CN111718336A - Quinolinone Schiff base compound and preparation method and application thereof - Google Patents

Quinolinone Schiff base compound and preparation method and application thereof Download PDF

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CN111718336A
CN111718336A CN202010651560.9A CN202010651560A CN111718336A CN 111718336 A CN111718336 A CN 111718336A CN 202010651560 A CN202010651560 A CN 202010651560A CN 111718336 A CN111718336 A CN 111718336A
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compound
seed
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seeds
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CN111718336B (en
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唐孝荣
程玮
肖婷婷
张婷婷
陆童
钱伟烽
蒋文静
张桂兰
伍微
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Xihua University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

Abstract

The invention relates to the field of pesticides, and particularly relates to a quinolinone Schiff base compound, and a preparation method and application thereof. The invention solves the technical problem of providing a compound serving as an insecticide and a vegetable seed germination promoter. The structural formula of the compound is shown as formula I; wherein X is oxygen, sulfur or nitrogen; r is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen. The compound has good poisoning effect on storage pests and good promotion effect on the germination of vegetable seeds.
Figure DDA0002575159190000011

Description

Quinolinone Schiff base compound and preparation method and application thereof
Technical Field
The invention relates to the field of pesticides, and particularly relates to a quinolinone Schiff base compound, and a preparation method and application thereof.
Background
It is known that furan ring is an electron-rich system, which easily forms intermolecular hydrogen bonds with various biological enzymes, and thus some furan ring-containing compounds, both natural and synthetic, have a broad spectrum of biological activities, such as bacteriostasis, antivirus, antitumor, insecticidal, herbicidal, etc. Meanwhile, the compounds generally have the characteristics of high efficiency, low toxicity, safety to non-target organisms, easiness in degradation in the environment, difficulty in generation of resistance by pests and the like, so that the compounds containing furan rings play more and more important roles in the research and development processes of pesticides.
Thiophene is an important member of heterocyclic compounds and plays a very important role. The study of thiophene derivatives also has a very major role in medicine and agrochemical chemistry. Thiophene derivatives have a wide variety of biological activities, for example, antibacterial, antiviral, antitumor, anti-inflammatory, insecticidal, herbicidal, and the like. Meanwhile, the thiophene ring-containing compounds generally have the characteristics of high efficiency, low toxicity, safety to non-target organisms, easiness in degradation in the environment, difficulty in generation of resistance by pests and the like, and compounds with novel structures and excellent performance are continuously published. Therefore, in the process of research and development of pesticides, compounds containing thiophene rings will receive more extensive attention and become hot spots for creating new pesticides.
Until now, no report is available on the use of quinolinone Schiff base compounds as pesticides and vegetable seed germination promoters.
Disclosure of Invention
The first technical problem solved by the invention is to provide a compound serving as an insecticide and a vegetable seed germination promoter.
The compound of the invention has a structural formula shown as a formula I:
Figure BDA0002575159170000011
wherein X is oxygen, sulfur or nitrogen; r is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
In one embodiment, X is oxygen, sulfur, or nitrogen; r is hydrogen, methyl, methoxy, hydroxymethyl, chlorine or bromine.
In one embodiment, X is oxygen, sulfur, or nitrogen; r is hydrogen, methyl, chlorine or bromine.
In one embodiment, X is oxygen or sulfur; r is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
In one embodiment, the compound has the following structural formula:
Figure BDA0002575159170000021
the second technical problem solved by the invention is to provide a preparation method of the compound.
The preparation method of the compound comprises the following steps:
a. dissolving 2-aminoacetophenone in absolute ethyl alcohol, adding NaOH ethanol solution, adding a mixed solution of a compound A and the absolute ethyl alcohol, and reacting at 0-5 ℃;
b. after the reaction is finished, adjusting the pH value of the reaction solution to be neutral, then adding p-toluenesulfonic acid into the reaction solution, and reacting at 65-70 ℃;
c. after the reaction is finished, pouring the reaction solution into ice water, adjusting the pH value of the solution to 7-9 by using triethylamine, separating out a precipitate, filtering, washing the precipitate, and recrystallizing by using absolute ethyl alcohol to obtain a quinolinone intermediate;
d. dissolving the quinolinone intermediate in acetic acid, adding a mixed solution of cyanoacethydrazide and absolute ethyl alcohol, reacting at 25-35 ℃, removing the solvent to obtain a solid mixture after the reaction is finished, and performing chromatographic separation by using a silica gel column to obtain a target compound;
wherein the compound A is
Figure BDA0002575159170000022
Wherein X is oxygen, sulfur or nitrogen; r is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
The invention also provides application of the compound in preparing a medicament for preventing and treating pests.
The compound of the invention has excellent insecticidal effect.
In one embodiment, the pest is a storage pest.
In one embodiment, the pest is at least one of elephant corn, clothes of grain and tribolium castaneum; preferably, when the pest is a corn weevil, the compound is compound 2 or compound 4; when the pests are the grain, the compound is compound 2, compound 3 or compound 5; when the pest is tribolium castaneum, the compound is compound 2, compound 3 or compound 5;
in a specific embodiment, when the pest is a zeamais pest, the compound is compound 2; when the pest is the grain, the compound is compound 2 or compound 5.
The invention also provides application of the compound in preparing a seed germination promoter.
Researches show that the compound can promote the germination of seeds and improve the germination rate of the seeds, and can be prepared into a seed germination promoter.
In one embodiment, the seed is a vegetable seed; in another embodiment, the vegetable seed is a cucumber seed, a green pepper seed, a tomato seed, or a celery seed;
in a specific embodiment, when the vegetable seed is cucumber seed, the compound is compound 2; when the vegetable seed is a green pepper seed, the compound is compound 1 or compound 4; when the vegetable seed is a tomato seed, the compound is compound 5; when the vegetable seed is celery seed, the compound is compound 4.
The invention has the beneficial effects that:
according to the invention, furan rings or thiophene rings are introduced into the molecular structure of quinolinone to synthesize some quinolinone Schiff base compounds, some active compounds or active lead compounds with novel structures and excellent activity are found, the synthesis process is simple, the insecticidal composition has a good poisoning effect on storage pests, and has a good promotion effect on the germination of vegetable seeds, so that a good foundation is laid for the creation of new pesticides.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the compound of example 1.
FIG. 1-a is a detailed view of a nuclear magnetic hydrogen spectrum of the compound of example 1.
FIG. 2 is a nuclear magnetic carbon spectrum of the compound of example 1.
FIG. 3 is a high resolution mass spectrum of the compound of example 1.
FIG. 4 is a nuclear magnetic hydrogen spectrum of the compound of example 2.
FIG. 4-a is a partial detail view of the nuclear magnetic hydrogen spectrum of the compound of example 2.
FIG. 5 is a nuclear magnetic carbon spectrum of the compound of example 2.
FIG. 6 is a high resolution mass spectrum of the compound of example 2.
FIG. 7 is a nuclear magnetic hydrogen spectrum of the compound of example 3.
FIG. 8 is a nuclear magnetic carbon spectrum of the compound of example 3.
FIG. 9 is a high resolution mass spectrum of the compound of example 3.
FIG. 10 is a nuclear magnetic hydrogen spectrum of the compound of example 4.
FIG. 11 is a nuclear magnetic carbon spectrum of the compound of example 4.
FIG. 12 is a high resolution mass spectrum of the compound of example 4.
FIG. 13 is a nuclear magnetic hydrogen spectrum of the compound of example 5.
FIG. 14 is a nuclear magnetic carbon spectrum of the compound of example 5.
FIG. 15 is a high resolution mass spectrum of the compound of example 5.
Detailed Description
The first technical problem solved by the invention is to provide a compound serving as an insecticide and a vegetable seed germination promoter.
The compound of the invention has a structural formula shown as a formula I:
Figure BDA0002575159170000041
wherein X is oxygen, sulfur or nitrogen; r is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
In one embodiment, X is oxygen, sulfur, or nitrogen; r is hydrogen, methyl, methoxy, hydroxymethyl, chlorine or bromine.
In one embodiment, X is oxygen, sulfur, or nitrogen; r is hydrogen, methyl, chlorine or bromine.
In one embodiment, X is oxygen or sulfur; r is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
In one embodiment, the compound has the following structural formula:
Figure BDA0002575159170000042
the second technical problem solved by the invention is to provide a preparation method of the compound.
The compound of the invention can be prepared by adopting a conventional chemical method.
In one embodiment, the following reaction procedure may be used.
Figure BDA0002575159170000051
Wherein X is oxygen, sulfur or nitrogen; r is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
The preparation method of the compound specifically comprises the following steps:
a. dissolving 2-aminoacetophenone in absolute ethyl alcohol, adding NaOH ethanol solution, stirring in an ice bath, adding a mixed solution of a compound A and the absolute ethyl alcohol, and reacting at 0-5 ℃;
b. after the reaction is finished, adjusting the pH value of the reaction solution to be neutral, then adding p-toluenesulfonic acid into the reaction solution, and reacting at 65-70 ℃;
c. after the reaction is finished, pouring the reaction solution into ice water, adjusting the pH value of the solution to 7-9 by using triethylamine, separating out a precipitate, filtering, washing to be neutral, and recrystallizing by using absolute ethyl alcohol to obtain a quinolinone intermediate;
d. dissolving the quinolinone intermediate in acetic acid, adding a mixed solution of cyanoacethydrazide and absolute ethyl alcohol, reacting at 25-35 ℃, removing the solvent to obtain a solid mixture after the reaction is finished, and performing chromatographic separation by using a silica gel column to obtain a target compound;
wherein the compound A is
Figure BDA0002575159170000052
Wherein X is oxygen, sulfur or nitrogen; r is hydrogen atom, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
The invention also provides application of the compound in preparing a medicament for preventing and treating pests.
The compound of the invention has excellent insecticidal effect.
In one embodiment, the pest is a storage pest.
In one embodiment, the pest is at least one of elephant corn, clothes of grain and tribolium castaneum;
in order to make the pesticidal effect of the pesticidal drug better, it is preferable that, when the pest is a zeamais, the compound is compound 2 or compound 4; when the pests are the grain, the compound is compound 2, compound 3 or compound 5; when the pest is tribolium castaneum, the compound is compound 2, compound 3 or compound 5; in a specific embodiment, when the pest is a zeamais pest, the compound is compound 2; when the pest is the grain, the compound is compound 2 or compound 5.
The invention also provides application of the compound in preparing a seed germination promoter.
Researches show that the compound can promote the germination of seeds and improve the germination rate of the seeds, and can be prepared into a seed germination promoter.
In one embodiment, the seed is a vegetable seed; in another embodiment, the vegetable seed is a cucumber seed, a green pepper seed, a tomato seed, or a celery seed; in a specific embodiment, when the vegetable seed is cucumber seed, the compound is compound 2; when the vegetable seed is a green pepper seed, the compound is compound 1 or compound 4; when the vegetable seed is a tomato seed, the compound is compound 5; when the vegetable seed is celery seed, the compound is compound 4.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1:
compound 1:
Figure BDA0002575159170000061
preparation of
0.01mol of 2-aminoacetophenone was dissolved in 10mL of anhydrous ethanol, and 10mL of 10% NaOH ethanol solution was added thereto. Stirring in an ice bath, slowly dropping a mixed solution of 0.01mol of furfural and 10mL of absolute ethyl alcohol into the mixed solution by using a constant-pressure dropping funnel, reacting at 0-5 ℃, and checking whether the reaction is finished by using a thin-layer silica gel plate (TLC). After the reaction was complete, the pH of the solution was adjusted to neutral with 10% HCl. Then, 0.01mol of p-toluenesulfonic acid is added into the reaction mixture, the reaction is carried out at 65-70 ℃, and the completion of the reaction is checked by TLC. And after the reaction is finished, pouring the reaction solution into 100mL of ice water, adjusting the pH value of the solution to 7-9 by using triethylamine, separating out a precipitate, filtering, washing with distilled water to be neutral, and recrystallizing with absolute ethyl alcohol to obtain a quinolinone intermediate.
0.01mol of the home-made intermediate was dissolved in 20mL of acetic acid. And slowly dropping a mixed solution of 0.02mol of cyanoacethydrazide and 10mL of absolute ethyl alcohol into the mixed solution by using a constant-pressure dropping funnel, reacting at 25-35 ℃, and checking whether the reaction is finished by using TLC. After the reaction is finished, removing the solvent by rotary evaporation to obtain a solid mixture, and separating by silica gel column chromatography (eluent is a mixture of ethyl acetate and petroleum ether with the volume ratio of 1: 20) to obtain the target compound, wherein the physicochemical properties of the target compound are as follows:
a light yellow powder; yield: 81 percent; the hydrogen spectrum is shown in figure 1, the carbon spectrum is shown in figure 2, the high resolution mass spectrum is shown in figure 3, and particularly,1HNMR(400MHz,DMSO-d6)(ppm):11.02(1H,s),7.84-7.82(1H,m),7.64(1H,dd,J＝8.0,1.2Hz),7.13-7.11(1H,m),6.79(1H,d,J＝8.4Hz),6.65(1H,d,J＝7.2Hz),6.62(1H,s),6.41(1H,dd,J＝3.2,1.6Hz),6.25(1H,d,J＝3.2Hz),4.60-4.55(1H,m),4.22(2H,s),3.00(1H,dd,J＝8.4,5.2Hz),2.92(1H,dd,J＝16.8,8.4Hz)；13C NMR(100MHz,DMSO-d6)(ppm):166.00,155.29,147.51,145.90,142.80,131.11,124.97,117.65,117.56,116.79,116.21,110.87,106.82,47.90,29.84,25.24；HRMS(ESI)m/z:Calcd for C16H14N4O2[M+H]+:295.1190,Found:295.1194.
example 2:
compound 2:
Figure BDA0002575159170000062
preparation of
0.01mol of 2-aminoacetophenone was dissolved in 10mL of anhydrous ethanol, and 10mL of 10% NaOH ethanol solution was added thereto. Stirring in an ice bath, slowly dropping a mixed solution of 0.01mol of 5-methylfurfural and 10mL of absolute ethanol into the mixed solution by using a constant-pressure dropping funnel, reacting at 0-5 ℃, and checking whether the reaction is finished by using a thin-layer silica gel plate (TLC). After the reaction was complete, the pH of the solution was adjusted to neutral with 10% HCl. Then, 0.01mol of p-toluenesulfonic acid is added into the reaction mixture, the reaction is carried out at 65-70 ℃, and the completion of the reaction is checked by TLC. And after the reaction is finished, pouring the reaction solution into 100mL of ice water, adjusting the pH value of the solution to 7-9 by using triethylamine, separating out a precipitate, filtering, washing with distilled water to be neutral, and recrystallizing with absolute ethyl alcohol to obtain a quinolinone intermediate.
0.01mol of the home-made intermediate was dissolved in 20mL of acetic acid. And slowly dropping a mixed solution of 0.02mol of cyanoacethydrazide and 10mL of absolute ethyl alcohol into the mixed solution by using a constant-pressure dropping funnel, reacting at 25-35 ℃, and checking whether the reaction is finished by using TLC. After the reaction is finished, removing the solvent by rotary evaporation to obtain a solid mixture, and separating by silica gel column chromatography (eluent is a mixture of ethyl acetate and petroleum ether with the volume ratio of 1: 20) to obtain the target compound, wherein the physicochemical properties of the target compound are as follows:
a brown powder; yield: 85 percent; the hydrogen spectrum is shown in fig. 4, the carbon spectrum is shown in fig. 5, the high resolution mass spectrum is shown in fig. 6, and particularly,1HNMR(400MHz,DMSO-d6)(ppm):11.01(1H,s),7.83-7.81(1H,m),7.12-7.10(1H,m),6.79(1H,d,J＝8.0Hz),6.63(1H,d,J＝7.2Hz),6.57(1H,s),6.12(1H,d,J＝3.2Hz),6.01-6.00(1H,m),4.49-4.45(1H,m),4.22(2H,s),2.99(1H,dd,J＝12.0,5.6Hz),2.86(1H,dd,J＝16.8,8.8Hz),2.25(3H,d,J＝4.0Hz)；13C NMR(100MHz,DMSO-d6)(ppm):165.97,153.40,153.27,151.31,147.60,146.12,131.08,124.96,117.60,116.79,116.21,107.54,106.82,47.98,29.91,25.23,13.81；HRMS(ESI)m/z:Calcd for C17H16N4O2[M+H]+:309.1346,Found:309.1346.
example 3:
compound 3:
Figure BDA0002575159170000071
preparation of
0.01mol of 2-aminoacetophenone was dissolved in 10mL of anhydrous ethanol, and 10mL of 10% NaOH ethanol solution was added thereto. Stirring in an ice bath, slowly dropping a mixed solution of 0.01mol of 5-bromofurfural and 10mL of absolute ethyl alcohol into the mixed solution by using a constant-pressure dropping funnel, reacting at 0-5 ℃, and checking whether the reaction is finished by using a thin-layer silica gel plate (TLC). After the reaction was complete, the pH of the solution was adjusted to neutral with 10% HCl. Then, 0.01mol of p-toluenesulfonic acid is added into the reaction mixture, the reaction is carried out at 65-70 ℃, and the completion of the reaction is checked by TLC. And after the reaction is finished, pouring the reaction solution into 100mL of ice water, adjusting the pH value of the solution to 7-9 by using triethylamine, separating out a precipitate, filtering, washing with distilled water to be neutral, and recrystallizing with absolute ethyl alcohol to obtain a quinolinone intermediate.
0.01mol of the home-made intermediate was dissolved in 20mL of acetic acid. And slowly dropping a mixed solution of 0.02mol of cyanoacethydrazide and 10mL of absolute ethyl alcohol into the mixed solution by using a constant-pressure dropping funnel, reacting at 25-35 ℃, and checking whether the reaction is finished by using TLC. After the reaction is finished, removing the solvent by rotary evaporation to obtain a solid mixture, and separating by silica gel column chromatography (eluent is a mixture of ethyl acetate and petroleum ether with the volume ratio of 1: 20) to obtain the target compound, wherein the physicochemical properties of the target compound are as follows:
a milky white powder; yield: 86 percent; the hydrogen spectrum is shown in fig. 7, the carbon spectrum is shown in fig. 8, the high resolution mass spectrum is shown in fig. 9, and specifically,1HNMR(400MHz,DMSO-d6)(ppm):11.01(1H,s),7.84-7.82(1H,m),7.14-7.10(1H,m),6.79(1H,d,J＝7.6Hz),6.67-6.65(1H,m),6.64-6.62(1H,m),6.51(1H,d,J＝3.2Hz),6.30(1H,dd,J＝3.6,0.8Hz),4.59-4.55(1H,m),4.22(2H,s),2.99(1H,dd,J＝11.6,5.2Hz),2.92(1H,dd,J＝16.8,8.0Hz)；13C NMR(100MHz,DMSO-d6)(ppm):166.00,157.60,147.22,145.53,131.17,124.98,120.79,117.81,117.55,116.76,116.21,112.79,109.93,47.84,29.52,25.23；HRMS(ESI)m/z:Calcd for C16H13BrN4O2[M+H]+:373.0295,Found:373.0281.
example 4:
compound 4:
Figure BDA0002575159170000081
preparation of
0.01mol of 2-aminoacetophenone was dissolved in 10mL of anhydrous ethanol, and 10mL of 10% NaOH ethanol solution was added thereto. Stirring in an ice bath, slowly dropping a mixed solution of 0.01mol of thiophene-2-formaldehyde and 10mL of absolute ethyl alcohol into the mixed solution by using a constant-pressure dropping funnel, reacting at 0-5 ℃, and checking whether the reaction is finished by using a thin-layer silica gel plate (TLC). After the reaction was complete, the pH of the solution was adjusted to neutral with 10% HCl. Then, 0.01mol of p-toluenesulfonic acid is added into the reaction mixture, the reaction is carried out at 65-70 ℃, and the completion of the reaction is checked by TLC. And after the reaction is finished, pouring the reaction solution into 100mL of ice water, adjusting the pH value of the solution to 7-9 by using triethylamine, separating out a precipitate, filtering, washing with distilled water to be neutral, and recrystallizing with absolute ethyl alcohol to obtain a quinolinone intermediate.
0.01mol of the home-made intermediate was dissolved in 20mL of acetic acid. And slowly dropping a mixed solution of 0.02mol of cyanoacethydrazide and 10mL of absolute ethyl alcohol into the mixed solution by using a constant-pressure dropping funnel, reacting at 25-35 ℃, and checking whether the reaction is finished by using TLC. After the reaction is finished, removing the solvent by rotary evaporation to obtain a solid mixture, and separating by silica gel column chromatography (eluent is a mixture of ethyl acetate and petroleum ether with the volume ratio of 1: 20) to obtain the target compound, wherein the physicochemical properties of the target compound are as follows:
a light yellow powder; yield: 92 percent; the hydrogen spectrum is shown in fig. 10, the carbon spectrum is shown in fig. 11, the high resolution mass spectrum is shown in fig. 12, and specifically,1H NMR(400MHz,DMSO-d6)(ppm):10.99(1H,s),7.83(1H,d,J＝8.0Hz),7.45(1H,dd,J＝5.2,1.2Hz),7.14(1H,d,J＝8.8Hz),7.10(1H,d,J＝3.6Hz),7.00(1H,dd,J＝5.2,3.6Hz),6.79(1H,d,J＝8.0Hz),6.74(1H,s),6.67-6.65(1H,m),4.77(1H,dd,J＝9.6,5.2Hz),4.21(2H,s),3.10(1H,dd,J＝16.4,4.4Hz),2.78(1H,dd,J＝16.4,9.2Hz)；13C NMR(100MHz,DMSO-d6)(ppm):165.93,147.70,146.97,146.02,131.13,127.14,125.38,125.25,125.01,117.82,117.70,116.76,116.34,50.40,34.10,25.21；HRMS(ESI)m/z:Calcd forC16H14N4OS[M+H]+:311.0961,Found:311.0966.
example 5:
compound 5:
Figure BDA0002575159170000091
preparation of
0.01mol of 2-aminoacetophenone was dissolved in 10mL of anhydrous ethanol, and 10mL of 10% NaOH ethanol solution was added thereto. Stirring in an ice bath, slowly dropping a mixed solution of 0.01mol of 5-chlorothiophene-2-formaldehyde and 10mL of absolute ethyl alcohol into the mixed solution by using a constant-pressure dropping funnel, reacting at 0-5 ℃, and checking whether the reaction is finished by using a thin-layer silica gel plate (TLC). After the reaction was complete, the pH of the solution was adjusted to neutral with 10% HCl. Then, 0.01mol of p-toluenesulfonic acid is added into the reaction mixture, the reaction is carried out at 65-70 ℃, and the completion of the reaction is checked by TLC. And after the reaction is finished, pouring the reaction solution into 100mL of ice water, adjusting the pH value of the solution to 7-9 by using triethylamine, separating out a precipitate, filtering, washing with distilled water to be neutral, and recrystallizing with absolute ethyl alcohol to obtain a quinolinone intermediate.
0.01mol of the home-made intermediate was dissolved in 20mL of acetic acid. And slowly dropping a mixed solution of 0.02mol of cyanoacethydrazide and 10mL of absolute ethyl alcohol into the mixed solution by using a constant-pressure dropping funnel, reacting at 25-35 ℃, and checking whether the reaction is finished by using TLC. After the reaction is finished, removing the solvent by rotary evaporation to obtain a solid mixture, and separating by silica gel column chromatography (eluent is a mixture of ethyl acetate and petroleum ether with the volume ratio of 1: 20) to obtain the target compound, wherein the physicochemical properties of the target compound are as follows:
a milky white powder; yield: 91%; the hydrogen spectrum is shown in fig. 13, the carbon spectrum is shown in fig. 14, the high-resolution mass spectrum is shown in fig. 15, and specifically,1H NMR(400MHz,DMSO-d6)(ppm):11.00(1H,s),7.83(1H,dd,J＝8.0,1.2Hz),7.16-7.14(1H,m),7.02-7.01(1H,m),6.95(1H,d,J＝4.0Hz),6.81-6.76(2H,m),6.69-6.66(1H,m),4.77-4.73(1H,m),4.22(2H,s),3.06(1H,dd,J＝16.4,4.4Hz),2.81(1H,dd,J＝16.8,8.8Hz)；13C NMR(100MHz,DMSO-d6)(ppm):165.99,159.42,147.20,146.53,145.48,131.23,127.17,126.82,125.05,118.04,117.75,116.74,116.37,50.49,33.42,25.22；HRMS(ESI)m/z:Calcd for C16H13ClN4OS[M+H]+:345.0571,Found:345.0559.
experimental example 1: determination of insecticidal Activity of Compounds of the present invention
(1) Test pest
Adult corn weevils, adult corn clothes and adult tribolium castaneum, which are all sensitive strains bred indoors for years.
(2) Measurement method
Adopting a feed mixing method: mixing the compound to be tested and the wheat feed uniformly according to a certain dosage. Weighing 100 g of the drug-mixed feed into 500mL wide-mouth bottles, putting 30 heads of tested pests into each bottle, wrapping the bottle mouth with white cloth, placing the bottles in a pest feeding room with the temperature of 28-30 ℃ and the relative humidity of 70-80% for continuous feeding, and taking the feed without the drug as a blank control. Mortality was recorded after 14 days, each experiment was repeated 3 times, and corrected mortality was calculated using the following formula:
Figure BDA0002575159170000101
(3) results of the experiment
The insecticidal results of the compounds of the present invention are shown in table 1.
TABLE 1 poisoning Activity of Compounds of the invention against storage pests
Figure BDA0002575159170000102
a: average of three replicates.
From Table 1 above, it is clear that the compounds of the present invention have a good poisoning activity against these pests.
Experimental example 2: measurement of Germination-promoting Effect of the Compound of the present invention on vegetable seeds
(1) Test seeds
Cucumber seeds (Zhongnong No. 8), green pepper seeds (Fengyuan No. 8), tomato seeds (Dongfeng No. 4), and celery seeds (Jinnanshi No. 1).
(2) Measurement method
The test compounds were dissolved in dimethyl sulfoxide and diluted to 20mg/L in tap water containing 0.1% Tween-80 for use. 10 g of cucumber seeds, 10 g of green pepper seeds, 5 g of tomato seeds and 5 g of celery seeds are respectively weighed. And respectively soaking the test solution into 20mL of the test solution, stirring for 30 minutes, fishing out the test solution into a small sieve, washing for 3-4 times by using tap water, and air-drying for later use. The corresponding solution without test compound was used as a blank. 100 seeds with uniform size and no defect treated by the liquid medicine are respectively selected and are horizontally placed in a culture dish (9cm) paved with double-layer filter paper. The water adding amount for the 1 st time is as follows: 9mL of cucumber, 7mL of green pepper, 5mL of tomato and 5mL of celery are put into a constant temperature box (25 +/-2 ℃) for accelerating germination, observed for 1 time every day and quantitatively supplemented when water is deficient. Each treatment was repeated 3 times. The germination of cucumber was checked after 1 day, the germination of green pepper after 5 days, the germination of tomato after 3 days, and the germination of celery after 9 days, and the average germination percentage was calculated for 3 replicates.
(3) Results of the experiment
The germination-promoting effect of the compounds of the present invention on vegetable seeds is shown in table 2.
TABLE 2 accelerating effect of the compound of the present invention on seed germination at 20mg/L
Figure BDA0002575159170000111
a: average of three replicates.
As is clear from Table 2, the compounds of the present invention have a good accelerating effect on the germination of the seeds of all of the above 4 vegetables.
The foregoing embodiments are intended to illustrate that the invention may be implemented or used by those skilled in the art, and modifications to the above embodiments will be apparent to those skilled in the art, and therefore the invention includes, but is not limited to, the above embodiments, any methods, processes, products, etc., consistent with the principles and novel and inventive features disclosed herein, and fall within the scope of the invention.

Claims (10)

1. A compound of formula I:
Figure FDA0002575159160000011
wherein X is oxygen, sulfur or nitrogen; r is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
2. A compound according to claim 1, wherein R is hydrogen, methyl, methoxy, hydroxymethyl, chloro or bromo.
3. A compound according to claim 1, wherein R is hydrogen, methyl, chloro or bromo.
4. The compound of claim 1, wherein X is oxygen or sulfur.
5. The compound of claim 1, having the formula:
Figure FDA0002575159160000012
6. a process for the preparation of a compound according to any one of claims 1 to 5, comprising the steps of:
a. dissolving 2-aminoacetophenone in absolute ethyl alcohol, adding NaOH ethanol solution, adding a mixed solution of a compound A and the absolute ethyl alcohol, and reacting at 0-5 ℃;
b. after the reaction is finished, adjusting the pH value of the reaction solution to be neutral, then adding p-toluenesulfonic acid into the reaction solution, and reacting at 65-70 ℃;
c. after the reaction is finished, pouring the reaction liquid into ice water, adjusting the pH value of the solution to 7-9 by using triethylamine until a precipitate is separated out, filtering, washing the precipitate, and recrystallizing by using absolute ethyl alcohol to obtain a quinolinone intermediate;
d. dissolving the quinolinone intermediate in acetic acid, adding a mixed solution of cyanoacethydrazide and absolute ethyl alcohol, reacting at 25-35 ℃, removing the solvent to obtain a solid mixture after the reaction is finished, and performing chromatographic separation by using a silica gel column to obtain a target compound;
wherein the compound A is
Figure FDA0002575159160000021
Wherein X is oxygen, sulfur or nitrogen; r is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
7. Use of a compound according to any one of claims 1 to 5 for the preparation of a medicament for controlling pests; preferably, the pests are storage pests.
8. Use of the compound according to claim 7 for the preparation of a medicament for controlling pests, wherein the pests are at least one of elephant corn, clothes of corn and tribolium castaneum;
preferably, when the pest is a corn weevil, the compound is compound 2 or compound 4; when the pests are the grain, the compound is compound 2, compound 3 or compound 5; when the pest is tribolium castaneum, the compound is compound 2, compound 3 or compound 5;
more preferably, when the pest is a corn elephant, the compound is compound 2; when the pest is the grain, the compound is compound 2 or compound 5.
9. Use of a compound according to any one of claims 1 to 5 for the preparation of a seed germination promoter.
10. Use of a compound according to claim 9 for the preparation of a seed germination promoter, wherein the seed is a vegetable seed; preferably, the vegetable seeds are cucumber seeds, green pepper seeds, tomato seeds or celery seeds; more preferably, when the vegetable seed is cucumber seed, the compound is compound 2; when the vegetable seed is a green pepper seed, the compound is compound 1 or compound 4; when the vegetable seed is a tomato seed, the compound is compound 5; when the vegetable seed is celery seed, the compound is compound 4.
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CN112939939B (en) * 2021-03-11 2023-12-26 西华大学 2- (4-chlorophenyl) pyridine compound and application thereof in pesticides

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