JPH0285283A - Sheath blight control agent - Google Patents

Abstract

PURPOSE:To provide a sheath blight control agent exhibiting a remarkable effect against rice sheath blight containing a 4H-3,1-benzooxazine derivative as an active ingredient. CONSTITUTION:The objective control agent contains a 4H-3,1-benzooxazine derivative of formula I (R is H, alkyloxy, alkenyloxy, alkynyloxy or alkylthio; X is halogen or lower alkyl) (e.g., a compound of formula II). The compound of formula I is prepared, e.g., by reacting a benzophenone derivative of formula III with an appropriate halogenating agent such as thioryl chloride in an inactive solvent such as methylene chloride as 70-150 deg.C and subsequently with the corresponding alcohol or thiol as 0-30 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a compound (I) in which R represents hydrogen, an alkyloxy group, an alkynyloxy group, an alkynyloxy group, or an alkylthio group, and X represents a halogen or a lower alkyl group. ) A rice sheath blight control agent containing the compound shown in
This invention relates to H-3,1-benzoxanone derivatives.

- The compound represented by removal allowance (I) is JP-A-59-157
It is a compound described in No. 489 and No. 80-152484. These publications include compounds of the general formula (II) (wherein X and Y independently represent a halogen atom or a lower alkyl group, and m is O-
2, and n represents an integer of O to 2. When m is 2 in Xm, the two Xs may be the same or different from each other,
When n is 2 in Yn, the two Y's may be the same or different. R is a hydrogen atom, an alkyloxy group,
Indicates an alkynyloxy group, an alkylthio group, or an alkenylthio group. ) is described to be effective against powdery mildew, rust, downy mildew, seedling blight, etc. of useful plants.

Also, Formula (III) Formula (IX) Formula (VI) Formula (X) r Formula (■) Formula (XI) t Formula (Xn) Formula (X■) Formula (xrv> Formula (XV) Formula (X[X ) t Formula (XVT) L Formula (XX) Formula (XX Engineering) CH+ Formula (XXII) The 4H-3,1-penzoxazine derivative represented by
This is a new substance whose physical properties are not described in the literature.

On the other hand, Yoiki arsenic agents have been used as control agents for rice sheath blight, but antibiotics have been developed to replace them due to problems such as environmental pollution and residual toxicity. However, antibiotics have drawbacks such as being expensive and insufficiently effective, and there has been a desire to develop an excellent sheath blight agent.

Therefore, as a result of intensive research on control agents for rice sheath blight, the present inventors found that among the compounds represented by the general formula (n) described in JP-A-59-157489 and JP-A-60-152484, , the compound included in the general formula (I) of the present invention, that is, the benzene ring portion of the benzoxazine ring is unsubstituted, and the 4th position of the phenyl group substituted at the 4th position of this benzoxazine ring is lower alkyl, We have discovered that a halogen-substituted compound has a significant effect on rice sheath blight.

As shown in Test Examples 1 and 2 below, the effect of the compound represented by the general formula (I) of the present invention on rice sheath blight is as follows: It is also clear from the fact that the compound represented by the general formula (I) of the present invention shows almost 100% preventive and therapeutic effects, whereas the compound shown by the general formula (I) of the present invention has almost no effect.

The effect of the compound of the present invention on rice sheath blight is as follows:
There is no mention of this in the above publication, and its effects are surprising.

In the compound represented by the general formula (I) of the present invention, the alkyloxy group and alkylthio group represented by R are:
Those having 1 to 6 carbon atoms are preferred, and alkenyloxy groups,
The alkynyloxy group preferably has 2 to 6 carbon atoms. Furthermore, the halogen atom represented by X is Cρ+Br
, I, etc., and the lower alkyl group preferably has 1 to 4 carbon atoms. Among these, particularly preferred compounds in the present invention are compounds in which R is an alkyloxy group having 1 to 3 carbon atoms and X is CΩ or a methyl group. These not only have excellent effects against rice sheath blight, but also have excellent toxicity, toxicity to fish, and the like.

- Removal allowance (I) and the compounds represented by formulas (III) to (XXII) can be produced, for example, in the following manner.

The general formula (
XXIII) A benzophenone derivative represented by It can be obtained by reacting at 70 to 150°C in an inert solvent such as, and then reacting the corresponding alcohol or thiol at 0 to 30°C. At this time, the reaction proceeds more smoothly by using a suitable deoxidizing agent such as triethylamine, pyridine, sodium chloride, potassium hydroxide, and sodium alkoxide.

In addition, a benzophytrol derivative represented by the general formula % (% formula %) (wherein X represents halogen or lower alkyl) known in JP-A-57-59867 etc. can be used as a suitable halogenating agent.
For example, it can be obtained by reacting with thionyl chloride, thionyl bromide, phosphorus trichloride, etc., if necessary, in a suitable inert solvent such as benzene, toluene, chloroform, etc. at 0 to 30'C.

Next, a manufacturing example will be shown and explained.

Production Example 1 The organic layer was washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the resulting reaction product was purified by silica gel chromatography (chloroform + methanol 1%) to obtain 4-(4-chlorophenyl)- 4-ethoxy-2-
(4-pyridyl)-4H-3,1-benzoxazine 3
Obtained 3.5g.

Production Example 2 Zazine (Compound No. 9) 2-(4-chlorobenzoyl)-isonicotine 72 l
150ml of 1,2-dichloroethane from 33.65g of J-do
8.7 ml of thionyl chloride was added dropwise to the suspension.
It was refluxed for 4 hours. After cooling, 40 ml of pyridine was added dropwise under water cooling, and then 60 ml of ethyl alcohol was added dropwise. 50 g of sodium hydrogen carbonate was added, and the mixture was further stirred at room temperature for 3 hours.

After adding 500 ml of water and stirring for 30 minutes, the organic layer was separated and the aqueous solution was extracted with methylene chloride. 33.85 g of 2-(4-chlorobenzoyl)-isonicotine anilide (compound of compound number 62 formula (■)) and 12 ml of pyridine were suspended in 150 ml of methylene chloride, and 8 ml of thionyl chloride was added to this under water cooling. dripped. After stirring at room temperature for 3 hours, 80 ml of methyl alcohol was added to the mixture.
The mixture was added and stirred for 1 hour. Triethylamine 60 under water cooling
ml was added, and the mixture was further stirred at room temperature for 2 hours.

The resulting reaction mixture was concentrated under reduced pressure, ethyl acetate was added,
The precipitated triethylamine hydrochloride was filtered off. Ethyl acetate was distilled off under reduced pressure, and the resulting reaction product was purified in the same manner as in Production Example 1 to obtain 4-(4-chlorophenyl)-4-methoxy-2-(4-pyridyl)-4H-3, 30.5 g of 1-benzoxazine was obtained.

Production Example 3 Sazin (compound number 82 compound of formula (I)) 2- (4
-Methylbenzoyl)-isonicotine anilide 31.8
g and 730ml of pyridine to 300ml of 1,2-dichloroethane
ml, 8 ml of thionyl chloride was added under water cooling, and the mixture was stirred for 2 hours under water cooling and then for 2 hours at room temperature. To this was added 15 ml of methyl alcohol under water cooling, the mixture was stirred for 30 minutes, washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained reaction product was purified in the same manner as in Production Example 1 to obtain 31.0 g of 4-(4-methylphenyl)-4-methoxy-2-(4-pyridyl)-4H-3,1-benzoxazine. Ta. Recrystallization from a small amount of ethyl alcohol gave a melting point of 121-2°C.

Production Example 4 Compound No. 39 Formula (V)) 31.8 g of 2-(4-methyl-α-hydroxybenzyl)-isonicotine anilide and 10 ml of pyridine were added to 300 ml of methylene chloride, and under water cooling, 8 ml of thionyl chloride was added.
Added l. The mixture was stirred for 1 hour under water cooling and then for 2 hours at room temperature, and the resulting reaction mixture was added little by little to a solution of 50 g of sodium hydrogen carbonate and 250 ml of water, and extracted with methylene chloride.

The evening layer was washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the resulting reaction product was purified by silica gel chromatography (chloroform/methanol 1%) to give 4-(4-methylphenyl)-2- 28.5 g of (4-pyridyl)-48-3,1-benzoxazine was obtained. When recrystallized from a mixed solvent of ethyl acetate and n-hexane, the melting point was 85-6°C.

Production Example 5 Dioxazine (compound of compound number 139 formula (IV)) 31.6 g of 2-(4-methylbenzoyl)-isonicotine anilide and 30 ml of pyridine were dissolved in 300 ml of chloroform.
ml, 8 ml of thionyl chloride was added under water cooling, and the mixture was stirred for 2 hours under water cooling and then for 2 hours at room temperature. To this was added 15 ml of n-propyl alcohol under water cooling, the mixture was stirred for 30 minutes, washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting reaction product was purified by silica gel chromatography (chloroform/methanol 1%) to yield 4-(4-methylphenyl)-
4-n-propoxy-2-(4-pyridyl)-48-3
, 31.5 g of 1-benzoxazine were obtained. Recrystallization from a small amount of ethyl alcohol gave a melting point of 100-101°C.

Compounds obtained in the same manner are shown in Table 1 below.

However, the present invention is not limited to these.

Note that R and X in the table are the same as those shown in - machining allowance (I).

/ / / Table 1 1) NMR (CDC1G) δ (ppm):
1. 20 (3H, t), 2.82 (2H, q
), 6°40 (IH,s), 8.71~7.40 (
8H, m), 7.83-7.95 (2H, m), 8
, EtO~8.70 (2H, m).

2) NMR (CDC13) δ (ppm): 2
．． 20 (8H, d), 2.55-3.75 (IH.

m), 6.39 (IH, s), 6.73~7゜65 (8H, m), 7.84~7.93 (2
H, m), 8.58-8.68 (2H, m).

3) NMR (CDC13) δ (ppm):
1. 15 (3H, t), 3.25-3.68 (
2H.

m), 6.85-7.57 (8H, m), 7°89-8.00 (2H, m), 8.62-8°7
3 (2H, m).

4) NMR (CDC13) δ (ppm):
1. 16 (3H, t), 2.33 (3H, s),
3゜18~3.78 (2H, m), 6.55~7
゜57 (8H, m), 7.94~8.05 (
2H, m), 8.80-8.71 (2H, m).

1 mark indicates that the physical properties are 2 in JP-A No. 60-152484.
! 2 compounds are shown.

General formula (I) constituting the present invention thus obtained
and compounds represented by formulas (III) to (XXI[),
Since it has osmotic transferability to plants, various treatment methods such as above-ground grass leaf treatment, seed treatment, water surface treatment, and soil treatment are possible.

Moreover, since the -removal allowance (I) and the compounds represented by the formulas ([[) to (XXI[)] do not have any adverse effects on the target useful plants, the timing of their use is before sowing of the useful plants; It can be used at any stage such as the sowing stage, seedling stage, growing stage or fruiting stage.

Furthermore, when actually using the compound constituting 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, it is preferable to use solids that are used in the preparation of general agricultural chemicals. It can be mixed with various liquid carriers to produce wettable powders, emulsions, oils, powders, granules, flowables, etc.

In addition, drugs include dispersants, diluents, emulsifiers, spreading agents, wetting agents,
Auxiliary agents such as adsorbents, thickeners, sinking agents, and antifreeze agents may also be added.

The carrier referred to herein may be either solid or liquid, or a combination thereof. Examples of these include talc, clay, bentonite, kaolin, diatomaceous earth, calcium carbonate, wood flour, starch, gum arabic, water, alcohol, chelone, naphtha, xylene, nclohexane,
Examples include methylnaphthalene, benzene, acetone, dimethylformamide, glycol ether, and N-methylpyrrolidone.

Examples of adjuvants include polyoxine ethylene alkylphenyl ether, polyoxyethylene sorbitan monooleate, ethylene oxide propylene oxide copolymer, lignin sulfonate, sorbitan ester, soap, Pi oxidized oils, alkyl sulfate ester salts, Petroleum sulfonates, dioctyl sulfosuccinate salts, alkylbenzene sulfonates, aliphatic amine salts, 4th
Examples include ammonium salts, alkylpyridinium salts, alkylaminoethylglycine, alkyldimethylbetaine, polyglycol sulfate, alkylamine sulfonic acid, isopropyl phosphate, carboxymethylcellulose, polyvinyl alcohol, hydroxypropylcellulose, ethylene glycol, xanthan gum, and the like.

It can also be used as an aerosol agent by mixing with a propellant such as fluorotrichloromethane or dichlorodifluoromethane, or as a fumigant or smoke agent by mixing with an appropriate blowing agent or combustion agent. can.

In formulation, the mixing ratio is generally - machining allowance (I)
and compounds represented by formulas (III) to (XXII) as weight%, 0.05 to 95%, preferably 0.1 to 8
0%, particularly preferably 1 to 70%, optimally 70 to 99% as a carrier and 0 to 20% as an adjuvant.

Moreover, by mixing with other fungicides, herbicides, plant growth regulators, insecticides, acaricides, and other agricultural chemicals, fertilizers, etc., a wider range of effects can be expected.

General formula (I) and formulas (III) to (X
When actually using the compound represented by Xn),
It goes without saying that the concentration should be selected appropriately depending on the time of use, weather conditions, method of use, dosage form, place of use, etc., but the concentration used is generally 0.5 to 11,000 pp, preferably 3 to 11,000 pp.
500 pl) m, and the amount used is generally 0.5 to 500 g per 10 are, preferably 10
It is 1 to 250 g per are.

Next, according to a test example, - machining allowance (I) and formula (III) ~C
The evening effect of the compound represented by XXU) as a rice sheath blight control agent will be explained.

Test Example 1 Rice sheath blight control test (preventive effect) 25 rice seeds (variety: Konhikari) were sown in Wagner pots with a diameter of 12 cm, and grown for 4 to 5 weeks in a greenhouse. A hydrating powder prepared according to Formulation Example 2 described below was diluted with water to a predetermined 1 degree, and 20 ml per pot was sprayed on rice seedlings with the fifth leaf developed. After air-drying, the Rhizoctonia blight fungus was cultured for 7 days on a rice grain medium.
5 olani) was placed in a greenhouse (28°C), and after 10 days, the length of the lesion formed on the rice leaf sheath was determined and the control value was calculated according to the following criteria.

Comparative compounds include JP-A-60-152 shown in the second bag.
Six samples (■ to ■) of the compound described in the No. 484 publication and samples (■ to ■) synthesized according to the methods of Production Examples 1 to 3 were used.

Table 2 15 (3H, t), 3.30-3. 70 (2
H, m), 6.95-7.00 (LH, m)7.
25-7.55 (7H, m), 7.95-8.05
(2H, m) 8.65-8.75 (2H, m).

The results of Test Example 1 are shown in the following table.

Table 3 NMR (CDC13) δ (ppm): 3.

75 (2H, m), 6.95~7゜m), 8
．． 00-8. 10 (28,70~8.80
(2H, m).

NMR (CDC13) δ (ppm): 1.

χ 1) oil 20~3° 65 (9H.

Hl m) + × 2) oil Test Example 2 Rice sheath blight control test (therapeutic effect) 25 rice seeds (variety: Koshihikari) were sown in Wagner pots with a diameter of 12 cm, and grown for 4 to 5 weeks in a greenhouse. . Rice seedlings with the fifth leaf developed were treated with Rhizatonia blight which was cultured for 7 days on rice bran medium.
5 olani) and placed in a greenhouse (28°C). After 3 days, the hydrating agent prepared according to Formulation Example 2 was diluted with water to a predetermined concentration, and 20 ml per pot was sprayed on rice seedlings.
Ten days later, the control value was calculated according to Test Example 1.

As comparative compounds, the compounds shown in Table 2 were used as in Test Example 1.

The results are shown in Table 4.

Table 4 Formulation examples are shown below. In the examples, "parts" indicate "parts by weight."

Formulation Example 1 Powder Compound No. 14 2 parts - 98 parts or more are mixed and pulverized to obtain a powder.

Formulation Example 2 Wettable Powder Compound No. 6 10 parts Alkylsulnenic acid so! / 5 parts
- Mix 85 parts or more and pulverize to obtain a wettable powder.

Formulation Example 3 Emulsion Compound No. 8 Calcium Y-rukylbene sulnenate polyoxyethylene alkylphenyl ether, 5 parts 4 parts 11 parts 10 parts 70 parts or more of chlorhexane xylene are mixed to obtain an emulsion.

Formulation example 4 Granule agent Compound number 13 Calcium lignin sulfate bent “night” Tarry Mix the above and add water, Dry to obtain granules.

Formulation Example 5 2 parts 2 parts 30 parts 66 parts After kneading, the floor was granulated. Compound No. 9 10 parts ethylene glyfur 5 parts xanthan gum 0.2 parts polyoxyethylene sorbitan monopacate
5 parts water 79.
A flowable agent is obtained by wet-pulverizing 8 parts or more.

Claims (1)

[Claims] 1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents hydrogen, an alkyloxy group, an alkenyloxy group, an alkynyloxy group, an alkylthio group,
represents a halogen or lower alkyl group. ) 4H indicated by
- A rice sheath blight control agent containing a 3,1-benzoxazine derivative as an active ingredient. 2) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 3) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 4) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 5) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 6) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 7) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 8) Compounds represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. 9) Compounds represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. 10) Compounds represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Compound. 11) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 12) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 13) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 14) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 15) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 16) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 17) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 18) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 19) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 20) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 21) A compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼.