CN116589419A - 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound and preparation method and application thereof - Google Patents
2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN116589419A CN116589419A CN202310336344.9A CN202310336344A CN116589419A CN 116589419 A CN116589419 A CN 116589419A CN 202310336344 A CN202310336344 A CN 202310336344A CN 116589419 A CN116589419 A CN 116589419A
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- compound shown
- plant
- reaction
- 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.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 72
- 239000005648 plant growth regulator Substances 0.000 claims abstract description 8
- 241000196324 Embryophyta Species 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 230000001737 promoting effect Effects 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Chemical group 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 230000003071 parasitic effect Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- 230000002401 inhibitory effect Effects 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000011161 development Methods 0.000 claims description 3
- 230000018109 developmental process Effects 0.000 claims description 3
- 230000007226 seed germination Effects 0.000 claims description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 2
- 241000336315 Cistanche salsa Species 0.000 claims description 2
- 230000003779 hair growth Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000009758 senescence Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 26
- 241000209094 Oryza Species 0.000 abstract description 20
- 235000007164 Oryza sativa Nutrition 0.000 abstract description 19
- 235000009566 rice Nutrition 0.000 abstract description 19
- 241000219194 Arabidopsis Species 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 108700020617 Arabidopsis MAIN Proteins 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 5
- 230000004071 biological effect Effects 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- XHSDUVBUZOUAOQ-WJQMYRPNSA-N (3e,3ar,8bs)-3-[[(2r)-4-methyl-5-oxo-2h-furan-2-yl]oxymethylidene]-4,8b-dihydro-3ah-indeno[1,2-b]furan-2-one Chemical compound O1C(=O)C(C)=C[C@@H]1O\C=C/1C(=O)O[C@@H]2C3=CC=CC=C3C[C@@H]2\1 XHSDUVBUZOUAOQ-WJQMYRPNSA-N 0.000 description 13
- PCSREBFOVZSWQV-UHFFFAOYSA-N 6-phenoxy-1-phenyl-2-(1,2,4-triazol-1-yl)hexan-1-one Chemical compound O(C1=CC=CC=C1)CCCCC(C(=O)C1=CC=CC=C1)N1N=CN=C1 PCSREBFOVZSWQV-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 230000012010 growth Effects 0.000 description 8
- 241000219195 Arabidopsis thaliana Species 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 238000012258 culturing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 230000002786 root growth Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 238000012271 agricultural production Methods 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- -1 carotenoid terpenoid lactone small molecules Chemical class 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- KRVGXFREOJHJAX-UHFFFAOYSA-N 2-bromo-1-(4-methylphenyl)ethanone Chemical compound CC1=CC=C(C(=O)CBr)C=C1 KRVGXFREOJHJAX-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 244000299507 Gossypium hirsutum Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000035790 physiological processes and functions Effects 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 239000013641 positive control Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000009331 sowing Methods 0.000 description 2
- 239000008223 sterile water Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- FOZVXADQAHVUSV-UHFFFAOYSA-N 1-bromo-2-(2-bromoethoxy)ethane Chemical compound BrCCOCCBr FOZVXADQAHVUSV-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000028446 budding cell bud growth Effects 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003375 plant hormone Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000026267 regulation of growth Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000021749 root development Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P21/00—Plant growth regulators
-
- 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
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental Sciences (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Botany (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application discloses a 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound, and a preparation method and application thereof. The structural formula is shown in formula I. The application provides a 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound which has simple structure, convenient synthesis and high biological activity, and when the compound is used for carrying out arabidopsis primary rosette She Fenzhi, arabidopsis main root elongation, arabidopsis hypocotyl elongation and rice tillering test, the result shows that the compound has better promotion activity on arabidopsis primary rosette branches, rice tillers and arabidopsis main root elongation, and is a plant growth regulator with wide application prospect.
Description
Technical Field
The application belongs to the technical field of plant growth regulators, and particularly relates to a 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound with strigolactone biosynthesis inhibitor activity, and a preparation method and application thereof.
Background
The plant growth regulator is used as a safe and green chemical pesticide, is widely used in agricultural production, and plays an important role in crop growth regulation, weed control and the like. Strigolactone (SLs) is a new class of natural plant hormones that has been attracting attention in recent years, and as a class of carotenoid terpenoid lactone small molecules, strigolactone was first found in cotton root secretions in 1966. In recent years, with the progress and promotion of scientific technology, more and more strigolactones are discovered, and more than 30 strigolactones are discovered in different plant varieties.
Dwarfing and multi-branching structures are ideal characters for improving crop yield and lodging resistance in agricultural production, strigolactone is taken as a naturally occurring plant signal molecule, and can effectively regulate and control plant overground part and root development, such as primary rooting, lateral root formation, lateral bud growth, branch branching/tillering, root parasitic weed seed germination and the like.
The strigolactone biosynthesis inhibitor is a chemical micromolecule which can inhibit the biosynthesis of endogenous strigolactone in plants so as to regulate the corresponding physiological process, and in recent years, strigolactone is widely valued, and research on strigolactone inhibitors is more and more popular, so that more novel physiological functions and action mechanisms of strigolactone can be better explored, and therefore, the strigolactone biosynthesis inhibitor with simple design and synthesis and novel structure has important significance.
Disclosure of Invention
The application aims to provide a 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound with strigolactone biosynthesis inhibitor activity, and a preparation method and application thereof. The 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound has important regulation effect on plant growth regulation, and can be used as a plant growth regulator in agriculture.
The application aims to provide 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compounds, the structural formula of which is shown as formula I:
in the formula I, R 1 Selected from: at least one of fluorine, chlorine, bromine, C1-C6 alkyl (e.g., methyl), C1-C6 alkoxy (e.g., methoxy), halogen substituted C1-C6 alkyl (e.g., trifluoromethyl);
R 2 is thatWherein n=1 to 6, and may be specifically 4; or R is 2 Is->
R 2 Is thatR 1 Preferably methyl, methoxy, trifluoromethyl and at least one of fluorine, chlorine and bromine;
R 2 is thatR 1 Preferably methyl, methoxy, trifluoromethyl and at least one of fluorine, chlorine and bromine.
Specifically, the compound shown in the formula I is any one of the following compounds:
the 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound shown in the formula I is prepared by a method comprising the following steps:
1) Reacting a compound shown in a formula II with 1H-1,2, 4-triazole under the action of an acid binding agent to obtain a 2- (1H-1, 2, 4-triazole) -acetophenone compound shown in a formula III;
wherein R in formula II, formula III 1 R in formula I 1 Is defined as follows;
2) Reacting a compound shown in a formula IV with phenol to obtain a compound shown in a formula V;
wherein R in formula IV, formula V 2 R in formula I 2 Is defined as follows;
3) Under the action of an acid binding agent, reacting a compound shown in a formula III with a compound shown in a formula V to obtain the 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound shown in the formula I.
In the step 1) of the method, the molar ratio of the compound shown in the formula II to the 1H-1,2, 4-triazole can be 1:1-2, and can be 1:1.5;
the acid binding agent is at least one of triethylamine and potassium carbonate;
the reaction is carried out in a solvent:
the solvent is at least one selected from acetone and dichloromethane;
the temperature of the reaction is room temperature, and the reaction time is 4-8 hours;
in the step 2), the molar ratio of the compound shown in the formula IV to phenol is 1-2:1, and can be 1.5:1 in particular,
the reaction is carried out in a solvent; the solvent is at least one of ultra-dry dichloromethane and N, N-dimethylformamide;
the temperature of the reaction is room temperature and the time is 6-12 hours;
in the step 3), the molar ratio of the compound shown in the formula III to the compound shown in the formula V is 1:1-2, and can be 1:2 specifically;
the reaction is carried out in a solvent; the solvent is at least one of dichloromethane and dimethyl sulfoxide;
the acid binding agent is at least one of sodium hydroxide and potassium hydroxide;
the reaction temperature is room temperature and the reaction time is 6-8 hours.
The method can further comprise the operation of purifying the system obtained in the step 3), wherein the purification method is column chromatography separation, and the solvent is ethyl acetate and petroleum ether in a volume ratio of 1:5.
The application of 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compounds shown in formula I as plant regulator.
The regulating action of the plant regulator comprises any one of the following components:
1) Promoting the branching development of plants;
2) Inhibiting root parasitic weed seed germination;
3) Promoting the elongation of hypocotyl of plant seedling;
4) Promoting elongation of main roots of plants;
5) Inhibiting root hair growth of the plant;
6) Delaying the senescence of plant leaves.
The plant may be specifically a dicotyledonous plant and a monocotyledonous plant, and may specifically be Arabidopsis, rice, maize, wheat or cotton.
The root parasitic weeds can be broomrape and strigola.
The application also provides a plant growth regulator which contains the 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound shown in the formula I.
The application provides a 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound which has simple structure, convenient synthesis and high biological activity, and when the compound is used for carrying out arabidopsis primary rosette She Fenzhi, arabidopsis main root elongation, arabidopsis hypocotyl elongation and rice tillering test, the result shows that the compound has better promotion activity on arabidopsis primary rosette branches, rice tillers and arabidopsis main root elongation, and is a plant growth regulator with wide application prospect.
Detailed Description
The following detailed description of the application is provided in connection with the accompanying drawings that are presented to illustrate the application and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the application in any way.
The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the product specifications. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
In the following examples, the synthesis of compounds A8 and B8 is taken as an example, and other compounds can be prepared from the corresponding reaction materials by the methods of the following examples.
Example 1 preparation of compound A8:
the reaction scheme is as follows:
1.7g of 1,2, 4-triazole is weighed into a 50mL round bottom flask, 15mL of acetone is added, 3.5g of 2-bromo-4' -methylacetophenone is added after complete dissolution, 2.3mL of triethylamine is dissolved in 10mL of acetone, the mixture is slowly added dropwise to the reaction system (> 5 min) in an ice bath, and the mixture is stirred to react for 5h at room temperature. After the reaction was completed, cooling to room temperature, evaporating the solvent under reduced pressure, adding water to quench, extracting with ethyl acetate, drying, and removing the solvent to obtain 3.0g of a crude product as a pale yellow solid, and separating the pale yellow solid by using a silica gel chromatographic column to obtain an intermediate product I as a yellow solid (1.86 g, 62%).
0.94g phenol was taken in a 50mL round bottom flask, 10mLN, N-dimethylformamide was added, stirred until dissolved, 2.60g 1, 4-dibromobutane was added sequentially, stirred at room temperature, and TLC monitored until the reaction was complete (reaction time 10 h). A large amount of water was poured into the reaction system to remove the solvent N, N-dimethylformamide, ethyl acetate was extracted, and after drying, ethyl acetate was distilled off under reduced pressure to obtain 2.24g of a crude product as a pale yellow solid, which was separated by a silica gel column chromatography to obtain intermediate II as a yellow solid (1.52 g, 68%).
1.3g of intermediate I was dissolved in 5mL of dimethyl sulfoxide, 0.78mL of 50% aqueous potassium hydroxide was added, the solution was stirred and dissolved, 1.48g of intermediate II was added, and the mixture was stirred at room temperature (8 h), and TLC was monitored until the reaction was completed. 15mL of water is added for quenching, 3X 20mL of dichloromethane is used for extraction, the organic phases are combined, 20mL of water is used for washing, the solvent is removed by evaporation under reduced pressure after drying, then anhydrous sodium sulfate is dried for 0.5h, concentration is carried out, and silica gel chromatographic column separation (ethyl acetate and petroleum ether with volume ratio of 1:5 are used as solvents) is used for obtaining the target product as white solid (1.36 g, 60%).
Preparation of example 2, compound B8:
the reaction scheme is as follows:
1.7g of 1,2, 4-triazole is weighed into a 50mL round bottom flask, 15mL of acetone is added, 3.5g of 2-bromo-4' -methylacetophenone is added after complete dissolution, 2.3mL of triethylamine is dissolved in 10mL of acetone, the mixture is slowly added dropwise to the reaction system (> 5 min) in an ice bath, and the mixture is stirred to react for 6h at room temperature. After the reaction was completed, cooling to room temperature, evaporating the solvent under reduced pressure, adding water to quench, extracting with ethyl acetate, drying, and removing the solvent to obtain 3.0g of a crude product as a pale yellow solid, and separating the pale yellow solid by using a silica gel chromatographic column to obtain an intermediate product I' as a yellow solid (1.86 g, 62%).
0.94g phenol was taken in a 50mL round bottom flask, 10mLN, N-dimethylformamide was added, stirred until dissolved, 2.78g 2,2' -dibromodiethyl ether was added sequentially, stirred at room temperature, and TLC monitored until the reaction was complete (12 h). A large amount of water was poured into the reaction system to remove N, N-dimethylformamide, extraction was performed with ethyl acetate, and the solvent was removed after drying to obtain 2.28g of a crude product as a pale yellow solid, which was separated by a silica gel column chromatography to obtain an intermediate product II' as a yellow solid (1.46 g, 64%).
1.2g of intermediate I 'was dissolved in 5mL of dimethyl sulfoxide, 0.72mL of 50% aqueous potassium hydroxide was added, the solution was stirred and dissolved, 1.46g of intermediate II' was added, and the mixture was stirred at room temperature, and TLC was monitored until the reaction was completed (8 h). 15mL of water was added, 3X 20mL of methylene chloride was used for extraction, the organic phases were combined, washed with 20mL of water, dried and evaporated under reduced pressure to remove the solvent, then dried over anhydrous sodium sulfate for 0.5h, concentrated and separated by a silica gel column to give the desired product as a white solid (1.17 g, 54%).
The other compounds mentioned above were prepared in the same manner as above, and the yields and the appearance of some of the compounds are shown in Table 1.
TABLE 1 numbering, yield and appearance of partial compounds
TABLE 2 partial Compound Nuclear magnetic resonance data of formula I
/>
/>
/>
/>
/>
Example 3 compounds of formula I were tested for arabidopsis primary rosette branching activity as follows:
sterilizing Arabidopsis seeds with 1% sodium hypochlorite solution for 15min, washing with sterile water, and sowing in 1/2MS culture medium (0.8% agar, 1% sucrose and a certain concentration of new compound); and (3) carrying out vernalization for 3 days in a refrigerator at 4 ℃, transferring to a climatic chamber, culturing in darkness (22 ℃) for 35 days, photographing the whole plant, and recording the branch number of the primary rosette leaves with the length of more than 5 mm. The results of all compound tests are shown in tables 3 and 4.
TABLE 3 screening of the branching Activity of Compounds of formula I on Arabidopsis primary rosettes
As can be seen from Table 3, the 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound has similar functions as a strigolactone inhibitor, has higher activity, is superior to CK and TIS108 in activity, has a better effect of promoting branching of arabidopsis thaliana rosettes by a plurality of compounds at the concentration of 3 mu M than the effect which can be achieved by the same concentration of TIS108, and has obvious activity of B-series compounds due to the A-series, and the B-series compounds generally have certain branching promoting activity. Among the two series of compounds, especially the compounds A7 and B4 showed remarkable branching promotion activity, and the promotion rate of the branching of the primary rosettes of the Arabidopsis reached 189.5% and 221.4%, respectively, which is far better than the promotion effect of TIS108.
TABLE 4 promoted Activity screening of partial active Compounds on Arabidopsis primary rosette branches
From Table 4, the branching promotion activity of the compound B4 at different concentrations is superior to that of the compounds A7 and TIS108, and the branching promotion activity is better in the concentration range of 0.1-10 mu M, and the evaluation result of the promotion activity of the Arabidopsis thaliana primary rosette She Fenzhi shows that the compound has the related activity of the strigolactone inhibitor, and the design cost is low, so that the compound has high application value under the same condition.
Example 4 Compounds of formula I were tested for rice tillering activity as follows:
rice seeds (Nippon-Qing) were surface sterilized by washing with 1.5% sodium hypochlorite for 30 minutes, then thoroughly rinsing the seeds with sterile deionized water, and culturing in water at 30℃for 2 days in the dark. The pre-germinated seeds were transferred to filter paper in a 90mm dish and incubated with fluorescent white light (130-180 μm 2 s -1 ) Culturing at 30deg.C for 1 week with photoperiod of 16 hr and light for 8 hr. Seedlings 7 days old were transferred to a hydroponic box containing nutrient solution and grown in a climatic chamber. Rice was treated with the compound of formula I at a concentration of 10. Mu.M using TIS108 as a positive control. The compound was administered twice a week for a total of three weeks. Tillering numbers were measured three weeks later for each strain, and the test results for all compounds are shown in table 5.
TABLE 5 promoting Activity of Compounds of formula I on tillering in Rice
From table 5, it can be seen that the compound B4 can significantly promote rice tillering, and further verifies that the target compound can play a role in promoting branches of aerial parts in dicotyledonous mode plant arabidopsis thaliana and monocotyledonous mode plant rice application, and has potential application value in agricultural factories.
Example 5 test of Rice growth
Rice seeds (Nippon-Qing) were surface sterilized by washing with 1.5% sodium hypochlorite for 30 minutes, then thoroughly rinsing the seeds with sterile deionized water, and culturing in water at 30℃for 2 days in the dark. The pre-germinated seeds were transferred to filter paper in a 90mm dish and incubated with fluorescent white light (130-180 μm 2 s -1 ) Culturing at 30deg.C for 1 week with photoperiod of 16 hr and light for 8 hr. Seedlings 7 days old were transferred to a hydroponic box containing nutrient solution and grown in a climatic chamber. Rice was treated with the compound of formula I at a concentration of 10. Mu.M using TIS108 as a positive control. The compound was administered twice a week for a total of 4 weeks. After 4 weeks each plant height, fresh weight and dry weight were measured and all compounds tested as shown in table 6.
TABLE 6 influence of partial Compounds on plant height, dry/fresh weight of Rice at 10. Mu.M
As can be seen from Table 6, the active compound B4 has good regulation and control effects on the plant growth of rice at 10 mu M, can inhibit the plant height, effectively improve the dry/fresh weight, can reduce the plant height elongation of the rice by 11.8%, promote the fresh weight to increase by 35.5%, and promote the dry weight to increase by 14.4%, compared with the active compound B4, the TIS108 has stronger inhibition effect on the plant height of the rice than the TIS108, and leads to the reduction of the quality of the dry matter of the rice, and the result shows that the side effect of the B4 on the growth and development stage of the rice is far weaker than that of the A7 and the TIS108, and has larger application potential in agricultural production.
Example 6 Columbia wild type Arabidopsis root growth assay:
sterilizing Arabidopsis seeds with 1% sodium hypochlorite solution for 15min, washing with sterile water, and sowing in 1/2MS culture medium (0.8% agar, 1% sucrose and new compound); the method comprises the steps of vernalizing for 3 days in a refrigerator at 4 ℃, transferring to a climatic chamber, culturing for 7 days in darkness (22 ℃), photographing the whole plant, and determining the length of main roots of arabidopsis by Image J software, wherein the length is represented by the following formula: main root growth promotion rate= (drug group main root length-blank group main root length)/blank group main root length×100%, and the growth promotion rate of each compound and control drug TIS108 on arabidopsis main root was calculated, and the results are shown in table 7.
TABLE 7 promotion of growth of Arabidopsis main root by active Compound and control drug
As can be seen from Table 7, the 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound can effectively promote the growth of main roots of Arabidopsis thaliana, can effectively promote the growth of the Arabidopsis thaliana roots at low concentration (0.1-10 mu M), and can reach 41.1% at 0.1 mu M. At a concentration of 100. Mu.M, the compound has an inhibition effect (-73.7%) on the growth of main roots of Arabidopsis thaliana, whereas the control drug TIS108 only shows the root growth promotion activity (28.7%) at a concentration of 0.1. Mu.M, and the growth of main roots of Arabidopsis thaliana starts to be inhibited (-25.7%) at a concentration of 10. Mu.M, so that the root growth promotion activity of the compound is superior to that of TIS108. Meanwhile, the compound has low synthesis cost, and the compound related by the application has higher utilization value under the same condition.
The present application is described in detail above. It will be apparent to those skilled in the art that the present application can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the application and without undue experimentation. While the application has been described with respect to specific embodiments, it will be appreciated that the application may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains.
Claims (8)
1. A compound of formula i:
in the formula I, R 1 Selected from: at least one of fluorine, chlorine, bromine, C1-C6 alkyl, C1-C6 alkoxy, halogen substituted C1-C6 alkyl;
R 2 is thatWherein n=1-6; or R is 2 Is->
2. A compound according to claim 1, characterized in that: r is R 2 Is thatR 1 Is at least one of methyl, methoxy, trifluoromethyl, fluorine, chlorine and bromine;
R 2 is thatR 1 Is at least one of methyl, methoxy, trifluoromethyl, fluorine, chlorine and bromine.
3. A process for preparing a compound of formula I according to claim 1 or 2, comprising the steps of:
1) Reacting a compound shown in a formula II with 1H-1,2, 4-triazole under the action of an acid binding agent to obtain a 2- (1H-1, 2, 4-triazole) -acetophenone compound shown in a formula III;
wherein R in formula II, formula III 1 R in formula I 1 Is defined as follows;
2) Reacting a compound shown in a formula IV with phenol to obtain a compound shown in a formula V;
wherein R in formula IV, formula V 2 R in formula I 2 Is defined as follows;
3) Under the action of an acid binding agent, reacting a compound shown in a formula III with a compound shown in a formula V to obtain the 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound shown in the formula I.
4. A method according to claim 3, characterized in that: in the step 1), the mol ratio of the compound shown in the formula II to the 1H-1,2, 4-triazole is 1:1-2;
the acid binding agent is at least one of triethylamine and potassium carbonate;
the reaction is carried out in a solvent:
the solvent is at least one selected from acetone and dichloromethane;
the temperature of the reaction is room temperature, and the reaction time is 4-8 hours;
in the step 2), the mol ratio of the compound shown in the formula IV to phenol is 1-2:1,
the reaction is carried out in a solvent; the solvent is at least one of ultra-dry dichloromethane and N, N-dimethylformamide;
the temperature of the reaction is room temperature and the time is 6-12 hours;
in the step 3), the molar ratio of the compound shown in the formula III to the compound shown in the formula V is 1:1-2;
the reaction is carried out in a solvent; the solvent is at least one of dichloromethane and dimethyl sulfoxide;
the acid binding agent is at least one of sodium hydroxide and potassium hydroxide;
the reaction temperature is room temperature and the reaction time is 6-8 hours.
5. Use of a compound of formula I according to claim 1 or 2, characterized in that: the compounds are useful for preparing plant growth regulators.
6. The use according to claim 5, characterized in that: the regulating action of the plant regulator comprises any one of the following components:
1) Promoting the branching development of plants;
2) Inhibiting root parasitic weed seed germination;
3) Promoting the elongation of hypocotyl of plant seedling;
4) Promoting elongation of main roots of plants;
5) Inhibiting root hair growth of the plant;
6) Delaying the senescence of plant leaves.
7. Use according to claim 5 or 6, characterized in that: the plant is a binary plant and a monocotyledonous plant;
the root parasitic weeds are broomrape and strigola.
8. A plant growth regulator comprising any one of the compounds of formula I in claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310336344.9A CN116589419A (en) | 2023-03-31 | 2023-03-31 | 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310336344.9A CN116589419A (en) | 2023-03-31 | 2023-03-31 | 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116589419A true CN116589419A (en) | 2023-08-15 |
Family
ID=87605125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310336344.9A Pending CN116589419A (en) | 2023-03-31 | 2023-03-31 | 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116589419A (en) |
-
2023
- 2023-03-31 CN CN202310336344.9A patent/CN116589419A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6004905A (en) | Hyperabas: biologically active abscisic acid analogs with unsaturated carbon substituents at the 8'-methyl or 9'-methyl carbon atoms | |
| US4479900A (en) | 1-Carbalkoxyalkyl-3-aryloxy-4-(2'-carboxyphenyl)-azetidin-2-ones | |
| US8822383B2 (en) | Germination-stimulant carbamate derivatives and process for preparation thereof | |
| WO1999045774A1 (en) | Plant growth regulating agents | |
| WO2010137662A1 (en) | Plant branching inhibitor, method for producing same, and plant branching inhibitory composition | |
| WO2019196904A1 (en) | Quinazolinedione compound, uses and pesticide/herbicide thereof | |
| CN106831494B (en) | A kind of mebenil base hexichol carbamide compounds and application thereof | |
| WO1994028011A1 (en) | Brassinosteroid derivatives and plant growth regulator containing the same | |
| CN113072544A (en) | Compound capable of promoting seed germination of parasitic plants prepared based on indole-3-carboxylic acid and preparation method thereof | |
| CN110746356B (en) | Preparation method and application of difluoromethyl pyrazole oxime ester containing 3-trifluoromethyl-5-chloropyrazole structure | |
| CN110845478B (en) | Preparation and use of pyrazole formyloxime derivatives containing 1-substituted pyridyl-3-trifluoromethylpyrazole units | |
| CN109956904B (en) | Pyrazole amide compound and application thereof and bactericide | |
| CN114874165B (en) | Phenethyl ester vinyl ether lactone compound with strigolactone activity and preparation and application thereof | |
| CN116589419A (en) | 2-phenoxy-2- (1H-1, 2, 4-triazole) -acetophenone compound and preparation method and application thereof | |
| US4604129A (en) | Influencing plant growth | |
| CN112979593A (en) | Compound capable of promoting germination of parasitic plant seeds prepared based on cinnamic acid compounds and preparation method thereof | |
| JP6902748B2 (en) | Plant growth regulator | |
| JP6842082B2 (en) | Plant growth regulator | |
| CN108863876A (en) | A kind of thiourea and preparation method and application with gibberellin function | |
| CN114369087B (en) | Synthesis and application of lactone analogue with indoline-2-ketone skeleton | |
| CN115353500B (en) | Cinnamamide lactone compound with strigolactone activity and preparation and application thereof | |
| AU595269B2 (en) | Plant growth promotion | |
| US4718936A (en) | 6-(3-thienylmethylamino)-purine, its preparation and its use | |
| JPH09241239A (en) | Esters of 4-chloroindole-3-acetic acid | |
| JP7325429B2 (en) | Plant salt tolerance improver |
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 |