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CN113979887A - Synthetic method of aromatic amine carboxylic acid derivative - Google Patents

Synthetic method of aromatic amine carboxylic acid derivative Download PDF

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CN113979887A
CN113979887A CN202111635561.5A CN202111635561A CN113979887A CN 113979887 A CN113979887 A CN 113979887A CN 202111635561 A CN202111635561 A CN 202111635561A CN 113979887 A CN113979887 A CN 113979887A
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pyridyl
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carboxylic acid
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曲文岩
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Beijing Yinong Biotechnology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00Preparation of carboxylic acid amides
    • C07C231/14Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00Preparation of carboxylic acid amides
    • C07C231/02Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00Preparation of carboxylic acid amides
    • C07C231/12Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00Preparation of carboxylic acid amides
    • C07C231/22Separation; Purification; Stabilisation; Use of additives
    • C07C231/24Separation; Purification

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Abstract

The invention discloses a synthetic method of aromatic amine carboxylic acid derivatives, which comprises the following steps: s1: preparation of compound iii: the structural formula of the compound III is
Figure 100004_DEST_PATH_IMAGE001
(ii) a S2: preparation of Compound IV: the structural formula of the compound IV is
Figure 100004_DEST_PATH_IMAGE002
(ii) a S3: preparation of Compound V: the structural formula of the compound V is
Figure 100004_DEST_PATH_IMAGE003
(ii) a S4: preparation of Compound VI: the structural formula of the compound VI is
Figure 100004_DEST_PATH_IMAGE004
(ii) a S5: preparation of compound viii: the structural formula of the compound VIII is

Description

Synthetic method of aromatic amine carboxylic acid derivative
Technical Field
The invention belongs to the technical field of synthesis of aromatic amide derivatives, and particularly relates to a synthesis method of aromatic amine carboxylic acid derivatives.
Background
The prior art discloses methods for synthesizing various amide derivatives having agricultural pest control effects, respectively. Although the conventional synthesis methods and the types of amide derivatives have been disclosed in the prior patents, the disclosed types are not comprehensive enough, and the preparation methods, yields, routes and the like have many disadvantages.
Disclosure of Invention
The present invention has been made in an effort to solve the above-mentioned problems occurring in the background art by devising and disclosing a number of novel aromatic amine carboxylic acid derivatives having an effect of controlling pests and providing a method for synthesizing the aromatic amine carboxylic acid derivatives.
The invention provides a synthetic route of aromatic amine carboxylic acid derivatives, which comprises the following steps:
the first step is as follows:
Figure 100002_DEST_PATH_IMAGE001
the second step is that:
Figure 100002_DEST_PATH_IMAGE002
the third step:
Figure 100002_DEST_PATH_IMAGE003
the fourth step:
Figure 100002_DEST_PATH_IMAGE004
the fifth step:
Figure 100002_DEST_PATH_IMAGE005
Figure 100002_DEST_PATH_IMAGE006
Figure 100002_DEST_PATH_IMAGE007
Figure 100002_DEST_PATH_IMAGE008
in order to achieve the purpose, the invention provides the following technical scheme: a synthetic method of aromatic amine carboxylic acid derivatives is characterized in that: the method comprises the following steps in sequence:
s1: preparation of compound iii: dissolving a compound I in dichloromethane, adding a compound II to react in the presence of alkali, and then sequentially washing, extracting, washing and drying to obtain a compound III;
s2: preparation of Compound IV: dissolving the compound III obtained in the step in tetrahydrofuran, adding LiHMDS under the protection of nitrogen, and then adding R1Reacting, and then sequentially carrying out quenching reaction, extraction, water washing and drying to obtain a compound IV;
s3: preparation of Compound V: adding the compound IV and sodium hydroxide in the steps into water for reaction, adding 1N hydrochloric acid aqueous solution after the reaction is finished, adjusting the pH to be =2, and performing suction filtration to obtain a compound V;
s4: preparation of Compound VI: adding the compound V in the step into thionyl chloride for reaction, and evaporating unreacted thionyl chloride from mother liquor under negative pressure after the reaction is finished to obtain a compound VI;
s5: preparation of compound viii: dissolving the compound VI and the compound VII obtained in the step in acetonitrile, reacting in the presence of alkali, and then sequentially extracting, washing with water, drying and purifying to obtain a compound VIII;
wherein the structural formula of the compound I is
Figure DEST_PATH_IMAGE009
The structural formula of the compound II is
Figure DEST_PATH_IMAGE010
The structural formula of the compound III is
Figure DEST_PATH_IMAGE011
The structural formula of the compound IV is
Figure DEST_PATH_IMAGE012
(ii) a The structural formula of the compound V is
Figure DEST_PATH_IMAGE013
The structural formula of the compound VI is
Figure DEST_PATH_IMAGE014
The structural formula of the compound VII is
Figure DEST_PATH_IMAGE015
The structural formula of the compound VIII is
Figure DEST_PATH_IMAGE016
And R is1Comprises one of H, Me, Et, n-Pr, n-Bu, acetyl and propionyl; r2Including phenyl, 4-fluorophenyl, 6- (trifluoromethyl) -3-pyridyl, 4-cyanophenyl, 2-fluorophenyl, 3-fluorophenyl, 2, 6-difluorophenyl, 3, 5-difluorophenyl, 2, 3-difluorophenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 6-chloro-2-pyridyl, 6-chloro-3-pyridyl, 5-fluoro-3-pyridyl, 6-fluoro-3-pyridyl, Me, CF3, Et, N-Pr, i-Pr, N-ethyl-N-methylaminocarbonyl, N-ethyl-aminocarbonyl, 2,2, 2-trifluoroethylaminocarbonyl, N-methyl-2-pyridyl, N-methyl-3-pyridyl, N-ethyl-aminocarbonyl, N-methyl-2-pyridyl, N-methyl-pyridyl, N-ethyl-2-pyridyl, 3-pyridyl, 2-cyano-pyridyl, N-methyl-2-pyridyl, N-methyl-pyridyl, N-ethyl-2-pyridyl, N-methyl-ethyl-2-pyridyl, N-ethyl-2-pyridyl, One of N- (2,2, 2-trifluoroethyl) -N-methylaminocarbonyl, 4-nitrophenyl and methoxymethyl; x1Including F, Cl, Br, I; x2Comprises one of H, Cl, Me and CF 3; x3Comprises one of H, Cl, Br and 3-chloro-5- (trifluoromethyl) pyridine-2-oxyl; x4Comprises one of 1,1,2, 2-tetrafluoroethoxy, 1,2,3,3, 3-hexafluoropropoxy, 1, 2-trifluoro-2-trifluoromethoxy-ethoxy, 2-chloro-4- (trifluoromethyl) phenoxy, 3-chloro-5- (trifluoromethyl) pyridine-2-oxy, Cl, F and heptafluoroisopropyl; x5One of H, Cl; x6Comprises one of H, Cl, F and Br.
Preferably, in step S1, the reaction conditions are 0 ℃, the reaction is carried out for 12h, the washing is performed with 1N hydrochloric acid aqueous solution, the extraction is performed with ethyl acetate, and the drying is performed with anhydrous sodium sulfate.
In any of the above schemes, preferably, in step S2, the reaction time is 1h, the quenching reaction is completed by adding acetic acid at 0 ℃, the extraction is performed by using ethyl acetate, and the drying is performed by using anhydrous sodium sulfate.
In any of the above schemes, preferably, in step S3, the reaction is performed under stirring at 60 ℃ for 2 h.
In any of the above schemes, preferably, in step S4, the reaction conditions are 75 ℃ stirring reaction for 2 h.
In any of the above schemes, preferably, in step S5, the reaction conditions are 110 ℃ for 3 h.
In any of the above schemes, preferably, in step S5, the extracting is performed with ethyl acetate, the drying is performed with anhydrous sodium sulfate, and the purifying is performed as a crude product by a silica gel column chromatography.
In any of the above schemes, preferably, in step S1, the base is one of pyridine, triethylamine, sodium hydroxide, and potassium hydroxide, but is not limited to the above three.
The invention has the technical effects and advantages that: the invention designs and synthesizes brand-new aromatic amine carboxylic acid derivatives, which provides resources for finding better pest control drugs with higher cost performance, and has the advantages of easily obtained raw materials, reasonable route design and easy industrialization; the invention discloses a plurality of brand-new compounds and preparation processes thereof, the compounds also have excellent pest control effect, and the preparation method is simple, high in yield and low in cost.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example is given by X1=F,R2= phenyl group as an example, but the present invention is not limited to this example.
Synthesis of 5-benzamido-2-fluoro-ethyl benzoate:
Figure 104000DEST_PATH_IMAGE017
dissolving 5-amino-2-fluoro-ethyl benzoate (400 mg, 2.184 mmol, 1 equiv) in dichloromethane, sequentially adding benzoyl chloride (306.95 mg, 2.184 mmol, 1 equiv), pyridine (345.5 mg, 4.368 mmol, 2 equiv) at 0 ℃, stirring at room temperature for 12h after the addition is finished, detecting by TLC (PE/EA =3:1, Rf = 0.5), adding 20ml of 1N hydrochloric acid aqueous solution to wash an organic phase, extracting with ethyl acetate, combining the organic phases, washing with water once, drying the organic phase with anhydrous sodium sulfate, evaporating the solvent under negative pressure, and purifying a crude product by a silica gel column (PE/EA =3: 1) to obtain 5-benzamido-2-fluoro-ethyl benzoate (600 mg, 96%) as a white solid.
1H NMR (400 MHz, DMSO-d 6) δ 10.48 (s, 1H), 8.35 (m, 1H), 8.06 (m, 1H), 8.01-7.95 (m, 2H), 7.65-7.51 (m, 3H), 7.35 (m, 1H), 4.34 (m, 2H), 1.32 (m, 3H)。
LCMS: (ESI, m/z): [M+1]+= 288.1。
Example 2
This example is given by X1=F,R2= phenyl, R1By way of example, Me is described, but the present invention is not limited to this example.
Synthesis of ethyl 2-fluoro-5- (N-methylbenzamido) benzoate:
Figure DEST_PATH_IMAGE018
dissolving 5-benzamido-2-fluoro-ethyl benzoate (1 g, 3.481 mmol, 1 equiv) in tetrahydrofuran (10ml), cooling to-78 ℃ with liquid nitrogen under the protection of nitrogen, starting to dropwise add LiHMDS (0.87 g, 5.221 mmol, 1.5 equiv), after dropwise addition, dropwise adding methyl iodide (0.74 g, 5.221 mmol, 1.5 equiv), after 10 min, stirring at room temperature for reaction for 1h, detecting by TLC (PE/EA =4:1, Rf = 0.5), after reaction, adding 2ml acetic acid at 0 ℃ for quenching reaction, extracting ethyl acetate, combining organic phases, washing once with water, drying the organic phases with anhydrous sodium sulfate, evaporating the solvent under negative pressure, purifying the crude product by a silica gel column (PE/EA =4: 1) to obtain 2-fluoro-5- (N-methylbenzamido) ethyl benzoate (750 mg, 72%) yellow oily liquid.
1H NMR (400 MHz, Chloroform-d) δ 7.69 (m, 1H), 7.32-7.26 (m, 3H), 7.21 (m, 2H), 7.12 (m, 1H), 6.96 (m, 1H), 4.36 (m, 2H), 3.49 (s, 3H), 1.37 (m, 3H)。
LCMS: (ESI, m/z): [M+1]+= 302.0。
Example 3
This example is given by X1=F,R2= phenyl, R1By way of example, Me is described, but the present invention is not limited to this example.
Synthesis of 2-fluoro-5- (N-methylbenzamido) benzoic acid
Figure 958824DEST_PATH_IMAGE019
Adding ethyl 2-fluoro-5- (N-methylbenzamido) benzoate (750 mg, 2.489 mmol, 1 equiv) and sodium hydroxide (199.11 mg, 4.978 mmol, 2 equiv) into water (10ml), stirring for reaction for 2h at 60 ℃, cooling to room temperature after TLC (PE/EA =1:1, Rf = 0.4) detection reaction is finished, adding 1N hydrochloric acid aqueous solution to adjust pH =2, extracting with ethyl acetate, washing an organic phase with water, drying with anhydrous sodium sulfate, and evaporating the solvent under negative pressure to obtain 2-fluoro-5- (N-methylbenzamido) benzoic acid (620 mg, 91%) yellow oily liquid.
1H NMR (400 MHz, Chloroform-d) δ 7.79 (m, 1H), 7.34-7.27 (m, 3H), 7.25-7.16 (m, 3H), 7.01 (m, 1H), 3.51 (s, 3H)。
LCMS: (ESI, m/z): [M+1]+= 274.0。
Example 4
This example is given by X1=F,X2=H,X3=Cl,X4=1,1,2,3,3, 3-hexafluoropropoxy, X5=H,X6=Cl,R2= phenyl, R1By way of example, Me is described, but the present invention is not limited to this example.
Synthesis of N- [2, 5-dichloro-4- (1,1,2,3,3, 3-hexafluoropropoxy) phenyl ] -2-fluoro-5- (N-methylbenzamido) benzamide
Figure DEST_PATH_IMAGE020
Adding 2-fluoro-5- (N-methylbenzamido) benzoic acid (50 mg, 0.183 mmol, 1 equiv) into thionyl chloride (1 ml), stirring and reacting at 75 ℃ for 2h, evaporating redundant thionyl chloride from the obtained mother liquor under negative pressure, and directly using the mother liquor for the next reaction without purification. 2, 5-dichloro-4- (1,1,2,3,3, 3-hexafluoropropoxy) aniline (42.02 mg, 0.128 mmol, 0.7 equiv) was dissolved in acetonitrile (1 ml), and KI (6.07 mg, 0.037 mmol, 0.2 equiv) and triethylamine (37.03 mg, 0.366 mmol, 2.0 equiv) were added in that order. At room temperature, the acyl chloride acetonitrile solution obtained in the previous step is added dropwise, and the reaction is carried out for 3 hours at the temperature of 110 ℃. After the reaction is finished, cooling to room temperature, adding water, extracting by ethyl acetate, washing an organic phase by water, drying by anhydrous sodium sulfate, evaporating the solvent under negative pressure, and purifying a crude product by a chromatographic silica gel column (PE/EA =9: 1) to obtain N- [2, 5-dichloro-4- (1,1,2,3,3, 3-hexafluoropropoxy) phenyl ] -2-fluoro-5- (N-methylbenzamide) benzamide (50.66 mg, 68%) as a white solid.
1H NMR (400 MHz, Chloroform-d) δ 9.11 (m, 1H), 8.82 (s, 1H), 7.99 (m, 1H), 7.44 (m, 1H), 7.35-7.27 (m, 3H), 7.26-7.15 (m, 3H), 7.06 (m, 1H), 5.08 (m, 1H), 3.52 (s, 3H)。
LCMS: (ESI, m/z): [M+1]+= 583.0。
Example 5:
this example is given by X1=F,R2= phenyl, R1Description will be made with = H as an example, but the present invention is not limited to this example.
Synthesis of 5-benzamido-2-fluoro-benzoic acid
Figure 174779DEST_PATH_IMAGE021
Adding 5-benzamido-2-fluoro-benzoic acid ethyl ester (300 mg, 1.044 mmol, 1 equiv) and sodium hydroxide (62.65 mg, 1.566 mmol, 1.5 equiv) into water (3 ml), stirring for reaction for 2h at 60 ℃, cooling to room temperature after TLC (PE/EA =1:1, Rf = 0.3) detection reaction is finished, adding 1N hydrochloric acid aqueous solution to adjust pH =2, and performing suction filtration to obtain 5-benzamido-2-fluoro-benzoic acid (235.5 mg, 87%) as a white solid.
1H NMR (400 MHz, DMSO-d 6) δ 10.45 (s, 1H), 8.34 (m, 1H), 8.07-7.91 (m, 3H), 7.56 (m, 3H), 7.31 (m, 1H)。
LCMS: (ESI, m/z): [M+1]+= 260.1。
Example 6
This example is given by X1=F,X2=H,X3=Cl,X4=1,1,2,3,3, 3-hexafluoropropoxy, X5=H,X6=Cl,R2= phenyl, R1Description will be made with = H as an example, but the present invention is not limited to this example.
Synthesis of 5-benzamido-N- [2, 5-dichloro-4- (1,1,2,3,3, 3-hexafluoropropoxy) phenyl ] -2-fluorobenzamide
Figure DEST_PATH_IMAGE022
5-benzamido-2-fluoro-benzoic acid (50 mg, 0.193 mmol, 1 equiv) is added into thionyl chloride (1 ml), the mixture is stirred and reacted for 2h at 75 ℃, and the obtained mother liquor is directly used for the next reaction without purification after excessive thionyl chloride is evaporated under negative pressure. 2, 5-dichloro-4- (1,1,2,3,3, 3-hexafluoropropoxy) aniline (44.29 mg, 0.135 mmol, 0.7 equiv) was dissolved in acetonitrile (1 ml), and KI (6.40 mg, 0.039 mmol, 0.2 equiv) and triethylamine (39.04 mg, 0.386 mmol, 2.0 equiv) were added in that order. At room temperature, the acyl chloride acetonitrile solution obtained in the previous step is added dropwise, and the reaction is carried out for 3 hours at the temperature of 110 ℃. After the reaction is finished, cooling to room temperature, adding water, extracting by ethyl acetate, washing an organic phase by water, drying by anhydrous sodium sulfate, evaporating the solvent under negative pressure, and purifying a crude product by a chromatographic silica gel column (PE/EA =9: 1) to obtain 5-benzamido-N- [2, 5-dichloro-4- (1,1,2,3,3, 3-hexafluoropropoxy) phenyl ] -2-fluorobenzamide (47.5 mg, 62%) as a white solid.
1H NMR (400 MHz, DMSO-d 6) δ 10.51 (s, 1H), 10.19 (s, 1H), 8.25 (m, 1H), 8.19 (s, 1H), 8.09-7.95 (m, 3H), 7.79 (m, 1H), 7.67-7.51 (m, 3H), 7.41 (m, 1H), 6.60 (m, 0H), 6.49 (m, 0H).
LCMS: (ESI, m/z): [M-1]-= 566.9.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.

Claims (8)

1. A synthetic method of aromatic amine carboxylic acid derivatives is characterized in that: the method comprises the following steps in sequence:
s1: preparation of compound iii: dissolving a compound I in dichloromethane, adding a compound II to react in the presence of alkali, and then sequentially washing, extracting, washing and drying to obtain a compound III;
s2: preparation of Compound IV: dissolving the compound III obtained in the step in tetrahydrofuran, adding LiHMDS under the protection of nitrogen, and then adding R1Reacting, and then sequentially carrying out quenching reaction, extraction, water washing and drying to obtain a compound IV;
s3: preparation of Compound V: adding the compound IV and sodium hydroxide in the steps into water for reaction, adding 1N hydrochloric acid aqueous solution after the reaction is finished, adjusting the pH to be =2, and performing suction filtration to obtain a compound V;
s4: preparation of Compound VI: adding the compound V in the step into thionyl chloride for reaction, and evaporating unreacted thionyl chloride from mother liquor under negative pressure after the reaction is finished to obtain a compound VI;
s5: preparation of compound viii: dissolving the compound VI and the compound VII obtained in the step in acetonitrile, reacting in the presence of alkali, and then sequentially extracting, washing with water, drying and purifying to obtain a compound VIII;
wherein the structural formula of the compound I is
Figure DEST_PATH_IMAGE001
The structural formula of the compound II is
Figure DEST_PATH_IMAGE002
The structural formula of the compound III is
Figure DEST_PATH_IMAGE003
The structural formula of the compound IV is
Figure DEST_PATH_IMAGE004
(ii) a The structural formula of the compound V is
Figure DEST_PATH_IMAGE005
The structural formula of the compound VI is
Figure DEST_PATH_IMAGE006
The structural formula of the compound VII is
Figure DEST_PATH_IMAGE007
The structural formula of the compound VIII is
Figure DEST_PATH_IMAGE008
And R is1Comprises one of H, Me, Et, n-Pr, n-Bu, acetyl and propionyl; r2Including phenyl, 4-fluorophenyl, 6- (trifluoromethyl) -3-pyridyl, 4-cyanophenyl, 2-fluorophenyl, 3-fluorophenyl, 2, 6-difluorophenyl, 3, 5-difluorophenyl, 2, 3-difluorophenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 6-chloro-2-pyridyl, 6-chloro-3-pyridyl, 5-fluoro-3-pyridyl, 6-fluoro-3-pyridyl, Me, CF3, Et, N-Pr, i-Pr, N-ethyl-N-methylaminocarbonyl, N-ethyl-aminocarbonyl, 2,2, 2-trifluoroethylaminocarbonyl, N-methyl-2-pyridyl, N-methyl-3-pyridyl, N-ethyl-aminocarbonyl, N-methyl-2-pyridyl, N-methyl-pyridyl, N-ethyl-2-pyridyl, 3-pyridyl, 2-cyano-pyridyl, N-methyl-2-pyridyl, N-methyl-pyridyl, N-ethyl-2-pyridyl, N-methyl-ethyl-2-pyridyl, N-ethyl-2-pyridyl, One of N- (2,2, 2-trifluoroethyl) -N-methylaminocarbonyl, 4-nitrophenyl and methoxymethyl; x1Including F, Cl, Br, I; x2Comprises one of H, Cl, Me and CF 3; x3Comprises one of H, Cl, Br and 3-chloro-5- (trifluoromethyl) pyridine-2-oxyl; x4Comprises one of 1,1,2, 2-tetrafluoroethoxy, 1,2,3,3, 3-hexafluoropropoxy, 1, 2-trifluoro-2-trifluoromethoxy-ethoxy, 2-chloro-4- (trifluoromethyl) phenoxy, 3-chloro-5- (trifluoromethyl) pyridine-2-oxy, Cl, F and heptafluoroisopropyl; x5One of H, Cl; x6Comprises one of H, Cl, F and Br.
2. The method for synthesizing an aromatic amine carboxylic acid derivative according to claim 1, wherein: in step S1, the reaction conditions were 0 ℃, the reaction time was 12 hours, the washing was performed with 1N hydrochloric acid aqueous solution, the extraction was performed with ethyl acetate, and the drying was performed with anhydrous sodium sulfate.
3. The method for synthesizing an aromatic amine carboxylic acid derivative according to claim 1, wherein: in step S2, the reaction time is 1h, the quenching reaction is completed by adding acetic acid at 0 ℃, the extraction is performed with ethyl acetate, and the drying is performed with anhydrous sodium sulfate.
4. The method for synthesizing an aromatic amine carboxylic acid derivative according to claim 1, wherein: in step S3, the reaction is carried out under the condition of 60 ℃ and stirring for 2 h.
5. The method for synthesizing an aromatic amine carboxylic acid derivative according to claim 1, wherein: in step S4, the reaction conditions were 75 ℃ stirring reaction for 2 h.
6. The method for synthesizing an aromatic amine carboxylic acid derivative according to claim 1, wherein: in step S5, the reaction condition is 110 ℃ for 3 h.
7. The method for synthesizing an aromatic amine carboxylic acid derivative according to claim 1, wherein: in step S5, ethyl acetate is used for extraction, anhydrous sodium sulfate is used for drying, and the crude product is purified by chromatography on silica gel column.
8. The method for synthesizing an aromatic amine carboxylic acid derivative according to claim 1, wherein: in step S1, the base is one of pyridine, triethylamine, sodium hydroxide, and potassium hydroxide.
CN202111635561.5A 2021-12-29 2021-12-29 Synthetic method of aromatic amine carboxylic acid derivative Pending CN113979887A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006306771A (en) * 2005-04-28 2006-11-09 Mitsui Chemicals Inc Agricultural/horticultural insecticide
CN102119144A (en) * 2008-08-13 2011-07-06 三井化学Agro株式会社 Method for producing amide derivative

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2253617A1 (en) * 2009-05-20 2010-11-24 Bayer CropScience AG Halogenated compounds as pesticides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006306771A (en) * 2005-04-28 2006-11-09 Mitsui Chemicals Inc Agricultural/horticultural insecticide
CN102119144A (en) * 2008-08-13 2011-07-06 三井化学Agro株式会社 Method for producing amide derivative

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
罗春艳等: ""新型含环丙基的间二酰胺类化合物的合成及其杀虫活性"", 《有机化学》 *

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