Steroidal 1, 2, 3-thiadiazole derivative as well as synthesis method and application thereof

Abstract

The invention belongs to the technical field of medicine synthesis, and particularly relates to a steroidal 1, 2, 3-thiadiazole derivative as well as a synthesis method and application thereof. The derivative has a chemical structure as shown in a formula (I), a formula (II), a formula (III) or a formula (IV). The invention provides a series of brand-new steroidal 1, 2, 3-thiadiazole derivatives for the first time. Besides, the invention further provides a synthesis method of the steroidal 1, 2, 3-thiadiazole derivative, dehydroepiandrosterone is used as a basic raw material, the steroidal 1, 2, 3-thiadiazole derivative is obtained through a series of reactions, the product prepared through the synthesis method is high in yield and easy to separate, and the synthesis method is the optimal method for preparing the steroidal 1, 2, 3-thiadiazole derivative. Bioassay proves that the steroidal 1, 2, 3-thiadiazole derivative provided by the invention shows good poisoning activity on aphids, spider mites and oriental mythimna separata and can be applied to plant pest control.

Description

Technical Field

[0001] This invention belongs to the field of pharmaceutical synthesis technology, specifically relating to steroidal 1,2,3-thiadiazole derivatives and their synthesis methods and applications. Background Technology

[0002] Heterocyclic compounds are ubiquitous in nature and have a wide range of applications, playing a vital role in people's daily lives. The vast majority of drugs and more than half of organic compounds are heterocyclic compounds. The synthesis of heterocyclic compounds and the investigation of their biological activities are important research areas in organic chemistry, medicinal chemistry, and pesticide development. In particular, certain heterocyclic compounds containing N and O heteroatoms have exhibited excellent bactericidal activity and have been widely used in pesticides, pharmaceuticals, and other fields.

[0003] Thiadiazole compounds in nitrogen-containing heterocycles have been one of the most active research and development areas in recent years due to their broad-spectrum biological activity. Their main applications are: in medicine, they can be used as anticancer, anti-inflammatory, and antipyretic drugs; in pesticides, they can be used as antibacterial agents and herbicides; at the same time, these compounds can also serve as important intermediates in organic synthesis.

[0004] Piercing-sucking and chewing pests, such as aphids, spider mites, and armyworms, are among the major pests affecting most crops in agriculture. However, due to the long-term and frequent use of pesticides, they have developed particularly serious resistance. Therefore, there is an urgent need to develop new and better insecticides. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art, and the primary purpose is to provide a series of novel steroidal 1,2,3-thiadiazole derivatives.

[0006] A second objective of this invention is to provide a method for synthesizing steroidal 1,2,3-thiadiazole derivatives in high yield;

[0007] A third objective of this invention is to provide the use of steroidal 1,2,3-thiadiazole derivatives.

[0008] The objective of this invention is achieved through the following technical solution: a steroidal 1,2,3-thiadiazole derivative, said derivative having a chemical structure as described in formula (I), (II), (III), or (IV):

[0009]

[0010] Wherein, R is any one of alkyl or phenyl substitution, and the alkyl group is an aliphatic chain or a cycloalkane.

[0011] As a preferred technical solution, R is (a) or (b):

[0012]

[0013] Where n is a positive integer;

[0014] R1 is a substituent at the ortho, meta, or para position, and is any one of halogen, methyl, methoxy, or nitro.

[0015] As a preferred technical solution, the chemical structural formula of the derivative is any one of 2 to 65:

[0016]

[0017]

[0018]

[0019]

[0020] The synthetic route for the above-mentioned steroidal 1,2,3-thiadiazole derivatives is as follows:

[0021]

[0022] As a preferred technical solution, step a specifically involves dissolving compound (A) in dichloromethane, adding acetic anhydride, 4-dimethylaminopyridine and triethylamine, and reacting at room temperature for 1 to 3 hours to obtain compound (B).

[0023] As a preferred technical solution, step b specifically involves dissolving compound (B) in anhydrous ethanol, adding aminourea hydrochloride and sodium acetate, and reacting at room temperature for 5–7 hours to generate compound (C).

[0024] As a preferred technical solution, step c specifically involves adding thionyl chloride to a dichloromethane solution of compound (C) and reacting at room temperature for 3–5 hours to generate compound (D); step d specifically involves adding potassium hydroxide to a methanol solution containing compound (D) and reacting in an oil bath at 55–65°C for 3–5 hours to generate compound (E).

[0025] As a preferred technical solution, step e specifically involves: adding 4-dimethylaminopyridine and benzoyl chloride and triethylamine containing various substituents sequentially to a dichloromethane solution containing compound (E), reacting at room temperature for 5-7 hours to obtain compound (I); step f specifically involves: adding potassium carbonate and benzyl bromide containing various substituents sequentially to an acetone solution containing compound (E), reacting at room temperature for 5-7 hours to obtain compound (II); step g specifically involves: adding 4-dimethylaminopyridine, EDCI and cinnamic acid containing various substituents sequentially to a dichloromethane solution containing compound (E), reacting at room temperature for 5-7 hours to obtain compound (III); step h specifically involves: adding 4-dimethylaminopyridine and benzenesulfonyl chloride and triethylamine containing various substituents sequentially to a dichloromethane solution containing compound (E), reacting at room temperature for 5-7 hours to obtain compound (IV).

[0026] That is, the reaction reagents and conditions for each step in the synthetic route are as follows:

[0027] Step a: Ac2O, DMAP, Et3N, DCM, rt;

[0028] Step b: EtOH, aminourea hydrochloride, CH3COONa, rt;

[0029] Step c: SOCl2, DCM, rt;

[0030] Step d: KOH, MeOH, 60℃;

[0031] Step e: Benzoyl chloride, DMAP, Et3N, DCM, rt;

[0032] Step f: Benzyl bromide, K2CO3, acetone, rt;

[0033] Step g: Cinnamic acid, DMAP, EDCI, DCM, rt;

[0034] Step h: Benzenesulfonyl chloride, DMAP, Et3N, DCM, rt.

[0035] Application of the above-mentioned steroidal 1,2,3-thiadiazole derivatives and the steroidal 1,2,3-thiadiazole derivatives prepared by the above method in the control of plant pests.

[0036] As a preferred technical solution, the plant pests are aphids, spider mites, and oriental armyworms.

[0037] To apply the steroidal 1,2,3-thiadiazole derivatives in agriculture and plant protection, those skilled in the art can use one or more of these derivatives as insecticidal active ingredients, combined with pesticide-acceptable carriers or other agricultural active ingredients, to prepare easily applicable formulations, such as water-dispersible granules, wettable powders, or dispersible oil suspensions. The effective content of the steroidal 1,2,3-thiadiazole derivatives in the insecticide ranges from 0.01% to 99.99%. When formulating the above-mentioned different formulations, those skilled in the art, in addition to using the selected fungicidal active ingredient, need to select various adjuvants. Different pesticide formulation adjuvants can be selected as needed. These adjuvants can be one or more of the following: dispersion medium, dispersant, emulsifier, wetting agent, thickener, defoamer, antifreeze, disintegrant, binder, filler, etc.

[0038] The present invention has the following advantages:

[0039] (1) This invention proposes for the first time a series of novel steroidal 1,2,3-thiadiazole derivatives. In addition, this invention also proposes a method for synthesizing steroidal 1,2,3-thiadiazole derivatives. Using dehydroepiandrosterone as a base material, the steroidal 1,2,3-thiadiazole derivatives of this invention are obtained through a series of reactions. The product prepared by this synthetic method has a high yield and is easy to separate, with a yield as high as 98.68%. The method disclosed in this invention is the optimal method for preparing steroidal 1,2,3-thiadiazole derivatives.

[0040] (2) The steroidal 1,2,3-thiadiazole derivatives provided by the present invention have been confirmed by bioassay to exhibit good toxicity against aphids, spider mites and oriental armyworms, and can be applied to the control of plant pests. Detailed Implementation

[0041] The present invention will be further described below with reference to embodiments, but the scope of protection of the present invention is not limited to the following description:

[0042] Example 1: The specific method for synthesizing steroidal 1,2,3-thiadiazole derivatives is as follows:

[0043] (1) Acetic anhydride (Ac₂O; 115 mg, 1.1 mmol), 4-dimethylaminopyridine (DMAP; 12 mg, 0.1 mmol), and triethylamine (Et₃N; 198 mg, 2 mmol) were added to compound (A) dehydroepiandrosterone (DHEA; 288.5 mg, 1 mmol) in a 100 mL dry round-bottom flask and dissolved in dry dichloromethane (DCM; 20 mL). The reaction mixture was stirred at room temperature for 2 h, then quenched with water and extracted three times with DCM. The combined organic layer was washed with brine, dried on Na₂SO₄, and concentrated under reduced pressure to give the corresponding product (B) (286 mg, 98.3%) as a pale white solid, which was used directly for the next step without further purification.

[0044] (2) In a 50 mL vial equipped with a stir bar, add 10 mL of anhydrous ethanol, followed by compound (B) (330 mg, 1 mmol), aminourea hydrochloride (555 mg, 5 mmol), and sodium acetate (410 mg, 5 mmol). React at room temperature for 6 h. Then concentrate the reaction mixture under reduced pressure. Extract three times with EtOAc and water. Combine the organic layers, dry on Na2SO4 (1.0 g), and concentrate under vacuum to give the corresponding product compound (C) (350 mg, 91%), a white solid that does not require purification and can be used directly in the next step.

[0045] (3) Compound (C) (387 mg, 1 mmol) was added to a 50 mL vial equipped with a stir bar and dissolved in dry dichloromethane (DCM; 15 mL). Thionyl chloride (1.8 mL, 2.5 mmol) was added, and the reaction was carried out at room temperature for 4 h, with the reaction monitored by TLC. After the reaction was completed, the reaction mixture was cooled to 23 °C, diluted with DCM (10 mL), washed with H2O (10 mL), and concentrated. The crude product was purified by silica gel column chromatography (dichloromethane / methanol, 40:1) to obtain product compound (D) (300 mg, 80%).

[0046] (4) Compound (D) (185 mg, 0.5 mmol) and potassium hydroxide (280 mg, 5 mmol) were reacted with methanol as solvent at 60 °C for 4 hours. After the reaction was completed, the solvent was removed, the pH was adjusted to 5-6 with 1 mol / L hydrochloric acid, and EtOAc (15 mL x 3) and water (15 mL x 3) were added for extraction. The product was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (dichloromethane / methanol, 30:1) to obtain product (E) (310 mg, 93%), a white solid.

[0047] (5) Product (E) (330 mg, 1 mmol), triethylamine (0.075 g, 0.75 mmol), DMAP (12 mg, 0.1 mmol), and benzoyl chloride (1.1 mmol) were added sequentially to DCM (10 mL), stirred at 0 °C for 0.5 h, and then reacted at room temperature for 4 h. TLC analysis showed complete conversion. The reaction mixture was then washed with water (30 mL × 3), the organic layer was dried on Na₂SO₄, and concentrated under vacuum. The crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate, 5:1 v / v) to produce compound (Ⅰ) 2-29 (71.5-95.5%) as a white solid. Product (E) (330 mg, 1 mmol), potassium carbonate (276 mg, 2 mmol), and benzyl bromide (1.1 mmol) were added sequentially to acetone (10 mL), and reacted at room temperature for 5 h. TLC analysis showed complete conversion. The reaction mixture was then washed with water (30 mL × 3), the organic layer was dried over Na₂SO₄, and concentrated under vacuum. The crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate, 4:1 v / v) to give compound (II) 30-44 (83.3-96.5%) as a white solid. Product (E) (330 mg, 1 mmol), EDCI (960 mg, 5 mmol), and cinnamic acid (1.5 mmol) were added sequentially to dichloromethane (10 mL), and the reaction was carried out at room temperature for 7 h. TLC analysis showed complete conversion. The reaction mixture was then washed with water (30 mL × 3), the organic layer was dried over Na₂SO₄, and concentrated under vacuum. The crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate, 3:1 v / v) to give compounds (III) 45-56 (79.6-98.68%) as white solids. Product (E) (330 mg, 1 mmol), triethylamine (0.075 g, 0.75 mmol), DMAP (12 mg, 0.1 mmol), and benzenesulfonyl chloride (1.1 mmol) were added sequentially to DCM (10 mL), stirred at 0 °C for 0.5 h, and then reacted at room temperature for 4 h. TLC analysis showed complete conversion. The reaction mixture was then washed with water (30 mL × 3), the organic layer was dried on Na₂SO₄, and concentrated under vacuum. The crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate, 5:1 v / v) to give compounds (IV) 57-65 (82.7-98.1%) as white solids.

[0048] The steroidal 1,2,3-thiadiazole derivative synthesized in Example 1 was subjected to... 1 H-NMR, 13 C-NMR confirmation was performed, and the specific results are as follows:

[0049] Compound 2:

[0050] 11H NMR (400 MHz, Chloroform-d) δ 8.76 (ddd, J = 4.8, 1.8, 0.9 Hz, 1H), 8.19–8.06 (m, 1H), 7.82 (td, J = 7.7, 1.8 Hz, 1H), 7.45 (ddd, J = 7.7, 4.7, 1.2 Hz, 1H), 5.44 (dt, J = 5.4, 2.1 Hz, 1H), 4.96 (tt, J = 11.3, 4.9 Hz, 1H), 3.03 (dd, J = 15.5, 6.3 Hz, 1H), 2.67–2.56 (m, 2H), 2.55–2.44 (m, 2H), 2.24 (dt, J = 11.7, 5.9 Hz, 1H), 2.13–2.02 (m, 2H), 1.97 (dd, J = 7.1, 3.8 Hz, 1H), 1.95–1.91 (m, 1H), 1.90–1.80 (m, 2H), 1.77 (td, J = 7.4, 6.1, 3.0 Hz, 2H), 1.74–1.68 (m, 1H), 1.29–1.21 (m, 2H), 1.14 (s, 3H), 1.11 (s, 3H).

[0051] 13 13C NMR (101 MHz, Chloroform-d) δ 179.96, 164.76, 153.98, 150.00, 148.51, 140.27, 137.07, 126.88, 125.25, 121.84, 75.37, 62.97, 50.45, 41.61, 38.08, 37.02, 36.95, 34.28, 31.06, 30.69, 27.67, 27.53, 20.41, 19.40, 17.79.

[0052] Compound 3:

[0053] 11H NMR (400 MHz, Chloroform-d) δ 8.10 (dd, J = 3.1, 1.2 Hz, 1H), 7.53 (dd, J = 5.1, 1.2 Hz, 1H), 7.31–7.29 (m, 1H), 5.48–5.42 (m, 1H), 4.90–4.77 (m, 1H), 3.08–3.00 (m, 1H), 2.69–2.61 (m, 1H), 2.48 (td, J = 9.6, 9.1, 4.7 Hz, 3H), 2.26 (td, J = 11.7, 6.4 Hz, 1H), 2.16–2.08 (m, 1H), 2.00–1.94 (m, 2H), 1.86–1.82 (m, 1H), 1.79 (dt, J = 7.2, 4.7 Hz, 2H), 1.76–1.69 (m, 2H), 1.29–1.23 (m, 2H), 1.22–1.17 (m, 1H), 1.15 (d, J = 6.9 Hz, 6H).

[0054] 13 13C NMR (101 MHz, Chloroform-d) δ 180.06, 162.35, 154.07, 140.45, 134.35, 132.64, 128.08, 126.05, 121.76, 74.12, 63.05, 50.54, 41.70, 38.34, 37.08, 36.98, 34.36, 31.14, 30.77, 27.93, 27.60, 20.49, 19.49, 17.86.

[0055] Compound 4:

[0056] 11H NMR (400 MHz, Chloroform-d) δ 9.01 (dd, J = 4.3, 1.8 Hz, 1H), 8.59 (d, J = 1.9 Hz, 1H), 8.34–8.26 (m, 2H), 8.15 (d, J = 8.8 Hz, 1H), 7.48 (dd, J = 8.2, 4.2 Hz, 1H), 5.48 (dq, J = 5.0, 1.6 Hz, 1H), 4.95 (dddd, J = 11.3, 9.3, 6.9, 4.5 Hz, 1H), 3.06 (dd, J = 15.5, 6.4 Hz, 1H), 2.65 (dd, J = 15.5, 11.9 Hz, 1H), 2.58–2.48 (m, 3H), 2.26 (td, J = 11.7, 6.4 Hz, 1H), 2.17–2.06 (m, 2H), 2.02–1.94 (m, 2H), 1.88–1.84 (m, 1H), 1.81 (t, J = 3.5 Hz, 2H), 1.78–1.73 (m, 1H), 1.31 (dd, J = 13.7, 3.9 Hz, 1H), 1.28–1.21 (m, 2H), 1.19 (s, 3H), 1.15 (s, 3H).

[0057] 13 13C NMR (101 MHz, Chloroform-d) δ 180.02, 165.60, 154.02, 152.60, 150.13, 140.31, 137.52, 131.02, 129.82, 129.18, 128.80, 127.54, 121.97, 121.93, 74.88, 63.03, 50.53, 41.67, 38.33, 37.09, 36.98, 34.35, 31.13, 30.76, 27.94, 27.58, 20.49, 19.50, 17.85.

[0058] Compound 5:

[0059] 11H NMR (400 MHz, Chloroform-d) δ 8.00 (dd, J = 1.5, 0.8 Hz, 1H), 7.42 (t, J = 1.7 Hz, 1H), 6.79–6.65 (m, 1H), 5.44 (dt, J = 5.4, 1.9 Hz, 1H), 4.91–4.71 (m, 1H), 3.05 (dd, J = 15.5, 6.3 Hz, 1H), 2.64 (dd, J = 15.5, 11.9 Hz, 1H), 2.52–2.43 (m, 3H), 2.25 (td, J = 11.7, 6.3 Hz, 1H), 2.11 (dtd, J = 17.0, 5.2, 2.3 Hz, 1H), 1.98 (dt, J = 11.2, 5.3 Hz, 2H), 1.94–1.90 (m, 1H), 1.86–1.82 (m, 1H), 1.79 (tq, J = 4.6, 2.6 Hz, 2H), 1.76 (t, J = 3.3 Hz, 1H), 1.73–1.69 (m, 1H), 1.27–1.20 (m, 2H), 1.14 (d, J = 4.7 Hz, 6H).

[0060] 13 13C NMR (101 MHz, Chloroform-d) δ 180.03, 162.70, 154.04, 147.73, 143.77, 140.39, 121.75, 119.94, 109.98, 73.89, 63.03, 50.51, 41.67, 38.29, 37.05, 36.94, 34.34, 31.11, 30.75, 27.87, 27.58, 20.47, 19.46, 17.84.

[0061] Compound 6:

[0062] 11H NMR (400 MHz, Chloroform-d) δ 9.25 (d, J = 1.4 Hz, 1H), 8.71 (d, J = 2.5 Hz, 1H), 8.68 (dd, J = 2.5, 1.4 Hz, 1H), 5.41 (dt, J = 5.5, 2.0 Hz, 1H), 5.00–4.86 (m, 1H), 3.00 (dd, J = 15.5, 6.4 Hz, 1H), 2.62–2.50 (m, 2H), 2.50–2.39 (m, 2H), 2.19 (td, J = 11.7, 6.4 Hz, 1H), 2.04 (dddd, J = 24.0, 13.4, 4.6, 2.2 Hz, 2H), 1.96–1.88 (m, 2H), 1.86–1.79 (m, 1H), 1.79–1.75 (m, 1H), 1.75–1.70 (m, 2H), 1.70–1.64 (m, 1H), 1.25–1.14 (m, 2H), 1.10 (s, 3H), 1.07 (s, 3H).

[0063] 13 13C NMR (101 MHz, Chloroform-d) δ 179.77, 163.30, 153.85, 147.56, 146.26, 144.40, 143.65, 139.81, 122.01, 75.78, 62.79, 50.29, 41.46, 37.90, 36.86, 36.74, 34.14, 30.92, 30.53, 27.54, 27.40, 20.29, 19.26, 17.67.

[0064] Compound 7:

[0065] 1 1H NMR (400 MHz, Chloroform-d) δ 8.01 (s, 1H), 7.77 (s, 1H), 5.51–5.40 (m, 1H), 4.89 (dtd, J = 12.6, 8.6, 4.5 Hz, 1H), 3.05 (dd, J = 15.5, 6.4 Hz, 1H), 2.

[0066] 13 C NMR(101MHz,Chloroform-d)δ179.97,157.13,153.99,153.32,143.14,139.91,133.39,122.21,75.3 9,62.98,50.47,41.65,38.10,37.00,36.85,34.31,31.09,30.71,27.75,27.56,20.46,19.42,17.83.

[0067] Compound 8:

[0068] 1 H NMR(400MHz,Chloroform-d)δ8.66(d,J=5.3Hz,1H),8.11(d,J=2.1Hz,1H),7.47(dd,J=5.2,2.0Hz,1H),5.47– 5.44(m,1H),4.96(td,J=11.4,5.7Hz,1H),3.04(dd,J=15.5,6.3Hz,1H),2.68–2.55(m,2H),2.54–2.46(m,2H), 2.24(td,J=11.7,6.3Hz,1H),2.08(dddd,J=24.5,12.7,5.1,2.7Hz,2H),1.97(ddt,J=10.6,6.0,3.5Hz,2H),1. 83(ddd,J=21.4,12.1,2.7Hz,3H),1.73(d,J=15.5Hz,2H),1.24(dd,J=13.2,4.5Hz,2H),1.14(d,J=8.8Hz,6H).

[0069] 13 C NMR(101MHz,Chloroform-d)δ179.97,163.69,153.97,150.85,149.91,145.44,140.14,127.07,125.75,122. 04,75.90,63.01,50.51,41.66,38.07,37.05,36.95,34.33,31.10,30.74,27.69,27.56,20.46,19.42,17.81.

[0070] Compound 9:

[0071] 11H NMR (400 MHz, Chloroform-d) δ 8.46 (q, J = 1.2 Hz, 1H), 5.46 (dt, J = 5.1, 1.7 Hz, 1H), 4.92–4.83 (m, 1H), 3.05 (dd, J = 15.5, 6.3 Hz, 1H), 2.64 (dd, J = 15.5, 11.9 Hz, 1H), 2.52–2.47 (m, 3H), 2.25 (dt, J = 11.7, 5.9 Hz, 1H), 2.11 (dddd, J = 13.4, 6.7, 3.4, 2.0 Hz, 1H), 2.05–1.97 (m, 2H), 1.96–1.92 (m, 1H), 1.82 (d, J = 4.2 Hz, 1H), 1.81–1.79 (m, 1H), 1.77 (s, 1H), 1.76–1.74 (m, 1H), 1.74–1.68 (m, 1H), 1.32–1.24 (m, 1H), 1.23–1.19 (m, 1H), 1.16 (s, 3H), 1.13 (s, 3H).

[0072] 13 13C NMR (101 MHz, Chloroform-d) δ 179.95, 160.15, 159.74, 159.64, 153.98, 148.45, 139.75, 133.82, 122.37, 120.63, 117.91, 76.31, 62.98, 50.46, 41.65, 38.07, 36.99, 36.81, 34.31, 31.09, 30.70, 27.75, 27.56, 20.46, 19.41, 17.82.

[0073] Compound 10:

[0074] 11H NMR (400 MHz, Chloroform-d) δ 9.01 (dt, J = 1.9, 0.8 Hz, 1H), 8.25 (dt, J = 8.2, 0.8 Hz, 1H), 8.09 (ddd, J = 8.2, 2.3, 0.7 Hz, 1H), 5.47 (dt, J = 5.4, 2.0 Hz, 1H), 4.99 (tt, J = 11.3, 4.9 Hz, 1H), 3.05 (dd, J = 15.5, 6.4 Hz, 1H), 2.68–2.57 (m, 2H), 2.56–2.43 (m, 2H), 2.25 (td, J = 11.7, 6.4 Hz, 1H), 2.10 (dddd, J = 24.2, 13.8, 5.0, 2.5 Hz, 2H), 2.​​​​​​​​​​​1H NMR (400 MHz, Chloroform-d) δ 5.40 (dt, J = 5.4, 1.9 Hz, 1H), 4.62 (tdd, J = 11.3, 5.7, 4.2 Hz, 1H), 3.04 (dd, J = 15.4, 6.4 Hz, 1H), 2.63 (dd, J = 15.5, 11.9 Hz, 1H), 2.47 (ddd, J = 11.6, 4.2, 1.5 Hz, 1H), 2.38–2.32 (m, 2H), 2.31–2.27 (m, 2H), 2.23 (dt, J = 11.8, 5.8 Hz, 1H), 2.14–2.02 (m, 1H), 1.99–1.89 (m, 2H), 1.88–1.84 (m, 1H), 1.82–1.78 (m, 1H), 1.77–1.72 (m, 2H), 1.72–1.64 (m, 1H), 1.64–1.54 (m, 1H), 1.24–1.20 (m, 1H), 1.20–1.17 (m, 1H), 1.16–1.13 (m, 2H), 1.12 (d, J = 1.4 Hz, 4H), 1.11 (d, J = 1.6 Hz, 3H).

[0078] 13 13C NMR (101 MHz, Chloroform-d) δ 180.02, 174.07, 154.03, 140.49, 121.55, 73.53, 63.02, 50.49, 41.65, 38.23, 37.01, 36.93, 34.33, 31.08, 30.73, 28.00, 27.80, 27.56, 20.44, 19.41, 17.82, 9.29.

[0079] Compound 12:

[0080] 11H NMR (400 MHz, Chloroform-d) δ 5.40 (dq, J = 5.0, 2.3 Hz, 1H), 4.74–4.57 (m, 1H), 3.03 (dd, J = 15.5, 6.3 Hz, 1H), 2.67–2.58 (m, 1H), 2.55–2.38 (m, 2H), 2.37–2.30 (m, 2H), 2.25 (t, J = 7.4 Hz, 2H), 2.08 (dtd, J = 17.0, 5.2, 2.3 Hz, 1H), 1.97–1.91 (m, 1H), 1.85 (ddd, J = 11.5, 5.9, 2.1 Hz, 2H), 1.80 (d, J = 3.8 Hz, 1H), 1.77–1.75 (m, 1H), 1.73 (dd, J = 6.6, 2.3 Hz, 1H), 1.71–1.66 (m, 1H), 1.64–1.59 (m, 2H), 1.19 (dd, J = 4.2, 2.0 Hz, 1H), 1.17–1.13 (m, 1H), 1.11 (s, 3H), 1.10 (d, J = 2.5 Hz, 3H), 0.96 (d, J = 9.5 Hz, 1H), 0.93 (s, 1H), 0.91 (d, J = 1.5 Hz, 1H), 0.91–0.86 (m, 1H).

[0081] 13 13C NMR (101 MHz, Chloroform-d) δ 205.55, 179.98, 173.23, 154.01, 153.99, 140.45, 140.10, 140.04, 121.86, 121.53, 73.43, 62.99, 62.96, 50.46, 50.43, 41.62, 38.22, 36.98, 36.91, 36.62, 34.30, 34.28, 31.05, 30.70, 30.67, 27.80, 27.54, 20.42, 19.39, 19.37, 18.61, 17.80, 17.00, 13.74.

[0082] Compound 13:

[0083] 11H NMR (400 MHz, Chloroform-d) δ 5.40 (dq, J = 4.9, 2.2 Hz, 1H), 4.75–4.50 (m, 1H), 3.03 (dd, J = 15.5, 6.4 Hz, 1H), 2.62 (dd, J = 15.5, 11.9 Hz, 1H), 2.48 (dddt, J = 17.5, 9.7, 5.1, 2.5 Hz, 2H), 2.36–2.31 (m, 2H), 2.24 (dd, J = 13.2, 7.0 Hz, 2H), 2.08 (dtd, J = 17.0, 5.2, 2.5 Hz, 1H), 1.95–1.90 (m, 1H), 1.89–1.86 (m, 1H), 1.78 (d, J = 8.3 Hz, 1H), 1.76–1.70 (m, 2H), 1.63–1.53 (m, 3H), 1.35–1.24 (m, 3H), 1.19–1.16 (m, 1H), 1.12–1.08 (m, 6H), 0.9 (tt, J = 6.9, 4.3 Hz, 5H).

[0084] 13 13C NMR (101 MHz, Chloroform-d) δ 180.04, 173.47, 154.02, 140.53, 121.56, 73.51, 63.07, 50.55, 41.69, 38.27, 37.05, 36.98, 34.55, 34.37, 31.12, 30.78, 29.84, 27.86, 27.58, 27.27, 22.38, 20.48, 19.44, 17.84, 13.88.

[0085] Compound 14:

[0086] 11H NMR (400 MHz, Chloroform-d) δ 5.41 (dq, J = 4.3, 2.0 Hz, 1H), 4.71–4.59 (m, 1H), 3.04 (dd, J = 15.5, 6.3 Hz, 1H), 2.63 (dd, J = 15.5, 11.9 Hz, 1H), 2.57–2.49 (m, 1H), 2.49–2.45 (m, 1H), 2.37–2.31 (m, 2H), 2.28 (d, J = 7.4 Hz, 1H), 2.26–2.20 (m, 1H), 2.12–2.05 (m, 1H), 1.93 (d, J = 5.8 Hz, 1H), 1.89 (dd, J = 6.9, 2.1 Hz, 1H), 1.87–1.83 (m, 1H), 1.82–1.80 (m, 1H), 1.77 (dd, J = 5.9, 3.1 Hz, 2H), 1.70 (dd, J = 7.3, 2.8 Hz, 1H), 1.62 (d, J = 7.3 Hz, 1H), 1.60–1.57 (m, 1H), 1.33 (s, 1H), 1.30 (d, J = 3.3 Hz, 1H), 1.28 (dd, J = 3.5, 1.3 Hz, 1H), 1.26–1.24 (m, 1H), 1.22 (dd, J = 6.7, 1.3 Hz, 1H), 1.19–1.16 (m, 1H), 1.12 (s, 3H), 1.11 (d, J = 2.6 Hz, 3H), 0.90 (d, J = 1.3 Hz, 1H), 0.89–0.88 (m, 2H), 0.87 (t, J = 1.8 Hz, 1H).

[0087] 13 13C NMR (101 MHz, Chloroform-d) δ 205.82, 180.02, 179.99, 173.45, 169.54, 154.03, 140.49, 121.87, 121.55, 74.62, 73.47, 63.03, 63.00, 59.53, 59.48, 50.50, 50.46, 41.87, 41.82, 41.65, 38.24, 38.05, 37.92, 37.01, 36.99, 36.94, 36.85, 36.82, 34.76, 34.33, 31.40, 31.38, 31.08, 30.74, 30.71, 29.70, 27.98, 27.82, 27.70, 27.56, 24.84, 23.29, 22.57, 22.44, 20.44, 19.42, 19.39, 17.82, 14.05, 13.96.

[0088] Compound 15:

[0089] 1 1H NMR (400 MHz, Chloroform-d) δ 5.40 (dt, J = 5.1, 1.9 Hz, 1H), 4.68–4.51 (m, 1H), 3.16–2.96 (m, 1H), 2.63 (dd, J = 15.5, 11.9 Hz, 1H), 2.48 (ddd, J = 11.6, 4.2, 1.5 Hz, 1H), 2.42–2.29 (m, 2H), 2.23 (td, J = 11.8, 6.4 Hz, 1H), 2.16–2.02 (m, 1H), 2.01–1.83 (m, 3H), 1.83–1.52 (m, 5H), 1.34–1.11 (m, 8H), 1.10–0.79 (m, 5H).

[0090] 13 13C NMR (101 MHz, Chloroform-d) δ 180.04, 174.45, 154.03, 140.52, 121.54, 73.68, 63.04, 50.50, 41.66, 38.27, 37.01, 36.95, 34.34, 31.10, 30.74, 27.84, 27.57, 20.46, 19.43, 17.83, 13.24, 8.52.

[0091] Compound 16:<0000-321>

[0092] 1 1H NMR (400 MHz, Chloroform-d) δ 5.41 (dt, J = 5.3, 2.0 Hz, 1H), 4.71–4.57 (m, 1H), 3.12–3.00 (m, 2H), 2.63 (dd, J = 15.5, 11.9 Hz, 1H), 2.48 (ddd, J = 11.7, 4.1, 2.1 Hz, 1H), 2.39–2.31 (m, 2H), 2.30–2.22 (m, 3H), 2.22–2.16 (m, 2H), 2.13–2.06 (m, 1H), 1.97 (td, J = 6.3, 2.1 Hz, 1H), 1.93–1.87 (m, 3H), 1.83–1.79 (m, 1H), 1.78–1.73 (m, 2H), 1.72–1.65 (m, 1H), 1.63–1.54 (m, 1H), 1.25–1.14 (m, 3H), 1.12 (s, {3H}), 1.11 (s, {3H}).

[0093] 13 Note: In the original text, there is a tag which might be a formatting or encoding issue. I've left it as <0000-321> in the translation for consistency. Also, the two "s, {3H}" in the translated text for ID=14 are to maintain the structure of the original text where it seems like there might be some specific formatting related to the "3H" which is not entirely clear from the given input. If this is incorrect, more context would be needed to accurately translate.C NMR(101MHz,Chloroform-d)δ180.04,175.11,154.04,140.53,121.53,73.42,63.04,50.50,41.67, 38.43,38.21,37.02,36.95,34.34,31.10,30.75,27.79,27.57,25.34,20.46,19.43,18.47,17.83.

[0094] Compound 17:

[0095] 1 H NMR(400MHz,Chloroform-d)δ5.39(dt,J=5.3,2.0Hz,1H),4.68–4.53(m,1H),3.03(dd,J= 15.5,6.3Hz,1H),2.70–2.57(m,2H),2.51–2.43(m,1H),2.33(tdd,J=11.3,5.2,2.8Hz,2H ),2.22(td,J=11.7,6.4Hz,1H),2.12–2.03(m,1H),1.97–1.89(m,2H),1.87(d,J=4.3Hz,1 H),1.84(ddt,J=4.8,2.8,1.7Hz,2H),1.82–1.77(m,2H),1.77–1.73(m,3H),1.73–1.70(m,

[0096] 1H),1.69(dd,J=2.8,1.5Hz,1H),1.68–1.64(m,1H),1.64–1.59(m,1H),1.55(ddt,J=9.2, 7.6,3.1Hz,2H),1.24–1.19(m,1H),1.16(dd,J=8.8,3.6Hz,1H),1.11(s,3H),1.11(s,3H).

[0097] 13 C NMR(101MHz,Chloroform-d)δ179.99,176.34,154.00,140.51,121.46,73.33,63.00,50.46,44.10, 41.62,38.18,36.99,36.92,34.31,31.06,30.71,30.11,27.76,27.54,25.92,20.42,19.41,17.80.

[0098] Compound 18:

[0099] 1 1H NMR (400 MHz, Chloroform-d) δ 5.39 (dt, J = 5.3, 1.9 Hz, 1H), 4.71–4.52 (m, 1H), 3.03 (dd, J = 15.5, 6.4 Hz, 1H), 2.62 (dd, J = 15.5, 11.9 Hz, 1H), 2.50–2.43 (m, 1H), 2.38–2.29 (m, 2H), 2.28–2.19 (m, 2H), 2.12–2.03 (m, 1H), 1.94–1.89 (m, 2H), 1.88–1.83 (m, 3H), 1.80–1.76 (m, 2H), 1.73 (ddd, J = 9.3, 3.9, 1.9 Hz, 3H), 1.70–1.64 (m, 1H), 1.61–1.55 (m, 1H), 1.46–1.36 (m, 2H), 1.32–1.26 (m, 1H), 1.26–1.20 (m, 3H), 1.19–1.16 (m, 1H), 1.16–1.12 (m, 1H),

[0100] 1.11 (s, 3H), 1.10 (s, 3H).

[0101] 13 13C NMR (101 MHz, Chloroform-d) δ 179.98, 175.68, 154.01, 140.49, 121.47, 73.15, 62.99, 50.45, 43.42, 41.62, 38.17, 36.98, 36.91, 34.30, 31.05, 30.70, 29.11, 27.76, 27.54, 25.86, 25.52, 20.42, 19.40, 17.80.

[0102] Compound 19:

[0103] 11H NMR (400 MHz, Chloroform-d) δ 7.89 (dd, J = 8.2, 1.5 Hz, 1H), 7.38 (td, J = 7.5, 1.5 Hz, 1H), 7.23 (d, J = 7.6 Hz, 2H), 5.46 (dd, J = 5.2, 2.5 Hz, 1H), 4.85 (tt, J = 10.7, 5.3 Hz, 1H), 3.05 (dd, J = 15.5, 6.3 Hz, 1H), 2.64–2.58 (m, 4H), 2.54–2.45 (m, 3H), 2.25 (td, J = 11.7, 6.4 Hz, 1H), 2.13–2.01 (m, 2H), 1.99–1.92 (m, 2H), 1.82 (d, J = 4.0 Hz, 1H), 1.81–1.77 (m, 2H), 1.77–1.71 (m, 2H), 1.24 (dd, J = 8.5, 5.3 Hz, 2H), 1.14 (d, J = 7.8 Hz, 6H).

[0104] 13 13C NMR (101 MHz, Chloroform-d) δ 180.00, 167.23, 154.03, 140.43, 139.96, 131.90, 131.74, 130.52, 130.28, 125.78, 121.71, 74.22, 63.00, 50.50, 41.65, 38.35, 37.06, 36.99, 34.32, 31.09, 30.73, 27.95, 27.55, 21.86, 20.45, 19.45, 17.82.

[0105] Compound 20:

[0106] 11H NMR (400 MHz, Chloroform-d) δ 7.78 (dd, J = 7.7, 1.7 Hz, 1H), 7.46–7.37 (m, 2H), 7.34–7.27 (m, 1H), 5.46 (dd, J = 4.9, 2.4 Hz, 1H), 4.94–4.81 (m, 1H), 3.05 (dd, J = 15.5, 6.3 Hz, 1H), 2.63 (dd, J = 15.6, 11.9 Hz, 1H), 2.56–2.46 (m, 3H), 2.25 (dt, J = 11.7, 5.9 Hz, 1H), 2.13–2.03 (m, 2H), 1.99–1.92 (m, 2H), 1.85–1.81 (m, 1H), 1.80–1.77 (m, 2H), 1.76–1.71 (m, 2H), 1.27–1.22 (m, 2H), 1.14 (d, J = 6.1 Hz, 6H).

[0107] 13 13C NMR (101 MHz, Chloroform-d) δ 179.99, 165.38, 154.04, 140.24, 133.52, 132.44, 131.25, 131.07, 130.88, 126.67, 121.88, 75.22, 62.99, 50.46, 41.64, 38.13, 37.04, 36.92, 34.31, 31.08, 30.71, 27.77, 27.55, 20.45, 19.43, 17.82.

[0108] Compound 21:

[0109] 1 1H NMR (400 MHz, Chloroform-d) δ 7.91 (td, J = 7.5, 1.9 Hz, 1H), 7.50 (dddd, J = 8.3, 7.0, 4.8, 1.9 Hz, 1H), 7.21–7.09 (m, 2H), 5.45 (dt, J = 5.3, 2.0 Hz, 1H), 4.98–4.69 (m, 1H), 3.05 (dd, J = 15.5, 6.4 Hz, 1H), 2.63 (dd, J = 15.5, 11.9 Hz, 1H), 2.53–2.46 (m, 3H), 2.25 (dt, J = 11.7, 5.9 Hz, 1H), 2.14–2.03 (m, 2H), 1.99–1.92 (m, 2H), 1.82 (d, J = 3.9 Hz, 1H), 1.79 (t, J = 3.2 Hz, 2H), 1.76–1.71 (m, 2H), 1.28–1.22 (m, 2H), 1.14 (d, J = 8.1 Hz, 6H).

[0110] 13 C NMR(101MHz,Chloroform-d)δ180.00,163.94,163.90,163.30,160.72,154.03,140.33,134.43,134.35,132.08,124.01,123.97,121.80,1 19.43,119.33,117.17,116.94,74.83,63.01,50.48,41.65,38.20,3 7.05,36.94,34.32,31.09,30.72,27.81,27.55,20.45,19.44,17.82.

[0111] Compound 22:

[0112] 1 H NMR(400MHz,Chloroform-d)δ7.90(dd,J=7.9,1.4Hz,1H),7.73(dd,J=7.5,1.7Hz,1H),7.69–7.60(m,2H),5 .46(dt,J=4.7,2.1Hz,1H),4.87(tt,J=11.5,4.8Hz,1H),3.04(dd,J=15.5,6.3Hz,1H),2.63(dd,J=15.5,11 .9Hz,1H),2.54–2.45(m,2H),2.41(ddt,J=12.9,10.8,2.8Hz,1H),2.24(td,J=11.7,6.4Hz,1H),2.15–2.01 (m,2H),1.97–1.91(m,2H),1.82–1.75(m,3H),1.74–1.68(m,2H),1.25–1.18(m,2H),1.11(d,J=3.8Hz,6H).

[0113] 13 C NMR(101MHz,Chloroform-d)δ179.98,164.96,154.04,148.21,139.99,133.03,131.69,129.94,128.20,123.95,1 22.04,76.16,62.97,50.45,41.63,37.59,36.99,36.82,34.29,31.07,30.68,27.53,27.29,20.43,19.38,17.80.

[0114] Compound 23:

[0115] 1 1H NMR (400 MHz, Chloroform-d) δ 7.87–7.81 (m, 2H), 7.37–7.28 (m, 2H), 5.45 (dt, J = 5.0, 1.8 Hz, 1H), 4.91–4.79 (m, 1H), 3.05 (dd, J = 15.5, 6.4 Hz, 1H), 2.64 (dd, J = 15.5, 11.9 Hz, 1H), 2.54–2.46 (m, 3H), 2.40 (s, 3H), 2.25 (td, J = 11.7, 6.4 Hz, 1H), 2.11 (dtd, J = 17.1, 5.3, 1.8 Hz, 1H), 2.05–2.00 (m, 1H), 1.99–1.95 (m, 1H), 1.95–1.90 (m, 1H), 1.86–1.81 (m, 1H), 1.79 (dq, J = 4.6, 3.0, 2.5 Hz, 2H), 1.76 (q, J = 2.9, 1.7 Hz, 1H), 1.74–1.70 (m, 1H), 1.27 (dd, J = 13.5, 3.7 Hz, 1H), 1.24–1.19 (m, 1H), 1.16 (s, 3H), 1.14 (s, 3H).

[0116] 13 13C NMR (101 MHz, Chloroform-d) δ 180.01, 166.26, 154.02, 140.44, 138.18, 133.68, 130.71, 130.16, 128.31, 126.78, 121.71, 74.26, 63.01, 50.51, 41.65, 38.30, 37.06, 36.97, 34.33, 31.10, 30.74, 27.89, 27.56, 21.39, 20.46, 19.47, 17.83.

[0117] Compound 24:

[0118] 11H NMR (400 MHz, Chloroform-d) δ 7.64 (dt, J = 7.6, 1.2 Hz, 1H), 7.56 (dd, J = 2.7, 1.5 Hz, 1H), 7.34 (t, J = 7.9 Hz, 1H), 7.10 (ddd, J = 8.2, 2.7, 1.0 Hz, 1H), 5.46 (dt, J = 5.2, 1.8 Hz, 1H), 4.91–4.83 (m, 1H), 3.86 (s, 3H), 3.06 (dd, J = 15.4, 6.4 Hz, 1H), 2.65 (dd, J = 15.5, 11.9 Hz, 1H), 2.54–2.47 (m, 3H), 2.26 (td, J = 11.7, 6.4 Hz, 1H), 2.12 (dtd, J = 17.1, 5.3, 2.1 Hz, 1H), 2.07–2.02 (m, 1H), 2.00–1.93 (m, 2H), 1.88–1.83 (m, 1H), 1.80 (tt, J = 4.9, 2.5 Hz, 2H), 1.78–1.72 (m, 2H), 1.30–1.26 (m, 1H), 1.25–1.21 (m, 1H), 1.17 (s, 3H), 1.15 (s, 3H).

[0119] 13 13C NMR (101 MHz, Chloroform-d) δ 180.05, 166.00, 159.65, 154.05, 140.45, 132.16, 129.47, 122.07, 121.78, 119.34, 114.24, 74.50, 63.06, 55.59, 50.54, 41.70, 38.30, 37.10, 36.99, 34.37, 31.14, 30.78, 27.90, 27.59, 20.50, 19.50, 17.86.

[0120] Compound 25:

[0121] 11H NMR (400 MHz, Chloroform-d) δ 8.06–7.96 (m, 1H), 7.93 (dt, J = 7.8, 1.4 Hz, 1H), 7.52 (ddd, J = 8.0, 2.2, 1.1 Hz, 1H), 7.38 (t, J = 7.9 Hz, 1H), 5.46 (dq, J = 5.0, 1.6 Hz, 1H), 4.87 (dddd, J = 11.4, 9.2, 7.1, 4.4 Hz, 1H), 3.05 (dd, J = 15.4, 6.4 Hz, 1H), 2.64 (dd, J = 15.5, 11.9 Hz, 1H), 2.54–2.47 (m, 3H), 2.25 (td, J = 11.7, 6.3 Hz, 1H), 2.15–2.07 (m, 1H), 2.07–2.01 (m, 1H), 2.00–1.92 (m, 2H), 1.87–1.82 (m, 1H), 1.80 (td, J = 3.9, 3.1, 1.5 Hz, 2H), 1.78–1.72 (m, 2H), 1.27 (dd, J = 8.5, 5.2 Hz, 1H), 1.22 (dd, J = 9.8, 4.9 Hz, 1H), 1.17 (s, 3H), 1.14 (s, 3H).

[0122] 13 13C NMR (101 MHz, Chloroform-d) δ 180.01, 164.87, 154.02, 140.25, 134.56, 132.96, 132.55, 129.78, 129.74, 127.83, 121.92, 74.88, 63.02, 50.51, 41.67, 38.23, 37.06, 36.94, 34.34, 31.12, 30.75, 27.85, 27.58, 20.48, 19.47, 17.84.

[0123] Compound 26:

[0124] 11H NMR (400 MHz, Chloroform-d) δ 8.85 (t, J = 1.9 Hz, 1H), 8.44–8.35 (m, 2H), 7.65 (t, J = 8.0 Hz, 1H), 5.54–5.35 (m, 1H), 4.92 (tdd, J = 9.5, 7.6, 4.5 Hz, 1H), 3.06 (dd, J = 15.5, 6.3 Hz, 1H), 2.65 (dd, J = 15.5, 11.9 Hz, 1H), 2.51 (tdd, J = 11.7, 4.3, 2.0 Hz, 3H), 2.26 (td, J = 11.7, 6.3 Hz, 1H), 2.15–1.96 (m, 4H), 1.86–1.80 (m, 3H), 1.77–1.73 (m, 1H), 1.67 (s, 1H), 1.30–1.24 (m, 2H), 1.18 (s, 3H), 1.14 (s, 3H).

[0125] 13 13C NMR (101 MHz, Chloroform-d) δ 180.01, 163.98, 154.05, 148.36, 140.07, 135.48, 132.57, 129.71, 127.44, 124.66, 122.13, 75.55, 63.02, 50.51, 41.68, 38.20, 37.07, 36.91, 34.34, 31.12, 30.75, 27.84, 27.58, 20.49, 19.47, 17.84.

[0126] Compound 27:

[0127] 11H NMR (400 MHz, Chloroform-d) δ 7.97–7.89 (m, 2H), 7.25–7.21 (m, 2H), 5.46 (dt, J=5.1, 1.9 Hz, 1H), 4.93–4.79 (m, 1H), 3.06 (dd, J=15.5, 6.3 Hz, 1H), 2.71–2.59 (m, 1H), 2.54–2.45 (m, 3H), 2.41 (s, 3H), 2.27 (dt, J=11.7, 5.9 Hz, 1H), 2.15–2.08 (m, 1H), 2.07–2.02 (m, 1H), 2.01–1.97 (m, 1H), 1.96–1.92 (m, 1H), 1.84–1.81 (m, 1H), 1.81–1.75 (m, 3H), 1.75–1.71 (m, 1H), 1.26 (dd, J=4.6, 2.7 Hz, 1H), 1.24–1.20 (m, 1H), 1.17 (s, 3H), 1.14 (s, 3H).

[0128] 13 13C NMR (101 MHz, Chloroform-d) δ 180.06, 166.21, 154.06, 143.59, 140.53, 129.71, 129.15, 128.09, 121.69, 74.16, 63.06, 50.55, 41.70, 38.35, 37.10, 37.01, 34.37, 31.14, 30.78, 27.94, 27.59, 21.80, 20.49, 19.50, 17.86.

[0129] Compound 28:

[0130] 1 1H NMR (400 MHz, Chloroform-d) δ 8.31–8.27 (m, 2H), 8.22–8.19 (m, 2H), 5.48 (dt, J=3.5, 1.7 Hz, 1H), 5.00–4.84 (m, 1H), 3.06 (dd, J=15.5, 6.4 Hz, 1H), 2.65 (dd, J=15.5, 11.9 Hz, 1H), 2.52 (d, J=7.8 Hz, 2H), 2.26 (td, J=11.7, 6.3 Hz, 1H), 2.15–2.04 (m, 2H), 2.02–1.94 (m, 2H), 1.85–1.80 (m, 3H), 1.79–1.73 (m, 2H), 1.64 (s, 1H), 1.28–1.24 (m, 2H), 1.18 (s, 3H), 1.15 (s, 3H).

[0131] 13 C NMR (101 MHz, Chloroform-d) δ 180.00, 164.21, 154.03, 150.59, 140.04, 136.21, 130.81, 123.63, 122.17, 75.59, 63.02, 50.51, 41.68, 38.19, 37.07, 36.91, 34.34, 31.13, 30.75, 27.83, 27.59, 20.49, 19.47, 17.85.

[0132] Compound 29:

[0133] 1 H NMR (400 MHz, Chloroform-d) δ 8.13–8.03 (m, 2H), 7.14–7.08 (m, 2H), 5.46 (dd, J = 4.7, 2.9 Hz, 1H), 4.86 (tdd, J = 10.7, 6.3, 4.5 Hz, 1H), 3.06 (dd, J = 15.5, 6.3 Hz, 1H), 2.65 (dd, J = 15.5, 11.9 Hz, 1H), 2.50 (dtt, J = 8.4, 5.1, 2.6 Hz, 3H), 2.26 (td, J = 11.7, 6.3 Hz, 1H), 2.12 (dtd, J = 17.1, 5.3, 2.1 Hz, 1H), 2.05–2.01 (m, 1H), 1.98 (dd, J = 4.2, 2.8 Hz, 1H), 1.96–1.93 (m, 1H), 1.83 (dd, J = 6.4, 4.6 Hz, 1H), 1.81–1.77 (m, 2H), 1.75 (q, J = 4.4 Hz, 1H), 1.31–1.26 (m, 1H), 1.25 (d, J = 3.4 Hz, 1H), 1.24–1.20 (m, 1H), 1.17 (s, 3H), 1.15 (s, 3H).

[0134] 13 C NMR (101 MHz, Chloroform-d) δ 180.06, 165.18, 154.13, 140.37, 132.26, 1,32.17, 127.07, 121.85, 115.68, 115.46, 74.57, 63.06, 50.54, 41.72, 38.32, 37.09, 36.98, 34.35, 31.14, 30.78, 27.92, 27.61, 20.50, 19.49, 17.85.

[0135] Compound 30:

[0136] 1 1H NMR (400 MHz, Chloroform-d) δ 7.36 (td, J = 7.7, 5.0 Hz, 1H), 7.11 (ddq, J = 7.6, 2.2, 1.0 Hz, 1H), 7.01 (dtdd, J = 11.3, 4.4, 2.2, 1.1 Hz, 2H), 5.33 (tdt, J = 4.6, 1.9, 0.9 Hz, 1H), 4.58 (t, J = 1.0 Hz, 2H), 3.84 (tt, J = 6.1, 3.3 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.52 (dd, J = 12.4, 4.9 Hz, 1H), 2.40 (ddq, J = 12.3, 6.0, 1.0 Hz, 1H), 2.35–2.28 (m, 1H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.62 (m, 7H), 1.60–1.46 (m, 2H), 1.40 (s, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0137] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 163.58, 161.57, 149.02, 140.11, 140.04, 139.88, 130.22, 130.16, 123.64, 123.62, 121.60, 115.07, 114.91, 114.39, 114.23, 77.32, 71.18, 71.15, 54.49, 48.45, 46.77, 38.52, 36.92, 35.74, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 19.42, 18.39.

[0138] Compound 31:

[0139] 1H NMR (400 MHz, Chloroform-d) δ 7.41–7.34 (m, 2H), 7.30 (ddd, J = 8.1, 2.2, 1.3 Hz, 1H), 7.23 (ddq, J = 7.9, 2.2, 1.0 Hz, 1H), 5.33 (tdt, J = 4.6, 2.0, 0.9 Hz, 1H), 4.62 (dt, J = 11.5, 1.0 Hz, 1H), 4.54 (dt, J = 11.6, 1.0 Hz, 1H), 3.85 (tt, J = 5.9, 3.4 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.52 (dd, J = 12.4, 4.9 Hz, 1H), 2.40 (ddq, J = 12.3, 6.0, 1.0 Hz, 1H), 2.35–2.28 (m, 1H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.85 (m, 1H), 1.88–1.82 (m, 1H), 1.85–1.76 (m, 1H), 1.79–1.72 (m, 1H), 1.75–1.67 (m, 2H), 1.70–1.62 (m, 1H), 1.60–1.46 (m, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0140] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 149.02, 139.88, 138.90, 134.30, 129.94, 128.66, 128.02, 126.59, 121.60, 77.31, 70.90, 54.49, 48.45, 46.77, 38.52, 36.92, 35.74, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 19.42, 18.39.

[0141] Compound 32:

[0142] 1H NMR (400 MHz, Chloroform-d) δ 7.47 (tt, J = 1.7, 0.9 Hz, 1H), 7.46–7.38 (m, 1H), 7.33–7.25 (m, 2H), 5.33 (tdt, J = 4.6, 1.9, 0.9 Hz, 1H), 4.64–4.54 (m, 2H), 3.85 (tt, J = 5.9, 3.4 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.52 (dd, J = 12.4, 4.9 Hz, 1H), 2.40 (ddq, J = 12.3, 6.0, 1.0 Hz, 1H), 2.35–2.28 (m, 1H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.62 (m, 7H), 1.60–1.46 (m, 2H), 1.40 (s, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0143] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 149.02, 139.88, 139.74, 131.26, 130.86, 130.19, 126.83, 123.13, 121.60, 77.31, 70.88, 54.49, 48.45, 46.77, 38.52, 36.92, 35.74, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 19.42, 18.39.

[0144] Compound 33:

[0145] 1H NMR (400 MHz, Chloroform-d) δ 7.31 (ddt, J = 8.0, 5.1, 1.1 Hz, 2H), 7.16–7.08 (m, 2H), 5.33 (tdt, J = 4.6, 1.9, 0.9 Hz, 1H), 4.50 (t, J = 1.0 Hz, 2H), 3.85 (tt, J = 5.9, 3.4 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.52 (dd, J = 12.4, 4.9 Hz, 1H), 2.40 (ddq, J = 12.3, 6.0, 1.0 Hz, 1H), 2.35–2.28 (m, 1H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.62 (m, 7H), 1.60–1.46 (m, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0146] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 163.64, 161.63, 149.02, 139.88, 134.39, 134.37, 129.93, 129.87, 121.60, 115.45, 115.29, 77.31, 70.35, 54.49, 48.45, 46.77, 38.52, 36.92, 35.74, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 19.42, 18.39.

[0147] Compound �

[0148] 11H NMR (400 MHz, Chloroform-d) δ 7.34–7.28 (m, 2H), 7.24 (dt, J = 8.1, 1.0 Hz, 2H), 5.33 (tdt, J = 4.6, 2.0, 0.9 Hz, 1H), 4.50 (t, J = 1.0 Hz, 2H), 3.85 (tt, J = 5.9, 3.4 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.52 (dd, J = 12.4, 4.9 Hz, 1H), 2.40 (ddq, J = 12.3, 6.0, 1.0 Hz, 1H), 2.35–2.28 (m, 1H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.85 (m, 1H), 1.88–1.82 (m, 1H), 1.85–1.76 (m, 1H), 1.79–1.72 (m, 1H), 1.75–1.67 (m, 2H), 1.70–1.62 (m, 1H), 1.60–1.46 (m, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0149] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 149.02, 139.88, 136.59, 134.08, 129.46, 128.65, 121.60, 77.31,70.92, 54.49, 48.45, 46.77, 38.52, 36.92, 35.74, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 19.42, 18.39.

[0150] Compound 35:

[0151] 11H NMR (400 MHz, Chloroform-d) δ 7.54–7.48 (m, 2H), 7.25 (dt, J = 8.1, 1.0 Hz, 2H), 5.33 (tdt, J = 4.6, 1.9, 0.9 Hz, 1H), 4.50 (t, J = 1.0 Hz, 2H), 3.85 (tt, J = 5.9, 3.4 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.52 (dd, J = 12.4, 4.9 Hz, 1H), 2.40 (ddq, J = 12.3, 6.0, 1.0 Hz, 1H), 2.35–2.28 (m, 1H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.85 (m, 1H), 1.88–1.82 (m, 1H), 1.85–1.76 (m, 1H), 1.79–1.67 (m, 3H), 1.70–1.62 (m, 1H), 1.60–1.46 (m, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0152] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 149.02, 139.88, 137.13, 131.49, 129.93, 123.04, 121.60, 77.31, 70.82, 54.49, 48.45, 46.77, 38.52, 36.92, 35.74, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 19.42, 18.39.

[0153] Compound 36:

[0154] 11H NMR (400 MHz, Chloroform-d) δ 7.13 (s, 1H), 5.33 (dddt, J = 4.6, 3.9, 1.9, 0.9 Hz, 1H), 4.50 (d, J = 0.8 Hz, 1H), 3.85 (tt, J = 6.0, 3.4 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.52 (dd, J = 12.4, 5.0 Hz, 1H), 2.40 (ddq, J = 12.3, 6.0, 1.0 Hz, 1H), 2.34 (s, 2H), 2.32 (ddt, J = 12.3, 3.1, 0.9 Hz, 1H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.62 (m, 7H), 1.60–1.46 (m, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0155] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 149.02, 139.88, 137.43, 135.51, 128.71, 128.28, 121.60, 77.31, 70.61, 54.49, 48.45, 46.77, 38.52, 36.92, 35.74, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 21.04, 19.42, 18.39.

[0156] Compound 37:

[0157] 1H NMR (400 MHz, Chloroform-d) δ 7.21 (dt, J = 8.3, 1.0 Hz, 2H), 6.93–6.87 (m, 2H), 5.33 (tdt, J = 4.6, 1.9, 0.9 Hz, 1H), 4.50 (t, J = 1.0 Hz, 2H), 3.84 (tt, J = 6.1, 3.4 Hz, 1H), 3.78 (s, 2H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.52 (dd, J = 12.4, 4.9 Hz, 1H), 2.40 (ddq, J = 12.3, 6.0, 1.0 Hz, 1H), 2.35–2.28 (m, 1H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.85 (m, 1H), 1.88–1.81 (m, 1H), 1.85–1.76 (m, 1H), 1.79–1.72 (m, 1H), 1.75–1.67 (m, 2H), 1.70–1.62 (m, 1H), 1.60–1.46 (m, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0158] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 159.56, 149.02, 139.88, 131.35, 129.54, 121.60, 113.97, 77.32, 70.86, 55.32, 54.49, 48.45, 46.77, 38.52, 36.92, 35.74, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 19.42, 18.39.

[0159] Compound 38:

[0160] 11H NMR (400 MHz, Chloroform-d) δ 7.24–7.17 (m, 1H), 7.13–7.06 (m, 3H), 5.33 (tdt, J=4.6, 1.9, 0.9 Hz, 1H), 4.55 (qt, J=11.5, 0.9 Hz, 2H), 3.85 (tt, J=5.9, 3.4 Hz, 1H), 2.93 (dd, J=12.4, 6.8 Hz, 1H), 2.52 (dd, J=12.4, 4.9 Hz, 1H), 2.40 (ddq, J=12.3, 6.0, 1.0 Hz, 1H), 2.35–2.28 (m, 1H), 2.32 (s, 3H), 2.24 (ddd, J=12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.85 (m, 1H), 1.88–1.81 (m, 1H), 1.85–1.76 (m, 1H), 1.79–1.72 (m, 1H), 1.75–1.67 (m, 2H), 1.70–1.62 (m, 1H), 1.60–1.46 (m, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0161] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 149.02, 139.88, 138.26, 137.63, 129.07, 128.70, 128.52, 125.76, 121.60, 77.31, 71.53, 54.49, 48.45, 46.77, 38.52, 36.92, 35.74, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 21.29, 19.42, 18.39.

[0162] Compound 39:

[0163] 11H NMR (400 MHz, Chloroform-d) δ 7.22 (t, J = 7.6 Hz, 1H), 7.04 (ddq, J = 7.7, 2.2, 1.1 Hz, 1H), 6.87 (ddd, J = 7.5, 2.2, 1.1 Hz, 1H), 6.82 (tt, J = 2.1, 1.0 Hz, 1H), 5.33 (tdt, J = 4.6, 1.9, 0.9 Hz, 1H), 4.57 (q, J = 0.9 Hz, 2H), 3.84 (tt, J = 6.1, 3.4 Hz, 1H), 3.81 (s, 2H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.52 (dd, J = 12.4, 4.9 Hz, 1H), 2.40 (ddq, J = 12.3, 6.0, 1.0 Hz, 1H), 2.35–2.28 (m, 1H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.62 (m, 7H), 1.60–1.46 (m, 2H), 1.40 (s, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0164] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 159.93, 149.02, 139.88, 139.49, 129.63, 121.60, 121.08, 1x3.10, 113.08, 77.32, 71.40, 55.14, 54.49, 48.45, 46.77, 38.52, 36.92, 35.74, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 19.42, 18.39.

[0165] Compound 40:

[0166] 11H NMR (400 MHz, Chloroform-d) δ 7.18–7.10 (m, 2H), 5.33 (tdt, J = 4.6, 1.9, 0.9 Hz, 1H), 4.74 (d, J = 13.2 Hz, 1H), 4.65 (d, J = 13.1 Hz, 1H), 3.87 (tt, J = 6.1, 3.4 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.52 (dd, J = 12.4, 4.9 Hz, 1H), 2.40 (ddq, J = 12.4, 6.0, 1.0 Hz, 1H), 2.36 (s, 3H), 2.32 (ddq, J = 12.5, 3.3, 1.0 Hz, 1H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.62 (m, 7H), 1.60–1.46 (m, 2H), 1.40 (s, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0167] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 149.02, 139.88, 137.45, 136.91, 129.32, 128.58, 128.44, 126.70, 121.60, 77.35, 69.85, 54.49, 48.45, 46.77, 38.52, 36.92, 35.74, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 19.43, 18.39.

[0168] Compound 41:

[0169] 11H NMR (400 MHz, Chloroform-d) δ 7.35–7.23 (m, 2H), 7.13 (td, J = 7.8, 1.3 Hz, 1H), 7.06 (td, J = 8.7, 1.4 Hz, 1H), 5.33 (tdt, J = 4.6, 1.9, 0.9 Hz, 1H), 4.67–4.57 (m, 2H), 3.87 (tt, J = 5.9, 3.4 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.52 (dd, J = 12.4, 4.9 Hz, 1H), 2.40 (ddq, J = 12.5, 6.0, 1.0 Hz, 1H), 2.32 (ddq, J = 12.5, 3.3, 1.0 Hz, 1H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.62 (m, 7H), 1.60–1.46 (m, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0170] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 163.06, 161.05, 149.02, 139.89, 130.47, 130.41, 129.94, 129.88, 125.39, 125.37, 124.87, 124.71, 121.60, 115.45, 115.29, 77.32, 66.23, 66.19, 54.49, 48.45, 46.77, 38.52, 36.92, 35.75, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 19.42, 18.39.

[0171] Compound 42:

[0172] 11H NMR (400 MHz, Chloroform-d) δ 7.43–7.36 (m, 1H), 7.30–7.25 (m, 2H), 7.28–7.21 (m, 1H), 5.33 (tdt, J=4.6, 1.9, 0.9 Hz, 1H), 4.67–4.57 (m, 2H), 3.87 (tt, J=6.1, 3.4 Hz, 1H), 2.93 (dd, J=12.4, 6.8 Hz, 1H), 2.52 (dd, J=12.4, 4.9 Hz, 1H), 2.40 (ddq, J=12.4, 6.0, 1.0 Hz, 1H), 2.32 (ddq, J=12.5, 3.3, 1.0 Hz, 1H), 2.24 (ddd, J=12. / 3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.85 (m, 1H), 1.88–1.82 (m, 1H), 1.85–1.76 (m, 1H), 1.79–1.72 (m, 1H), 1.75–1.67 (m, 2H), 1.70–1.62 (m, 1H), 1.60–1.46 (m, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).<000051 / 0><000051 / 1> 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 149.02, 139.89, 135.27, 134.17, 129.89, 129.42, 128.76, 127.36, 121.60, 77.35, 69.09, 54.49, 48.45, 46.77, 38.52, 36.92, 35.75, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 19.42, 18.39.<000051 / 2><000051 / 3>Compound 43:<000051 / 4><000051 / 5>

[0175] 11H NMR (400 MHz, Chloroform-d) δ 7.25–7.14 (m, 2H), 6.91–6.84 (m, 2H), 5.33 (tdt, J = 4.6, 1.9, 0.9 Hz, 1H), 4.60 (d, J = 0.9 Hz, 2H), 3.85 (tt, J = 6.1, 3.4 Hz, 1H), 3.80 (s, 2H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.52 (dd, J = 12.4, 4.9 Hz, 1H), 2.40 (ddq, J = 12.5, 6.0, 1.0 Hz, 1H), 2.32 (ddq, J = 12.5, 3.3, 1.0 Hz, 1H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.62 (m, 7H), 1.60–1.46 (m, 2H), 1.40 (s, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0176] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 157.96, 149.02, 139.89, 129.60, 128.88, 127.28, 121.60, 113.43, 77.30, 66.92, 55.46, 54.49, 48.45, 46.77, 38.52, 36.92, 35.75, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 19.42, 18.39.

[0177] Compound 44:

[0178] 11H NMR (400 MHz, Chloroform-d) δ 7.61–7.53 (m, 1H), 7.33–7.25 (m, 2H), 7.28–7.22 (m, 1H), 5.33 (tdt, J=4.6, 2.0, 0.9 Hz, 1H), 4.69–4.59 (m, 2H), 3.87 (tt, J=6.1, 3.4 Hz, 1H), 2.93 (dd, J=12.4, 6.8 Hz, 1H), 2.52 (dd, J=12.4, 4.9 Hz, 1H), 2.40 (ddq, J=12.5, 6.0, 1.0 Hz, 1H), 2.32 (ddq, J=12.5, 3.3, 1.0 Hz, 1H), 2.24 (ddd, J=12.3, 9.5, 6.8 Hz, 1H), 2.07–1.93 (m, 2H), 1.93–1.62 (m, 7H), 1.60–1.46 (m, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0179] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 149.02, 139.89, 136.17, 132.11, 130.56, 128.87, 128.67, 125.26, 121.60, 77.35, 71.75, 54.49, 48.45, 46.77, 38.52, 36.92, 35.75, 34.66, 32.59, 32.28, 28.80, 28.39, 22.29, 19.42, 18.39.

[0180] Compound 45:

[0181] 1 1H NMR (400 MHz, Chloroform-d) δ 8.08 (d, J=16.0 Hz, 1H), 7.62 (dd, J=7.3, 2.1 Hz, 1H), 7.45–7.38 (m, 1H), 7.33–7.26 (m, 2H), 6.42 (d, J=16.0 Hz, 1H), 5.45 (dt, J=5.4, 2.0 Hz, 1H), 4.84–4.70 (m, 1H), 3.05 (dd, J=15.5, 6.4 Hz, 1H), 2.64 (dd, J=15.5, 11.9 Hz, 1H), 2.53–2.42 (m, 3H), 2.25 (td, J=11.7, 6.3 Hz, 1H), 2.11 (dtd, J=17.0, 5.2, 2.3 Hz, 1H), 2.02–1.91 (m, 3H),

[0182] 1.87–1.76 (m, 3H), 1.76–1.68 (m, 2H), 1.28–1.20 (m, 2H), 1.15 (s, 3H), 1.14 (s, 3H).

[0183] 13 C NMR (101 MHz, Chloroform-d) δ 180.03, 166.02, 154.04, 140.46, 140.41, 135.04, 132.86, 131.13, 130.30, 127.74, 127.20, 121.74, 121.33, 74.12, 63.04, 50.52, 41.67, 38.28, 37.05, 36.96, 34.35, 31.11, 30.75, 27.87, 27.57, 20.47, 19.46, 17.84.

[0184] Compound 46:

[0185] 1H NMR (400 MHz, Chloroform-d) δ 7.96 (d, J = 15.9 Hz, 1H), 7.55 (dd, J = 8.1, 1.5 Hz, 1H), 7.28–7.26 (m, 1H), 7.22–7.18 (m, 2H), 6.35 (d, J = 15.9 Hz, 1H), 5.44 (dt, J = 5.4, 2.0 Hz, 1H), 4.76 (tdd, J = 11.2, 5.7, 4.3 Hz, 1H), 3.05 (dd, J = 15.5, 6.3 Hz, 1H), 2.63 (dd, J = 15.5, 11.9 Hz, 1H), 2.50–2.42 (m, 6H), 2.25 (td, J = 11.7, 6.4 Hz, 1H), 2.13–2.06 (m, 1H), 1.96 (ddd, J = 15.8, 10.2, 4.6 Hz, 3H), 1.83–1.75 (m, 3H), 1.75–1.67 (m, 2H), 1.26–1.19 (m, 2H), 1.14 (d, J = 4.8 Hz, 6H).

[0186] 13C NMR(101MHz,Chloroform-d)δ179.98,166.56,153.99,142.36,140.46,137.72,133.50,130.88,130.07,126.49,126.42,121.64,119.64,73.87,63.02,50.51,41.65,38.31,37.04,36.96,34.34,31.09,30.73,27.89,27.54,20.45,19.91,19.43,17.82.

[0187] Compound 47:

[0188] 1H NMR(400MHz,Chloroform-d)δ8.04(dq,J=15.8,2.3Hz,1H),7.69(dt,J=7.8,2.1Hz,2H),7.56(td,J=7.8,1.3Hz,1H),7.49–7.44(m,1H),6.39(d,J=15.8Hz,1H),5.44(dt,J=5.4,2.0Hz,1H),4.85–4.68(m,1H),3.05(dd,J=15.5,6.3Hz,1H),2.63(dd,J=15.5,11.9Hz,1H),2.46(tdt,J=14.1,7.7,3.2Hz,3H),2.24(td,J=11.7,6.3Hz,1H),2.15–2.07(m,1H),2.01–1.90(m,3H),1.78(tt,J=11.5,3.7Hz,3H),1.74–1.66(m,2H),1.22(ddd,J=13.6,9.9,5.2Hz,2H),1.14(d,J=4.9Hz,6H).

[0189] 13C NMR(101MHz,Chloroform-d)δ180.02,165.62,154.03,140.39,140.15,140.13,133.57,133.55,132.20,129.66,129.10,128.80,128.01,126.36,126.31,126.25,126.20,123.00,121.76,74.28,63.06,50.54,41.69,38.26,37.06,36.96,34.37,31.12,30.77,27.86,27.57,20.49,19.45,17.84.

[0190] Compound 48:

[0191] 1H NMR(400MHz,Chloroform-d)δ7.80(d,J=16.2Hz,1H),7.53(td,J=7.6,1.8Hz,1H),7.38–7.32(m,1H),7.18–7.06(m,2 H),6.52(d,J=16.2Hz,1H),5.44(dt,J=5.3,1.9Hz,1H),4.82–4.71(m,1H),3.05(dd,J=15.5,6.4Hz,1H),2.64(dd,J= 15.5,11.9Hz,1H),2.46(tdd,J=13.5,7.4,3.1Hz,3H),2.25(td,J=11.7,6.4Hz,1H),2.10(dtd,J=17.0,5.2,2.2Hz,1 H),2.00–1.90(m,3H),1.83–1.75(m,3H),1.74–1.65(m,2H),1.23(td,J=10.1,5.8Hz,2H),1.14(s,3H),1.13(s,3H).

[0192] 13C NMR(101MHz,Chloroform-d)δ180.02,166.32,162.70,160.18,154.03,140.4 2,137.28,137.26,131.81,131.72,129.18,129.15,124.58,124.54,122.68,1 22.56,121.70,121.28,121.21,116.42,116.20,74.02,63.02,50.51,41.66,38.28,37.04,36.95,34.34,31.10,30.74,27.87,27.56,20.46,19.44,17.83.

[0193] Compound 49:

[0194] 1H NMR (400 MHz, Chloroform-d) δ 7.67 (t, J = 1.8 Hz, 1H), 7.59 (d, J = 16.0 Hz, 1H), 7.50 (ddd, J = 8.0, 2.0, 1.0 Hz, 1H), 7.44 (dt, J = 7.8, 1.4 Hz, 1H), 7.26 (s, 1H), 6.42 (d, J = 16.0 Hz, 1H), 5.45 (dt, J = 5.4, 1.9 Hz, 1H), 4.84–4.63 (m, 1H), 3.05 (dd, J = 15.5, 6.4 Hz, 1H), 2.64 (dd, J = 15.5, 11.9 Hz, 1H), 2.51–2.40 (m, 3H), 2.26 (dt, J = 11.7, 5.9 Hz, 1H), 2.14–2.05 (m, 1H), 1.94 (dtd, J = 10.8, 5.9, 5.4, 3.4 Hz, 3H), 1.87–1.77 (m, 3H), 1.76–1.68 (m, 2H), 1.25 (s, 2H), 1.14 (d, J = 3.4 Hz, 6H).

[0195] 13C NMR (101 MHz, Chloroform-d) δ 180.04, 166.06, 154.02, 142.96, 140.39, 136.69, 133.13, 130.85, 130.54, 126.79, 123.15, 121.78, 120.20, 74.12, 63.05, 50.54, 41.68, 38.29, 37.06, 36.96, 34.36, 31.13, 30.76, 29.83, 27.89, 27.59, 20.48, 19.46, 17.86.

[0196] Compound 50:

[0197] 1H NMR ((400 MHz, Chloroform-d) δ 8.14 (t, J = 2.0 Hz, 1H), 7.88–7.81 (m, 1H), 7.74 (dd, J = 10.2, 7.6 Hz, 1H), 7.65 (ddd, J = 7.9, 2.5, 1.3 Hz, 1H), 7.58–7.51 (m, 1H), 6.38 (d, J = 16.1 Hz, 1H), 5.36 (tdt, J = 4.6, 1.9, 1.1 Hz, 1H), 4.73 (tt, J = 6.1, 3.4 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.56–2.45 (m, 2H), 2.37–2.30 (m, 1H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.03 (dddd, J = 9.2, 7.0, 4.9, 2.4 Hz, 1H), 2.01–1.91 (m, 1H), 1.93–1.81 (m, 3H), 1.80–1.47 (m, 6H), 1.40 (s, 2H), 1.19–1.11 (m, 1H), 1.01 (s, 2H).

[0198] 13C NMR (101 MHz, Chloroform-d) δ 167.09, 165.24, 149.02, 145.59, 139.82, 134.35, 134.34, 134.32, 134.31, 131.87, 131.61, 129.98, 129.96, 129.94, 129.93, 129.54, 126.77, 126.73, 126.70, 126.67, 126.52, 126.49, 126.46, 126.42, 126.41, 124.26, 122.12, 121.63, 117.39, 73.21, 54.46, 48.45, 46.77, 37.63, 37.09, 36.91, 34.66, 32.59, 32.28, 28.80, 26.64, 22.29, 19.42, 18.39.

[0199] Compound 51:

[0200] 1H NMR (400 MHz, Chloroform-d) δ 7.59 (d, J = 16.0 Hz, 1H), 7.50 (t, J = 1.8 Hz, 1H), 7.39 (dt, J = 6.9, 1.8 Hz, 1H), 7.36–7.29 (m, 2H), 6.42 (d, J = 16.0 Hz, 1H), 5.44 (dt, J = 5.3, 2.0 Hz, 1H), 4.82–4.69 (m, 1H), 3.04 (dd, J = 15.5, 6.3 Hz, 1H), 2.63 (dd, J = 15.5, 11.9 Hz, 1H), 2.45 (dtt, J = 16.1, 11.3, 2.9 Hz, 3H), 2.24 (td, J = 11.7, 6.3 Hz, 1H), 2.13–2.05 (m, 1H), 2.00–1.90 (m, 3H), 1.79 (td, J = 11.4, 10.5, 5.4 Hz, 3H), 1.74–1.64 (m, 2H), 1.27–1.19 (m, 2H), 1.14 (d, J = 3.8 Hz, 6H).

[0201] 13 13C NMR (101 MHz, Chloroform-d) δ 180.00, 166.04, 154.01, 143.02, 140.34, 136.38, 134.99, 130.25, 130.19, 127.87, 126.33, 121.75, 120.14, 74.08, 63.00, 50.49, 41.64, 38.26, 37.02, 36.93, 34.32, 31.09, 30.72, 27.86, 27.55, 20.45, 19.42, 17.82.

[0202] Compound 52:

[0203] 11H NMR (400 MHz, Chloroform-d) δ 7.62 (d, J = 16.0 Hz, 1H), 7.35 (td, J = 7.9, 5.7 Hz, 1H), 7.28 (dt, J = 7.8, 1.4 Hz, 1H), 7.21 (dt, J = 9.5, 2.1 Hz, 1H), 7.07 (tdd, J = 8.3, 2.6, 1.1 Hz, 1H), 6.41 (d, J = 16.0 Hz, 1H), 5.44 (dt, J = 5.2, 2.0 Hz, 1H), 4.81–4.70 (m, 1H), 3.05 (dd, J = 15.5, 6.4 Hz, 1H), 2.63 (dd, J = 15.5, 11.9 Hz, 1H), 2.46 (dddd, J = 13.6, 10.5, 8.4, 2.7 Hz, 3H), 2.25 (td, J = 11.7, 6.3 Hz, 1H), 2.14–2.06 (m, 1H), 1.96 (ddt, J = 13.0, 10.1, 4.5 Hz, 3H), 1.82–1.75 (m, 3H), 1.74–1.64 (m, 2H), 1.26–1.18 (m, 2H), 1.14 (d, J = 4.1 Hz, 6H).

[0204] 13 13C NMR (101 MHz, Chloroform-d) δ 180.01, 166.10, 164.33, 161.87, 154.02, 143.27, 143.24, 140.36, 136.85, 136.77, 130.60, 130.52, 124.18, 124.15, 121.75, 120.08, 117.31, 117.10, 114.48, 114.26, 74.08, 63.02, 50.51, 41.66, 38.27, 37.03, 36.94, 34.33, 31.10, 30.73, 27.87, 27.56, 20.46, 19.43, 17.83.

[0205] Compound 53:

[0206] 11H NMR (400 MHz, Chloroform-d) δ 7.68 (d, J = 16.0 Hz, 1H), 7.63 (d, J = 1.5 Hz, 4H), 6.49 (d, J = 16.0 Hz, 1H), 5.44 (dt, J = 5.3, 2.0 Hz, 1H), 4.82–4.72 (m, 1H), 3.05 (dd, J = 15.5, 6.3 Hz, 1H), 2.63 (dd, J = 15.5, 11.9 Hz, 1H), 2.46 (tdd, J = 13.3, 7.1, 3.0 Hz, 3H), 2.25 (td, J = 11.7, 6.4 Hz, 1H), 2.14–2.06 (m, 1H), 1.96 (ddt, J = 13.2, 9.5, 4.4 Hz, 3H), 1.83–1.75 (m, 3H), 1.74–1.67 (m, 2H), 1.24 (ddt, J = 11.0, 5.5, 3.0 Hz, 2H), 1.14 (d, J = 4.4 Hz, 6H).

[0207] 13 13C NMR (101 MHz, Chloroform-d) δ 180.02, 165.92, 154.01, 142.79, 140.34, 137.98, 128.28, 128.01, 126.04, 126.00, 125.97, 125.93, 121.83, 121.29, 74.27, 63.06, 50.56, 41.69, 38.29, 37.07, 36.97, 34.37, 31.12, 30.78, 27.89, 27.58, 20.49, 19.45, 17.84.

[0208] Compound 54:

[0209] 11H NMR (400 MHz, Chloroform-d) δ 7.62 (d, J = 16.1 Hz, 1H), 7.48–7.43 (m, 2H), 7.38–7.31 (m, 2H), 6.39 (d, J = 16.0 Hz, 1H), 5.44 (dt, J = 5.4, 2.0 Hz, 1H), 4.83–4.70 (m, 1H), 3.05 (dd, J = 15.5, 6.3 Hz, 1H), 2.64 (dd, J = 15.5, 11.9 Hz, 1H), 2.52–2.39 (m, 3H), 2.25 (td, J = 11.7, 6.3 Hz, 1H), 2.11 (dtd, J = 16.9, 5.2, 2.2 Hz, 1H), 2.00–1.91 (m, 3H), 1.79 (tdd, J = 11.3, 7.4, 3.9 Hz, 3H), 1.74–1.70 (m, 1H), .......

[0210] 13 13C NMR (101 MHz, Chloroform-d) δ 180.03, 166.25, 154.03, 143.24, 140.39, 136.25, 133.07, 129.33, 129.30, 121.76, 119.26, 74.03, 63.04, 50.53, 41.68, 38.30, 37.05, 36.96, 34.35, 31.11, 30.75, 27.89, 27.58, 20.47, 19.45, 17.84.

[0211] Compound 55:

[0212] 1 It should be noted that there seems to be an ellipsis in the translation of the 1H NMR part in the original text you provided. I have tried my best to complete the translation according to the context. If you have any other questions, please feel free to let me know.1H NMR (400 MHz, Chloroform-d) δ 7.64 (d, J = 16.0 Hz, 1H), 7.53–7.49 (m, 2H), 7.10–7.05 (m, 2H), 6.35 (d, J = 16.0 Hz, 1H), 5.45 (dt, J = 5.3, 2.0 Hz, 1H), 4.86–4.66 (m, 1H), 3.05 (dd, J = 15.5, 6.4 Hz, 1H), 2.64 (dd, J = 15.5, 11.9 Hz, 1H), 2.52–2.41 (m, 3H), 2.25 (td, J = 11.7, 6.3 Hz, 1H), 2.14–2.06 (m, 1H), 1.96 (td, J = 11.3, 10.6, 5.3 Hz, 3H), 1.80 (td, J = 11.6, 10.8, 5.4 Hz, 3H), 1.75–1.68 (m, 2H), 1.26–1.19 (m, 2H), 1.14 (d, J = 3.4 Hz, 6H).

[0213] 13 13C NMR (101 MHz, Chloroform-d) δ 180.04, 166.40, 154.04, 143.40, 140.44, 130.85, 130.82, 130.08, 129.99, 121.74, 118.45, 118.42, 116.29, 116.07, 73.95, 63.05, 50.54, 41.69, 38.33, 37.07, 36.98, 34.36, 31.13, 30.77, 27.92, 27.59, 20.48, 19.46, 17.85.

[0214] Compound 56:

[0215] 11H NMR (400 MHz, Chloroform-d) δ 8.04 (d, J = 15.9 Hz, 1H), 7.61 (dt, J = 7.8, 1.6 Hz, 2H), 7.32 (td, J = 7.5, 1.3 Hz, 1H), 7.22 (td, J = 7.6, 1.7 Hz, 1H), 6.38 (d, J = 15.9 Hz, 1H), 5.45 (dt, J = 5.5, 2.0 Hz, 1H), 4.86–4.63 (m, 1H), 3.05 (dd, J = 15.5, 6.4 Hz, 1H), 2.64 (dd, J = 15.5, 11.9 Hz, 1H), 2.54–2.38 (m, 3H), 2.25 (td, J = 11.7, 6.3 Hz, 1H), 2.11 (dtd, J = 17.0, 5.2, 2.4 Hz, 1H), 2.02–1.90 (m, 2H), 1.87–1.68 (m, 5H), 1.35–1.17 (m, 2H), 1.14 (d, J = 4.3 Hz, 6H), 0.88–0.81 (m, 1H).

[0216] 13 13C NMR (101 MHz, Chloroform-d) δ 180.04, 165.92, 154.06, 143.03, 140.42, 134.65, 133.56, 131.29, 127.88, 127.83, 125.44, 121.74, 121.51, 74.14, 63.04, 50.52, 41.68, 38.28, 37.05, 36.96, 34.34, 31.12, 30.75, 27.88, 27.58, 20.47, 19.46, 17.84.

[0217] Compound 57:

[0218] 11H NMR (400 MHz, Chloroform-d) δ 7.89 (ddd, J = 9.1, 5.0, 1.5 Hz, 1H), 7.54–7.41 (m, 2H), 7.26 (td, J = 7.8, 1.6 Hz, 1H), 5.34 (tdt, J = 4.8, 1.9, 1.1 Hz, 1H), 4.54 (tt, J = 6.6, 5.1 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.58–2.48 (m, 3H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.91 (m, 2H), 1.94–1.81 (m, 4H), 1.80–1.56 (m, 4H), 1.59–1.50 (m, 1H), 1.40 (s, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0219] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 158.82, 156.81, 149.02, 138.58, 135.45, 135.39, 130.34, 130.28, 127.48, 127.32, 125.46, 125.44, 121.60, 117.85, 117.69, 80.48, 54.49, 48.45, 46.77, 37.08, 36.92, 35.38, 34.66, 32.59, 32.28, 28.80, 27.20, 22.29, 19.42, 18.39.

[0220] Compound 58:

[0221] 1 1H NMR (400 MHz, Chloroform-d) δ 7.88–7.82 (m, 1H), 7.56–7.49 (m, 2H), 7.49–7.43 (m, 1H), 5.34 (tdt, J = 4.8, 1.9, 1.1 Hz, 1H), 4.54 (tt, J = 6.6, 5.0 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.56–2.49 (m, 3H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.81 (m, 6H), 1.80–1.57 (m, 4H), 1.55 (dddd, J = 12.5, 9.5, 6.8, 3.9 Hz, 1H), 1.40 (s, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0222] 13 C NMR(101MHz,Chloroform-d)δ165.24,149.02,138.58,136.32,134.12,132.43,131.75,130.91,128.04,121. 60,80.47,54.49,48.45,46.77,37.08,36.92,35.38,34.66,32.59,32.28,28.80,27.20,22.29,19.42,18.39.

[0223] Compound 59:

[0224] 1 H NMR(400MHz,Chloroform-d)δ7.83(dd,J=8.1,1.3Hz,1H),7.75(dd,J=8.1,1.6Hz,1H),7.56(ddd,J=8.2,7.1,1.5Hz,1H ),7.39(ddd,J=8.2,7.1,1.4Hz,1H),5.34(tdt,J=4.8,1.9,1.1Hz,1H),4.59–4.50(m,1H),2.93(dd,J=12.4,6.8Hz,1H) ,2.58–2.49(m,3H),2.24(ddd,J=12.3,9.5,6.8Hz,1H),2.07–1.91(m,2H),1.94–1.81(m,4H),1.80–1.66(m,2H),1.70– 1.63(m,1H),1.66–1.57(m,1H),1.55(dddd,J=12.5,9.5,6.8,3.9Hz,1H),1.40(s,2H),1.18–1.10(m,1H),1.01(s,2H).

[0225] 13 C NMR(101MHz,Chloroform-d)δ165.24,149.02,138.58,137.81,135.07,133.30,129.93,129.02,121.60,121. 21,80.47,54.49,48.45,46.77,37.08,36.92,35.38,34.66,32.59,32.28,28.80,27.20,22.29,19.42,18.39.

[0226] Compound 60:

[0227] 1 1H NMR (400 MHz, Chloroform-d) δ 7.75 (ddd, J = 8.2, 2.1, 1.3 Hz, 1H), 7.63–7.57 (m, 1H), 7.60–7.54 (m, 1H), 7.16 (tdd, J = 7.9, 1.8, 1.1 Hz, 1H), 5.34 (tdt, J = 4.8, 1.9, 1.1 Hz, 1H), 4.54 (tt, J = 6.6, 5.3 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.56–2.49 (m, 3H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.90 (m, 2H), 1.93–1.81 (m, 4H), 1.80–1.56 (m, 4H), 1.59–1.50 (m, 1H), 1.40 (s, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0228] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 161.50, 159.48, 149.02,​​​​​​​1H NMR (400 MHz, Chloroform-d) δ 7.81 (ddd, J = 8.4, 2.0, 1.3 Hz, 1H), 7.71 (d, J = 3.9 Hz, 0H), 7.71 (s, 1H), 7.58–7.51 (m, 1H), 7.46 (ddd, J = 7.7, 1.8, 1.1 Hz, 1H), 5.34 (tdt, J = 4.8, 1.9, 1.1 Hz, 1H), 4.55 (tt, J = 6.7, 5.3 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.56–2.49 (m, 3H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.81 (m, 6H), 1.80–1.72 (m, 1H), 1.75–1.66 (m, 1H), 1.69–1.62 (m, 1H), 1.65–1.56 (m, 1H), 1.59–1.50 (m, 1H), 1.40 (s, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0231] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 149.02, 138.81, 138.58, 133.66, 133.34, 131.15, 128.14, 127.05, 121.60, 81.29, 54.49, 48.45, 46.77, 36.97, 36.92, 35.38, 34.66, 32.59, 32.28, 28.80, 27.19, 22.29, 19.42, 18.39.

[0232] Compound 62:

[0233] 11H NMR (400 MHz, Chloroform-d) δ 7.87–7.81 (m, 1H), 7.75 (t, J = 1.9 Hz, 1H), 7.66–7.60 (m, 1H), 7.56 (t, J = 8.1 Hz, 1H), 5.34 (tdt, J = 4.8, 1.9, 1.1 Hz, 1H), 4.55 (tt, J = 6.6, 5.1 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.56–2.49 (m, 3H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.81 (m, 6H), 1.80–1.72 (m, 1H), 1.75–1.66 (m, 1H), 1.69–1.62 (m, 1H), 1.65–1.56 (m, 1H), 1.59–1.50 (m, 1H), 1.40 (s, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0234] 13 13C NMR (101 MHz, Chloroform-d) δ 165.24, 149.02, 138.98, 138.58, 136.00, 131.24, 130.34, 127.36, 121.81, 121.60, 81.29, 54.49, 48.45, 46.77, 36.97, 36.92, 35.38, 34.66, 32.59, 32.28, 28.80, 27.19, 22.29, 19.42, 18.39.

[0235] Compound 63:

[0236] 1 1H NMR (400 MHz, Chloroform-d) δ 7.90–7.83 (m, 2H), 7.30–7.23 (m, 2H), 5.34 (tdt, J = 4.8, 1.9, 1.1 Hz, 1H), 4.55 (tt, J = 6.6, 5.3 Hz, 1H), 2.93 (dd, J = 12.4, 6.8 Hz, 1H), 2.56–2.49 (m, 3H), 2.24 (ddd, J = 12.3, 9.5, 6.8 Hz, 1H), 2.07–1.81 (m, 6H), 1.80–1.50 (m, 5H), 1.40 (s, 2H), 1.18–1.10 (m, 1H), 1.01 (s, 2H).

[0237] 13C NMR(101MHz,Chloroform-d)δ165.82,165.24,163.80,149.02,138.58,133.80,133.78,131.24,131.18,121.60,116. 90,116.74,81.66,54.49,48.45,46.77,36.97,36.92,35.38,34.66,32.59,32.28,28.80,27.19,22.29,19.42,18.39.

[0238] Compound 64:

[0239] 1H NMR(400MHz,Chloroform-d)δ7.85–7.79(m,2H),7.55–7.49(m,2H),5.34(tdt,J=4.8,1.9,1.1Hz, 1H), 4.55 (tt, J=6.6, 5.3Hz, 1H), 2.93 (dd, J=12.4, 6.8Hz, 1H), 2.56–2.49 (m, 3H), 2.24 (ddd, J=12. 3,9.5,6.8Hz,1H),2.07–1.90(m,2H),1.93–1.81(m,4H),1.80–1.72(m,1H),1.75–1.66(m,1H),1.6 9–1.62(m,1H),1.65–1.56(m,1H),1.59–1.50(m,1H),1.40(s,2H),1.18–1.10(m,1H),1.01(s,2H).

[0240] 13 C NMR(101MHz,Chloroform-d)δ165.24,149.02,138.58,137.01,136.09,129.65,129.34,121.60,81.6 6,54.49,48.45,46.77,36.97,36.92,35.38,34.66,32.59,32.28,28.80,27.19,22.29,19.42,18.39.

[0241] Compound 65:

[0242] 1H NMR(400MHz,Chloroform-d)δ7.81–7.75(m,2H),7.72–7.66(m,2H),5.34(tdt,J=4.8,1.9,1.1Hz,1H),4.55(t t,J=6.6,5.3Hz,1H),2.93(dd,J=12.4,6.8Hz,1H),2.56–2.49(m,3H),2.24(ddd,J=12.3,9.5,6.8Hz,1H),2.0 3(dddd,J=9.2,7.0,4.9,2.4Hz,1H),2.01–1.90(m,1H),1.93–1.81(m,4H),1.80–1.68(m,2H),1.70–1.63(m,1 H),1.66–1.57(m,1H),1.55(dddd,J=12.5,9.5,6.8,3.9Hz,1H),1.40(s,2H),1.18–1.10(m,1H),1.01(s,2H).

[0243] 13 C NMR(101MHz,Chloroform-d)δ165.24,149.02,138.58,136.79,133.20,129.91,129.57,121.60,81.6 6,54.49,48.45,46.77,36.97,36.92,35.38,34.66,32.59,32.28,28.80,27.19,22.29,19.42,18.39.

[0244] Example 2: Study on the biological activities of steroidal 1,2,3-thiadiazole derivatives on aphids, spider mites and armyworms (1) Experiment on the effect of steroidal 1,2,3-thiadiazole derivatives on aphid activity

[0245] The inhibitory activity of the steroidal 1,2,3-thiadiazole derivatives listed in Table 1 against aphids was determined using the slide immersion method. Specific method: A certain amount of the test compound was accurately weighed and dissolved in acetone. A solution with a concentration of 100 μg / mL was prepared by adding 0.1% Tween-80 aqueous solution. The solution was allowed to stand at room temperature for half an hour until completely dissolved before storage. Aphids were attached to a slide containing double-sided tape. The slide containing the aphids was then immersed in the prepared drug solution for 5 seconds. The remaining drug solution was blotted dry with absorbent paper. Thiamethoxam was used as the positive control, and 0.1% Tween-80 aqueous solution was used as the negative control. After 48 hours of humidified culture in petri dishes, the mortality rate was observed. The results are shown in Table 1.

[0246] Table 1. Bioactivity of steroidal 1,2,3-thiadiazole derivatives against *Hemiberlesia javanica* at 100 μg / mL.

[0247]

[0248] Table 1 shows the results of indoor bioassays, indicating that all tested compounds have some activity against apple aphids, with some compounds showing better activity. At a concentration of 100 μg / mL, the mortality rate of apple aphids was greater than 80%.

[0249] (2) Bioactivity of steroidal 1,2,3-thiadiazole derivatives against Tetranychus cinnabarinus at 100 μg / mL

[0250] The inhibitory activity of the steroidal 1,2,3-thiadiazole derivatives listed in Table 2 against the carmine spider mite was determined using the slide immersion method, the same method as for the apple aphid. The results are shown in Table 2.

[0251] Table 2. Inhibitory activity of steroidal 1,2,3-thiadiazole derivatives against spider mites at 100 μg / mL.

[0252]

[0253]

[0254] Table 2 shows that the results of indoor bioassays indicate that the tested compounds have good biological activity against spider mites, and some compounds have similar killing effects to pyridaben.

[0255] (3) Experiment on the effects of steroidal 1,2,3-thiadiazole derivatives on the bioactivity of *Hemiberlesia orientalis*

[0256] The third instar larvae of the Eastern armyworm were used as test insects in a 24-hour starvation treatment experiment. Chlorfenapyr was used as a positive control. The activity was determined using the leaf-dish method. In the initial screening stage, the test samples were prepared as a 500 μg / mL / acetone solution, and the control agent chlorfenapyr was prepared as a 100 μg / mL / acetone solution. Fresh wheat leaves were cut into 5 mm × 5 mm square pieces and immersed in the prepared solution for 5 seconds. After the acetone was completely evaporated, the leaf-dish pieces were added to the wells of a 24-well plate containing third instar larvae of the Eastern armyworm, one leaf-dish per well and one test insect per well. Each sample was tested in triplicate, with 12 test insects per group. Leaves treated with acetone served as a blank control. The number of live armyworms was recorded after 48 hours, and the mortality rate was calculated. The results are shown in Table 3.

[0257] Table 3. Inhibitory activity of steroidal 1,2,3-thiadiazole derivatives against *Hemiberlesia orientalis*.

[0258]

[0259]

[0260] Table 3 shows the results of indoor biological assays, indicating that the tested compound *Armoria spp.* showed good activity, and compound (47) had a similar insecticidal effect to chlorfenapyr.

[0261] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, are covered within the scope of protection of the present invention.

Claims

1. A steroidal 1,2,3-thiadiazole derivative, characterized in that, The derivatives have the chemical structures described in formula (I), formula (II), formula (III) or formula (IV): Wherein, R is any one of alkyl or phenyl substitution, and the alkyl group is an aliphatic chain or a cycloalkane.

2. The steroidal 1,2,3-thiadiazole derivative according to claim 1, characterized in that, The R is (a) or (b): Where n is a positive integer; R1 is a substituent at the ortho, meta, or para position, and is any one of halogen, methyl, methoxy, or nitro.

3. The steroidal 1,2,3-thiadiazole derivative according to claim 1, characterized in that, The chemical structural formula of the derivative is any one of 2 to 65:

4. The method for synthesizing steroidal 1,2,3-thiadiazole derivatives according to claim 1, characterized in that, The synthetic route is as follows:

5. The method for synthesizing steroidal 1,2,3-thiadiazole derivatives according to claim 4, characterized in that, Step a specifically involves dissolving compound (A) in dichloromethane, adding acetic anhydride, 4-dimethylaminopyridine, and triethylamine, and reacting at room temperature for 1–3 hours to obtain compound (B).

6. The method for synthesizing steroidal 1,2,3-thiadiazole derivatives according to claim 4, characterized in that, Step b specifically involves dissolving compound (B) in anhydrous ethanol, adding aminourea hydrochloride and sodium acetate, and reacting at room temperature for 5–7 hours to generate compound (C).

7. The method for synthesizing steroidal 1,2,3-thiadiazole derivatives according to claim 4, characterized in that, Step c specifically involves adding thionyl chloride to a dichloromethane solution of compound (C) and reacting at room temperature for 3–5 hours to generate compound (D); Step d specifically involves adding potassium hydroxide to a methanol solution containing compound (D) and reacting in an oil bath at 55–65°C for 3–5 hours to generate compound (E).

8. The method for synthesizing steroidal 1,2,3-thiadiazole derivatives according to claim 4, characterized in that, Step e specifically involves adding 4-dimethylaminopyridine and benzoyl chloride and triethylamine containing various substituents sequentially to a dichloromethane solution containing compound (E), reacting at room temperature for 5–7 h to obtain compound (I); Step f specifically involves adding potassium carbonate and benzyl bromide containing various substituents sequentially to an acetone solution containing compound (E), reacting at room temperature for 5–7 h to obtain compound (II); Step g specifically involves adding 4-dimethylaminopyridine, EDCI and cinnamic acid containing various substituents sequentially to a dichloromethane solution containing compound (E), reacting at room temperature for 5–7 h to obtain compound (III); Step h specifically involves adding 4-dimethylaminopyridine and benzyl sulfonyl chloride and triethylamine containing various substituents sequentially to a dichloromethane solution containing compound (E), reacting at room temperature for 5–7 h to obtain compound (IV).

9. The application of the steroidal 1,2,3-thiadiazole derivatives according to any one of claims 1-3, and the steroidal 1,2,3-thiadiazole derivatives prepared by the method according to any one of claims 4-8, in the control of plant pests.

10. The application according to claim 9, characterized in that, The plant pests mentioned are aphids, spider mites, and oriental armyworms.

Images