Palladium-catalyzed amination suzuki-miyaura coupling method of arylthianthrenium salts with arylboronic acids and dpph

Abstract

This invention provides a palladium-catalyzed Suzuki-Miyaura coupling method for the amination of arylthianthaneonium salts with arylboronic acid and DPPH. This method uses arylthianthaneonium salts as electrophilic arylating agents, arylboronic acid as coupling nucleophiles, and DPPH as a nitrogen source to obtain structurally diverse aromatic amines in moderate to good yields, and exhibits good tolerance to a variety of functional groups.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis, specifically relating to a palladium-catalyzed Suzuki-Miyaura coupling method for the amination of arylthianthaneon salts with arylboronic acid and DPPH. Background Technology

[0002] Aromatic amines are not only important structural units widely found in drug molecules, natural products, and functional materials, but also key synthetic intermediates for constructing various nitrogen-containing molecular skeletons. Among the various methods developed to date, the synthesis of aromatic amines via the Buchwald–Hartwig or Ullmann–Ma C−N cross-coupling reaction of halogenated aromatic hydrocarbons with amines is one of the most efficient routes. In recent years, a new method for preparing aromatic amines by inserting a bridging nitrogen atom between a nucleophile and an electrophile has proven to be an effective alternative to traditional amination cross-coupling reactions. For example, Liu's group pioneered two highly efficient palladium-catalyzed amination Suzuki–Miyaura coupling reactions, using aryl halides (or pseudohalides) as coupling electrophiles, aryl or alkylboron as nucleophiles, and O-(diphenylphosphino)hydroxylamine (DPPH) as a linking atom to conveniently construct aromatic amines. This novel strategy is a clever improvement on traditional two-component cross-coupling reactions, enabling the efficient assembly of structurally diverse aromatic amines. Further work by Jin and Tao shows that this palladium-catalyzed three-component amination Suzuki–Miyaura coupling scheme can be extended to use benzyl bromide as the coupling electrophile and carried out under photocatalysis.

[0003] In recent years, the academic community has been committed to developing novel coupling reagents to replace traditional organohalide electrophilic reagents. Among the various novel coupling electrophilic reagents developed to date, aryl thiathanenium salts can be conveniently prepared through the selective C−H thiathanelation reaction of aromatics. They have been proven by Ritter and other researchers to be robust and multifunctional arylation reagents, capable of effectively participating in a variety of organic transformations, and thus becoming a powerful alternative to traditional aryl halides and pseudohalides. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide an efficient method for synthesizing aromatic amines: using a palladium-catalyzed amination Suzuki-Miyaura coupling strategy, with arylthianthaneonium salt as an electrophilic arylation reagent, arylboronic acid as a coupling nucleophile, and DPPH as a nitrogen source, structurally diverse aromatic amines are obtained in moderate to good yields, and they exhibit good tolerance to a variety of functional groups.

[0005] This invention provides a method for preparing a compound of formula III or a salt thereof, the method comprising the step of reacting a compound of formula I, a compound of formula II, and diphenylphosphonohydroxylamine in the presence of a palladium catalyst to form a compound of formula III.

[0006]

[0007] Among them, R 1 Each is independently selected from halogen, cyano, nitro, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, 3- to 6-membered heterocycloalkyl, PhO- or PhS-, or adjacent R 1 Form C with adjacent atoms 3-6 Cycloalkyl or 3- to 6-membered heterocyclic alkyl;

[0008] R 2 Selected from phenyl or 5- or 6-membered heteroaryl, wherein the phenyl or 5- or 6-membered heteroaryl group is optionally selected from one or more R 2a Replaced; R 2a Selected from halogen, cyano, nitro, C 1-6 Alkyl, C 1-6 Haloalkyl, C 1-6 Alkoxy, C 1-6 Halogenated alkoxy groups, PhO-, Ph-, -COOR 2aa or -SOOR 2aa , or R 2a Form C with adjacent atoms 3-6 Cycloalkyl, 3- to 6-membered heterocyclic alkyl or phenyl; R 2aa Selected from hydrogen or C 1-6 alkyl;

[0009] o can be selected from 0, 1, 2 or 3.

[0010] In some implementation schemes, R 1 Selected from halogen, cyano, C 1-6 Alkyl (such as methyl or ethyl). In some embodiments, R 1 Selected from PhO- or PhS-. In some implementations, R 1 Selected from C 3-6 Cycloalkyl groups, such as cyclohexyl. In some embodiments, R 1 Selected from C 1-6 Alkyl groups, such as methoxy or ethoxy groups.

[0011] In some implementations, adjacent R 1 It forms 3 to 6-membered heterocyclic alkyl groups with adjacent atoms.

[0012] In some implementation schemes, R 2 Selected from phenyl, wherein the phenyl group is optionally selected from one or more R 2a Replaced by, R 2a As defined above. In some implementations, R 2aSelected from halogens (such as fluorine, chlorine, or bromine). In some embodiments, R 2a Selected from cyano or nitro. In some embodiments, R 2a Selected from C 1-6 Alkyl groups, such as methyl or ethyl. In some embodiments, R 2a Selected from C 1-6 Alkyl groups, such as methoxy or ethoxy. In some embodiments, R 2a Selected from C 1-6 Halogenated alkyl or C 1-6 Alkyl groups, such as trifluoromethyl or trifluoromethoxy.

[0013] In some embodiments, the compound represented by Formula I is selected from: , , , , , , , , , , , or .

[0014] In some embodiments, the compound represented by Formula I is selected from: , , , , or .

[0015] In some embodiments, the compound represented by Formula A is selected from... , , , , , , , , , , , , , , , , , , , or .

[0016] In some embodiments, the compound represented by Formula A is selected from... , , , , or .

[0017] In some embodiments, the palladium catalyst used in the reaction is selected from... t BuBrettPhos Pd G3 (CAS: 1536473-72-9).

[0018] In some embodiments, the palladium catalyst is used in an amount of 1% to 10% of the molar amount of the compound of Formula I, such as 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, or 10%. In some embodiments, the palladium catalyst is used in an amount of 5% of the molar amount of the compound of Formula I.

[0019] In some embodiments, the reaction further contains a base, wherein the base is selected from inorganic or organic bases. In some embodiments, the base is selected from... t BuONa, Cs2CO3, NaOH, KOH, or CH3ONa. In some embodiments, the base is selected from... t BuONa.

[0020] In some embodiments, the amount of catalyst ligand used in the reaction is 1 to 6 equivalents of the molar amount of the compound of Formula I, including 2, 3, and 4 equivalents. In some embodiments, the amount of catalyst ligand used in the reaction is 4 equivalents of the molar amount of the compound of Formula I.

[0021] In some embodiments, the amount of diphenylphosphonohydroxylamine (DPPH) used in the reaction is 1 to 4 equivalents of the molar amount of the compound of Formula I, including 1.5 equivalents, 2 equivalents, 2.5 equivalents, 3 equivalents, 3.5 equivalents, and 4 equivalents. In some embodiments, the amount of the catalyst ligand used in the reaction is 1.5 equivalents of the molar amount of the compound of Formula I.

[0022] In some embodiments, the compound shown in Formula I, the compound shown in Formula II, and diphenylphosphonohydroxylamine are... t BuBrettPhos Pd G3 and t The compound shown in Formula III is formed by the reaction in the presence of BuONa.

[0023] The preparation method of the present invention also includes one or more steps such as filtration, extraction, drying, concentration or purification (e.g., column chromatography).

[0024] "Optionally" or "optionally" means that the event or environment described below may but does not have to occur, and the description includes the possibility or absence of the event or environment. For example, "optionally halogenated or cyano-substituted C1-6 alkyl" means that a halogen or cyano group may but does not have to be present, and the description includes cases where the alkyl group is substituted with a halogen or cyano group and cases where the alkyl group is not substituted with a halogen or cyano group.

[0025] "alkyl" refers to a saturated aliphatic hydrocarbon group, including straight-chain and branched groups with 1 to 8 carbon atoms. Non-limiting examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and their various branched isomers. The alkyl group may be substituted or unsubstituted.

[0026] The term "halogenation" refers to the substitution of one or more atoms selected from fluorine, chlorine, bromine, and iodine.

[0027] "Substituted" refers to one or more hydrogen atoms in a group, preferably up to five, more preferably one to three hydrogen atoms, which are independently substituted by the corresponding number of substituents. It goes without saying that the substituents are only in their possible chemical positions, and those skilled in the art can determine (by experiment or theory) possible or impossible substitutions without much effort.

[0028] The term "alkoxy" refers to -O-(alkyl), where alkyl is defined as described above. Non-limiting examples of alkoxy groups include: methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy, cyclopentoxy, and cyclohexyloxy. Alkoxy groups can be substituted or unsubstituted. When substituted, the substituent can be replaced at any usable connection point, preferably one or more of the following groups, including but not limited to halogens.

[0029] The term "heterocycloalkyl" or "alicyclic heterocycle" refers to a saturated or partially unsaturated monocyclic or polycyclic hydrocarbon substituent containing 3 to 14 ring atoms, such as 4 or 5 ring atoms, wherein one or more ring atoms are selected from nitrogen, oxygen, or S(O). m Heteroatoms (where m is an integer from 0 to 2), excluding the ring moiety of -OO-, -OS-, or -SS-, with the remaining ring atoms being carbon. Non-limiting examples of "heterocyclic alkyl" include: , or And so on. Heterocyclic alkyl groups can be optionally substituted or unsubstituted.

[0030] The term "aryl" or "aromatic ring" refers to a 6- to 10-membered all-carbon monocyclic or fused polycyclic (i.e., a ring sharing adjacent carbon atom pairs) group with a conjugated π-electron system, such as phenyl and naphthyl.

[0031] The term "heteroaryl" or "heteroary ring" refers to a heteroaryl system containing 1 to 4 heteroatoms and 5 to 10 ring atoms, wherein the heteroatoms are selected from oxygen, sulfur, and nitrogen. The heteroaryl group is preferably 5 to 10-membered, such as 7-membered, 8-membered, or 9-membered, and more preferably 5-membered or 6-membered.

[0032] The "substituents" of this invention include, but are not limited to, halogens (such as chlorine and fluorine), cyano, nitro, amino, and C. 1-6 Alkyl, C 1-6 Alkoxy, the C 1-6 Alkyl, C 1-6 The alkoxy group may be optionally replaced by one or more halogens, hydroxyl groups, cyano groups, nitro groups, amino groups, or C groups. 1-6 Alkyl or C 1-6 Alkyl-substituted.

[0033] "Hydroxy" refers to the -OH group.

[0034] “Cyano” refers to the -CN group.

[0035] "Halogen" refers to fluorine, chlorine, bromine, or iodine.

[0036] The term "filtration" in this invention is merely a description of one method of separating solids and liquids, and does not refer to only one specific operation. In actual production, methods such as centrifugation or spin-filtering also fall into this category.

[0037] The values ​​in this invention are instrument measurements and are subject to a certain degree of error. Generally speaking, ±20% is within the reasonable error range. Of course, the context in which the value is used needs to be considered, and it can be ±9%, ±8%, ±7%, ±6%, ±5%, ±4%, ±3%, ±2%, or ±1%, preferably ±5%.

[0038] The structure of the compounds was determined by nuclear magnetic resonance (NMR) and / or mass spectrometry (MS). NMR shifts (δ) are given in units of 10⁻⁶ (ppm). NMR measurements were performed using a Bruker AVANCE-400 NMR spectrometer with deuterated dimethyl sulfoxide (DMSO-d6), deuterated chloroform (CDCl₃), and deuterated methanol (Methanol-d4) as solvents, and tetramethylsilane (TMS) as the internal standard. Detailed Implementation

[0039] The present invention will be further described below with reference to specific embodiments, so that those skilled in the art can better understand and implement the present invention, but the embodiments are not intended to limit the present invention.

[0040] Unless otherwise specified, all raw materials used in the examples are commercially available.

[0041] The onium salt (Formula I) used in this invention was synthesized with reference to the following literature, and the relevant content is incorporated herein by reference for illustration: J. Zhang, L.-C. Wang, Z.-P. Bao, X.-F. Wu, Site-Selective Carbonylation of Arenes via C(sp 2 )–H Thianthrenation: Direct Access to 1,2-Diarylethanones. Chem. Sci. 2023, 14, 7637–7641. and X. Kong, Y. Chen, Q. Liu, W. Wang, S. Zhang, Q. Zhang, X. Chen, Y.-Q. Xu, Z.-Y. Cao, Selective Fluorosulfonylation ofThianthrenium Salts Enabled by Electrochemistry. Org. Lett. 2023, 25, 581–586.

[0042] General preparation method:

[0043]

[0044] In a 100 mL round-bottom flask equipped with a magnetic stirrer, dichloromethane (50 mL), thiathracene (5.0 g, 23 mmol, 1.0 equivalent), sodium bromide (0.10 g, 0.97 mmol, 4.2 mol%), ferric nitrate nonahydrate (9.3 g, 23 mmol, 1.0 equivalent), and acetic acid (1.0 mL, 1.1 g, 17 mmol, 0.76 equivalent) were added. The reaction mixture was stirred at 25°C for 3 hours. After the reaction was completed as monitored by TLC, water (50 mL) was added to the reaction mixture. The organic layer was separated, and the aqueous layer was extracted with dichloromethane (50 mL × 2). The organic layers were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting solid was recrystallized from ethyl acetate. The crystallized product was collected, washed with diethyl ether (20 mL), and dried under vacuum to give thiathracene-S-oxide in 82% yield (4.38 g) as colorless needle-like crystals.

[0045]

[0046] In a 100 mL round-bottom flask equipped with a magnetic stirrer, aromatic hydrocarbons (10 mmol, 1 equivalent), thiathracene-S-oxide (2.56 g, 11 mmol, 1.1 equivalent), and dichloromethane (30 mL) were added sequentially under nitrogen protection. The reaction mixture was cooled to -40°C, and trifluoromethanesulfonic anhydride (2 mL, 12 mmol, 1.2 equivalent) was added dropwise. The reaction mixture was stirred at -40°C for 30 min, followed by stirring at room temperature for 12 h. After the reaction was completed as monitored by TLC, saturated sodium bicarbonate aqueous solution (30 mL) was added to the reaction mixture. The organic layer was separated, and the aqueous layer was extracted with dichloromethane (40 mL × 2). The organic extracts were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated to dryness under reduced pressure. The crude product was purified by recrystallization from a dichloromethane / diethyl ether system to obtain the corresponding arylthiathracene salt.

[0047] Example 1

[0048]

[0049]

[0050] In a dry, sealed tube equipped with a magnetic stirrer, arylthianonium salt 1a (0.5 mmol, 1 equivalent), arylboronic acid 2 (1 mmol, 2 equivalents), DPPH (174.9 mg, 0.75 mmol, 1.5 equivalents), tBuBrettPhos PdG3 (21.4 mg, 0.025 mmol, 5 mol%), and potassium hydroxide (91 mg, 2 mmol, 4 equivalents) were added sequentially. The sealed tube was purged three times with nitrogen, followed by the addition of anhydrous acetonitrile (3 mL). The mixture was stirred at 80 °C for 12 hours. After the reaction was complete, the yield of target product 3a was determined by nuclear magnetic resonance (NMR) using 1,3,5-trimethoxybenzene as an internal standard. The data are as follows:

[0051] Table 1

[0052]

[0053] Note: b. Nuclear magnetic resonance (NMR) detection; c. using 5 mol% Pd catalyst; d. using 2.5 mol% Pd catalyst; e. using... t BuONa replaces KOH; f represents the separation yield.

[0054] Compound (3a): 73% yield, 66.7 mg. White solid. 1H NMR (400 MHz, CDCl3): δ= 7.22 (ddd, J = 8.3, 7.4, 0.8 Hz, 2H), 7.10 – 7.05 (m, 2H), 6.99 (ddd, J =8.5, 2.5, 1.5 Hz, 4H), 6.86 (ddd, J = 8.3, 6.8, 1.0 Hz, 1H), 5.59 (s, 1H), 2.29 (s, 3H) ppm. 13 C NMR (100 MHz, CDCl3): δ = 143.8, 140.2, 130.9, 129.8,129.3, 120.2, 118.8, 116.8, 20.7 ppm. IR (KBr): 2915, 1596, 1513, 1499, 1308,809, 746, 693, 506 cm -1 HRMS (m / z): calcd for C 13 H 14 N [M+H] + 184.1121, found: 184.1124.

[0055] Example 2

[0056] Following the method of Example 1, acetonitrile was replaced with other solvents for the reaction. The yield of the target product was determined by nuclear magnetic resonance (NMR) using 1,3,5-trimethoxybenzene as an internal standard. The data are as follows:

[0057]

[0058]

[0059] Example 3

[0060] Following the method of Example 1, potassium hydroxide was replaced with other bases for the reaction. The yield of the target product was determined by nuclear magnetic resonance (NMR) using 1,3,5-trimethoxybenzene as an internal standard. The data are as follows:

[0061]

[0062]

[0063] Note: b-nuclear magnetic resonance (NMR) detection

[0064] Example 4

[0065]

[0066] In a dry, sealed tube equipped with a magnetic stir bar, arylthiananthium salt 1b-n (0.5 mmol, 1 equivalent), arylboronic acid 2a (1 mmol, 2 equivalents), DPPH (174.9 mg, 0.75 mmol, 1.5 equivalents), tBuBrettPhosPd G3 (21.4 mg, 0.025 mmol, 5 mol%), and sodium tert-butoxide (192.2 mg, 2 mmol, 4 equivalents) were added sequentially. The mixture was purged three times with nitrogen, and anhydrous acetonitrile (3 mL) was added. The mixture was stirred at 80 °C for 12 hours.

[0067] The solution was quenched with saturated sodium bicarbonate solution (10 mL) and extracted with ethyl acetate (20 mL × 3). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The extract was concentrated under reduced pressure to obtain the crude product, which was further purified by silica gel column chromatography (using ethyl acetate / petroleum ether as eluent) to give product 3b-n.

[0068]

[0069]

[0070] Compound (3b): 46% yield, 43.3 mg. Yellow oil. 1 H NMR (400 MHz, CDCl3): δ =7.28 – 7.24 (m, 2H), 7.08 – 7.03 (m, 2H), 7.01 – 6.96 (m, 4H), 6.90 (tt, J =7.4, 1.2 Hz, 1H), 5.59 (s, 1H) ppm. 19 F NMR (376 MHz, CDCl3): δ = -121.89 (s,1F) ppm. 13 C NMR (100 MHz, CDCl3): δ = 158.0 (d, J = 239.9 Hz), 143.9, 138.8 (d, J = 1.7 Hz), 129.4, 120.54, 120.46, 116.7, 115.9 (d, J = 22.4 Hz) ppm. IR(KBr):1596, 1509, 1316, 1217, 818, 774, 746, 693 cm -1 HRMS (m / z): calcd forC 12 H 11 FN [M+H] +188.0870, found: 188.0873.

[0071] Compound (3c): 59% yield, 60.2 mg. Yellow solid. 1 H NMR (400 MHz, CDCl3): δ= 7.32 – 7.27 (m, 2H), 7.24 – 7.20 (m, 2H), 7.08 – 7.04 (m, 2H), 7.02 – 6.95(m, 3H), 5.69 (s, 1H) ppm. 13 C NMR (100 MHz, CDCl3): δ = 142.5, 141.7, 129.4,129.2, 125.4, 121.4, 118.7, 118.0 ppm. IR (KBr): 3060, 1589, 1504, 1442, 1310,1089, 750, 691, 503cm -1 HRMS (m / z): calcd for C 12 H 11 ClN [M+H] + 204.0575, found: 204.0581.

[0072] Compound (3d): 72% yield, 70.5 mg. Yellow solid. 1 H NMR (400 MHz, CDCl3): δ = 7.33 – 7.27 (m, 2H), 7.17 (d, J = 8.1 Hz, 2H), 7.08 (dd, J = 8.5, 2.3 Hz, 4H), 6.95 (t, J = 7.3 Hz, 1H), 5.67 (s, 1H), 2.67 (q, J = 7.6 Hz, 2H), 1.30 (t, J = 7.6 Hz, 3H) ppm. 13 C NMR (100 MHz, CDCl3): δ =143.8, 140.4, 137.3,129.2, 128.6, 120.2, 118.7, 116.8, 28.1, 15.8 ppm. IR (KBr): 2961, 2923, 1595,1514, 1500, 1367, 1312, 742, 692cm -1 HRMS (m / z): calcd for C14 H 16 N [M+H] + 198.1277, found: 198.1279.

[0073] Compound (3e): 73% yield, 81.9 mg. Yellow solid. 1 H NMR (400 MHz, CDCl3): δ= 7.37 – 7.33 (m, 2H), 7.30 (dd, J = 8.5, 7.2 Hz, 2H), 7.11 – 7.06 (m, 4H), 6.94 (tt, J = 7.3, 1.1 Hz, 1H), 5.68 (s, 1H), 1.37 (s, 9H) ppm. 13 C NMR (100MHz, CDCl3): δ = 144.1, 143.6, 140.2, 129.3, 126.1, 120.3, 118.0, 117.0,34.1, 31.4 ppm. IR (KBr): 2959, 1594, 1515, 1497, 1304, 1265, 743, 692cm -1 .HRMS (m / z): calcd for C 16 H 20 N [M+H] + 226.1590, found: 226.1591.

[0074] Compound (3f): 79% yield, 99.1 mg. Yellow oil. 1 H NMR (400 MHz, CDCl3): δ= 7.30 – 7.25 (m, 2H), 7.17 – 7.13 (m, 2H), 7.08 – 7.03 (m, 4H), 6.92 (tt, J= 7.3, 1.1 Hz, 1H), 5.64 (s, 1H), 2.53 – 2.45 (m, 1H), 1.94 – 1.85 (m, 4H), 1.81 – 1.75 (m, 1H), 1.43 (td, J = 9.1, 2.8 Hz, 4H), 1.34 – 1.26 (m, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ = 143.7, 141.3, 140.6, 129.2, 127.5, 120.3, 118.5,117.0, 43.8, 34.6, 26.9, 26.1 ppm. IR (KBr): 2922, 2849, 1598, 1515, 1497,1312, 745, 693 cm -1 HRMS (m / z): calcd for C 18 H 22 N [M+H] + 252.1747, found: 252.1746.

[0075] Compound (3g): 76% yield, 74.8 mg. Green solid. 1 H NMR (400 MHz, CDCl3): δ= 7.29 – 7.25 (m, 2H), 7.09 – 7.02 (m, 3H), 6.94 – 6.87 (m, 3H), 5.59 (s,1H), 2.26 (s, 3H), 2.25 (s, 3H) ppm. 13 C NMR (100 MHz, CDCl3): δ = 143.9,140.5, 137.5, 130.3, 129.6, 129.2, 120.3, 120.1, 116.8, 116.2, 19.9, 19.0ppm. IR (KBr): 3389, 2924, 1597, 1502, 1312, 865, 826, 743, 691 cm -1 HRMS (m / z): calcd for C 14 H 16 N [M+H] + 198.1277, found: 198.1275.

[0076] Compound (3h): 81% yield, 80.6 mg. White solid. 1¹H NMR (400 MHz, CDCl₃): δ= 7.25 – 7.19 (m, 2H), 7.11 – 7.06 (m, 2H), 6.92 (dt, J = 7.7, 1.1 Hz, 2H), 6.89 – 6.81 (m, 3H), 5.51 (s, 1H), 3.81 (s, 3H) ppm. 13 ¹³C NMR (100 MHz, CDCl₃): δ = 155.2, 145.1, 135.7, 129.3, 122.2, 119.5, 115.6, 114.6, 55.6 ppm. IR (KBr): 2831, 1628, 1597, 1512, 1365, 1317, 1168, 774, 751 cm -1 . HRMS (m / z): calcd for C 13 H 14 NO [M+H] + 199.0997, found: 199.0999.

[0077] Compound (3i): yield 69%, 79.6 mg. White solid. 1 ¹H NMR (400 MHz, CDCl₃): δ=7.25 – 7.20 (m, 2H), 6.96 – 6.92 (m, 2H), 6.85 (tt, J = 7.3, 1.1 Hz, 1H), 6.80 (d, J = 8.5 Hz, 1H), 6.71 (d, J = 2.5 Hz, 1H), 6.67 (dd, J = 8.5, 2.5Hz, 1H), 5.54 (s, 1H), 3.86 (s, 3H), 3.82 (s, 3H) ppm. 13 ¹³C NMR (100 MHz, CDCl₃): δ =149.5, 144.8, 144.5, 136.1, 129.3, 119.7, 115.9, 112.04, 111.95, 105.2, 56.2, 55.8 ppm. IR (KBr):3380, 2833, 1596, 1514, 1261, 1025, 746, 694, 503 cm -1 . HRMS (m / z): calcd for C 14 H 16 NO₂ [M+H]+ 230.1176, found: 230.1176.

[0078] Compound (3j): 44% yield, 57.8 mg. Grey solid. 1 H NMR (400 MHz, CDCl3): δ =7.36 – 7.30 (m, 2H), 7.29 – 7.24 (m, 2H), 7.11 – 7.05 (m, 3H), 7.05 – 6.96(m, 6H), 6.91 (tt, J = 7.4, 1.1 Hz, 1H), 5.62 (s, 1H) ppm. 13 C NMR (100 MHz, CDCl3): δ = 158.1, 151.2, 143.9, 138.7, 129.6, 129.4, 122.6 (2C), 120.5,120.3, 117.9, 116.8 ppm. IR (KBr): 2778, 1509, 1489, 1283, 1229, 1013, 895,747, 692 cm -1 HRMS (m / z): calcd for C 18 H 16 NO [M+H] + 262.1226, found: 262.1221.

[0079] Compound (3k): 52% yield, 71.5 mg. Yellow solid. 1 H NMR (400 MHz, CDCl3): δ= 7.38 – 7.33 (m, 2H), 7.32 – 7.26 (m, 2H), 7.25 – 7.18 (m, 4H), 7.15 – 7.07(m, 3H), 7.16 – 7.12 (m, 1H), 7.11 – 7.07 (m, 2H), 5.76 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ = 143.7, 142.8, 138.7, 135.3, 129.4, 128.9, 128.0, 125.7,123.3, 121.9, 118.9, 117.5 ppm. IR (KBr): 2830, 1585, 1505, 1475, 1365, 1313,750, 741, 689 cm -1 HRMS (m / z): calcd for C 18 H 16 NS [M+H] + 278.0998, found: 278.0999.

[0080] Compound (3l): 75% yield, 92.6 mg. Grey solid. 1 H NMR (400 MHz, CDCl3): δ =7.64 – 7.61 (m, 2H), 7.58 – 7.54 (m, 2H), 7.50 – 7.45 (m, 2H), 7.38 – 7.32(m, 3H), 7.20 – 7.18 (m, 1H), 7.17 – 7.16 (m, 2H), 7.15 – 7.14 (m, 1H), 7.03– 6.98 (m, 1H), 5.82 (s, 1H) ppm. 13 C NMR (100 MHz, CDCl3): δ = 142.7, 142.4,140.8, 133.6, 129.4, 128.7, 127.9, 126.54, 126.47, 121.1, 118.0, 117.7 ppm.IR (KBr): 3025, 1597, 1524, 1504, 1324, 846, 759, 745, 693 cm -1 HRMS (m / z):calcd for C 18 H 16 N [M+H] + 246.1277, found: 246.1280.

[0081] Compound (3m): 66% yield, 85.4 mg. White solid. 1H NMR (400 MHz, CDCl3): δ= 7.86 – 7.83 (m, 1H), 7.67 (d, J = 2.4 Hz, 1H), 7.52 (d, J = 8.2 Hz, 1H), 7.46 (d, J = 8.7 Hz, 1H), 7.42 (ddd, J = 8.4, 7.2, 1.4 Hz, 1H), 7.28 (td, J =7.5, 1.0 Hz, 1H), 7.23 (dd, J = 8.2, 1.0 Hz, 2H), 7.18 (dd, J = 8.7, 2.3 Hz,1H), 7.00 (dd, J = 8.6, 1.2 Hz, 2H), 6.90 – 6.85 (m, 1H), 5.71 (s, 1H) ppm. 13 C NMR (100 MHz, CDCl3): δ =156.8, 152.1, 144.8, 138.1, 129.4, 127.2, 125.0,124.1, 122.5, 120.68, 120.66, 120.2, 116.3, 112.2, 111.7, 111.6 ppm. IR(KBr):2830, 1598, 1447, 1358, 1194, 1175, 745, 692, 546 cm -1 HRMS (m / z):calcd for C 18 H 14 NO [M+H] + 260.1070, found: 260.1075.

[0082] Example 5

[0083]

[0084] Following the method in Example 4, crude compound 4 was prepared and further purified by silica gel column chromatography (using ethyl acetate / petroleum ether as eluent) to finally obtain product 4b-4u.

[0085]

[0086]

[0087]

[0088]

[0089] Compound (4b): 45% yield, 46.5 mg. White solid. 1 H NMR (400 MHz, CDCl3): δ =7.47 – 7.43 (m, 2H), 7.17 (d, J = 8.1 Hz, 2H), 7.09 – 7.05 (m, 2H), 6.92 –6.88 (m, 2H), 6.01 (s, 1H), 2.35 (s, 3H)ppm. 13 C NMR (100 MHz, CDCl3): δ =148.6, 137.1, 134.0, 133.7, 130.1, 122.0, 120.1, 114.3, 100.6, 20.8 ppm. IR(KBr): 2831, 1600, 1514, 1366, 1219, 1111, 828, 545, 500cm -1 HRMS (m / z):calcd for C 14 H 13 N2 [M+H] + 209.1073, found: 209.1076.

[0090]

[0091] Compound (4c): 74% yield, 89.8 mg. White solid. 1 H NMR (400 MHz, CDCl3): δ= 7.89 (d, J = 8.7 Hz, 2H), 7.15 (d, J = 8.1 Hz, 2H), 7.08 (d, J = 8.3 Hz, 2H), 6.95 – 6.89 (m, 2H), 5.97 (s, 1H), 3.87 (s, 3H), 2.34 (s, 3H) ppm. 13 CNMR (100 MHz, CDCl3): δ = 167.0, 148.7, 137.9, 133.1, 131.5, 130.0, 121.3,120.4, 113.9, 51.7, 20.8 ppm. IR (KBr): 2939, 1700, 1597, 1527, 1434, 1281,1171, 773, 504 cm -1HRMS (m / z): calcd for C 15 H 16 NO2 [M+H] + 242.1176, found: 242.1179.

[0092]

[0093] Compound (4d): 57% yield, 74.8 mg. Yellow solid. 1 H NMR (400 MHz, CDCl3): δ = 7.74 – 7.69 (m, 2H), 7.17 (d, J = 8.0 Hz, 2H), 7.09 (d, J = 8.1 Hz, 2H), 6.98 – 6.94 (m, 2H), 6.04 (s, 1H), 3.02 (s, 3H), 2.35 (s, 3H) ppm. 13 C NMR (100 MHz, CDCl3): δ = 149.8, 143.7, 137.3, 130.3, 129.5, 124.5, 122.3, 114.1,45.1, 21.0 ppm. IR (KBr): 1592, 1517, 1286, 1136, 1093, 964, 823, 774, 518cm -1 HRMS (m / z): calcd for C 14 H 16 NO2S [M+H] + 262.0896, found: 262.0894.

[0094]

[0095] Compound (4e): 76% yield, 86.6 mg. Yellow solid. 1 H NMR (400 MHz, CDCl3): δ= 8.14 – 8.04 (m, 2H), 7.20 (d, J = 8.1 Hz, 2H), 7.13 – 7.09 (m, 2H), 6.92 –6.82 (m, 2H), 6.32 (s, 1H), 2.36 (s, 3H)ppm. 13C NMR (100 MHz, CDCl3): δ =150.8, 139.2, 136.6, 134.7, 130.2, 126.2, 122.6, 113.1, 20.9 ppm. IR (KBr): 3330, 2830, 1607, 1366, 1304, 1179, 1111, 774cm -1 HRMS (m / z): calcd forC 13 H 13 N₂O₂ [M+H] + 229.0972, found: 229.0981.

[0096]

[0097] Compound (4f): 67% yield, 70.9 mg. Yellow solid. 1 H NMR (400 MHz, CDCl3): δ= 9.77 (s, 1H), 7.74 – 7.70 (m, 2H), 7.18 (d, J = 8.2 Hz, 2H), 7.11 (d, J =8.4 Hz, 2H), 6.99 – 6.94 (m, 2H), 6.31 (s, 1H), 2.35 (s, 3H) ppm. 13 C NMR (100MHz, CDCl3): δ = 190.4, 150.5, 137.2, 133.9, 132.2, 130.1, 127.9, 122.1,113.9, 20.9 ppm. IR (KBr): 3324, 1585, 1568, 1522, 1490, 1336, 1225, 1162, 825cm -1 HRMS (m / z): calcd for C 14 H 14 NO [M+H] + 212.1070, found: 212.1075.

[0098]

[0099] Compound (4g): 49% yield, 61.8 mg. White solid. 1¹H NMR (400 MHz, CDCl₃): δ=7.47 – 7.43 (m, 2H), 7.18 – 7.13 (m, 2H), 7.09 – 7.05 (m, 2H), 7.00 – 6.95 (m, 2H), 5.83 (s, 1H), 2.35 (s, 3H) ppm. 19 ¹⁹F NMR (376 MHz, CDCl₃): δ = -61.22 (s, 3F) ppm. 13 ¹³C NMR (100 MHz, CDCl₃): δ = 147.5, 138.3, 133.0, 130.1, 126.6 (q, J = 3.9 Hz), 124.7 (q, J = 269.2 Hz), 121.02, 120.98 (q, J = 32.5 Hz), 114.6, 20.8 ppm. IR (KBr): 2924, 2778, 1609, 1515, 1326, 1164, 1113, 1068, 828 cm -1 ⁻¹. HRMS (m / z): calcd for C 14 ₁₅H 13 ₁₄F₃NO [M+H] + ⁺ 252.0995, found: 252.0992.

[0100]

[0101] Compound (4h): Yield 66%, 88.3 mg. Yellow solid. 1 ¹H NMR (400 MHz, CDCl₃): δ = 7.15 – 7.07 (m, 4H), 7.03 – 6.95 (m, 4H), 5.64 (s, 1H), 2.33 (s, 3H) ppm. 19 ¹⁹F NMR (376 MHz, CDCl₃): δ = -58.21 (s, 3F) ppm. 1313C NMR (100 MHz, CDCl3): δ = 142.9, 142.2, 139.6, 131.7, 130.0, 122.3, 120.6 (q, J = 254.5 Hz), 119.4, 117.0, 20.7 ppm. IR (KBr): 2924, 1520, 1297, 1266, 1204, 1158, 1010, 919, 811 cm-1 -1 . HRMS (m / z): calcd for C 14 16H14 13 F3NO [M+H]+ + 268.0944, found: 268.0938.

[0102]

[0103] Compound (4i): Yield 72%, 72.5 mg. Brown solid. 1 1H NMR (400 MHz, CDCl3): δ= 7.10 – 7.06 (m, 2H), 7.02 – 6.95 (m, 4H), 6.94 – 6.91 (m, 2H), 5.51 (s, 1H), 2.30 (s, 3H) ppm. 19 19F NMR (376 MHz, CDCl3): δ = -122.99 (s, 1F) ppm. 13 13C NMR (100 MHz, CDCl3): δ = 157.6 (d, J = 239.4 Hz), 141.1, 139.8, 130.5, 129.9, 119.3 (d, J = 7.7 Hz), 117.8, 115.8 (d, J = 22.4 Hz), 20.6 ppm. IR (KBr): 3415, 2830, 1610, 1509, 1365, 1223, 1154, 813, 774 cm-1 -1 . HRMS (m / z): calcd for C13 13 H14 13 FN [M+H]+ + 202.1027, found: 202.1029.

[0104]

[0105] Compound (4j): 74% yield, 80.0 mg. Brown solid. 1 H NMR (400 MHz, CDCl3): δ= 7.21 – 7.17 (m, 2H), 7.13 – 7.09 (m, 2H), 7.01 – 6.97 (m, 2H), 6.95 – 6.91(m, 2H), 5.60 (s, 1H), 2.33 (s, 3H)ppm. 13 C NMR (100 MHz, CDCl3): δ = 142.6,139.7, 131.4, 129.9, 129.1, 124.6, 119.1, 117.7, 20.7 ppm. IR (KBr): 2889, 2672, 1455, 1262, 1012, 892, 807, 726, 577cm -1 HRMS (m / z): calcd forC 13 H 13 ClN [M+H] + 218.0731, found: 218.0737.

[0106]

[0107] Compound (4k): 62% yield, 67.5 mg. White solid. 1 H NMR (400 MHz, CDCl3): δ= 7.16 – 7.11 (m, 3H), 7.04 – 7.00 (m, 2H), 6.97 (t, J = 2.1 Hz, 1H), 6.84 –6.80 (m, 2H), 5.65 (s, 1H), 2.33 (s, 3H)ppm. 13 C NMR (100 MHz, CDCl3): δ =145.6, 139.0, 135.0, 132.1, 130.3, 130.0, 120.1, 119.7, 115.7, 114.3, 20.7ppm. IR (KBr): 3415, 2972, 2830, 1608, 1366, 1162, 1050, 861, 774 cm -1 HRMS(m / z): calcd for C 13 H 13 ClN [M+H] +218.0731, found: 218.0727.

[0108]

[0109] Compound (4l): 69% yield, 90.3 mg. Brown solid. 1 H NMR (400 MHz, CDCl3): δ= 7.19 (d, J = 8.8 Hz, 2H), 7.13 – 7.09 (m, 2H), 7.00 – 6.97 (m, 2H), 6.95 –6.91 (m, 2H), 5.58 (s, 1H), 2.33 (s, 3H)ppm. 13 C NMR (100 MHz, CDCl3): δ =142.7, 139.8, 131.5, 129.9, 129.2, 124.7, 119.2, 117.8, 20.7 ppm. IR (KBr): 3409, 2830, 1608, 1518, 1365, 1322, 1160, 1090, 774cm -1 HRMS (m / z): calcdfor C 13 H 13 BrN [M+H] + 262.0226, found: 262.0219.

[0110]

[0111] Compound (4m): 71% yield, 70.4 mg. White solid. 1 H NMR (400 MHz, CDCl3): δ= 7.10 – 7.06 (m, 4H), 6.98 – 6.94 (m, 4H), 5.52 (s, 1H), 2.31 (s, 6H) ppm. 13 C NMR (100 MHz, CDCl3): δ = 141.1, 130.1, 129.8, 117.8, 20.6 ppm. IR (KBr): 3418, 2830, 1609, 1519, 1365, 1320, 1177, 807, 774, 510 cm -1 HRMS (m / z):calcd for C 14 H 16N [M+H] + 198.1277, found: 198.1275.

[0112]

[0113] Compound (4n): 75% yield, 89.9 mg. Yellow oil. 1 H NMR (400 MHz, CDCl3): δ =7.32 – 7.28 (m, 2H), 7.12 – 7.08 (m, 2H), 7.03 – 6.98 (m, 4H), 5.57 (s, 1H), 2.33 (s, 3H), 1.34 (s, 9H) ppm. 13 C NMR (100 MHz, CDCl3): δ = 143.3, 141.0,140.7, 130.2, 129.7, 126.0, 118.0, 117.0, 34.1, 31.4, 20.6 ppm. IR (KBr): 2961, 1608, 1517, 1364, 1312, 1268, 1190, 816, 774 cm -1 HRMS (m / z): calcd forC 17 H 22 N [M+H] + 240.1747, found: 240.1753.

[0114]

[0115] Compound (4o): 85% yield, 103.6 mg. Brown oil. 1 H NMR (400 MHz, CDCl3): δ =7.08 – 7.03 (m, 2H), 6.92 – 6.86 (m, 2H), 6.80 (d, J = 8.5 Hz, 1H), 6.68 (d,J = 2.5 Hz, 1H), 6.62 (dd, J = 8.5, 2.5 Hz, 1H), 5.44 (s, 1H), 3.86 (s, 3H), 3.83 (s, 3H), 2.29 (s, 3H) ppm. 13¹³C NMR (100 MHz, CDCl₃): δ = 149.6, 144.1, 142.0, 137.1, 129.8, 129.6, 116.9, 112.2, 110.9, 104.3, 56.3, 55.8, 20.6 ppm. IR (KBr): 2931, 2831, 1608, 1511, 1463, 1257, 1230, 1135, 1026, 813 cm -1 . HRMS (m / z): calcd for C 15 H 18 NO₂ [M+H] + 244.1332, found: 244.1330.

[0116]

[0117] Compound (4p): yield 51%, 57.9 mg. Brown oil. 1 ¹H NMR (400 MHz, CDCl₃): δ = 7.06 (d, J = 8.1 Hz, 2H), 6.91 – 6.86 (m, 2H), 6.73 (d, J = 8.2 Hz, 1H), 6.66 (d, J = 2.2 Hz, 1H), 6.50 (dd, J = 8.3, 2.2 Hz, 1H), 5.93 (s, 2H), 5.43 (s, 1H), 2.30 (s, 3H) ppm. 13 ¹³C NMR (100 MHz, CDCl₃): δ = 148.1, 142.2, 141.7, 138.2, 129.8 (2C), 117.2, 111.6, 108.5, 101.5, 100.9, 20.6 ppm. IR (KBr): 2887, 1517, 1501, 1487, 1242, 1190, 1038, 931, 810 cm -1 . HRMS (m / z): calcd for C 14 H 14 NO₂ [M+H] + 228.1019, found: 228.1016.

[0118]

[0119] Compound (4q): 82% yield, 113.2 mg. Yellow solid. 1 H NMR (400 MHz, CDCl3): δ = 7.36 – 7.30 (m, 2H), 7.09 (ddd, J = 8.5, 7.0, 1.7 Hz, 3H), 7.05 (q, J =1.5 Hz, 1H), 7.03 – 7.01 (m, 2H), 7.01 – 6.95 (m, 5H), 5.54 (s, 1H), 2.32 (s, 3H) ppm. 13 C NMR (100 MHz, CDCl3): δ = 158.3, 129.9, 129.6 (3C), 122.5, 120.6,119.2, 117.9, 117.7 (3C), 20.6 ppm. IR (KBr): 3023, 1508, 1489, 1263, 1231,823, 809, 741, 690 cm -1 HRMS (m / z): calcd for C 19 H 18 NO [M+H] + 276.1383, found: 276.1379.

[0120]

[0121] Compound (4r): 78% yield, 100.9 mg. White solid. 1 H NMR (400 MHz, CDCl3): δ= 7.64 – 7.60 (m, 2H), 7.57 – 7.52 (m, 2H), 7.50 – 7.44 (m, 2H), 7.35 (td, J= 7.2, 1.3 Hz, 1H), 7.17 (d, J = 8.3 Hz, 2H), 7.14 – 7.07 (m, 4H), 5.72 (s, 1H), 2.38 (s, 3H) ppm. 1313C NMR (100 MHz, CDCl3): δ = 143.3, 140.8, 139.9, 132.9, 131.1, 129.9, 128.7, 127.9, 126.4, 119.0, 116.8, 20.7 ppm. IR (KBr): 2913, 1609, 1528, 1515, 1409, 1315, 820, 754, 687 cm -1 . HRMS (m / z): calcd for C 19 H 18 N [M+H] + 260.1434, found: 260.1435.

[0122]

[0123] Compound (4s): Yield 82%, 95.7 mg. Brown solid. 1 1H NMR (400 MHz, CDCl3): δ= 7.75 – 7.72 (m, 2H), 7.63 (d, J = 8.2 Hz, 1H), 7.42 – 7.36 (m, 2H), 7.29 (ddd, J = 8.1, 6.8, 1.3 Hz, 1H), 7.19 (dd, J = 8.8, 2.4 Hz, 1H), 7.17 – 7.09 (m, 4H), 5.78 (s, 1H), 2.35 (s, 3H) ppm. 13 13C NMR (100 MHz, CDCl3): δ = 141.7, 140.1, 134.7, 131.4, 129.9, 129.1, 128.8, 127.6, 126.4, 126.3, 123.1, 119.5, 119.3, 110.2, 20.7 ppm. IR (KBr): 2913, 1511, 1310, 1237, 952, 813, 740, 502, 470 cm -1 . HRMS (m / z): calcd for C 17 H 16 N [M+H] + 234.1277, found: 234.1278.

[0124]

[0125] Compound (4t): 56% yield, 65.8 mg. Red oil. 1 H NMR (400 MHz, CDCl3): δ =8.05 – 8.01 (m, 1H), 7.89 – 7.85 (m, 1H), 7.55 – 7.47 (m, 3H), 7.38 (t, J =7.8 Hz, 1H), 7.30 (dd, J = 7.4, 1.2 Hz, 1H), 7.13 – 7.08 (m, 2H), 6.99 – 6.95(m, 2H), 5.91 (s, 1H), 2.33 (s, 3H) ppm. 13 C NMR (100 MHz, CDCl3): δ = 141.7,139.5, 134.6, 130.4, 129.8, 128.5, 126.9, 126.1, 126.0, 125.5, 122.0, 121.5,118.4, 114.0, 20.7 ppm. IR (KBr):2830, 1626, 1606, 1515, 1401, 1366, 1307,1157, 774 cm -1 HRMS (m / z): calcd for C 17 H 16 N [M+H] + 234.1277, found: 234.1277.

[0126]

[0127] Compound (4u): 42% yield, 39.6 mg. Brown solid. 1 H NMR (400 MHz, CDCl3): δ= 7.24 (dd, J = 5.1, 3.1 Hz, 1H), 7.07 (dt, J = 8.0, 0.7 Hz, 2H), 6.94 – 6.88(m, 3H), 6.67 (ddd, J = 3.1, 1.5, 0.7 Hz, 1H), 5.63 (s, 1H), 2.29 (s, 3H)ppm. 13C NMR (100 MHz, CDCl3): δ = 142.3, 142.0, 129.8, 129.5, 125.1, 122.5,116.2, 104.9, 20.6 ppm. IR (KBr):2917, 1557, 1515, 1440, 1358, 1311, 1244,809, 734 cm -1 . HRMS (m / z): calcd for C 11 H 12 NS [M+H] + 190.0685, found: 190.0684.

Claims

1. A method for preparing a compound of formula III or a salt thereof, the method comprising the step of reacting a compound of formula I, a compound of formula II, and diphenylphosphonohydroxylamine in the presence of a palladium catalyst to form a compound of formula III. in, R 1 Each is independently selected from halogen, cyano, nitro, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, 3- to 6-membered heterocycloalkyl, PhO- or PhS-, or adjacent R 1 Form C with adjacent atoms 3-6 Cycloalkyl or 3- to 6-membered heterocyclic alkyl; R 2 Selected from phenyl or 5- or 6-membered heteroaryl, wherein the phenyl or 5- or 6-membered heteroaryl group is optionally selected from one or more R 2a Replaced; R 2a Selected from halogen, cyano, nitro, C 1-6 Alkyl, C 1-6 Haloalkyl, C 1-6 Alkoxy, C 1-6 Halogenated alkoxy groups, PhO-, Ph-, -COOR 2aa or -SOOR 2aa , or R 2a Form C with adjacent atoms 3-6 Cycloalkyl, 3- to 6-membered heterocyclic alkyl or phenyl; R 2aa Selected from hydrogen or C 1-6 alkyl; o can be selected from 0, 1, 2 or 3.

2. The method according to claim 1, characterized in that, The palladium catalyst is selected from... t BuBrettPhos Pd G3.

3. The method according to claim 1 or 2, characterized in that, The amount of palladium catalyst used is 1% to 10% of the molar amount of the compound of formula I, for example, 5%.

4. The method according to any one of claims 1-3, characterized in that, The reaction also involves a base, preferably an inorganic base. t BuONa.

5. The method according to claim 4, characterized in that, The amount of alkali used is 1 to 6 equivalents of the molar amount of the compound of Formula I, for example, 4 equivalents.

6. The method according to any one of claims 1-5, characterized in that, The solvent used in the reaction is acetonitrile.

7. The method according to any one of claims 1-6, characterized in that, The amount of diphenylphosphonohydroxylamine used is 1 to 4 equivalents of the molar amount of the compound of formula I, for example, 1.5 equivalents.

8. The method according to any one of claims 1-7, characterized in that, The compound shown in Formula I is selected from: , , , , , , , , , , , or .

9. The method according to any one of claims 1-8, characterized in that, The compound shown in Formula II is selected from: , , , , , , , , , , , , , , , , , , , or .

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