Quinolinone derivative as well as synthesis method and application thereof
By developing and synthesizing novel structures of quinolinone derivatives, the problem of pests in the prior art resistance to control agents is solved, and effective insecticidal effect on piercing pests such as aphids is achieved.
Patent Information
- Application Number
- CN202411529156.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-30
- Publication Date
- 2025-02-11
- Estimated Expiration
- 2044-10-30
AI Technical Summary
The prior art is difficult to effectively prevent and control resistance to puncture-absorbing pests such as aphids and whiteflies, resulting in serious losses in crop yield and quality.
A series of novel structures of quinolinone derivatives were developed and their synthetic methods were prepared. Quinolinone derivatives were obtained through a series of reactions based on indenone at different hydroxyl positions, and applied to plant pest control.
Quinolinone derivatives show good toxic activity against aphids, pedicle mites, rice planthoppers and whiteflies, which effectively solves the problem of pest resistance in the prior art.
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Figure CN119409629A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of drug synthesis, and specifically relates to quinolinone derivatives and synthesis methods and applications thereof. Background Art
[0002] The isolation of secondary metabolites from plants has a history of thousands of years. However, due to their complex structure and high difficulty in extraction, their activity is lower than that of chemical pesticides. Therefore, modifying natural products to improve their activity has become a hot topic in the synthesis of new pesticides in recent years.
[0003] Quinolinone is a common broad-spectrum heterocyclic structure skeleton, which exists in a variety of natural products and drug molecules and has significant biological activity and medicinal value. 3,4-dihydro-2 (1H) -quinolinone is an important class of nitrogen-containing heterocyclic compounds containing quinoline ring structure. Natural 3,4-dihydro-2 (1H) -quinolinone compounds can be extracted from plants such as Evodia rutaecarpa and evergreen trees. It is understood that these compounds and derivatives not only play an important role in pharmaceutical development, but are also intermediates in the synthesis of pesticides such as fungicides and herbicides. Piercing-sucking pests are one of the most serious pests in agriculture. For example, aphids, whiteflies, etc. can harm most crops, causing serious losses to their yield and quality. However, most of the currently effective control agents have developed serious resistance to piercing-sucking pests after long-term use. Therefore, it is urgent to screen out new control agents. Summary of the invention
[0004] The purpose of the present invention is to overcome the shortcomings of the prior art. The first purpose is to provide a series of novel quinolinone derivatives.
[0005] The second object of the present invention is to provide a method for preparing quinolinone derivatives.
[0006] The third object of the present invention is to provide applications of quinolinone derivatives.
[0007] The object of the present invention is achieved by the following technical scheme: a quinolinone derivative having a chemical structure as shown in formula (I):
[0008]
[0009] Wherein, the OR1 is located at position 5, 6, 7 or 8, and OR1 is any one of OH, CH3COO or C5H9O2; the R2 is a substituted phenyl at the ortho, meta or para position, and R2 is any one of phenyl halogen, trifluoromethyl, methyl, nitro or methoxy.
[0010] As a preferred technical solution, the quinolinone derivative has a chemical structure as shown in any one of formulas (1) to (45):
[0011]
[0012]
[0013]
[0014]
[0015] Wherein, OR1 in any of the chemical structural formulas (1)-(45) is located at the 5th, 6th, 7th or 8th position.
[0016] The synthesis method of quinolinone derivatives, the synthesis route is:
[0017]
[0018] Furthermore, the reaction conditions of step i are: using acetone as solvent, adding indanone at different hydroxyl positions, K2CO3 and benzyl bromide, heating and reflux at 65-75°C for 3.5-4.5h;
[0019] The reaction conditions of step ii are: using ethanol as solvent, adding sodium acetate and hydroxylamine hydrochloride, heating under reflux at 75-85° C. for 1.5-2.5 h;
[0020] The reaction conditions of step iii are: using acetonitrile as solvent, adding indium bromide and silver trifluoromethanesulfonate, and reflux at a temperature of 75-85°C for 2.5-3.5h under nitrogen protection;
[0021] The reaction conditions of step iv are: using dichloromethane as solvent, adding 4-dimethylaminopyridine at room temperature, adding triethylamine and R-Cl at 0°C, reacting at a temperature of 0-25°C for 3-7 minutes, and then returning to room temperature to continue reacting for 7-9 hours.
[0022] Furthermore, using ethanol as solvent and Pb / C as catalyst, hydrogen is added to react for 10 to 14 hours to obtain a compound in which OR1 is OH.
[0023] Furthermore, 4-methylbenzenesulfonate pyridine and 3,4-dihydro-2H-pyran are added to the product obtained by the reaction in which OR1 is an OH compound, and dichloromethane is used as a solvent. The mixture is refluxed at a temperature of 45 to 55° C. for 3 to 5 hours to obtain a compound in which OR1 is C5H9O2.
[0024] Furthermore, acetic anhydride, triethylamine and 4-dimethylaminopyridine are added to the product obtained by the reaction in which OR1 is an OH compound, and dichloromethane is used as a solvent. The reaction is carried out at room temperature for 3 to 5 hours to obtain a compound in which OR1 is CH3COO.
[0025] Application of the above-mentioned quinolinone derivatives in plant pest control.
[0026] Furthermore, the plant pests are aphids, whiteflies, rice planthoppers and mites.
[0027] An insecticide comprising at least the above-mentioned quinolinone derivatives.
[0028] The effective content of the quinolinone derivatives in the insecticide is 0.01% to 99.99%.
[0029] In order to apply the quinolinone derivatives in the field of agriculture and plant protection, a person skilled in the art can use one or more of the quinolinone derivatives as insecticidal active ingredients, in combination with a pesticide-acceptable carrier, or other agricultural active ingredients, to prepare a preparation that is easy to apply, such as a water-dispersible granule, a wettable powder, or a dispersible oil suspension. When preparing the above-mentioned different dosage forms, a person skilled in the art needs to use a variety of auxiliary agents in addition to the optional insecticidal active ingredients, and can choose to use different pesticide preparation auxiliary ingredients (auxiliaries) as needed. The auxiliary ingredients can be one or more of a dispersion medium, a dispersant, an emulsifier, a wetting agent, a thickener, a defoamer, an antifreeze, a disintegrant, a binder, a filler, etc.
[0030] The present invention has the following advantages: the present invention proposes a series of brand-new quinolinone derivatives for the first time. In addition, the present invention also proposes a method for synthesizing quinolinone derivatives, using indanones at different hydroxyl positions as basic raw materials and obtaining the quinolinone derivatives of the present invention through a series of reactions. The product prepared by the synthesis method has a high yield and is easy to separate, and is the best method for preparing quinolinone derivatives. The present invention also provides new uses of quinolinone derivatives, which have been confirmed by bioassays to exhibit good toxicity against piercing-sucking insects such as aphids, armyworms, spider mites, rice planthoppers, and whiteflies, and can be used in plant pest control. DETAILED DESCRIPTION
[0031] The present invention is further described below in conjunction with the examples, and the protection scope of the present invention is not limited to the following: Example 1: Synthesis of quinolinone derivatives
[0032] The synthesis strategy is as follows: first, benzyl-protect the indanone (A) at different hydroxyl positions to obtain a series of compounds (B), then add sodium acetate and hydroxylamine hydrochloride with ethanol as solvent to carry out oximation reaction to obtain a series of compounds (C), then carry out Beckmann rearrangement to obtain a series of compounds (D), derive the amino group to obtain a series of compounds (E), and use Pb / C hydrogenation to remove the benzyl protection to obtain a series of compounds (I) with OR1 being OH; use THP to protect the hydroxyl group to obtain a series of compounds (I) with OR1 being -C5H9O2, and use ester group to protect the hydroxyl group to obtain a series of compounds (I) with OR1 being -C5H9O2.
[0033]
[0034] (1) Indanone (3.28 g, 20.00 mmol) with different hydroxyl positions, i.e., compound (A), K2CO3 (4.14 g, 30.00 mmol) and benzyl bromide (40.00 mmol) were weighed into four reaction bottles respectively, acetone was added as solvent, and the mixture was heated to reflux at 70°C for 4 h. Then, the pH of the reaction solution was adjusted to neutral with 1 mol / L HCl, and extracted with water and DCM (dichloromethane) three times. The organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to silica gel column chromatography to obtain a series of compounds (B).
[0035] (2) Different series of compounds (B) (4.58 g, 18.00 mmol), sodium acetate (8.86 g, 108.00 mmol) and hydroxylamine hydrochloride (5.63 g, 81.00 mmol) were weighed into 4 reaction bottles respectively, 10 ml of ethanol was added, and the mixture was heated to reflux at 80°C for 2 h. After the reaction was completed, the solvent was concentrated under reduced pressure to obtain a white solid, which was then added with ice water and filtered to obtain a series of compounds (C).
[0036] (3) Using CH3CN as solvent, different series of compounds (C) (4.70 g, 17.50 mmol), InBr3 (0.94 g, 2.63 mmol) and AgOTf (2.02 g, 7.875 mmol) were weighed and dissolved in acetonitrile respectively. The mixture was refluxed at 80°C for 3 h under nitrogen protection. After the reaction was completed, the solvent was removed by concentration under reduced pressure. The mixture was extracted three times with DCM and water. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain a series of compounds (D).
[0037] (4) Different series of compounds (D) (0.16 g, 0.6 mmol) and DMAP (0.073 g, 0.6 mmol) were weighed into four 50 ml reaction bottles, and then DCM was added as solvent. Et3N (1.20 mmol) and R-Cl (1.2 mmol) were added at 0°C. After reacting at 0°C for 5 min, the mixture was transferred to room temperature and the reaction was continued for 8 h. After the reaction was completed, the mixture was extracted three times with water and DCM (dichloromethane). The organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a series of compounds (E).
[0038] (5) Weigh different series of compounds (E) (0.5 mmol) and dissolve them in anhydrous methanol (10 mL) solution, then add wet Pd / C (0.1 mmol, 5%) to the above solution, introduce H2 into the reaction solution at room temperature for 12 h, and after the reaction is completed, filter the reaction solution with diatomaceous earth to obtain a filtrate, and then concentrate under reduced pressure to obtain a series of compounds (I) in which OR1 is OH;
[0039] The series of compounds (Ⅰ) (1 mmol) wherein OR1 is OH are dissolved in anhydrous DCM (5 mL) solution, and then PPTS (0.2 mmol) and DHP (2 mmol) are added to the above solution, and heated to reflux at 50°C for 4 h. After the reaction is completed, the organic phase is washed three times with water, and then concentrated under reduced pressure to obtain the series of compounds (Ⅰ) wherein OR1 is -C5H9O2;
[0040] A series of compounds (Ⅰ) (1 mmol) in which OR1 is OH were dissolved in three portions of anhydrous DCM (5 mL) solutions respectively, and then acetic anhydride (1.1 mmol), triethylamine (2 mmol) and DMAP (1 mmol) were added to the above solutions. The reaction was carried out at room temperature for 4 hours. After the reaction was completed, the organic phase was washed three times with water, and then concentrated under reduced pressure to obtain a series of compounds (Ⅰ) in which OR1 is CH3COO.
[0041] Embodiment 2:
[0042] The quinolinone derivatives prepared by the method of Example 1 are 1 H-NMR, 13 C-NMR was used to confirm that we named the OR1 series compounds at position 5 as E series, the OR1 series compounds at position 6 as F series, the OR1 series compounds at position 7 as G series, and the OR1 series compounds at position 8 as H series. The specific results are as follows: F series compounds:
[0043] Compound F(1)
[0044]
[0045] 116.70,116.48,114.88,113.87,33.62,25.40.
[0046] Compound F(16)
[0047]
[0048] 6.5,3.7,3.2 Hz,1H).
[0049] 13 C NMR(101MHz,Chloroform-d)δ172.32,170.20,164.54,153.53,132.78,132.34,127.05,125. 65,118.02,116.36,115.37,114.32,96.57,61.97,55.57,32.21,30.27,25.89,25.13,18.73.
[0050] Compound F(31)
[0051]
[0052] 131.75,130.19,128.57,118.98,116.83,116.61,115.39,114.13,86.25,32.44,25.49.
[0053] Compound F(2)
[0054]
[0055] 116.48,114.88,113.87,33.62,25.40.
[0056] Compound F(17)
[0057]
[0058] 134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0059] Compound F(32)
[0060]
[0061] 131.75,130.19,128.57,118.98,116.83,116.61,115.39,114.13,86.25,32.44,25.49.
[0062] Compound F(3)
[0063]
[0064] Compound F(18)
[0065]
[0066] Compound F(33)
[0067]
[0068] Compound F(4)
[0069]
[0070] Compound F(19)
[0071]
[0072] 132.63,131.99,130.70,128.99,127.93,125.58,125.30,124.97,124.85,120.88,119.70,119.48,115.88,112.87,33.62,25.40.
[0073] Compound F(34)
[0074]
[0075] Compound F(5)
[0076]
[0077] 114.02,32.73,25.50.
[0078] Compound F(20)
[0079]
[0080] 134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0081] Compound F(35)
[0082]
[0083] Compound F(6)
[0084]
[0085] 130.06,129.59,128.75,119.30,115.31,115.23,114.10,114.02,32.58,25.52.
[0086] Compound F(21)
[0087]
[0088] 134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0089] Compound F(36)
[0090]
[0091] Compound F(7)
[0092]
[0093] 131.74,129.33,128.23,128.05,124.09,118.61,114.54,113.62,34.43,25.29.
[0094] Compound F(22)
[0095]
[0096] 134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0097] Compound F(37)
[0098]
[0099] Compound F(8)
[0100]
[0101] Compound F(23)
[0102]
[0103] 13 C NMR(101MHz,DMSO-d6)δ172.42,168.36,160.92,158.41,155.04,134.72,134.63,131.07,130.79,128 .96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0104] Compound F(38)
[0105]
[0106] 130.19,118.57,118.18,117.83,116.61,115.39,114.13,86.25,32.44,23.49.
[0107] Compound F(9)
[0108]
[0109] Compound F(24)
[0110]
[0111] 134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0112] Compound F(39)
[0113]
[0114] Compound F(10)
[0115]
[0116] Compound F(25)
[0117]
[0118] 13 C NMR(101MHz,DMSO-d6)δ172.42,168.36,160.92,158.41,155.04,134.72,134.63,131.07,130.79,128 .96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0119] Compound F(40)
[0120]
[0121] Compound F(11)
[0122]
[0123] Compound F(26)
[0124] 1H NMR (400MHz, Chloroform-d) δ7.60 (ddd, J=7.9, 4.0, 1.7Hz, 1H), 7.53 (ddd,
[0125] 116.48,114.88,113.87,33.62,25.40.
[0126] Compound F(41)
[0127]
[0128] Compound F(12)
[0129]
[0130] 129.47,126.20,120.29,115.15,115.06,114.08,113.99,32.90,25.51.
[0131] Compound F(27)
[0132]
[0133] 134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0134] Compound F(42)
[0135]
[0136] Compound F(13)
[0137] 1 H NMR (400MHz, DMSO-d6) δ9.43 (s, 0H), 7.54 (dd, J = 7.9, 1.8Hz, 1H), 7.50–
[0138]
[0139] 131.19,130.94,128.94,125.66,122.47,121.06,114.62,114.54,113.47,113.39,112.14,56.02,33.82,25.47. Compound F (28)
[0140]
[0141] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0142] Compound F(43)
[0143]
[0144] 130.75,130.19,118.57,118.18,117.83,116.61,115.39,114.13,86.25,53.97,32.44,23.49. Compound F (14)
[0145]
[0146] 55.76,32.42,25.55.
[0147] Compound F(29)
[0148]
[0149] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0150] Compound F(44)
[0151]
[0152] Compound F(15)
[0153]
[0154] 125.81,118.02,115.50,115.01,114.12,56.20,32.12,25.49.
[0155] Compound F(30)
[0156]
[0157] 2.65(qd,J=6.4,5.7,2.8Hz,2H).
[0158] 13 C NMR (101 MHz, DMSO-d6) δ 172.42, 168.36, 160.92, 158.41, 155.04, 136.25, 134.72, 134.63, 131.07, 130.79, 128.96, 128.93, 125.38, 125.35, 124.97, 124.85, 121.88, 116.70, 116.48, 114.88, 113.87, 33.62, 25.40. Compound F (45)
[0159]
[0160] 130.19,118.57,118.18,117.83,116.61,115.39,114.13,86.25,53.97,32.44,23.49
[0161] G series compounds:
[0162] Compound G(1)
[0163]
[0164] 116.94,112.10,112.02,106.25,106.16,33.27,24.37.
[0165] Compound G(16)
[0166]
[0167] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0168] Compound G(31)
[0169]
[0170] 130.19,118.57,118.18,117.83,116.61,115.39,114.13,86.25,32.44,22.49.
[0171] Compound G(2)
[0172]
[0173] 116.59,111.60,104.57,32.57,24.43.
[0174] Compound G(17)
[0175]
[0176] 13 C NMR (101 MHz, DMSO-d6) δ 172.42, 168.36, 160.92, 158.41, 155.04, 136.25, 134.72, 134.63, 131.07, 130.79, 128.96, 128.93, 125.38, 125.35, 124.97, 124.85, 121.88, 116.70, 116.48, 114.88, 113.87, 33.62, 25.40. Compound G (32)
[0177]
[0178] Compound G(3)
[0179]
[0180] 133.79,133.71,130.15,130.13,129.72,117.17,116.99,116.50,111.41,104.13,32.44,24.42.
[0181] Compound G(18)
[0182]
[0183] 13 C NMR (101 MHz, DMSO-d6) δ 172.42, 168.36, 160.92, 158.41, 155.04, 136.25, 134.72, 134.63, 131.07, 130.79, 128.96, 128.93, 125.38, 125.35, 124.97, 124.85, 121.88, 116.70, 116.48, 114.88, 113.87, 33.62, 25.40. Compound G (33)
[0184]
[0185] 118.57,118.18,117.83,116.61,115.39,114.13,86.25,32.44,22.49.
[0186] Compound G(4)
[0187]
[0188] 44.70,44.54,44.37,44.20,38.81,29.12.
[0189] Compound G(19)
[0190]
[0191] 13 C NMR(101MHz,DMSO-d6)δ172.42,168.36,160.92,158.41,155.04,136.25,134.72,134.63,131.07,130.79 ,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0192] Compound G(34)
[0193]
[0194] 130.19,118.57,118.18,117.83,116.61,115.39,114.13,86.25,32.44,22.49.
[0195] Compound G(5)
[0196]
[0197] 134.48,131.70,129.61,129.47,128.86,116.94,111.64,104.71,32.59,24.41.
[0198] Compound G(20)
[0199]
[0200] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0201] Compound G(35)
[0202]
[0203] Compound G(6)
[0204]
[0205] Compound G(21)
[0206]
[0207] 136.25,134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0208] Compound G(36)
[0209]
[0210] Compound G(7)
[0211]
[0212] 129.94,129.65,116.64,111.50,104.35,32.49,24.40.
[0213] Compound G(22)
[0214]
[0215] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0216] Compound G(37)
[0217]
[0218] 130.19,118.57,118.18,117.83,116.61,115.39,114.13,86.25,32.44,22.49.
[0219] Compound G(8)
[0220]
[0221] Compound G(23)
[0222]
[0223] 116.70,116.48,114.88,113.87,33.62,25.40.
[0224] Compound G(38)
[0225]
[0226] Compound G(9)
[0227]
[0228] Compound G(24)
[0229]
[0230] 13 C NMR (101 MHz, DMSO-d6) δ 172.42, 168.36, 160.92, 158.41, 155.04, 136.25, 134.72, 134.63, 131.07, 130.79, 128.96, 128.93, 125.38, 125.35, 124.97, 124.85, 121.88, 116.70, 116.48, 114.88, 113.87, 33.62, 25.40. Compound G (39)
[0231]
[0232] 130.19,118.57,118.18,117.83,116.61,115.39,114.13,86.25,32.44,22.49.
[0233] Compound G(10)
[0234]
[0235] 109.26,34.16,23.71.
[0236] Compound G(25)
[0237]
[0238] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0239] Compound G(40)
[0240]
[0241] Compound G(11)
[0242]
[0243] 105.09,32.74,24.44.
[0244] Compound G(26)
[0245]
[0246] 13 C NMR(101MHz,DMSO-d6)δ172.42,168.36,160.92,158.41,155.04,136.25,134.72,134.63,131.07,130.79 ,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0247] Compound G(41)
[0248]
[0249] Compound G(12)
[0250]
[0251] 32.73,24.42.
[0252] Compound G(27)
[0253]
[0254] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0255] Compound G(42)
[0256]
[0257] Compound G(13)
[0258]
[0259] Compound G(28)
[0260]
[0261] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0262] Compound G(43)
[0263]
[0264] 118.57,118.18,117.83,116.61,115.39,114.13,86.25,53.97,32.44,23.49.
[0265] Compound G(14)
[0266]
[0267] Compound G(29)
[0268]
[0269] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0270] Compound G(44)
[0271]
[0272] Compound G(15)
[0273]
[0274] 127.86,125.81,118.02,115.49,115.01,114.11,56.21,32.12,25.49.
[0275] Compound G(30)
[0276]
[0277] 2.65(qd,J=6.4,5.7,2.8Hz,2H).
[0278] 13 C NMR (101 MHz, DMSO-d6) δ 172.42, 168.36, 160.92, 158.41, 155.04, 136.25, 134.72, 134.63, 131.07, 130.79, 128.96, 128.93, 125.38, 125.35, 124.97, 124.85, 121.88, 116.70, 116.48, 114.88, 113.87, 33.62, 25.40. Compound G (45)
[0279]
[0280] 118.57,118.18,117.83,116.61,115.39,114.13,86.25,53.97,32.44,23.49
[0281] E series compounds
[0282] Compound E(1)
[0283]
[0284] 131.78,127.77,125.61,125.58,123.73,117.20,116.98,114.47,112.05,109.85,32.38,18.52.
[0285] Compound E(16)
[0286]
[0287] 114.88,113.87,33.62,25.40.
[0288] Compound E(31)
[0289]
[0290] Compound E(2)
[0291] 18.65.
[0293] Compound E(17)
[0294]
[0295] 114.88,113.87,33.62,25.40.
[0296] Compound E(32)
[0297]
[0298] Compound E(3)
[0299]
[0300] 130.13,130.11,128.06,117.09,116.86,112.69,111.62,107.94,31.56,18.65.
[0301] Compound E(18)
[0302] 1 H NMR(400MHz,Chloroform-d)δ7.60(ddd,J=7.9,4.0,1.7Hz,1H),7.56(ddd,J=9.0,4.1,2.1Hz,1H), 7.33(qd,J=8.0,3.5Hz,1H),7.15(dq,J=8.3,5.4,3.9Hz,1H),6.64(q,J=2.8Hz,1H),6.60–6.46(m,
[0303]
[0304] Compound E(33)
[0305]
[0306] Compound E(4)
[0307]
[0308] Compound E(19)
[0309]
[0310] Compound E(34)
[0311]
[0312] Compound E(5)
[0313]
[0314] Compound E(20)
[0315]
[0316] 134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40.
[0317] Compound E(35)
[0318]
[0319] Compound E(6)
[0320]
[0321] Compound E(21)
[0322]
[0323] Compound E(36)
[0324]
[0325] Compound E(7)
[0326]
[0327] Compound E(22)
[0328]
[0329] 116.70,116.48,114.88,113.87,33.62,25.40.
[0330] Compound E(37)
[0331] 1H NMR (400MHz, DMSO-d6) δ7.65–7.59(m,2H),7.31–7.25(m,2H),6.53(t,J=1.5Hz,1H),6.46
[0332]
[0333] Compound E(8)
[0334]
[0335] Compound E(23)
[0336]
[0337] Compound E(38)
[0338]
[0339] Compound E(9)
[0340]
[0341] Compound E(24)
[0342]
[0343] 116.70,116.48,114.88,113.87,33.62,25.40.
[0344] Compound E(39)
[0345] 1 H NMR (400MHz, DMSO-d6) δ7.65–7.59(m,2H),7.31–7.25(m,2H),6.53(t,J=1.5Hz,1H) ,6.46(d,J=1.4Hz,2H),3.12(s,3H),2.96(dd,J=8.5,5.8Hz,2H),2.53–2.16(m,2H).
[0346] 13 C NMR(101MHz,DMSO-d6)δ176.04,172.36,172.26152.48,136.12,130.75,130 .19,118.57,118.18,117.83,116.61,115.39,114.13,86.25,32.44,22.49.
[0347]
[0348] Compound E(10)
[0349]
[0350] Compound E(25)
[0351]
[0352] 114.88,113.87,33.62,25.40.
[0353] Compound E(40)
[0354]
[0355] Compound E(11)
[0356]
[0357] Compound E(26)
[0358]
[0359] 114.88,113.87,33.62,25.40.
[0360] Compound E(41)
[0361]
[0362] Compound E(12)
[0363]
[0364] Compound E(27)
[0365]
[0366] 116.70,116.48,114.88,113.87,33.62,25.40.
[0367] Compound E(42)
[0368]
[0369] Compound E(13)
[0370]
[0371] Compound E(28)
[0372]
[0373] Compound E(43)
[0374] 1 H NMR (400MHz, DMSO-d6) δ7.85–7.79(m,2H),7.33–7.25(m,2H),6.43(t,J=1.5Hz,1H),6. 36(d,J=1.4Hz,2H),3.22(s,3H),3.10(s,3H),2.86(dd,J=8.5,5.8Hz,2H),2.63(m,2H).
[0375] 13 C NMR(101MHz,DMSO-d6)δ174.04,173.22,170.19153.48,136.42,130.75,130.19,118.57,118.18,
[0376] 117.83,116.61,115.39,114.13,86.25,53.97,32.44,23.49 Compound E (14)
[0377]
[0378] Compound E(29)
[0379] 25.47.
[0381] Compound E(44)
[0382]
[0383] Compound E(15)
[0384]
[0385] 122.94,121.18,116.33,114.69,111.30,104.10,55.96,32.39,24.44.
[0386] Compound E(30)
[0387] 25.47.
[0389] Compound E(45)
[0390]
[0391] 118.18,117.83,116.61,115.39,114.13,86.25,53.97,32.44,23.49H series compounds
[0392] Compound H(1)
[0393]
[0394] Compound H(16)
[0395]
[0396] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40
[0397] Compound H(31)
[0398]
[0399] Compound H(2)
[0400]
[0401] Compound H(17)
[0402]
[0403] 13 CNMR(101MHz,DMSO-d6)δ172.42,168.36,160.92,158.41,155.04,136.25,134.72,134.63,131.07,130.7 9,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40
[0404] Compound H(32)
[0405]
[0406] Compound H(3)
[0407]
[0408] 13C NMR(126MHz,DMSO-d6)δ173.27,171.38,155.09,139.15,137.45,136.07,132 .37,131.86,129.29,128.01,122.76,113.18,111.77,108.55,31.73,18.66.
[0409] Compound H(18)
[0410]
[0411] 13 C NMR (101 MHz, DMSO-d6) δ 172.42, 168.36, 160.92, 158.41, 155.04, 136.25, 134.72, 134.63, 131.07, 130.79, 128.96, 128.93, 125.38, 125.35, 124.97, 124.85, 121.88, 116.70, 116.48, 114.88, 113.87, 33.62, 25.40 Compound H (33)
[0412]
[0413] Compound H(4)
[0414]
[0415] Compound H(19)
[0416]
[0417] 13 C NMR (101 MHz, DMSO-d6) δ 172.42, 168.36, 160.92, 158.41, 155.04, 136.25, 134.72, 134.63, 131.07, 130.79, 128.96, 128.93, 125.38, 125.35, 124.97, 124.85, 121.88, 116.70, 116.48, 114.88, 113.87, 33.62, 25.40 Compound H (34)
[0418]
[0419] Compound H(5)
[0420]
[0421] Compound H(20)
[0422]
[0423] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40
[0424] Compound H(35)
[0425]
[0426] Compound H(6)
[0427]
[0428] 132.37,131.86,129.29,128.01,122.76,113.18,111.77,108.55,31.73,18.66.
[0429] Compound H(21)
[0430]
[0431] 13 C NMR (101 MHz, DMSO-d6) δ 172.42, 168.36, 160.92, 158.41, 155.04, 136.25, 134.72, 134.63, 131.07, 130.79, 128.96, 128.93, 125.38, 125.35, 124.97, 124.85, 121.88, 116.70, 116.48, 114.88, 113.87, 33.62, 25.40 Compound H (36)
[0432]
[0433] 130.19,118.57,118.18,117.83,116.61,115.39,114.13,86.25,32.44,22.49.
[0434] Compound H(7)
[0435]
[0436] 131.86,129.29,128.01,122.76,113.18,111.77,108.55,31.73,18.66.
[0437] Compound H(22)
[0438] 1 H NMR (400MHz, Chloroform-d) δ7.60 (ddd, J=7.9, 4.0, 1.7Hz, 1H), 7.56 (ddd, J=
[0439]
[0440] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40
[0441] Compound H(37)
[0442]
[0443] 130.19,118.57,118.18,117.83,116.61,115.39,114.13,86.25,32.44,22.49.
[0444] Compound H(8)
[0445]
[0446] Compound H(23)
[0447]
[0448] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40
[0449] Compound H(38)
[0450]
[0451] 118.57,118.18,117.83,116.61,115.39,114.13,86.25,32.44,22.49.
[0452] Compound H(9)
[0453]
[0454] Compound H(24)
[0455]
[0456] 13 C NMR(101MHz,DMSO-d6)δ172.42,168.36,160.92,158.41,155.04,136.25,134.72,134.63,131.07,130.79 ,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40
[0457] Compound H(39)
[0458]
[0459] 130.19,118.57,118.18,117.83,116.61,115.39,114.13,86.25,32.44,22.49.
[0460] Compound H(10)
[0461]
[0462] 132.37,131.86,129.29,128.01,122.76,113.18,111.77,108.55,31.73,18.66.
[0463] Compound H(25)
[0464]
[0465] 136.25,134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40
[0466] Compound H(40)
[0467]
[0468] 130.75,130.19,118.57,118.18,117.83,116.61,115.39,114.13,86.25,32.44,22.49.
[0469] Compound H(11)
[0470]
[0471] Compound H(26)
[0472]
[0473] 13 C NMR(101MHz,DMSO-d6)δ172.42,168.36,164.23,160.92,158.41,155.04,136.25,134.72,134.63,131.07,13 0.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40
[0474] Compound H(41)
[0475]
[0476] Compound H(12)
[0477]
[0478] Compound H(27)
[0479]
[0480] 13 C NMR(101MHz,DMSO-d6)δ172.42,168.36,165.22,160.92,158.41,155.04,136.25,134.72,134.63,131.07,13 0.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,33.62,25.40
[0481] Compound H(42)
[0482]
[0483] 130.75,130.19,118.57,118.18,117.83,116.61,115.39,114.13,86.25,32.44,22.49
[0484] Compound H(13)
[0485]
[0486] Compound H(28)
[0487]
[0488] 134.72,134.63,131.07,130.79,128.96,128.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,49.65,33.62,25.40
[0489] Compound H(43)
[0490]
[0491] Compound H(14)
[0492]
[0493] Compound H(29)
[0494]
[0495] 134.72,134.63,131.07,130.79,129.96,129.93,125.38,125.35,124.97,124.85,121.88,116.70,116.48,114.88,113.87,50.87,33.62,25.40
[0496] Compound H(44)
[0497]
[0498] Compound H(15)
[0499]
[0500] 132.37,131.86,129.29,129.01,121.76,110.18,109.77,108.55,53.24,31.73,18.66.
[0501] Compound H(30)
[0502]
[0503] 13 C NMR(101MHz,DMSO-d6)δ179.42,161.36,160.22,157.41,155.04,136.25,134.72,132.63,131.07,130.79,12 8.96,128.93,125.38,125.35,124.99,124.85,121.88,116.70,116.48,114.88,113.87,48.34,33.62,25.40
[0504] Compound H(45)
[0505]
[0506] Example 3: Study on the biological activity of quinolinone derivatives
[0507] (1) Experiments on the effects of quinolinone derivatives on aphids
[0508] The insect immersion method was used to determine the inhibitory activity of the quinolinone derivatives listed in Table 1 and Table 2 against tobacco aphids, apple yellow aphids, cabbage aphids, and wheat aphids. Specific method: First, weigh a certain amount of the test agent and dilute it with acetone to form a mother solution. Then, use 0.1% Tween-80 to dilute the mother solution to 100μg / ml and 50μg / ml solutions. Use 0.1% Tween-80 as a blank control and 98% thiamethoxam original drug as a positive control. Then, take fresh leaves with test insects, select 30-50 healthy and lively test insects of basically the same size, and immerse them in the solution for 5s with tweezers, then take them out, put them in a culture dish and seal it with a sealing film, and repeat each treatment 4 times. After 48h, check and record the number of dead and live insects, and calculate the corrected mortality rate. The death standard is to touch the test insect body with a brush. If the insect body does not move, it is dead. Table 1 is the corrected mortality rate, and Table 2 is the LC 50 The experimental results are shown in Table 3, Table 4 and Table 5.
[0509] Table 1 Mortality of quinolinone derivatives against aphids
[0510]
[0511]
[0512]
[0513] Table 2 LC of compounds against Rhizopus graminearum50 value
[0514]
[0515] Table 3 LC of compounds against apple yellow aphid 50 value
[0516]
[0517]
[0518] Table 4 LC of compounds against Zanthoxylum bungeanum 50 value
[0519]
[0520] Table 5 LC of compounds against green peach aphid 50 value
[0521]
[0522] The indoor bioassay results in Tables 1 to 5 show that the test compounds have good biological activities against wheat aphids, apple yellow aphids, pepper aphids and peach aphids, and some compounds have similar insecticidal effects to thiamethoxam.
[0523] (2) Experiments on the effects of quinolinone derivatives on mite activity
[0524] Table 6 Inhibitory activity of quinolinone derivatives against Tetranychus cinnabarinus
[0525]
[0526] The slide immersion method was used to determine the acaricidal activity of the quinolinone derivatives listed in Table 6 against Tetranychus cinnabarinus. The specific method was the same as that for aphids. The results are shown in Table 6:
[0527] The indoor bioassay results in Table 6 showed that the tested compounds had good biological activity against Tetranychus truncatus, and some compounds had similar insecticidal effects to pyridaben.
[0528] (3) Experiments on the effects of quinolinone derivatives on the activity of armyworms
[0529] The leaf immersion method was used to determine the toxicity of the quinolinone derivatives listed in Table 7 against armyworms. Specific method: Accurately weigh a certain amount of the test compound, dissolve it in acetone to 500μg / ml and 200μg / ml and store it for later use. Immerse 5×5mm corn leaves in the solution for 3-5 seconds, wait for it to dry naturally, and then place the armyworms to be tested on the leaves of the plant. The positive control is dimethoate urea, and the negative control is acetone. Observe the number of deaths after 3 days and calculate the corrected mortality rate. The results are shown in Table 7:
[0530] Table 7 Inhibitory activity of quinolinone derivatives against armyworms
[0531]
[0532] The indoor bioassay results in Table 7 show that the tested compounds have good biological activity against Mythimna separata, and some compounds have similar insecticidal effects to diafenthiuron.
[0533] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which are all covered by the protection scope of the present invention.
Claims
1. A quinolinone derivative, characterized in that: It has a chemical structure as shown in formula (I): Wherein, the OR1 is located at position 5, 6, 7 or 8, and OR1 is any one of OH, CH3COO or C5H9O2; the R2 is a substituted phenyl at the ortho, meta or para position, and R2 is any one of phenyl halogen, trifluoromethyl, methyl, nitro or methoxy.
2. The quinolinone derivative according to claim 1, characterized in that: The quinolinone derivative has a chemical structure as shown in any one of formulas (1) to (45): Wherein, OR1 in any of the chemical structural formulas (1)-(45) is located at the 5th, 6th, 7th or 8th position.
3. The method for synthesizing quinolinone derivatives according to claim 1, characterized in that: The synthetic route is:
4. The method for synthesizing quinolinone derivatives according to claim 3, characterized in that: The reaction conditions of step i are: using acetone as solvent, adding indanone at different hydroxyl positions, K2CO3 and benzyl bromide, heating under reflux at 65-75°C for 3.5-4.5h; The reaction conditions of step ii are: using ethanol as solvent, adding sodium acetate and hydroxylamine hydrochloride, heating under reflux at 75-85° C. for 1.5-2.5 h; The reaction conditions of step iii are: using acetonitrile as solvent, adding indium bromide and silver trifluoromethanesulfonate, and reflux at a temperature of 75 to 85° C. for 2.5 to 3.5 hours under nitrogen protection; The reaction conditions of step iv are: using dichloromethane as solvent, adding 4-dimethylaminopyridine at room temperature, adding triethylamine and R-Cl at 0°C, reacting at a temperature of 0-25°C for 3-7 minutes, and then returning to room temperature to continue reacting for 7-9 hours.
5. The method for synthesizing quinolinone derivatives according to claim 3, characterized in that: The reaction conditions of step v are: using ethanol as solvent, using Pb / C as catalyst, adding hydrogen and reacting for 10 to 14 hours to obtain a compound in which OR1 is OH.
6. The method for synthesizing quinolinone derivatives according to claim 5, characterized in that: Add 4-methylbenzenesulfonate pyridine and 3,4-dihydro-2H-pyran to the product obtained by the reaction in which OR1 is an OH compound, use dichloromethane as a solvent, and reflux at a temperature of 45 to 55° C. for 3 to 5 hours to obtain a compound in which OR1 is C5H9O2.
7. The method for synthesizing quinolinone derivatives according to claim 5, characterized in that: Add acetic anhydride, triethylamine and 4-dimethylaminopyridine to the product obtained by the reaction in which OR1 is an OH compound, use dichloromethane as a solvent, and react at room temperature for 3 to 5 hours to obtain a compound in which OR1 is CH3COO.
8. Use of the quinolinone derivatives according to any one of claims 1 to 7 in controlling plant pests.
9. The use according to claim 8, characterized in that: The plant pests are aphids, whiteflies, rice planthoppers and mites.
10. An insecticide, characterized in that: At least comprising the quinolinone derivatives according to claim 1.
Citation Information
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