CN116730932A - Preparation and application of propylene pimara (1, 5-o-nitrobenzyl) -1,2, 4-triazole - Google Patents
Preparation and application of propylene pimara (1, 5-o-nitrobenzyl) -1,2, 4-triazole Download PDFInfo
- Publication number
- CN116730932A CN116730932A CN202310688196.7A CN202310688196A CN116730932A CN 116730932 A CN116730932 A CN 116730932A CN 202310688196 A CN202310688196 A CN 202310688196A CN 116730932 A CN116730932 A CN 116730932A
- Authority
- CN
- China
- Prior art keywords
- triazole
- pimaric
- nitrobenzyl
- acid
- propylene
- 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.)
- Granted
Links
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 241000233616 Phytophthora capsici Species 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 235000002566 Capsicum Nutrition 0.000 claims description 11
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 claims description 10
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 125000006278 bromobenzyl group Chemical group 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 240000008574 Capsicum frutescens Species 0.000 claims description 5
- 239000001390 capsicum minimum Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 4
- 235000011613 Pinus brutia Nutrition 0.000 claims description 4
- 241000018646 Pinus brutia Species 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 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
- 238000003756 stirring Methods 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- RXCMFQDTWCCLBL-UHFFFAOYSA-N 4-amino-3-hydroxynaphthalene-1-sulfonic acid Chemical class C1=CC=C2C(N)=C(O)C=C(S(O)(=O)=O)C2=C1 RXCMFQDTWCCLBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 230000020477 pH reduction Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
- 230000001717 pathogenic effect Effects 0.000 abstract description 7
- 244000052769 pathogen Species 0.000 abstract description 6
- 239000000575 pesticide Substances 0.000 abstract description 6
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 4
- 238000012827 research and development Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 239000003814 drug Substances 0.000 description 7
- 229940079593 drug Drugs 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 241000758706 Piperaceae Species 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 201000010099 disease Diseases 0.000 description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 4
- 238000001727 in vivo Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 description 1
- 125000006280 2-bromobenzyl group Chemical group [H]C1=C([H])C(Br)=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000186427 Cutibacterium acnes Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 241000233654 Oomycetes Species 0.000 description 1
- 239000006002 Pepper Substances 0.000 description 1
- 235000016761 Piper aduncum Nutrition 0.000 description 1
- 235000017804 Piper guineense Nutrition 0.000 description 1
- 244000203593 Piper nigrum Species 0.000 description 1
- 235000008184 Piper nigrum Nutrition 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229940055019 propionibacterium acne Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000611 regression analysis Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 230000001225 therapeutic effect 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
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
-
- 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
- A01P3/00—Fungicides
-
- 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)
- 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)
- Microbiology (AREA)
- Mycology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application discloses a preparation method and application of propylene pimaric (1, 5-o-nitrobenzyl) -1,2, 4-triazole, and the structural formula of the propylene pimaric (1, 5-o-nitrobenzyl) -1,2, 4-triazole is shown in a formula I. According to the application, active group-1, 2, 4-triazole benzyl is introduced into an acrylic pimaric acid skeleton, so that the acrylic pimaric (1, 5-o-nitrobenzyl) -1,2, 4-triazole is prepared and synthesized, the operation steps are simple, the reaction conditions are mild, and the obtained compound shows good antibacterial activity to phytophthora capsici by virtue of an anti-plant pathogen activity test, so that an important scientific basis is provided for research and development and creation of new pesticides.
Description
Technical Field
The application relates to the technical field of botanical pesticides, in particular to a preparation method of propylene pimaricus (1, 5-o-nitrobenzyl) -1,2, 4-triazole and application thereof in phytophthora capsici resistance.
Background
Phytophthora capsici, an important plant pathogenic oomycete in pepper production, can infect various important crops including peppers, tomatoes, tobacco, eggplants and the like. Causing various symptoms such as stem wilt, leaf wilt, root rot and fruit rot. This disease initially causes brown dead zones in roots, stems and crowns, and later causes fruit and leaf contamination by rain water splatter or irrigation, which progresses rapidly after onset, and is often seriously ill.
Currently, chemical pesticides remain considered as the primary strategy for controlling this plant disease because of the lack of phytophthora capsici resistant varieties. However, the development of novel and safe antibacterial agents is critical due to the problems of increased resistance of chemical pesticides and difficult degradation of chemical residues. According to the application, 1,2, 4-triazole benzyl is connected to the acrylic pimaric acid skeleton, so that the high-efficiency low-toxicity antibacterial agent is prepared, and a foundation is laid for further developing high-activity plant source pesticides.
Disclosure of Invention
The application provides a preparation method of propylene sea pine (1, 5-o-nitrobenzyl) -1,2, 4-triazole, which can realize effective control of phytophthora capsici.
In order to solve the technical problems, the technical scheme adopted by the application is as follows:
a propylene pimaric (1, 5-o-nitrobenzyl) -1,2, 4-triazole, which has the structural formula:
the propylene pimaric (1, 5-o-nitrobenzyl) -1,2, 4-triazole is prepared from 3-propylene pimaric-1, 2, 4-triazole and 2-NO 2 The bromobenzyl is prepared by reaction.
Further, the preparation method comprises the following steps: mixing 3-propenes pimaric group-1, 2, 4-triazole and acid binding agent in ethanol for dissolving, and then adding 2-NO 2 And (3) bromobenzyl is subjected to reflux reaction for 6 hours at the temperature of 75 ℃, and column chromatography is carried out after acid washing, alkali washing and water washing to obtain the (1, 5-o-nitrobenzyl) -1,2, 4-triazole of the propylene sea pine.
The 3-propenylpimaric-1, 2, 4-triazole, acid-binding agent and 2-NO 2 The molar ratio of bromobenzyl is 1:4:5, a step of; the acid binding agent is sodium carbonate or potassium carbonate; column chromatography uses petroleum ether and ethyl acetate with volume ratio of 2:1 as eluent.
As a specific implementation scheme, the preparation method of the propylene pimaric (1, 5-o-nitrobenzyl) -1,2, 4-triazole comprises the following steps:
1) Dissolving the acrylic pimaric acid in dichloromethane, adding thionyl chloride, heating and refluxing for 5 hours, and removing excessive thionyl chloride and dichloromethane by rotary evaporation to obtain acrylic pimaric acyl chloride;
2) Pyridine, sodium carbonate and thiosemicarbazide are sequentially added into a three-neck flask, after stirring and dissolution, the pimaric acid chloride is diluted by pyridine and slowly dripped, the reaction is carried out for 2-3 hours at room temperature, a large amount of distilled water is added to separate out solids, the dried solids are mixed with 5% sodium hydroxide solution, heating and refluxing are carried out for 4 hours, acetic acid is acidified to PH=5-7 after the reaction is finished, a large amount of solids can be separated out, filter residues are collected through suction filtration, and after drying, the 3-propenoic pimaric base-1, 2, 4-triazole can be obtained through separation and purification of column chromatography (gradient elution proportion ethyl acetate/petroleum ether=2/1).
The application takes the acrylic pimaric acid as the initial raw material, and the synthetic route of the application is as follows:
the application has the beneficial effects that: according to the application, the (1, 5-o-nitrobenzyl) -1,2, 4-triazole of the propylene pimaricus is synthesized, and the test on the anti-plant pathogen activity of the compound shows that the compound has good antibacterial activity on phytophthora capsici. Compared with the high-activity compound reported in the earlier work of the subject group, the patent introduces 1,2, 4-triazole groups on the skeleton of the acrylic pimaric acid, and the compound has novel structure and good activity, thereby providing an important scientific basis for the research and development and the creation of new pesticides.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of (1, 5-o-nitrobenzyl) -1,2, 4-triazole of propylene pimara according to the present application;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of the propylene pimaric (1, 5-o-nitrobenzyl) -1,2, 4-triazole of the present application;
FIG. 3 is a mass spectrum of the propylene pimaric (1, 5-o-nitrobenzyl) -1,2, 4-triazole of the present application;
FIG. 4 is an in-dish experiment of the present application with propylene pimaric (1, 5-o-nitrobenzyl) -1,2, 4-triazole on Phytophthora capsici;
FIG. 5 is an in vivo experiment of the present application on P.capsici with propylene pimara (1, 5-o-nitrobenzyl) -1,2, 4-triazole;
Detailed Description
The present application will now be described in detail with reference to the accompanying drawings and examples.
Example 1
Firstly, preparing the propylene sea pine acyl chloride:
to a three-necked flask, acrylic acid (20 mmol), methylene chloride (80 mL) and thionyl chloride (16 mL) were sequentially added, and after refluxing for 4 hours, excess thionyl chloride and methylene chloride were removed by rotary evaporation to give acrylic acid pimaric acid chloride with a yield of 95%.
Secondly, preparing 3-propenes pimaric-1, 2, 4-triazole:
pyridine (80 mL), sodium carbonate (48 mmol) and thiosemicarbazide (48 mmol) are sequentially added into a three-neck flask, after stirring and dissolving, the acrylic pimaric acid chloride obtained in the first step is diluted by pyridine and slowly added dropwise (60 drops/min), after the dropwise addition is finished, the reaction is carried out for 2-3h at room temperature, and after the reaction is finished, a large amount of distilled water is added, so that solid can be separated out. Mixing the dried solid (20 g) with 5% sodium hydroxide solution (100 mL), heating and refluxing for 4h, acidifying with glacial acetic acid to pH=5-7 after the reaction is finished, precipitating a large amount of solid, filtering the solid, collecting filter residues, washing and drying the filter residues, and separating and purifying by a column chromatography (gradient elution ratio of ethyl acetate/petroleum ether=2/1) to obtain the 3-propenside-1, 2, 4-triazole with the yield of 70%.
Thirdly, preparing the propylene pimon (1, 5-o-nitrobenzyl) -1,2, 4-triazole:
into a three-necked flask, ethanol solution (80 mL), 3-propenylpimaric-1, 2, 4-triazole (5 mmol) and sodium carbonate (20 mmol) were sequentially added, followed by stirring and dissolution, and then 2-NO was added 2 Bromobenzyl (25 mmol) is heated to 75 ℃, reflux reaction is carried out for 6h, TLC detects the reaction end point, and after acid washing, alkali washing and water washing, column chromatography (gradient elution proportion of ethyl acetate/petroleum ether=2/1) is carried out, thus obtaining the propylene pimaric (1, 5-o-nitrobenzyl) -1,2, 4-triazole with the yield of 65 percent.
The structure of the propylene pimaric (1, 5-o-nitrobenzyl) -1,2, 4-triazole is characterized by using a nuclear magnetic resonance and liquid phase mass spectrometer, and the result is as follows:
a pale yellow viscous liquid; IR (cm) -1 ):2922,2862(-CH 3 ,-CH 2 )；1608(-C＝N)；856(-Ar). 1 H NMR(DMSO-d 6 .δ/mg/L.400MHz),7.18-8.24(m,8H,Ar-H)；6.61(s,1H,-CH＝C)；4.92-5.24(m,4H,-SCH 2 )；3.85-3.99(m,4H,-NCH 2 )；2.28(m,H,-CH-C)；1.67(s,3H,-CH)；1.81(m,1H,-CH-(CH 3 ) 2 -)；1.26-1.47,1.81,2.53(m,14H,-CH 2 -)；0.54-1.11(m,12H,-CH 3 ). 13 C NMR(DMSO-d 6 .δ/mg/L.100MHz),190.32,170.50,154.61,148.62,147.71,147.30,138.73,137.11,134.96,134.71,134.55,134.21,134.14,133.85,133.77,133.33,132.65,132.46,131.94,131.42,131.00,130.25,129.95,129.74,129.43,129.29,129.08,128.80,128.28,125.60,125.36,125.26,125.03,124.87,124.75,124.69,124.57,68.77,66.21,65.87,64.53,62.73,60.31,53.43,40.54,39.29,33.50,30.46,20.93,19.12,15.40,14.48,13.98.ESI-MS m/z＝1025.3750[M+H] + .
Determination of anti-plant pathogen Activity in Propionibacterium acnes (1, 5-o-nitrobenzyl) -1,2, 4-triazole
Firstly, the compound is dissolved in dimethyl sulfoxide (DMSO) to prepare medicines with the concentration of 50mg/L,25mg/L,12.5mg/L,6.25mg/L,3.125mg/L and 1.5625mg/LAnd (3) liquid. And then pouring the prepared liquid medicine into a potato culture medium, uniformly mixing, subpackaging into culture dishes, and setting the non-drug culture medium as a blank control CK. A5 mm cake was punched out with a punch and inoculated onto the medium, each repeated three times. Culturing in a constant temperature incubator at 28deg.C after inoculation, measuring colony diameter by crisscross method, calculating the inhibition rate of target compound to Phytophthora capsici by using formula 1-1, performing correlation regression analysis on compound concentration and inhibition rate by using SPSS software, and calculating EC thereof 50 。
Inhibition ratio (%) = [ (control colony diameter/mm-agent treated colony diameter/mm)/(control colony diameter/mm-5) ]100 (1-1)
Determination of anti-plant pathogen Activity of Acetopimaric (1, 5-o-nitrobenzyl) -1,2, 4-triazole in vivo
First, 20mg of the compound was weighed, dissolved in 1mL of DMSO to prepare a 20mg/mL stock solution, and then diluted into two sets of 10mL drug solutions of different concentrations (200, 100, and 50 mg/L). For in vivo protective activity, the prepared drug solution is uniformly sprayed on fresh healthy capsicum with uniform size. After 24 hours, the pathogen was inoculated and 10mL distilled water (containing 0.2mL DMSO) was used as a blank. Then, the peppers were placed in an illumination incubator (relative humidity 98%, temperature 25 ℃) for 3 days. For in vivo therapeutic activity, capsicum was first inoculated with pathogen, cultured for 24 hours, and the prepared drug solution was uniformly sprayed on capsicum, and 10mL of distilled water (containing 0.2mL of DMSO) was used as a blank control. Then, all treatments were placed in an illumination incubator (relative humidity 98%, temperature 25 ℃) for 5 days. The grading standard is determined according to the diameter of the lesions on the peppers. The specific grade is grade 0, and no spots exist; 1 grade, 0-1 cm; 3 grade, 1-2 cm; grade 5, 2-3 cm; 7 grade, 3-4 cm; grade 9, greater than 4cm. The capsicum Disease Index (DI) and protective treatment (PE) or treatment (CE) results were calculated using formulas 1-2 and 1-3.
DI＝Σ(N i ×i)×100/N×i H (1-2) wherein N i Is the number of diseased peppers at all levels, i and i H Values representing the relative level and the highest level, respectively, N representing the total number of peppers tested;
PE/CE (%) = (C-DI)/C.times.100 (1-3) where DI and C are disease indices of control and treated samples, respectively.
The antibacterial result is as follows:
from tables 1,2 and 4, and 5, it can be seen that the compound has a certain inhibition effect on phytophthora capsici, and when the concentration is 1.5625mg/L, the inhibition rate of the compound on phytophthora capsici is over 50%, the antibacterial activity is high, the dosage of the drug is small, and the compound is safe and environment-friendly. Therefore, the compound propylene pimaric (1, 5-o-nitrobenzyl) -1,2, 4-triazole provided by the application can be used as an important compound for inhibiting phytophthora capsici.
Claims (7)
1. A process for preparing (1, 5-o-nitrobenzyl) -1,2, 4-triazole of propylene pimara, which is characterized in that: the structural formula is as follows:
2. the process for preparing (1, 5-o-nitrobenzyl) -1,2, 4-triazole of propylene pimara according to claim 1, wherein the process comprises the steps of: from 3-propenylpimaric-1, 2, 4-triazole and 2-NO 2 The bromobenzyl is prepared by reaction.
3. The method of manufacturing as claimed in claim 2, wherein: mixing 3-propenes pimaric-1, 2, 4-triazole and acid-binding agent in ethanol, dissolving, and adding 2-NO 2 And (3) bromobenzyl is subjected to reflux reaction for 6 hours at the temperature of 75 ℃, and column chromatography is carried out after acid washing, alkali washing and water washing to obtain the (1, 5-o-nitrobenzyl) -1,2, 4-triazole of the propylene sea pine.
4. A method of preparation as claimed in claim 3, wherein: 3-propenylpimaric-1, 2, 4-triazole, acid-binding agent and 2-NO 2 The molar ratio of bromobenzyl is 1:4:5, a step of; the acid binding agent is sodium carbonate or potassium carbonate; column chromatography uses petroleum ether and ethyl acetate with volume ratio of 2:1 as eluent.
5. The method of claim 3 or 4, wherein: the preparation process of the 3-propenes pimaric-1, 2, 4-triazole is as follows:
1) Dissolving the acrylic pimaric acid in dichloromethane, adding thionyl chloride, heating and refluxing for 5 hours, and removing excessive thionyl chloride and dichloromethane by rotary evaporation to obtain acrylic pimaric acyl chloride;
2) Pyridine, sodium carbonate and thiosemicarbazide are sequentially added into a three-neck flask, after stirring and dissolution, the pimaric acid chloride is diluted by pyridine and slowly dripped, the reaction is carried out for 2-3 hours at room temperature, a large amount of distilled water is added to separate out solids, the dried solids are mixed with 5% sodium hydroxide solution, heating and refluxing are carried out for 4 hours, acetic acid is acidified to PH=5-7 after the reaction is finished, a large amount of solids can be separated out, filter residues are collected through suction filtration, and after drying, the 3-propenoic pimaric base-1, 2, 4-triazole can be obtained through separation and purification of column chromatography (gradient elution proportion ethyl acetate/petroleum ether=2/1).
6. The method of manufacturing according to claim 5, wherein: in step 1), the molar amount of the pimaric acid is as follows: the molar dosage of thionyl chloride is 1:8, 8; in the step 2), the molar amount of the acrylic pimaric acid chloride is as follows: molar amount of sodium carbonate: the molar dosage of thiosemicarbazide is 1:2.4:2.4; the reagent used for acidification is glacial acetic acid.
7. The propylene pimon (1, 5-o-nitrobenzyl) -1,2, 4-triazole according to claim 1 or 2, characterized in that: is used for preventing and treating phytophthora capsici of capsicum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310688196.7A CN116730932B (en) | 2023-06-12 | 2023-06-12 | Preparation and application of propylene pimaric (1-o-nitrobenzyl-5-o-nitrobenzyl sulfide) -1,2, 4-triazole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310688196.7A CN116730932B (en) | 2023-06-12 | 2023-06-12 | Preparation and application of propylene pimaric (1-o-nitrobenzyl-5-o-nitrobenzyl sulfide) -1,2, 4-triazole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116730932A true CN116730932A (en) | 2023-09-12 |
| CN116730932B CN116730932B (en) | 2024-06-18 |
Family
ID=87914474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310688196.7A Active CN116730932B (en) | 2023-06-12 | 2023-06-12 | Preparation and application of propylene pimaric (1-o-nitrobenzyl-5-o-nitrobenzyl sulfide) -1,2, 4-triazole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116730932B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870663A (en) * | 2010-07-15 | 2010-10-27 | 中国林业科学研究院林产化学工业研究所 | Acrylpimaric amide derivative as well as preparation method and application thereof |
| CN102219707A (en) * | 2011-04-22 | 2011-10-19 | 中国林业科学研究院林产化学工业研究所 | Acrylpimaric dioxime derivative as well as preparation method and application thereof |
| CN102875487A (en) * | 2012-10-17 | 2013-01-16 | 广西大学 | Synthesis method for acrylpimaric acid base dithiadiazole derivative |
| US20190127338A1 (en) * | 2016-07-15 | 2019-05-02 | Oriental (Luzhou) Agrochemicals Co., Ltd. | Method of synthesizing 1,2,4-triazole-3-thione compounds and intermediates thereof |
| CN115974797A (en) * | 2022-12-26 | 2023-04-18 | 西北农林科技大学 | 1, 5-disubstituted (4-F) benzyl-3-dehydroabietyl-1, 2, 4-triazole, preparation method and application thereof |
-
2023
- 2023-06-12 CN CN202310688196.7A patent/CN116730932B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870663A (en) * | 2010-07-15 | 2010-10-27 | 中国林业科学研究院林产化学工业研究所 | Acrylpimaric amide derivative as well as preparation method and application thereof |
| CN102219707A (en) * | 2011-04-22 | 2011-10-19 | 中国林业科学研究院林产化学工业研究所 | Acrylpimaric dioxime derivative as well as preparation method and application thereof |
| CN102875487A (en) * | 2012-10-17 | 2013-01-16 | 广西大学 | Synthesis method for acrylpimaric acid base dithiadiazole derivative |
| US20190127338A1 (en) * | 2016-07-15 | 2019-05-02 | Oriental (Luzhou) Agrochemicals Co., Ltd. | Method of synthesizing 1,2,4-triazole-3-thione compounds and intermediates thereof |
| CN115974797A (en) * | 2022-12-26 | 2023-04-18 | 西北农林科技大学 | 1, 5-disubstituted (4-F) benzyl-3-dehydroabietyl-1, 2, 4-triazole, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李健;饶小平;商士斌;高艳清;: "丙烯海松双酰基硫脲衍生物的合成及抑菌活性研究", 林产化学与工业, no. 05, pages 985 - 987 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116730932B (en) | 2024-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7082709B2 (en) | Quinazoline dione compounds, their use and pesticide herbicides | |
| JPH01250365A (en) | Pyrimidine derivative and herbicide | |
| CN113004196B (en) | N- (benzyloxy) -2-chloronicotinamides compound and preparation method and application thereof | |
| Satpute et al. | Synthesis and antibacterial activity of novel 3-hydroxy benzoic acid hybrid derivative [Part I] | |
| CN108191629B (en) | Ferulic acid derivative and application thereof | |
| CN116730932B (en) | Preparation and application of propylene pimaric (1-o-nitrobenzyl-5-o-nitrobenzyl sulfide) -1,2, 4-triazole | |
| CN115974797B (en) | 1, 5-disubstituted (4-F) benzyl-3-dehydroabietyl-1, 2, 4-triazole, and preparation method and application thereof | |
| CN1194975C (en) | Helerocyclic substituted benzoxazine cyclic compound having biological activity | |
| CN109942427B (en) | Monoterpene phenol derivative, and synthesis method and application thereof in pesticide | |
| CN114794115B (en) | Application of Penicillium poland extract in preparing herbicide | |
| CN113683529B (en) | Tetrahydrolinalyl Schiff base compound and preparation method and weeding application thereof | |
| CN109206395A (en) | The synthetic method and its agricultural biological activity of benzo oxa- class compound | |
| EP1529040A1 (en) | Endiandric acid h derivatives as c-maf inhibitors for using against asthma | |
| CN110143946B (en) | Quinoline compound and synthesis method and application thereof | |
| CN108558683B (en) | 2- (2-diethylaminoethoxy) -5-nitrophenol and preparation method and application thereof | |
| CN110178857B (en) | Application of seabuckthorn endophytic fungus strain SJ1 fermentation extract | |
| CN108840792B (en) | Enantiomeric isopimarane diterpene and preparation method and application thereof | |
| CN110396078B (en) | Osthole derivative and preparation method and application thereof | |
| CN111499554A (en) | Phenyl pyrrole compound and application of bactericidal activity thereof | |
| CN110687242B (en) | Method for testing phytotoxicity activity of NEO-clerodane diterpenoid compounds on ryegrass | |
| Kalambe | Synthesis and Study of 2–Hydroxy Substituted Quinoxaline Effects on Different Crop Plant Growth | |
| CN112961185B (en) | Fluorine-containing coumarin phosphate derivative and preparation method and application thereof | |
| CN111018826B (en) | 2-cyano-5-oxo-ethyl valerate compound and application thereof | |
| CN110963931B (en) | 2- (2-methoxy-5-nitro-phenoxy) ethyl triethyl ammonium halide and preparation method and application thereof | |
| CN110759905B (en) | 9S-acyloxy cinchonine derivative, preparation method and application thereof, and botanical pesticide |
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 |