JP3117382B2 - 2,6-Dioxabicyclo [3,3,0] octane derivatives, process for producing the same, and herbicides containing them as active ingredients - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 2,6-dioxabicyclo [3,3,0] octane derivative and a herbicide containing the same as an active ingredient.

[0002]

2. Description of the Related Art 2,6-Dioxabicyclo [3,3,
[0] There are very few synthetic examples of compounds having an octane ring, and the herbicidal activity is known from JP-A-63-1468.
No. 85 only. This patent includes a compound of the general formula (IV)

[0003]

Embedded image[Wherein, R₁ , R_Two , R_Three , R_Four And R_Five Are the same
May be different, each independently a hydrogen atom, or
One or more having an atomic number of 9 to 35 according to
1 to 5 optionally substituted with the above halogen atom
Or an alkyl group containing a carbon atom of_Three , R_Four 
And R_Five Is an alkyl containing 2 to 4 carbon atoms
Nyl or alkynyl group and 6 to 10 carbon atoms
Optionally substituted mono- or bicyclic ring containing
R is selected from cycloaliphatic or aryl groups;_Three 
And R_Four Is 5 together with the carbon atom to which they are attached
Form a cycloaliphatic ring containing 6 ring carbon atoms; and
R is an unsaturated hydrocarbon group containing 2 to 4 carbon atoms,
Aromatic groups containing up to 14 carbon atoms, O, S or N
Having one or two heteroatoms each selected from
Heterocyclic groups containing up to 14 carbon atoms or N-hetero
N-oxide or acid addition salts of cyclic groups, cyano groups,
Cycloalkenyl groups containing 7 carbon atoms and 3
Selected from cycloalkyl groups containing from 10 to 10 carbon atoms
These groups may be optionally substituted; and
And its stereoisomeric forms or mixtures thereof]
Is disclosed. However, in the example of this patent,
Is represented by R in the general formula (IV)_Three Or R _Four Is aryl
Group (eg, unsubstituted or substituted phenyl group)
There is no description of the compound and its configuration is also clear.
It has not been neglected. Also, Japanese Patent Application Laid-Open No. 63-14688
No. 5 discloses a compound represented by the general formula (IV):
It is disclosed that the compound can be produced according to the reaction formula (Formula 5).
You.

[0004]

Embedded image [Wherein, R, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent the same meaning as in the general formula (IV). ]

That is, after a compound of the general formula (VI) is used as a raw material, and a lactone form of the general formula (VIII) is obtained through steps A and B, when R ₃ and R ₄ are hydrogen atoms, step C, It describes that compound (IV) can be produced via step D and step F when R ₃ and R ₄ are other than a hydrogen atom via step E. In this production method, the compound (I
The synthesis of V) requires four steps and is expensive (metal)
It is necessary to use a lot of reagents. In particular, R of the general formula (IV)
_In order to introduce a substituent into ₃ and R ₄ , it is necessary to use a metal reagent such as a Grignard reagent in Step D.
Therefore, the types of substituents that can be introduced into R ₃ and R ₄ are limited, and it has not been possible to stereoselectively introduce a substituent into R ₃ or R ₄ with high accuracy.

[0006]

Many herbicides for fields or paddy fields have been developed to date, but there is no sufficient herbicidal activity or selectivity for crops. JP 6
2, which is specifically disclosed in JP-A-3-146885.
The 6-dioxabicyclo [3,3,0] octane derivative is not effective because it has insufficient herbicidal activity and causes severe chemical damage to important crops such as paddy rice. Therefore, an object of the present invention is to find a compound which does not cause harm to useful crops under any conditions and has excellent herbicidal activity when used in fields and paddy fields. That is, while the present invention is sufficiently safe for paddy rice, it shows strong herbicidal activity against annual weeds such as Nobie, Tamayatsuri, Konagi, Kikushigusa and perennial weeds such as fireflies, Spodoptera striata, Krogwai, and Pineby, and is useful for rice. An object is to find a compound having excellent performance as a herbicide. In addition, by soil treatment or foliage treatment in the field, it is also effective on rice, rice, etc. It is an object of the present invention to find a compound which is effective not only as a herbicide for field use but also as a herbicide for field action and other non-agricultural land.

[0007]

Means for Solving the Problems and Actions The present inventors have studied methods for producing a novel 2,6-dioxabicyclo [3,3,0] octane compound in order to solve the above-mentioned problems, and Were synthesized and their herbicidal activities were examined in various ways. As a result, they have found a compound that is not only effective as a paddy rice herbicide, but also as a field-acting herbicide and other herbicides for non-agricultural lands, and completed the present invention.
That is, the present invention relates to a compound represented by the general formula (I):

[0008]

Embedded image [Wherein R ₁ represents a lower alkyl group, a halogen-substituted lower alkyl group, a lower alkoxyalkyl group, a lower alkylthio group alkyl group or a lower alkenyl group, R ₂ represents a lower alkyl group, a lower alkoxy group or a halogen atom; ₃ and R ₄ represent a hydrogen atom, a lower alkyl group or a halogen-substituted lower alkyl group, R ₅ represents a lower alkyl group, R ₆ represents a lower alkyl group, a lower alkoxy group,
A halogen atom, a halogen-substituted lower alkyl group or a halogen-substituted lower alkoxy group, m and n each represent an integer of 0 to 4, and when m and n are 2 to 4, R ₂ and R ₆ may be the same or different; good. ], A herbicide characterized by comprising a method for producing the derivative, and containing them as an active ingredient.

In the compound of the present invention, a lower alkyl group,
A lower alkoxy group, a lower alkylthio group or a lower alkenyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, respectively. And halogen atom refer to fluorine atom, chlorine atom, bromine atom and iodine atom. The compound (I) of the present invention has the following reaction formula (Formula 7)

[0010]

Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and m,
n represents the above-mentioned meaning, and R ₇ represents a lower alkyl group or a lower acyl group. ), A tetrahydrofuran derivative represented by the general formula (II) and a styrene derivative represented by the general formula (III) are reacted in the presence of an acid catalyst in one step.

The compound of the general formula (II) is a known compound, Org. Chem. , 50 , 4786 (198
5) and the method described in US Pat. No. 4,534,785. Usually, these are obtained as a mixture of α-form and β-form, but can be used as they are in the next reaction. Of course, the isomers can be separated by silica gel chromatography or the like and used for the next reaction. The compounds of the general formula (III) are also known compounds, and many of them are easily available as commercial products. Compound (II) wherein R ₇ is an acyl group is compound (I)
I) R ₇ of the alkyl group is a compound having a well-known general method (for example, Chem. Ind., 27 , 547 (19)
68)).

In the step (G), the compound of the general formula (I) is converted into a compound of the general formula (II) and the compound of the general formula (III) by
Tetrahydrofuran, nitrobenzene, chlorobenzene, methylene chloride, chloroform, carbon tetrachloride, 1,2
-Lewis acid such as tin tetrachloride, titanium tetrachloride, aluminum chloride, ferric chloride, boron trifluoride diethyl ether complex or perchloric acid, sulfuric acid, nitric acid in an inert solvent such as dichloroethane, carbon disulfide, acetonitrile, etc. ,hydrochloric acid,
It can be produced by reacting in the presence of a mineral acid such as chlorosulfonic acid, phosphoric acid, benzenesulfonic acid or trifluoromethanesulfonic acid or an organic acid. This reaction can also be performed without a solvent. The reaction temperature can range from -70 ° C to the boiling point of the solvent, but is preferably from -20 ° C to 80 ° C, and an even more suitable temperature is -1 ° C.
0 ° C to 70 ° C. After completion of the reaction, post-treatment is carried out as usual, and the target compound can be obtained by recrystallization or purification by column chromatography.

The compound of the present invention obtained by this production method has a single configuration with respect to the 7-position of the general formula (I) [the bonding position of the substituent R ₅ and the (substituted) phenyl group of the general formula (I)]. It is characterized by taking. This production method is an extremely stereospecific reaction since it is expected that a compound having an epi-position at the 7-position as shown in the following chemical structural formula (Chemical formula 8) will be obtained by a usual reaction.

[0014]

Embedded image The compound of the general formula (I) obtained by the production method of the present invention is represented by 7
It has a single steric structure in terms of position, and its steric configuration was determined by two-dimensional NMR measurement. As an example of the measurement results,
FIG. 1 shows a two-dimensional NMR of Compound No. 1 of the present invention.

The starting material for producing compound No. 1 is methyl 5-deoxy-3-O- (2-fluorobenzyl) -5-C-
Methyl-D-xylofuranoside. This compound is easily obtained by the production method shown in Reference Example 1, but its configuration is derived from D-glucose. Therefore, the 3, 4, and 5 positions of the compound of the present invention retain the configuration of the raw material for synthesis, and have the R, S, and S configurations, respectively. On the other hand, as a result of two-dimensional NMR measurement of Compound 1, NOE (nuclear Overhauser effect) is observed between the hydrogen atom at the 5-position and the hydrogen atom at the 1- and 7-methyl groups. The hydrogen atom at the 7-position and the methyl group at the 7-position are on the same plane as the hydrogen atom at the 5-position. Since the condensed ring of the five-membered rings takes a cis conformation, the 1- and 7-positions were determined to be R and R configurations, respectively. Further, since the NOE is observed between the hydrogen atom at the 1-position and the hydrogen atom at the 8-position where NOE is observed (8a in FIG. 1) and the hydrogen atom at the methyl group at the 7-position, the solid at the 7-position is R The configuration was supported. From the above measurement results, the configuration of Compound 1 was determined to be (1R, 3R, 4S, 5S, 7R).

On the other hand, in the production method disclosed in JP-A-63-146885, four steps are required for the production of compound (IV), and in step B, a carbomethoxymethylenetriphenylphosphorane derivative is added in step D. In this case, it is necessary to use a metal reagent such as a Grignard reagent to introduce the substituents R ₃ and R ₄ , which is not an industrially easy production method. Moreover,
It is not possible to introduce the substituents R ₃ and R ₄ stereoselectively.

That is, the compound of the present invention is disclosed in
The compound has stereospecificity that cannot be produced by the production method disclosed in Japanese Patent No. 46885, and can be produced for the first time by the production method of the present invention. Further, as shown in the examples of the present invention, in order for the 2,6-dioxabicyclo [3,3,0] octane derivative to exhibit high herbicidal activity, 1,
The configurations at positions 3, 4 and 5 and the substituents at positions 7 and 8 have very important significance. That is, in order to exhibit high herbicidal activity, positions 1, 3, 4, and 5 are (1)
(R, 3R, 4S, 5S) coordination and the presence of two substituents at the 7-position are essential, and the herbicidal activity and selectivity to useful crops vary greatly depending on the type of substituent. Hereinafter, this will be described in detail.

In order to clarify the excellent performance of the compound of the present invention as a herbicide, the performance was compared with the compound disclosed in JP-A-63-1468854. That is, for the compound (V) (Chem. 9) described in Example 4 of JP-A-63-1468854, the configuration at the 1, 3, 4 and 5 positions is unknown.

[0019]

Embedded image Therefore, the compound (XII) in which the configuration of the ring and the 3- and 4-positions are completely identical to the compound of the present invention (Chem. 10)

[0020]

Embedded image In addition, the compound (XIII) (compound 11) in which only the stereochemistry at the 4-position was inverted from the compound (XII) was used as a comparative compound in Test Examples 1 to 4 of the present invention.

[0021]

Embedded image Further, as an example in which the 7-position is substituted with only one substituent, compound (XIV) (Formula 12) was also used as a comparative compound in Test Examples 1 to 4 of the present invention.

[0022]

Embedded image As is evident from the results, the compound of the present invention showed extremely excellent herbicidal activity and selectivity under any treatment conditions, but the comparative compound (XII) showed a high dose in Test Examples 1 to 3. Despite herbicidal activity, these doses were insufficiently selective, causing significant phytotoxicity to crops such as rice. On the other hand, comparative compounds (XIII) and (XIV)
Showed no herbicidal activity in any of the tests.

While the compounds of the present invention are extremely safe against paddy rice, either pre-emergence or during the growing season, annual weeds such as Nobie, Tamaya-tsuri, Konagi and Kikashigusa as well as fireflies, Mizugaya-tsuri, Krogwai,
Shows strong herbicidal activity against perennial weeds such as pine trees,
It has excellent performance as a herbicide for paddy rice. In addition, soybean, cotton, sugar beet, corn, sugarcane, wheat and other useful crops in any of the soil treatment or foliage treatment, and has high selectivity to useful crops, such as Meechishiba, Hakobe, Tade, Inubiyu, Kogomeyatsuri, Suberihigyu, Noborogiku, Shows herbicidal activity on white flies, hamazuge, convolvulus, clovergrass, bluegrass, sparrow lily, spruce catalysium, napsuna, enokorogosa, etc., and is effective not only as a herbicide for paddy rice but also as a herbicide for field action and other non-agricultural lands. .

As is clear from the above results, in order for the 2,6-dioxabicyclo [3,3,0] octane derivative of the present invention to exhibit high herbicidal activity and selectivity, it was disclosed in the present invention. The steric structure of the compound and the substituent at the 7-position are essential. These facts are not described in Japanese Patent Application Laid-Open No. 63-146885 and cannot be expected at all from the content thereof, and have been clarified for the first time by the present invention.

The compound (I) of the present invention may be used as it is for the plant to be treated, but it is generally mixed with an inert liquid or solid to prepare a generally used preparation.
For example, it is used after adjusting to powders, granules, wettable powders, emulsions, flowable preparations and the like. If necessary for the preparation, an auxiliary agent can be added.

As the carrier, any solid or liquid carrier can be used as long as it is generally used for agricultural and horticultural medicines, and it is not limited to a specific one. For example, as a solid carrier, clay, talc, bentonite, calcium carbonate, diatomaceous earth, mineral powder such as white carbon, soybean powder, vegetable powder such as starch, petroleum resin, polyvinyl alcohol, polyalkylene glycol and the like Polymer compounds, urea, waxes and the like. Examples of the liquid carrier include various oils, various organic solvents, water and the like. Surfactants, binders, stabilizers and the like which are usually used for agricultural and horticultural medicines can be used alone or in combination as necessary. Further, in some cases, an industrial bactericide or a bactericidal / antifungal agent can be added for bactericidal / fungal control.

As the surfactant, a nonionic, anionic, cationic or amphoteric surfactant can be used as appropriate. Preferred examples include alkyl phenols, higher alcohols, alkyl naphthols, higher fatty acids, fatty acid esters, dialkyl phosphate amines and the like, which are obtained by polymerizing ethylene oxide and propylene oxide, alkyl sulfate salts (such as sodium lauryl sulfate), and alkyl sulfonate salts. (Sodium 2-ethylhexene sulfonate, etc.), aryl sulfonates (sodium lignin sulfonate, sodium dodecylbenzene sulfonate, etc.)
Is mentioned. The content of the compound of the general formula (I) in the herbicide according to the present invention varies depending on the form of preparation, but is usually 1 to 20% by weight for powder and 20 to 6 for wettable powder.
0% by weight, 1-30% by weight for granules, 1-50% for emulsions
%, 10 to 50% by weight for the flowable preparation, and 20 to 90% by weight for the dry flowable preparation. The content of the adjuvant is 0 to 80% by weight, and the content of the carrier is 10%.
It is the amount obtained by subtracting the contents of the active ingredient compound and the adjuvant from 0% by weight.

The herbicide according to the present invention can be used for treating flooded soil,
It is effective in all treatment methods such as soil treatment, soil mixed layer treatment, foliage spraying treatment, and the application rate is as active ingredient amount,
Although it can be used in a wide range of 0.01 kg to 10 kg / ha, it is preferably used in a range of 0.05 kg to 5 kg / ha.

The herbicide of the present invention can be used by mixing with one or more other herbicides, pesticides such as insecticides and plant growth regulators, soil conditioners or fertilizers. However, it is also possible to prepare a mixed preparation with these, and a synergistic effect can be expected in some cases. In this case, it is particularly advantageous to use it as a mixture with other herbicides. Other herbicides include, for example, phenoxyacetic acid herbicides, benzoic acid herbicides, chlorinated carboxylic acid herbicides, carbamate herbicides, urea herbicides, sulfonylurea herbicides, acid amide herbicides, complex Cyclic herbicides (triazine herbicides, diazine herbicides, etc.), phenolic herbicides, diphenyl ether herbicides, dipyridinium herbicides, dinitroaniline herbicides, organophosphate herbicides, phosphorus-containing amino acids Herbicides, imidazolidinone herbicides, pyridine herbicides, quinoline herbicides, sulfonamide herbicides, cyclohexanone herbicides, other organic herbicides, and inorganic herbicides.

[0030]

Next, the present invention will be described in more detail by way of examples. First, an example of production of the compound of the general formula (II) will be described as a reference example. Reference Example 1 Production of methyl 5-deoxy-3-O- (2-fluorobenzyl) -5-C-methyl-D-xylofuranoside 5-deoxy-3-O- (2-fluorobenzyl)-
1,2-O-isopropylidene-5-C-methyl-α-
70.97 g of D-xylofuranoose was dissolved in methanol (30
0 ml), and p-toluenesulfonic acid was dissolved in 0.1 ml.
5 g was added and the mixture was heated under reflux for 10 hours. After cooling, the reaction solution was neutralized with an aqueous sodium hydrogen carbonate solution, and the solvent was distilled off under reduced pressure. Add this to water and add ether and ethyl acetate (1: 1)
After extraction with a mixed solvent, the organic layer was washed with water. This was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily crude product. This was purified by silica gel chromatography (developing solvent; n-hexane: ethyl acetate = 3: 1) to obtain 64.21 g of the desired compound as an anomeric mixture of α-form and β-form. (Yield 99.2%) The anomeric mixture of α-form and β-form obtained here is precisely purified by silica gel chromatography (developing solvent; n-hexane: ethyl acetate = 5: 1) to obtain α And β-isomers.

Reference Example 2 Production of methyl 5-deoxy-3-O- (2-methylbenzyl) -D-xylofuranoside 5-deoxy-3-O- (2-methylbenzyl) -1,
After dissolving 10.68 g of 2-O-isopropylidene-α-D-xylofuranoose in methanol (100 ml), 0.5 g of p-toluenesulfonic acid was added, and the mixture was heated under reflux for 10 hours. After cooling, the same post-treatment as in Reference Example 1 was performed.
9.25 g of the target compound was obtained as an anomeric mixture of α-form and β-form. (Yield 95.6%) Next, Production Examples of the compound of the general formula (I) of the present invention will be described as Examples.

Embodiment 1 (1R, 3R, 4S, 5S, 7
R) -3-Ethyl-4- (2-fluorobenzyloxy) -7-methyl-7-phenyl-2,6-dioxabicyclo [3,3,0] octane (compound number of general formula (I) Production of 1) Methyl 5-deoxy-3-O- (2-
After dissolving 2.0 g of (fluorobenzyl) -5-C-methyl-D-xylofuranoside and 1.5 g of α-methylstyrene in 30 ml of tetrahydrofuran, a catalytic amount of concentrated sulfuric acid was added, and the mixture was heated under reflux for 10 hours. After cooling, the mixture was neutralized with a saturated aqueous solution of sodium hydrogen carbonate, and the solvent was distilled off under reduced pressure. After water was added thereto and extracted with ethyl acetate, the organic layer was washed with water. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain an oily crude product. The crude product was purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 9/1) to obtain 1.7 g of the desired product as an oil. (55% yield)

Embodiment 2 (1R, 3R, 4S, 5S, 7
R) -3-Ethyl-4- (2-chlorobenzylooxy)
Preparation of -7-methyl-7-phenyl-2,6-dioxabicyclo [3,3,0] octane (Compound No. 3 of General Formula (I)) Methyl 5 obtained by the same method as in Reference Example 1. -Deoxy-3-O- (2-chlorobenzyl) -5-C-methyl-
2.0 g of D-xylofuranoside and α-methylstyrene 1
5.0 g were mixed and dissolved, and boron trifluoride diethyl ether complex (1.3 ml) was added, followed by stirring at 60 ° C. for 10 hours.
After allowing to cool, the same post-treatment as in Example 1 was performed to obtain 1.5 g of the target compound as an oil. (58% yield)

Embodiment 3 (1R, 3R, 4S, 5S, 7
R) -3-Methyl-4- (2-methylbenzylooxy)
Production of -7-methyl-7-phenyl-2,6-dioxabicyclo [3,3,0] octane (Compound No. 29 of the general formula (I)) Methyl 5-deoxy-3 obtained in Reference Example 2. -O-
(2-methylbenzyl) -D-xylofuranoside 2.0
g and 1.5 g of α-methylstyrene in acetonitrile 30
Then, 1.00 g of 70% perchloric acid was added under ice cooling, and the mixture was stirred at room temperature for 24 hours. The same post-treatment as in Example 1 was carried out to obtain 1.7 g of the target compound as an oil. (Yield 61
%) The compounds of the general formula (I) that can be produced in this example are shown in Table 1 (Tables 1 and 2), and their physical properties are shown in Table 2 (Tables 3 to 5).

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

Next, preparation examples of the herbicide according to the present invention and test examples of herbicidal activity are shown. Formulation Example 1 (Wettable powder) Compound (1) of the present invention: 20 parts by weight, neoperex (trade name, manufactured by Kao; sodium dodecylbenzenesulfonate): 2 parts by weight, Neugen EA80 (trade name, manufactured by Daiichi Kogyo Seiyaku) Polyoxyethylene nonylphenyl ether): 1 part by weight, 10 parts by weight of white carbon, and 67 parts by weight of diatomaceous earth were sufficiently pulverized and mixed to obtain a wettable powder.

Formulation Example 2 (Wettable powder) Compound (3) of the present invention: 20 parts by weight, sodium alkylbenzenesulfonate: 2 parts by weight, polyoxyethylene alkylphenyl ether: 1 part by weight, white carbon: 10 parts by weight, and sieg Light: 67 parts by weight was well pulverized and mixed to obtain a wettable powder.

Formulation Example 3 (Wettable powder) Compound (8) of the present invention: 50 parts by weight, white carbon:
30 parts by weight, ammonium polyoxyethylene alkylphenyl ether sulfate: 6 parts by weight, sodium ligninsulfonate: 2 parts by weight, and diatomaceous earth: 12 parts by weight were thoroughly pulverized and mixed to obtain a wettable powder.

Formulation Example 4 (Floable agent) Compound (2) of the present invention: 5 parts by weight, sodium ligninsulfonate: 2 parts by weight, polyoxyethylene alkylaryl ether: 1 part by weight, water: 91.7 parts by weight Was added and mixed, and the mixture was pulverized using a sand grinder, and then 0.3 parts by weight of xanthan gum was added to obtain a flowable agent.

Formulation Example 5 (Floable agent) Compound (5) of the present invention: 30 parts by weight of sun extract P252 dissolved in 50 parts by weight of water (trade name, as described above): 10
Parts by weight were wet-pulverized and mixed, and then dissolved in 9.6 parts by weight of water, Kerzan S (trade name, manufactured by Kelco; xanthan gum): 0.2 part by weight and Deltop (trade name, manufactured by Takeda Pharmaceutical: organic iodine-based) Fungicide): 0.2 parts by weight were added and mixed to obtain a flowable agent.

Formulation Example 6 (Powder) Compound (4) of the present invention: 1 part by weight, Emulgen 910 (trade name, manufactured by Kao; polyoxyethylene nonylphenyl ether): 0.5 part by weight, and kaolin clay: 98.5
The parts by weight were pulverized and mixed well to obtain a powder.

Formulation Example 7 (Powder) Compound (9) of the present invention: 3 parts by weight, sodium ligninsulfonate: 3 parts by weight, polyoxyethylene alkylaryl ether: 2 parts by weight, and clay: 92 parts by weight were mixed and pulverized. A powder was obtained.

Formulation Example 8 (Water-dispersible granules) Compound (2) of the present invention: 55 parts by weight, toxanone 60PN
(Trade name, manufactured by Sanyo Chemical Industries; polyacrylate): 5 parts by weight, polyoxyethylene alkyl aryl ether:
After well mixing 5 parts by weight and 35 parts by weight of white carbon, an appropriate amount of water was added to wet the mixture, and the mixture was extruded and granulated by a horizontal extrusion granulator. This was dried at 30 to 60 ° C. and crushed, and then sized with a sizing machine to 0.3 to 0.5 mm to obtain a wettable powder.

Formulation Example 9 (Granules) Compound (7) of the present invention: 3.0 parts by weight, Neoperex (trade name, as described above): 2 parts by weight, Sun extract P25
2 (trade name, manufactured by Sanyo Kokusaku Pulp; sodium ligninsulfonate): 2 parts by weight, 70.0 parts by weight of bentonite and 23 parts by weight of talc were mixed well, and then an appropriate amount of water was added to wet the mixture. And extruded by a horizontal extrusion granulator. This was air-dried at 30 to 60 ° C and crushed, and then sized with a sizing machine to 0.3 to 1 mm to obtain granules.

Formulation Example 10 (granules) 0.5 part by weight of compound (27) of the present invention, gohsenol (G
osenol) GL-05s (PV from Nippon Gohsei)
A): 2 parts by weight, sun extract P252 (sodium lignin sulfonate manufactured by Sanyo Kokusaku Pulp): 2 parts by weight and clay:
After 95.5 parts by weight were mixed well, an appropriate amount of water was added to make it wet, and then extruded and granulated by a horizontal extrusion granulator.
This was air-dried at 60 to 90 ° C. and crushed.
A granule was obtained by sizing to 3 to 1 mm.

Formulation Example 11 (Emulsion) Compound (1) of the present invention: 10 parts by weight, Solpol 800A
(Trade name, manufactured by Toho Chemical; a mixture of a nonionic surfactant and an anionic surfactant): 10 parts by weight and o-xylene: 80 parts by weight were mixed and dissolved to obtain an emulsion.

Formulation Example 12 (oil-in-water emulsion EW) Compound (2) of the present invention: 5 parts by weight, toxanone FW-10
(Trade name, manufactured by Sanyo Chemical Industries; polymer-based anion): 4 parts by weight, xanthan gum: 0.3 parts by weight, Deltop:
88.5 parts by weight of water was added to 0.2 parts by weight and 2 parts by weight of polyoxyethylene alkylaryl ether, and emulsified by a homomixer to obtain an oil-in-water emulsion EW.

Test Example 1 Flooded Soil Treatment Test (Pretreatment before Occurrence) Soil was packed in a 1/5000 arel wagner pot, and seeds of red snapper, oak, firefly, and azalea were sowed and flooded. Rice seedlings (2-
Two strains were used as one strain, and the two strains were transplanted and grown in a greenhouse. One day later (before weed development), the test compound
A predetermined amount of granules (prepared according to the method described in Formulation Example 9) were used to treat Kg / ha and 0.5 Kg / ha, and after 30 days, the occurrence of weeds and paddy rice Was observed and investigated. The results are shown in Table 3 (Tables 6 and 7). In the table, the degree of damage to the test plant and the degree of phytotoxicity to the crop are indicated by the following criteria in comparison with the case where the growth state of the plant is untreated.表示 Indication Growth rate (%) 50 to 5 (death) 46 to 10 (Severe harm) 3 11-40 (Medium harm) 2 41-70 (Small harm) 171-90 (Slight harm) 0 91-100 (Harmless) 無───────

[0053]

[Table 6]

[0054]

[Table 7]

Test Example 2 Submerged Soil Treatment Test (Growth Season Treatment) The soil was packed in a 1/5000 arel wagner pot, and seeds of red snapper, oak, firefly, and azalea were sowed and flooded. Rice seedlings (2-
Two strains were used as one strain, and the two strains were transplanted and grown in a greenhouse. When the millet became two leaves, the test compound was 2
Predetermined amount of granules (prepared according to the method described in Formulation Example 9) so as to have a dosage of Kg / ha and 0.5 kg / ha
After 30 days, the occurrence of weeds and the status of chemical damage to rice were observed and investigated. The results are shown in Table 4 (Tables 8 to
9). In the table, the degree of damage to the test plant and the degree of phytotoxicity to the crop are indicated in the same manner as in Test Example 1.

[0056]

[Table 8]

[0057]

[Table 9]

Test Example 3 Upland soil treatment test (pre-emergence treatment) A 1/2500 arel resin pot was filled with soil, and this was filled with barnyardgrass, crabgrass, enokorogusa, chickweed, aobiu,
The soil mixed with soybeans and cotton seeds was covered with a soil of 1 to 2 cm, and grown in a greenhouse. One day later (before the emergence of weeds), a predetermined amount of wettable powder (prepared according to the method described in Formulation Example 1) was diluted with water so that the test compound had a dosage of 3 kg / ha, and 1 A spraying liquid amount equivalent to 10 L per are was sprayed uniformly on the soil surface using a pressurized micro sprayer. Thirty days after the application of the chemical, the growth of the weed and the phytotoxicity of the crop were observed and investigated. The results are shown in Table 5 (Table 1).
0). In the table, the degree of damage to the test plant and the degree of phytotoxicity to the crop are indicated in the same manner as in Test Example 1.

[0059]

[Table 10]

Test Example 4 Upland Field Foliage Treatment (Growing Season Treatment) A 1/10000 ares resin pot was filled with soil, and this was filled with barnyardgrass, crabgrass, enokorogusa, chickweed, aoville,
Soybeans and cotton were sown one by one and grown in a greenhouse. When each plant has 2-3 leaves, the test compound is 3 kg / ha.
A predetermined amount of a wettable powder (prepared according to the method described in Formulation Example 2) was diluted with water and adjusted to have a dosage of 1
Spraying was uniformly performed using a pressurized micro atomizer at a spraying liquid amount equivalent to 10 L per are. Thirty days after the application of the chemical, the growth of the weed and the phytotoxicity of the crop were observed and investigated. The results are shown in Table 6 (Table 11). In the table, Test Example 1 shows the degree of damage to the test plant and the degree of chemical damage to the crop.
Displayed in the same way as.

[0061]

[Table 11]

[0062]

The compound of the present invention represented by the general formula (I) is a novel compound having a 2,6-dioxabicyclo [3,3,0] octane ring and has excellent herbicidal activity and selectivity. Show. That is, when the compound of the present invention is used in a paddy field, it has excellent selectivity for paddy rice and shows a high herbicidal effect against important weeds such as foxtails, puppies, fireflies and azaleas. In addition, the compound of the present invention has high selectivity for crops such as soybeans and cotton even in upland cropping, and shows a high herbicidal effect on important weeds such as barnyardgrass, crabgrass, enokorogusa, chickweed, and bluegrass. Therefore, the compound of the present invention can be applied as a paddy and upland herbicide.

[Brief description of the drawings]

FIG. 1 is a diagram showing (1R, 3R, 4S, 5S, 7R)-
3-ethyl-4- (2-fluorobenzylooxy) -7
2 is a two-dimensional NMR spectrum of -methyl-7-phenyl-2,6-dioxabicyclo [3,3,0] octane (Compound No. 1 of the general formula (I)).

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 493/04 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound of the general formula (I) [Wherein R ₁ is a lower alkyl group, halogen-substituted lower alkyl group, a lower alkoxyalkyl group, a lower alkylthioalkyl group or a lower alkenyl group, R ₂ represents a lower alkyl group, a lower alkoxy group or a halogen atom, R ₃ And R ₄ each represent a hydrogen atom, a lower alkyl group, or a halogen-substituted lower alkyl group; R ₅ represents a lower alkyl group; R ₆ represents a lower alkyl group, a lower alkoxy group, a halogen atom, a halogen-substituted lower alkyl group or In the halogen-substituted lower alkoxy group, m and n represent an integer of 0 to 4, and when m and n are 2 to 4, R ₂ and R ₆ may be the same or different. A 2,6-dioxabicyclo [3,3,0] octane derivative represented by the formula: 2. A compound represented by the general formula (II): [Wherein R ₁ is a lower alkyl group, halogen-substituted lower alkyl group, a lower alkoxyalkyl group, a lower alkylthioalkyl group or a lower alkenyl group, R ₂ represents a lower alkyl group, a lower alkoxy group or a halogen atom, R ₇ Represents a lower alkyl group or a lower acyl group,
m represents an integer of 0 to 4, and when m is 2 to 4, R ₂ may be the same or different. And a substituted tetrahydrofuran derivative represented by the following general formula (III): [Wherein R ₃ and R ₄ each represent a hydrogen atom, a lower alkyl group or a halogen-substituted lower alkyl group, R ₅ is a lower alkyl group, R ₆ is a lower alkyl group, a lower alkoxy group, a halogen atom, a halogen-substituted lower alkyl group. Represents a group or a halogen-substituted lower alkoxy group, n represents an integer of 0 to 4, and when n is 2 to 4, R ₆ may be the same or different. Production of a 2,6-dioxabicyclo [3,3,0] octane derivative represented by the general formula (I) according to claim 1 by reacting the styrene derivative represented by the formula (1) in the presence of an acid catalyst. Method. 3. A herbicide comprising a 2,6-dioxabicyclo [3,3,0] octane derivative represented by the general formula (I) according to claim 1 as an active ingredient.