JPS60126267A - Schiff base derivative, its preparation and fungicide for agricultural and horticultural purposes containing the same - Google Patents

Abstract

NEW MATERIAL:A Schiff base derivative of formula I (X is halogen, lower alkyl; Y is halogen, lower alkyl, lower alkyloxy; m, n are 0, 1, 2). EXAMPLE:4-Chloro-2-(alpha-hydroxybenzyl)-N-4-pyridylmethylenaniline. USE:It is effective against Phycomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes, especially against powdery mildew, rust, downy mildew and damping-off of useful crops and shows low toxicity to men, animals, fishes and crops. PREPARATION:The reaction of isonicotinaldehyde of formula II with an aminobenzhydrol derivative of formula III gives a compound of formula I .

Description

Detailed Description of the Invention The present invention is based on the general formula CI) (wherein, X represents a halogen atom or a lower alkyl group; Indicates an integer of θ to 2. When n is 2, X and Y may be the same or different.) Schiff base derivatives represented by
The present invention relates to a method for producing the same and an agricultural and horticultural fungicide characterized by containing one or more of these ship base derivatives.

Many synthetic organic compounds and antibiotics with bactericidal properties have already been discovered, and many substances have been developed as fungicides for agriculture and horticulture.

However, in recent years, the emergence of resistant bacteria and environmental pollution due to mass spraying have become problems.

Specification 7; rT' F: (No change in content) In order to compensate for these drawbacks, the present inventors have made earnest efforts to develop a drug that has a novel skeleton and exhibits strong effects even in small amounts. The present invention was completed.

The compound of the present invention represented by the general formula [■] is a novel compound that exhibits excellent effects against diseases of useful cultivated crops, is highly safe for humans, livestock, and fish, and is effective against crops. It does not show any adverse effects on

The compound of the present invention represented by the general formula [■] can be used as an agricultural and horticultural fungicide for both prevention and treatment of fungi, ascomycetes, basidiomycetes, deuteromycetes, etc. It can be widely applied. In particular, it shows excellent efficacy against powdery mildew, rust, downy mildew, seedling blight, etc. of useful plants.

The method for producing the compound of the present invention represented by general formula [I] is formula C
I) isonicotinaldehyde represented by the general formula (III
) (wherein, In the case of , X and Y may be the same or different.

Since this condensation reaction is a dehydration condensation reaction, the most effective method is to use a filter medium that is azeotropic with water and does not mix with water, such as benzene, toluene, etc. It is desirable to close the method of removal to the outside. As a method for continuously removing water, a water fractionator (for example, De3nsand 5tark water 5
eparator, (A, 1. Vogel, A
Textbook of Practical Orga
nic Chemistry, P, 429, L
ongmansGreen, London) etc.)
There are two methods: one using molecular sieves (Molecular 5 revs) and the like as a dehydrating agent. Further, in this case, the reaction can be made to proceed better by using p-toluenesulfonic acid, naphthalene-2-sulfonic acid, etc. as a catalyst.

In addition, as another production method, isonicotinaldehyde [11] and aminobenzhydrol compound (I[l) are produced by using alcohols such as methyl alcohol and ethyl alcohol that are mixed with water, or acetic acid as a bath medium. The compound (1) of the present invention can also be obtained by reaction.

Next, a manufacturing example will be shown and explained in more detail.

Production example 1゜4-ri plow 2-(α-hydroxybendiAI)-N-
4-Pyridylmethyleneaniline (Compound No. 2) Add 3.6 f of isonicotinaldehyde and 7.82 g of 2-amino-5-di-tetralobenzhydrol to 300 ml of benzene, attach a water fractionator, and heat for 6 hours. Stir and reflux. After the completion of the process, the benzene was distilled off under reduced pressure, and the resulting reaction product was mixed with 1 bag of vinegar, ethyl ester, and hexane.
The desired product 8.9 (yield: 80%) was obtained by recrystallization from the solvent. Melting point: 126-127°C.

Elemental analysis value: 01gH150fiN20 molecule Σ'13
22.79 as OHN total RfJi (:'6 70.70 4.68 8.68
Experimental value (goods) 70.62 4.62 8.71 Production example λ 2-(2,4-dichloro-α-hydroxybendi/L/
)-N-4-pyridylmethyleneaniline (compound number 1
2) According to the method of Production Example 1, 2-amino-2,I,i/- was used instead of 2-amino-5-pp-benzhydrol.
When dicyclobenzhydro/I/8.9 f is reacted with toluene instead of benzene, the target product 9.8 f is obtained.
(yield 82%). Melting point: 123-124°C.

Elemental analysis value: 019H14012N20 Molecular weight 35
OHN calculation as 7.24 σ [C house ≦) 63.88 3.95 7.84
Experimental value (1) 63,81 3.91 7.87 Production example 3゜2-(4-chloro-α-hydroxybenzyl)-5-chloroc+-5-methyl-N-4-pyridylmethyleneaniline (compound number 21 ) According to the method of Production Example 1, 2-amino-4'-promo-4-chloro-3-methylbenzhydrol was used instead of 2-amino-5-chlorobenzhydrol.
- Operate in the same manner using 0, 9f, and target object 11,
8f (yield 85%) was obtained. Melting point 165-168°C.

Elemental analysis value: 026H16BrOJiN20 molecular weight 4
OHN as 15.71 Calculated value (1) 57.79 3.88 6.74 Experimental value (Foundation) 57.83 3.84 6.69 Production example book 2-(4-ri0ta-α-human tetraxybendi /L/)-N
-4-Viridyl-methyleneaniline (Compound No. 4) Isonicotinaldehyde 3.61 and 2-amino-4'-
7.8y of chlorobenzhydrol and 50π7 of p-)luenesulfonic acid were added to 300ml of benzene, a water fractionator was attached, and the mixture was heated under stirring and refluxed for 3 hours. After the reaction is complete,
Benzene was distilled off under reduced pressure, and the resulting reaction product was recrystallized from a mixed solvent of ethyl acetate-exo-hexane to obtain the target product 9.7r (yield 90%). Melting point 159~
160℃0 Elemental analysis value: 019H150kN20 Molecular weight 322.79 OHN Calculated value (to) 70.70 4.68 8.68 Experimental value (to) 70.74 4.60 8.73 Manufacturing example 5゜2-(4 -4-fluoro0-N-4-pyridylmethyleneaniline (Compound No. 10) According to the method of Production Example 4, instead of 2-amino-4'-chlorobenzhydrol 2-amino-4'-chloro-o-5-
Fluorobenzhito4-/L/8.4f was reacted in the same manner using toluene instead of benzene and 7talene-2-sulfonic acid instead of P-)/l'enesulfonic acid to obtain the desired product 9. 79 (yield 85%) was obtained. Melting point 108~1
09℃.

Elemental analysis value: 019H1401FN20 molecular weight 340
．． 78 as OHN Calculated value c4) 66.97 4.14 8.22 Experimental value (to) 67.01 4.09 8.24 Production example 6゜2- (4-chlorop-α-hydroxybenzyl)-6-
Methyl-N-4-pyridylmethyleneaniline (Compound No. 26) In Production Example 4, 2-amino-4'-dihydro-3-methylbenzhydrol was used instead of 2-amino-4'-chlorobenzhydrol. Roll 8.3f? Operate similarly using
The target product 10.1 F (yield 90χ) was obtained. Melting point 15
3-154℃.

Elemental analysis value: 0zoHt70'NzO molecular weight 336
．． HN as 81 Calculated value (To) 71.32 5.06 8.32 Experimental value (To) 71.38 5.08 8.25 Production example 7゜2- (2-Fluore-α-Hitotakibendi&)- N
-4-Viridyl-methyleneaniline (Compound No. 5) Isonicotinaldehyde 3.6t and 2-amino-2'-
After adding 7.2 tons of fluorobenzhitosol to 300 grams of benzene and adding molecular sieve 4A51,
The mixture was heated under reflux for 6 hours. After the reaction was completed, the molecular sieve was removed, the benzene was distilled off under reduced pressure, and the reaction product was recrystallized from a mixed heating medium of ethyl acetate-external-hexane to obtain the desired product 8.72 (yield 85%). . Melting point 131~
132℃.

Elemental analysis value: 019H15FN20 molecular weight 306.3
4 as OHN Calculated value (To) 74.50 494 9.14 Experimental value (
) 74.56 4.87 9.20 Production example 8゜4-bromo 2-(α-human p-xybenzyl)-N-4
-Pyridylmethyleneaniline (Compound No. 3) Same procedure as in Production Example 4 using 2-amino-5-bromobenzhydrol 9.3f instead of 2-amino-4'-chlorobenzhydrol 0-A/ Target 10, 4 f
(yield 85%). Melting point: 137-138°C.

Elemental analysis value: 01gH15BrN2O molecular weight 367
．． OHN as 24 Calculated value (to) 62.14 4.12 7.63 Experimental value (to) 62.07 4.10 7.65 Production example 9゜4-chloro-2-[4-chlorop-α-hydroxy benzyl)-NT4-pyridylmethyleneimine (compound no. 7
) Follow the same procedure as in Production Example 4 using 2-amino-4,4'-diq-tetrap-benzhydrol (8.92 g) instead of 2-amino-4'-chlorobenzhydrol to obtain the desired product 10.
1? (Yield 85y) was obtained. Melting point 167-168℃
.

Elemental analysis value: 019H140μ2N20 molecular weight 357
．． OHN calculated as 24 63.8B 3.95 7.84 Experimental value 63.93 4.00 7.79 The compounds of the present invention thus obtained are shown in Table 1. However, this does not limit the compounds of the present invention.

In addition, the compound numbers in Table 1 are also applied to the following test examples and formulation examples.

Furthermore, in Table 1, the positions of the substituents X and Y in the compound of the present invention represented by the general formula (1) are indicated as follows.

Since the compound of the present invention thus obtained has systemic transferability to plants, any treatment methods such as above-ground foliage treatment, 1 seed treatment, water surface treatment, or soil treatment are possible.

In addition, since the compounds of the present invention do not have any adverse effects on the target useful plants, the timing of use of the compounds of the present invention is as follows:
It can be used at any stage of useful plants, such as before bolting, during the clearing stage, during the seedling stage, during the growing stage, or during the fruiting stage.

When actually using the compound of the present invention, it is possible to use it as it is without adding other ingredients, but in order to make it more convenient to use, solid and liquid persimmons, which are used in the preparation of general agricultural chemicals, can be used. By mixing with a carrier, it can be manufactured into wettable powders, emulsions, oil solutions, powders, two-grain preparations, flowable preparations, etc. In addition, drugs include dispersants, diluents, emulsifiers, spreading agents, wetting agents,
Adsorption side.

Auxiliary agents such as thickeners, antiseptic agents, and antifreeze agents may also be added.

The carrier referred to herein may be either solid or liquid, or a combination thereof. Listing these examples,
Kuruk, clay, bentonite.

Kaolin, diatomaceous earth, calcium carbonate, wood flour, starch, gum arabic, water, alcohol, kerosene.

Examples include naphtha, xylene, cyclohexanone, methylnaphthalene, benzene, acetone, dimethylbormamide, glycol ether, and N-methylpyrrolidone.

Examples of adjuvants include polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan monooleate, ethylene oxide propylene oxyto copolymer, lignin sulfonate, sorbitan ester, soaps, and sulfated oils.

Argyl sulfate salts 1 Petroleum sulfonates.

Dioctylsulfosuccinate salts, argylbenzenesulfonate r Jlr aliphatic amine salt a=, 4th
M ammonium salts, argylpyridinium salts.

Examples include alkylaminoethylglycine, alkyldimethylbetaine, polyglycol sulfate, alkylamine sulfonic acid, impropyl phosphate, carboxymethyl cellulose, polyvinyl alcohol hydroxypropylcellulose, ethylene glycol, xanthan gum, and the like.

It can also be used as an aerosol agent by mixing it with a propellant such as fluorotrichloromethane or difluorodifluorotetramethane, or as a fumigant or smoking agent by mixing it with an appropriate blowing agent or combustion agent. I can do it.

In formulation, the mixing ratio is generally 0.05 to 95%, preferably 0.1 to 80% by weight of the compound of the present invention.
z, particularly preferably 1 to 70%, and 7 as a carrier.
0-99%, optimally 0-20% as an adjuvant. Also, other fungicides or herbicides, plant growth regulators, insecticides,
By using it in combination with pesticides such as acaricides, fertilizers, etc., a wider range of effects can be expected.

When actually using the compound of the present invention, the timing of use,
Weather conditions, method of use, dosage form, location of use, target diseases,
It goes without saying that it is selected appropriately depending on the target crop, etc., but the concentration used is generally 0.5 to 1000 pQ, preferably 3 to 5001 pQ, and the amount used (as the compound of the present invention) is generally 0.5 to 5001 per 10 are, preferably 1 to 250 f per 10 are? It is.

Next, the usefulness of the compound of the present invention as a fungicide for agriculture and horticulture will be explained using test examples.

Test Example 1゜Cucumber powdery mildew control test (preventive effect) Unglazed needles with a diameter of 15 are filled with granular horticultural soil and applied to cucumbers (variety: Takasago)
Ten seeds were sown. This was cultivated in a greenhouse for 10 days, and young seedlings with expanded cotyledons were used as samples.

The hydrating powder of the compound of the present invention obtained in Formulation Example 2 was diluted to a predetermined concentration and sprayed onto these seedlings in an amount of 15 m6 per needle. After air-drying the chemical solution, cucumber powdery mildew fungus (8 phaer
A conidial suspension of ot11eca fuliginea) was spray inoculated onto the shoots and leaves. After inoculation, the plants were cultivated for 10 days under greenhouse conditions at 23 to 26°C, and then the disease state was investigated.

The disease severity was calculated by the following method.

That is, depending on the lesion area of the investigated leaf, the following formula is used: <0.
The disease was classified into severity indexes of 1, 2, 3, and 4.5.

Based on the disease severity index thus obtained, the disease severity was calculated using the formula below, and the pest control value was determined from the comparison with the disease severity in the untreated area using the formula below.

The results are shown in Table 2.

Table 2 Cucumber powdery mildew control test (therapeutic effect) Fill a clay pot with a diameter of 15 an inch with horticultural soil, and add cucumber (variety: Takasago) 1
0 seeds were sown and cultivated in a greenhouse for 1° day, and young seedlings with fully expanded cotyledons were used as samples.

This young seedling is infected with cucumber powdery mildew fungus (8 pbaeroth).
cafuliginea) was inoculated with a conidial suspension, and after leaving it in a greenhouse at 23 to 26°C for 1 day, Formulation Example 3
The emulsion of the compound of the present invention obtained was diluted with water to a predetermined concentration and sprayed at 15 vte per pot. After air drying,
After cultivating for 10 days under greenhouse conditions at 23 to 26°C, the disease state was investigated.

Disease state index 2 disease severity and control value are in accordance with Test Example 1.

The results are shown in Table 3.

Test Example 3 Wheat powdery mildew control test (preventive effect) A clay pot with a diameter of 12 cn1 was filled with Arakida soil, and 15 grains of wheat (variety: Norin No. 61) were sown. I put this in a greenhouse for 12
Seedlings that had been cultivated for several days and had developed their first leaves were used as samples.

The emulsion of the compound of the present invention obtained by the method of Formulation Example 4 was diluted with water to a predetermined concentration and sprayed onto the seedlings in an amount of 15 ml per seedling.

After air drying, wheat powdery mildew fungus (Brysiphe gra
minii) was inoculated by spraying with a conidial suspension. After inoculation, the plants were cultivated for 10 days under greenhouse conditions at 20 to 24°C, and then the disease state was investigated.

Disease severity index 1 Disease severity and control value are based on Test Example 1.

The results are shown in Table 4.

Table 4 Test Example 4゜Wheat powdery mildew control test M (therapeutic effect) Fill a clay needle with a diameter of 12 an with Arakida soil, and fill it with wheat (variety:
15 seeds (i-bayashi No. 61) were sown, cultivated in a greenhouse for 12 days, and the seedlings whose first leaves had developed were used as samples.

This young seedling is infected with wheat powdery mildew fungus (Ery@1phe gr
Aminis) conidial suspension was inoculated by spraying, and a few days after inoculation under greenhouse conditions at 20 to 23°C, a wettable powder of the compound of the present invention obtained by the method of Formulation Example 2 was added to a predetermined amount with water. The seeds were diluted to a specific concentration and sprayed at 15 tall per pot, air-dried and then cultivated in a greenhouse at 20-24°C for 10 days, after which the disease state was investigated.

Disease severity index 1 Disease severity and control value are based on Test Example 1 (t
do.

The results are shown in Table 5.

Test example 5゜Cucumber and disease control effect (preventive effect) Unglazed needles with a diameter of 12 cm were filled with soil culture (manufactured by Kureha), cucumbers (variety: Ochiai Aocho-Kusei) were sown, and the seeds were placed in a greenhouse for 10 minutes.
Young cucumber seedlings that had been cultivated for several days and had developed cotyledons were used.

Sprayed on leaves and foliage so that it adheres to the leaves. After spraying the chemical solution, cultivation was carried out in a greenhouse for 2 days, and cucumbers and disease (P5eudo-p.
A conidial suspension of Eronospora cubensis was inoculated by spraying. The plants were placed under humid conditions at 21-22℃ for 3 days, and then cultivated for 3 days under strong light illumination at 21-22℃ to develop the disease. Yo, su0,1,2゜3,4
．． Expressed as an index of 5.

Using this index, the disease severity was calculated using the following formula.

Next, the control value was calculated using the following formula.

The results are shown in Table 6.

Table 6.

Test Example 6 Cucumber seedling damping-off control effect Field soil was packed in Neubauerbot and cucumber seedling damping-off fungus (Pythium aphanidernatum)
) was mixed and inoculated to a depth of two layers above the surface.

After that, the emulsion of the test drug obtained by the method of Formulation Example 4 was diluted with water after being kept in a superhumidified state for 24 hours at a temperature of 28°C.
A predetermined amount was poured into one soil. On top of it, 10 seeds of cucumber (variety: Ochiai Aonaga Seishi) were sown per pot and covered with soil. After cultivating for two weeks in a greenhouse, the disease state was checked and the percentage of healthy seedlings was calculated.

The results are shown in Table 7.

Formulation examples are shown below. In the example, "part" indicates "heavy claw part".

Formulation example 1 powder Compound number 17 2 parts Clay 98 parts The above ingredients are mixed and pulverized to obtain a powder.

Formulation example 2 Hydrating agent Compound number 4 10 parts Sodium alkyl sulfonate 5 parts Clay 85 parts The above ingredients are mixed and pulverized to obtain a wettable powder.

Formulation example 3 emulsion Compound number 21 5 parts Alkylbenzenesulfonic acid Calcium 4 parts polyoxyethylene alkyl Phenylethe/L/11 parts Siku ν hexanone 10 parts Xylene 70 parts The above is mixed to obtain an emulsion.

Formulation example 4 emulsion Compound number 26 10 parts Alkylbenzenesulfonic acid Calcium 3 parts polyoxyethylene alkyl Phenyl ether 12 parts Dimethylformamide 10 parts xylene 65 parts The above is mixed to obtain an emulsion.

Formulation Example 5 Granule Compound No. 10 2 parts Calcium ligninsulfonate 2 parts Bentonite 30 parts Tar 66 parts or more are mixed, water is added, kneaded, granulated and dried to obtain granules.

Formulation Example 6 Flowable Agent Compound No. 11 10 parts Ethylene glycol 5 parts Xanthan gum 0.2 parts Polyoxyethylene sorbitan monooleate 5 Fine ice Wet-pulverize 79.8 parts or more to obtain a flowable agent0 Applicant Chugai Pharmaceutical Co., Ltd. Procedural amendment (To Kazuo Wakasugi, Director General of the Expo Patent Office, April 20, 1981, 1, Indication of the case, Patent Application No. 236531, filed in 1982, 2, Name of the invention: Ship base derivatives, their manufacturing methods, and the products containing them) Agricultural and Horticultural Fungicide 3, Relationship with the case of the person making the amendment Patent applicant Kimio Ueno, 5-6-1 (331) Ukima, Kita-ku, Tokyo, Representative of Chugai Pharmaceutical Co., Ltd. 6, of the specification subject to the amendment Column 7 for detailed description of the invention, contents of amendment (I:II'1
I-f history tjcυ clear mlF page 5 is corrected as shown in the attached sheet.

Claims (1)

[Claims] 1) General formula (wherein, X represents a halogen atom or a lower alkyl group, Y represents a halogen atom, a lower alkyl group, or a lower alkyloxy group, and n and Indicates an integer. When X and Y are 2, X and Y may be the same or different, respectively. 2) isonicotinaldehyde represented by the formula and the general formula (wherein, X represents a halogen atom or a lower alkyl group, and Y
represents a halogen atom, a lower alkyl group, or a lower alkyloxy group, and m and n represent integers of 0 to 2. In the case of 2 and 2, X and Y may be the same or different. ), wherein X represents a halogen atom or a lower alkyl group, and Y represents a halogen atom, a lower alkyl group, or a lower alkyloxy group. , and 〇 and 〇 are integers from 0 to 2. When 〇 and 〇 are 2, X and Y may be the same or different.) . 3) As an active ingredient, use the general formula (wherein, X represents a halogen atom or a lower alkyl group, Y represents a halogen atom, a lower alkyl group, or a lower alkyloxy group; 1 of the ship base derivatives represented by
An agricultural and horticultural fungicide characterized by containing a species or two or more species.