CN114644645B - 3-indole substituted phenylborozole compound and preparation method and application thereof - Google Patents

3-indole substituted phenylborozole compound and preparation method and application thereof Download PDF

Info

Publication number
CN114644645B
CN114644645B CN202210228760.2A CN202210228760A CN114644645B CN 114644645 B CN114644645 B CN 114644645B CN 202210228760 A CN202210228760 A CN 202210228760A CN 114644645 B CN114644645 B CN 114644645B
Authority
CN
China
Prior art keywords
substituted
indole
phenylborozole
compound
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210228760.2A
Other languages
Chinese (zh)
Other versions
CN114644645A (en
Inventor
张明智
黄代钏
何卓
邓放
郭大乐
刘佳木
张悦嘉
淡正阳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Agricultural University
Original Assignee
Nanjing Agricultural University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Agricultural University filed Critical Nanjing Agricultural University
Priority to CN202210228760.2A priority Critical patent/CN114644645B/en
Publication of CN114644645A publication Critical patent/CN114644645A/en
Application granted granted Critical
Publication of CN114644645B publication Critical patent/CN114644645B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/08—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing boron
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention discloses a 3-indole substituted phenylborozole compound with a structure shown in a formula I: r is R 1 Selected from H, F, cl, br, I or C 1 ‑C 3 An alkoxy group; r is R 2 Selected from H, F, cl, br, I, C 1 ‑C 3 Alkyl or C 1 ‑C 3 An alkoxy group; but does not include: r is R 1 Selected from H, F, cl, me, OMe substituted at the 5 'position and F substituted at the 6' position. The invention also discloses application of the 3-indole substituted benzoborozole compound in killing pathogenic bacteria of crops. The crop pathogenic bacteria are Botrytis cinerea, alternaria solani, alternaria wheat, rhizoctonia solani, spot disease of apple, and anthracnose of cucumber.

Description

3-indole substituted phenylborozole compound and preparation method and application thereof
Technical Field
The invention relates to an agricultural bactericide, in particular to a 3-indole substituted phenylborozole compound, a preparation method thereof and application thereof in sterilization.
Background
The 3-indole substituted phenylborozole compounds have more reports, the phenylborozole has various physiological activities and applications, and the corresponding synthetic method is limited, so that the development of the synthetic method containing the phenylborozole skeleton has positive significance for the research on the chemical application and the pharmaceutical activity of the compound. Indole skeletons are important building blocks widely existing in natural products and drug molecules, and development of complex molecular synthesis strategies containing indole skeletons has been a focus of research in organic chemistry and pharmaceutical chemistry. The indole skeleton is introduced into the phenylborozole molecules, and a method for efficiently and conveniently synthesizing heterocyclic substituted phenylborozole molecules is developed, so that the method has positive significance in the fields of pharmaceutical science and organic methodology.
The inventor consults the related data to know that reports about 3-indole substituted phenylborozole compounds are less, and researches on the 3-indole substituted phenylborozole compounds are mainly focused on resisting Alzheimer's disease, but the 3-indole substituted phenylborozole compounds are rarely used as agricultural bactericides.
Disclosure of Invention
The invention aims to provide a series of novel 3-indole substituted phenylborozole compounds, and the sterilization activity of the novel 3-indole substituted phenylborozole compounds is improved and the sterilization spectrum of the novel 3-indole substituted phenylborole compounds is enlarged by combining o-formylphenylboronic acid with substituted indole.
The invention aims at realizing the following technical scheme:
3-indole substituted phenylborozole compound shown in structural formula I:
Figure BDA0003537330740000011
wherein R is 1 Selected from H, F, cl, br, I or C 1 -C 3 An alkoxy group; r is R 2 Selected from H, F, cl, br, I, C 1 -C 3 Alkyl or C 1 -C 3 An alkoxy group; but does not include: r is R 1 Selected from H, F, cl, me, OMe substituted at the 5 'position and F substituted at the 6' position.
Preferably, R 1 Selected from H, R 2 Selected from Cl, br, I, C substituted at the 6' position, C substituted at the 4' position or 7' position 1 -C 3 An alkyl group;
R 1 selected from F, cl, br, I or C 1 -C 3 Alkoxy, R 2 F, cl substituted at H,5 'or 6' position,Br, I, C substituted at 4', 5' or 7 1 -C 3 Alkyl, C 1 -C 3 An alkoxy group.
Further preferably, R 1 Selected from H, R 2 Selected from Cl substituted at the 6' position, methyl substituted at the 4' position or 7' position;
R 1 selected from F, cl, br or I, R 2 Selected from the group consisting of H, F, cl, br, I substituted at the 5 'or 6' position, methyl substituted at the 4 'position, 5' or 7 'position, methoxy substituted at the 5' position;
R 1 selected from methoxy, R 2 Selected from the group consisting of H, F, cl, br, I substituted at the 5' position or the 6' position, methyl substituted at the 4' position.
Most preferably, R 1 Selected from H, R 2 Selected from Cl substituted at the 6' position, methyl substituted at the 4' position or 7' position;
R 1 selected from F, cl, br or I, R 2 A methyl group selected from the group consisting of an H,5' or 6' substituted F, cl, br, I, 4', 5' or 7' substituted methyl group;
R 1 selected from methoxy, R 2 Selected from Cl substituted at the 5' position.
In the present invention, R 1 Preferably a substitution at position 5.
The invention also aims to provide a preparation method of the 3-indole substituted phenylborozole compound, which comprises the following synthetic route:
Figure BDA0003537330740000021
wherein R is 1 、R 2 As previously described.
Comprising the following steps: and (3) taking deionized water as a solvent, and carrying out Friedel-Crafts reaction on the o-formylphenylboronic acid shown in the formula III and the substituted or unsubstituted indole shown in the formula IV to obtain the 3-indole substituted phenylborozole compound shown in the formula I.
The molar ratio of the substituted or unsubstituted indole to the o-formylphenylboronic acid is more than 1:1, and generally 1.5:1 is selected. The substituted or unsubstituted indole is in excess to ensure complete reaction of the o-formylphenylboronic acid.
The temperature of the Friedel-Crafts reaction is room temperature.
The preparation method of the 3-indole substituted phenylborozole compound further comprises purification of the target compound, and the purification method is not particularly required, and various purification methods conventionally used by those skilled in the art can be adopted, for example, extraction with an extractant, drying with a drying agent, and impurity removal by column chromatography and the like can be adopted.
The 3-indole substituted phenylborozole compound provided by the invention has high-efficiency and/or broad-spectrum bactericidal activity. Therefore, another object of the invention is to provide the application of the 3-indole substituted benzoborozole compound in killing pathogenic bacteria of crops.
The crop pathogenic bacteria are Botrytis cinerea, alternaria solani, alternaria wheat, rhizoctonia solani, spot bacteria of apples and anthracnose bacteria of cucumbers; preferably, the plant is Botrytis cinerea, alternaria wheat, rhizoctonia solani, sporotrichum apple, and anthracis cucumber.
The invention also aims to provide the application of the 3-indole substituted benzoborozole compound with the structure shown in the formula II in killing crop pathogenic bacteria:
Figure BDA0003537330740000031
wherein R is 2 Selected from H, F, cl, me, OMe substituted at the 5 'position, F substituted at the 6' position.
The crop pathogenic bacteria are Botrytis cinerea, alternaria wheat, rhizoctonia solani, spot pathogen of apple, and anthracnose pathogen of cucumber; preferably, the bacterial species are Botrytis cinerea and Bacillus anthracis.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses o-formylphenylboronic acid and various substituted indoles as starting materials, and the 3-indole substituted phenylborozole compound can be obtained through one-step simple reaction.
2. The 3-indole substituted phenylborozole compound has good bactericidal activity, and the 3-indole substituted phenylborozole compound has high-efficiency and/or broad-spectrum bactericidal activity and can be applied to crop diseases caused by fungi.
Detailed Description
The technical scheme of the present invention will be described in detail by examples. In the following examples, all of the starting materials used in this example were commercially available and all had analytically pure purity levels, unless otherwise specified. The room temperature was 25 ℃.
Example 1
The 3-indole substituted phenylborozole compound shown in the formula I is synthesized by taking O-formylphenylboronic acid shown in the formula III and substituted indole shown in the formula IV as raw materials, and the synthetic route is as follows:
Figure BDA0003537330740000032
the method comprises the following specific steps:
taking a 100mL round-bottom flask, sequentially adding O-formylphenylboronic acid (2 mmol), substituted indole (3 mmol) and deionized water 40mL, reacting at room temperature, and monitoring the reaction progress by TLC; after the reaction is finished, extracting with dichloromethane, adding silica gel, stirring, eluting with 17-20% ethyl acetate/petroleum ether as eluent, purifying by silica gel column chromatography to obtain the target compound, drying, and weighing. Calculate the yield by 1 H NMR、 13 C NMR, IR and MS characterize its structure.
The obtained 3-indole substituted phenylborozole compounds are shown in table 1.
TABLE 1.3-indole substituted phenylboroazoles
Numbering of compounds R 1 R 2 Numbering of compounds R 1 R 2
I-1a H H I-1b 5-F H
I-2a H 5’-F I-2b 5-F 5’-F
I-3a H 5’-Cl I-3b 5-F 5’-Cl
I-4a H 5’-Me I-4b 5-F 5’-Me
I-5a H 5’-OMe I-5b 5-F 5’-OMe
I-6a H 6’-F I-6b 5-F 6’-F
I-7a H 6’-Cl I-7b 5-F 6’-Cl
I-8a H 4’-Me I-8b 5-F 4’-Me
I-9a H 7’-Me I-9b 5-F 7’-Me
I-1c 5-Cl H I-1d 5-OMe H
I-2c 5-Cl 5’-F I-2d 5-OMe 5’-F
I-3c 5-Cl 5’-Cl I-3d 5-OMe 5’-Cl
I-4c 5-Cl 5’-Me I-4d 5-OMe 5’-Me
I-5c 5-Cl 5’-OMe I-5d 5-OMe 5’-OMe
I-6c 5-Cl 6’-F I-6d 5-OMe 6’-F
I-7c 5-Cl 6’-Cl I-7d 5-OMe 6’-Cl
I-8c 5-Cl 4’-Me I-8d 5-OMe 4’-Me
I-9c 5-Cl 7’-Me I-9d 5-OMe 7’-Me
The spectrum data of the target compound are as follows:
compound I-1a: 3-indole substituted 3-phenylborozole; pale red solid, yield: 95%. 1 H NMR(400MHz,DMSO)δ11.06(s,1H),9.17(s,1H),7.81(d,J＝6.5Hz,1H),7.45–7.29(m,4H),7.19(d,J＝7.0Hz,1H),7.03(t,J＝7.3Hz,1H),6.97(d,J＝7.8Hz,1H),6.83(t,J＝7.3Hz,1H),6.43(s,1H).HR-MS(ESI):m/z calcd for C 15 H 12 BNO 2 ([M+H] + )250.1034,Found 250.1047.
Compound I-2a:3- (5-fluoro) -indole substituted 3-phenylborozole; pale yellow solid, yield: 53%. 1 H NMR(400MHz,DMSO)δ11.19(s,1H),9.22(s,1H),7.82(d,J＝6.8Hz,1H),7.49–7.32(m,4H),7.21(d,J＝7.2Hz,1H),6.89(td,J＝9.2,2.5Hz,1H),6.60(dd,J＝10.1,2.4Hz,1H),6.42(s,1H).HR-MS(ESI):m/z calcd for C 15 H 11 BFNO 2 ([M+H] + )268.0940,Found 268.0957.
Compound I-3a:3- (5-chloro) -indole substituted 3-phenylborozole; white solid, yield: 54%. 1 H NMR(400MHz,DMSO)δ11.29(s,1H),9.25(s,1H),7.83(d,J＝6.9Hz,1H),7.42(ddd,J＝17.3,12.7,4.7Hz,4H),7.21(d,J＝7.2Hz,1H),7.05(dd,J＝8.6,1.9Hz,1H),6.96(d,J＝1.6Hz,1H),6.44(s,1H).HR-MS(ESI):m/z calcd for C 15 H 11 BClNO 2 ([M+H] + )268.0644,Found 268.0666.
Compound I-4a:3- (5-methyl) -indole substituted 3-phenylborozole; white solid, yield: 51%. 1 H NMR(400MHz,DMSO)δ10.92(s,1H),9.16(s,1H),7.80(d,J＝6.9Hz,1H),7.43(td,J＝7.4,1.3Hz,1H),7.38(t,J＝7.0Hz,1H),7.26–7.19(m,3H),6.87(d,J＝8.3Hz,1H),6.83(s,1H),6.40(s,1H),2.23(s,3H).HR-MS(ESI):m/z calcd for C 16 H 14 BNO 2 ([M+H] + )264.1190,Found 264.1208.
Compound I-5a:3- (5-methoxy) -indole substituted 3-phenylborozole; white solid, yield: 45%. 1 H NMR(400MHz,DMSO)δ10.91(s,1H),9.17(s,1H),7.82(d,J＝7.0Hz,1H),7.44(td,J＝7.4,1.2Hz,1H),7.39(t,J＝7.1Hz,1H),7.27–7.20(m,3H),6.71(dd,J＝8.8,2.4Hz,1H),6.48(d,J＝2.2Hz,1H),6.43(s,1H),3.57(s,3H).HR-MS(ESI):m/z calcd for C 16 H 14 BNO 3 ([M+H] + )280.1140,Found280.1142.
Compound I-6a:3- (6-fluoro) -indole substituted 3-phenylborozole; pale yellow solid, yield: 55%. 1 H NMR(400MHz,DMSO)δ11.14(s,1H),9.22(s,1H),7.82(d,J＝6.8Hz,1H),7.46–7.41(m,1H),7.38(t,J＝7.0Hz,1H),7.34(d,J＝2.3Hz,1H),7.20(d,J＝7.2Hz,1H),7.14(dd,J＝10.1,2.2Hz,1H),6.94(dd,J＝8.7,5.5Hz,1H),6.73(td,J＝9.8,2.3Hz,1H),6.42(s,1H).HR-MS(ESI):m/z calcd for C 15 H 11 BFNO 2 ([M+H] + )268.0940,Found 268.0942.
Compound I-7a:3- (6-chloro) -indole-substituted 3-phenylborozole; pale red solid, yield: 32%. 1 H NMR(400MHz,DMSO)δ11.21(s,1H),9.23(s,1H),7.81(d,J＝7.1Hz,1H),7.41(dd,J＝18.6,7.1Hz,4H),7.19(d,J＝7.3Hz,1H),6.96(d,J＝8.4Hz,1H),6.88(d,J＝8.5Hz,1H),6.42(s,1H).HR-MS(ESI):m/z calcd for C 15 H 11 BClNO 2 ([M+H] + )284.0644,Found 284.0650.
Compound I-8a:3- (4-methyl) -indole substituted 3-phenylborozole; pale yellow solid, yield: 28%. 1 H NMR(400MHz,DMSO)δ11.00(s,1H),9.10(s,1H),7.79(d,J＝7.2Hz,1H),7.50(t,J＝7.4Hz,1H),7.41(t,J＝7.2Hz,1H),7.37(d,J＝7.5Hz,1H),7.21(d,J＝8.1Hz,1H),7.00(t,J＝7.6Hz,1H),6.80(d,J＝7.1Hz,1H),6.71(d,J＝2.3Hz,1H),6.68(s,1H),2.66(s,3H).HR-MS(ESI):m/z calcd for C 16 H 14 BNO 2 ([M+H] + )264.1190,Found 264.1206.
Compound I-9a:3- (7-methyl) -indole substituted 3-phenylborozole; pale red solid, yield: 38%. 1 H NMR(400MHz,DMSO)δ11.03(s,1H),9.17(s,1H),7.80(d,J＝6.6Hz,1H),7.43–7.39(m,1H),7.36(d,J＝7.1Hz,1H),7.31(d,J＝2.5Hz,1H),7.18(d,J＝7.0Hz,1H),6.81(dd,J＝13.7,7.2Hz,2H),6.76–6.70(m,1H),6.42(s,1H),2.43(s,3H).HR-MS(ESI):m/z calcd for C 16 H 14 BNO 2 ([M+H] + )264.1190,Found 264.1210.
Compound I-1b: 3-indole substituted 3- (5-fluoro) -phenylborozole; brown solid, yield: 45%. 1 H NMR(400MHz,DMSO)δ11.11(s,1H),9.27(s,1H),7.85(dd,J＝7.9,5.9Hz,1H),7.37(t,J＝5.4Hz,2H),7.25–7.19(m,1H),7.05(t,J＝7.5Hz,1H),6.98(dd,J＝8.4,4.1Hz,2H),6.86(t,J＝7.4Hz,1H),6.43(s,1H).HR-MS(ESI):m/z calcd for C 15 H 11 BFNO 2 ([M+H] + )268.0940,Found 268.0966.
Compound I-2b:3- (5-fluoro) -indole substituted 3- (5-fluoro) -phenylborozole; pale yellow solid, yield: 48%. 1 H NMR(400MHz,DMSO)δ11.24(s,1H),9.31(s,1H),7.86(dd,J＝8.0,5.8Hz,1H),7.44(d,J＝2.5Hz,1H),7.38(dd,J＝8.8,4.6Hz,1H),7.28–7.20(m,1H),7.01(dd,J＝9.2,1.8Hz,1H),6.91(td,J＝9.2,2.5Hz,1H),6.67(dd,J＝10.1,2.5Hz,1H),6.43(s,1H).HR-MS(ESI):m/z calcd for C 15 H 10 BF 2 NO 2 ([M+H] + )286.0845,Found 286.0872.
Compound I-3b:3- (5-chloro) -indole substituted 3- (5-fluoro) -phenylborozole; pale red solid, yield: 30%. 1 H NMR(400MHz,DMSO)δ11.33(s,1H),9.32(s,1H),7.85(dd,J＝8.0,5.8Hz,1H),7.43(d,J＝2.5Hz,1H),7.39(d,J＝8.6Hz,1H),7.28–7.21(m,1H),7.06(dd,J＝8.6,2.0Hz,1H),7.01(dd,J＝12.4,1.9Hz,2H),6.43(s,1H).HR-MS(ESI):m/z calcd for C 15 H 10 BClFNO 2 ([M+H] + )302.0550,Found 302.0571.
Compound I-4b:3- (5-methyl) -indole substituted 3- (5-fluoro) -phenylborozole; pale red solid, yield: 30%. 1 H NMR(400MHz,DMSO)δ10.96(s,1H),9.23(s,1H),7.84(dd,J＝8.0,5.8Hz,1H),7.28–7.18(m,3H),6.98(dd,J＝9.3,1.8Hz,1H),6.88(d,J＝8.3Hz,1H),6.83(s,1H),6.40(s,1H),2.24(s,3H).HR-MS(ESI):m/z calcd for C 16 H 13 BFNO 2 ([M+H] + )282.1096,Found 282.1128.
Compound I-5b:3- (5-methoxy) -indole substituted 3- (5-fluoro) -phenylborozole; pale red solid, yield: 23%. 1 H NMR(400MHz,DMSO)δ10.95(s,1H),9.24(s,1H),7.84(dd,J＝8.0,5.8Hz,1H),7.28–7.19(m,3H),7.00(dd,J＝9.3,1.8Hz,1H),6.72(dd,J＝8.8,2.4Hz,1H),6.49(d,J＝2.3Hz,1H),6.42(s,1H),3.59(s,3H).HR-MS(ESI):m/z calcd for C 16 H 13 BFNO 3 ([M+H] + )298.1045,Found298.1083.
Compound I-6b:3- (6-fluoro) -indole substituted 3- (5-fluoro) -phenylborozole; yellow solid, yield: 36%. 1 H NMR(400MHz,DMSO)δ11.18(s,1H),9.29(s,1H),7.85(dd,J＝8.0,5.9Hz,1H),7.36(d,J＝2.3Hz,1H),7.27–7.19(m,1H),7.15(dd,J＝10.1,2.2Hz,1H),7.02–6.93(m,2H),6.79–6.71(m,1H),6.42(s,1H).HR-MS(ESI):m/z calcd for C 15 H 10 BF 2 NO 2 ([M+H] + )286.0845,Found 286.0873.
Compound I-7b:3- (6-chloro) -indole substituted 3- (5-fluoro) -phenylborozole; red colorSolid, yield: 28%. 1 H NMR(400MHz,DMSO)δ11.26(s,1H),9.30(s,1H),7.85(dd,J＝8.0,5.8Hz,1H),7.41(dd,J＝4.5,2.1Hz,2H),7.27–7.19(m,1H),6.99(d,J＝8.4Hz,2H),6.91(dd,J＝8.5,1.8Hz,1H),6.42(s,1H).HR-MS(ESI):m/z calcd for C 15 H 10 BClFNO 2 ([M+H] + )302.0550,Found 302.0587.
Compound I-8b:3- (4-methyl) -indole substituted 3- (5-fluoro) -phenylborozole; white solid, yield: 23%. 1 H NMR(400MHz,DMSO)δ11.04(s,1H),9.16(s,1H),7.82(dd,J＝8.0,5.9Hz,1H),7.26(dd,J＝11.7,3.8Hz,1H),7.22(d,J＝8.4Hz,1H),7.16(d,J＝9.3Hz,1H),7.00(t,J＝7.6Hz,1H),6.80(d,J＝7.1Hz,1H),6.77(d,J＝2.2Hz,1H),6.67(s,1H),2.66(s,3H).HR-MS(ESI):m/z calcd for C 16 H 13 BFNO 2 ([M+H] + )282.1096,Found 282.1132.
Compound I-9b:3- (7-methyl) -indole substituted 3- (5-fluoro) -phenylborozole; pale red solid, yield: 70%. 1 H NMR(400MHz,DMSO)δ11.09(s,1H),9.26(s,1H),7.84(dd,J＝8.0,5.8Hz,1H),7.35(d,J＝2.5Hz,1H),7.26–7.18(m,1H),6.95(dd,J＝9.3,1.8Hz,1H),6.85(d,J＝6.6Hz,1H),6.78(dt,J＝14.6,7.5Hz,2H),6.42(s,1H),2.44(s,3H).HR-MS(ESI):m/z calcd for C 16 H 13 BFNO 2 ([M+H] + )282.1096,Found 282.1134.
Compound I-1c: 3-indole substituted 3- (5-chloro) -benzoborozole; red solid, yield: 52%. 1 H NMR(400MHz,DMSO)δ11.12(s,1H),9.36(s,1H),7.81(d,J＝7.8Hz,1H),7.44(d,J＝7.8Hz,1H),7.37(d,J＝8.0Hz,2H),7.20(s,1H),7.05(t,J＝7.4Hz,1H),6.96(d,J＝7.9Hz,1H),6.85(t,J＝7.4Hz,1H),6.44(s,1H).HR-MS(ESI):m/z calcd for C 15 H 11 BClNO 2 ([M+H] + )284.0644,Found 284.0647.
Compound I-2c:3- (5-fluoro) -indole substituted 3- (5-chloro) -phenylborozole; pale red solid, yield: 36%. 1 H NMR(400MHz,DMSO)δ11.25(s,1H),9.39(s,1H),7.83(d,J＝7.8Hz,1H),7.46(dd,J＝11.4,1.9Hz,2H),7.38(dd,J＝8.8,4.6Hz,1H),7.24(s,1H),6.91(td,J＝9.2,2.5Hz,1H),6.67(dd,J＝10.0,2.3Hz,1H),6.44(s,1H).HR-MS(ESI):m/z calcd for C 15 H 10 BClFNO 2 ([M+H] + )302.0550,Found 302.0567.
Compound I-3c:3- (5-chloro) -indole substituted 3- (5-chloro) -phenylborozole; yellow solid, yield: 51%. 1 H NMR(400MHz,DMSO)δ11.34(s,1H),9.42(s,1H),7.82(d,J＝7.8Hz,1H),7.50–7.43(m,2H),7.40(d,J＝8.6Hz,1H),7.24(s,1H),7.07(dd,J＝8.6,1.9Hz,1H),7.00(s,1H),6.45(s,1H).HR-MS(ESI):m/z calcd for C 15 H 10 BCl 2 NO 2 ([M+H] + )318.0254,Found 318.0268.
Compound I-4c:3- (5-methyl) -indole substituted 3- (5-chloro) -phenylborozole; red solid, yield: 47%. 1 H NMR(400MHz,DMSO)δ10.97(s,1H),9.33(s,1H),7.81(d,J＝7.9Hz,1H),7.44(dd,J＝7.8,1.4Hz,1H),7.29–7.23(m,2H),7.21(d,J＝0.7Hz,1H),6.88(d,J＝8.3Hz,1H),6.83(s,1H),6.41(s,1H),2.24(s,3H).HR-MS(ESI):m/z calcd for C 16 H 13 BClNO 2 ([M+H] + )298.0801,Found298.0825.
Compound I-5c:3- (5-methoxy) -indole substituted 3- (5-chloro) -phenylborozole; pale red solid, yield: 24%. 1 H NMR(400MHz,DMSO)δ10.96(s,1H),9.33(s,1H),7.81(d,J＝7.8Hz,1H),7.45(dd,J＝7.8,1.5Hz,1H),7.26(dd,J＝5.6,3.1Hz,2H),7.23(s,1H),6.72(dd,J＝8.8,2.4Hz,1H),6.47(d,J＝2.3Hz,1H),6.43(s,1H),3.59(s,3H).HR-MS(ESI):m/z calcd for C 16 H 13 BClNO 3 ([M+H] + )314.0750,Found 314.0776.
Compound I-6c:3- (6-fluoro) -indole substituted 3- (5-chloro) -phenylborozole; red solid, yield: 39%. 1 H NMR(400MHz,DMSO)δ11.19(s,1H),9.38(s,1H),7.81(d,J＝7.8Hz,1H),7.45(dd,J＝7.8,1.2Hz,1H),7.38(d,J＝2.4Hz,1H),7.21(s,1H),7.15(dd,J＝10.1,2.3Hz,1H),6.95(dd,J＝8.7,5.5Hz,1H),6.75(td,J＝9.8,2.3Hz,1H),6.43(s,1H).HR-MS(ESI):m/z calcd for C 15 H 10 BClFNO 2 ([M+H] + )302.0550,Found 302.0568.
Compound I-7c:3- (6-chloro) -indole substituted 3- (5-chloro) -phenylborozole; yellow solid, yield: 60%. 1 H NMR(400MHz,DMSO)δ11.27(s,1H),9.41(s,1H),7.81(d,J＝7.7Hz,1H),7.51–7.38(m,3H),7.21(s,1H),6.94(dd,J＝24.6,8.0Hz,2H),6.43(s,1H).HR-MS(ESI):m/z calcd for C 15 H 10 BCl 2 NO 2 ([M+H] + )318.0254,Found 318.0281.
Compound I-8c:3- (4-methyl) -indole substituted 3- (5-chloro) -phenylborozole; white solid, yield: 22%. 1 H NMR(400MHz,DMSO)δ11.05(s,1H),9.25(s,1H),7.79(d,J＝7.8Hz,1H),7.48(dd,J＝7.8,1.2Hz,1H),7.38(s,1H),7.22(d,J＝8.1Hz,1H),7.00(t,J＝7.6Hz,1H),6.79(dd,J＝9.6,4.7Hz,2H),6.68(s,1H),2.63(s,3H).HR-MS(ESI):m/z calcd for C 16 H 13 BClNO 2 ([M+H] + )298.0801,Found298.0826.
Compound I-9c:3- (7-methyl) -indole substituted 3- (5-chloro) -phenylborozole; red solid, yield: 51%. 1 H NMR(400MHz,DMSO)δ11.09(s,1H),9.35(s,1H),7.81(d,J＝7.8Hz,1H),7.46–7.42(m,1H),7.37(d,J＝2.6Hz,1H),7.19–7.17(m,1H),6.87–6.83(m,1H),6.81–6.73(m,2H),6.43(s,1H),2.44(s,3H).HR-MS(ESI):m/z calcd for C 16 H 13 BClNO 2 ([M+H] + )298.0801,Found 298.0835.
Compound I-1d: 3-indole substituted 3- (5-methoxy) -benzoborozole; red solid, yield: 64%. 1 H NMR(400MHz,DMSO)δ11.06(s,1H),9.01(s,1H),7.72(d,J＝8.0Hz,1H),7.40–7.32(m,2H),7.08–7.00(m,2H),6.96(d,J＝6.9Hz,1H),6.85(t,J＝7.4Hz,1H),6.70(s,1H),6.36(s,1H),3.69(s,3H).HR-MS(ESI):m/z calcd for C 16 H 14 BNO 3 ([M+H] + )280.1140,Found 280.1167.
Compound I-2d:3- (5-fluoro) -indole substituted 3- (5-methoxy) -phenylborozole; pale red solid, yield: 28%. 1 H NMR(400MHz,DMSO)δ11.18(s,1H),9.04(s,1H),7.72(d,J＝8.1Hz,1H),7.42(d,J＝2.3Hz,1H),7.36(dd,J＝8.8,4.6Hz,1H),6.97(dd,J＝8.1,1.9Hz,1H),6.90(td,J＝9.2,2.4Hz,1H),6.73–6.64(m,2H),6.35(s,1H),3.71(s,3H).HR-MS(ESI):m/z calcd for C 16 H 13 BFNO 3 ([M+H] + )298.1045,Found 298.1077.
Compounds of formula (I)I-3d:3- (5-chloro) -indole substituted 3- (5-methoxy) -phenylborozole; yellow solid, yield: 30%. 1 H NMR(400MHz,DMSO)δ11.28(s,1H),9.06(s,1H),7.72(d,J＝8.0Hz,1H),7.43(s,1H),7.38(d,J＝8.3Hz,2H),7.09–6.92(m,3H),6.71(s,1H),6.35(s,1H),3.71(s,2H).HR-MS(ESI):m/zcalcd for C 16 H 13 BClNO 3 ([M+H] + )314.0750,Found 314.0776.
Compound I-4d:3- (5-methyl) -indole substituted 3- (5-methoxy) -phenylborozole; red solid, yield: 55%. 1 H NMR(400MHz,DMSO)δ10.91(s,1H),8.97(s,1H),7.70(d,J＝8.1Hz,1H),7.23(dd,J＝9.8,5.2Hz,2H),6.95(dd,J＝8.1,1.7Hz,1H),6.91–6.86(m,2H),6.70(s,1H),6.33(s,1H),3.70(s,3H),2.25(s,3H).HR-MS(ESI):m/z calcd for C 17 H 16 BNO 3 ([M+H] + )294.1296,Found 294.1332.
Compound I-5d:3- (5-methoxy) -indole substituted 3- (5-methoxy) -phenylborozole; gray solid, yield: 35%. 1 H NMR(400MHz,DMSO)δ10.89(s,1H),8.98(s,1H),7.70(d,J＝8.1Hz,1H),7.28–7.20(m,2H),6.96(d,J＝8.0Hz,1H),6.71(d,J＝7.0Hz,2H),6.54(s,1H),6.34(s,1H),3.71(s,3H),3.59(s,3H).HR-MS(ESI):m/z calcd for C 17 H 16 BNO 4 ([M+H] + )310.1245,Found 310.1278.
Compound I-6d:3- (6-fluoro) -indole substituted 3- (5-methoxy) -phenylborozole; pale yellow solid, yield: 40%. 1 H NMR(400MHz,DMSO)δ11.13(s,1H),9.02(s,1H),7.71(d,J＝8.1Hz,1H),7.35(s,1H),7.13(d,J＝9.9Hz,1H),7.01–6.92(m,2H),6.73(dd,J＝19.3,10.6Hz,2H),6.34(s,1H),3.70(s,3H).HR-MS(ESI):m/z calcd for C 16 H 13 BFNO 3 ([M+H] + )298.1045,Found 298.1084.
Compound I-7d:3- (6-chloro) -indole substituted 3- (5-methoxy) -phenylborozole; white solid, yield: 29%. 1 H NMR(400MHz,DMSO)δ11.20(s,1H),9.03(s,1H),7.70(d,J＝8.1Hz,1H),7.40(dd,J＝6.6,2.1Hz,2H),7.01(d,J＝8.5Hz,1H),6.96(dd,J＝8.1,2.0Hz,1H),6.89(dd,J＝8.5,1.8Hz,1H),6.69(d,J＝1.6Hz,1H),6.34(s,1H),3.70(s,3H).HR-MS(ESI):m/z calcd for C 16 H 13 BClNO 3 ([M+H] + )314.0750,Found 314.0797.
Compound I-8d:3- (4-methyl) -indole substituted 3- (5-methoxy) -phenylborozole; white solid, yield: 59%. 1 H NMR(400MHz,DMSO)δ10.99(s,1H),8.91(s,1H),7.69(d,J＝8.1Hz,1H),7.22(d,J＝8.1Hz,1H),6.99(t,J＝7.4Hz,2H),6.88(s,1H),6.82–6.75(m,2H),6.61(s,1H),3.77(s,3H),2.67(s,3H).HR-MS(ESI):m/z calcd for C 16 H 13 BClNO 3 ([M+H] + )294.1328,Found 294.1336.
Compound I-9d:3- (7-methyl) -indole substituted 3- (5-methoxy) -phenylborozole; red solid, yield: 20%. 1 H NMR(400MHz,DMSO)δ11.04(s,1H),8.99(s,1H),7.70(d,J＝8.1Hz,1H),7.32(t,J＝3.9Hz,1H),6.94(dd,J＝8.1,2.1Hz,1H),6.84(d,J＝7.6Hz,2H),6.77–6.73(m,1H),6.67(d,J＝2.1Hz,1H),6.34(s,1H),3.69(s,3H),2.43(s,3H).HR-MS(ESI):m/z calcd for C 16 H 13 BClNO 3 ([M+H] + )294.1328,Found 294.1337.
Example 2
Detection of bactericidal activity of target compound
Six agricultural common plant pathogenic fungi of Botrytis cinerea, rhizoctonia solani (Rhizoctonia solani), rhizoctonia solani (Alternaria solani), alternaria wheat (Gibberella zeae), cucumber anthracnose (Colletotrichum lagenarium) and apple alternaria alternate (Alternaria leaf spot) are taken as experimental objects, a hypha growth rate method is adopted to perform antibacterial activity test on all synthesized target compounds, and the antibacterial activity is primarily screened.
Experimental facilities: culture dish (Hefei Xinen Biotechnology Co., ltd.), autoclave (TOMY SX-700), electrothermal constant temperature biochemical incubator (Shanghai Sema laboratory equipment Co., ltd.), eppendof pipetting gun, double-sided purification workbench (Suzhou purification equipment Co., ltd.), puncher, etc.
Preparing experimental materials: preparing Potato Dextrose Agar (PDA); six strains to be tested are transferred onto Potato Dextrose Agar (PDA) before the experiment, cultured for 3-10d at 25+/-1 ℃, and mycelium blocks with the diameter of 5mm are taken at the edge of the mycelium for measurement.
The experimental method comprises the following steps: the antibacterial activity of 36 target compounds was initially screened by hypha growth rate method. Experimental group: 2.5mg of the test compound was weighed and dissolved in 0.1mL of Dimethylsulfoxide (DMSO) to prepare a mother liquor of 25mg/mL, which was then dissolved in PDA medium to give a concentration of 50. Mu.g/mL. The pre-prepared mycelium pellet was inoculated onto PDA medium plates, incubated at 25℃for 2-15d, colony diameters were checked and recorded, and the percentage of inhibition of mycelium growth for each treatment was calculated. The control of the non-drug plate and the commercial drug (flutriafol, boscalid, osthole) plate was set, and the treatment method and the amount of the added solvent were the same as those of the experimental group. Each sample was run in triplicate. The specific experimental data are shown in table 2.
Respectively selecting target compounds with the initial screening inhibition rate of 70% -100% for the Botrytis cinerea, 80% -100% for the Botrytis cinerea and 50% -100% for the Rhizoctonia cerealis, using DMSO to dilute mother solution with the concentration of 25mg/mL in a gradient manner to obtain a series of test solutions, adding the mother solution or the test solution into a PDA culture medium to ensure that the concentration of the target compounds is 50, 25, 12.5, 6.25 and 3.125 mu g/mL respectively, and obtaining the antibacterial activity EC of the target compounds on the fungi according to the experimental method 50 。
TABLE 2 primary screening results of antibacterial Activity of target Compounds [ inhibition Rate eta (%) ]
Figure BDA0003537330740000101
/>
Figure BDA0003537330740000111
Note that: all compounds were tested at a concentration of 50 μg/mL for bacteriostatic activity.
Table 2 shows the primary results of the medium sterilization test, from which the following conclusions can be drawn:
1. the 3-indole substituted benzoborazole compound has certain antibacterial activity on common agricultural fungi, partial antibacterial effect reaches 100%, and the inhibition activity on partial fungi is obviously higher than that of commercial pesticides (osthole, boscalid and flutriafol) of test control.
2. Under the tested concentration, the inhibition rate of the target compound to the strawberry gray mold bacteria and the cucumber anthracnose bacteria is higher than that of osthole; the inhibition rate of the tomato early blight bacteria is generally lower than that of osthole and boscalid; wherein, the compounds I-3c, I-4c and I-7c have higher inhibition activity on six fungi.
3. Under the tested concentration, the target compound shows better antibacterial activity on the Botrytis cinerea, the wheat gibberella, the Rhizoctonia solani, the apple alternaria and the cucumber anthracnose, and especially the inhibition rate of I-2a, I-8a, I-9a, I-1b, I-2b, I-6b, I-8b, I-9b, I-3c, I-4c and the like on the cucumber anthracnose reaches 100 percent, which is superior to that of the control agents osthole and boscalid.
4. The antibacterial effect of the electron withdrawing group such as halogen introduced into the 5 # position of the benzoborozole is better than that of the electron pushing group such as methoxy, and the antibacterial effect of the electron withdrawing group such as halogen introduced into the 5' -position of the indole ring is better than that of the electron pushing groups such as methyl and methoxy, for example: the inhibition rate of the compound I-1b with halogen at the 5 th position of the benzoborozole to the gibberella wheat germs is obviously better than that of the compound I-1d with methoxy at the 5 th position of the benzoborozole; the inhibition rate of the compounds I-2a and I-2b with halogen introduced at the 5 'position of the indole ring on cucumber anthracnose is obviously better than that of the compounds I-4a, I-5a, I-4b and I-5b with methyl and methoxy introduced at the 5' position of the indole ring.
5. The 5-chloro substitution on the borazole benzene ring is best, followed by the 5-fluoro substitution, then no substitution, and worst by the 5-methoxy substitution. Namely: 5-Cl >5-F > H >5-OMe.
6. In the whole, the 5-chlorine substitution on the borazole benzene ring and the 6 '-chlorine substitution on the indole benzene ring, and the 7' -methyl substitution I-7c and I-9c show better broad-spectrum bactericidal activity, and have better bactericidal activity on Botrytis cinerea, alternaria solani, alternaria alternata, alternaria maliciosa and cucumber anthracnose, and the inhibition rate is superior to that of osthole and boscalid.
TABLE 3 antibacterial Activity of partial target Compounds against Botrytis cinerea EC 50 Results (. Mu.g/mL)
Figure BDA0003537330740000121
/>
Figure BDA0003537330740000131
Note that: the initial screening inhibition rate of the selected compound is 70-100%.
TABLE 4 antibacterial Activity of partial target Compounds against wheat scab EC 50 Results (. Mu.g/mL)
Figure BDA0003537330740000132
/>
Figure BDA0003537330740000141
Note that: 1. the initial screening inhibition rate of the selected compound is 80% -100%;
2. boscalid has poor activity against gibberella wheat germs, so the tebuconazole used.
TABLE 5 antibacterial Activity of partial target Compounds against Rhizoctonia solani EC 50 Results (. Mu.g/mL)
Figure BDA0003537330740000142
/>
Figure BDA0003537330740000151
Note that: the initial screening inhibition rate of the selected compound is 50-100%.

Claims (11)

1. 3-indole substituted phenylborozole compound shown in structural formula I:
Figure FDA0004122292020000011
wherein R is 1 Selected from H, F, cl, br, I or C 1 -C 3 An alkoxy group; r is R 2 Selected from H, F, cl, br, I, C 1 -C 3 Alkyl or C 1 -C 3 An alkoxy group; but does not include: r is R 1 Selected from H, R 2 Selected from 5 '-substituted F, cl, br, me, OMe, 6' -substituted F; r is R 1 、R 2 Simultaneously selected from H; r is R 1 Selected from F, R substituted in the 4-position 2 Selected from H; r is R 1 Selected from F, R substituted in position 6 2 Selected from the group consisting of Br substituted at the 5' position.
2. The 3-indole-substituted phenylborozole compound according to claim 1, wherein: r is R 1 Selected from H, R 2 Selected from Cl, br, I, C substituted at the 6' position, C substituted at the 4' position or 7' position 1 -C 3 An alkyl group;
R 1 selected from F, cl, br, I or C 1 -C 3 Alkoxy, R 2 F, cl, br, I substituted at H,5 'or 6', C substituted at 4', 5' or 7 1 -C 3 Alkyl, C 1 -C 3 Alkoxy, but does not include: r is R 1 Selected from F, R substituted in the 4-position 2 Selected from H; r is R 1 Selected from F, R substituted in position 6 2 Selected from the group consisting of Br substituted at the 5' position.
3. The 3-indole-substituted phenylborozole compound according to claim 2, wherein: r is R 1 Selected from H, R 2 Selected from Cl substituted at the 6' position, methyl substituted at the 4' position or 7' position;
R 1 selected from F, cl, br or I, R 2 Selected from the group consisting of H,5 'or 6' substituted F, cl, br, I, 4', 5' or 7 'substituted methyl, 5' substituted methylOxy, but does not include: r is R 1 Selected from F, R substituted in the 4-position 2 Selected from H; r is R 1 Selected from F, R substituted in position 6 2 Selected from Br substituted at the 5' position;
R 1 selected from methoxy, R 2 Selected from the group consisting of H, F, cl, br, I substituted at the 5' position or the 6' position, methyl substituted at the 4' position.
4. The 3-indole-substituted phenylborozole compound according to claim 2, wherein: r is R 1 Selected from H, R 2 Selected from Cl substituted at the 6' position, methyl substituted at the 4' position or 7' position;
R 1 selected from F, cl, br or I, R 2 A methyl group selected from the group consisting of H,5' or 6' substituted F, cl, br, I, 4', 5' or 7' substituted methyl groups, but excluding: r is R 1 Selected from F, R substituted in the 4-position 2 Selected from H; r is R 1 Selected from F, R substituted in position 6 2 Selected from Br substituted at the 5' position;
R 1 selected from methoxy, R 2 Selected from Cl substituted at the 5' position.
5. A process for the preparation of 3-indole-substituted phenylborozoles as claimed in any one of claims 1 to 4, characterized in that: the synthetic route is as follows:
Figure FDA0004122292020000021
6. the method for preparing the 3-indole-substituted phenylborozole compound, which is shown in claim 5, is characterized in that: comprising the following steps: taking deionized water as a solvent, and carrying out Friedel-Crafts reaction on o-formylphenylboronic acid shown in a formula III and substituted or unsubstituted indole shown in a formula IV to obtain a 3-indole substituted phenylborozole compound shown in a formula I; wherein the molar ratio of the substituted or unsubstituted indole to the o-formylphenylboronic acid is more than 1:1.
7. Use of the 3-indole substituted benzoborozole compounds according to any one of claims 1 to 4 for killing pathogenic bacteria in crops.
8. The use according to claim 7, wherein the pathogenic bacteria of the crop are botrytis cinerea, early blight of tomato, gibberella wheat, sheath blight of rice, alternaria mali, anthracnose of cucumber.
9. The application of the 3-indole substituted benzoborozole compound with the structure shown in the formula II in killing pathogenic bacteria of crops:
Figure FDA0004122292020000022
wherein R is 2 Selected from H, F, cl, me, OMe substituted at the 5 'position, F substituted at the 6' position.
10. The use according to claim 9, characterized in that: the crop pathogenic bacteria are Botrytis cinerea, alternaria wheat, rhizoctonia solani, spot pathogen of apple, and anthracnose pathogen of cucumber.
11. The use according to claim 10, characterized in that: the crop pathogenic bacteria are Botrytis cinerea and anthracnose of cucumber.
CN202210228760.2A 2022-03-08 2022-03-08 3-indole substituted phenylborozole compound and preparation method and application thereof Active CN114644645B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210228760.2A CN114644645B (en) 2022-03-08 2022-03-08 3-indole substituted phenylborozole compound and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210228760.2A CN114644645B (en) 2022-03-08 2022-03-08 3-indole substituted phenylborozole compound and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114644645A CN114644645A (en) 2022-06-21
CN114644645B true CN114644645B (en) 2023-05-26

Family

ID=81992871

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210228760.2A Active CN114644645B (en) 2022-03-08 2022-03-08 3-indole substituted phenylborozole compound and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114644645B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1155286A (en) * 1994-06-09 1997-07-23 曾尼卡有限公司 Oxaboroles and salts thereof, and thire use as biocides
CN101160124A (en) * 2005-02-16 2008-04-09 安纳考尔医药公司 Boron-containing small molecules
CN103857289A (en) * 2011-10-07 2014-06-11 先正达参股股份有限公司 Method for protecting useful plants or plant propagation material
CN107108661A (en) * 2015-01-13 2017-08-29 先正达参股股份有限公司 Kill the benzoxaborole heterocyclic pentene of microorganism

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008070257A2 (en) * 2006-09-29 2008-06-12 Anacor Pharmaceuticals, Inc. Crystal structure of a trna synthetase
US20170000133A1 (en) * 2013-12-23 2017-01-05 Syngenta Participations Ag Benzoxaborole fungicides
CN105968332A (en) * 2016-07-12 2016-09-28 安徽红太阳新材料有限公司 Benzoborazole metal complex for catalyzing cyclic ester polymerization and application thereof
CN112920208B (en) * 2021-01-28 2022-11-08 山东大学 Boric acid-containing indole aryl sulfone derivative and preparation method and application thereof
CN113185503B (en) * 2021-04-12 2023-02-28 南京农业大学 Natural product Pimpirinine derivative and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1155286A (en) * 1994-06-09 1997-07-23 曾尼卡有限公司 Oxaboroles and salts thereof, and thire use as biocides
CN101160124A (en) * 2005-02-16 2008-04-09 安纳考尔医药公司 Boron-containing small molecules
CN103857289A (en) * 2011-10-07 2014-06-11 先正达参股股份有限公司 Method for protecting useful plants or plant propagation material
CN107108661A (en) * 2015-01-13 2017-08-29 先正达参股股份有限公司 Kill the benzoxaborole heterocyclic pentene of microorganism

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"新型含类苯酞骨架的双杂环化合物的合成研究";沈少春;《博士电子期刊，工程科技Ⅰ辑》;第100-101页 *

Also Published As

Publication number Publication date
CN114644645A (en) 2022-06-21

Similar Documents

Publication Publication Date Title
CN103333122A (en) Pinanyl-2-aminopyrimidine compounds as well as synthesis and application thereof
Deepthi et al. Carbohydrate triazole tethered 2-pyridyl-benzimidazole ligands: Synthesis of their palladium (II) complexes and antimicrobial activities
CN109467533A (en) A kind of 8-hydroxyquinoline class compound and preparation method thereof and the purposes in prevention and treatment agricultural disease
CN111642504A (en) Quinoline 4-hydroxypyridine formate compound and application thereof in preventing and treating rice blast germs
CN113185503B (en) Natural product Pimpirinine derivative and preparation method and application thereof
CN114644645B (en) 3-indole substituted phenylborozole compound and preparation method and application thereof
CN111303148B (en) 1-substituted beta-carboline derivatives and application thereof
CN113666859A (en) Preparation method of nitrogen heterocyclic ring substituted trifluoromethyl olefin and Michael addition product thereof
CN104892602A (en) Hydrazone derivative containing 1,2,4-triazole [4,3-a] pyridine ring as well as preparation and application of hydrazone derivative
Subhashini et al. Microwave-assisted synthesis of pyrazole-based 1, 2, 3-triazole derivatives and evaluation of their antimicrobial activity
CN112341365B (en) 1-sulfonyl naphthol derivative and preparation method thereof
CN111892597B (en) Quinoxalinyl pyridopyrazine compound and preparation method and application thereof
CN111039933B (en) 5-heterocyclic substituted pyrazole compound and application thereof in pesticides
CN107810961B (en) Application of Topsentin alkaloid in resisting plant viruses and germs
CN113603694A (en) 1, 2-diketone compound and preparation method and application thereof
CN114041471A (en) Application of dehydrobufotenine
NO152840B (en) PROCEDURE FOR THE PREPARATION OF DIBENZYLETERS
CN106234385B (en) A kind of application of 1,2,4- triazole derivatives of the structure containing benzopyrazines as fungicide
CN107814790B (en) Topsentin derivative, preparation method thereof and application thereof in resisting plant viruses and germs
CN111018848A (en) 1,3, 5-trisubstituted-4, 5-dihydropyrazole derivative and application thereof in pesticides
CN114680114B (en) Application of melatonin derivative in preventing and treating plant fungal diseases
CN105017249B (en) A kind of preparation method of the hydazone derivative of 1,2,4-triazole [4,3-α] pyridine ring
CN103936619A (en) Preparation method and application of pyruvate acetal p-nitrobenzoylhydrazone
CN114085199B (en) Chalcone derivative containing sulfonyl piperazine as well as preparation method and application thereof
CN109897052B (en) N-pyrimidinyl-1, 3-oxaza bridge ring compound and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant