JPH01254680A - Heterocyclic compounds, their production methods, and fungicides containing them as active ingredients - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel heterocyclic compound, a method for producing the same, and a fungicide characterized by containing the same as an active ingredient.

<Prior Art and Problems to be Solved by the Invention> Conventionally, various compounds have been used as disinfectants. However, these compounds require high ``ffi'' to achieve sufficient efficacy, show high activity in prophylactic use but not sufficient effect in therapeutic use, or have a narrow bactericidal spectrum. There were problems such as.
Even though some drugs have shown excellent bactericidal activity in the past, due to the spread of drug-resistant bacteria, it is no longer possible to obtain sufficient control effects.

Furthermore, the fact that a certain type of heterocyclic compound has bactericidal activity is reported in Angewandte Chemie, 77, 827.
(1965), JP-A-6i9-77070, JP-A-58-68785, JP-A-58-68786, etc. However, these compounds cannot necessarily be said to be sufficient in terms of their bactericidal efficacy and bactericidal spectrum.

Means for Solving the Problems> In view of the above circumstances, the present inventors conducted various studies in order to develop a compound with excellent bactericidal activity. The inventors discovered that a cyclic compound or an acid addition salt thereof has excellent bactericidal activity, leading to the present invention.

That is, the present invention is based on the general formula [wherein X is the same or different and represents a halogen atom or a lower haloalkyl group, and n represents 0.1 or 2. ] The present invention relates to a heterocyclic compound represented by the above or an acid addition salt thereof (hereinafter referred to as the compound of the present invention), a method for producing the same, and a bactericide containing the same as an active ingredient.

In the above formula, lower represents a carbon number of 1 to 4.

Acids that form acid addition salts include acids that are physiologically acceptable to plants, such as inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, formic acid, acetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. Examples include organic acids such as acids.

The compounds of the present invention exhibit excellent control effects on various plant diseases in terms of preventive effects, therapeutic effects, and systemic transfer effects.

Plant diseases for which the compound of the present invention has an excellent control effect include rice blast disease (Pyricularia oryzae).
zae), sesame leaf blight (Cochl 1ohulus
mlyabeanus), sheath blight (Rh1zoct
oniasolani), powdery mildew of wheat (Er.
ysiphe graminisf, sp, hor
dei, E, g, f, sp, tritici
), Pyrenophora teres
), Gibberellazeae,
Rust ()'uccinia striiformis
, P.

graminis, P. recondita, P.
, hordei ), snow rot ('l'yphula
sp,, Micronectriella n1va
lis), naked smut (Ustilago triti)
ci, tJ, nuda), black grass disease (Til
letia caries), eye spot disease (Pseudo
c-ercosporella herpotric
hoides), Rhy-nchospor
ium 5ecalis), leaf blight (5eptor
iatritici), blight (Leptospha
eria nodorum), citrus black spot (D
iaporthe citri), scab disease (Els
inoefawcetti), fruit rot disease (Peni
cillium digitatqm.

P, italicum), apple monilia disease (5
clerotiniarnali), rot disease (Val
sa mali), powdery mildew (Podosphae
ra 1eucotricha), leaf spot disease (Al
ternaria mali), Vent
uria 1naequalis), pear scab disease (
Venturia nashicola, V, pi
rina), black spot (Alternaria ki)
kuchiana), Gym-ospor
angium haraeanum), Scle-rotinia cinerea, Cladosporium car-pophi
lum ), 7 omobsis fg septicemia (Phomops
i ssp, ), Elsinoe
atnpelina), late rot (Glomerell
a cingulata), powdery mildew (Llnci
nula necator), rust (Phalco
psora amp-elopsidis), Blacklot disease (Guignardiabidwellii)
), oyster anthracnose (Gloeosporium kak
i), leaf fall disease (Cercospora kaki,
Mycosphaerella nawae), cucurbit anthracnose (CCo11etotrichu lagen)
arium), powdery mildew (Sphaerothec
a fuliginea), vine blight (Mycosp
haerella melonis), Toma h ring disease (Alternaria 5olani),! Mildew (Cladosporium fulvum), eggplant listing 7Pi (Phomopsis vexans)
, powdery mildew (Erysiphe cicborace)
arum), black spot of cruciferous vegetables (Altern
aria japonica), vitiligo disease (Cerc
osporella bra3sicae), green onion rust ()'uccinia allii), soybean purpura (Cercosporakikuchii)
, Elsinoe glycines ,
Diaportbe phasenlorum
var, 5 ojae), green bean anthrax) 丙(C
olletotrichum lindemthian
um), Mycosphaere
lla personatum), brown spot disease (Cerco
spora arachidicola), powdery mildew of pea (Erysiphe pisi), summer blight of potato (Alternaria 5olani)
), strawberry powdery mildew (5pbaerothec
a humuli), Chi+ (7) HA rice blast disease (E
xobasidium reticulatum),
ElsinoeleucoBpila, Alteria long-ipcs of tobacco
), powdery mildew (Erysipbe cichora
cearurn), anthracnose (CCo11etotri
chu tabacum), brown spot disease of sugar beet (Cer.
cospora beticola), Diplocarpon rosae, powdery mildew (5phaerot-heca pannosa)
, chrysanthemum brown spot (5eptoria chr-ysan)
themi 1ndici), white rust (Pucci
nia horiana), gray mold of plate crops (
Botrytis cinerea), Sclerotinia (5c
lerotinia sclerotiorum) and the like.

The following method is mentioned as a typical manufacturing method of this yA light compound.

θ) General formula E In the formula, X and n represent the same meanings as above, and Y is a chlorine atom, bromine atom, iodine atom or
Represents a group represented by E. Here, E represents a lower alkyl group or a phenyl group which may be substituted with a lower alkyl group. ] 'a represented by the general formula [I] by reacting the compound represented by and 2,6-dimethylmorpholine,
How to obtain elementary ring compounds.

The compound represented by the general formula E In the formula, X and n have the same meanings as above, and L represents a halogen atom. ] A method for obtaining a heterocyclic compound represented by the general formula [I] by reacting with a compound represented by the formula [I].

In method (2), a solvent is not necessarily required during production, but if a solvent is used, ethers such as diethyl ether, tetrahydrofuran, and dioxane, alcohols such as ethylene glycol, glycerin, methanol, and ethanol, N, N- Dimethylacetamide, dimethyl sulfoxide, etc. or a mixed solvent thereof is used, and 2,6-
Dimethylmorpholine is used in a proportion of 1 to 10 moles. The reaction temperature is usually -20 to 200"C1, preferably θ~
At 150"C, the reaction time is usually 5 minutes to 100 hours, preferably 5 minutes to 20 hours. After the reaction is completed, the reaction product is neutralized or basic, extracted, I8 condensed, and if necessary chromatography. The desired compound can be obtained by performing usual post-treatments such as distillation.

In the method (2), a solvent is not necessarily required during production, but if a solvent is used, N.

N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, etc. or a mixture thereof is used as a 6-solvent, and per mol of the compound represented by the general formula [IY], The indicated compounds are used in amounts of 0.1 to 10 mol. The reaction temperature is usually 0 to 8
00°C1 preferably 50-250"C1 reaction time is
The time is 5 minutes to 200 hours, preferably 80 minutes to 100 hours. In addition, during the reaction, hydroxide (hylithium, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, metallic lithium, metallic strium, metallic potassium, etc.) is usually used. Alternatively, using a mixture thereof as a deoxidizing agent, the general formula [
111] to 0.1 to 1 mole of the compound represented by
0 mol can be used. Further, if necessary, as a reaction catalyst, a copper compound such as metallic copper, copper oxide, cuprous chloride, cupric chloride, or a mixture thereof, or a mixture thereof, is added in an amount of 0. 001 to 10 moles can be used.

After the reaction is completed, the desired compound can be obtained by carrying out usual post-treatments.

In addition, the compound represented by the general formula [I] includes hydrochloric acid, sulfuric acid,
Acid addition salts can be easily formed with inorganic acids such as nitric acid, and organic acids such as formic acid, acetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, and 1)-1 to luenesulfonic acids. A solvent is not necessarily required when the compound represented by the general formula [I] is made into an acid addition salt, but when a solvent is used, ethers such as diethyl ether, tetrahydrofuran, dioxane, benzene, toluene, Aromatics such as chlorobenzene, halogenated compounds such as chloroform, dichloromethane, and perchloromethane, alcohols such as methanol and ethanol, or a mixed solvent thereof are used, and usually per mole of the compound represented by the general formula [I]. The inorganic acid or organic acid is used in an amount of 0.1 to 10 moles. The reaction temperature is usually 0 to 800°C, preferably θ to 100°C, and the reaction time is 1 minute to 200 hours, preferably 5 minutes to 100 hours. can be obtained.

Depending on the configuration of the methyl group of morpholine in the compound of the present invention, there are two types of geometric isomers, cis form and trans form, and the present invention includes both the cis form, the trans form, and the cis/trans mixture. Can be used as a disinfectant.

In addition, the raw material compounds used in the above-mentioned methods for producing ■ and ω are, for example, the following reaction formulas (a), (b) and (
It can be manufactured according to C).

In addition, in the following reaction formula, X and n represent the same meanings as above.

CI+) instead of Ph”'OO*0zHs (0tH60)
-D=CCO C2H5Hs Crystal 1 ○I H2 Kugo CHg (!H-CH!-YCHI (m) When using the compound of the present invention as a fungicide, it may be used as it is without adding any other ingredients, but Usually, it is mixed with a solid carrier, a liquid carrier, a surfactant, and other auxiliary agents for formulation into emulsions, wettable powders, suspensions, powders, granules, and the like.

In this case, the content of the active ingredient of the compound of the present invention in the preparation is 0.1 to 99.9% by weight, preferably 1 to 90% by weight.

Examples of the solid carriers mentioned above include kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, sulfuric acid, ammonium, synthetic hydrous silicon oxide, etc. Liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone; Examples include vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, acetonitrile, and water.

Surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfate salts, alkyl (aryl)
Anionic surfactants such as sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers, polyoxyethylene polyoxybrobylene flock copolymer , sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and other nonionic surfactants.

As formulation adjuvants, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(carboxymethylcellulose), PAP (isopropyl acid phosphate), and the like.

When the compound of the present invention is used as an active ingredient of a fungicide, the application rate of the active ingredient is 1 tk per m 1 are, 1 to 100 y, preferably about 02 to 2 Of, emulsions, wettable powders, When applying a suspension agent etc. after diluting it with water, the application concentration is about 0.001 to 10%, preferably about 0.005 to 1%, and powders, granules, etc. can be applied without diluting it in any way. It can be applied as is.

The compound of the present invention can also be used as a dish disinfectant,
Furthermore, by mixing it with other fungicides, it can be expected to increase the bactericidal efficacy.

Furthermore, it can also be used in combination with insecticides, acaricides, nematicides, herbicides, plant growth regulators, and fertilizers.

<Effects of the Invention> The compound of the present invention has a broad fungicidal spectrum and is highly effective against plant diseases caused by various plant pathogenic bacteria, and therefore can be used for various purposes as an active ingredient of fungicides.

<Examples> The present invention will be explained in more detail below using production examples and test examples, but the present invention is not limited to these examples.

First, a manufacturing example will be shown.

Production Example 1 8-[nl-(8-chloro-5-trifluoromethylpyridin-2-yloxy)phenyl]-2-methylpropyl p-toluenesulfonate 1. Ogr8100-C
The mixture was added dropwise to 8.0y of 2,6-dimethylmorpholine with stirring. Aged at the same temperature for 80 minutes. Next, water 1
The mixture was made basic by adding 00- and 20TIIt from a 15% sodium hydroxide aqueous bath, extracted 8 times with 50-diethyl ether, the ether layers were combined, washed with saturated brine, dried over magnesium sulfate, and concentrated once under reduced pressure. . The residue was subjected to column chromatography to obtain the trans form of 4-18-(rn-(8-chloro-5-trifluoromethylpyridin-2-yloxy)phenyl)-2-methylpropyl J-2,6-dimethylmorpholine. .15gr1 cis form 0.89gr is obtained.

Production example 2 60% sodium hydride 0.12 in nitrogen 3A atmosphere
gr and dimethylformamide 5d, then 4-[8-(8-
hydroxyphenyl)-2-methyl-propyl]-2,
Add 0.8 gr of 6-dimethylmorpholine over 80 minutes
, and then stirred at room temperature for 2 hours. To this, 2-chloro-5
-0.54 gr of trifluoromethylpyridine and 0.1 gr of cuprous chloride were added, and the mixture was stirred under heating under reflux for 10 hours. After the reaction, add 100 ml of water to the reaction solution, filter through Celite, wash the Celite with toluene 200, and after separating the toluene layer, add 15% sodium hydroxide aqueous FjH80I.
ILt was added and the mixture was shaken and separated, and the toluene layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure.

The residue was subjected to column chromatography to obtain 4-[8-(m
-(5-1-Lifluoromethylpyridin-2-yloxy)phenyl)-2-methylpropyl]-2,6-dimethylmorpholine trans form 0.05 gr and cis form 0
．． 21 gr e got 1 piece.

Some of the compounds of the present invention obtained in this way are
Shown in the table.

Table 1 Next, test examples show that the compounds of the present invention are useful as fungicides. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table 2 Control efficacy is determined by visually observing the disease state of the test plants at the time of investigation, i.e., the degree of bacterial flora and lesions on leaves, stems, etc., and if no bacterial flora or lesions are observed, it is rated "5";``4'' if 10% is recognized, ``3'' if 30% is recognized, ``2'' if 50% is recognized, ``1'' if approximately 70% is recognized,
If there is no difference from the disease onset state when no compound is tested, it is considered FOJ and evaluated on a 6-level scale, with 5, 4, 8, 2, and 1°0, respectively.

Test Example 1 Powdery Mildew Control Test on Wheat A plastic pot was filled with sandy loam, and wheat (Agricultural and Forestry 78
No.) was sown and grown in a greenhouse for 10 days. One strain of the emulsion of the test compound was diluted with water to a predetermined concentration according to Formulation Example 4 on a video of wheat in which the second vegetable had developed, and the mixture was sprayed on the foliage so that it would sufficiently adhere to the leaf surface. After spraying, spores of wheat powdery mildew fungus were sprinkled and inoculated.

After inoculation, they were grown in a greenhouse at 15-C for 10 days and their preventive efficacy was investigated.

In addition, in a therapeutic efficacy test, spores of powdery mildew were sprinkled on wheat that had developed its second leaves, kept at 15°C for 2 days, and then a water diluted solution of the above test compound was sprayed. 6 at 15”C after spraying
They were grown for several days and their therapeutic efficacy was investigated.

The results are summarized in Table 8.

8th Test Example 2 Cucumber anthracnose control test (preventive effect) A plastic pot was filled with sandy loam, and cucumbers (Sagami Hanshiro) were layer-warmed and grown in a greenhouse for 14 days. A test compound prepared as a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined concentration on cucumber seedlings with developed cotyledons, and the mixture was sprayed on the foliage so as to sufficiently adhere to the leaf surface. After spraying, a spore suspension of cucumber anthracnose was inoculated by spraying.

After inoculation, it was left in a humid environment at 28'C for one day, and further Ill!
The plants were grown indoors for 4 days and their pest control efficacy was investigated.

The results are shown in Table 4.

Table 4 Test Example 8 Groundnut brown spot control test (preventive effect) Peanuts (Chiba semi-erect) were sown in plastic pots filled with sandy loam and grown in a greenhouse for 14 days. The test chemicals prepared as emulsions were diluted with water to a predetermined concentration, and the emulsions were sprayed on the leaves so that the emulsions were sufficiently adhered to the leaves. After spraying, the plants were air-dried and inoculated with a spore suspension of brown spot.

After inoculation, 2B"C was kept in a humid environment for 7 days, and then grown in a greenhouse for another 7 days to investigate its pesticidal efficacy.

The results are shown in Table 5.

Table 5 Test Example 4 Apple scab control test (preventive effect) A plastic pot was filled with sandy loam, and apples (Fuji) were sown and grown in a greenhouse for 20 days. On the moving surface of the apple where the 4th to 5th true leaves have developed, dilute the test drug made into a suspension according to Formulation Example 2 with water to a predetermined concentration, and apply it to the leaf surface so that it fully adheres to the leaf surface. Spread. After spraying, a spore suspension of the apple scab fungus was sprayed and inoculated. After being plated, the plants were left at 15° C. for 4 days under high humidity, and then grown under lighting for 15 days, and the control effect was determined by feeding M1.

The results are shown in Table 6.

Table 6 Procedural Amendment (Method) 1. Indication of the case 1988 Patent Application No. 081823 2 Name of the invention Heterocyclic compound, its manufacturing method and a deoccluding agent containing it as an active ingredient 3 Person making the amendment Relationship to the case Patent applicant Kitahama, Higashi-ku, Osaka City 5-15 (209) Sumitomo Chemical Co., Ltd. Contact address: (06) 220-340.45 Date of amendment order (all dates of sending) June 28, 1985 6. Detailed Explanation Column 7, Contents of Amendment (1) Between the second and third lines of page 3 of the specification, “3
, "Detailed Description of the Invention".

that's all

Claims (3)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X is the same or different and represents a halogen atom or a lower haloalkyl group, and n represents 0, 1 or 2. ] A heterocyclic compound or an acid addition salt thereof. (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, Y represents a chlorine atom, a bromine atom, an iodine atom, or a group represented by the general formula -OSO_2E. Here, E represents a lower alkyl group or a phenyl group optionally substituted with a lower alkyl group, and X is the same or different,
It represents a halogen atom or a lower haloalkyl group, and n represents 0, 1 or 2. ] and 2,6
- The method for producing a heterocyclic compound according to item 1, which comprises reacting with dimethylmorpholine. (3) Compounds represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and general formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is the same or different and represents a halogen atom or a lower haloalkyl group. , L represents a halogen atom. ] A first method characterized by reacting with a compound represented by
A method for producing the heterocyclic compound described in Section 1. (4) A disinfectant characterized by containing the heterocyclic compound or its acid addition salt according to item 1 as an active ingredient.