Quinolinone derivatives, processes for their synthesis and use thereof

Abstract

The application belongs to the technical field of medicine synthesis, and particularly relates to quinolinone derivatives, a synthesis method and application thereof. The quinolinone derivatives have a chemical structure as shown in formula (I). A series of novel quinolinone derivatives are first proposed in the application. In addition, the application further proposes a synthesis method of the quinolinone derivatives. The quinolinone derivatives are obtained through a series of reactions based on an indanone with different hydroxyl positions as a basic raw material. The product prepared by the synthesis method has high yield and is easy to separate, and the synthesis method is the optimal method for preparing the quinolinone derivatives. The application further provides a new use of the quinolinone derivatives. Biological tests prove that the quinolinone derivatives have good toxic killing activity on piercing-sucking insects such as aphids, armyworms, spider mites, rice planthoppers and whiteflies, and can be applied to plant pest control.

Description

Technical Field

[0001] The present invention belongs to the technical field of drug synthesis, and in particular relates to quinolinone derivatives and a synthesis method and application thereof. Background Art

[0002] Isolating secondary metabolites from plants has a history of thousands of years. However, due to their complex structures and the difficulty of extraction, their activity is lower than that of chemical pesticides. Therefore, modifying natural products to enhance 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 found in a variety of natural products and pharmaceutical molecules, exhibiting significant biological activity and medicinal value. 3,4-Dihydro-2(1H)-quinolinone is an important class of nitrogen-containing heterocyclic compounds containing a quinoline ring structure. Natural 3,4-dihydro-2(1H)-quinolinone compounds can be extracted from plants such as Evodia rutaecarpa and evergreen trees. These compounds and derivatives are known to play an important role in pharmaceutical development and also serve as intermediates in the synthesis of pesticides such as fungicides and herbicides. Piercing-sucking pests are among the most serious agricultural pests. Aphids and whiteflies, for example, can infect most crops, causing significant losses in yield and quality. However, most currently effective pest control agents have developed significant resistance to these pests after long-term use. Therefore, the identification of new pest control agents is urgently needed. Summary of the Invention

[0004] The purpose of the present invention is to overcome the shortcomings of the prior art, and 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 solution: 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 group 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 5, 6, 7 or 8 position.

[0016] The synthesis method of quinolinone derivatives, the synthesis route is:

[0017]

[0018] Furthermore, the reaction conditions of step i are as follows: using acetone as solvent, adding indanone with different hydroxyl positions, K2CO3 and benzyl bromide, heating under 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 hours;

[0020] The reaction conditions of step iii are: using acetonitrile as solvent, adding indium bromide and silver trifluoromethanesulfonate, and refluxing at a temperature of 75-85°C under nitrogen protection for 2.5-3.5 hours;

[0021] The reaction conditions of step iv are as follows: 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 and reacted for 10 to 14 hours to obtain a compound wherein 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 fields of agriculture and plant protection, those 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 agriculturally active ingredients, to prepare a formulation 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 formulations, those skilled in the art will need to use, in addition to the insecticidal active ingredients available for selection, a variety of adjuvants, and can select different pesticide formulation 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: It proposes, for the first time, a series of novel quinolinone derivatives. Furthermore, it provides a method for synthesizing these quinolinone derivatives. Using indanones with different hydroxyl groups as starting materials, the quinolinone derivatives are obtained through a series of reactions. This method produces products in high yields and is easily separated, making it an optimal method for preparing quinolinone derivatives. The present invention also provides novel uses for these quinolinone derivatives, which have been shown in bioassays to exhibit excellent toxicity against piercing-sucking insects such as aphids, armyworms, spider mites, rice planthoppers, and whiteflies, and can be used for plant pest control. DETAILED DESCRIPTION

[0031] The present invention is further described below with reference to the following examples. The scope of protection of the present invention is not limited to the following examples: Example 1: Synthesis of quinolinone derivatives

[0032] The synthetic strategy is as follows: first, benzyl protection is performed on indanone (A) at different hydroxyl positions to obtain a series of compounds (B), and then sodium acetate and hydroxylamine hydrochloride are added with ethanol as a solvent to carry out an oximation reaction to obtain a series of compounds (C), followed by Beckmann rearrangement to obtain a series of compounds (D), and amino groups are derivatized to obtain a series of compounds (E), and the benzyl protection is removed by Pb / C hydrogenation to obtain a series of compounds (I) with OR1 being OH; the hydroxyl group is protected with THP to obtain a series of compounds (I) with OR1 being -C5H9O2, and the hydroxyl group is protected with an ester 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, acetone was added as solvent, and the mixture was heated to reflux at 70°C for 4 h. The pH of the reaction solution was then adjusted to neutral with 1 mol / L HCl, and 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 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 four reaction bottles, 10 ml of ethanol was added, and the mixture was heated under 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 to ice water and filtered to obtain 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). Then, wet Pd / C (0.1 mmol, 5%) was added to the above solution. H2 was introduced into the reaction solution at room temperature for 12 h. After the reaction was completed, the reaction solution was filtered through diatomaceous earth to obtain a filtrate, which was then concentrated under reduced pressure to obtain a series of compounds (I) in which OR1 is OH.

[0039] A series of compounds (I) (1 mmol) wherein OR1 is OH were dissolved in anhydrous DCM (5 mL) solution, and PPTS (0.2 mmol) and DHP (2 mmol) were added to the above solution. The mixture was heated to reflux at 50°C for 4 h. 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) 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) solution, and then acetic anhydride (1.1 mmol), triethylamine (2 mmol) and DMAP (1 mmol) were added to the above solution. The reaction was carried out at room temperature for 4 h. 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] Example 2:

[0042] The quinolinone derivatives prepared by the method of Example 1 were 1 H-NMR, 13 C-NMR was used to confirm that the OR1 series compounds at position 5 were named E series, the OR1 series compounds at position 6 were named F series, the OR1 series compounds at position 7 were named G series, and the OR1 series compounds at position 8 were named 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] 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

[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] 1H 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 stock solution. Then, use 0.1% Tween-80 to dilute the stock solution to 100μg / ml and 50μg / ml solutions. Use 0.1% Tween-80 as a blank control and 98% thiamethoxam 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 drug solution for 5s with tweezers. Then, take them out and put them in a culture dish and seal it with sealing film. 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 aphids 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 showed that the test compounds had good biological activity against wheat aphids, apple yellow aphids, pepper aphids and peach aphids, and some compounds had 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 acaricidal activity of the quinolinone derivatives listed in Table 6 against Tetranychus cinnabarinus was determined by the slide immersion method. 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 test compounds had good biological activity against Tetranychus truncatus, and some compounds had similar insecticidal effects to pyridabenz.

[0528] (3) Experiments on the effects of quinolinone derivatives on the activity of sticky insects

[0529] The toxicity of the quinolinone derivatives listed in Table 7 against armyworms was determined using the leaf dip method. Specific procedures: Accurately weigh a predetermined amount of the test compound and dissolve it in acetone to 500 μg / ml and 200 μg / ml, respectively. Dip a 5×5 mm corn leaf into the solution for 3-5 seconds. Allow it to dry naturally, and then place the test armyworms on the plant leaf. The positive control was diafenthiuron, and the negative control was acetone. The number of deaths after 3 days was observed, and the adjusted mortality rate was calculated. 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 showed that the test compounds had good biological activity against Mythimna separata, and some compounds had similar insecticidal effects to diafenthiuron.

[0533] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes based on the technical solutions and inventive concepts of the present invention within the technical scope disclosed by the present invention, and they are all covered by the scope of protection of the present invention.

Claims

1. Quinolinone derivatives, 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 or CH3COO; R2 is trifluoromethyl or methoxy.

2. Quinolinone derivatives, characterized in that The quinolinone derivatives have a chemical structure as shown in any one of formulas (1) to (45): Wherein, OR1 in any of the chemical structural formulas in (1)-(45) is located at position 5, 6, 7 or 8, and OR1 is any one of OH, CH3COO or C5H9O2.

3. The method for synthesizing quinolinone derivatives according to claim 1, wherein: The synthetic route is:

4. The method for synthesizing quinolinone derivatives according to claim 3, wherein: The reaction conditions of step v are: using ethanol as solvent, Pb / C as catalyst, adding hydrogen and reacting for 10 to 14 hours to obtain a compound wherein OR1 is OH.

5. The method for synthesizing quinolinone derivatives according to claim 4, characterized in that: 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.

6. Use of the quinolinone derivatives according to claim 1 or 2 in controlling plant pests, wherein the plant pests are aphids, whiteflies, rice planthoppers and mites.

7. An insecticide, characterized in that At least comprising the quinolinone derivatives according to claim 1 or 2.

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