JPS63156779A - Pyridazinone derivative, production thereof and herbicide - Google Patents

Abstract

NEW MATERIAL:A pyridazinone derivative shown by formula I [X is H or F and Y is halogen; R is -ZR1 (Z is O or S; R1 is H, phenoxy, carboxy, lower alkoxy, lower alkylthio, cycloalkoxycarbonyl, cyano, phenyl, etc.) or -COOR2 (R2 is H, lower alkoxycarbonyl or lower alkyl)]. EXAMPLE:2-(4-Chloro-2-fluoro-5-hydroxyphenyl)-5,6,7,8-tetrahydrobenzo( d)pyrida zinon-1(2H)-one. Useful as a herbicide showing wide activity against various weeds with a small amount and high selectivity for crops such as rice plant, wheat, etc. PREPARATION:1,3,4,5,6,7-Hexahydro-3-hydroxy-isobenzofuran-1-one shown by formula II is reacted with a compound shown by formula III to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel compound, a method for producing the same, and a herbicide containing the compound as an active ingredient.

[Conventional technology]

In the cultivation of agricultural and horticultural crops, many herbicides have come to be used to control weeds, which have traditionally required a great deal of labor. However, because they cause chemical damage to crops and remain in the environment, contaminating the environment, it is difficult to develop a drug that is both effective and can be used completely at low doses.

The following are known as herbicides having a pyridazinone skeleton similar to the compound of the present invention.

Powder powders are widely used as herbicides to control broad-leaved weeds that occur mainly in sugar beet fields.

[Problem that the invention seeks to solve]

The object of the present invention is to produce a new pyridazinone derivative industrially and advantageously, and to provide a herbicide with a wide range of selectivity between crops and weeds, reliable efficacy, and high integrity.

[Means for solving problems]

The present invention provides a group represented by the general formula [wherein, A hydrogen atom or a phenoxy group, a carboxyl group, a lower alkoxy group, a lower alkylthio group, a cycloalkoxycarbonyl group, a cyano group, a phenyl group, or a lower alkoxycarbonyl group that may be substituted with a (lower alkoxycarbonyl group or lower alkylthio group). represents an optionally substituted fatty acid hydrocarbon group) or the formula -COOR2 (wherein R2 represents a hydrogen atom or a lower alkyl group optionally substituted with a lower alkoxycarbonyl group, a lower alkoxy group, or a phenyl group) ) represents a group. ], a method for producing the compound, and a herbicide containing the compound as an active ingredient.

The compound of the present invention exhibits a wide range of activities against various weeds at extremely low doses, and exhibits high selectivity for crops such as rice, wheat, corn, and soybean.

This compound is effective in soil treatment before weed emergence and in weed control in forests, lawns, open spaces, etc. other than agricultural land after weed emergence. In producing the compound of the present invention, 1,3.4.5.6.7-hexahydro-
3-Hydroxy-isohencyfuran-1-one and a hydrazine derivative represented by the general formula are condensed.

Condensation conditions include heating in acetic acid at 50° C. to 118° C. (reflux) or in a solvent such as benzene, toluene, xylene, etc., with azeotropic dehydration. After the reaction is completed, the desired product can be obtained by carrying out usual post-treatments.

The raw material compound represented by formula [II] can be easily obtained, for example, by reducing tetrahydrophthalic anhydride with a reducing agent such as NaBHa in a solvent such as DMF or THF.

In addition, when R1 or R2 in the general formula (1) of the present invention compound is other than a hydrogen atom, the present invention compound can also be produced according to the following reaction formula, and this reaction may be more advantageous depending on the substituent. In some cases.

(a) R=-YR, (However, R3 is not a hydrogen atom.

)(IV) (V) (Vl)(b
) R=COORz (However, R2 is a hydrogen atom, so there is no need for it.)
゜) [■] [■] [■] The structure of the present invention was determined by IR, NMR, M, ASS, etc.

〔Example〕

Next, the present invention will be explained in detail with reference to Examples.

Example 1 (Synthesis of 2-(4-chloro-2-fluoro-5-hydroxyphenyl) 5+16+meth71,8-tetrahydrobenzo(d)pyridazin-1(2H)-one) [Compound No. 1] : Bl 3.a 4th "u' 6., 7-hexahydro-
3-Hydroxy-isobenzofuran-1-one 6, Og
Then, 9.8 g of 4-chloro-2-fluoro-5-hydroxyphenylhydrazine hydrochloride was added to 50 mffL of acetic acid, further 4.8 g of sodium acetate was added, and the mixture was heated under reflux for 2 hours. After cooling, the reaction solution was added to ice water and tl? The resulting crystals were collected by filtration, washed with water and dried to obtain 8.5 g of the desired product. Melting point 231-232"ClExample 2II 2-(4-chloro-2-fluoro-5-('2-propynyloxy)fenyll-5,46, #7.A 8
-Tetrahydrohenzo(d)pyridazine-1(2H)-
Synthesis of on. (Compound No. 2): 2-(4-chloro-2
-fluoro-5-hydroxyphenyl) -5,46,
,7,,8-tetrahydrobenzo(d)pyridazine-1
1 g of (2H)-one was added to 30 mA of acetonitrile, and 0.40 g of propargyl bromide and 0.47 g of anhydrous potassium carbonate were added thereto, and the mixture was heated under reflux for 3 hours. After the reaction solution was cooled, the precipitated inorganic substances were filtered off, the acetonitrile was distilled off under reduced pressure, water and ether were added, the ether layer was separated and dried over anhydrous magnesium sulfate, and the ether was distilled off. The residue was purified by column chromatography to obtain 1.0 g of the desired product.

Melting point: 142-143°C Representative examples of the compounds of the present invention are shown in Table 1, including the above examples.

Means for Solving Problems - Herbicide] The herbicide of the present invention contains one or more of the compounds represented by the above general formula [1] as an active ingredient, and has a form similar to that of ordinary agricultural chemicals. . That is, the auxiliary compound is generally used in the form of a wettable powder, an emulsion, a granule, an aqueous solution, a flowable preparation, etc. by mixing an appropriate amount with a carrier. As a fixed carrier, talc,
Examples include white carbon, bentonite, clay, diatomaceous earth, etc., and examples of liquid carriers include water, alcohol, benzene, xylene, kerosene, mineral oil, cyclohexane,
Cyclohexanone, dimethylformamide, etc. are used. If necessary, a surfactant may be added in order to obtain a uniform and stable form in these preparations.

The concentration of the active ingredient in the herbicide of the present invention varies depending on the form of the formulation mentioned above, but for example, in a wettable powder, it is 5 to 70%, preferably 10 to 30%:
3 to 70% for emulsions, preferably 5 to 20%; 0.01 to 20% for double grains, preferably 0.05 to 20%
A concentration of 10% is used.

The wettable powders and emulsions thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion, and the granules are sprayed or mixed into the soil before or after weed germination. It is processed. When actually applying the herbicide of the present invention, an appropriate amount of 1 g or more of the active ingredient is applied per 10 ares.

In addition, the herbicide of the present invention is a known bactericide, insecticide, acaricide,
It can also be used in combination with herbicides, plant growth regulators, etc. In particular, when used in combination with herbicides, not only the amount of chemicals used can be reduced and labor savings can be achieved, but even higher effects can be expected due to the synergistic effects of the mixed chemicals. In that case, combinations with multiple known herbicides are also possible. Chemicals suitable for use in combination with the herbicide of the present invention include carbamate herbicides such as bentiocarb, molinate, MY-93 (S-2,2-dimethylpencyl) l-piperidine carbothioate, and thiocarbamate herbicides. herbicide,
Acid amide herbicides such as pucchlor and pretilachlor, diphenyl ether herbicides such as chromethoxynil and bifenox, pyrazole herbicides such as virazolate and j°razoxifene, sulfonylurea herbicides such as chlorsulfuron and sulfometuron-methyl, and imazaquin. , imidacillin herbicides such as imazavir, MCP,
, phenoxyalkane carboxylic acid herbicides such as MCPB, phenoxyphenoxypropionic acid herbicides such as diclofop-methyl, pyridyloxyphenoxypropionic acid herbicides such as fluadipump butyl, and others such as piverophos, Daimeron, pentacin, Oxacyacin, NTN-80,1 (2-benzothiazol-2-yloxy-N-methylacetanilide), Naproanilide, HW-52 (4-ethoxymethoxybenz-2'.

3'-cycloanilide), KNW-242 (1-
(3-methylphenyl)-5-phenyl-I H-1,
2,4,-) lyazole-3-carboxamide), S
Examples include cyclohexanedione-based herbicides such as -47(N-(2,2-dimethylbenzyl)-d~dibromo-butylacetamide, setoxydim, alloxydimousodium, etc.).

Vegetable oils and oil concentrates can also be added to these combinations.

[Example - Herbicide]

Next, some formulation examples regarding the herbicide of the present invention will be shown, but the active ingredient compounds, additives, and addition ratios are not limited to these examples and can be varied within a wide range.

l Example 3I Permanent agent Compound 9 of the present invention 20 parts White carbon 20 parts Diatomaceous material ±
52 parts alkyl sulfate soda
At least 8 parts were uniformly mixed and finely ground to obtain a wettable powder containing 20% of the active ingredient.

1 Example 41 Emulsion Compound 17 of the present invention 20 parts
Shin
55 parts dimethylformamide
15 parts polyoxyethylene phenyl ether At least 10 parts were mixed and dissolved to obtain an emulsion containing 20% of the active ingredient.

7 Example 9/ Granule Compound 1 of the present invention 5 parts Tal
the law of nature
40 copies -
38
Part bentonite 10 parts Sodium alkyl sulfate 7 parts or more were uniformly mixed and finely pulverized, and then granulated into particles with a diameter of 0.5 to 1.0 mm to obtain granules containing 5% of the active ingredient.

〔Effect of the invention〕

Next, test examples regarding the effect of the herbicide of the present invention will be shown.

Test Example 11 Water 1) Test method: 200cn! Fill the pot with paddy soil, sow the seeds of Japanese grasshopper, Kumagayatsu, Omodaka, and Hotarui.
After lightly covering with soil, add 1 rice plant (variety Nihonbare) at the 2-3 leaf stage (
Two plants per plant) were transplanted. The next day, while maintaining a water depth of 2 to 3 cm, granules of each compound were treated with the starting dose and grown in a greenhouse. Three weeks after the chemical treatment, the growth status of rice and each weed was investigated according to the following criteria, and the results shown in Table 2 were obtained.

0% 0 20-29% 2 40-49% 4 60-69% 6 80-89% 8 100% 10 Also, the numbers for 1, 3, 5, 7, and 9 are 0, 2.2, and 4, respectively.
．． It shows an intermediate value between 4, 62.6, 8.8 and 10.

Weed killing rate (%) - Weight of above-ground plants in untreated area Table 2 Table 3 Su(2H)-one (Pyrazone) 7 Test Example 21 Stalk and foliage spraying treatment A 200 cJ pot was filled with soil, and the surface layer was filled with soil. Seeds of , pigweed, purslane, and purslane were sown, lightly covered with soil, and grown in a greenhouse. When each weed grew to a height of 5 to 10 am, a chemical solution prepared by diluting an emulsion of each test compound with water was sprayed onto the foliage of the weed at a ratio of 1006/10 am using a small sprayer. Three weeks later, the growth status of weeds was investigated according to the investigation criteria of Test Example 1, and the results shown in Table 3 were obtained.

Table 3 Table 3

Claims (3)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, atom or sulfur atom, R_1 is a hydrogen atom or a phenoxy group, a carboxy group, a lower alkoxy group, a lower alkylthio group, a cycloalkoxycarbonyl group, a cyano group,
Indicates an aliphatic hydrocarbon group which may be substituted with a phenyl group or a lower alkoxycarbonyl group (which may be substituted with a lower alkoxycarbonyl group or a lower alkylthio group). } or the formula -COOR_2 (where R_2
represents a hydrogen atom or a lower alkyl group optionally substituted with a lower alkoxycarbonyl group, a lower alkoxy group, or a phenyl group. ) represents a group. ] A compound represented by (2) 1,3,4,5,6,7-hexahydro- expressed by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
3-Hydroxy-isobenzofuran-1-one and the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is a hydrogen atom or a fluorine atom, Y is a halogen atom, and R is represented by the formula Group {wherein Z is an oxygen atom or a sulfur atom, R_1 is a hydrogen atom or a phenoxy group, a carboxy group, a lower alkoxy group, a lower alkylthio group, a cycloalkoxycarbonyl group, a cyano group,
Indicates an aliphatic hydrocarbon group optionally substituted with a phenyl group or a lower alkoxycarbonyl group optionally substituted with a lower alkoxycarbonyl group or a lower alkylthio group. } or the formula -COOR_2 (where R_2
represents a hydrogen atom or a lower alkyl group optionally substituted with a lower alkoxycarbonyl group, a lower alkoxy group, or a phenyl group. ) represents a group. It is characterized by being reacted with a compound represented by A method for producing a compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X, Y, and R have the same meanings as above.) (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, atom or sulfur atom, R_1 is a hydrogen atom or a phenoxy group, a carboxy group, a lower alkoxy group, a lower alkylthio group, a cycloalkoxycarbonyl group, a cyano group,
Indicates an aliphatic hydrocarbon group optionally substituted with a phenyl group or a lower alkoxycarbonyl group optionally substituted with a (lower alkoxycarbonyl group or lower alkylthio group). } or the formula -COOR_2 (wherein R
_2 represents a hydrogen atom or a lower alkyl group optionally substituted with a lower alkoxycarbonyl group, a lower alkoxy group, or a phenyl group. ) represents a group. ]
A herbicide characterized by containing one or more compounds represented by as an active ingredient.