPE1800 3.33% and "Tween" 85 1.67%.

【table】

Claims (1)

[Claims] Primary formula (I): (wherein W is -CH= or =N-; Q is phenyl, halophenyl, alkylphenyl, alkoxyphenyl, haloalkylphenyl, or a phenyl group substituted with both halogen and an alkyl group; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and are hydrogen, C _1-4 alkyl or trifluoromethyl group; R ⁷ and R ⁸ may be the same or different or _{stereoisomers} thereof, or acid addition salts or metal complexes thereof. 2. The compound according to claim 1, wherein W is =N- or =CH-; ^R1 to ^R8 are hydrogen, _C1-4 alkyl, or phenyl group. 3 W is =N-; R ¹ to R ⁸ are hydrogen, C _1-4 alkyl or phenyl group Claim 1
A compound according to item 1 or item 2. 4 Q is phenyl, 2-, 3- or 4-chlorophenyl, 2,4- or 2,6-dichlorophenyl, 2,4- or 2,6-difluorophenyl,
2-,3- or 4-fluorophenyl, 2-,3
- or 4-bromophenyl, 2-, 3- or 4-
Methoxyphenyl, 2,4-dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-
Fluoro-4-chlorophenyl, 2-chloro-4
-fluorophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl,
2-, 3- or 4-trifluoromethylphenyl, 2-chloro-4-methylphenyl, 2-fluoro-4-methylphenyl, 4-isopropylphenyl, 2-methyl-4-chlorophenyl or 2
The compound according to any one of claims 1 to 3, which is a -methyl-4-fluorophenyl group. 5 R ¹ to R ⁸ may be the same or different, hydrogen,
Phenyl, or methyl, ethyl, propyl (m- or isopropyl) and butyl (n-, sec
5. The compound according to any one of claims 1 to 4, which is a straight-chain or branched alkyl group having 1 to 4 carbon atoms, including (-, iso, or t-butyl group). 6 Chemical name: 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-3-prop-1-yltetrahydrofuran (Compound No. 3); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-4-prop-1-yltetrahydrofuran (Compound No. 4); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-3-ethyltetrahydrofuran (Compound No. 5); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-5,5-dimethyltetrahydrofuran (Compound No. 6); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-4-ethyltetrahydrofuran (Compound No. 8); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-4-methyltetrahydrofuran (Compound No. 13); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-3-methyltetrahydrofuran (Compound No. 14); 2-(2,4-dichlorophenyl)-2-(1,
2,4-triazol-1-yl)methyl-4-
Prop-1-yltetrahydrofuran (Compound No.
17); 2-(2,4-dichlorophenyl)-2-(1,
2,4-triazol-1-yl)methyltetrahydrofuran (Compound No. 18); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-5-methyltetrahydrofuran, dilatational isomer A (compound No.
24); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-5-methyltetrahydrofuran, dilatational isomer B (compound No.
25); 2-(4-chlorophenyl)-2-(1,2,4
2-(4-chlorophenyl)-2-(1,2,4
2-(2-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-5-methyltetrahydrofuran, dilatational isomer A (compound No.
49); 2-(2,4-dichlorophenyl)-2-(1,
2,4-triazol-1-yl)methyl-5-
Methyltetrahydrofuran (Compound No. 61); 2-(4-chlorophenyl)-2-(1,2,4
-triazol-1-yl)methyl-4,4-dimethyltetrahydrofuran (Compound No. 62); 2-(2,4-dichlorophenyl)-2-(1,
2,4-triazol-1-yl)methyl-5,
5-Dimethyltetrahydrofuran (Compound No.
63); 2-(4-isopropylphenyl)-2-(1,
2,4-triazol-1-yl)methyl-5,
5-Dimethyltetrahydrofuran (Compound No.
69); 2-(4-methylphenyl)-2-(1,2,4
-triazol-1-yl)methyl-5,5-dimethyltetrahydrofuran (Compound No. 70); 2-(4-methoxyphenyl)-2-(1,2,
4-triazol-1-yl)methyl-5,5-
Dimethyltetrahydrofuran (Compound No. 72);
8, 13, 14, 17, 18, 24, 25, 30, 32, 49, 61,
62, 63, 69, 70 and 72. A compound according to any one of claims 1 to 5, which includes compounds Nos. 62, 63, 69, 70 and 72. 7th formula (): (In the formula, Q, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and
R ⁸ is as defined below and A is a halogen), with either a 1,2,4-triazole or an imidazole, respectively in the presence of an acid binder or a triazole. or in the form of one of the alkali metal salts of imidazole (I), characterized in that the reaction is carried out in a convenient solvent at a convenient temperature; (wherein W is -CH= or =N-; Q is phenyl, halophenyl, alkylphenyl, alkoxyphenyl, haloalkylphenyl, or a phenyl group substituted with both halogen and an alkyl group; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and are hydrogen, C _1-4 alkyl or trifluoromethyl group; R ⁷ and R ⁸ may be the same or different a hydrogen, C _1-4 alkyl or phenyl group). 8 Halides of the above formula () can be prepared by treatment with a halogen in a suitable solvent such as dichloromethane in the presence of an acid binder such as pyridine to form a halide of the following formula (): Claim 7: Prepared from the olefinic alcohol (wherein Q, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ have the above-mentioned meanings) Method described. 9 The above formula () in which R ¹ and R ² are both hydrogen
The olefinic alcohol of formula (2) can be prepared by treatment with a reducing agent such as lithium aluminum hydride in a suitable solvent such as diethyl ether or tetrahydrofuran. (In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and Q have the above meanings, and R ⁹ is an alkyl, alkenyl, alkynyl, optionally substituted phenyl or aralkyl group. 9. The method according to claim 8, wherein the method is prepared from an olefinic ester of 10 Olefinic alcohols of the above formula () in which R ¹ and R ² are the same but not hydrogen can be prepared by converting the olefinic ester of the above formula () in a suitable solvent such as diethyl ether or tetrahydrofuran to the following formula (): R 9. A method according to claim 8, which is prepared by treatment with a Grignard reagent of ¹ -Mg-A () in which R ¹ and A have the meanings given above. 11 The olefinic alcohol of the above formula () is represented by the following formula (): (wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and Q have the above-mentioned meanings), the carbonyl compound of the following formula (): R ¹ -Mg-A () 9. A method according to claim 8, wherein R ¹ and A have the meanings given above. 12 The carbonyl compound of the formula () in which R ² is hydrogen can be obtained by selectively reducing the olefinic ester of the formula () with, for example, diisobutylaluminum hydride in a suitable solvent such as diethyl ether, usually at a low temperature; Alternatively, in a suitable solvent such as dichloromethane, the formula () (provided that R ¹ and
R ² is hydrogen) by selective oxidation of an olefinic alcohol with, for example, ^{pyridinium dichromate} ; and R ² is not hydrogen)
12. The method of claim 11 prepared by oxidizing an olefinic alcohol. 13 The olefinic ester of the above formula () is
For example, using alkylidene triphenylphosphorane in a suitable solvent such as dimethyl sulfoxide, diethyl ether or tetrahydrofuran, the following formula (VII): 10. The method according to claim 9, which is prepared by olefinizing a γ-keto ester of (wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ and Q have the above-mentioned meanings). 14 The γ-ketoester of the above formula (VII) (where R ³ is hydrogen) can be prepared by the formula (VIII): The aldehyde of Q-CHO(VIII) (in the formula, Q has the above-mentioned meaning) is expressed by the following formula (): 14. A process according to claim 13, prepared by reaction with an α,β-unsaturated ester of the formula ( ^R4 , ^R5 , ^R6 and ^R9 have the meanings given above). 15 The carbonyl compound of the above formula () is the following formula (): (In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and Q have the above meanings, and R ¹⁰ and R ¹¹ are an alkyl, alkenyl or alkynyl group or together The acetals/ketals of formula () are prepared by acid-promoted hydrolysis, and the acetals/ketals of formula () are themselves combined with a suitable compound such as dimethyl sulfoxide, diethyl ether or tetrahydrofuran. Using, for example, a suitable alkylidene triphenylphosphorane in a solvent, the following formula (XI): (In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ and Q
12. The method according to claim 11, which is prepared by olefinizing a ketone (having the above meaning). 16 The ketone of the formula (XI) can be prepared by the following formula (XIII) using, for example, pyridinium dichromate in (a) dimethylformamide: (In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ and Q
has the above meaning), or (b) the following formula (XIII): (In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ and A
has the meaning given above) with a nitrile of the following formula (XV): Q-CN (XV), where Q has the meaning given above, in a suitable solvent such as diethyl ether or tetrahydrofuran. , by subsequent hydrolysis and optionally selective reacetalization, or
or (c) the Grignard reagent of formula (XIII) above in a suitable solvent such as diethyl ether or tetrahydrofuran, often at low temperature, as shown in formula (XVI): 16. A process according to claim 15, prepared by reacting with an acid halide, wherein Q and A have the meanings given above. 17 The γ-ketoester of the above formula () is the following formula (XXI): (wherein Q, R ³ , R ⁴ , R ⁵ and R ⁶ have the abovementioned meaning) is esterified with an alcohol of the following formula: R ⁹ OH (wherein R ⁹ has the abovementioned meaning) 14. A method according to claim 13, which is prepared by: 18 The acid of formula (XXI) above (wherein Q is an optionally substituted aryl group) can be used to form a compound QH in the presence of a Lewis acid such as aluminum chloride.
(However, Q is an optionally substituted aryl group)
and the following formula (XXII): 18. A process according to claim 17, prepared by the reaction between succinic anhydride (R ³ , R ⁴ , R ⁵ and R ⁶ have the meanings given above). 19 The halide of the above formula () can be reacted with the following formula (XXV) in the presence of a suitable catalyst such as palladium supported on charcoal: (wherein R ¹ , R ² , R ⁷ , R ⁸ , Q and A have the meaning given above) is hydrogenated and the cyclization is carried out simultaneously with loss of water under the same conditions or as described in the chemical literature. 8. A process according to claim 7, prepared by subsequent cyclization by one of the numerous methods described. 20 The olefinic alcohol of the above formula () can be prepared by the following formula (XXIX) in a suitable solvent such as diethyl ether or tetrahydrofuran: The aldehyde or ketone (wherein R ¹ and R ² have the above-mentioned meanings) is represented by the following formula (XXX): (wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , A and Q have the above-mentioned meanings) Method. 21 The Grignard reagent of the above formula (XXX) is
By standard methods described in the chemical literature, the following formula (XXXI): 21. A process according to claim 20, prepared from the corresponding halides of the formula (R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , A and Q have the meanings given above). 22 The halide of the above formula (XXXI) can be converted to the following formula (XXXII) by standard methods described in chemical literature: (wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and Q have the above meanings), and the homoallyl alcohol of the formula (XXXII) itself is suitable. 22. A method according to claim 21, prepared by any known method. 23 The olefinic alcohol of formula () above can be prepared by the following formula (XXXIII) using, for example, alkylidene triphenylphosphorane in a suitable solvent such as dimethyl sulfoxide, diethyl ether or tetrahydrofuran: The method according to claim 8, which is prepared by olefinizing the ketone of (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and Q have the above-mentioned meanings). 24 The ketone of formula (XXXIII) above can be converted into the following formula (XXXIV) under standard conditions by methods known per se: ^{prepared by} acid ^- promoted ^{hydrolysis of the ketal of} 24. The method according to claim 23. 25 The ketal of the above formula (XXXIV) can be obtained by converting the aldehyde or ketone of the above formula (XXIX) to the following formula (XXXV) in a suitable solvent such as diethyl ether or tetrahydrofuran: (In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , Q and A
has the abovementioned meaning) with the Grignard reagent.
The method described in section. 26 The Grignard reagent of the above formula (XXXV) is
According to the standard method, the following formula (XXXVI): (In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , A and Q
has the meaning given above), and the halide of the formula (XXXVI) is itself formed under acidic conditions into the following formula (XXXVII): (wherein R ³ , R ⁴ , R ⁵ , R ⁶ , Q and A have the above-mentioned meanings) can be replaced with an alcohol or diol (especially ethylene glycol or propane-1,3-diol) of the following formula: R ¹⁰ OH. 26. The method according to claim 25, wherein the method is prepared by reacting with 27 The ketone of the above formula (XXXVII) (where Q is an optionally substituted phenyl ring) is reacted with the compound QH of the following formula (XXXVIII) in the presence of an acidic Lewis acid: (wherein R ³ , R ⁴ , R ⁵ , R ⁶ and A have the meanings given above and X is a halogen atom, especially a chlorine or bromine atom) with an acid halide. The method according to scope item 26. 28 The olefinic ester of the above formula () is
The following formula (XXXXIII): (wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ and Q have the above-mentioned meanings) is expressed by the following formula (XXXXIV): (In the formula, R ³ , R ⁴ and R ⁹ have the above meanings, but
R ⁹ is preferably a methyl or ethyl group)
11. The method according to claim 9 or 10, wherein the method is prepared by heating together with an orthoester of. 29 Formula (XVII): (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ ,
(Q and W have the meanings given below) of the following formula (): (wherein W is -CH= or =N-; Q is phenyl, halophenyl, alkylphenyl, alkoxyphenyl, haloalkylphenyl, or a phenyl group substituted with both halogen and an alkyl group; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and are hydrogen, C _1-4 alkyl or trifluoromethyl group; R ⁷ and R ⁸ may be the same or different (which may also be hydrogen, C _1-4 alkyl or phenyl group). 30 The diol of formula (XVII) above (wherein R ¹ and R ² are both hydrogen) can be prepared by the following reaction using a suitable reducing agent such as lithium aluminum hydride in a suitable solvent such as diethyl ether or tetrahydrofuran. Formula (XVIII): (wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , Q and W have the above-mentioned meanings) or the following formula (XIX): (wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , Q and W have the above-mentioned meanings) Second
The method described in Section 9. 31 The diol of formula (XVII) above (wherein R ¹ and R ² are the same but not hydrogen) can be synthesized with the lactone of formula (XVIII) or the formula (XIX) in a suitable solvent such as diethyl ether or tetrahydrofuran. ) is prepared by treating any of the esters of formula () with a Grignard reagent of formula (); using alcohol of the following formula: R ⁹ OH (in the formula
30. A process according to claim 29, wherein R ⁹ has the meaning given above. 32 The lactone of the above formula (XVIII) has the following formula (XX): (In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and Q have the above meanings)
- either a triazole or an imidazole,
60-160°C in a convenient solvent such as dimethylformamide or acetonitrile, each in the presence of an acid binder or in the form of one of its alkali metal salts.
prepared by treatment at an appropriate temperature such as
The epoxide of formula (XX) itself can be prepared by (a) γ of formula (VII) using methods described in the chemical literature.
- by treating the ketoester with either dimethylsulfonium methylide or dimethyloxosulfonium methylide (R ⁷ =R ⁸ =H); or (b)
31. A process according to claim 30, prepared by oxidizing an olefinic ester of formula (), for example with peracid, in a suitable solvent by methods described in the chemical literature. 33rd formula (XXIII): Acetylene diol (wherein R ¹ , R ² , R ⁷ , R ⁸ , Q and W have the meanings given below) is subjected to hydrogenation in the presence of a suitable catalyst, such as palladium supported on charcoal, to remove water. The cyclization to give the desired compound is carried out either simultaneously under the same reaction conditions or in a subsequent step by one of a number of methods known per se: (wherein W is -CH= or =N-; Q is phenyl, halophenyl, alkylphenyl, alkoxyphenyl, haloalkylphenyl, or a phenyl group substituted with both halogen and an alkyl group; R ¹ and R ² may be the same or different and are hydrogen, C _1-4 alkyl or trifluoromethyl group; R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms;
R ⁷ and R ⁸ are hydrogen, C _1-4 alkyl or phenyl groups. 34 The acetylenic diol of the above formula (XXIII) is either 1,2,4-triazole or imidazole and is represented by the following formula (XXIV): (wherein R ¹ , R ² , R ⁷ , R ⁸ and Q have the meanings given above) or the following formula (XXV): (in which R ¹ , R ² , R ⁷ , R ⁸ , Q and A have the meanings given above), each in the presence of an acid binder or of an alkali metal salt of a triazole or imidazole. 34. A process according to claim 33, in which the treatment is carried out in one of its forms in a convenient solvent such as dimethylformamide or acetonitrile at a convenient temperature. 35 The epoxide of the formula (XXIV) or the halohydrin of the formula (XXV) or a mixture containing both the epoxide (XXIV) and the halohydrin (XXV) can be prepared by the following formula (XXXVI) in a suitable solvent such as tetrahydrofuran: (In the formula, R ⁷ , R ⁸ and A have the above meanings)
The ketone is expressed by the following formula (XXVII): [In the formula, R ¹ and R ² have the above-mentioned meanings, and M is a metal atom or a hybrid of a metal atom and one or more halogen atoms, such as lithium or magnesium-A (however, A is the above-mentioned (has the significance of)
35. The method of claim 34, wherein the method is prepared by treatment with a metalated acetylene of 36 The metalated acetylene of the above formula (XXVII) can be prepared by the following formula (XXVIII) by standard methods described in the chemical literature: 36. A process according to claim 35, prepared by metalation of a raw acetylene, in which R ¹ and R ² have the meanings given above. 37 The following formula (XXXIX): (wherein R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , Q and W have the meanings given below) is subjected to an acid-promoted cyclization reaction. The following formula (I) consists of: (wherein W is -CH= or =N-; Q is phenyl, halophenyl, alkylphenyl, alkoxyphenyl, haloalkylphenyl, or a phenyl group substituted with both a halogen and an alkyl group; R ¹ , R ² , R ³ , R ⁵ and R ⁶ may be the same or different and are hydrogen, C _1-4 alkyl or trifluoromethyl group; R ⁴ is a hydrogen atom, R ⁷
and R ⁸ is hydrogen, C _1-4 alkyl or phenyl group). 38 The above formula () (where R ⁴ is a hydrogen atom)
The compound has the following formula (XXXXI): (wherein R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , A and Q have the above-mentioned meanings) is subjected to an acid-promoted cyclization reaction. 38. The method of claim 37, wherein the method is produced by: 39 Formula (XXXX): (In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹² ,
R ¹³ , W and Q have the meanings given below) of the following formula (I): [In the formula, R ¹ is equivalent to the group -CHR ¹² R ¹³ (wherein R ¹² and R ¹³ may be the same or different and are H, alkyl, cycloalkyl or aralkyl group); W is -CH= or =N-, Q is phenyl, halophenyl, alkylphenyl, alkoxyphenyl, haloalkylphenyl, or phenyl group substituted with both halogen and alkyl group; R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and are hydrogen, C _1-4 alkyl or trifluoromethyl group; R ⁷ and R ⁸ may be the same or different and are hydrogen, C _1-4 alkyl or phenyl group A method for producing a compound. 40 The compound of the above formula () (wherein R ¹ is equivalent to the group CHR ¹² R ¹³ ) has the following formula (XXXXII): (In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹² ,
40. The method of claim 39, wherein the olefinic alcohol (R ¹³ , Q and A have the meanings given above) is subjected to an acid-promoted cyclization reaction. 41 The following formula (I) as active ingredient, together with a carrier or diluent: (wherein W is -CH= or =N-; Q is phenyl, halophenyl, alkylphenyl, alkoxyphenyl, haloalkylphenyl, or a phenyl group substituted with both halogen and an alkyl group; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and are hydrogen, C _1-4 alkyl or trifluoromethyl group; R ⁷ and R ⁸ may be the same or different A fungicidal composition comprising a compound (often hydrogen, C _1-4 alkyl or phenyl group) or a salt or complex thereof. 42 The following formula (I) as active ingredient, together with a carrier or diluent: (wherein W is -CH= or =N-; Q is phenyl, halophenyl, alkylphenyl, alkoxyphenyl, haloalkylphenyl, or a phenyl group substituted with both halogen and an alkyl group; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and are hydrogen, C _1-4 alkyl or trifluoromethyl group; R ⁷ and R ⁸ may be the same or different 1. A plant growth regulator composition containing a compound (often hydrogen, C _1-4 alkyl or phenyl group) or a salt or complex thereof.