CN116621905A - Diene thiazole derivative and synthetic method and application thereof - Google Patents

Diene thiazole derivative and synthetic method and application thereof Download PDF

Info

Publication number
CN116621905A
CN116621905A CN202310662271.2A CN202310662271A CN116621905A CN 116621905 A CN116621905 A CN 116621905A CN 202310662271 A CN202310662271 A CN 202310662271A CN 116621905 A CN116621905 A CN 116621905A
Authority
CN
China
Prior art keywords
diene
thiazole derivative
follows
compound
reaction conditions
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
Application number
CN202310662271.2A
Other languages
Chinese (zh)
Inventor
师宝君
胡玉晓
王强平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northwest A&F University
Original Assignee
Northwest A&F University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northwest A&F University filed Critical Northwest A&F University
Priority to CN202310662271.2A priority Critical patent/CN116621905A/en
Publication of CN116621905A publication Critical patent/CN116621905A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J43/00—Normal steroids having a nitrogen-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton
    • C07J43/003—Normal steroids having a nitrogen-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton not condensed
    • 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
    • A01N45/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds having three or more carbocyclic rings condensed among themselves, at least one ring not being a six-membered ring
    • 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
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Insects & Arthropods (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to the technical field of medicine synthesis, in particular to a diene thiazole derivative, a synthesis method and application thereof. The invention discloses a series of brand new compounds, which are first proposed, wherein the diene thiazole derivative has a chemical structure shown in a general formula (1). The synthesis method of the diene thiazole derivative uses 16-DPA as a basic raw material, and obtains the diene thiazole derivative through a series of different reactions. Biological tests prove that the diene thiazole derivative has good poisoning activity on aphids, oriental armyworms, plutella xylostella, whiteflies and other pests, and can be used for preparing single agricultural pesticides or mixed preparations containing the diene thiazole derivative.

Description

Diene thiazole derivative and synthetic method and application thereof
Technical Field
The invention relates to the technical field of medicine synthesis, in particular to a diene thiazole derivative, a synthesis method and application thereof.
Background
Heterocyclic compounds are a class of compounds that are based on five-, six-or fused ring systems containing one or more heteroatoms (O, N or S). Furan produced by Scheele in 1870 and Meyer in 1882 found thiophene since 1857 by Anderson separated pyrrole from bone tar has been developed to a striking number for over a century. The number of heterocyclic compounds described in the manual of bayer setan organic chemistry in the thirty of this century is about 1/3 of the hundreds of thousands of organic compounds known at the time. Of these compounds, the heterocyclic compounds containing a nitrogen atom are particularly important.
The thiazole heterocycle is an important five-membered aromatic heterocycle containing nitrogen and sulfur heteroatoms and having rich electrons, which is easy to form hydrogen bonds, coordinate with metal ions, and form pi-pi stacking, static electricity, hydrophobic interaction and other non-covalent bond interactions, and the structure endows the thiazole compound with a plurality of special properties, and particularly, along with a series of thiazole compounds successfully applied to clinical and agricultural production, the research and development of the thiazole compounds becomes one of hot spot fields in recent years, and the thiazole compounds have wide potential application in a plurality of fields.
Piercing-sucking mouth parts pests are a larger group of garden plant pests. The plant juice is extracted from the plants, and the plant juice is used for drawing nutrition, so that the branches, the leaves and the flowers curl, and even the whole plant withers or dies. While inducing a coal-borne disease, sometimes the pest itself is a transmission medium for the viral disease. The pests can be harmful to most crops, and cause serious loss of the yield and quality of the crops, but most of the current effective control agents generate serious drug resistance to piercing-sucking mouthparts pests after long-term use. The chewing insect pest damages plants and is characterized by various forms of mechanical damage, such as scars and holes caused by feeding the leaves, and when serious, the mesophyll is eaten, only the reticular veins are left, and even the whole leaves are eaten. Therefore, there is a need for urgent screening of new control agents.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a diene thiazole derivative, a synthesis method and application thereof.
The aim of the invention is achieved by the following technical scheme: the diene thiazole derivative has a chemical structure shown in a general formula (1):
wherein R is any one of alkyl, phenyl or substituted phenyl, and the alkyl is a fatty chain or cycloparaffin.
Further, the alkyl group is (a) or (b):
further, the phenyl group or the substituted phenyl group is any one of (c) to (i):
further, the diene thiazole derivative has the following chemical structural formula:
the synthetic method of the diene thiazole derivative comprises the following synthetic routes:
wherein, the reaction conditions of the step a are as follows: adding 4-dimethylaminopyridine, triethylamine and acyl chloride containing various substituents into dichloromethane dissolved with a compound (2) respectively, and reacting for 5-7 hours, preferably 6 hours at normal temperature;
the reaction conditions in step b are: tetrahydrofuran is used as a solvent, tetrabutylammonium fluoride trihydrate is added, and reflux reaction is carried out for 3 to 5 hours, preferably 4 hours.
Further, the synthetic route of the compound (2) is as follows:
wherein, the reaction conditions of the step c are as follows: adding bromoketone into tetrahydrofuran solution of the compound (4), and reacting for 6-10 h at 63-68 ℃, preferably for 8h at 65 ℃;
the reaction conditions of the step d are as follows: ethanol is taken as a solvent, thiourea is added, and the mixture is reacted for 6 to 10 hours at the temperature of 63 to 68 ℃, preferably for 8 hours at the temperature of 65 ℃;
the reaction conditions of the step e are as follows: methanol is taken as solvent, na is added 2 CO 3 Reacting for 3-5 h at 75-85 ℃, preferably for 4h at 80 ℃;
the reaction conditions of the step f are as follows: the compound (7) is dissolved in N, N-dimethylformamide, imidazole and tert-butyldimethylchlorosilane are added, and the reaction is carried out for 10 to 14 hours, preferably 12 hours, at room temperature.
The application of the diene thiazole derivative prepared by the method in plant pest control.
Further, the plant pests are sucking and chewing pests.
Further, the piercing-sucking and chewing pests are aphids, oriental armyworms, plutella xylostella and whiteflies.
An insecticide contains the above-mentioned diene thiazole derivative, and the diene thiazole derivative prepared by the above-mentioned method.
Further, the effective mass percentage of the diene thiazole derivative is 0.01% -99.99%.
In order to apply the diene thiazole derivatives in the fields of agriculture and plant protection, one or more of the diene thiazole derivatives can be used as an insecticidal active ingredient by a person skilled in the art, and can be combined with an agropharmaceutically acceptable carrier or other agricultural active ingredients to prepare preparations which are convenient to apply, such as water dispersible granules, wettable powder or dispersible oil suspension and the like. In preparing the above-mentioned different dosage forms, it is necessary for those skilled in the art to use a plurality of auxiliary agents in addition to the optional bactericidal active ingredient, and different auxiliary ingredients (auxiliary agents) for the pesticide preparation can be selected according to the need. The auxiliary component can be one or more of dispersing medium, dispersing agent, emulsifying agent, wetting agent, thickening agent, defoaming agent, antifreezing agent, disintegrating agent, binding agent, filler and the like. The invention is not stated with respect to the method of formulating a single dose or a combination formulation containing said bis-allylthiazole derivative.
The invention has the following advantages:
(1) The invention discloses a series of novel diene thiazole derivatives, which are provided for the first time. In addition, the invention also provides a synthesis method of the diene thiazole derivative, which uses 16-DPA as a basic raw material, and obtains the diene thiazole derivative through a series of different reactions.
(2) Biological tests prove that the diene thiazole derivative has good poisoning activity on aphids, oriental armyworms, plutella xylostella, whiteflies and other pests, and can be used for preparing single agricultural pesticides or mixed preparations containing the diene thiazole derivative.
Drawings
FIG. 1 shows single crystal diffraction patterns of the objective compounds (1) -9.
Detailed Description
The invention will be further described with reference to the accompanying drawings and examples, to which the scope of the invention is not limited:
the diene thiazole derivative has a chemical structure shown in a general formula (1):
wherein R is any one of alkyl, phenyl or substituted phenyl, and the alkyl is a fatty chain or cycloparaffin.
The synthetic method of the diene thiazole derivative comprises the following synthetic routes:
wherein, the synthetic route of the compound (2) is as follows:
the reaction conditions of each step are as follows:
step a, R (C=O) Cl, et 3 N,DMAP,rt；
Step b, TBAF, DMF and rt;
step c, cuBr 2 ,THF,reflus；
Step d, thiourea, etOH and reflus;
step e, na 2 CO 3 ,MeOH,80℃；
Step f, DMF, TBSCl, imidozole, rt.
The specific operation is as follows:
the synthesis and preparation of diene thiazole derivatives:
(1) Firstly, enabling dehydropregnenolone acetate to react with brominated ketone to generate a compound (5); then adding thiourea into ethanol as solvent to obtain compound (6), and adding methanol as solvent and Na 2 CO 3 Reacting, and removing acetyl protection; and finally, dissolving the compound (7) in N, N-dimethylformamide, and reacting with imidazole and tert-butyldimethyl chlorosilane to obtain the compound (2).
(2) The method comprises the steps of taking a compound (2) as a reaction raw material, taking dichloromethane as a solvent, respectively adding 4-dimethylaminopyridine, triethylamine and acyl chloride containing various substituents to react to obtain a compound (3), and then taking tetrahydrofuran as the solvent, and adding tetrabutylammonium fluoride trihydrate to obtain the compound (1).
Example 1: the synthesis steps of the diene thiazole derivative are as follows:
3.57g of dehydropregnenolone acetate (10 mmol) was dissolved in tetrahydrofuran (60 mL), and 4.50g of CuBr was added 2 (20 mmol), reaction was carried out at 65℃for 12h. Concentrating under reduced pressure, extracting with saturated aqueous NaCl solution and dichloromethane, drying the organic phase over anhydrous sodium sulfate, concentrating under reduced pressure to give 4.00g of a white solid compound (5); then, 3.48g of the compound (5) (8 mmol) was dissolved in 70mL of ethanol, and then 0.92g of thiourea (12 mmol) 2 was added thereto for reaction at 80℃for 8 hours. Concentrating under reduced pressure, filtering with dichloromethane to obtain a brown yellow liquid, drying with anhydrous sodium sulfate, and concentrating under reduced pressure to obtain 3.22g of yellow solid compound (6); 2.06g of compound (6) (5 mmol) was dissolved in methanol (40 mL), followed by addition of 0.80g of sodium carbonate (7.5 mmol) and reaction at 70℃for 5h. Concentrating under reduced pressure, and suction filtering with ice water to obtain 1.78g of pale yellow solid compound (7); 1.48g of compound (7) (4 mmol) was added to the reaction flask, dissolved in DCM (50 mL), and 603mg TBSCl (2.4 mmol) and 816mg imidazole (12 mmol) were added. The reaction was carried out at 0℃for 8 hours. After completion of TLC detection reaction, DCM and H were added 2 O extraction, anhydrous Na 2 SO 4 Drying and concentration under reduced pressure gave 1.85g of compound (2) as a yellow solid.
121.2mg of Compound (2) (0.25 mmol) was dissolved in methylene chloride, and 30mg of DMAP (0.25 mmol) and 150mg of Et were added 3 N (1.5 mmol) and acyl chloride (1.0 mmol) containing different substituents, reacting for 4h at room temperature, then extracting with water and dichloromethane, drying the organic phase with anhydrous sodium sulfate, concentrating under reduced pressure to obtain compound (3); compound (3) (0.20 mmol) was dissolved in anhydrous THF (5 mL), 0.16g of tetrabutylammonium fluoride trihydrate (0.6 mmol) was added, stirred at room temperature for 2h, extracted with diethyl ether and ethyl acetate, and concentrated under reduced pressure to give compound (1).
The diene thiazole derivative prepared by the method is prepared by 1 H-NMR、 13 C-NMR was confirmed in which the structures of the compounds (1) -9 were confirmed by single crystal diffraction, as shown in FIG. 1, and the specific results were as follows:
1. compound (1) -1
1 H NMR(500MHz,CDCl 3 )δ＝6.77(s,1H),6.27(s,1H),5.38(s,1H),3.63–3.36(m,1H),2.77–2.66(m,1H),2.33(dd,J＝13.1,1.9Hz,1H),2.26(td,J＝6.7,3.9Hz,3H),2.24–2.21(m,1H),2.10–1.97(m,2H),1.86(s,3H),1.85(s,1H),1.80(dd,J＝7.9,6.0Hz,2H),1.76(d,J＝7.0Hz,2H),1.75–1.68(m,3H),1.68–1.54(m,6H),1.55(s,2H),1.52(d,J＝8.0Hz,2H),1.25(d,J＝2.1Hz,1H),1.07(s,4H),1.04(s,3H).
13 C NMR(125MHz,CDCl 3 )δ＝174.30,157.83,148.56,145.82,141.15,128.93,121.39,107.22,71.74,57.44,50.52,46.39,45.43,42.35,37.20,36.72,35.67,31.67,31.58,31.41,30.33,30.13,26.04,21.02,19.36,16.18.
2. Compounds (1) -2
1 H NMR(500MHz,CDCl 3 )δ＝10.63(s,1H),6.77(s,1H),6.28(s,1H),5.38(d,J＝5.0Hz,1H),3.54(tt,J＝10.9,4.5Hz,1H),2.68(d,J＝8.0Hz,1H),2.30(s,1H),2.27(d,J＝12.5Hz,1H),2.23(s,1H),2.23–2.19(m,1H),2.07(d,J＝5.4Hz,1H),2.06–1.97(m,2H),1.87(s,2H),1.84(s,2H),1.76(s,1H),1.67(d,J＝6.5Hz,3H),1.57–1.49(m,4H),1.07(s,3H),1.03(s,3H).
13 C NMR(125MHz,CDCl 3 )δ＝174.72,158.42,148.56,145.70,141.24,129.11,121.46,107.27,71.80,57.58,50.59,46.43,45.39,42.40,37.27,36.80,35.76,31.72,31.68,31.51,30.55,30.38,30.20,26.17,21.10,19.46,16.26.
3. Compounds (1) -3
1 H NMR(500MHz,CDCl 3 )δ＝8.08(dd,J＝7.4,2.0Hz,1H),7.80(dd,J＝7.4,2.1Hz,1H),7.70(td,J＝7.5,2.0Hz,1H),7.62(td,J＝7.5,2.0Hz,1H),7.32(s,1H),δ7.26(s,1H),5.65(s,1H),5.39(s,1H),3.97(d,J＝5.1Hz,1H),3.55(d,J＝5.1Hz,1H),2.30(d,J＝15.7Hz,1H),2.17(dt,J＝13.0,1.0Hz,1H),2.10(s,1H),2.05–1.98(m,1H),1.92(d,J＝13.0Hz,1H),1.82–1.73(m,3H),1.69(s,1H),1.64–1.58(m,2H),1.45–1.36(m,1H),1.39–1.33(m,1H),1.27(s,2H),1.15(s,2H).
13 C NMR(125MHz,CDCl 3 )δ＝169.31,167.49,147.56,145.24,143.97,139.23,134.97,133.17,133.11,133.06,128.19,127.17,125.60,125.06,δ71.74,57.27,56.32,50.46,46.42,42.35,37.21,36.72,35.62,31.67,31.56,31.41,30.35,21.05,19.38.
4. Compounds (1) -4
1 H NMR(500MHz,MeOD)δ＝7.58(d,J＝7.6Hz,1H),7.54–7.46(m,2H),7.42(td,J＝7.3,2.1Hz,1H),6.99(s,1H),6.26(s,1H),5.37(d,J＝5.0Hz,1H),3.41(tt,J＝10.6,4.9Hz,1H),2.34(dt,J＝12.2,3.6Hz,1H),2.27(d,J＝8.4Hz,1H),2.24(d,J＝5.6Hz,1H),2.23–2.17(m,1H),2.04(d,J＝17.5Hz,2H),2.01(s,1H),2.00(d,J＝5.9Hz,2H),1.90–1.76(m,2H),1.77(s,1H),1.70(d,J＝12.7Hz,2H),1.70–1.64(m,2H),1.54(s,1H),1.51(d,J＝5.9Hz,1H),1.47(s,2H),1.24(t,J＝7.1Hz,1H),1.08(s,3H),1.04(s,3H).
13 C NMR(125MHz,MeOD)δ＝167.07,158.32,150.01,147.98,142.56,135.63,133.10,132.45,131.31,130.42,129.59,128.26,122.27,108.80,79.46,58.68,47.53,43.05,38.46,37.86,36.72,32.67,32.28,32.23,31.66,22.13,19.84,16.58.
5. Compounds (1) -5
1 H NMR(500MHz,MeOD)δ＝8.14(d,J＝1.9Hz,1H),7.94(d,J＝7.7Hz,1H),7.90(d,J＝2.0Hz,1H),7.74(d,J＝30.6Hz,2H),6.88(s,1H),5.34(d,J＝5.0Hz,1H),3.41(dq,J＝10.5,5.5Hz,1H),2.27(q,J＝4.0,2.8Hz,2H),2.23(s,2H),2.21(dd,J＝6.2,3.1Hz,1H),2.17(d,J＝6.2Hz,1H),2.01(s,2H),1.97–1.88(m,1H),1.81(ddd,J＝20.8,11.3,3.6Hz,3H),1.66(q,J＝6.1,5.1Hz,2H),1.51(d,J＝6.2Hz,1H),1.47(d,J＝6.4Hz,1H),1.45(d,J＝6.1Hz,2H),1.23(t,J＝7.2Hz,1H),1.05(s,3H),1.01(s,3H).
13 C NMR(125MHz,MeOD)δ＝170.58,165.86,147.05,142.24,136.85,136.62,136.34,135.70,132.96,131.31,128.42,127.46,123.58,72.10,51.67,48.49,47.53,47.29,42.78,38.19,37.62,36.48,35.68,32.43,32.03,31.34,19.80,16.60.
6. Compounds (1) -6
1 H NMR(500MHz,CDCl 3 )δ＝7.68(d,J＝7.0Hz,1H),7.57(d,J＝8.0Hz,1H),7.52(t,J＝5.8Hz,2H),7.05(s,1H),6.06(s,1H),5.36(d,J＝5.3Hz,1H),3.53(d,J＝12.5Hz,1H),2.30(q,J＝6.3,5.6Hz,1H),2.25(d,J＝11.1Hz,1H),2.19–2.12(m,1H),2.04(s,1H),1.96(d,J＝13.8Hz,2H),1.92(s,1H),1.84(d,J＝10.1Hz,2H),1.71(s,1H),1.63(d,J＝17.4Hz,2H),1.52–1.45(m,1H),1.44(s,1H),1.39–1.21(m,2H),1.05(s,3H),0.86(s,3H).
13 C NMR(125MHz,CDCl 3 )δ＝168.24,165.56,149.83,147.96,141.24,133.63,132.03,131.63,131.13,130.59,129.82,129.40,127.82,127.75,121.47,71.83,57.12,50.52,46.59,46.27,42.38,37.27,36.79,35.59,35.06,31.70,31.61,31.58,30.38.
7. Compounds (1) -7
1 H NMR(500MHz,CDCl 3 )δ＝7.75(d,J＝5.1Hz,2H),7.22–7.14(m,2H),6.77(s,1H),6.04(s,1H),5.36(s,1H),3.56(td,J＝11.3,6.5Hz,1H),3.85(s,2H),2.33(d,J＝19.1Hz,1H),2.28(s,1H),2.25(d,J＝12.6Hz,1H),2.17(d,J＝11.4Hz,1H),2.01(d,J＝28.5Hz,2H),1.96–1.92(m,1H),1.86(d,J＝12.5Hz,3H),1.70–1.65(m,1H),1.61(s,1H),1.55(d,J＝13.2Hz,1H),1.51(s,1H),1.38(t,J＝12.4Hz,1H),1.29–1.20(m,1H),1.08(s,1H),1.05(s,3H),0.98–0.94(m,3H).
13 C NMR(126MHz,CDCl 3 )δ＝165.49,158.72,147.89,146.02,143.37,141.10,129.65,129.53,129.04,127.82,121.42,107.10,71.73,56.75,55.93,50.63,46.05,42.33,37.29,36.69,35.32,31.64,31.50,31.24,30.15,21.73,20.99,19.35.
8. Compounds (1) -8
1 H NMR(500MHz,CDCl 3 )δ＝7.84(dd,J＝7.5,2.0Hz,1H),7.62(t,J＝7.5Hz,1H),7.39(s,1H),7.20(dd,J＝7.5,2.0Hz,1H),5.72(s,1H),5.46(s,1H),4.05(d,J＝5.1Hz,1H),3.56(d,J＝4.9Hz,1H),2.41–2.34(m,2H),2.25(t,J＝1.0Hz,1H),2.17(s,1H),2.09(dt,J＝18.1,1.0Hz,1H),1.99(d,J＝13.0Hz,1H),1.89–1.80(m,3H),1.77(s,1H),1.72–1.65(m,2H),1.52–1.44(m,2H),1.08(s,3H),1.04(s,3H).
13 C NMR(125MHz,CDCl 3 )δ＝168.24,165.56,147.96,147.40,141.24,141.20,133.63,131.63,130.59,127.82,124.63,121.47,114.54,71.83,57.12,50.52,42.38,37.27,36.79,31.70,31.58,30.38,19.42,15.92.
9. Compounds (1) -9
1 H NMR(500MHz,CDCl 3 )δ＝7.47(t,J＝5.6Hz,1H),7.34(s,1H),7.32–7.29(m,2H),7.03(dd,J＝8.2,2.7Hz,1H),5.99(t,J＝2.6Hz,1H),5.34(s,1H),3.74(s,3H),2.35–2.26(m,2H),2.24(d,J＝11.2Hz,1H),2.22–2.15(m,1H),2.16–2.08(m,1H),2.08–1.94(m,2H),1.94(s,1H),1.84(dt,J＝23.1,13.0Hz,3H),1.76–1.69(m,1H),1.69–1.59(m,2H),1.48(s,1H),1.41(dt,J＝10.8,4.9Hz,1H),1.26(d,J＝6.5Hz,1H),1.19(dt,J＝12.2,6.0Hz,1H),1.05(s,3H),0.99(s,4H).
13 C NMR(125MHz,CDCl 3 )δ＝170.45,165.19,159.80,146.11,141.19,135.06,129.91,129.81,129.11,128.82,121.62,119.62,113.85,110.67,71.74,57.03,55.46,50.49,46.55,46.25,42.36,37.27,37.24,36.73,35.43,34.80,30.33,19.40,19.36.
Example 2:
mortality of the diene thiazole derivatives listed in table 1 was determined by slide dipping on wheat binary aphid (Schizaphis graminum), cabbage aphid (Brevicoryne brassicae Linn), cotton aphid (Aphis gossypii), apple yellow aphid (Aphis citricolavander Goot) and peach aphid (Myzus persicae). The specific method comprises the following steps: accurately weighing a certain amount of compound to be measured, using acetone as a solvent, dissolving the compound, preparing a solution with the concentration of 100 mug/mL by using a 0.1% Tween-80 aqueous solution, standing for half an hour at room temperature, and preserving for later use after the sample is completely dissolved. And sticking aphids to be detected on a glass slide containing double faced adhesive tape, immersing the glass slide containing the aphids in the prepared liquid medicine for 5s, taking out, sucking the residual liquid medicine by using water absorption paper, wherein the positive control is acetamiprid, and the negative control is 0.1% Tween-80 aqueous solution. The mortality was observed after 48h of incubation in the petri dish and the results are shown in table 1.
TABLE 1 mortality of five aphids with the Diene thiazole derivatives of formula (1) of the present invention
In the table-represent inactivity
The indoor bioassay results in table 1 show that the test compound has better biological activity on wheat binary aphids, cabbage aphids, cotton aphids, apple yellow aphids and peach aphids, and part of the compounds have similar insecticidal effects with flonicamid.
Example 3:
the mortality of the dienothiazoles derivatives listed in Table 2 on Oriental armyworms and plutella xylostella was determined by the leaf dipping method, and the method was as follows: accurately weighing a certain amount of compound to be tested, taking acetone as a solvent, dissolving the compound, preparing a solution with the concentration of 1000 mug/mL and 200 mug/mL by using a 0.1% Tween-80 aqueous solution, standing for half an hour at room temperature, and preserving for later use after the sample is completely dissolved. Cutting fresh wheat leaves into 0.5X0.5 cm, placing each leaf into the prepared solution for 3-5s, taking out, and air drying; putting the 3-instar larvae of the armyworms into 24-hole plates, and respectively feeding the dried wheat leaves; the positive control was avermectin (concentration 10. Mu.g/mL and 2. Mu.g/mL, respectively) and the negative control was 0.1% Tween-80 in water. After 72 hours the mortality was observed and the results are shown in Table 2.
TABLE 2 mortality of Oriental armyworms by the Diene thiazole derivatives of formula (1) of the present invention
Note that: the concentrations of chlorfenapyr are 50 mug/mL and 10 mug/mL respectively
The indoor bioassay results in table 2 show that the test compound has better biological activity on Oriental myxoma, and part of the compounds have similar insecticidal effects with abamectin.
Example 4:
the poisoning activity of the diene thiazole derivatives shown in Table 3 on plutella xylostella was measured by a leaf dipping method. The positive control was chlorfenapyr (concentrations 1000. Mu.g/mL and 200. Mu.g/mL, respectively) and the negative control was acetone. The number of deaths after 72h was observed and the corrected mortality was calculated, the results are shown in table 3:
TABLE 3 mortality of Dienethiazole derivatives of formula (1) of the present invention on plutella xylostella
Note that: the concentrations of chlorfenapyr are 50 mug/mL and 10 mug/mL respectively
The indoor bioassay results in table 3 show that the test compound has better bioactivity on plutella xylostella, and partial compounds have similar insecticidal effects with chlorfenapyr.
Example 5:
the poisoning activity of the diene thiazole derivatives shown in Table 4 on whiteflies was measured by a foliar spray method. The specific method comprises the following steps: accurately weighing a certain amount of compound to be tested, dissolving the compound with acetone, preparing a solution with the concentration of 100 and 50 mug/mL by using a 0.1% Tween 80 aqueous solution, and preserving the solution for later use. Spraying the liquid medicine on the back of cucumber leaves, and putting the whiteflies to be detected on plant leaves after the liquid medicine is naturally dried. The positive control was thiamethoxam and the negative control was acetone. The number of deaths after 7d was observed and the corrected mortality was calculated and the results are shown in table 4.
TABLE 4 mortality of Dienethiazole derivatives of formula (1) of the present invention to Bemisia tabaci
The indoor bioassay results in table 4 show that the test compounds have better biological activity on whiteflies, and that some of the compounds have similar insecticidal effects as thiamethoxam.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art who is skilled in the art to which the present invention pertains will appreciate that the technical scheme and the inventive concept according to the present invention are equally substituted or changed within the scope of the present invention.

Claims (10)

1. The diene thiazole derivative is characterized by having a chemical structure shown in a general formula (1):
wherein R is any one of alkyl, phenyl or substituted phenyl, and the alkyl is a fatty chain or cycloparaffin.
2. The bis-alkenylthiazole derivative according to claim 1, wherein the alkyl group is (a) or (b):
3. the bis-alkenylthiazole derivative according to claim 1, wherein the phenyl group or the substituted phenyl group is any one of (c) to (i):
4. the bis-vinyl thiazole derivative according to claim 1, wherein the bis-vinyl thiazole derivative has the following chemical structural formula:
5. the method for synthesizing the diene thiazole derivative according to claim 1, wherein the synthetic route is as follows:
wherein, the reaction conditions of the step a are as follows: adding 4-dimethylaminopyridine, triethylamine and acyl chloride containing various substituents into dichloromethane dissolved with a compound (2) respectively, and reacting for 5-7 h at normal temperature;
the reaction conditions in step b are: tetrahydrofuran is used as a solvent, tetrabutylammonium fluoride trihydrate is added, and reflux reaction is carried out for 3 to 5 hours.
6. The method for synthesizing a bis-vinyl thiazole derivative according to claim 5, wherein the synthetic route of the compound (2) is as follows:
wherein, the reaction conditions of the step c are as follows: adding bromoketone into tetrahydrofuran solution of the compound (4) to react for 6-10 h at 63-68 ℃;
the reaction conditions of the step d are as follows: ethanol is taken as a solvent, thiourea is added, and the mixture reacts for 6 to 10 hours at the temperature of 63 to 68 ℃;
the reaction conditions of the step e are as follows: methanol is taken as solvent, na is added 2 CO 3 Reacting for 3-5 h at 75-85 ℃;
the reaction conditions of the step f are as follows: the compound (7) is dissolved in N, N-dimethylformamide, imidazole and tertiary butyl dimethyl chlorosilane are added, and the reaction is carried out for 10 to 14 hours at room temperature.
7. Use of the dienothiazole derivatives prepared by the method of claims 1 to 4 in plant pest control.
8. The use according to claim 7, wherein the plant insect pest is aphid, oriental myxoplasma, plutella xylostella and Bemisia tabaci.
9. An insecticide comprising the dienothiazole derivative according to any one of claims 1 to 4, and the dienothiazole derivative prepared by the method according to claim 5 or 6.
10. An insecticide according to claim 9, wherein the effective mass percentage of said dienothiazole derivatives is 0.01% -99.99%.
CN202310662271.2A 2023-06-06 2023-06-06 Diene thiazole derivative and synthetic method and application thereof Pending CN116621905A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310662271.2A CN116621905A (en) 2023-06-06 2023-06-06 Diene thiazole derivative and synthetic method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310662271.2A CN116621905A (en) 2023-06-06 2023-06-06 Diene thiazole derivative and synthetic method and application thereof

Publications (1)

Publication Number Publication Date
CN116621905A true CN116621905A (en) 2023-08-22

Family

ID=87609697

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310662271.2A Pending CN116621905A (en) 2023-06-06 2023-06-06 Diene thiazole derivative and synthetic method and application thereof

Country Status (1)

Country Link
CN (1) CN116621905A (en)

Similar Documents

Publication Publication Date Title
KR20050055767A (en) Heterocyclocarboxamide derivatives
CN103109816A (en) Thiobenzamide compounds and application thereof
AU2018201101A1 (en) Novel cyclic depsipeptide derivative and pest control agent comprising same
CN112457288A (en) Piperine acid derivative and application thereof
CN103214461B (en) Quinoline derivative and application thereof
CN109503562B (en) 2- [4- (2-thienyl) ] pyrimidyl urea derivative and preparation method and application thereof
CN110734417B (en) 2-butenolide acetamide compound and preparation method and application thereof
CN109422745A (en) Matrine acyl hydrazone derivative and its preparation and the application in terms of preventing and treating plant pest
CN111763199B (en) 2-thienyl quinolinone derivative and preparation method and application thereof
CN116621905A (en) Diene thiazole derivative and synthetic method and application thereof
CN111747943A (en) 3- (2-furan methylene) quinolinone compound and preparation method and application thereof
CN109422744A (en) Matrine derivative and its synthesis and the application in terms of preventing and treating plant pest
CN114409664B (en) Spiro heterocyclic tetrahydropyran compound and preparation method and application thereof
CN107987024B (en) Pyrimidine amine compound with biological activity and preparation method thereof
CN111718336B (en) Quinolinone Schiff base compound and preparation method and application thereof
CN107501368B (en) Synthesis of doramectin derivative and insecticidal application thereof
CN113943238B (en) Substituted diphenyl sulfide compound and application thereof
CN110156867B (en) Aminoformic acid phellodendron ketoxime ester and preparation method and application thereof
CN109535136B (en) 2- [4- (2-furyl) ] pyrimidylurea compound and preparation method and application thereof
Li et al. Antifeedant activity of camptothecin and its semisynthetic derivatives against Spodoptera litura (Fabricius)(Lepidoptera: Noctuidae) larvae
CN106146497A (en) Matrine oxime ester derivative and preparation method and application
DE2943019C2 (en)
CN111747940A (en) Quinolinone semicarbazone derivative and preparation method and application thereof
CN118420691B (en) Avermectin derivative containing nitrobenzyl oxycarbonyl ester and its synthesis and use
CN116621906A (en) Epiandrosterone pyrazole derivative and synthetic 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