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 PDFInfo
- 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
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 25
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 22
- 241000123650 Botrytis cinerea Species 0.000 claims abstract description 14
- 240000008067 Cucumis sativus Species 0.000 claims abstract description 13
- 244000052616 bacterial pathogen Species 0.000 claims abstract description 13
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 claims abstract description 12
- 241000209140 Triticum Species 0.000 claims abstract description 11
- 235000021307 Triticum Nutrition 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 241000813090 Rhizoctonia solani Species 0.000 claims abstract description 10
- 241000223600 Alternaria Species 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- DGUWACLYDSWXRZ-UHFFFAOYSA-N (2-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1C=O DGUWACLYDSWXRZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000002475 indoles Chemical class 0.000 claims description 9
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 8
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 8
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 8
- 241000223218 Fusarium Species 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 244000052769 pathogen Species 0.000 claims description 4
- 230000001717 pathogenic effect Effects 0.000 claims description 4
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 241000412366 Alternaria mali Species 0.000 claims 1
- 241000198596 Alternaria tomatophila Species 0.000 claims 1
- 241001617088 Thanatephorus sasakii Species 0.000 claims 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical class [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims 1
- 241000213004 Alternaria solani Species 0.000 abstract description 4
- 201000010099 disease Diseases 0.000 abstract description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 78
- 238000004896 high resolution mass spectrometry Methods 0.000 description 36
- 239000007787 solid Substances 0.000 description 35
- 230000000844 anti-bacterial effect Effects 0.000 description 21
- 125000001309 chloro group Chemical group Cl* 0.000 description 18
- 230000005764 inhibitory process Effects 0.000 description 14
- CVICEEPAFUYBJG-UHFFFAOYSA-N 5-chloro-2,2-difluoro-1,3-benzodioxole Chemical group C1=C(Cl)C=C2OC(F)(F)OC2=C1 CVICEEPAFUYBJG-UHFFFAOYSA-N 0.000 description 10
- 238000006467 substitution reaction Methods 0.000 description 8
- 239000001965 potato dextrose agar Substances 0.000 description 7
- 239000005740 Boscalid Substances 0.000 description 6
- HPUXDMUGCAWDFW-UHFFFAOYSA-N Osthole Natural products COc1ccc2CCC(=O)Oc2c1C=CC(=O)C HPUXDMUGCAWDFW-UHFFFAOYSA-N 0.000 description 6
- WYEMLYFITZORAB-UHFFFAOYSA-N boscalid Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl WYEMLYFITZORAB-UHFFFAOYSA-N 0.000 description 6
- 229940118790 boscalid Drugs 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 125000001041 indolyl group Chemical group 0.000 description 6
- MBRLOUHOWLUMFF-UHFFFAOYSA-N osthole Chemical compound C1=CC(=O)OC2=C(CC=C(C)C)C(OC)=CC=C21 MBRLOUHOWLUMFF-UHFFFAOYSA-N 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 241000233866 Fungi Species 0.000 description 5
- 241000220225 Malus Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- JWUCHKBSVLQQCO-UHFFFAOYSA-N 1-(2-fluorophenyl)-1-(4-fluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanol Chemical compound C=1C=C(F)C=CC=1C(C=1C(=CC=CC=1)F)(O)CN1C=NC=N1 JWUCHKBSVLQQCO-UHFFFAOYSA-N 0.000 description 2
- YPSXFMHXRZAGTG-UHFFFAOYSA-N 4-methoxy-2-[2-(5-methoxy-2-nitrosophenyl)ethyl]-1-nitrosobenzene Chemical compound COC1=CC=C(N=O)C(CCC=2C(=CC=C(OC)C=2)N=O)=C1 YPSXFMHXRZAGTG-UHFFFAOYSA-N 0.000 description 2
- 241000223602 Alternaria alternata Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005787 Flutriafol Substances 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- -1 nthracis Species 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- CFEUXFGXHSBLHP-UHFFFAOYSA-N B1C=CC=C1C1=CC=CC=C1 Chemical class B1C=CC=C1C1=CC=CC=C1 CFEUXFGXHSBLHP-UHFFFAOYSA-N 0.000 description 1
- 241000193738 Bacillus anthracis Species 0.000 description 1
- 241001290235 Ceratobasidium cereale Species 0.000 description 1
- 241000222235 Colletotrichum orbiculare Species 0.000 description 1
- 235000009849 Cucumis sativus Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 241000223195 Fusarium graminearum Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 241001085826 Sporotrichum Species 0.000 description 1
- 239000005839 Tebuconazole Substances 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 229940065181 bacillus anthracis Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HAXSCOGBPLMKKV-UHFFFAOYSA-N benzene;1h-indole Chemical group C1=CC=CC=C1.C1=CC=C2NC=CC2=C1 HAXSCOGBPLMKKV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 244000000004 fungal plant pathogen Species 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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 Table
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Indole Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
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
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:
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:
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:
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:
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 (%) ]
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)
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)
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)
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:
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.
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.
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.
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)
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)
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 |
-
2022
- 2022-03-08 CN CN202210228760.2A patent/CN114644645B/en active Active
Patent Citations (4)
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)
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 | |
CN111303148B (en) | 1-substituted beta-carboline derivatives 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 | |
CN113666859A (en) | Preparation method of nitrogen heterocyclic ring substituted trifluoromethyl olefin and Michael addition product thereof | |
CN114041471B (en) | Application of dehydrobufotenine | |
CN112341365B (en) | 1-sulfonyl naphthol derivative and preparation method thereof | |
CN111892597B (en) | Quinoxalinyl pyridopyrazine compound and preparation method and application thereof | |
Subhashini et al. | Microwave-assisted synthesis of pyrazole-based 1, 2, 3-triazole derivatives and evaluation of their antimicrobial activity | |
CN113045474B (en) | Application of alkaloid arnodine and derivatives thereof in preventing and treating plant virus and bacterial diseases | |
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 | |
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 | |
CN114957215A (en) | Methylene bridged quinoline and 1,2, 3-triazole diheterocyclic 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 |