JPH07110833B2 - α-Substituted phenylacetic acid derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Use) The present invention provides a novel α-substituted phenylacetic acid derivative useful as a bactericide.

(Problems to be Solved by Conventional Techniques and Inventions) Many phenylacetic acid derivatives have hitherto been synthesized. For example, as a herbicide for fields (Proceeds of the East Africa Weed Control Conference)
ngs of the East Africa Weed Control Conference) 5th (1974)), (West German Patent Specification No. 2458156) and other phenylacetic acid derivatives are known.

However, no literature has confirmed the bactericidal activity of these phenylacetic acid ester derivatives. As a result of confirming the bactericidal activity of the phenylacetic acid ester derivative by the present inventors, the bactericidal activity was not high.

(Means for Solving Problems) The present inventors have succeeded in synthesizing a series of novel phenylacetic acid derivatives and studied the bactericidal activity of these compounds. As a result, they have found that a specific phenylacetic acid derivative has extremely strong bactericidal activity as compared with conventionally known phenylacetic acid derivatives, and can be effectively used as a bactericidal agent, and completed the present invention.

The present invention has the general formula [However, A is (However, X ₁ represents a halogen atom, an alkyl group, a halogenoalkyl group or an alkoxy group, and X ₂ , X ₃ and X ₄ represent a hydrogen atom, a halogen atom, an alkyl group, a halogenoalkyl group or an alkoxy group.). R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, a halogenoalkyl group or an alkoxy group, and R ₂ represents a hydrogen atom or an alkyl group. ] An α-substituted phenylacetic acid derivative represented by

In the general formula [I] Specific examples of X ₁ , X ₂ , X ₃ , X ₄ in the A group represented by and the halogen atom represented by R ₁ in the general formula [I] include chlorine, bromine and iodine atoms. To be Also,
In the general formula, X ₁ , X ₂ , X ₃ , X ₄ in the A group represented by and the alkyl group represented by R ₁ and R ₂ in the general formula [I] are not particularly limited and may be linear or branched. The shape is used. Also,
The number of carbon atoms is also not particularly limited, but those having 1 to 6 carbon atoms are preferable from the viewpoint of easy availability of raw materials. Examples of suitable alkyl groups in the present invention include a methyl group, an ethyl group,
n-propyl group, iso-propyl group, t-butyl group, iso
-Butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group and the like. Further, in the general formula [I], Examples of X ₁ , X ₂ , X ₃ , X ₄ in the A group represented by and the group represented by R ₁ in the general formula [I] include all or part of the hydrogen atoms in the alkyl group described above. Those substituted with a halogen atom are preferred. Specific examples of such a halogenoalkyl group include a fluoromethyl group, a chloromethyl group, a bromethyl group, an iodopropyl group, a chlorobutyl group, a difluoromethyl group, a dichloroethyl group, a dibromopropyl group, a silylfluoromethyl group and a trichloromethyl group. Group, tribromopropyl group, pentafluoroethyl group,
Etc. In the general formula [I], The X ₁ , X ₂ , X ₃ , X ₄ in the A group represented by and the alkoxy group represented by R ₁ in the general formula [I] are not particularly limited and may be linear or branched. Is used. The number of carbon atoms is also not particularly limited, but those having 1 to 6 carbon atoms are generally suitable.

Examples of suitable alkoxy groups in the present invention include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-pentoxy group, n-hexoxy group. Groups and the like.

The present invention also has the following general formula [II], [However, Ar is (However, X ₁ , X ₂ , X ₃ and X ₄ are a hydrogen atom, a halogen atom,
An alkyl group, a halogenoalkyl group or an alkoxy group is shown. ), R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, a halogenoalkyl group or an alkoxy group, and R ₂ represents a hydrogen atom or an alkyl group. ] It also provides a fungicide containing the α-substituted phenylacetic acid derivative represented by the following as an active ingredient.

Here, for the compound represented by the general formula [II],
Each group represented by Ar, R ₁ and R ₂ is the same as each group represented by A, R ₁ and R ₂ in the above-mentioned general formula [I]. However,
In Ar The substituent X ₁ in the group includes a hydrogen atom.

The structure of the α-substituted phenylacetic acid derivative represented by the above general formulas [I] and [II] can be confirmed by the following means.

(A) By measuring the infrared absorption spectrum (IR), the absorption based on the CH bond near 3150 to 2800 cm ^-1 , 1650 to
Characteristic absorption based on a carbonyl bond of a carboxyl group or an ester group can be observed near 1780 cm ^-1 . As a specific example, the infrared absorption spectrum of ethyl α-1′-naphthyloxyphenyl acetate is shown in FIG.

(B) Measure each mass spectrum (MS) and observe each
(Generally, ion mass number m is divided by ion charge number e)
Calculate the composition formula corresponding to the value expressed in m / e)
Therefore, the molecular weight of the compound used for measurement and
You can know the bonding mode of each atomic group in the child.
That is, the sample used for measurement is represented by the general formula [I]In general, the molecular ion peak (hereinafter M When
Abbreviated) is the number of halogen atoms contained in the molecule
Accordingly, the intensity ratio is observed according to the isotope abundance ratio.
The molecular weight of the compound used for the measurement can be determined.

Further, regarding the α-substituted phenylacetic acid derivative represented by the above general formula [I], generally, A characteristic peak corresponding to is observed.

(C) by measuring the ¹ H- nuclear magnetic resonance spectra ⁽¹ H-NMR), to know the binding mode of the hydrogen atoms present in the α- substituted phenylacetic acid derivative represented by the general formula [I] it can. As a specific example of ¹ H-NMR (δ-ppm: tetramethylsilane standard, in deuterated chloroform solvent) of the α-substituted phenylacetic acid derivative represented by the general formula [I],
α-1'- ¹ H-NM naphthyl oxyphenyl ethyl acetate
The R diagram is shown in FIG. 2, and the analysis results are as follows.

That is, a triplet corresponding to three protons was observed at 1.13 ppm, which was a methyl group proton (a) in the ethyl group.
Can be attributed to A quartet corresponding to two protons was observed at 4.13 ppm, which can be attributed to the methylene group (b) in the ethyl group. A singlet corresponding to one proton is observed at 5.73 ppm, which can be attributed to the methyl group (c). In addition, a multiplet corresponding to 12 protons was observed at 7.0 to 7.8 ppm, which can be attributed to the proton (d) substituted in the phenyl group and the naphthyl group.

Summarizing the ¹ H-NMR characteristics of the α-substituted phenylacetic acid derivative represented by the above general formula [I], absorption based on the proton of the methine group at the α-position is observed in the singlet at around 5.4 to 6.5 ppm. In addition, multiple lines based on protons substituted on the benzene ring are observed at 6.3 to 7.8 ppm.

(D) When carbon, hydrogen, nitrogen, halogen, and sulfur are contained by elemental analysis, each weight% of sulfur is calculated, and the sum of the recognized weight% of each element is subtracted from 100 to obtain the weight of oxygen. % Can be calculated,
Therefore, the composition formula can be determined.

Further, the α-substituted phenylacetic acid derivative has slightly different properties depending on the types of A, R ₁ and R _{2 in} the above-mentioned general formula [I], but it is generally a colorless or pale yellow viscous liquid at room temperature and normal pressure or It is a solid and often has a high boiling point. Specifically, as shown in a synthesis example described later, the boiling point of the above compound tends to be higher as the molecular weight is larger, like the general organic compounds. The compound is soluble in general organic solvents such as benzene, ether, alcohol, chloroform, carbon tetrachloride, aratonitrile, N, N-dimethylformamide, and dimethylsulfoxide, but is hardly soluble in water.

The α-substituted phenylacetic acid derivative represented by the general formula [I] can be obtained by any method. The following method can be mentioned as a typical manufacturing method.

(I) A method of reacting an aromatic alcohol or an alkali metal aromatic alcoholate with an α-halogenoacetic acid compound or an α-sulfonyloxyacetic acid compound.

[Wherein A, R ₁ and R ₂ are the same as in the case of the general formula [I], M represents a hydrogen atom or an alkali metal, Y ₁ represents a halogen atom or R ₃ —SO ₂ —O— (However, R ₃ has 1 to 1 carbon atoms.
6 represents a phenyl group in which one alkyl group of 6 or one hydrogen atom of a benzene ring is substituted with an alkyl group having 1 to 4 carbon atoms or an unsubstituted phenyl group. ) Represents a group represented by. ] (Ii) A method of reacting a halogenated aromatic compound with an α-hydroxyphenylacetic acid derivative.

(However, in the formula, A, R ₁ and R ₂ are the same as in the case of the general formula [I], and Y ₂ represents a halogen atom.) The reaction represented by the above (i) [hereinafter, the reaction (i) Abbreviated], as the alkali metal of the alkali metal aromatic alcoholate,
Usually, sodium, potassium, lithium and the like are used.
Further, the alkali metal aromatic alcoholate may be formed during the reaction. The conditions for producing the alkali metal aromatic alcoholate may be appropriately determined as necessary, but generally, it can be produced by coexisting an aromatic alcohol and an alkali metal hydroxide or an alkali metal salt in a solvent. Here, as the alkali metal hydroxide, any alkali metal hydroxide described above can be used without any limitation. The alkali metal salt may be the alkali metal salt described above, but generally an alkali metal carbonate is preferably used. Illustrative examples of the alkali metal carbon salt preferably used include sodium carbon, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, barium carbonate, calcium carbonate, lithium carbonate and the like. Further, when the aromatic alcohol is reacted with the α-halogenophenylacetic acid compound in the reaction (i), it is preferable that a catalyst is present. As the catalyst, tertiary amines such as triethylamine, trimethylamine, triethylenediamine and dimethylparatoluidine; nitrogen-containing aromatic bases such as pyridine, picoline, collidine and pyrazine are preferably used.

In the reaction (i), the charged molar ratio of both compounds may be appropriately determined as necessary, but it is common to use equimolar amounts or a slight excess of aromatic alcohol or alkali metal aromatic alcoholate.

In the reaction (i), no solvent may be used, but it is generally preferable to use an organic solvent. Examples of those preferably used as the solvent include aliphatic or aromatic hydrocarbons such as benzene, toluene, xylene, hexane, heptane, petroleum ether, chloroform, methylene chloride and ethylene chloride, or halogenated hydrocarbons. Ethers such as diethyl ether, dioxane and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone;
Nitriles such as acetonitrile; N, N-dialkylamides such as N, N-dimethylformamide and N, N-diethylformamide; dimethylsulfoxide and the like.

The order of adding the raw materials in the reaction (i) is not particularly limited. The reaction temperature can be selected from a wide range,
Generally, it is sufficient to select from the range of -20 ° C to -150 ° C, preferably 0 ° C to 120 ° C. Although the reaction time varies depending on the kind of the raw material, it is usually sufficient to select it in the range of 5 minutes to 10 days, preferably 1 to 40 hours. Further, it is preferable to stir during the reaction. It is sufficient to select from the range of 0 ° C to 120 ° C. Although the reaction time varies depending on the kind of the raw material, it is usually sufficient to select it in the range of 5 minutes to 10 days, preferably 1 to 50 hours. Further, it is preferable to stir during the reaction.

In the reaction represented by the above (ii) (hereinafter abbreviated as the reaction (ii)), the charged molar ratio of both compounds may be appropriately determined as necessary, but it is common to use equimolar amounts. is there. In the reaction (ii), the reaction is generally performed in the presence of an alkali metal, an alkali metal hydride or the like. Examples of the alkali metal include sodium, potassium,
Examples thereof include lithium. The same reaction can be performed by using an alkaline earth metal instead of the alkali metal. In addition, it is generally preferable to use an organic solvent for the reaction (ii), and as the solvent, those used in the reaction (i) are preferably used. A catalyst is preferably used in the reaction (ii). Examples of the catalyst include steel, cuprous iodide, cuprous bromide, cuprous chloride, cuprous oxide, cupric oxide and other metallic copper, or copper compounds such as copper halides and copper oxides. Etc. The conditions such as the reaction temperature and the reaction time in the reaction (ii) can be the same as those in the reaction (i).

Further, in the compound represented by the general formula [I], wherein R ₂ is a hydrogen atom, the reaction (i) or (i
It can also be obtained by hydrolyzing the ester compound in which R ₂ synthesized in i) is an alkyl group. For the hydrolysis reaction, a conventional method such as a method of heating and stirring an ester type compound in an aqueous alkali hydroxide solution can be used without any limitation.

The method for isolating and producing the desired product, that is, the α-substituted phenylacetic acid derivative represented by the general formula [I] from the reaction system is not particularly limited, and a known method can be adopted. For example, in the reactions (i) and (ii), the reaction solvent and excess reaction reagent are distilled off from the reaction solution, and then the residue is converted to chloroform,
Extract with an organic solvent such as benzene or ether. The target substance can be obtained by drying the organic layer with a desiccant such as sodium sulfate and calcium chloride, distilling off the organic solvent, and vacuum-steaming the residue. In addition to isolation and purification by vacuum distillation, purification by chromatography or, if the product is fixed, recrystallization is also possible.

〔effect〕

The 2-substituted phenylacetic acid derivative represented by the above general formula [I] of the present invention exhibits a remarkably excellent effect as a bactericide. The bactericidal activity is found in almost all the compounds represented by the above general formula [I], but there is some difference in the degree depending on the types of A, R ₁ and R ₂ . In particular, the above general formula [I]
In the above, the compound in which R ₁ is a hydrogen atom, a halogen atom or a halogenalkyl group is characterized by exhibiting strong bactericidal activity.

The compound represented by the above general formula [I] of the present invention is, for example,
It can be widely used against various pathogens belonging to basidiomycetes, soybean fungi, ascomycetes, incomplete fungi and bacteria, but is particularly preferably used as an agricultural and horticultural fungicide. In particular, the α-substituted phenylacetic acid compound of the present invention is a bacterial wilt fungus, sesame leaf blight fungus, blast fungus, vine cracker fungus, powdery mildew fungus,
Shows excellent bactericidal activity against white bacteria and Staphylococcus aureus.

Further, the α-substituted phenylacetic acid derivative represented by the general formula [I] affects plant growth and is therefore useful as a paddy field herbicide. The herbicidal activity is somewhat different depending on the types of A, R ₁ and R ₂ , but especially A In, the compounds in which X ₁ , X ₂ , X ₃ and X ₄ are hydrogen atoms or halogen atoms show excellent herbicidal activity and have a safe property for rice.

The α-substituted phenylacetic acid derivative exerts an excellent herbicidal effect on paddy field weeds, but shows a remarkable effect particularly on the treatment of water-bearing soil before and after germination of Cyperaceae weeds and broadleaf weeds. Further, it is a major feature of this compound that it shows no phytotoxicity even in high-dose treatment and transplantation of miscellaneous bacteria to rice, and has high safety.

Further, since the α-substituted phenylacetic acid derivative represented by the general formula [I] affects the growth of plants, a herbicide,
It can also be used as a growth regulator, a defoliant, a germination inhibitor, and a fruit picking agent for sweet citrus.

When the α-substituted phenylacetic acid derivative represented by the above general formula [I] of the present invention is treated as a bactericide, it can be selected in a wide range depending on the subject to be treated. For example, when treating plant parts, concentrations may generally be used between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.
When treating seeds, generally, an amount of 0.001 to 50 g, preferably 0.01 to 10 g of the compound of the present invention may be used per 1 kg of seeds. Further, when treating the soil, generally, a concentration of the compound of the present invention of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, may be treated at the place of action.

When the α-substituted phenylacetic acid derivative represented by the general formula [I] of the present invention is treated as a herbicide, generally 2 g to 2000 g, preferably 50 g to 1500 g per 10 ares is used as an active ingredient amount. good.

The mode of use of the α-substituted phenylacetic acid derivative represented by the general formula [I] of the present invention is not particularly limited, and the mode of use of known herbicides can be used as it is. For example, it can be used in any dosage form such as granules, powders, emulsions, wettable powders, tablets, oils, aerosols, smoke agents, etc. by using an incompatible solid carrier, liquid carrier, emulsifying dispersant and the like. . Of course, auxiliary agents for lumber, such as spreading agents, diluents, surfactants, solvents, etc., can be appropriately added.

The α-substituted phenylacetic acid derivative represented by the above general formula [I] of the present invention can also be used as a mixture with insecticides, other fungicides, other pesticides, fertilizer substances, soil conditioners and the like.

(Examples) In order to more specifically describe the present invention, examples and comparative examples will be described below, but the present invention is not limited to these examples.

Example 1-A 1.2 g of sodium hydroxide, 60 ml of ethanol and 4.32 g of α-naphthol were placed in a 200 ml snubber type flask and stirred at room temperature for 3 hours, and then ethanol was removed by an evaporator. Then, after sufficiently removing ethanol under reduced pressure, 6 g of ethyl α-chlorophenylacetate and 60 ml of N, N-dimethylalumamide were added to the residue.
Was added and the mixture was heated and stirred for 12 hours on an oil bath at 120 ° C. Next, transfer the reaction solution to a separating funnel, add 300 ml of water and extract with ether,
The ether layer was dried over anhydrous sodium sulfate to remove ether and then distilled under reduced pressure to obtain 5.48 g (bp182) of a pale yellow liquid.
℃ / 0.15mmHg) was obtained.

As a result of measuring the infrared absorption spectrum of this product, 3040,2
The absorption at 970,2800 cm ^-1 was due to the C--H bond, and at 1735 cm ^-1 was the strong absorption due to the carbonyl bond of the ester group.
Its elemental analysis C77.80%, formula A H5.82% C ₂₀ H ₁₈
Calculated value for O ₃ (306.369) C78.41%, H5.92%
Well matched.

Also, when the mass spectrum was measured,
To the peak m / e233 corresponding toCorresponding to the peak, m / e163The peak corresponding to

Further, the result of ¹ H-NMR (δ; ppm: tetramethylsilane standard, deuterated chloroform solvent) was as follows.

A triplet corresponding to three protons was shown at 1.13 ppm, which corresponded to the methyl proton of (a) in the ethyl group.

A quartet for two protons was shown at 4.13 ppm, which corresponds to the methyl proton of (b) in the ethyl group.

A singlet for one proton is shown at 5.73 ppm, which corresponds to the methyl proton in (c).

Multiple lines for 12 protons are shown at 7.0-7.8 ppm, (d)
Corresponding to the protons of the benzene ring and naphthalene ring.

From the above results, it became clear that the isolated product was ethyl α-1′-naphthoxyphenylacetate (Compound No. 1).

The yield was 59.7%.

Example 2-B 3.6 g ethyl mandelate, xylene in a 100 ml eggplant-shaped flask
After adding 40 ml and 0.8 g of sodium hydroxide and heating and stirring in an oil bath at 100 ° C, 5.2 g of α-iodonaphthalene and cuprous iodide were added.
2 g was added and the mixture was heated under reflux for 24 hours. Next, the reaction solution was filtered, xylene was distilled off, and the residue was distilled under reduced pressure to obtain 0.9 g of a pale yellow liquid. The infrared absorption spectrum, mass spectrum and ¹ H-nuclear magnetic resonance spectrum of this product were identical with those of Compound No. 1. The yield was 14.7%.

Example 1-C To a 200 ml round-bottomed flask, 6.7 g of ethyl α-p-toluenesulfonyloxyphenylacetate, 80 ml of acetonitr, 2.8 g of well-dried potassium carbonate and 3 g of α-naphthol were placed and heated under reflux for 24 hours. Next, the reaction solution was filtered, acetonitrile was distilled off, and the residue was distilled to obtain 3.7 g of a pale yellow liquid. The infrared absorption spectrum, mass spectrum and ¹ H-nuclear magnetic resonance spectrum of this product were identical with those of Compound No. 1. The yield was 60.5%.

Example 2 The same operation as in Example 1-A was carried out except that 4.32 g of β-naphthol was used as a raw material, and finally α-2′-naphthoxyphenyl was purified by column chromatography (developing solvent: benzene). 0.87 g of ethyl acetate (Compound No. 2) was obtained. The yield was 9.5%. The measurement results of infrared absorption spectrum, elemental analysis, mass spectrum, ¹ H-nuclear magnetic resonance spectrum are shown below.

Infrared absorption spectrum 3050, 2980 cm^-1... based on C-H bond
Absorb 1750 cm^-1... Absorption based on C = O bond Elemental analysis C₂₀H₁₈O₃＝ 306.36 Measured value C78.83% H5.82% Calculated value C78.41% H5.92% Mass spectrum m / e 306 …… M   ¹H-nuclear magnetic resonance spectrum (δ; ppm: telluramethylsilane standard, deuterated chloroform solution)
Medium)(A) 1.04 triplet protons (b) 4.06 quadruple protons (c) 5.73 singlet protons (d) 6.6 to 7.8 multiline protons 11 (e) 8.33 to 8.50 multiplexes One line proton Example 3 Ethyl α-chlorophenylacetate 5 in a 100 ml eggplant-shaped flask
50 ml of N, N-dimethylformamide, well dried and ground
Add 7 g of potassium carbonate and 7.3 g of 2-quinoxalinol to 100
The mixture was heated and stirred for 16 hours on an oil bath at ℃. Put the reactants in a separating funnel.
Transfer, add 300 ml of water, extract with ether, and dry with anhydrous sodium sulfate.
After drying in a column, ether was removed and the residue was subjected to column chromatography.
With topography (developing solvent benzene: acetone = 20: 1)
By purification, α-2'-quinolyl ol of pale yellow liquid was obtained.
Obtained 3.80 g of ethyl xyphenylacetate (Compound No. 3)
It was The yield was 49.1%. The infrared absorption spectrum,
Elemental analysis, mass spectrum,¹H-nuclear magnetic resonance spectrum
The measurement results of are shown below.

Infrared absorption spectrum 2980 cm^-1... Absorption based on CH bond
1750 cm^-1... Absorption based on C = O bond Elemental analysis C₁₉H₁₇NO₃＝ 307.35 Measured value C74.19% H5.46% N4.42% Calculated value C74.25% H5.58% N4.56% Mass spectrum m / e 307… M   ¹H-nuclear magnetic resonance spectrum (δ; ppm: telluramethylsilane standard, deuterated chloroform solution)
Medium)(A) 1.19 triplet protons (b) 4.15 quadruple protons (c) 6.30 singlet protons (d) 6.8 to 8.1 multiplet protons 11 Example 4 100 ml eggplant-shaped flask 30m of 10% aqueous sodium hydroxide solution
l, α-2′-quinolyloxyphene synthesized in Example 3
Add 2.0 g of ethyl nyl acetate (Compound No. 3) and heat it for 18 hours.
Shed Next, after cooling to room temperature, acidify with hydrochloric acid and separate.
The mixture was transferred to a funnel and extracted with chloroform. Chloroform layer
Was dried over anhydrous sodium sulfate and chloroform was distilled off.
Recrystallized with benzene-hexane to give a pale yellow orange
Colored crystals of α-2'-quinolyloxyphenylacetic acid (compound
Product number 4) 0.78 g was obtained. The yield was 42.9%. still,
Infrared absorption spectrum, elemental analysis, mass spectrum,¹H-
The measurement results of the nuclear magnetic resonance spectrum are shown below.

Infrared absorption spectrum 1720 cm^-1... Absorption based on C = O bond
Elemental analysis C₁₇H₁₃NO₃＝ 279.30 Measured value C73.31% H4.67% N5.04% Calculated value C73.11% H4.69% N5.01% Mass spectrum m / e 279… M   ¹H-nuclear magnetic resonance spectrum (δ; ppm: telluramethylsilane standard, deuterated chloroform solution)
Medium)(A) 6.35 1 singlet proton (b) 6.8 to 8.0 11 multiplet protons (c) 9.2 to 9.9 1 singlet proton Example 5 Example except that 4.4 g of 8-quinolinol was used as the starting material.
Perform the same operation as 1-A, and finally distill under reduced pressure.
Is a pale yellow liquid with a boiling point of 180 ° C / 0.15 mmHg, α-
Ethyl 8'-quinolyloxyphenylacetate (Compound number
5) Obtained 3.86 g. The yield was 41.4%. In addition, infrared absorption
Absorption spectrum, elemental analysis, mass spectrum,¹H-nuclear magnetism
The measurement results of the resonance spectrum are shown below.

Infrared absorption spectrum 3050,2970cm^-1... Based on C-H bond
Tsukuba absorption 1740 cm^-1... Absorption based on C = O bond Elemental analysis C₁₉H₁₇NO₃= 307.35 Measured value C74.20% H5.57% N4.58% Calculated value C74.25% H5.58% N4.56% Mass spectrum m / e 308… M   ¹H-nuclear magnetic resonance spectrum (δ; ppm: telluramethylsilane standard, deuterated chloroform solution)
Medium)(A) 1.08 triplet protons (b) 4.11 quadruple protons (c) 6.08 singlet protons (d) 6.9 to 8.1 multiplet protons (e) 8.7 to 8.9 multiplexes One line proton Example 6 Except that 2.92 g of 2-quinoxalinol was used as a raw material.
The same operation as in Example 1-A was performed, and finally the column cross
It can be purified by means of chromatography (developing solvent benzene).
With α-2'-quinoxalyloxyphenylacetic acid
1.04 g of chill (Compound No. 6) was obtained. Yield is 16.8%
It was. In addition, infrared absorption spectrum, elemental analysis, mass spectrum
Tor,¹The measurement results of the H-nuclear magnetic resonance spectrum are shown below.
You

Infrared absorption spectrum 3050,2970cm^-1... Based on C-H bond
Absorption 1730cm^-1... Absorption based on C = O bond Elemental analysis C₁₈H₁₆N₂O₃= 308.34 Measured value C70.09% H5.08% N9.02% Calculated value C70.12% H5.23% N9.09% Mass spectrum m / e 308… M   ¹H-nuclear magnetic resonance spectrum (δ; ppm: tetramethylsilane standard, deuterated chloroform solution)
Medium)(A) 1.20 triplet protons (b) 4.17 quadruple protons (c) 6.28 singlet protons (d) 7.2-8.1 multiplet protons 9 (e) 8.55 singlet protons One example Example 7 Except that 2.7 g of benzoxazolinone was used as a raw material.
The same operation as in Example 1-A was performed, and finally column chromatography was performed.
Purified by chromatography (developing solvent chloroform) and α-
Ethyl 2'-benzoxazolylphenylacetate (compound
No. 7) 2.94 g was obtained. The yield was 51.7%. Incidentally, red
External absorption spectrum, elemental analysis, mass spectrum,¹H-Nucleus
The measurement results of the magnetic resonance spectrum are shown below.

Infrared absorption spectrum 2980,2940cm^-1... Based on C-H bond
Tsukuba absorption 1760 cm^-1... Absorption based on C = O bond Elemental analysis C₁₇H₁₅NO_Four= 297.31 Measured value C68.42% H5.06% N5.07% Calculated value C68.68% H5.09% N4.71% Mass spectrum m / e 297… M   ¹H-nuclear magnetic resonance spectrum (δ; ppm: tetramethylsilane standard, deuterated chloroform solution)
Medium)(A) 1.26 triplet protons (b) 4.28 quadruple protons (c) 6.20 singlet protons (d) 6.5-7.2 multiplet protons (e) 7.30 singlet protons 5 pieces Example 8 In Example 3, the raw material compounds used are replaced with those shown in Table 1.
The described α-substituted phenylacetic acid derivatives were synthesized. Synthesis
The compound is a colorless or pale yellow viscous liquid or solid.
In the infrared absorption spectrum, 1650 to 1780 cm^-1Carboni
The characteristic absorption based on the Ru coupling is shown. It was obtained in Table 1.
The structure, yield, and elemental analysis value of the compound are also shown.

Formulation Example 1 (wettable powder) 10 parts by weight of the compound synthesized in Example 1, 2 parts by weight of polyoxyethylene nonylphenyl ether, 40 parts by weight of finely powdered clay, and 48 parts by weight of Zyklite were pulverized and mixed by a hammer mill to give 10 % Wettable powder was obtained.

Formulation Example 2 (emulsion) 20% by weight of the compound synthesized in Example 3, 70 parts by weight of xylene, 5 parts by weight of polyoxyethylene alkylallyl ether, and 5 parts by weight of sodium alkylbenzene sulfonate are mixed and dissolved to obtain a 20% emulsion. It was

Formulation Example 3 (granule) 10 parts by weight of the compound (Compound No. 6) synthesized in Example 6,
1 part by weight of dioctyl succinate, 3 parts by weight of sodium lignin sulfonate, 30 parts by weight of bentonite, and talc 56
After mixing and pulverizing parts by weight, water was added and kneaded, and then the mixture was granulated and dried, and then granulated to 14 to 32 mesh to obtain 10% granules.

Example 9 A nutrient medium containing 1.5% agar was sterilized by heating at 121 ° C. for 15 minutes, then cooled to 50 ° C., and a suspension of pre-grown cells or spores in sterile water was added. The mixture was mixed well, poured into a dish, and solidified into a flat plate. Example 1
Dip a circular paper with a diameter of 8 mm into a methanol solution containing about 15% of the compound Nos. 1 to 7 synthesized in
The surplus was removed on paper and placed on solidified agar medium.
After culturing at 30 ° C for 24 to 96 hours, the diameter of the inhibition circle was measured.

The bacteria used are shown below.

Escherichic coli B: Escherichic coli Batillus subtilis (natto Sawamura): (Bacillus subtilis) Aspergillus niger: (Black mold) Cochliobolus miyabeanus: (Sesame leaf blight) Trichophyton rubrum: (Hydrophyte) Fusarium oxysporum: (Bacterial wilt) Antibacterial The test results are shown in Table 2.

Example 10 The compound shown in Table 1 was subjected to an antibacterial test in the same manner as in Example 9, and the diameter of the inhibition circle was measured. The results are shown in Table 3. In addition, Table 3 also shows the test results of the following compounds as comparative examples.

Example 11 The leaves of a wheat seedling grown in a porcelain pot having a diameter of 12 cm were sprayed with a predetermined amount of a 50% wettable powder of each compound diluted with water, and the next day, the powdery mildew of wheat (Erysiphe graminis De CANDOLL
E) sprinkled with spores. 2 experimental plants in the greenhouse
It was left at a temperature of 0-25 ° C and a relative air humidity of 75-80%. The result of examining the incidence of powdery mildew 7 days later
Shown in the table.

The evaluation was carried out by observing the observation results in 5 stages from- (no disease occurrence) to (complete disease occurrence).

Evaluation -... No illness occurrence ± ... Slight illness + ... Slight illness Soft leaf damage ... Moderate onset. Moderate leaf damage ... complete illness. Severe leaf damage Example 12 A rice pot (variety: Akinishiki) at the 3 leaf stage was filled to a depth of 2 cm after filling a 1/8850 arm porcelain pot with water and stirring the paddy soil (alluvial soil) and sowing the paddy weeds. It was transplanted, and water was added to make it water resistant to 2 cm. Then, a predetermined amount of a water-diluted solution of a wettable powder of each compound was dropped at the time of germination of weeds. After the treatment, the plants were grown in a greenhouse at an average temperature of 25 ° C., and after 3 weeks, the herbicidal effect of each test compound was investigated and the results are shown in Table 5. The evaluation has 6 levels, and the evaluation of herbicidal effect is 0 to 5 as follows.
It was represented by the number.

0… Weed control rate 0-9% 1… 〃 10-29% 2… 〃 30-49% 3… 〃 50-69% 4… 〃 70-89% 5… 〃 90-100% Plant height for phytotoxicity of transplanted rice , The number of divisions, and the ratio of the total amount (air dried amount) to the untreated area were calculated, and the worst one of the three factors was taken and evaluated from 0 to 5.

0… to untreated area ratio 100% 1… 〃 90 to 99% 2… 〃 80 to 89% 3… 〃 60 to 79% 4… 〃 40 to 59% 5… 〃 0 to 39%

[Brief description of drawings]

1 and 2 show the infrared absorption spectrum and ₁ H-nuclear magnetic resonance spectrum of ethyl α-1′-naphthyloxyphenylacetate obtained in Example 1, respectively.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 69/734 Z 9546-4H C07D 215/20 215/22 215/26 241/44 263/58

Claims (2)

[Claims] 1. A general formula [However, A is (However, X ₁ represents a halogen atom, an alkyl group, a halogenoalkyl group or an alkoxy group, and X ₂ , X ₃ and X ₄ represent a hydrogen atom, a halogen atom, an alkyl group, a halogenoalkyl or an alkoxy group). R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, a halogenoalkyl group or an alkoxy group, and R ₂ represents a hydrogen atom or an alkyl group. ] Α-Substituted phenylacetic acid derivative represented by 2. General formula [However, Ar is (However, X ₁ , X ₂ , X ₃ and X ₄ are a hydrogen atom, a halogen atom,
An alkyl group, a halogenoalkyl group or an alkoxy group is shown. ), R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, a halogenoalkyl group or an alkoxy group, and R ₂ represents a hydrogen atom or an alkyl group. ] A disinfectant containing an α-substituted phenylacetic acid derivative represented by the following as an active ingredient.