WO2012042608A1 - 3-aminobenzoic acid derivative and method for producing same - Google Patents
3-aminobenzoic acid derivative and method for producing same Download PDFInfo
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- WO2012042608A1 WO2012042608A1 PCT/JP2010/066908 JP2010066908W WO2012042608A1 WO 2012042608 A1 WO2012042608 A1 WO 2012042608A1 JP 2010066908 W JP2010066908 W JP 2010066908W WO 2012042608 A1 WO2012042608 A1 WO 2012042608A1
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- 0 *C(c1cccc(NC(C(N*)=O)=O)c1)=O Chemical compound *C(c1cccc(NC(C(N*)=O)=O)c1)=O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/56—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having carbon atoms of carboxamide groups bound to carbon atoms of carboxyl groups, e.g. oxamides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/46—N-acyl derivatives
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
Definitions
- the present invention relates to a novel 3-aminobenzoic acid derivative and a method for producing the same.
- 3-Oxamoylaminobenzamide derivatives are known to have insecticidal and acaricidal activity (for example, Patent Documents 1 and 2).
- An object of the present invention is to provide a novel 3-aminobenzoic acid derivative useful as an intermediate in the production of a 3-oxamoylaminobenzamide derivative and a method for producing the same.
- the present invention provides the following general formula [I]: ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ [I] (Wherein, R 1 is alkoxy of C 1 ⁇ represents an alkyl group of C 4 .R 2 is .R 3 represents an alkyl group which may be C 1 ⁇ C 4 substituted with a fluorine atom C 1 ⁇ C 4 Group or a hydroxyl group.) And a method for producing the same.
- the 3-aminobenzoic acid derivative of the present invention is represented by the following general formula [I]. ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ [I]
- R 1 is alkoxy of C 1 ⁇ represents an alkyl group of C 4 .
- R 2 is .
- R 3 represents an alkyl group which may be C 1 ⁇ C 4 substituted with a fluorine atom C 1 ⁇ C 4 Group or hydroxyl group.
- the C 1 -C 4 alkyl group represented by R 1 is a linear or branched alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Preferred examples include n-butyl group, isobutyl group, sec-butyl group and tert-butyl group.
- the alkyl part of the C 1 -C 4 alkyl group which may be substituted with a fluorine atom represented by R 2 is a linear or branched alkyl group such as a methyl group, ethyl group, Preferred examples include a group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. If substituted by fluorine atoms have been made, the number of fluorine atoms 1-9, preferably 1-5.
- Examples of the C 1 -C 4 alkyl group substituted with a fluorine atom include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, and 2,2-difluoro.
- the C 1 -C 4 alkoxy group represented by R 3 is a linear or branched alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, or an isopropoxy group. , n- butoxy group, isobutoxy group, sec- butoxy group, etc. tert- butoxy group suitably.
- the compound of the present invention represented by the general formula [I] is represented by the following general formula [II]: ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ [II]
- R 3 is as defined in the general formula [I]. It is obtained by reacting with a 3-aminobenzoic acid derivative represented by:
- R 1 and R 2 are as defined in the general formula [I].
- R 3 is as defined in the general formula [I].
- Suitable examples of the halogen atom for X include chlorine and bromine.
- the acid halide of the general formula [II] and the 3-aminobenzoic acid derivative of the general formula [III] are both known compounds or can be easily synthesized according to known methods.
- the reaction of the acid halide of the general formula [II] and the 3-aminobenzoic acid derivative of the general formula [III] can be performed in the presence of a solvent and in the presence or absence of a base.
- the solvent is not particularly limited as long as it does not directly participate in this reaction, and for example, aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; chloroform and Halogenated hydrocarbons such as methylene chloride; esters such as methyl acetate and ethyl acetate; or ethers such as tetrahydrofuran, dioxane, diethyl ether and 1,2-dimethoxyethane; water; acetonitrile and N, N - dimethylformamide, N- methylpyrrolidone, a mixed solvent of polar solvents or the solvent such as dimethyl sul
- Bases include organic bases such as triethylamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 4-dimethylaminopyridine; alkali metals such as sodium hydroxide and potassium hydroxide Hydroxides; alkaline earth metal hydroxides such as calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate; alkali metal hydrogen carbonates such as sodium bicarbonate Salts; metal alkoxides such as sodium methoxide and potassium ethoxide.
- the reaction temperature is, for example, ⁇ 30 ° C. to 150 ° C., preferably ⁇ 5 ° C. to 80 ° C.
- the target product can be isolated from the reaction system by a conventional method. If necessary, it can be further purified by washing with a solvent, recrystallization, column chromatography and the like.
- R 1 and R 2 are as defined in the general formula [I], and R 4 represents a C 1 -C 4 alkyl group.
- the ester represented by can also be obtained by a hydrolysis reaction using an alkali metal salt.
- the ester represented by the general formula [IV] is a compound in which R 3 is a C 1 -C 4 alkoxy group in the general formula [I]. Therefore, the ester represented by the general formula [IV] can be obtained according to the method for producing the compound represented by the above general formula [I].
- the hydrolysis reaction of the ester represented by the general formula [IV] can be carried out in the presence or absence of a solvent and in the presence of a base.
- a solvent for example, water; methanol, ethanol, propanol, a mixed solvent of an alcohol or the solvent such as ethylene glycol.
- Bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonate sodium, an alkali metal carbonate such as potassium hydrogen carbonate; calcium carbonate, alkaline earth metal carbonates such as magnesium carbonate.
- the reaction temperature is, for example, 5 to 150 ° C., preferably 10 to 110 ° C.
- isolation of the target compound is made acidic with mineral acids such as hydrochloric acid and sulfuric acid and / or organic acids such as acetic acid and propionic acid, and then the precipitate is collected by filtration, washed with water and dried. It can be carried out.
- the compound of the present invention represented by the general formula [I] can be used as an intermediate for producing a 3-oxamoylaminobenzamide derivative having insecticidal and acaricidal activity.
- 3-oxamoylaminobenzoic acid represented by the general formula [V] is reacted with a halogenating agent to form an acid halide represented by the general formula [VI].
- a 3-oxamoylaminobenzamide derivative represented by the general formula [VIII] can be produced by reacting with the aniline derivative represented by the general formula [VII].
- R 1 and R 2 in the general formulas [V], [VI] and [VIII] are as defined in the general formula [I].
- R 5 and R 6 in the general formulas [VII] and [VIII] each independently represent a C 1 to C 4 alkyl group or a halogen atom.
- the C 1 -C 4 alkyl group represented by R 5 and R 6 is a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, isopropyl, n- butyl group, isobutyl group, sec- butyl group, a tert- butyl group are preferably exemplified.
- the compound represented by the general formula [V] is a compound wherein R 3 is a hydroxyl group in the general formula [I].
- the compound represented by the general formula [V] is obtained by subjecting the compound of the general formula [I] where R 3 is a C 1 -C 4 alkoxy group to a hydrolysis reaction using the above alkali metal salt. Can be obtained.
- halogenating agent to be reacted with 3-oxamoylaminobenzoic acid represented by the general formula [V] include thionyl chloride, phosphorus oxychloride and thionyl bromide.
- the reaction between 3-oxamoylaminobenzoic acid represented by the general formula [V] and the halogenating agent can be carried out in the presence or absence of a solvent and in the presence or absence of a base.
- the solvent include benzene, toluene and xylene.
- the reaction temperature is, for example, 50 to 140 ° C., preferably 70 to 110 ° C.
- the target acid halide represented by the general formula [VI] can be isolated and / or purified from the reaction system by a conventional method.
- the reaction between the acid halide represented by the general formula [VI] and the aniline derivative represented by the general formula [VII] should be carried out in the presence or absence of a solvent and in the presence or absence of a base. Can do.
- the aniline derivative represented by the general formula [VII] is a known compound or can be easily synthesized according to a known method.
- the solvent include DMI (1,3-dimethyl-2-imidazolidinone) and N-methylpyrrolidone.
- the reaction temperature is, for example, 10 to 150 ° C., preferably 20 to 100 ° C.
- the target 3-oxamoylaminobenzamide derivative represented by the general formula [VIII] can be isolated and / or purified from the reaction system by a conventional method.
- a 3-oxamoylaminobenzamide derivative By using the 3-aminobenzoic acid derivative represented by the general formula [I] of the present invention as a production intermediate, a 3-oxamoylaminobenzamide derivative can be obtained with high purity and high yield.
- the obtained 3-oxamoylaminobenzamide derivative can be used as an active ingredient of insecticides and acaricides as described in Patent Documents 1 and 2.
- Example 1 Synthesis of 3- [N-methyl-N- (2,2,2-trifluoroethyl) oxamoylamino] benzoic acid 2.74 g of 3-aminobenzoic acid was suspended in 50 ml of water and 5.04 g of sodium bicarbonate was added. . Under ice cooling (5-10 ° C), a THF solution of 3.34 g of N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride was added dropwise and stirred for 2 hours. The precipitated crystals were filtered, washed with water, and dried to obtain 3.21 g of the desired product. The melting point was 157-159 ° C.
- Example 2 Synthesis of methyl 3- [N-methyl-N- (2,2,2-trifluoroethyl) oxamoylamino] benzoate After dissolving 3.02g of methyl 3-aminobenzoate in 20ml of THF and adding 3.1ml of triethylamine , 4.27 g of N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride was added dropwise under ice cooling (5 to 10 ° C.). The reaction mixture is filtered and the precipitate deposited was added dilute hydrochloric acid to, washed with water to obtain the desired compound 5.79g and dried. The melting point was 117-119 ° C.
- Example 3 Synthesis of methyl 3- (N-ethyl-N-methyloxamoylamino) benzoate Instead of N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride, N-ethyl-N-methyl The compound was synthesized by the same procedure as in Example 2 except that oxamoyl chloride was used.
- Example 4 Synthesis of 3- (N-ethyl-N-methyloxamoylamino) benzoic acid N-ethyl-N-methyloxamoyl instead of N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride
- the compound was synthesized by the same procedure as in Example 1 except that chloride was used.
- the melting point was 168-171 ° C.
- Example 5 Synthesis of methyl 3- (N- (t-butyl) -N-methyloxamoylamino) benzoate N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride instead of N- ( The compound was synthesized by the same procedure as in Example 2 except that t-butyl) -N-methyloxamoyl chloride was used. The melting point was 144-146 ° C.
- Example 6 Synthesis of 3- [N- (t-butyl) -N-methyloxamoylamino] benzoic acid 1.75 g of the benzoic acid methyl ester obtained in Example 5 was suspended in 5 ml of methanol and 2 ml of water, and 20% hydroxylated. under ice-cooling an aqueous solution of sodium 2.52g (5 ⁇ 10 °C) after the addition, the reaction mixture was cooled to room temperature. Dilute hydrochloric acid was added to acidify the reaction solution, and the precipitated crystals were filtered, washed with water, and dried to obtain 1.67 g of the desired product. The melting point was 174 ° C. (decomposition).
- Reference example 2 Synthesis of 3- [N-methyl-N- (2,2,2-trifluoroethyl) oxamoylamino] -N- (2,6-dimethyl-4-heptafluoroisopropyl) phenylbenzamide 2,6-Dimethyl- Dissolve 5.78 g of 4-heptafluoroisopropylaniline and 7.75 g of the acid chloride obtained in Reference Example 1 in 40 ml of DMI (1,3-dimethyl-2-imidazolidinone) and react at room temperature (20-25 ° C) for 10 hours.
- DMI 1,3-dimethyl-2-imidazolidinone
- Reference Example 3 Insecticidal effect on the larvae of the diamondback moth The seeds were raised for 3 weeks after sowing seeds in a jiffy pot. A water-diluted solution of an emulsion containing the compound obtained in Reference Example 2 as an active ingredient was sufficiently sprayed onto the leaves of this pot planted plant using an airbrush (one concentration, one repetition). After the chemical solution was air-dried, it was kept in a constant temperature room at 25 ° C., and after 5 days of larvae, mortality and bitterness of the larvae were investigated, and the insecticidal rate (%) was determined by dying the bitter worm. The compound of Reference Example 2 showed an insecticidal rate of 100% at a concentration of 500 ppm.
- the present invention can be used for the production of 3-oxamoylaminobenzamide derivatives having insecticidal and acaricidal activity.
Abstract
Provided is a novel 3-aminobenzoic acid derivative, said derivative being useful as an intermediate in the production of a 3-oxamoylaminobenzamide derivative which has a pesticidal and miticidal activity, and a method for producing the same.
The 3-aminobenzoic acid derivative is represented by general formula [I].
In general formula [I]: R1 represents a C1 to C4 alkyl group; R2 represents an optionally fluorinated C1 to C4 alkyl group; and R3 represents a C1 to C4 alkoxy group or a hydroxyl group.
Description
本発明は、新規な3-アミノ安息香酸誘導体およびその製造方法に関する。
The present invention relates to a novel 3-aminobenzoic acid derivative and a method for producing the same.
3-オキサモイルアミノベンズアミド誘導体は、殺虫及び殺ダニ活性を有することが知られている（例えば特許文献１～２）。
3-Oxamoylaminobenzamide derivatives are known to have insecticidal and acaricidal activity (for example, Patent Documents 1 and 2).
本発明は、3-オキサモイルアミノベンズアミド誘導体の製造における中間体として有用な、新規な3-アミノ安息香酸誘導体およびその製造法を提供することを目的とする。
An object of the present invention is to provide a novel 3-aminobenzoic acid derivative useful as an intermediate in the production of a 3-oxamoylaminobenzamide derivative and a method for producing the same.
本発明者らは、前記課題を解決すべく鋭意努力した結果、下記一般式[I]で表される化合物を使用することにより、殺虫及び殺ダニ活性を有する3-オキサモイルアミノベンズアミド誘導体を高純度かつ高収率で容易に合成することができることを見出し、本発明に到達したものである。
即ち、本発明は、下記一般式[I]：
・・・・・・[I]
（式中、Ｒ1はＣ1～Ｃ4のアルキル基を示す。Ｒ2はフッ素原子で置換されてもよいＣ1～Ｃ4のアルキル基を示す。Ｒ3はＣ1～Ｃ4のアルコキシ基またはヒドロキシル基を示す。）で表される化合物及びその製造方法に関するものである。 As a result of diligent efforts to solve the above problems, the present inventors have increased the 3-oxamoylaminobenzamide derivative having insecticidal and acaricidal activity by using a compound represented by the following general formula [I]. It found that can be readily synthesized in purity and in high yield is obtained by reaching the present invention.
That is, the present invention provides the following general formula [I]:
・ ・ ・ ・ ・ ・ [I]
(Wherein, R 1 is alkoxy of C 1 ~ represents an alkyl group of C 4 .R 2 is .R 3 represents an alkyl group which may be C 1 ~ C 4 substituted with a fluorine atom C 1 ~ C 4 Group or a hydroxyl group.) And a method for producing the same.
即ち、本発明は、下記一般式[I]：
（式中、Ｒ1はＣ1～Ｃ4のアルキル基を示す。Ｒ2はフッ素原子で置換されてもよいＣ1～Ｃ4のアルキル基を示す。Ｒ3はＣ1～Ｃ4のアルコキシ基またはヒドロキシル基を示す。）で表される化合物及びその製造方法に関するものである。 As a result of diligent efforts to solve the above problems, the present inventors have increased the 3-oxamoylaminobenzamide derivative having insecticidal and acaricidal activity by using a compound represented by the following general formula [I]. It found that can be readily synthesized in purity and in high yield is obtained by reaching the present invention.
That is, the present invention provides the following general formula [I]:
(Wherein, R 1 is alkoxy of C 1 ~ represents an alkyl group of C 4 .R 2 is .R 3 represents an alkyl group which may be C 1 ~ C 4 substituted with a fluorine atom C 1 ~ C 4 Group or a hydroxyl group.) And a method for producing the same.
以下、本発明について、詳細に説明する。
本発明の3-アミノ安息香酸誘導体は、下記一般式[I]で示される。
・・・・・・[I]
Hereinafter, the present invention will be described in detail.
The 3-aminobenzoic acid derivative of the present invention is represented by the following general formula [I].
・ ・ ・ ・ ・ ・ [I]
本発明の3-アミノ安息香酸誘導体は、下記一般式[I]で示される。
The 3-aminobenzoic acid derivative of the present invention is represented by the following general formula [I].
（式中、Ｒ1はＣ1～Ｃ4のアルキル基を示す。Ｒ2はフッ素原子で置換されてもよいＣ1～Ｃ4のアルキル基を示す。Ｒ3はＣ1～Ｃ4のアルコキシ基またはヒドロキシル基を示す。）
Ｒ1で表されるＣ1～Ｃ4のアルキル基としては、直鎖状でも分岐を有していてもよいアルキル基であり、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基などが好適に挙げられる。
Ｒ2で表されるフッ素原子で置換されてもよいＣ1～Ｃ4のアルキル基のアルキル部分は、直鎖状でも分岐を有していてもよいアルキル基であり、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基などが好適に挙げられる。フッ素原子による置換がなされている場合、フッ素原子の数は１～９、好ましくは１～５である。フッ素原子で置換されたＣ1～Ｃ4のアルキル基としては、例えば、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、1-フルオロエチル基、2-フルオロエチル基、2,2-ジフルオロエチル基、2,2,2-トリフルオロエチル基、ペンタフルオロエチル基、3-フルオロプロピル基、1,3-ジフルオロ-2-プロピル基、3,3,3-トリフルオロプロピル基、1,1,1-トリフルオロ-2-プロピル基、1,1,1,3,3,3-ヘキサフルオロ-2-プロピル基、2,2,3,3,3-ペンタフルオロプロピル基、ヘプタフルオロイソプロピル基、ヘプタフルオロ-n-プロピル基、4-フルオロブチル基、4,4,4-トリフルオロブチル基、ノナフルオロ-n-ブチル基、ノナフルオロ-2-ブチル基などが好適に挙げられる。
Ｒ3で表されるＣ1～Ｃ4のアルコキシ基としては、直鎖状でも分岐を有していてもよいアルコキシ基であり、例えば、メトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、sec-ブトキシ基、tert-ブトキシ基などが好適に挙げられる。 (Wherein, R 1 is alkoxy of C 1 ~ represents an alkyl group of C 4 .R 2 is .R 3 represents an alkyl group which may be C 1 ~ C 4 substituted with a fluorine atom C 1 ~ C 4 Group or hydroxyl group.)
The C 1 -C 4 alkyl group represented by R 1 is a linear or branched alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Preferred examples include n-butyl group, isobutyl group, sec-butyl group and tert-butyl group.
The alkyl part of the C 1 -C 4 alkyl group which may be substituted with a fluorine atom represented by R 2 is a linear or branched alkyl group such as a methyl group, ethyl group, Preferred examples include a group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. If substituted by fluorine atoms have been made, the number of fluorine atoms 1-9, preferably 1-5. Examples of the C 1 -C 4 alkyl group substituted with a fluorine atom include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, and 2,2-difluoro. Ethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 1,3-difluoro-2-propyl group, 3,3,3-trifluoropropyl group, 1,1 , 1-trifluoro-2-propyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, 2,2,3,3,3-pentafluoropropyl group, heptafluoroisopropyl group Suitable examples include heptafluoro-n-propyl group, 4-fluorobutyl group, 4,4,4-trifluorobutyl group, nonafluoro-n-butyl group, nonafluoro-2-butyl group and the like.
The C 1 -C 4 alkoxy group represented by R 3 is a linear or branched alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, or an isopropoxy group. , n- butoxy group, isobutoxy group, sec- butoxy group, etc. tert- butoxy group suitably.
Ｒ1で表されるＣ1～Ｃ4のアルキル基としては、直鎖状でも分岐を有していてもよいアルキル基であり、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基などが好適に挙げられる。
Ｒ2で表されるフッ素原子で置換されてもよいＣ1～Ｃ4のアルキル基のアルキル部分は、直鎖状でも分岐を有していてもよいアルキル基であり、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基などが好適に挙げられる。フッ素原子による置換がなされている場合、フッ素原子の数は１～９、好ましくは１～５である。フッ素原子で置換されたＣ1～Ｃ4のアルキル基としては、例えば、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、1-フルオロエチル基、2-フルオロエチル基、2,2-ジフルオロエチル基、2,2,2-トリフルオロエチル基、ペンタフルオロエチル基、3-フルオロプロピル基、1,3-ジフルオロ-2-プロピル基、3,3,3-トリフルオロプロピル基、1,1,1-トリフルオロ-2-プロピル基、1,1,1,3,3,3-ヘキサフルオロ-2-プロピル基、2,2,3,3,3-ペンタフルオロプロピル基、ヘプタフルオロイソプロピル基、ヘプタフルオロ-n-プロピル基、4-フルオロブチル基、4,4,4-トリフルオロブチル基、ノナフルオロ-n-ブチル基、ノナフルオロ-2-ブチル基などが好適に挙げられる。
Ｒ3で表されるＣ1～Ｃ4のアルコキシ基としては、直鎖状でも分岐を有していてもよいアルコキシ基であり、例えば、メトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、sec-ブトキシ基、tert-ブトキシ基などが好適に挙げられる。 (Wherein, R 1 is alkoxy of C 1 ~ represents an alkyl group of C 4 .R 2 is .R 3 represents an alkyl group which may be C 1 ~ C 4 substituted with a fluorine atom C 1 ~ C 4 Group or hydroxyl group.)
The C 1 -C 4 alkyl group represented by R 1 is a linear or branched alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Preferred examples include n-butyl group, isobutyl group, sec-butyl group and tert-butyl group.
The alkyl part of the C 1 -C 4 alkyl group which may be substituted with a fluorine atom represented by R 2 is a linear or branched alkyl group such as a methyl group, ethyl group, Preferred examples include a group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. If substituted by fluorine atoms have been made, the number of fluorine atoms 1-9, preferably 1-5. Examples of the C 1 -C 4 alkyl group substituted with a fluorine atom include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, and 2,2-difluoro. Ethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 1,3-difluoro-2-propyl group, 3,3,3-trifluoropropyl group, 1,1 , 1-trifluoro-2-propyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, 2,2,3,3,3-pentafluoropropyl group, heptafluoroisopropyl group Suitable examples include heptafluoro-n-propyl group, 4-fluorobutyl group, 4,4,4-trifluorobutyl group, nonafluoro-n-butyl group, nonafluoro-2-butyl group and the like.
The C 1 -C 4 alkoxy group represented by R 3 is a linear or branched alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, or an isopropoxy group. , n- butoxy group, isobutoxy group, sec- butoxy group, etc. tert- butoxy group suitably.
一般式[I]で表される本発明の化合物は、下記一般式[II]：
・・・・・・[II]
The compound of the present invention represented by the general formula [I] is represented by the following general formula [II]:
・ ・ ・ ・ ・ ・ [II]
（式中、Ｒ1およびＲ2は前記一般式[I]で定義したとおりであり、Ｘはハロゲン原子を示す。）
で表される酸ハライドを、
下記一般式[III]：
・・・・・・[III]
(In the formula, R 1 and R 2 are as defined in the general formula [I], X is a halogen atom.)
An acid halide represented by
The following general formula [III]:
・ ・ ・ ・ ・ ・ [III]
で表される酸ハライドを、
下記一般式[III]：
An acid halide represented by
The following general formula [III]:
（式中、Ｒ3は前記一般式[I]で定義したとおりである。）
で表される3-アミノ安息香酸誘導体と反応させることにより得られる。
一般式[II]において、Ｒ1およびＲ2は前記一般式[I]で定義したとおりである。
一般式[III]において、Ｒ3は前記一般式[I]で定義したとおりである。Ｘのハロゲン原子としては、例えば、塩素や臭素などが好適に挙げられる。
一般式[II]の酸ハライド及び一般式[III]の3-アミノ安息香酸誘導体は、いずれも公知の化合物であるか、または公知の方法に従って容易に合成することができる。 (In the formula, R 3 is as defined in the general formula [I].)
It is obtained by reacting with a 3-aminobenzoic acid derivative represented by:
In the general formula [II], R 1 and R 2 are as defined in the general formula [I].
In the general formula [III], R 3 is as defined in the general formula [I]. Suitable examples of the halogen atom for X include chlorine and bromine.
The acid halide of the general formula [II] and the 3-aminobenzoic acid derivative of the general formula [III] are both known compounds or can be easily synthesized according to known methods.
で表される3-アミノ安息香酸誘導体と反応させることにより得られる。
一般式[II]において、Ｒ1およびＲ2は前記一般式[I]で定義したとおりである。
一般式[III]において、Ｒ3は前記一般式[I]で定義したとおりである。Ｘのハロゲン原子としては、例えば、塩素や臭素などが好適に挙げられる。
一般式[II]の酸ハライド及び一般式[III]の3-アミノ安息香酸誘導体は、いずれも公知の化合物であるか、または公知の方法に従って容易に合成することができる。 (In the formula, R 3 is as defined in the general formula [I].)
It is obtained by reacting with a 3-aminobenzoic acid derivative represented by:
In the general formula [II], R 1 and R 2 are as defined in the general formula [I].
In the general formula [III], R 3 is as defined in the general formula [I]. Suitable examples of the halogen atom for X include chlorine and bromine.
The acid halide of the general formula [II] and the 3-aminobenzoic acid derivative of the general formula [III] are both known compounds or can be easily synthesized according to known methods.
一般式[II]の酸ハライドと一般式[III]の3-アミノ安息香酸誘導体との反応は、溶媒の存在下、かつ、塩基の存在下又は非存在下行うことができる。
溶媒としては、本反応に直接関与しないものであれば、特に限定されず、例えばベンゼンや、トルエン、キシレンなどの芳香族炭化水素類;アセトンや、メチルエチルケトン、メチルイソブチルケトンなどのケトン類;クロロホルムや、塩化メチレンなどのハロゲン化炭化水素類;酢酸メチルや、酢酸エチルなどのエステル類;又はテトラヒドロフランや、ジオキサン、ジエチルエーテル、1,2-ジメトキシエタンなどのエーテル類;水;アセトニトリルや、N,N-ジメチルホルムアミド、N-メチルピロリドン、ジメチルスルホキシドなどの極性溶媒類又は前記溶媒の混合溶媒が挙げられる。 The reaction of the acid halide of the general formula [II] and the 3-aminobenzoic acid derivative of the general formula [III] can be performed in the presence of a solvent and in the presence or absence of a base.
The solvent is not particularly limited as long as it does not directly participate in this reaction, and for example, aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; chloroform and Halogenated hydrocarbons such as methylene chloride; esters such as methyl acetate and ethyl acetate; or ethers such as tetrahydrofuran, dioxane, diethyl ether and 1,2-dimethoxyethane; water; acetonitrile and N, N - dimethylformamide, N- methylpyrrolidone, a mixed solvent of polar solvents or the solvent such as dimethyl sulfoxide.
溶媒としては、本反応に直接関与しないものであれば、特に限定されず、例えばベンゼンや、トルエン、キシレンなどの芳香族炭化水素類;アセトンや、メチルエチルケトン、メチルイソブチルケトンなどのケトン類;クロロホルムや、塩化メチレンなどのハロゲン化炭化水素類;酢酸メチルや、酢酸エチルなどのエステル類;又はテトラヒドロフランや、ジオキサン、ジエチルエーテル、1,2-ジメトキシエタンなどのエーテル類;水;アセトニトリルや、N,N-ジメチルホルムアミド、N-メチルピロリドン、ジメチルスルホキシドなどの極性溶媒類又は前記溶媒の混合溶媒が挙げられる。 The reaction of the acid halide of the general formula [II] and the 3-aminobenzoic acid derivative of the general formula [III] can be performed in the presence of a solvent and in the presence or absence of a base.
The solvent is not particularly limited as long as it does not directly participate in this reaction, and for example, aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; chloroform and Halogenated hydrocarbons such as methylene chloride; esters such as methyl acetate and ethyl acetate; or ethers such as tetrahydrofuran, dioxane, diethyl ether and 1,2-dimethoxyethane; water; acetonitrile and N, N - dimethylformamide, N- methylpyrrolidone, a mixed solvent of polar solvents or the solvent such as dimethyl sulfoxide.
塩基としては、トリエチルアミンや、ピリジン、1,8-ジアザビシクロ[5.4.0]ウンデカ‐7-エン(DBU)、4‐ジメチルアミノピリジンなどの有機塩基;水酸化ナトリウムや、水酸化カリウムなどのアルカリ金属水酸化物;水酸化カルシウムなどのアルカリ土類金属水酸化物;炭酸ナトリウムや、炭酸カリウムなどのアルカリ金属炭酸塩;炭酸カルシウムなどのアルカリ土類金属炭酸塩;炭酸水素ナトリウムなどのアルカリ金属炭酸水素塩;ナトリウムメトキシドや、カリウムエトキシドなどの金属アルコキシドが挙げられる。
反応温度は、例えば、－30℃～150℃、好ましくは、－5℃～80℃である。
反応終了後、目的物は、常法により反応系から単離することができる。必要により、更に、溶媒による洗浄、再結晶、カラムクロマトグラフィーなどで精製することができる。 Bases include organic bases such as triethylamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 4-dimethylaminopyridine; alkali metals such as sodium hydroxide and potassium hydroxide Hydroxides; alkaline earth metal hydroxides such as calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate; alkali metal hydrogen carbonates such as sodium bicarbonate Salts; metal alkoxides such as sodium methoxide and potassium ethoxide.
The reaction temperature is, for example, −30 ° C. to 150 ° C., preferably −5 ° C. to 80 ° C.
After completion of the reaction, the target product can be isolated from the reaction system by a conventional method. If necessary, it can be further purified by washing with a solvent, recrystallization, column chromatography and the like.
反応温度は、例えば、－30℃～150℃、好ましくは、－5℃～80℃である。
反応終了後、目的物は、常法により反応系から単離することができる。必要により、更に、溶媒による洗浄、再結晶、カラムクロマトグラフィーなどで精製することができる。 Bases include organic bases such as triethylamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 4-dimethylaminopyridine; alkali metals such as sodium hydroxide and potassium hydroxide Hydroxides; alkaline earth metal hydroxides such as calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate; alkali metal hydrogen carbonates such as sodium bicarbonate Salts; metal alkoxides such as sodium methoxide and potassium ethoxide.
The reaction temperature is, for example, −30 ° C. to 150 ° C., preferably −5 ° C. to 80 ° C.
After completion of the reaction, the target product can be isolated from the reaction system by a conventional method. If necessary, it can be further purified by washing with a solvent, recrystallization, column chromatography and the like.
一般式[I]においてＲ3がヒドロキシル基である化合物は、下記一般式[IV]：
・・・・・・[IV]
The compound in which R 3 is a hydroxyl group in the general formula [I] is represented by the following general formula [IV]:
・ ・ ・ ・ ・ ・ [IV]
（式中、Ｒ1およびＲ2は前記一般式[I]で定義したとおりであり、Ｒ4はＣ1～Ｃ4のアルキル基を示す。）
で表されるエステルを、アルカリ金属塩を用いて加水分解反応することによっても得ることができる。 (In the formula, R 1 and R 2 are as defined in the general formula [I], and R 4 represents a C 1 -C 4 alkyl group.)
The ester represented by can also be obtained by a hydrolysis reaction using an alkali metal salt.
で表されるエステルを、アルカリ金属塩を用いて加水分解反応することによっても得ることができる。 (In the formula, R 1 and R 2 are as defined in the general formula [I], and R 4 represents a C 1 -C 4 alkyl group.)
The ester represented by can also be obtained by a hydrolysis reaction using an alkali metal salt.
一般式[IV]で表されるエステルは、一般式[I]においてＲ3がＣ1～Ｃ4のアルコキシ基である化合物である。したがって、一般式[IV]で表されるエステルは、上述の一般式[I]で表される化合物の製造方法に従い得ることができる。
The ester represented by the general formula [IV] is a compound in which R 3 is a C 1 -C 4 alkoxy group in the general formula [I]. Therefore, the ester represented by the general formula [IV] can be obtained according to the method for producing the compound represented by the above general formula [I].
一般式[IV]で表されるエステルの加水分解反応は、溶媒の存在下又は非存在下、かつ、塩基の存在下で行うことができる。
溶媒としては、例えば、水；メタノール、エタノール、プロパノール、エチレングリコール等のアルコール類又は上記溶媒の混合溶媒が挙げられる。
塩基としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物；水酸化マグネシウム、水酸化カルシウム等のアルカリ土類金属水酸化物；炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩；炭酸水素ナトリウム、炭酸水素カリウム等のアルカリ金属炭酸塩；炭酸カルシウム、炭酸マグネシウム等のアルカリ土類金属炭酸塩が挙げられる。
反応温度は、例えば、5～150℃、好ましくは、10～110℃である。
加水分解反応後、目的の化合物の単離を、塩酸や硫酸等の鉱酸及び／又は酢酸やプロピオン酸等の有機酸で酸性にした後、析出物を濾取し、水洗後乾燥することで行うことができる。 The hydrolysis reaction of the ester represented by the general formula [IV] can be carried out in the presence or absence of a solvent and in the presence of a base.
As the solvent, for example, water; methanol, ethanol, propanol, a mixed solvent of an alcohol or the solvent such as ethylene glycol.
Bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonate sodium, an alkali metal carbonate such as potassium hydrogen carbonate; calcium carbonate, alkaline earth metal carbonates such as magnesium carbonate.
The reaction temperature is, for example, 5 to 150 ° C., preferably 10 to 110 ° C.
After the hydrolysis reaction, isolation of the target compound is made acidic with mineral acids such as hydrochloric acid and sulfuric acid and / or organic acids such as acetic acid and propionic acid, and then the precipitate is collected by filtration, washed with water and dried. It can be carried out.
溶媒としては、例えば、水；メタノール、エタノール、プロパノール、エチレングリコール等のアルコール類又は上記溶媒の混合溶媒が挙げられる。
塩基としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物；水酸化マグネシウム、水酸化カルシウム等のアルカリ土類金属水酸化物；炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩；炭酸水素ナトリウム、炭酸水素カリウム等のアルカリ金属炭酸塩；炭酸カルシウム、炭酸マグネシウム等のアルカリ土類金属炭酸塩が挙げられる。
反応温度は、例えば、5～150℃、好ましくは、10～110℃である。
加水分解反応後、目的の化合物の単離を、塩酸や硫酸等の鉱酸及び／又は酢酸やプロピオン酸等の有機酸で酸性にした後、析出物を濾取し、水洗後乾燥することで行うことができる。 The hydrolysis reaction of the ester represented by the general formula [IV] can be carried out in the presence or absence of a solvent and in the presence of a base.
As the solvent, for example, water; methanol, ethanol, propanol, a mixed solvent of an alcohol or the solvent such as ethylene glycol.
Bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonate sodium, an alkali metal carbonate such as potassium hydrogen carbonate; calcium carbonate, alkaline earth metal carbonates such as magnesium carbonate.
The reaction temperature is, for example, 5 to 150 ° C., preferably 10 to 110 ° C.
After the hydrolysis reaction, isolation of the target compound is made acidic with mineral acids such as hydrochloric acid and sulfuric acid and / or organic acids such as acetic acid and propionic acid, and then the precipitate is collected by filtration, washed with water and dried. It can be carried out.
一般式[I]で表される本発明の化合物は、殺虫及び殺ダニ活性を有する3-オキサモイルアミノベンズアミド誘導体の製造中間体として利用することができる。
例えば、下記反応スキームに示すように、一般式[V]で表される3-オキサモイルアミノ安息香酸とハロゲン化剤とを反応させて一般式[VI]で表される酸ハライドとし、これを一般式[VII]で表されるアニリン誘導体と反応させることで一般式[VIII]で表される3-オキサモイルアミノベンズアミド誘導体を製造することができる。
The compound of the present invention represented by the general formula [I] can be used as an intermediate for producing a 3-oxamoylaminobenzamide derivative having insecticidal and acaricidal activity.
For example, as shown in the following reaction scheme, 3-oxamoylaminobenzoic acid represented by the general formula [V] is reacted with a halogenating agent to form an acid halide represented by the general formula [VI]. A 3-oxamoylaminobenzamide derivative represented by the general formula [VIII] can be produced by reacting with the aniline derivative represented by the general formula [VII].
例えば、下記反応スキームに示すように、一般式[V]で表される3-オキサモイルアミノ安息香酸とハロゲン化剤とを反応させて一般式[VI]で表される酸ハライドとし、これを一般式[VII]で表されるアニリン誘導体と反応させることで一般式[VIII]で表される3-オキサモイルアミノベンズアミド誘導体を製造することができる。
For example, as shown in the following reaction scheme, 3-oxamoylaminobenzoic acid represented by the general formula [V] is reacted with a halogenating agent to form an acid halide represented by the general formula [VI]. A 3-oxamoylaminobenzamide derivative represented by the general formula [VIII] can be produced by reacting with the aniline derivative represented by the general formula [VII].
上記反応スキーム中、一般式[V]、[VI]及び[VIII]におけるＲ1およびＲ2は前記一般式[I]で定義したとおりである。一般式[VII]及び[VIII]におけるＲ5およびＲ6は、それぞれ独立にＣ1～Ｃ4のアルキル基またはハロゲン原子を示す。Ｒ5およびＲ6で表されるＣ1～Ｃ4のアルキル基としては、直鎖状でも分岐を有していてもよいアルキル基であり、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基などが好適に挙げられる。ハロゲン原子としては、例えば、塩素や臭素などが好適に挙げられる。
なお、一般式[V]で表される化合物は、一般式[I]においてＲ3がヒドロキシル基である化合物である。
また、一般式[V]で表される化合物は、一般式[I]においてＲ3がＣ1～Ｃ4のアルコキシ基である化合物を上述のアルカリ金属塩を用いた加水分解反応に付することにより得ることができる。 In the above reaction scheme, R 1 and R 2 in the general formulas [V], [VI] and [VIII] are as defined in the general formula [I]. R 5 and R 6 in the general formulas [VII] and [VIII] each independently represent a C 1 to C 4 alkyl group or a halogen atom. The C 1 -C 4 alkyl group represented by R 5 and R 6 is a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, isopropyl, n- butyl group, isobutyl group, sec- butyl group, a tert- butyl group are preferably exemplified. Preferred examples of the halogen atom include chlorine and bromine.
The compound represented by the general formula [V] is a compound wherein R 3 is a hydroxyl group in the general formula [I].
In addition, the compound represented by the general formula [V] is obtained by subjecting the compound of the general formula [I] where R 3 is a C 1 -C 4 alkoxy group to a hydrolysis reaction using the above alkali metal salt. Can be obtained.
なお、一般式[V]で表される化合物は、一般式[I]においてＲ3がヒドロキシル基である化合物である。
また、一般式[V]で表される化合物は、一般式[I]においてＲ3がＣ1～Ｃ4のアルコキシ基である化合物を上述のアルカリ金属塩を用いた加水分解反応に付することにより得ることができる。 In the above reaction scheme, R 1 and R 2 in the general formulas [V], [VI] and [VIII] are as defined in the general formula [I]. R 5 and R 6 in the general formulas [VII] and [VIII] each independently represent a C 1 to C 4 alkyl group or a halogen atom. The C 1 -C 4 alkyl group represented by R 5 and R 6 is a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, isopropyl, n- butyl group, isobutyl group, sec- butyl group, a tert- butyl group are preferably exemplified. Preferred examples of the halogen atom include chlorine and bromine.
The compound represented by the general formula [V] is a compound wherein R 3 is a hydroxyl group in the general formula [I].
In addition, the compound represented by the general formula [V] is obtained by subjecting the compound of the general formula [I] where R 3 is a C 1 -C 4 alkoxy group to a hydrolysis reaction using the above alkali metal salt. Can be obtained.
一般式[V]で表される3-オキサモイルアミノ安息香酸と反応させるハロゲン化剤としては、例えば、塩化チオニル、オキシ塩化リンや臭化チオニルなどが好適に挙げられる。
一般式[V]で表される3-オキサモイルアミノ安息香酸とハロゲン化剤との反応は、溶媒の存在下又は非存在下、かつ、塩基の存在下又は非存在下で行うことができる。
溶媒としては、例えば、ベンゼン、トルエンやキシレンなどが挙げられる。
反応温度は、例えば、５０～１４０℃、好ましくは７０～１１０℃である。
反応終了後、目的物である一般式[VI]で表される酸ハライドは、常法により反応系から単離及び／又は精製することができる。 Preferable examples of the halogenating agent to be reacted with 3-oxamoylaminobenzoic acid represented by the general formula [V] include thionyl chloride, phosphorus oxychloride and thionyl bromide.
The reaction between 3-oxamoylaminobenzoic acid represented by the general formula [V] and the halogenating agent can be carried out in the presence or absence of a solvent and in the presence or absence of a base.
Examples of the solvent include benzene, toluene and xylene.
The reaction temperature is, for example, 50 to 140 ° C., preferably 70 to 110 ° C.
After completion of the reaction, the target acid halide represented by the general formula [VI] can be isolated and / or purified from the reaction system by a conventional method.
一般式[V]で表される3-オキサモイルアミノ安息香酸とハロゲン化剤との反応は、溶媒の存在下又は非存在下、かつ、塩基の存在下又は非存在下で行うことができる。
溶媒としては、例えば、ベンゼン、トルエンやキシレンなどが挙げられる。
反応温度は、例えば、５０～１４０℃、好ましくは７０～１１０℃である。
反応終了後、目的物である一般式[VI]で表される酸ハライドは、常法により反応系から単離及び／又は精製することができる。 Preferable examples of the halogenating agent to be reacted with 3-oxamoylaminobenzoic acid represented by the general formula [V] include thionyl chloride, phosphorus oxychloride and thionyl bromide.
The reaction between 3-oxamoylaminobenzoic acid represented by the general formula [V] and the halogenating agent can be carried out in the presence or absence of a solvent and in the presence or absence of a base.
Examples of the solvent include benzene, toluene and xylene.
The reaction temperature is, for example, 50 to 140 ° C., preferably 70 to 110 ° C.
After completion of the reaction, the target acid halide represented by the general formula [VI] can be isolated and / or purified from the reaction system by a conventional method.
一般式[VI]で表される酸ハライドと一般式[VII]で表されるアニリン誘導体との反応は、溶媒の存在下又は非存在下、かつ、塩基の存在下又は非存在下で行うことができる。
一般式[VII]で表されるアニリン誘導体は、公知の化合物であるか、または公知の方法に従って容易に合成することができる。
溶媒としては、例えば、ＤＭＩ(1,3‐ジメチル‐2‐イミダゾリジノン)やＮ－メチルピロリドンなどが挙げられる。
反応温度は、例えば、１０～１５０℃、好ましくは２０～１００℃である。
反応終了後、目的物である一般式[VIII]で表される3-オキサモイルアミノベンズアミド誘導体は、常法により反応系から単離及び／又は精製することができる。 The reaction between the acid halide represented by the general formula [VI] and the aniline derivative represented by the general formula [VII] should be carried out in the presence or absence of a solvent and in the presence or absence of a base. Can do.
The aniline derivative represented by the general formula [VII] is a known compound or can be easily synthesized according to a known method.
Examples of the solvent include DMI (1,3-dimethyl-2-imidazolidinone) and N-methylpyrrolidone.
The reaction temperature is, for example, 10 to 150 ° C., preferably 20 to 100 ° C.
After completion of the reaction, the target 3-oxamoylaminobenzamide derivative represented by the general formula [VIII] can be isolated and / or purified from the reaction system by a conventional method.
一般式[VII]で表されるアニリン誘導体は、公知の化合物であるか、または公知の方法に従って容易に合成することができる。
溶媒としては、例えば、ＤＭＩ(1,3‐ジメチル‐2‐イミダゾリジノン)やＮ－メチルピロリドンなどが挙げられる。
反応温度は、例えば、１０～１５０℃、好ましくは２０～１００℃である。
反応終了後、目的物である一般式[VIII]で表される3-オキサモイルアミノベンズアミド誘導体は、常法により反応系から単離及び／又は精製することができる。 The reaction between the acid halide represented by the general formula [VI] and the aniline derivative represented by the general formula [VII] should be carried out in the presence or absence of a solvent and in the presence or absence of a base. Can do.
The aniline derivative represented by the general formula [VII] is a known compound or can be easily synthesized according to a known method.
Examples of the solvent include DMI (1,3-dimethyl-2-imidazolidinone) and N-methylpyrrolidone.
The reaction temperature is, for example, 10 to 150 ° C., preferably 20 to 100 ° C.
After completion of the reaction, the target 3-oxamoylaminobenzamide derivative represented by the general formula [VIII] can be isolated and / or purified from the reaction system by a conventional method.
本発明の一般式[I]で表される3-アミノ安息香酸誘導体を製造中間体として用いることにより、3-オキサモイルアミノベンズアミド誘導体を高純度かつ高収率で得ることができる。
得られた3-オキサモイルアミノベンズアミド誘導体は、特許文献１及び２に記載されるように、殺虫剤及び殺ダニ剤の有効成分として利用することができる。 By using the 3-aminobenzoic acid derivative represented by the general formula [I] of the present invention as a production intermediate, a 3-oxamoylaminobenzamide derivative can be obtained with high purity and high yield.
The obtained 3-oxamoylaminobenzamide derivative can be used as an active ingredient of insecticides and acaricides as described in Patent Documents 1 and 2.
得られた3-オキサモイルアミノベンズアミド誘導体は、特許文献１及び２に記載されるように、殺虫剤及び殺ダニ剤の有効成分として利用することができる。 By using the 3-aminobenzoic acid derivative represented by the general formula [I] of the present invention as a production intermediate, a 3-oxamoylaminobenzamide derivative can be obtained with high purity and high yield.
The obtained 3-oxamoylaminobenzamide derivative can be used as an active ingredient of insecticides and acaricides as described in Patent Documents 1 and 2.
以下に、実施例及び参考例によって本発明を更に詳細に説明するが、本発明の範囲は、これらの実施例及び参考例によって何ら限定されるものではない。
Hereinafter, the present invention will be described in more detail with reference to Examples and Reference Examples, but the scope of the present invention is not limited by these Examples and Reference Examples.
実施例1
3-[ N-メチル-N-(2,2,2-トリフルオロエチル)オキサモイルアミノ]安息香酸の合成
3-アミノ安息香酸2.74gを水50mlに懸濁させ炭酸水素ナトリウム5.04gを加えた。氷冷下（５～１０℃）、N-(2,2,2-トリフルオロエチル)-N-メチルオキサモイルクロリド3.34gのTHF溶液を滴下し2時間撹拌後、濃塩酸を加え酸性とし、析出した結晶をろ過、水洗、乾燥して目的物3.21gを得た。融点は157～159℃であった。
1H-NMR(CDCl3)δppm：3.22+3.64(3H,s)、4.15+4.88(2H,q)、7.50(1H,t)、7.91-7.97(2H,m)、8.28-8.32(1H,m)、9.37+9.47(1H,s) Example 1
Synthesis of 3- [N-methyl-N- (2,2,2-trifluoroethyl) oxamoylamino] benzoic acid 2.74 g of 3-aminobenzoic acid was suspended in 50 ml of water and 5.04 g of sodium bicarbonate was added. . Under ice cooling (5-10 ° C), a THF solution of 3.34 g of N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride was added dropwise and stirred for 2 hours. The precipitated crystals were filtered, washed with water, and dried to obtain 3.21 g of the desired product. The melting point was 157-159 ° C.
1 H-NMR (CDCl 3 ) δ ppm: 3.22 + 3.64 (3H, s), 4.15 + 4.88 (2H, q), 7.50 (1H, t), 7.91-7.97 (2H, m), 8.28-8.32 (1H, m), 9.37 + 9.47 (1H, s)
3-[ N-メチル-N-(2,2,2-トリフルオロエチル)オキサモイルアミノ]安息香酸の合成
3-アミノ安息香酸2.74gを水50mlに懸濁させ炭酸水素ナトリウム5.04gを加えた。氷冷下（５～１０℃）、N-(2,2,2-トリフルオロエチル)-N-メチルオキサモイルクロリド3.34gのTHF溶液を滴下し2時間撹拌後、濃塩酸を加え酸性とし、析出した結晶をろ過、水洗、乾燥して目的物3.21gを得た。融点は157～159℃であった。
1H-NMR(CDCl3)δppm：3.22+3.64(3H,s)、4.15+4.88(2H,q)、7.50(1H,t)、7.91-7.97(2H,m)、8.28-8.32(1H,m)、9.37+9.47(1H,s) Example 1
Synthesis of 3- [N-methyl-N- (2,2,2-trifluoroethyl) oxamoylamino] benzoic acid 2.74 g of 3-aminobenzoic acid was suspended in 50 ml of water and 5.04 g of sodium bicarbonate was added. . Under ice cooling (5-10 ° C), a THF solution of 3.34 g of N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride was added dropwise and stirred for 2 hours. The precipitated crystals were filtered, washed with water, and dried to obtain 3.21 g of the desired product. The melting point was 157-159 ° C.
1 H-NMR (CDCl 3 ) δ ppm: 3.22 + 3.64 (3H, s), 4.15 + 4.88 (2H, q), 7.50 (1H, t), 7.91-7.97 (2H, m), 8.28-8.32 (1H, m), 9.37 + 9.47 (1H, s)
実施例2
3-[ N-メチル-N-(2,2,2-トリフルオロエチル)オキサモイルアミノ]安息香酸メチルの合成
3‐アミノ安息香酸メチル3.02gをＴＨＦ20mlに溶解させ、トリエチルアミン3.1mlを加えた後、N-(2,2,2-トリフルオロエチル)-N-メチルオキサモイルクロリド4.27gを氷冷下（５～１０℃）滴下した。反応液に希塩酸を加え析出した沈殿を濾過、水洗、乾燥して目的物5.79ｇを得た。融点は117～119℃であった。
1H-NMR(CDCl3)δppm：3.20+3.64(3H,s)、3.94(3H,s)、4.14+4.88(2H,q)、7.46(1H,t)、7.84-7.88(2H,m)、8.19-8.23(1H,m)、9.28+9.39(1H,bs) Example 2
Synthesis of methyl 3- [N-methyl-N- (2,2,2-trifluoroethyl) oxamoylamino] benzoate After dissolving 3.02g of methyl 3-aminobenzoate in 20ml of THF and adding 3.1ml of triethylamine , 4.27 g of N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride was added dropwise under ice cooling (5 to 10 ° C.). The reaction mixture is filtered and the precipitate deposited was added dilute hydrochloric acid to, washed with water to obtain the desired compound 5.79g and dried. The melting point was 117-119 ° C.
1 H-NMR (CDCl 3 ) δ ppm: 3.20 + 3.64 (3H, s), 3.94 (3H, s), 4.14 + 4.88 (2H, q), 7.46 (1H, t), 7.84-7.88 (2H, m) , 8.19-8.23 (1H, m), 9.28 + 9.39 (1H, bs)
3-[ N-メチル-N-(2,2,2-トリフルオロエチル)オキサモイルアミノ]安息香酸メチルの合成
3‐アミノ安息香酸メチル3.02gをＴＨＦ20mlに溶解させ、トリエチルアミン3.1mlを加えた後、N-(2,2,2-トリフルオロエチル)-N-メチルオキサモイルクロリド4.27gを氷冷下（５～１０℃）滴下した。反応液に希塩酸を加え析出した沈殿を濾過、水洗、乾燥して目的物5.79ｇを得た。融点は117～119℃であった。
1H-NMR(CDCl3)δppm：3.20+3.64(3H,s)、3.94(3H,s)、4.14+4.88(2H,q)、7.46(1H,t)、7.84-7.88(2H,m)、8.19-8.23(1H,m)、9.28+9.39(1H,bs) Example 2
Synthesis of methyl 3- [N-methyl-N- (2,2,2-trifluoroethyl) oxamoylamino] benzoate After dissolving 3.02g of methyl 3-aminobenzoate in 20ml of THF and adding 3.1ml of triethylamine , 4.27 g of N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride was added dropwise under ice cooling (5 to 10 ° C.). The reaction mixture is filtered and the precipitate deposited was added dilute hydrochloric acid to, washed with water to obtain the desired compound 5.79g and dried. The melting point was 117-119 ° C.
1 H-NMR (CDCl 3 ) δ ppm: 3.20 + 3.64 (3H, s), 3.94 (3H, s), 4.14 + 4.88 (2H, q), 7.46 (1H, t), 7.84-7.88 (2H, m) , 8.19-8.23 (1H, m), 9.28 + 9.39 (1H, bs)
実施例3
3-(N-エチル-N-メチルオキサモイルアミノ)安息香酸メチルの合成
N-(2,2,2-トリフルオロエチル)-N-メチルオキサモイルクロリドの代わりに、N-エチル-N-メチルオキサモイルクロリドを用いたことを除いて実施例2と同様の手順により合成した。
1H-NMR(CDCl3)δppm：1.22+1.33(3H,t)、3.08+3.49(3H,s)、3.53+3.94(2H,q)、3.93(3H,s)、7.44(1H,t)、7.82-7.89(2H,m)、8.22(1H,q)、9.39(1H,br) Example 3
Synthesis of methyl 3- (N-ethyl-N-methyloxamoylamino) benzoate Instead of N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride, N-ethyl-N-methyl The compound was synthesized by the same procedure as in Example 2 except that oxamoyl chloride was used.
1 H-NMR (CDCl 3 ) δ ppm: 1.22 + 1.33 (3H, t), 3.08 + 3.49 (3H, s), 3.53 + 3.94 (2H, q), 3.93 (3H, s), 7.44 (1H, t) , 7.82-7.89 (2H, m), 8.22 (1H, q), 9.39 (1H, br)
3-(N-エチル-N-メチルオキサモイルアミノ)安息香酸メチルの合成
N-(2,2,2-トリフルオロエチル)-N-メチルオキサモイルクロリドの代わりに、N-エチル-N-メチルオキサモイルクロリドを用いたことを除いて実施例2と同様の手順により合成した。
1H-NMR(CDCl3)δppm：1.22+1.33(3H,t)、3.08+3.49(3H,s)、3.53+3.94(2H,q)、3.93(3H,s)、7.44(1H,t)、7.82-7.89(2H,m)、8.22(1H,q)、9.39(1H,br) Example 3
Synthesis of methyl 3- (N-ethyl-N-methyloxamoylamino) benzoate Instead of N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride, N-ethyl-N-methyl The compound was synthesized by the same procedure as in Example 2 except that oxamoyl chloride was used.
1 H-NMR (CDCl 3 ) δ ppm: 1.22 + 1.33 (3H, t), 3.08 + 3.49 (3H, s), 3.53 + 3.94 (2H, q), 3.93 (3H, s), 7.44 (1H, t) , 7.82-7.89 (2H, m), 8.22 (1H, q), 9.39 (1H, br)
実施例4
3-(N-エチル-N-メチルオキサモイルアミノ)安息香酸の合成
N-(2,2,2-トリフルオロエチル)-N-メチルオキサモイルクロリドの代わりにN-エチル-N-メチルオキサモイルクロリドを用いたことを除いて実施例1と同様の手順により合成した。融点は168～171℃であった。
1H-NMR(CDCl3)δppm：1.23+1.34(3H,t)、3.08+3.48(3H,s)、3.54+3.92(2H,q)、7.48(1H,t)、7.89(1H,dt)、7.99-8.03(1H,m)、8.31(1H,s)、9.56+9.59(1H,s) Example 4
Synthesis of 3- (N-ethyl-N-methyloxamoylamino) benzoic acid N-ethyl-N-methyloxamoyl instead of N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride The compound was synthesized by the same procedure as in Example 1 except that chloride was used. The melting point was 168-171 ° C.
1 H-NMR (CDCl 3 ) δ ppm: 1.23 + 1.34 (3H, t), 3.08 + 3.48 (3H, s), 3.54 + 3.92 (2H, q), 7.48 (1H, t), 7.89 (1H, dt) , 7.99-8.03 (1H, m), 8.31 (1H, s), 9.56 + 9.59 (1H, s)
3-(N-エチル-N-メチルオキサモイルアミノ)安息香酸の合成
N-(2,2,2-トリフルオロエチル)-N-メチルオキサモイルクロリドの代わりにN-エチル-N-メチルオキサモイルクロリドを用いたことを除いて実施例1と同様の手順により合成した。融点は168～171℃であった。
1H-NMR(CDCl3)δppm：1.23+1.34(3H,t)、3.08+3.48(3H,s)、3.54+3.92(2H,q)、7.48(1H,t)、7.89(1H,dt)、7.99-8.03(1H,m)、8.31(1H,s)、9.56+9.59(1H,s) Example 4
Synthesis of 3- (N-ethyl-N-methyloxamoylamino) benzoic acid N-ethyl-N-methyloxamoyl instead of N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride The compound was synthesized by the same procedure as in Example 1 except that chloride was used. The melting point was 168-171 ° C.
1 H-NMR (CDCl 3 ) δ ppm: 1.23 + 1.34 (3H, t), 3.08 + 3.48 (3H, s), 3.54 + 3.92 (2H, q), 7.48 (1H, t), 7.89 (1H, dt) , 7.99-8.03 (1H, m), 8.31 (1H, s), 9.56 + 9.59 (1H, s)
実施例5
3-(N-(t-ブチル)-N-メチルオキサモイルアミノ)安息香酸メチルの合成
N-(2,2,2-トリフルオロエチル)-N-メチルオキサモイルクロリドの代わりに、N-(t-ブチル)-N-メチルオキサモイルクロリドを用いたことを除いて実施例2と同様の手順により合成した。融点は144～146℃であった。
1H-NMR(CDCl3)δppm：1.48(9H,s)、3.24(3H,s)、3.92(3H,s)、7.44(1H,t)、7.81-7.88(2H,m)、8.24(1H,t)、9.10(1H,br) Example 5
Synthesis of methyl 3- (N- (t-butyl) -N-methyloxamoylamino) benzoate N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride instead of N- ( The compound was synthesized by the same procedure as in Example 2 except that t-butyl) -N-methyloxamoyl chloride was used. The melting point was 144-146 ° C.
1 H-NMR (CDCl 3 ) δ ppm: 1.48 (9H, s), 3.24 (3H, s), 3.92 (3H, s), 7.44 (1H, t), 7.81-7.88 (2H, m), 8.24 (1H , t), 9.10 (1H, br)
3-(N-(t-ブチル)-N-メチルオキサモイルアミノ)安息香酸メチルの合成
N-(2,2,2-トリフルオロエチル)-N-メチルオキサモイルクロリドの代わりに、N-(t-ブチル)-N-メチルオキサモイルクロリドを用いたことを除いて実施例2と同様の手順により合成した。融点は144～146℃であった。
1H-NMR(CDCl3)δppm：1.48(9H,s)、3.24(3H,s)、3.92(3H,s)、7.44(1H,t)、7.81-7.88(2H,m)、8.24(1H,t)、9.10(1H,br) Example 5
Synthesis of methyl 3- (N- (t-butyl) -N-methyloxamoylamino) benzoate N- (2,2,2-trifluoroethyl) -N-methyloxamoyl chloride instead of N- ( The compound was synthesized by the same procedure as in Example 2 except that t-butyl) -N-methyloxamoyl chloride was used. The melting point was 144-146 ° C.
1 H-NMR (CDCl 3 ) δ ppm: 1.48 (9H, s), 3.24 (3H, s), 3.92 (3H, s), 7.44 (1H, t), 7.81-7.88 (2H, m), 8.24 (1H , t), 9.10 (1H, br)
実施例6
3-[N-(t-ブチル)-N-メチルオキサモイルアミノ]安息香酸の合成
実施例5で得た安息香酸メチルエステル体1.75ｇをメタノール5mlと水2mlに懸濁させ、20％水酸化ナトリウム水溶液2.52gを氷冷下（５～１０℃）滴下後、反応液を室温にした。希塩酸を加え反応液を酸性にし、析出した結晶を濾過、水洗、乾燥して目的物1.67gを得た。融点は174℃(分解)であった。
1H-NMR(CDCl3)δppm：1.50(9H,s)、3.24(3H,s)、7.47(1H,t)、7.87(1H,dt)、8.02-8.06(1H,m)、8.25(1H,t)、9.26(1H,br) Example 6
Synthesis of 3- [N- (t-butyl) -N-methyloxamoylamino] benzoic acid 1.75 g of the benzoic acid methyl ester obtained in Example 5 was suspended in 5 ml of methanol and 2 ml of water, and 20% hydroxylated. under ice-cooling an aqueous solution of sodium 2.52g (5 ~ 10 ℃) after the addition, the reaction mixture was cooled to room temperature. Dilute hydrochloric acid was added to acidify the reaction solution, and the precipitated crystals were filtered, washed with water, and dried to obtain 1.67 g of the desired product. The melting point was 174 ° C. (decomposition).
1 H-NMR (CDCl 3 ) δ ppm: 1.50 (9H, s), 3.24 (3H, s), 7.47 (1H, t), 7.87 (1H, dt), 8.02-8.06 (1H, m), 8.25 (1H , t), 9.26 (1H, br)
3-[N-(t-ブチル)-N-メチルオキサモイルアミノ]安息香酸の合成
実施例5で得た安息香酸メチルエステル体1.75ｇをメタノール5mlと水2mlに懸濁させ、20％水酸化ナトリウム水溶液2.52gを氷冷下（５～１０℃）滴下後、反応液を室温にした。希塩酸を加え反応液を酸性にし、析出した結晶を濾過、水洗、乾燥して目的物1.67gを得た。融点は174℃(分解)であった。
1H-NMR(CDCl3)δppm：1.50(9H,s)、3.24(3H,s)、7.47(1H,t)、7.87(1H,dt)、8.02-8.06(1H,m)、8.25(1H,t)、9.26(1H,br) Example 6
Synthesis of 3- [N- (t-butyl) -N-methyloxamoylamino] benzoic acid 1.75 g of the benzoic acid methyl ester obtained in Example 5 was suspended in 5 ml of methanol and 2 ml of water, and 20% hydroxylated. under ice-cooling an aqueous solution of sodium 2.52g (5 ~ 10 ℃) after the addition, the reaction mixture was cooled to room temperature. Dilute hydrochloric acid was added to acidify the reaction solution, and the precipitated crystals were filtered, washed with water, and dried to obtain 1.67 g of the desired product. The melting point was 174 ° C. (decomposition).
1 H-NMR (CDCl 3 ) δ ppm: 1.50 (9H, s), 3.24 (3H, s), 7.47 (1H, t), 7.87 (1H, dt), 8.02-8.06 (1H, m), 8.25 (1H , t), 9.26 (1H, br)
参考例1
3-[ N-メチル-N-(2,2,2-トリフルオロエチル)オキサモイルアミノ]安息香酸クロリドの合成
実施例１で得た3-[N-メチルN-(2,2,2-トリフルオロエチル)オキサモイルアミノ]安息香酸2.55gをトルエン8mlに懸濁させ、塩化チオニル3mlを加え80℃で3時間撹拌した。トルエン等を減圧下留去して目的物2.61gを得た。融点は106～108℃であった。
1H-NMR(CDCl3)δppm：3.22+3.65(3H,s)、4.15+4.87(2H,q)、7.54(1H,t)、7.93-7.98(2H,m)、8.34-8.40(1H,m)、9.38+9.48(1H,s) Reference example 1
Synthesis of 3- [N-methyl-N- (2,2,2-trifluoroethyl) oxamoylamino] benzoic acid chloride 3- [N-methyl N- (2,2,2-) obtained in Example 1 (Trifluoroethyl) oxamoylamino] benzoic acid (2.55 g) was suspended in toluene (8 ml), thionyl chloride (3 ml) was added, and the mixture was stirred at 80 ° C. for 3 hours. Toluene and the like were distilled off under reduced pressure to obtain 2.61 g of the desired product. The melting point was 106-108 ° C.
1 H-NMR (CDCl 3 ) δ ppm: 3.22 + 3.65 (3H, s), 4.15 + 4.87 (2H, q), 7.54 (1H, t), 7.93–7.98 (2H, m), 8.34–8.40 (1H, m), 9.38 + 9.48 (1H, s)
3-[ N-メチル-N-(2,2,2-トリフルオロエチル)オキサモイルアミノ]安息香酸クロリドの合成
実施例１で得た3-[N-メチルN-(2,2,2-トリフルオロエチル)オキサモイルアミノ]安息香酸2.55gをトルエン8mlに懸濁させ、塩化チオニル3mlを加え80℃で3時間撹拌した。トルエン等を減圧下留去して目的物2.61gを得た。融点は106～108℃であった。
1H-NMR(CDCl3)δppm：3.22+3.65(3H,s)、4.15+4.87(2H,q)、7.54(1H,t)、7.93-7.98(2H,m)、8.34-8.40(1H,m)、9.38+9.48(1H,s) Reference example 1
Synthesis of 3- [N-methyl-N- (2,2,2-trifluoroethyl) oxamoylamino] benzoic acid chloride 3- [N-methyl N- (2,2,2-) obtained in Example 1 (Trifluoroethyl) oxamoylamino] benzoic acid (2.55 g) was suspended in toluene (8 ml), thionyl chloride (3 ml) was added, and the mixture was stirred at 80 ° C. for 3 hours. Toluene and the like were distilled off under reduced pressure to obtain 2.61 g of the desired product. The melting point was 106-108 ° C.
1 H-NMR (CDCl 3 ) δ ppm: 3.22 + 3.65 (3H, s), 4.15 + 4.87 (2H, q), 7.54 (1H, t), 7.93–7.98 (2H, m), 8.34–8.40 (1H, m), 9.38 + 9.48 (1H, s)
参考例2
3-[ N-メチル-N-(2,2,2-トリフルオロエチル)オキサモイルアミノ]-N-(2,6-ジメチル-4-ヘプタフルオロイソプロピル)フェニルベンズアミドの合成
2,6-ジメチル-4-ヘプタフルオロイソプロピルアニリン5.78gと参考例1で得た酸クロリド7.75gをＤＭＩ (1,3‐ジメチル‐2‐イミダゾリジノン)40mlに溶かし、室温（２０～２５℃）で１０時間反応させ、反応液に水100mlを加え4時間撹拌後、酢酸エチルで抽出、水、炭酸水素ナトリウム水溶液、飽和食塩水で洗浄、硫酸マグネシウムで脱水後、溶媒を減圧下留去して目的物11.8gを得た。無定形であった。
1H-NMR(CDCl3)δppm：2.33(6H,s)、3.20+3.61(3H,s)、4.13+4.85(2H,q)、7.35(2H,s) 、7.50(1H,t) 、7.60(1H,s)、7.70-7.80(2H,m)、8.25(1H,s)、9.39+9.49(1H,s) Reference example 2
Synthesis of 3- [N-methyl-N- (2,2,2-trifluoroethyl) oxamoylamino] -N- (2,6-dimethyl-4-heptafluoroisopropyl) phenylbenzamide 2,6-Dimethyl- Dissolve 5.78 g of 4-heptafluoroisopropylaniline and 7.75 g of the acid chloride obtained in Reference Example 1 in 40 ml of DMI (1,3-dimethyl-2-imidazolidinone) and react at room temperature (20-25 ° C) for 10 hours. The reaction solution was added with 100 ml of water, stirred for 4 hours, extracted with ethyl acetate, washed with water, aqueous sodium hydrogen carbonate solution and saturated brine, dehydrated with magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain 11.8 g of the desired product. Obtained. It was amorphous.
1 H-NMR (CDCl 3 ) δ ppm: 2.33 (6H, s), 3.20 + 3.61 (3H, s), 4.13 + 4.85 (2H, q), 7.35 (2H, s), 7.50 (1H, t), 7.60 (1H, s), 7.70-7.80 (2H, m), 8.25 (1H, s), 9.39 + 9.49 (1H, s)
3-[ N-メチル-N-(2,2,2-トリフルオロエチル)オキサモイルアミノ]-N-(2,6-ジメチル-4-ヘプタフルオロイソプロピル)フェニルベンズアミドの合成
2,6-ジメチル-4-ヘプタフルオロイソプロピルアニリン5.78gと参考例1で得た酸クロリド7.75gをＤＭＩ (1,3‐ジメチル‐2‐イミダゾリジノン)40mlに溶かし、室温（２０～２５℃）で１０時間反応させ、反応液に水100mlを加え4時間撹拌後、酢酸エチルで抽出、水、炭酸水素ナトリウム水溶液、飽和食塩水で洗浄、硫酸マグネシウムで脱水後、溶媒を減圧下留去して目的物11.8gを得た。無定形であった。
1H-NMR(CDCl3)δppm：2.33(6H,s)、3.20+3.61(3H,s)、4.13+4.85(2H,q)、7.35(2H,s) 、7.50(1H,t) 、7.60(1H,s)、7.70-7.80(2H,m)、8.25(1H,s)、9.39+9.49(1H,s) Reference example 2
Synthesis of 3- [N-methyl-N- (2,2,2-trifluoroethyl) oxamoylamino] -N- (2,6-dimethyl-4-heptafluoroisopropyl) phenylbenzamide 2,6-Dimethyl- Dissolve 5.78 g of 4-heptafluoroisopropylaniline and 7.75 g of the acid chloride obtained in Reference Example 1 in 40 ml of DMI (1,3-dimethyl-2-imidazolidinone) and react at room temperature (20-25 ° C) for 10 hours. The reaction solution was added with 100 ml of water, stirred for 4 hours, extracted with ethyl acetate, washed with water, aqueous sodium hydrogen carbonate solution and saturated brine, dehydrated with magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain 11.8 g of the desired product. Obtained. It was amorphous.
1 H-NMR (CDCl 3 ) δ ppm: 2.33 (6H, s), 3.20 + 3.61 (3H, s), 4.13 + 4.85 (2H, q), 7.35 (2H, s), 7.50 (1H, t), 7.60 (1H, s), 7.70-7.80 (2H, m), 8.25 (1H, s), 9.39 + 9.49 (1H, s)
参考例3
コナガの幼虫に対する殺虫効果
はくさいの種をジフィーポットに播種した後3週間育苗した。このポット植え植物の葉部に、参考例2で得た化合物を有効成分とする乳剤の水希釈液を茎葉部にエアーブラシを用いて十分散布した(1濃度、1反復）。薬液を風乾燥した後、25℃の恒温室内に保持し、放虫5日後に幼虫の生死及び苦悶を調査し、苦悶虫を死として殺虫率(％)を求めた。参考例2の化合物は、500ppmの濃度において100%の殺虫率を示した。 Reference Example 3
Insecticidal effect on the larvae of the diamondback moth The seeds were raised for 3 weeks after sowing seeds in a jiffy pot. A water-diluted solution of an emulsion containing the compound obtained in Reference Example 2 as an active ingredient was sufficiently sprayed onto the leaves of this pot planted plant using an airbrush (one concentration, one repetition). After the chemical solution was air-dried, it was kept in a constant temperature room at 25 ° C., and after 5 days of larvae, mortality and bitterness of the larvae were investigated, and the insecticidal rate (%) was determined by dying the bitter worm. The compound of Reference Example 2 showed an insecticidal rate of 100% at a concentration of 500 ppm.
コナガの幼虫に対する殺虫効果
はくさいの種をジフィーポットに播種した後3週間育苗した。このポット植え植物の葉部に、参考例2で得た化合物を有効成分とする乳剤の水希釈液を茎葉部にエアーブラシを用いて十分散布した(1濃度、1反復）。薬液を風乾燥した後、25℃の恒温室内に保持し、放虫5日後に幼虫の生死及び苦悶を調査し、苦悶虫を死として殺虫率(％)を求めた。参考例2の化合物は、500ppmの濃度において100%の殺虫率を示した。 Reference Example 3
Insecticidal effect on the larvae of the diamondback moth The seeds were raised for 3 weeks after sowing seeds in a jiffy pot. A water-diluted solution of an emulsion containing the compound obtained in Reference Example 2 as an active ingredient was sufficiently sprayed onto the leaves of this pot planted plant using an airbrush (one concentration, one repetition). After the chemical solution was air-dried, it was kept in a constant temperature room at 25 ° C., and after 5 days of larvae, mortality and bitterness of the larvae were investigated, and the insecticidal rate (%) was determined by dying the bitter worm. The compound of Reference Example 2 showed an insecticidal rate of 100% at a concentration of 500 ppm.
本発明は、殺虫及び殺ダニ活性を有する3-オキサモイルアミノベンズアミド誘導体の製造に利用することができる。
The present invention can be used for the production of 3-oxamoylaminobenzamide derivatives having insecticidal and acaricidal activity.
Claims (3)
- 一般式[I]で表される3-アミノ安息香酸誘導体。
・・・・・・[I]
（式中、Ｒ1はＣ1～Ｃ4のアルキル基を示す。Ｒ2はフッ素原子で置換されてもよいＣ1～Ｃ4のアルキル基を示す。Ｒ3はＣ1～Ｃ4のアルコキシ基またはヒドロキシル基を示す。） A 3-aminobenzoic acid derivative represented by the general formula [I].
・ ・ ・ ・ ・ ・ [I]
(Wherein, R 1 is alkoxy of C 1 ~ represents an alkyl group of C 4 .R 2 is .R 3 represents an alkyl group which may be C 1 ~ C 4 substituted with a fluorine atom C 1 ~ C 4 Group or hydroxyl group.) - 請求項1に記載の3-アミノ安息香酸誘導体を製造する方法であって、
一般式[II]：
・・・・・・[II]
（式中、Ｒ1およびＲ2は前記一般式[I]で定義したとおりであり、Ｘはハロゲン原子を示す。）
で表される酸ハライドを、
一般式[III]：
・・・・・・[III]
（式中、Ｒ3は前記一般式[I]で定義したとおりである。）
で表される3-アミノ安息香酸誘導体と反応させることを特徴とする方法。 A method for producing the 3-aminobenzoic acid derivative according to claim 1,
General formula [II]:
・ ・ ・ ・ ・ ・ [II]
(In the formula, R 1 and R 2 are as defined in the general formula [I], X is a halogen atom.)
An acid halide represented by
General formula [III]:
・ ・ ・ ・ ・ ・ [III]
(In the formula, R 3 is as defined in the general formula [I].)
And reacting with a 3-aminobenzoic acid derivative represented by the formula: - 請求項1に記載の3-アミノ安息香酸誘導体（式中、Ｒ3はヒドロキシル基である）を製造する方法であって、
一般式[IV]：
・・・・・・[IV]
（式中、Ｒ1およびＲ2は前記一般式[I]で定義したとおりであり、Ｒ4はＣ1～Ｃ4のアルキル基を示す。）
で表されるエステルを、アルカリ金属塩を用いて加水分解することを特徴とする方法。 A method for producing the 3-aminobenzoic acid derivative according to claim 1, wherein R 3 is a hydroxyl group,
General formula [IV]:
・ ・ ・ ・ ・ ・ [IV]
(In the formula, R 1 and R 2 are as defined in the general formula [I], and R 4 represents a C 1 -C 4 alkyl group.)
The ester represented by these is hydrolyzed using an alkali metal salt.
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| WO2016143650A1 (en) * | 2015-03-06 | 2016-09-15 | 住友化学株式会社 | 3-aminooxalylaminobenzamide compound and use for controlling harmful arthropod |
| WO2016143652A1 (en) * | 2015-03-06 | 2016-09-15 | 住友化学株式会社 | 3-aminooxalylaminobenzamide compound and use for controlling harmful arthropod |
| WO2016163379A1 (en) * | 2015-04-09 | 2016-10-13 | 住友化学株式会社 | Oxalyl amide compound and use thereof for noxious arthropod control |
| WO2016163383A1 (en) * | 2015-04-09 | 2016-10-13 | 住友化学株式会社 | Oxalyl amide compound and use thereof for noxious arthropod control |
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| WO2003011028A1 (en) * | 2001-08-01 | 2003-02-13 | Nissan Chemical Industries, Ltd. | Substituted amides and pest controllers |
| WO2007082079A2 (en) * | 2006-01-12 | 2007-07-19 | The Scripps Research Institute | Piperidine amide derivatives as protein kinase inhibitors |
| WO2010090282A1 (en) * | 2009-02-06 | 2010-08-12 | アグロカネショウ株式会社 | 3-aminoxalylaminobenzamide derivatives, and insecticidal and miticidal agents containing same as active ingredient |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003011028A1 (en) * | 2001-08-01 | 2003-02-13 | Nissan Chemical Industries, Ltd. | Substituted amides and pest controllers |
| WO2007082079A2 (en) * | 2006-01-12 | 2007-07-19 | The Scripps Research Institute | Piperidine amide derivatives as protein kinase inhibitors |
| WO2010090282A1 (en) * | 2009-02-06 | 2010-08-12 | アグロカネショウ株式会社 | 3-aminoxalylaminobenzamide derivatives, and insecticidal and miticidal agents containing same as active ingredient |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016143650A1 (en) * | 2015-03-06 | 2016-09-15 | 住友化学株式会社 | 3-aminooxalylaminobenzamide compound and use for controlling harmful arthropod |
| WO2016143652A1 (en) * | 2015-03-06 | 2016-09-15 | 住友化学株式会社 | 3-aminooxalylaminobenzamide compound and use for controlling harmful arthropod |
| WO2016163379A1 (en) * | 2015-04-09 | 2016-10-13 | 住友化学株式会社 | Oxalyl amide compound and use thereof for noxious arthropod control |
| WO2016163383A1 (en) * | 2015-04-09 | 2016-10-13 | 住友化学株式会社 | Oxalyl amide compound and use thereof for noxious arthropod control |
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