Compound, organic hole transport layer material, and perovskite solar cell

Abstract

Disclosed are a compound, an organic hole transport layer material, and a perovskite solar cell, relating to the technical field of perovskite solar cells. The compound has a structure represented by formula I, uses a carboxyl group, a sulfonic acid group, and a phosphoric acid group as anchor groups, and is connected to a carbon position at an active reaction site in an N-containing fused ring (the number of rings is greater than or equal to 3) by means of a double bond, thereby maintaining the long-axis rigidity of a molecule, so that the compound can be more effectively conjugated, and a functional group is introduced on the short axis of the molecule, thereby improving the overall rigidity and functionality of the compound. The use of the compound as an organic hole transport material can improve the extraction and transport of holes. The introduction of the functional group on the short axis of the molecule further improves perovskite thin film crystallization and passivates interface defects. The design of the structure of the compound in the organic hole transport material achieves more excellent HOMO energy level and valence band energy level matching between the organic hole transport material and an active layer material, thereby further improving the device efficiency and stability of perovskite cells.

Description

A compound and organic hole transport layer material, perovskite solar cells

[0001] This application claims priority to Chinese Patent Application No. 202410670180.8, filed on May 28, 2024, entitled "A Compound and Organic Hole Transport Layer Material, Perovskite Solar Cell", the entire contents of which are incorporated herein by reference. Technical Field

[0002] This invention relates to the field of perovskite solar cell technology, and more particularly to a compound and an organic hole transport layer material, and a perovskite solar cell. Background Technology

[0003] Green and sustainable solar energy is receiving increasing attention from researchers and industry. Perovskite solar cells are solar cells that use perovskite-type organometal halide semiconductors as light-absorbing materials. They belong to the third generation of solar cells and are also known as new concept solar cells, representing an effective utilization of green and sustainable solar energy.

[0004] Currently, the certified photoelectric conversion efficiency of perovskite solar cells has reached as high as 26.14%, which is inseparable from their excellent photoelectric performance and fabrication process. Hole transport materials, as an important component of high-efficiency perovskite solar cells, are mainly used to collect and transport holes injected by the perovskite absorber layer, achieving effective electron-hole separation. Currently, a large number of organic hole transport materials have been designed, synthesized, and successfully applied to perovskite solar cells. However, these commonly used hole transport layer materials still have some drawbacks, such as the high cost and low hole mobility of 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (spiro-OMeTAD), the energy level mismatch and wettability issues of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)]amine (PTAA), and the corrosion, hygroscopicity, and parasitic absorption problems of poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS).

[0005] In recent years, self-assembling organic small molecule hole transport materials with anchoring groups have attracted widespread attention from researchers. Thanks to their diverse structural designs, they can effectively extract charge carriers, and by controlling energy level alignment, passivating substrate defects, and adjusting the morphology of the active layer, they hold promise for achieving high-performance photovoltaic devices. However, the reported organic small molecule hole transport materials with anchoring groups still face problems such as poor charge transport capabilities and insufficient device efficiency and stability.

[0006] Therefore, it is of great significance to study and develop a novel compound as an organic small molecule hole transport material. Summary of the Invention

[0007] In view of this, the technical problem to be solved by the present invention is to provide a compound and an organic hole transport layer material, and a perovskite solar cell. The compound has a rigid long axis and a functional short axis, and its use as an organic hole transport layer material significantly improves the device efficiency and stability of the perovskite solar cell.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] This invention provides a compound having the structure shown in Formula I:

[0010] in, It is an anchoring group, selected from carboxyl, sulfonic acid, or phosphate groups;

[0011] R a Selected from H, halogens, or C1-C 10 Straight-chain or branched alkyl groups;

[0012] The C1~C 10 Straight-chain or branched alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.

[0013] R b Selected from halogens, CN, SH, OH, CO2R f , where R f Selected from C1 to C 10 Straight-chain or branched alkyl groups;

[0014] Ar1 and Ar2 are independently selected from C6 to C6. 16 Aryl or C4~C 18 Mixed aromatics;

[0015] The C6~C 18 Aryl groups include, but are not limited to, phenyl, naphthyl, benzyl, biphenyl, linear terphenyl, anthracene, phenanthryl, pyrene, fluorene, etc.

[0016] The C4~C 18 Heteroaryl groups include, but are not limited to, pyridyl, indolyl, quinoxalinyl, quinolinyl, isoquinolinyl, furanyl, pyrroleyl, thiazolyl, thiopheneyl, pyranyl, carbazoleyl, benzimidazolyl, benzothiopheneyl, benzofuranyl, benzopyranyl, benzothiazolyl, benzooxazolyl, dibenzimidazolyl, dibenzipheneyl, dibenzifuranyl, dibenziranyl, dibenzimidazolyl, dibenziranyl, dibenzimidazolyl, dibenziranyl, etc.

[0017] R c R e Independently selected from H, halogen, hydroxyl, amino, cyano, phenyl, C1-C 10 One or more of straight-chain or branched alkyl groups, C1-C4 alkoxy groups, and 5-6-membered heteroaryl groups;

[0018] R d Selected from H, C1~C 10 Straight-chain or branched alkyl groups, C1-C6 straight-chain or branched alkyl groups with S or NH substitution for carbon atoms, C1-C6 alkoxy groups, C6-C6 alkoxy groups 16 Aryl or C4~C 18 Mixed aromatics;

[0019] Or, R c R d And its atom forms a fused ring 1 with Ar2, and R e R d And its constituent atoms form a fused ring with Ar1;

[0020] Or, R c R d And its atom forms a fused ring with Ar2;

[0021] Or, R e R d And its constituent atoms form a fused ring with Ar1;

[0022] The heteroatoms in fused ring 1 and fused ring 2 are independently selected from O, S, Se, N, One or more of the following, and at least containing N;

[0023] y is selected from single bond, O, S, Se,

[0024] R g and R h Independently selected from H, C1~C 10 One or more of the following: straight-chain or branched alkyl, C1-C6 alkoxy, S- or NH-substituted carbon atom C1-C6 straight-chain or branched alkyl, and 5- or 6-membered heteroaryl.

[0025] Preferably, in this invention, the R a Selected from H or C1-C4 straight-chain or branched alkyl groups;

[0026] The R b Selected from halogens, CN, CO2R f , where R f Selected from C1-C4 straight-chain or branched alkyl groups;

[0027] Ar1 and Ar2 are independently selected from C6 to C6.14 Aryl or C4~C 16 Mixed aromatics;

[0028] R c R e Independently selected from one or more of H, chlorine, bromine, hydroxyl, amino, cyano, phenyl, C1-C6 straight-chain or branched alkyl, C1-C3 alkoxy, and 5-6 heteroaryl;

[0029] R d Selected from C1-C5 straight-chain or branched alkyl groups, C1-C4 straight-chain or branched alkyl groups, C1-C4 alkoxy groups, and C6-C4 straight-chain or branched alkyl groups with S or NH substituted carbon atoms. 12 Aryl or C4~C 12 Mixed aromatics;

[0030] The C1-C6 straight-chain or branched alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, and hexyl.

[0031] The 5- to 6-membered heteroaryl groups include, but are not limited to, isoquinolinyl, furanyl, pyrroleyl, thiazolyl, thiophenyl, pyranyl, pyridyl, quinolinyl, and pyranyl.

[0032] Or, R c R d And its atom forms a fused ring 1 with Ar2, and R e R d And its constituent atoms form a fused ring with Ar1;

[0033] Or, R c R d And its atom forms a fused ring with Ar2;

[0034] Or, R e R d And its constituent atoms form a fused ring with Ar1;

[0035] The rings containing the heteroatoms in fused ring 1 and fused ring 2 are independently selected from six-membered heterocycles containing N and O, or six-membered heterocycles containing N and S, or five-membered heterocycles containing only N;

[0036] y is selected from single bond, O, S,

[0037] R g and R h Independently selected from one or more C1-C6 straight-chain or branched alkyl groups.

[0038] More preferably, the compound of the present invention has the structure shown in Formula I-1:

[0039] in, R a R b Ar1, Ar2, R c R d R e y, R g and R h The range of values ​​is the same as above, and will not be repeated here.

[0040] More preferably, the compound has any of the following structures:

[0041] In formulas I-1-1, I-1-2, and I-1-3, y is independently selected from one or more of single bonds, C(CH3)2, O, and S;

[0042] The R a R b Ar1, Ar2, R c R d R e The range of values ​​is the same as above, and will not be repeated here.

[0043] In a further preferred embodiment of the present invention, the R c R d And its atom forms a fused ring 1 with Ar2, and R e R d And its constituent atoms form a fused ring with Ar1;

[0044] Or, R c R d And its atom forms a fused ring with Ar2;

[0045] Or, R e R d And its constituent atoms form a fused ring with Ar1;

[0046] The heteroatoms in fused ring 1 and fused ring 2 are independently selected from one or more of O, S, and N, and contain at least N;

[0047] The fused ring 1 and fused ring 2 are independently selected from 5-membered or 6-membered heteroaromatic rings.

[0048] The five-membered heterocyclic aromatic rings include, but are not limited to, furan, thiophene, pyrrole, thiazole, imidazole, etc.

[0049] The six-membered heteroaryl rings include, but are not limited to, pyridine, pyrazine, pyrimidine, pyridazine, etc.

[0050] Preferably, in this invention, C1 to C 10The linear or branched alkyl, C1-C4 linear or branched alkyl, C1-C6 linear or branched alkyl, C1-C5 linear or branched alkyl, and C1-C4 alkoxy groups further contain substituents selected from one or more of halogens, hydroxyl groups, amino groups, cyano groups, nitro groups, carboxyl groups, sulfonic acid groups, boric acid groups, ester groups, SiH3, and SMe.

[0051] The C6~C 16 Aryl, C6~C 14 Aryl, C6~C 12 Aryl, C4~C 18 heteroaryl, C4-C 16 heteroaryl, C4-C 12 Heteroaryl groups and 5-6-membered heteroaryl groups further contain substituents selected from D, C1-C6 straight-chain or branched alkyl groups, S or NH-substituted carbon atoms of C1-C6 straight-chain or branched alkyl groups, C1-C4 alkoxy groups, C3-C6... 15 cycloalkyl, C4-C 16 heteroaryl, C6-C 16 Aryl, halogen, hydroxyl, mercapto, amino, cyano, nitro, carboxyl, sulfonic acid, boric acid, ester, SiH3, SMe, OR1', SR1', SeR1', TeR1' One or more of the following;

[0052] The The "-" in the text indicates the connection position.

[0053] R1', R2', and R3' are independently selected from H, D, C1-C6 straight-chain or branched alkyl groups, C3-C6... 15 cycloalkyl, C6-C 16 Aryl, C4~C 18 Mixed aromatics;

[0054] The C4~C 18 heteroaryl, 5-6 quinary heteroaryl, C4-C 16 heteroaryl, C4-C 12 The heteroatoms in the heteroaryl group are selected from one or more of Si, Ge, N, P, O, S, and Se, and the number of heteroatoms is independently selected from 1, 2, or 3.

[0055] Preferably, in this invention, the R a Selected from H, methyl, or ethyl;

[0056] The R b Selected from F, CN, CO2CH3, or CO2CH2CH3;

[0057] Ar1 and Ar2 are independently selected from any of the following structures:

[0058] R c R e Independently selected from one or more of H, chlorine, bromine, hydroxyl, amino, cyano, methyl, trifluoromethyl, methoxy, benzoxy, thiophene, and pyridyl;

[0059] R d Choose from any of the following structures:

[0060] L1 and L2 are independently selected from H, D, C1 to C1. 20 Straight-chain or branched alkyl groups, C3-C 15 cycloalkyl, C6-C 18 Aryl, C4~C 18 Mixed aromatics;

[0061] Or, R c R d And its atom forms a fused ring 1 with Ar2, and R e R d And its constituent atoms form a fused ring with Ar1;

[0062] The rings containing the heteroatoms in fused ring 1 and fused ring 2 are independently selected from six-membered heterocycles containing N and O, or six-membered heterocycles containing N and S, or five-membered heterocycles containing only N;

[0063] y is selected from single bond, O, S,

[0064] R g and R h Independently selected from one or more of methyl or ethyl.

[0065] The major and minor axes of the compound described in this invention are shown in the following schematic diagram:

[0066] The compounds, anchored by carboxylic acids, sulfonic acids, or phosphoric acids, are linked to highly reactive carbon sites in N-containing fused rings (≥3 rings) via double bonds. This effectively extends conjugation, increases the rigidity of the long axis of the molecule, and introduces functional groups along the short axis, resulting in compounds with both excellent hole transport performance and strong interfacial passivation capabilities. Their application in organic fused-ring hole transport materials is more conducive to molecular self-assembly and charge transport, making them suitable for fabricating highly efficient and stable perovskite photovoltaic devices.

[0067] Preferably, the compound of the present invention has any of the structures shown in formulas A1-1 to A6-45:

[0068] Preferably, FG (i.e., anchoring group) Selected from CO2H, SO3H, or PO3H2;

[0069] Preferably, R1 and R2 are independently selected from H, D, F, Cl, Br, I, OH, SH, NH2, NO2, CN, carboxyl, sulfonic acid, boric acid, C1-C6 straight-chain or C3-C6 branched alkyl, S or NH substituted carbon atom C1-C6 straight-chain or branched alkyl, C1-C4 alkoxy, C3-C 15 cycloalkyl, C4-C 16 heteroaryl, C6-C 16 Aryl, SiH3, SMe, -OR1', -SR1', -SeR1', -TeR1' With one or more of the aromatic groups or heteroaromatic groups containing the above-mentioned groups;

[0070] Preferably, R1', R2', and R3' are independently selected from H, D, C1-C6 straight-chain or branched alkyl groups, C3-C6... 15 cycloalkyl, C6-C 16 Aryl, C4~C 18 Mixed aromatics;

[0071] The C4~C 18 heteroaryl, 5-6 quinary heteroaryl, C4-C 16 heteroaryl, C4-C 12 The heteroatoms in the heteroaryl group are selected from one or more of Si, Ge, N, P, O, S, and Se, and the number of heteroatoms is independently selected from 1, 2, or 3.

[0072] Preferably, R3 to R8 are independently selected from C1 to C6 straight-chain alkyl groups, C3 to C6 branched alkyl groups, and C3 to C6 branched alkyl groups. 15 cycloalkyl, C6-C 30 Aryl, C5~C 30 Mixed aromatics;

[0073] Preferably, the heteroaryl group or C5-C5 group containing the above-mentioned groups is... 30 The heteroatom in the heteroaryl group is selected from one or more of Si, N, P, O, S, Se and Ge.

[0074] Preferably, the C1-C6 straight-chain alkyl group, C3-C6 branched alkyl group, and C3-C6 branched alkyl group are used in this invention. 15 cycloalkyl, C6-C 30 Aryl, C5~C30 The heteroaryl group and the aromatic group or heteroaryl group containing the above-mentioned groups also contain substituents;

[0075] Preferably, the substituent is selected from one or more of halogen, hydroxyl, nitro, and amino groups.

[0076] More preferably, the compound has any of the following structures:

[0077] In a further preferred embodiment of the present invention, the compound has any of the following structures:

[0078] The present invention also provides an organic hole transport material comprising one or more of the compounds described above. The present invention further provides a perovskite solar cell comprising the organic hole transport material described above.

[0079] Preferably, the perovskite solar cell of the present invention comprises, in sequence, a conductive oxide substrate, an organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer, and an electrode layer; or, the perovskite solar cell comprises, in sequence, a conductive oxide substrate, an inorganic p-type semiconductor hole transport layer, an organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer, and an electrode layer.

[0080] Preferably, the organic hole transport layer comprises the organic hole transport material described above.

[0081] The material of the inorganic p-type semiconductor hole transport layer is preferably one or more of nickel oxide, copper aluminum oxide, copper iron oxide, copper oxide, copper iodide, tungsten oxide, molybdenum oxide, copper sulfide, ferrous sulfide, and cuprous thiocyanate.

[0082] The aforementioned perovskite solar cells include single-junction cells or tandem cells. When they are tandem cells, they are preferably one of the following: all-perovskite cells, perovskite / crystalline silicon tandem cells, perovskite / organic tandem cells, and perovskite / copper indium gallium selenide tandem cells.

[0083] Compared with the prior art, the compound provided by the present invention has the structure shown in Formula I, wherein, It is an anchoring group, selected from carboxyl, sulfonic acid, or phosphate groups; R a Selected from H, halogens, or C1-C 10 Straight-chain or branched alkyl groups; R b Selected from halogens, CN, SH, OH, CO2R f , where R f Selected from C1 to C 10 Straight-chain or branched alkyl groups; Ar1 ​​and Ar2 are independently selected from C6 to C6. 16 Aryl or C4~C 18 heteroaryl; R c R e Independently selected from H, halogen, hydroxyl, amino, cyano, phenyl, C1-C 10 One or more of the following: straight-chain or branched alkyl groups, C1-C4 alkoxy groups, and 5-6-membered heteroaryl groups; R d Selected from H, C1~C 10 Straight-chain or branched alkyl groups, C1-C6 straight-chain or branched alkyl groups with S or NH substitution for carbon atoms, C1-C6 alkoxy groups, C6-C6 alkoxy groups 16 Aryl or C4~C 18 heteroaryl; or, R c R d And its atom forms a fused ring 1 with Ar2, and R e R d And its atom forms a fused ring 2 with Ar1; or, R c R d And its atom forms a fused ring 1 with Ar2; or, R e R d The atoms contained therein form a fused ring 2 with Ar1; the heteroatoms in the fused ring 1 and fused ring 2 are independently selected from O, S, Se, N, One or more of the following, and at least N; y is selected from single bonds, O, S, Se, R g and R h Independently selected from H, C1~C 10The compound comprises one or more of the following: straight-chain or branched alkyl groups, C1-C6 alkoxy groups, S- or NH-substituted carbon atoms in a C1-C6 straight-chain or branched alkyl group, and 5-6 membered heteroaryl groups. The compound uses carboxyl, sulfonic acid, and phosphate groups as anchoring groups, and is connected to the active reactive carbon sites in N-containing fused rings (≥3 rings) via double bonds. This maintains the rigidity of the long axis of the molecule, enabling more effective conjugation. Functional groups are introduced onto the short axis of the molecule to improve the overall rigidity and functionality of the compound. Using this compound as an organic hole transport material can improve hole extraction and transport. Introducing functional groups onto the short axis of the molecule further improves the crystallization of perovskite thin films and passivates interface defects. The design of the compound structure in the organic hole transport material achieves better HOMO and valence band energy level matching between the organic hole transport material and the active layer material, thereby further improving the device efficiency and stability of perovskite solar cells. Attached Figure Description

[0084] Figure 1 is a schematic diagram of the perovskite solar cell structure device prepared in Example 1;

[0085] Figure 2 shows the J / V curve of the perovskite solar cell (i.e., device 1) prepared using compound A2-39-1 provided by the present invention as the hole transport material;

[0086] Figure 3 shows the J / V curve of the perovskite solar cell (i.e., device 2) prepared using compound A2-38-1 provided by the present invention as the hole transport material;

[0087] Figure 4 shows the J / V curve of the perovskite solar cell (i.e., device 3) prepared using compound Al-13-1 provided by the present invention as the hole transport material;

[0088] Figure 5 shows the J / V curve of the perovskite solar cell (i.e., device 4) prepared using compound Al-14-1 provided by the present invention as the hole transport material;

[0089] Figure 6 shows the J / V curve of the perovskite solar cell (i.e., device 5) prepared using compound Al-9-1 provided by the present invention as a hole transport material;

[0090] Figure 7 shows the J / V curve of the perovskite solar cell (i.e., device 6) prepared using compound Al-8-1 provided by the present invention as a hole transport material;

[0091] Figure 8 shows the J / V curve of the perovskite solar cell (i.e., device 7) prepared using compound Al-2-7 provided by the present invention as a hole transport material;

[0092] Figure 9 shows the J / V curve of the perovskite solar cell (i.e., device 8) prepared using compound Al-4-6 provided by the present invention as a hole transport material;

[0093] Figure 10 shows the J / V curve of the perovskite solar cell (i.e., device 9) prepared using compound Al-24-1 provided by the present invention as the hole transport material;

[0094] Figure 11 shows the J / V curve of the perovskite solar cell (i.e., device 10) prepared using compound Al-25-1 provided by the present invention as the hole transport material;

[0095] Figure 12 shows the J / V curve of the perovskite solar cell (i.e., device 11) prepared using compound Al-5-1 provided by the present invention as a hole transport material.

[0096] Figure 13 shows the J / V curve of the perovskite solar cell (i.e., device 12) prepared using compound Al-6-1 provided by the present invention as a hole transport material;

[0097] Figure 14 shows the J / V curve of the perovskite solar cell (i.e., device 13) prepared using compound Al-27-1 provided by the present invention as the hole transport material;

[0098] Figure 15 shows the J / V curve of the perovskite solar cell (i.e., device 14) prepared using compound Al-28-1 provided by the present invention as the hole transport material;

[0099] Figure 16 shows the J / V curve of the perovskite solar cell (i.e., device 15) prepared using compound A2-22-2 provided by the present invention as the hole transport material;

[0100] Figure 17 shows the J / V curve of the perovskite solar cell (i.e., device 16) prepared using compound A2-22-4 provided by the present invention as the hole transport material;

[0101] Figure 18 shows the J / V curve of the perovskite solar cell (i.e., device 17) prepared using compound A2-23-4 provided by the present invention as the hole transport material;

[0102] Figure 19 shows the J / V curve of the perovskite solar cell (i.e., device 18) prepared using compound A2-23-5 provided by the present invention as the hole transport material;

[0103] Figure 20 shows the J / V curve of the perovskite solar cell (i.e., device 19) prepared using compound A2-31-2 provided by the present invention as the hole transport material;

[0104] Figure 21 shows the J / V curve of the perovskite solar cell (i.e., device 20) prepared using compound A2-32-4 provided by the present invention as the hole transport material;

[0105] Figure 22 shows the J / V curve of the perovskite solar cell (i.e., device 21) prepared using compound A2-6-1 provided by the present invention as a hole transport material;

[0106] Figure 23 shows the J / V curve of the perovskite solar cell (i.e., device 22) prepared using compound A2-20-1 provided by the present invention as the hole transport material;

[0107] Figure 24 shows the J / V curve of the perovskite solar cell (i.e., device 23) prepared using compound A2-18-1 provided by the present invention as the hole transport material;

[0108] Figure 25 shows the J / V curve of the perovskite solar cell (i.e., device 24) prepared using compound A2-14-1 provided in this invention as the hole transport material;

[0109] Figure 26 shows the J / V curve of the perovskite solar cell (i.e., device 25) prepared using compound A2-15-1 provided by the present invention as the hole transport material;

[0110] Figure 27 shows the J / V curve of the perovskite solar cell (i.e., device 26) prepared using compound Al-18-1 provided by the present invention as the hole transport material;

[0111] Figure 28 shows the J / V curve of the perovskite solar cell (i.e., device 27) prepared using compound Al-19-1 provided by the present invention as a hole transport material;

[0112] Figure 29 shows the J / V curve of the perovskite solar cell (i.e., device 28) prepared using compound A3-13-1 provided by the present invention as the hole transport material;

[0113] Figure 30 shows the J / V curve of the perovskite solar cell (i.e., device 29) prepared using compound A5-13-1 provided by the present invention as the hole transport material;

[0114] Figure 31 shows the J / V curve of the perovskite solar cell (i.e., device 30) prepared using compound A5-18-1 provided by the present invention as the hole transport material;

[0115] Figure 32 shows the J / V curve of a perovskite solar cell (i.e., reference device 1) prepared using the commercially available hole transport material 2PACz. Detailed Implementation

[0116] To further illustrate the present invention, the compounds, organic hole transport layer materials, and perovskite solar cells provided by the present invention are described in detail below with reference to embodiments.

[0117] Example 1

[0118] The reaction formula is as follows:

[0119] Synthesis of intermediate 1-2: Under an argon atmosphere, 1-1 (2.1 g), 4-bromoanisole (1.6 g), tri-tert-butylphosphine tetrafluoroborate (0.1 g), tris(dibenzylacetone)dipalladium (0.7 g), and sodium tert-butoxide (1.1 g) were weighed sequentially into a 50 mL Schlenk flask. 20 mL of anhydrous toluene was added to the flask, the temperature was raised to 100 °C, and the reaction was stirred for 12 hours. After cooling to room temperature, the reaction solution was extracted with dichloromethane. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 1-2 (2.4 g, yield: 82%).

[0120] Elemental analysis structure (C 27 H 19 N): Theoretical values ​​C, 86.84; H, 5.13; N, 3.75; Test values ​​C, 86.79; H, 5.11; N, 3.72.

[0121] ESI-MS analysis: Theoretical value 373.1; Experimental value 374.2 ([M+H]) + ).

[0122] Synthesis of intermediates 1-3: Under an argon atmosphere, 1-2 (1.8 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask, the temperature was lowered to 0 °C, 1.4 mL of phosphorus oxychloride was added, and the mixture was stirred for 0.5 h. The temperature was then raised to 70 °C, and the mixture was stirred for another 2 h. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 1-3 (1.5 g, yield: 80%).

[0123] Elemental analysis structure (C 28 H 19 NO2): Theoretical values: C, 83.77; H, 4.77; N, 3.49; Test values: C, 83.74; H, 4.75; N, 3.50.

[0124] ESI-MS analysis: Theoretical value 401.1; Experimental value 402.3 ([M+H]) + ).

[0125] Synthesis of intermediates 1-4: Under an argon atmosphere, intermediate 1-3 (1.6 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the mixture was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 1-3 (1.1 g, yield: 70%).

[0126] Elemental analysis structure (C 34 H 29 N2O4P): Theoretical values: C, 72.85; H, 5.21; N, 5.00; Test values: C, 72.82; H, 5.20; N, 5.03.

[0127] ESI-MS analysis: Theoretical value 560.2; Experimental value 561.3 ([M+H]) + ).

[0128] Synthesis of A2-39-1: Under an argon atmosphere, intermediate 1-4 (1.1 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A2-39-1 (0.4 g, yield: 44%).

[0129] Elemental analysis structure (C 30 H 21 N2O4P): Theoretical values: C, 71.43; H, 4.20; N, 5.55; Test values: C, 71.41; H, 4.22; N, 5.53.

[0130] ESI-MS analysis: Theoretical value 504.1; Experimental value 502.9 ([MH]) - ).

[0131] Example 2

[0132] The reaction formula is as follows:

[0133] Synthesis of intermediate 2-2: Under an argon atmosphere, 2-1 (2.4 g), 4-bromoanisole (1.6 g), tri-tert-butylphosphine tetrafluoroborate (0.1 g), tris(dibenzylacetone)dipalladium (0.7 g), and sodium tert-butoxide (1.1 g) were weighed sequentially into a 50 mL Schlenk flask. 20 mL of anhydrous toluene was added to the flask, the temperature was raised to 100 °C, and the reaction was stirred for 12 hours. After cooling to room temperature, the reaction solution was extracted with dichloromethane. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 2-1 (2.6 g, yield: 80%).

[0134] Elemental analysis structure (C 27 H 19 NOS): Theoretical values: C, 79.97; H, 4.72; N, 3.45; S, 7.91; Test values: C, 79.93; H, 4.71; N, 3.47; S, 7.90.

[0135] ESI-MS analysis: Theoretical value 405.5; Experimental value 406.3 ([M+H]) + ).

[0136] Synthesis of intermediate 2-3: Under an argon atmosphere, 2-2 (2.0 g) was weighed into a 50 mL Schlenk flask, followed by 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 h, then heated to 70 °C and stirred for another 2 h. After cooling to room temperature, the pH of the reaction mixture was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 2-3 (1.7 g, yield: 80%).

[0137] Elemental analysis structure (C 28 H 19 NO2S): Theoretical values: C, 77.58; H, 4.42; N, 3.23; O, 7.38; S, 7.40; Test values: C, 77.57; H, 4.40; N, 3.25; S, 7.41.

[0138] ESI-MS analysis: Theoretical value 433.1; Experimental value 434.2 ([M+H]) + ).

[0139] Synthesis of intermediate 2-4: Under an argon atmosphere, intermediate 2-3 (1.7 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the reaction was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the reaction was stirred for another 4 h. After cooling to room temperature, the reaction solution was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 2-4 (1.5 g, yield: 65%).

[0140] Elemental analysis structure (C 34 H 29 N2O4PS): Theoretical values: C, 68.91; H, 4.93; N, 4.73; O, 10.80; P, 5.23; S, 5.41; Test values: C, 68.92; H, 4.91; N, 4.72; S, 5.43.

[0141] MALDI-TOF-MS analysis: Theoretical value 592.2; Experimental value 592.3 ([M] + ).

[0142] Synthesis of A2-38-1: Under an argon atmosphere, intermediate 2-4 (1.2 g) was weighed into a 50 mL Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A2-38-1 (0.4 g, yield: 40%).

[0143] Elemental analysis structure (C 30 H 21 N2O4PS): Theoretical values: C, 67.16; H, 3.95; N, 5.22; S, 5.98; Test values: C, 67.18; H, 3.93; N, 5.21; S, 5.97.

[0144] ESI-MS analysis: Theoretical value 536.1; Experimental value 535.0 ([MH]) - ).

[0145] Example 3

[0146] The reaction formula is as follows:

[0147] Synthesis of intermediate 3-2: Under an argon atmosphere, 3-1 (1.4 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask, the temperature was lowered to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then the temperature was raised to 70 °C, and the mixture was stirred for another 2 hours. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with sodium hydroxide aqueous solution. The organic phase was separated and washed three times each with distilled water and sodium chloride aqueous solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 3-2 (1.3 g, yield: 84%).

[0148] Elemental analysis structure (C 19 H 11 NOS): Theoretical values: C, 75.73; H, 3.68; N, 4.65; S, 10.64; Test values: C, 75.71; H, 3.67; N, 4.64; S, 10.63.

[0149] ESI-MS analysis: Theoretical value 301.3; Experimental value 302.3 ([M+H]) + ).

[0150] Synthesis of intermediate 3-3: Under an argon atmosphere, intermediate 3-2 (1.2 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask, and the mixture was heated to 70 °C and stirred for 0.5 h. Then, 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 3-3 (1.4 g, yield: 78%).

[0151] Elemental analysis structure (C 25 H 21 N2O3PS): Theoretical values: C, 65.21; H, 4.60; N, 6.08; S, 6.96; Test values: C, 65.24; H, 4.61; N, 6.07; S, 6.94.

[0152] ESI-MS analysis: Theoretical value 460.5; Experimental value 461.6 ([M+H]) + ).

[0153] Synthesis of A1-13-1: Under an argon atmosphere, intermediate 3-3 (0.9 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A1-13-1 (0.4 g, yield: 50%).

[0154] Elemental analysis structure (C 21 H 13 N2O3PS): Theoretical values: C, 62.37; H, 3.24; N, 6.93; S, 7.93; Test values: C, 62.39; H, 3.25; N, 6.94; S, 7.94.

[0155] ESI-MS analysis: Theoretical value 404.4; Experimental value 403.3 ([MH]) - ).

[0156] Example 4

[0157] The reaction formula is as follows:

[0158] Synthesis of intermediate 4-2: Under an argon atmosphere, 1.2 g of 4-1 was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask, the temperature was lowered to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then the temperature was raised to 70 °C, and the mixture was stirred for another 2 hours. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 4-2 (1.1 g, yield: 83%).

[0159] Elemental analysis structure (C 19 H 11 NO): Theoretical values ​​C, 84.74; H, 4.12; N, 5.20; Test values ​​C, 84.76; H, 4.13; N, 5.21.

[0160] ESI-MS analysis: Theoretical value 269.3; Experimental value 270.4 ([M+H]) + ).

[0161] Synthesis of intermediate 4-3: Under an argon atmosphere, intermediate 4-2 (1.0 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the mixture was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 4-3 (1.3 g, yield: 82%).

[0162] Elemental analysis structure (C 25 H 21 N2O3P): Theoretical values: C, 70.09; H, 4.94; N, 6.54; Measured values: C, 70.11; H, 4.95; N, 6.55.

[0163] ESI-MS analysis: Theoretical value 428.4; Experimental value 429.6 ([M+H]) + ).

[0164] Synthesis of A1-14-1: Under an argon atmosphere, intermediate 4-3 (0.8 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A1-14-1 (0.4 g, yield: 54%).

[0165] Elemental analysis structure (C 21 H 13 N2O3P): Theoretical values: C, 67.75; H, 3.52; N, 7.52; Test values: C, 67.77; H, 3.53; N, 7.53.

[0166] ESI-MS analysis: Theoretical value 372.3; Experimental value 371.2 ([MH]) - ).

[0167] Example 5

[0168] The reaction formula is as follows:

[0169] Synthesis of intermediate 5-2: Under an argon atmosphere, 5-1 (1.4 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask, the temperature was lowered to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then the temperature was raised to 70 °C, and the mixture was stirred for another 2 hours. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with sodium hydroxide aqueous solution. The organic phase was separated and washed three times each with distilled water and sodium chloride aqueous solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 5-2 (1.2 g, yield: 80%).

[0170] Elemental analysis structure (C 23 H 13 NO): Theoretical values ​​C, 86.50; H, 4.10; N, 4.39; Test values ​​C, 86.51; H, 4.11; N, 4.38.

[0171] ESI-MS analysis: Theoretical value 319.4; Experimental value 320.4 ([M+H]) + ).

[0172] Synthesis of intermediate 5-3: Under an argon atmosphere, intermediate 5-2 (1.3 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask, and the mixture was heated to 70 °C and stirred for 0.5 h. Then, 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 5-3 (1.5 g, yield: 77%).

[0173] Elemental analysis structure (C 29 H 23 N2O3P): Theoretical values: C, 72.80; H, 4.85; N, 5.85; Test values: C, 72.82; H, 4.86; N, 5.86.

[0174] ESI-MS analysis: Theoretical value 478.5; Experimental value 479.6 ([M+H]) + ).

[0175] Synthesis of A1-9-1: Under an argon atmosphere, intermediate 5-3 (1.0 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A1-9-1 (0.4 g, yield: 46%).

[0176] Elemental analysis structure (C 25 H 15 N2O3P): Theoretical values: C, 71.09; H, 3.58; N, 6.63; Test values: C, 71.11; H, 3.59; N, 6.64.

[0177] ESI-MS analysis: Theoretical value 422.4; Experimental value 421.2 ([MH]) - ).

[0178] Example 6

[0179] The reaction formula is as follows:

[0180] Synthesis of intermediate 6-2: Under an argon atmosphere, 1.6 g of 6-1 was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask, the temperature was lowered to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then the temperature was raised to 70 °C, and the reaction was stirred for another 2 hours. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 6-2 (1.3 g, yield: 75%).

[0181] Elemental analysis structure (C 22 H 13 NS): Theoretical values ​​C, 81.70; H, 4.05; N, 4.33; S, 9.91; Test values ​​C, 81.73; H, 4.06; N, 4.34; S, 9.92.

[0182] ESI-MS analysis: Theoretical value 323.4; Experimental value 324.4 ([M+H]) + ).

[0183] Synthesis of intermediate 6-3: Under an argon atmosphere, intermediate 6-2 (1.4 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The mixture was then heated to 70 °C and stirred for 0.5 h. 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 6-3 (1.4 g, yield: 69%).

[0184] Elemental analysis structure (C 29 H 23N2O3PS): Theoretical values: C, 68.22; H, 4.54; N, 5.49; S, 6.28; Test values: C, 68.24; H, 4.55; N, 5.50; S, 6.29.

[0185] ESI-MS analysis: Theoretical value 510.5; Experimental value 511.5 ([M+H]) + ).

[0186] Synthesis of A1-8-1: Under an argon atmosphere, intermediate 6-3 (1.0 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A1-8-1 (0.5 g, yield: 56%).

[0187] Elemental analysis structure (C 25 H 15 N2O3PS): Theoretical values: C, 66.08; H, 3.33; N, 6.16; S, 7.05; Test values: C, 66.10; H, 3.34; N, 6.17; S, 7.06.

[0188] ESI-MS analysis: Theoretical value 454.4; Experimental value 453.4 ([MH]) - ).

[0189] Example 7

[0190] The reaction formula is as follows:

[0191] Synthesis of intermediate 7-2: Under an argon atmosphere, 2.0 g of 7-1 was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask, the temperature was lowered to 0 °C, 1.4 mL of phosphorus oxychloride was added, and the mixture was stirred for 0.5 hours. Then the temperature was raised to 70 °C, and the mixture was stirred for another 2 hours. After cooling to room temperature, the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 7-2 (1.7 g, yield: 80%).

[0192] Elemental analysis structure (C 22 H 16 BrNOS): Theoretical values: C, 62.57; H, 3.82; N, 3.32; S, 7.59; Test values: C, 62.58; H, 3.83; N, 3.33; S, 7.60.

[0193] ESI-MS analysis: Theoretical value 422.3; Experimental value 423.4 ([M+H]) + ).

[0194] Synthesis of intermediate 7-3: Under an argon atmosphere, intermediate 7-2 (1.7 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The mixture was then heated to 70 °C and stirred for 0.5 h. 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 7-3 (1.7 g, yield: 73%).

[0195] Elemental analysis structure (C 28 H 26 BrN2O3PS): Theoretical values: C, 57.84; H, 4.51; N, 4.82; S, 5.51; Test values: C, 57.86; H, 4.52; N, 4.83; S, 5.52.

[0196] MALDI-TOF-MS analysis: Theoretical value 581.4; Experimental value 581.4 ([M] + ).

[0197] Synthesis of A1-2-7: Under an argon atmosphere, intermediate 7-3 (1.2 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A1-2-7 (0.6 g, yield: 55%).

[0198] Elemental analysis structure (C 24 H 18 BrN2O3PS): Theoretical values: C, 54.87; H, 3.45; N, 5.33; S, 6.10; Test values: C, 54.89; H, 3.46; N, 5.34; S, 6.11.

[0199] MALDI-TOF-MS analysis: Theoretical value 525.3; Experimental value 524.2 ([MH]) - ).

[0200] Example 8

[0201] The reaction formula is as follows:

[0202] Synthesis of intermediate 8-2: Under an argon atmosphere, 2.0 g of 8-1 was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask, the temperature was lowered to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then the temperature was raised to 70 °C, and the mixture was stirred for another 2 hours. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 8-2 (1.7 g, yield: 80%).

[0203] Elemental analysis structure (C 25 H 22 BrNO): Theoretical values: C, 69.45; H, 5.13; N, 3.24; Test values: C, 69.47; H, 5.14; N, 3.25.

[0204] ESI-MS analysis: Theoretical value 432.3; Experimental value 433.3 ([M+H]) + ).

[0205] Synthesis of intermediate 8-3: Under an argon atmosphere, intermediate 8-2 (1.7 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the mixture was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 8-3 (1.7 g, yield: 73%).

[0206] Elemental analysis structure (C 31 H 32 BrN2O3P): Theoretical values: C, 62.95; H, 5.45; N, 4.74; Test values: C, 62.97; H, 5.46; N, 4.75.

[0207] MALDI-TOF-MS analysis: Theoretical value 591.5; Experimental value 591.6 ([M] + ).

[0208] Synthesis of A1-4-6: Under an argon atmosphere, intermediate 8-3 (1.2 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A1-4-6 (0.5 g, yield: 46%).

[0209] Elemental analysis structure (C 27 H 24 BrN2O3P): Theoretical values: C, 60.57; H, 4.52; N, 5.23; Test values: C, 60.59; H, 4.53; N, 5.25.

[0210] MALDI-TOF-MS analysis: Theoretical value 535.3; Experimental value 534.3 ([MH]) - ).

[0211] Example 9

[0212] The reaction formula is as follows:

[0213] Synthesis of intermediate 9-2: Under an argon atmosphere, 9-1 (1.8 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask, the temperature was lowered to 0 °C, 1.4 mL of phosphorus oxychloride was added, and the mixture was stirred for 0.5 h. The temperature was then raised to 70 °C, and the mixture was stirred for another 2 h. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with sodium hydroxide aqueous solution. The organic phase was separated and washed three times each with distilled water and sodium chloride aqueous solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 9-2 (1.7 g, yield: 88%).

[0214] Elemental analysis structure (C 25 H 21 NOS): Theoretical values: C, 78.30; H, 5.52; N, 3.65; S, 8.36; Test values: C, 78.32; H, 5.53; N, 3.66; S, 8.37.

[0215] ESI-MS analysis: Theoretical value 383.5; Experimental value 384.5 ([M+H]) + ).

[0216] Synthesis of intermediate 9-3: Under an argon atmosphere, intermediate 9-2 (1.7 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask, and the mixture was heated to 70 °C and stirred for 0.5 h. Then, 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 9-3 (1.7 g, yield: 71%).

[0217] Elemental analysis structure (C 31 H 31 N2O3PS): Theoretical values: C, 68.62; H, 5.76; N, 5.16; S, 5.91; Test values: C, 68.64; H, 5.78; N, 5.17; S, 5.93.

[0218] MALDI-TOF-MS analysis: Theoretical value 542.6; Experimental value 542.5 ([M] + ).

[0219] Synthesis of A1-24-1: Under an argon atmosphere, intermediate 9-3 (1.1 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A1-24-1 (0.5 g, yield: 50%).

[0220] Elemental analysis structure (C 27 H 23 N2O3PS): Theoretical values: C, 66.66; H, 4.77; N, 5.76; S, 6.59; Test values: C, 66.68; H, 4.78; N, 5.77; S, 6.60.

[0221] ESI-MS analysis: Theoretical value 486.5; Experimental value 485.4 ([MH]) - ).

[0222] Example 10

[0223] The reaction formula is as follows:

[0224] Synthesis of intermediate 10⁻²: Under an argon atmosphere, 10⁻¹ (1.4 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 h, then heated to 70 °C and stirred for another 2 h. After cooling to room temperature, the pH of the reaction mixture was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 10⁻² (1.2 g, yield: 80%).

[0225] Elemental analysis structure (C 25 H 21 NO2): Theoretical values: C, 81.72; H, 5.76; N, 3.81; Test values: C, 81.74; H, 5.77; N, 3.82.

[0226] ESI-MS analysis: Theoretical value 367.4; Experimental value 368.5 ([M+H]) + ).

[0227] Synthesis of intermediate 10⁻³: Under an argon atmosphere, intermediate 10⁻² (1.5 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added sequentially to the flask. The mixture was then heated to 70 °C and stirred for 0.5 h. 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with an aqueous sodium chloride solution and dried over anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 10⁻³ (1.2 g, yield: 74%).

[0228] Elemental analysis structure (C 31 H 31 N2O4P): Theoretical values: C, 70.71; H, 5.93; N, 5.32; Test values: C, 70.73; H, 5.94; N, 5.33.

[0229] MALDI-TOF-MS analysis: Theoretical value 526.6; Experimental value 526.7 ([M] + ).

[0230] Synthesis of A1-25-1: Under an argon atmosphere, 10-3 (1.0 g) of intermediate was weighed into a 50 mL Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A1-25-1 (0.5 g, yield: 55%).

[0231] Elemental analysis structure (C 27 H 23 N2O4P): Theoretical values: C, 68.93; H, 4.93; N, 5.95; Test values: C, 68.95; H, 4.94; N, 5.96.

[0232] ESI-MS analysis: Theoretical value 470.5; Experimental value 469.4 ([MH]) - ).

[0233] Example 11

[0234] The reaction formula is as follows:

[0235] Synthesis of intermediate 11-2: Under an argon atmosphere, 11-1 (1.4 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then heated to 70 °C and stirred for another 2 hours. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 11-2 (1.2 g, yield: 78%).

[0236] Elemental analysis structure (C 19 H 11 NO3): Theoretical values: C, 75.74; H, 3.68; N, 4.65; Test values: C, 75.76; H, 3.69; N, 4.66.

[0237] ESI-MS analysis: Theoretical value 301.3; Experimental value 302.3 ([M+H]) + ).

[0238] Synthesis of intermediate 11-3: Under an argon atmosphere, intermediate 11-2 (1.2 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the mixture was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 11-3 (1.2 g, yield: 65%).

[0239] Elemental analysis structure (C 25 H 21 N2O5P): Theoretical values: C, 65.22; H, 4.60; N, 6.08; Test values: C, 65.24; H, 4.61; N, 6.09.

[0240] ESI-MS analysis: Theoretical value 460.4; Experimental value 461.4 ([M+H]) + ).

[0241] Synthesis of A1-5-1: Under an argon atmosphere, intermediate 11-3 (0.9 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A1-5-1 (0.4 g, yield: 51%).

[0242] Elemental analysis structure (C 21 H 13 N2O5P): Theoretical values: C, 62.38; H, 3.24; N, 6.93; Test values: C, 62.40; H, 3.25; N, 6.94.

[0243] ESI-MS analysis: Theoretical value 404.3; Experimental value 403.2 ([MH]) - ).

[0244] Example 12

[0245] The reaction formula is as follows:

[0246] Synthesis of intermediate 12-2: Under an argon atmosphere, 12-1 (1.5 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then heated to 70 °C and stirred for another 2 hours. After cooling to room temperature, the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 12-2 (1.2 g, yield: 74%).

[0247] Elemental analysis structure (C 19 H 11 NOS2): Theoretical values: C, 68.44; H, 3.33; N, 4.20; S, 19.23; Test values: C, 68.46; H, 3.34; N, 4.21; S, 19.25.

[0248] ESI-MS analysis: Theoretical value 333.4; Experimental value 334.4 ([M+H]) + ).

[0249] Synthesis of intermediate 12-3: Under an argon atmosphere, intermediate 12-2 (1.3 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the mixture was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 12-3 (1.3 g, yield: 68%).

[0250] Elemental analysis structure (C 25 H 21 N2O3PS2): Theoretical values: C, 60.96; H, 4.30; N, 5.69; S, 13.02; Test values: C, 60.98; H, 4.31; N, 5.70; S, 13.03.

[0251] ESI-MS analysis: Theoretical value 492.5; Experimental value 493.6 ([M+H]) + ).

[0252] Synthesis of A1-6-1: Under an argon atmosphere, intermediate 12-3 (1.0 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A1-6-1 (0.4 g, yield: 46%).

[0253] Elemental analysis structure (C 21 H 13 N2O3PS2): Theoretical values: C, 57.79; H, 3.00; N, 6.42; S, 14.69; Test values: C, 57.81; H, 3.01; N, 6.43; S, 14.70.

[0254] ESI-MS analysis: Theoretical value 436.4; Experimental value 435.4 ([MH]) - ).

[0255] Example 13

[0256] The reaction formula is as follows:

[0257] Synthesis of intermediate 13-2: Under an argon atmosphere, 13-1 (1.4 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then heated to 70 °C and stirred for another 2 hours. After cooling to room temperature, the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 13-2 (1.2 g, yield: 78%).

[0258] Elemental analysis structure (C 19 H9NO4): Theoretical values: C, 72.38; H, 2.88; N, 4.44; Test values: C, 72.40; H, 2.89; N, 4.45.

[0259] ESI-MS analysis: Theoretical value 315.2; Experimental value 316.3 ([M+H]) + ).

[0260] Synthesis of intermediate 13-3: Under an argon atmosphere, intermediate 13-2 (1.3 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The mixture was then heated to 70 °C and stirred for 0.5 h. 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 13-3 (1.3 g, yield: 66%).

[0261] Elemental analysis structure (C 25 H 19 N2O6P): Theoretical values: C, 63.29; H, 4.04; N, 5.91; Test values: C, 63.31; H, 4.05; N, 5.92.

[0262] ESI-MS analysis: Theoretical value 474.4; Experimental value 475.5 ([M+H]) + ).

[0263] Synthesis of A1-27-1: Under an argon atmosphere, intermediate 13-3 (0.8 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A1-27-1 (0.4 g, yield: 59%).

[0264] Elemental analysis structure (C 21 H 11 N2O6P): Theoretical values: C, 60.30; H, 2.65; N, 6.70; Test values: C, 60.32; H, 2.66; N, 6.71.

[0265] ESI-MS analysis: Theoretical value 418.3; Experimental value 417.3 ([MH]) - ).

[0266] Example 14

[0267] The reaction formula is as follows:

[0268] Synthesis of intermediate 14-2: Under an argon atmosphere, 14-1 (1.7 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask, the temperature was lowered to 0 °C, 1.4 mL of phosphorus oxychloride was added, and the mixture was stirred for 0.5 h. The temperature was then raised to 70 °C, and the mixture was stirred for another 2 h. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 14-2 (1.3 g, yield: 71%).

[0269] Elemental analysis structure (C 19 H9NOS3): Theoretical values: C, 62.79; H, 2.50; N, 3.85; S, 26.46; Test values: C, 62.81; H, 2.51; N, 3.86; S, 26.48.

[0270] ESI-MS analysis: Theoretical value 363.4; Experimental value 364.4 ([M+H]) + ).

[0271] Synthesis of intermediate 14-3: Under an argon atmosphere, intermediate 14-2 (1.5 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The mixture was then heated to 70 °C and stirred for 0.5 h. 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 14-3 (1.5 g, yield: 70%).

[0272] Elemental analysis structure (C 25 H 19 N2O3PS3): Theoretical values: C, 57.46; H, 3.66; N, 5.36; S, 18.40; Test values: C, 57.49; H, 3.67; N, 5.38; S, 18.42.

[0273] MALDI-TOF-MS analysis: Theoretical value 522.5; Experimental value 523.5 ([M+H]) + ).

[0274] Synthesis of A1-28-1: Under an argon atmosphere, intermediate 14-3 (1.0 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A1-28-1 (0.4 g, yield: 45%).

[0275] Elemental analysis structure (C 21 H 11 N2O3PS3): Theoretical values: C, 54.07; H, 2.38; N, 6.01; S, 20.62; Test values: C, 54.09; H, 2.39; N, 6.02; S, 20.64.

[0276] ESI-MS analysis: Theoretical value 466.4; Experimental value 465.4 ([MH]) - ).

[0277] Example 15

[0278] The reaction formula is as follows:

[0279] Synthesis of intermediate 15-2: Under an argon atmosphere, 15-1 (1.4 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then heated to 70 °C and stirred for another 2 hours. After cooling to room temperature, the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 15-2 (1.4 g, yield: 91%).

[0280] Elemental analysis structure (C 20 H 15 NO2): Theoretical values: C, 79.72; H, 5.02; N, 4.65; Test values: C, 79.74; H, 5.03; N, 4.66.

[0281] ESI-MS analysis: Theoretical value 301.3; Experimental value 302.4 ([M+H]) + ).

[0282] Synthesis of intermediate 15-3: Under an argon atmosphere, intermediate 15-2 (1.2 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The mixture was then heated to 70 °C and stirred for 0.5 h. 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 15-3 (1.2 g, yield: 65%).

[0283] Elemental analysis structure (C 26 H 25 N2O4P): Theoretical values: C, 67.82; H, 5.47; N, 6.08; Measured values: C, 67.84; H, 5.48; N, 6.09.

[0284] ESI-MS analysis: Theoretical value 460.4; Experimental value 461.4 ([M+H]) + ).

[0285] Synthesis of A2-22-2: Under an argon atmosphere, intermediate 15-3 (0.9 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A2-22-2 (0.4 g, yield: 50%).

[0286] Elemental analysis structure (C 22 H 17 N2O4P): Theoretical values: C, 65.35; H, 4.24; N, 6.93; Test values: C, 65.37; H, 4.25; N, 6.94.

[0287] ESI-MS analysis: Theoretical value 404.3; Experimental value 405.3 ([MH]) - ).

[0288] Example 16

[0289] The reaction formula is as follows:

[0290] Synthesis of intermediate 16-2: Under an argon atmosphere, 16-1 (1.4 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 h, then heated to 70 °C and stirred for another 2 h. After cooling to room temperature, the pH of the reaction mixture was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 16-2 (1.2 g, yield: 78%).

[0291] Elemental analysis structure (C 20 H 15 NO3): Theoretical values: C, 75.70; H, 4.76; N, 4.41; Test values: C, 75.73; H, 4.77; N, 4.42.

[0292] ESI-MS analysis: Theoretical value 317.3; Experimental value 318.3 ([M+H]) + ).

[0293] Synthesis of intermediate 16-3: Under an argon atmosphere, intermediate 16-2 (1.7 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The mixture was then heated to 70 °C and stirred for 0.5 h. 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 16-3 (1.3 g, yield: 67%).

[0294] Elemental analysis structure (C 26 H 25 N2O5P): Theoretical values: C, 65.54; H, 5.29; N, 5.88; Measured values: C, 65.57; H, 5.30; N, 5.89.

[0295] ESI-MS analysis: Theoretical value 476.4; Experimental value 477.4 ([M+H]) + ).

[0296] Synthesis of A2-22-4: Under an argon atmosphere, intermediate 16-3 (1.0 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 3 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A2-22-4 (0.4 g, yield: 46%).

[0297] Elemental analysis structure (C 22 H 17 N2O5P): Theoretical values: C, 62.86; H, 4.08; N, 6.66; Test values: C, 62.89; H, 4.09; N, 6.67.

[0298] ESI-MS analysis: Theoretical value 420.3; Experimental value 419.3 ([MH]) - ).

[0299] Example 17

[0300] The reaction formula is as follows:

[0301] Synthesis of intermediate 17-2: Under an argon atmosphere, 17-1 (1.5 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then heated to 70 °C and stirred for another 2 hours. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 17-2 (1.2 g, yield: 73%).

[0302] Elemental analysis structure (C 20 H 15 NO2S): Theoretical values: C, 72.05; H, 4.54; N, 4.20; S, 9.62; Test values: C, 72.07; H, 4.55; N, 4.21; S, 9.63.

[0303] ESI-MS analysis: Theoretical value 333.4; Experimental value 334.4 ([M+H]) + ).

[0304] Synthesis of intermediate 17-3: Under an argon atmosphere, intermediate 17-2 (1.3 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the reaction was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the reaction was stirred for another 4 h. After cooling to room temperature, the reaction solution was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 17-3 (1.3 g, yield: 68%).

[0305] Elemental analysis structure (C 26 H 25 N2O4PS): Theoretical values: C, 63.40; H, 5.12; N, 5.69; S, 6.51; Test values: C, 63.43; H, 5.13; N, 5.70; S, 6.52.

[0306] ESI-MS analysis: Theoretical value 492.5; Experimental value 493.5 ([M+H]) + ).

[0307] Synthesis of A2-23-4: Under an argon atmosphere, intermediate 17-3 (1.0 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A2-23-4 (0.5 g, yield: 57%).

[0308] Elemental analysis structure (C 22 H 17 N2O4PS): Theoretical values: C, 60.55; H, 3.93; N, 6.42; S, 7.35; Test values: C, 60.57; H, 3.94; N, 6.43; S, 7.36.

[0309] ESI-MS analysis: Theoretical value 436.4; Experimental value 435.3 ([MH]) - ).

[0310] Example 18

[0311] The reaction formula is as follows:

[0312] Synthesis of intermediate 18-2: Under an argon atmosphere, 18-1 (1.6 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then heated to 70 °C and stirred for another 2 hours. After cooling to room temperature, the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 18-2 (1.2 g, yield: 69%).

[0313] Elemental analysis structure (C 20 H 15 NOS2): Theoretical values: C, 68.74; H, 4.33; N, 4.01; S, 18.35; Test values: C, 68.76; H, 4.34; N, 4.02; S, 18.36.

[0314] ESI-MS analysis: Theoretical value 349.4; Experimental value 350.5 ([M+H]) + ).

[0315] Synthesis of intermediate 18-3: Under an argon atmosphere, intermediate 18-2 (1.4 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the reaction was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the reaction was stirred for another 4 h. After cooling to room temperature, the reaction solution was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 18-3 (1.4 g, yield: 70%).

[0316] Elemental analysis structure (C 26 H 25 N2O3PS2): Theoretical values: C, 61.40; H, 4.95; N, 5.51; S, 12.61; Test values: C, 61.43; H, 4.96; N, 5.52; S, 12.63.

[0317] MALDI-TOF-MS analysis: Theoretical value 508.5; Experimental value 508.4 ([M] + ).

[0318] Synthesis of A2-23-5: Under an argon atmosphere, intermediate 18-3 (1 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A2-23-5 (0.4 g, yield: 46%).

[0319] Elemental analysis structure (C 22 H 17 N2O3PS2): Theoretical values: C, 58.40; H, 3.79; N, 6.19; S, 14.17; Test values: C, 58.43; H, 3.80; N, 6.20; S, 14.18.

[0320] ESI-MS analysis: Theoretical value 452.4; Experimental value 451.4 ([MH]) - ).

[0321] Example 19

[0322] The reaction formula is as follows:

[0323] Synthesis of intermediate 19-2: Under an argon atmosphere, 19-1 (1.9 g), 4-bromoanisole (1.8 g), tri-tert-butylphosphine tetrafluoroborate (0.1 g), tris(dibenzylacetone)dipalladium (0.7 g), and sodium tert-butoxide (1.1 g) were weighed sequentially into a 50 mL Schlenk flask. 20 mL of anhydrous toluene was added to the flask, the temperature was raised to 100 °C, and the reaction was stirred for 12 hours. After cooling to room temperature, the reaction solution was extracted with dichloromethane. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 19-2 (2.0 g, yield: 70%).

[0324] Elemental analysis structure (C 23 H 17 NS2): Theoretical values ​​C, 74.36; H, 4.61; N, 3.77; S, 17.26; Test values ​​C, 74.38; H, 4.62; N, 3.78; S, 17.27.

[0325] ESI-MS analysis: Theoretical value 371.5; Experimental value 372.5 ([M+H]) + ).

[0326] Synthesis of intermediate 19-3: Under an argon atmosphere, 19-2 (1.9 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask, the temperature was lowered to 0 °C, 1.4 mL of phosphorus oxychloride was added, and the mixture was stirred for 0.5 h. The temperature was then raised to 70 °C, and the mixture was stirred for another 2 h. After cooling to room temperature, the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 19-3 (1.5 g, yield: 73%).

[0327] Elemental analysis structure (C 24 H 17 NOS2): Theoretical values: C, 72.15; H, 4.29; N, 3.51; S, 16.05; Test values: C, 72.18; H, 4.30; N, 3.52; S, 16.06.

[0328] ESI-MS analysis: Theoretical value 399.5; Experimental value 400.6 ([M+H]) + ).

[0329] Synthesis of intermediate 19-4: Under an argon atmosphere, intermediate 19-4 (1.6 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the reaction was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the reaction was stirred for another 4 h. After cooling to room temperature, the reaction solution was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 19-4 (1.4 g, yield: 63%).

[0330] Elemental analysis structure (C 30 H 27 N2O3PS2): Theoretical values: C, 64.50; H, 4.87; N, 5.01; S, 11.48; Test values: C, 64.53; H, 4.88; N, 5.02; S, 11.49.

[0331] MALDI-TOF-MS analysis: Theoretical value 558.6; Experimental value 559.6 ([M+H]) + ).

[0332] Synthesis of A2-31-2: Under an argon atmosphere, intermediate 19-4 (1.1 g) was weighed into a 50 mL Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying, the mixture was ultrasonically washed three times with water to obtain compound A2-31-2 (0.5 g, yield: 51%).

[0333] Elemental analysis structure (C 26 H 19 N2O3PS2): Theoretical values: C, 62.14; H, 3.81; N, 5.57; S, 12.76; Test values: C, 62.17; H, 3.82; N, 5.58; S, 12.77.

[0334] ESI-MS analysis: Theoretical value 502.5; Experimental value 501.5 ([MH]) - ).

[0335] Example 20

[0336] The reaction formula is as follows:

[0337] Synthesis of intermediate 20-2: Under an argon atmosphere, 20-1 (1.7 g), 4-bromoanisole (1.8 g), tri-tert-butylphosphine tetrafluoroborate (0.1 g), tris(dibenzylacetone)dipalladium (0.7 g), and sodium tert-butoxide (1.1 g) were weighed sequentially into a 50 mL Schlenk flask. 20 mL of anhydrous toluene was added to the flask, the temperature was raised to 100 °C, and the reaction was stirred for 12 hours. After cooling to room temperature, the reaction solution was extracted with dichloromethane. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 20-2 (2.1 g, yield: 79%).

[0338] Elemental analysis structure (C 23 H 17 NS): Theoretical values ​​C, 81.38; H, 5.05; N, 4.13; S, 9.44; Test values ​​C, 81.41; H, 5.06; N, 4.14; S, 9.45.

[0339] ESI-MS analysis: Theoretical value 339.4; Experimental value 340.4 ([M+H]) + ).

[0340] Synthesis of intermediate 20-3: Under an argon atmosphere, 20-2 (1.7 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 h, then heated to 70 °C and stirred for another 2 h. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 20-3 (1.4 g, yield: 76%).

[0341] Elemental analysis structure (C 24 H 17 NOS): Theoretical values: C, 78.45; H, 4.66; N, 3.81; S, 8.72; Test values: C, 78.48; H, 4.67; N, 3.82; S, 8.73.

[0342] ESI-MS analysis: Theoretical value 367.4; Experimental value 368.4 ([M+H]) + ).

[0343] Synthesis of intermediate 20-4: Under an argon atmosphere, intermediate 20-4 (1.5 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the reaction was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the reaction was stirred for another 4 h. After cooling to room temperature, the reaction solution was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 20-4 (1.5 g, yield: 70%).

[0344] Elemental analysis structure (C 30 H 27 N2O3PS): Theoretical values: C, 68.43; H, 5.17; N, 5.32; S, 6.09; Test values: C, 68.47; H, 5.18; N, 5.33; S, 6.10.

[0345] MALDI-TOF-MS analysis: Theoretical value 526.5; Experimental value 526.6 ([M] + ).

[0346] Synthesis of A2-32-4: Under an argon atmosphere, intermediate 20-4 (1.0 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A2-32-4 (0.5 g, yield: 56%).

[0347] Elemental analysis structure (C 26 H 19 N2O3PS): Theoretical values: C, 66.38; H, 4.07; N, 5.95; S, 6.81; Test values: C, 66.40; H, 4.08; N, 5.96; S, 6.82.

[0348] ESI-MS analysis: Theoretical value 470.4; Experimental value 469.4 ([MH]) - ).

[0349] Example 21

[0350] The reaction formula is as follows:

[0351] Synthesis of intermediate 21-2: Under an argon atmosphere, 21-1 (2.0 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 h, then heated to 70 °C and stirred for another 2 h. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 21-2 (1.5 g, yield: 70%).

[0352] Elemental analysis structure (C 31 H 20 N2O): Theoretical values: C, 85.30; H, 4.62; N, 6.42; Test values: C, 85.33; H, 4.63; N, 6.43.

[0353] ESI-MS analysis: Theoretical value 436.5; Experimental value 437.5 ([M+H]) + ).

[0354] Synthesis of intermediate 21-3: Under an argon atmosphere, intermediate 21-2 (1.7 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The mixture was then heated to 70 °C and stirred for 0.5 h. 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 21-3 (1.6 g, yield: 69%).

[0355] Elemental analysis structure (C 37 H 30 N3O3P): Theoretical values: C, 74.61; H, 5.08; N, 7.05; Test values: C, 74.64; H, 5.09; N, 7.06.

[0356] MALDI-TOF-MS analysis: Theoretical value 595.6; Experimental value 595.7 ([M] + ).

[0357] Synthesis of A2-6-1: Under an argon atmosphere, intermediate 21-3 (1.2 g) was weighed into a 50 mL Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A2-6-1 (0.6 g, yield: 55%).

[0358] Elemental analysis structure (C 33 H 22 N3O3P): Theoretical values: C, 73.46; H, 4.11; N, 7.79; Test values: C, 73.49; H, 4.12; N, 7.80.

[0359] MALDI-TOF-MS analysis: Theoretical value 539.5; Experimental value 539.7 ([MH]) - ).

[0360] Example 22

[0361] The reaction formula is as follows:

[0362] Synthesis of intermediate 22-2: Under an argon atmosphere, 22-1 (1.3 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask, the temperature was lowered to 0 °C, 1.4 mL of phosphorus oxychloride was added, and the mixture was stirred for 0.5 h. The temperature was then raised to 70 °C, and the mixture was stirred for another 2 h. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 22-2 (1.1 g, yield: 76%).

[0363] Elemental analysis structure (C 15 H9NOS2): Theoretical values: C, 63.58; H, 3.20; N, 4.94; S, 22.63; Test values: C, 63.53; H, 3.21; N, 4.96; S, 22.66.

[0364] ESI-MS analysis: Theoretical value 283.0; Experimental value 284.1 ([M+H]) + )

[0365] Synthesis of intermediate 22-3: Under an argon atmosphere, intermediate 22-2 (1.1 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The mixture was then heated to 70 °C and stirred for 0.5 h. 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 22-3 (1.1 g, yield: 64%).

[0366] Elemental analysis structure (C 21 H 19 N2O3PS2): Theoretical values: C, 57.00; H, 4.33; N, 6.33; S, 14.49; Test values: C, 57.05; H, 4.30; N, 6.35; S, 14.43.

[0367] ESI-MS analysis: Theoretical value 442.1; Experimental value 443.2 ([M+H]) + )

[0368] Synthesis of A2-20-1: Under an argon atmosphere, intermediate 22-3 (0.9 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A2-20-1 (0.4 g, yield: 52%).

[0369] Elemental analysis structure (C 17 H 11 N2O3PS2): Theoretical values: C, 52.85; H, 2.87; N, 7.25; S, 16.60; Test values: C, 52.88; H, 2.83; N, 7.27; S, 16.64.

[0370] ESI-MS analysis: Theoretical value 386.0; Experimental value 384.8 ([MH]) - )

[0371] Example 23

[0372] The reaction formula is as follows:

[0373] Synthesis of intermediate 23-2: Under an argon atmosphere, 23-1 (1.9 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 h, then heated to 70 °C and stirred for another 2 h. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 23-2 (1.5 g, yield: 73%).

[0374] Elemental analysis structure (C 23 H 16 N2OS2): Theoretical values: C, 68.97; H, 4.03; N, 6.99; S, 16.01; Test values: C, 68.92; H, 4.05; N, 6.94; S, 16.05.

[0375] ESI-MS analysis: Theoretical value 400.1; Experimental value 401.2 ([M+H]) + ).

[0376] Synthesis of intermediate 23-3: Under an argon atmosphere, intermediate 23-2 (1.6 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the mixture was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 23-3 (1.5 g, yield: 67%).

[0377] Elemental analysis structure (C 29 H 26 N3O3PS2): Theoretical values: C, 62.24; H, 4.68; N, 7.51; S, 11.46; Test values: C, 62.20; H, 4.65; N, 7.53; S, 11.49.

[0378] MALDI-TOF-MS analysis: Theoretical value 559.1; Experimental value 558.9 ([M] + ).

[0379] Synthesis of A2-18-1: Under an argon atmosphere, intermediate 23-3 (1.1 g) was weighed into a 50 mL Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A2-18-1 (0.5 g, yield: 51%).

[0380] Elemental analysis structure (C 25 H 18 N3O3PS2): Theoretical values: C, 59.63; H, 3.60; N, 8.35; S, 12.73; Test values: C, 59.58; H, 3.63; N, 8.32; S, 12.76.

[0381] ESI-MS analysis: Theoretical value 503.1; Experimental value 501.9 ([MH]) - ).

[0382] Example 24

[0383] The reaction formula is as follows:

[0384] Synthesis of intermediate 24-2: Under an argon atmosphere, 24-1 (1.8 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 h, then heated to 70 °C and stirred for another 2 h. After cooling to room temperature, the pH of the reaction mixture was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 24-2 (1.5 g, yield: 77%).

[0385] Elemental analysis structure (C 25 H 18 N2OS): Theoretical values: C, 76.12; H, 4.60; N, 7.10; S, 8.13; Test values: C, 76.08; H, 4.63; N, 7.12; S, 8.07.

[0386] ESI-MS analysis: Theoretical value 394.1; Experimental value 395.3 ([M+H]) + ).

[0387] Synthesis of intermediate 24-3: Under an argon atmosphere, intermediate 24-2 (1.6 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The mixture was then heated to 70 °C and stirred for 0.5 h. 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 24-3 (1.5 g, yield: 67%).

[0388] Elemental analysis structure (C 31 H 28 N3O3PS): Theoretical values: C, 67.26; H, 5.10; N, 7.59; S, 5.79; Test values: C, 67.31; H, 5.08; N, 7.53; S, 5.74.

[0389] ESI-MS analysis: Theoretical value 553.2; Experimental value 554.3 ([M+H]) + ).

[0390] Synthesis of A2-14-1: Under an argon atmosphere, intermediate 24-3 (1.1 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A2-14-1 (0.5 g, yield: 51%).

[0391] Elemental analysis structure (C 27 H 20 N3O3PS): Theoretical values: C, 65.18; H, 4.05; N, 8.45; S, 6.44; Test values: C, 65.13; H, 4.04; N, 8.48; S, 6.46.

[0392] ESI-MS analysis: Theoretical value 497.1; Experimental value 496.0 ([MH]) - ).

[0393] Example 25

[0394] The reaction formula is as follows:

[0395] Synthesis of intermediate 25-2: Under an argon atmosphere, 1.8 g of 25-1 was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then heated to 70 °C and stirred for another 2 hours. After cooling to room temperature, the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 25-2 (1.5 g, yield: 77%).

[0396] Elemental analysis structure (C 25 H 18 N2OS): Theoretical values: C, 76.12; H, 4.60; N, 7.10; S, 8.13; Test values: C, 76.09; H, 4.63; N, 7.15; S, 8.10.

[0397] ESI-MS analysis: Theoretical value 394.1; Experimental value 395.0 ([M+H]) + ).

[0398] Synthesis of intermediate 25-3: Under an argon atmosphere, intermediate 25-2 (1.6 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The mixture was then heated to 70 °C and stirred for 0.5 h. 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 25-3 (1.5 g, yield: 67%).

[0399] Elemental analysis structure (C 31 H 28 N3O3PS): Theoretical values: C, 67.26; H, 5.10; N, 7.59; S, 5.79; Test values: C, 67.21; H, 5.05; N, 7.63; S, 5.78.

[0400] ESI-MS analysis: Theoretical value 553.2; Experimental value 554.1 ([M+H]) + ).

[0401] Synthesis of A2-15-1: Under an argon atmosphere, intermediate 25-3 (1.1 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A2-15-1 (0.5 g, yield: 51%).

[0402] Elemental analysis structure (C 27 H 20 N3O3PS): Theoretical values: C, 65.18; H, 4.05; N, 8.45; S, 6.44; Test values: C, 65.13; H, 4.04; N, 8.47; S, 6.47.

[0403] ESI-MS analysis: Theoretical value 497.1; Experimental value 498.0 ([MH]) - ).

[0404] Example 26

[0405] The reaction formula is as follows:

[0406] Synthesis of intermediate 26-2: Under an argon atmosphere, 1.5 g of 26-1 was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask, the temperature was lowered to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then heated to 70 °C and stirred for another 2 hours. After cooling to room temperature, the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 26-2 (1.2 g, yield: 73%).

[0407] Elemental analysis structure (C 23 H 13 NO): Theoretical values ​​C, 86.50; H, 4.10; N, 4.39; Test values ​​C, 86.44; H, 4.08; N, 4.42.

[0408] ESI-MS analysis: Theoretical value 319.1; Experimental value 320.2 ([M+H]) + ).

[0409] Synthesis of intermediate 26-3: Under an argon atmosphere, intermediate 26-2 (1.3 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the reaction was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the reaction was stirred for another 4 h. After cooling to room temperature, the reaction solution was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 26-3 (1.2 g, yield: 62%).

[0410] Elemental analysis structure (C 29 H 23 N2O3P): Theoretical values: C, 72.80; H, 4.85; N, 5.85; Test values: C, 72.76; H, 4.82; N, 5.86.

[0411] ESI-MS analysis: Theoretical value 478.1; Experimental value 477.1 ([M+H]) + ).

[0412] Synthesis of A1-18-1: Under an argon atmosphere, intermediate 26-3 (1.0 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A1-18-1 (0.5 g, yield: 57%).

[0413] Elemental analysis structure (C 25 H 15 N2O3P): Theoretical values: C, 71.09; H, 3.58; N, 6.63; Test values: C, 71.04; H, 3.54; N, 6.65.

[0414] ESI-MS analysis: Theoretical value 422.1; Experimental value 420.9 ([MH]) - ).

[0415] Example 27

[0416] The reaction formula is as follows:

[0417] Synthesis of intermediate 27-2: Under an argon atmosphere, 27-1 (1.7 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask, the temperature was lowered to 0 °C, 1.4 mL of phosphorus oxychloride was added, and the mixture was stirred for 0.5 h. The temperature was then raised to 70 °C, and the mixture was stirred for another 2 h. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with sodium hydroxide aqueous solution. The organic phase was separated and washed three times each with distilled water and sodium chloride aqueous solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 27-2 (1.3 g, yield: 71%).

[0418] Elemental analysis structure (C 26 H 19 NO): Theoretical values ​​C, 86.40; H, 5.30; N, 3.88; Test values ​​C, 86.36; H, 5.33; N, 3.87.

[0419] ESI-MS analysis: Theoretical value 361.1; Experimental value 362.3 ([M+H]) + ).

[0420] Synthesis of intermediate 27-3: Under an argon atmosphere, intermediate 27-2 (1.4 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the reaction was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the reaction was stirred for another 4 h. After cooling to room temperature, the reaction solution was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 27-3 (1.3 g, yield: 65%).

[0421] Elemental analysis structure (C 32 H 29 N2O3P): Theoretical values: C, 73.83; H, 5.62; N, 5.38; Test values: C, 73.78; H, 5.66; N, 5.36.

[0422] ESI-MS analysis: Theoretical value 520.2; Experimental value 521.1 ([M+H]) + ).

[0423] Synthesis of A1-19-1: Under an argon atmosphere, intermediate 27-3 (1.0 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying, the mixture was ultrasonically washed three times with water to obtain compound A1-19-1 (0.5 g, yield: 56%).

[0424] Elemental analysis structure (C 28 H 21 N2O3P): Theoretical values: C, 72.41; H, 4.56; N, 6.03; Test values: C, 72.42; H, 4.56; N, 6.06.

[0425] ESI-MS analysis: Theoretical value 464.1; Experimental value 463.1 ([MH]) - ).

[0426] Example 28

[0427] The reaction formula is as follows:

[0428] Synthesis of intermediate 28-2: Under an argon atmosphere, 28-1 (2.0 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 h, then heated to 70 °C and stirred for another 2 h. After cooling to room temperature, the pH of the reaction mixture was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 28-2 (1.5 g, yield: 71%).

[0429] Elemental analysis structure (C 27 H 16 N2O2S): Theoretical C, 74.98; H, 3.73; N, 6.48; S, 7.41; Tested values ​​C, 74.96; H, 3.70; N, 6.53; S, 7.44.

[0430] ESI-MS analysis: Theoretical value 432.1; Experimental value 433.3 ([M+H]) + ).

[0431] Synthesis of intermediate 28-3: Under an argon atmosphere, intermediate 28-2 (1.7 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the mixture was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 28-3 (1.4 g, yield: 61%).

[0432] Elemental analysis structure (C 33 H 26 N3O4PS): Theoretical values: C, 67.00; H, 4.43; N, 7.10; S, 5.42; Test values: C, 66.95; H, 4.39; N, 7.13; S, 5.42.

[0433] MALDI-TOF-MS analysis: Theoretical value 591.1; Experimental value 591.3 ([M] + ).

[0434] Synthesis of A3-13-1: Under an argon atmosphere, intermediate 28-3 (1.2 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying, the mixture was ultrasonically washed three times with water to obtain compound A3-13-1 (0.6 g, yield: 55%).

[0435] Elemental analysis structure (C 29 H 18 N3O4PS): Theoretical values: C, 65.04; H, 3.39; N, 7.85; S, 5.99; Test values: C, 65.00; H, 3.35; N, 7.88; S, 6.02.

[0436] MALDI-TOF-MS analysis: Theoretical value 535.1; Experimental value 534.0 ([MH]) - ).

[0437] Example 29

[0438] The reaction formula is as follows:

[0439] Synthesis of intermediate 29-2: Under an argon atmosphere, 29-1 (2.1 g) was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 h, then heated to 70 °C and stirred for another 2 h. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with sodium hydroxide aqueous solution. The organic phase was separated and washed three times each with distilled water and sodium chloride aqueous solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 29-2 (1.6 g, yield: 71%).

[0440] Elemental analysis structure (C 27 H 16 N2OS2): Theoretical values: C, 72.30; H, 3.60; N, 6.25; S, 14.29; Test values: C, 72.31; H, 3.60; N, 6.22; S, 14.31.

[0441] ESI-MS analysis: Theoretical value 448.1; Experimental value 449.3 ([M+H]) + ).

[0442] Synthesis of intermediate 29-3: Under an argon atmosphere, intermediate 29-2 (1.8 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The mixture was then heated to 70 °C and stirred for 0.5 h. 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 29-3 (1.5 g, yield: 62%).

[0443] Elemental analysis structure (C 33 H 26 N3O3PS2): Theoretical values: C, 65.23; H, 4.31; N, 6.91; S, 10.55; Test values: C, 65.26; H, 4.28; N, 6.93; S, 10.58.

[0444] MALDI-TOF-MS analysis: Theoretical value 607.1; Experimental value 607.2 ([M] + ).

[0445] Synthesis of A5-13-1: Under an argon atmosphere, intermediate 29-3 (1.2 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried under vacuum. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying under vacuum, the mixture was ultrasonically washed three times with water to obtain compound A5-13-1 (0.6 g, yield: 55%).

[0446] Elemental analysis structure (C 29 H 18 N3O3PS2): Theoretical values: C, 63.15; H, 3.29; N, 7.62; S, 11.62; Test values: C, 63.17; H, 3.23; N, 7.65; S, 11.64.

[0447] MALDI-TOF-MS analysis: Theoretical value 551.1; Experimental value 550.1 ([MH]) - ).

[0448] Example 30

[0449] The reaction formula is as follows:

[0450] Synthesis of intermediate 30-2: Under an argon atmosphere, 2.1 g of 30-1 was weighed into a 50 mL Schlenk flask. 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 hours, then heated to 70 °C and stirred for another 2 hours. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 30-2 (1.6 g, yield: 72%).

[0451] Elemental analysis structure (C 25 H 14 N2OS3): Theoretical values: C, 66.06; H, 3.10; N, 6.16; S, 21.16; Test values: C, 66.10; H, 3.13; N, 6.12; S, 21.10.

[0452] ESI-MS analysis: Theoretical value 454.0; Experimental value 455.2 ([M+H]) + ).

[0453] Synthesis of intermediate 30-3: Under an argon atmosphere, intermediate 30-2 (1.8 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the mixture was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 30-3 (1.6 g, yield: 66%).

[0454] Elemental analysis structure (C 31 H 24 N3O3PS3): Theoretical values: C, 60.67; H, 3.94; N, 6.85; S, 15.67; Test values: C, 60.61; H, 3.97; N, 6.86; S, 15.65.

[0455] MALDI-TOF-MS analysis: Theoretical value 613.1; Experimental value 612.0 ([M] + ).

[0456] Synthesis of A5-18-1: Under an argon atmosphere, intermediate 30-3 (1.2 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying, the mixture was ultrasonically washed three times with water to obtain compound A5-18-1 (0.6 g, yield: 55%).

[0457] Elemental analysis structure (C 27 H 16 N3O3PS3): Theoretical values: C, 58.16; H, 2.89; N, 7.54; S, 17.25; Test values: C, 58.19; H, 2.83; N, 7.56; S, 17.29.

[0458] MALDI-TOF-MS analysis: Theoretical value 557.0; Experimental value 555.9 ([MH]) - ).

[0459] Example 31

[0460] The reaction formula is as follows:

[0461] Synthesis of intermediate 31-2: Under an argon atmosphere, 30-1 (1.5 g) was weighed into a 50 mL Schlenk flask, followed by 20 mL of chloroform and 1.2 mL of N,N-dimethylformamide. The mixture was cooled to 0 °C, and 1.4 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 h, then heated to 70 °C and stirred for another 2 h. After cooling to room temperature, the pH of the reaction mixture was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 31-2 (1.2 g, yield: 72%).

[0462] Elemental analysis structure (C 19 H 14 N2O2S): Theoretical values: C, 68.25; H, 4.22; N, 8.38; S, 9.59; Test values: C, 68.27; H, 4.20; N, 8.33; S, 9.56.

[0463] ESI-MS analysis: Theoretical value 334.1; Experimental value 335.2 ([M+H]) + ).

[0464] Synthesis of intermediate 31-3: Under an argon atmosphere, intermediate 30-2 (1.2 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask, and the mixture was heated to 70 °C and stirred for 0.5 h. Then, 1.2 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 31-3 (1.3 g, yield: 75%).

[0465] Elemental analysis structure (C 25 H 24 N3O4PS): Theoretical values: C, 60.84; H, 4.90; N, 8.51; S, 6.50; Test values: C, 60.83; H, 4.91; N, 8.49; S, 6.52.

[0466] ESI-MS analysis: Theoretical value 493.1; Experimental value 493.0 ([M+H]) + ).

[0467] Synthesis of A4-23-2: Under an argon atmosphere, intermediate 30-3 (1.2 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying, the mixture was ultrasonically washed three times with water to obtain compound A4-23-2 (0.6 g, yield: 54%).

[0468] Elemental analysis structure (C 21 H 16 N3O4PS): Theoretical values: C, 57.66; H, 3.69; N, 9.61; S, 7.33; Test values: C, 57.65; H, 3.68; N, 9.60; S, 7.35.

[0469] ESI-MS analysis: Theoretical value 437.1; Experimental value 436.1 ([MH]) - ).

[0470] Example 32

[0471] The reaction formula is as follows:

[0472] Synthesis of intermediate 32-2: Under an argon atmosphere, 30-1 (2.4 g) was weighed into a 50 mL Schlenk flask. 30 mL of chloroform and 2.4 mL of N,N-dimethylformamide were added to the flask sequentially. The mixture was cooled to 0 °C, and 2.8 mL of phosphorus oxychloride was added. The mixture was stirred for 0.5 h, then heated to 70 °C and stirred for another 2 h. The mixture was cooled to room temperature, and the pH of the reaction solution was adjusted to 7 with an aqueous sodium hydroxide solution. The organic phase was separated and washed three times each with distilled water and an aqueous sodium chloride solution, and then dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 32-2 (1.9 g, yield: 69%).

[0473] Elemental analysis structure (C 16 H 15 NO3): Theoretical values: C, 71.36; H, 5.61; N, 5.20; Test values: C, 71.36; H, 5.62; N, 5.21.

[0474] ESI-MS analysis: Theoretical value 269.1; Experimental value 270.2 ([M+H]) + ).

[0475] Synthesis of intermediate 32-3: Under an argon atmosphere, intermediate 30-2 (1.8 g) and zinc chloride (1.0 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.75 mL of diethyl cyanomethylphosphonate were added to the flask, and the mixture was heated to 70 °C and stirred for 0.5 h. Then, 1.5 mL of triethylamine was added, and the mixture was stirred for another 4 h. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 32-3 (1.8 g, yield: 73%).

[0476] Elemental analysis structure (C 22 H 25 N2O5P): Theoretical values: C, 61.68; H, 5.88; N, 6.54; Test values: C, 61.63; H, 5.84; N, 6.56.

[0477] ESI-MS analysis: Theoretical value 428.2; Experimental value 429.4 ([M+H]) + ).

[0478] Synthesis of A6-22-2: Under an argon atmosphere, intermediate 30-3 (1.5 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying, the mixture was ultrasonically washed three times with water to obtain compound A4-23-2 (0.65 g, yield: 50%).

[0479] Elemental analysis structure (C 18 H 17 N2O5P): Theoretical values: C, 58.07; H, 4.60; N, 7.52; Test values: C, 58.02; H, 4.63; N, 7.50.

[0480] ESI-MS analysis: Theoretical value 372.1; Experimental value 370.9 ([MH]) - ).

[0481] Example 33

[0482] The reaction formula is as follows:

[0483] Synthesis of A1-13-2: Aldehyde starting material 3-2 (1.5 g) and cyanoacetic acid (1.3 g) were added to a reaction flask and completely dissolved in 36 mL of chloroform. Under argon protection, 1.2 mL of piperidine was added, and the mixture was refluxed for 12 hours. The reaction was stopped, cooled to room temperature, acidified twice with 2 M hydrochloric acid aqueous solution, washed twice with water, concentrated, and separated by silica gel column chromatography to obtain compound A1-13-2 (1.2 g, yield: 63%).

[0484] Elemental analysis structure (C 22 H 12 N2O2S): Theoretical values: C, 71.72; H, 3.28; N, 7.60; Test values: C, 71.70; H, 3.28; N, 7.61.

[0485] ESI-MS analysis: Theoretical value 368.1; Experimental value 367.0 ([MH]) - ).

[0486] Example 34

[0487] The reaction formula is as follows:

[0488] Synthesis of A1-13-3: Aldehyde starting material 3-2 (1.5 g), tetrabutylammonium bromide (0.64 g), sodium cyanomethanesulfonate (2.5 g), and 45 mL of acetonitrile were added to a reaction flask. Under argon protection, 1.2 mL of piperidine was added, and the mixture was refluxed for 20 hours. After cooling to room temperature, the solvent was removed under vacuum. The residue was purified by silica gel column chromatography to obtain compound A1-13-3 (0.6 g, yield: 32%).

[0489] Elemental analysis structure (C 21 H 12 N2O3S2): Theoretical values: C, 62.36; H, 2.99; N, 6.93; S, 15.85; Measured values: C, 62.35; H, 2.97; N, 6.93; S, 15.88.

[0490] ESI-MS analysis: Theoretical value 404.0; Experimental value 403.1 ([MH]) - ).

[0491] Example 35

[0492] The reaction formula is as follows:

[0493] Synthesis of intermediate 35-2: Under an argon atmosphere, starting material 3-1 (2.7 g), anhydrous aluminum trichloride (2.4 g), and 15 mL of carbon disulfide were added to a 50 mL Schlenk flask. A carbon disulfide solution of acetic anhydride (2.7 g) (30 mL) was slowly added dropwise under an ice-water bath. The mixture was gradually brought to room temperature. After reacting at room temperature for 36 h, the mixture was poured into ice water, and then 3 M hydrochloric acid aqueous solution was added and stirred for 5 min. The aqueous phase was extracted three times with dichloromethane. The combined organic phases were washed successively with water, 10% sodium bicarbonate aqueous solution, and saturated brine. After drying and concentration, the mixture was separated by silica gel column chromatography to obtain intermediate 35-2 (1.9 g, yield: 61%).

[0494] Elemental analysis structure (C 20 H 13 NOS): Theoretical values ​​C, 76.17; H, 4.15; N, 4.44; S, 10.17; Test values ​​C, 76.12; H, 4.13; N, 4.47; S, 10.13.

[0495] ESI-MS analysis: Theoretical value 315.1; Experimental value 316.2 ([M+H]) + ).

[0496] Synthesis of intermediate 35-3: Under an argon atmosphere, intermediate 35-2 (1.2 g) and zinc chloride (0.8 g) were weighed into a 50 mL Schlenk flask. 20 mL of 1,4-dioxane and 0.6 mL of diethyl cyanomethylphosphonate were added to the flask sequentially. The temperature was then raised to 70 °C, and the reaction was stirred for 0.5 h. 1.2 mL of triethylamine was then added, and the reaction was stirred for another 4 h. After cooling to room temperature, the reaction solution was extracted with ethyl acetate. The organic phase was washed three times with sodium chloride aqueous solution and dried with anhydrous sodium sulfate. The organic phase was concentrated and separated by silica gel column chromatography to obtain intermediate 35-3 (0.94 g, yield: 50%).

[0497] Elemental analysis structure (C 26 H 23 N2O3PS): Theoretical values: C, 65.81; H, 4.89; N, 5.90; S, 6.76; Test values: C, 65.78; H, 4.85; N, 5.94; S, 6.77.

[0498] ESI-MS analysis: Theoretical value 474.1; Experimental value 475.3 ([M+H]) + ).

[0499] Synthesis of A1-13-5: Under an argon atmosphere, intermediate 30-3 (0.9 g) was weighed into a 50 mL L Schlenk flask. 20 mL of dichloromethane and 2 mL of trimethylbromosilane were added to the flask in sequence. After stirring at room temperature for 24 hours, the mixture was dried. Then, 5 mL of methanol was added, and the mixture was stirred at room temperature for another 8 hours. After drying, the mixture was ultrasonically washed three times with water to obtain compound A1-13-5 (0.46 g, yield: 58%).

[0500] Elemental analysis structure (C 22 H 15 N2O3PS): Theoretical values: C, 63.15; H, 3.61; N, 6.70; S, 7.66; Test values: C, 63.18; H, 3.58; N, 6.74; S, 7.63.

[0501] ESI-MS analysis: Theoretical value 418.1; Experimental value 417.0 ([MH]) - ).

[0502] The perovskite solar cell device prepared using the compound of the present invention as a hole transport material is specifically as follows:

[0503] 1) Substrate cleaning: The glass substrate with indium tin oxide (ITO) coating was ultrasonically cleaned with deionized water, acetone and isopropanol for 10 minutes in sequence, and then dried for later use.

[0504] 2) Preparation of hole transport layer: Dissolve the hole transport material in anhydrous ethanol, then spin-coat it onto a clean ITO surface, anneal at 100°C for 10 minutes, and cool to room temperature for later use.

[0505] 3) Preparation of the perovskite layer: Prepare 1.5M Cs 0.05 FA 0.85 MA 0.1 PbI 0.83 The perovskite precursor solution contained N,N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1. Spin coating was performed in two stages: the first stage involved a spin coating speed of 1000 rpm for 10 seconds, and the second stage involved a spin coating speed of 5000 rpm for 40 seconds. Five seconds before the end of the second stage, 200 μL of chlorobenzene was added to the surface. After spin coating was stopped, the film was annealed at 100°C for 30 minutes on a hot plate to obtain the final perovskite film.

[0506] 4) Fabrication of electron transport layer and hole blocking layer: using a vacuum evaporation apparatus (<5×10⁻⁶). -4 Pa) sequentially evaporates 25nm C 60 and 6nm BCP;

[0507] 5) Preparation of the back electrode: using a vacuum evaporation apparatus (<5×10⁻⁶). -4 100nm silver was deposited by vapor deposition (Pa);

[0508] Figure 1 shows the perovskite solar cell prepared in Example 1 of the present invention. Its structure includes a transparent conductive oxide substrate, an organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer, and an electrode layer. An Ag back electrode is disposed on the transparent conductive oxide electrode layer, and the organic hole transport layer contains the hole transport material shown in compound A2-39-1.

[0509] Device 1

[0510] Perovskite solar cells prepared using compound A2-39-1 provided by this invention as a hole transport material;

[0511] Device 2

[0512] Perovskite solar cells prepared using compound A2-38-1 provided by this invention as a hole transport material;

[0513] Device 3

[0514] Perovskite solar cells prepared using compound Al-13-1 provided by this invention as a hole transport material

[0515] Device 4

[0516] Perovskite solar cells prepared using compound Al-14-1 provided by this invention as a hole transport material;

[0517] Device 5

[0518] Perovskite solar cells prepared using compound Al-9-1 provided by this invention as a hole transport material;

[0519] Device 6

[0520] Perovskite solar cells prepared using compound Al-8-1 provided by this invention as a hole transport material;

[0521] Device 7

[0522] Perovskite solar cells prepared using compound Al-2-7 provided in this invention as a hole transport material;

[0523] Device 8

[0524] Perovskite solar cells prepared using compound Al-4-6 provided in this invention as a hole transport material;

[0525] Device 9

[0526] Perovskite solar cells prepared using compound Al-24-1 provided by this invention as a hole transport material;

[0527] Device 10

[0528] Perovskite solar cells prepared using compound Al-25-1 provided by this invention as a hole transport material;

[0529] Device 11

[0530] Perovskite solar cells prepared using compound Al-5-1 provided by this invention as a hole transport material;

[0531] Device 12

[0532] Perovskite solar cells prepared using compound Al-6-1 provided by this invention as a hole transport material;

[0533] Device 13

[0534] Perovskite solar cells prepared using compound Al-27-1 provided by this invention as a hole transport material;

[0535] Device 14

[0536] Perovskite solar cells prepared using compound Al-28-1 provided by this invention as a hole transport material;

[0537] Device 15

[0538] Perovskite solar cells prepared using compound A2-22-2 provided by this invention as a hole transport material;

[0539] Device 16

[0540] Perovskite solar cells prepared using compound A2-22-4 provided in this invention as a hole transport material;

[0541] Device 17

[0542] Perovskite solar cells prepared using compound A2-23-4 provided in this invention as a hole transport material;

[0543] Device 18

[0544] Perovskite solar cells prepared using compound A2-23-5 provided in this invention as a hole transport material;

[0545] Device 19

[0546] Perovskite solar cells prepared using compound A2-31-2 provided by this invention as a hole transport material;

[0547] Device 20

[0548] Perovskite solar cells prepared using compound A2-32-4 provided in this invention as a hole transport material;

[0549] Device 21

[0550] Perovskite solar cells prepared using compound A2-6-1 provided by this invention as a hole transport material;

[0551] Device 22

[0552] Perovskite solar cells prepared using compound A2-20-1 provided by this invention as a hole transport material;

[0553] Device 23

[0554] Perovskite solar cells prepared using compound A2-18-1 provided by this invention as a hole transport material;

[0555] Device 24

[0556] Perovskite solar cells prepared using compound A2-14-1 provided by this invention as a hole transport material;

[0557] Device 25

[0558] Perovskite solar cells prepared using compound A2-15-1 provided by this invention as a hole transport material;

[0559] Device 26

[0560] Perovskite solar cells prepared using compound Al-18-1 provided by this invention as a hole transport material;

[0561] Device 27

[0562] Perovskite solar cells prepared using compound Al-19-1 provided by this invention as a hole transport material;

[0563] Device 28

[0564] Perovskite solar cells prepared using compound A3-13-1 provided in this invention as a hole transport material;

[0565] Device 29

[0566] Perovskite solar cells prepared using compound A5-13-1 provided by this invention as a hole transport material;

[0567] Device 30

[0568] Perovskite solar cells prepared using compound A5-18-1 provided by this invention as a hole transport material;

[0569] Device 31

[0570] Perovskite solar cells prepared using compound A4-23-2 provided in this invention as a hole transport material;

[0571] Device 32

[0572] Perovskite solar cells prepared using compound A6-22-1 provided by this invention as a hole transport material;

[0573] Device 33

[0574] For example, a perovskite solar cell prepared using compound Al-13-2 provided by this invention as a hole transport material;

[0575] Device 34

[0576] Perovskite solar cells prepared using compound Al-13-3 provided in this invention as a hole transport material;

[0577] Device 35

[0578] Perovskite solar cells prepared using compound Al-13-5 provided in this invention as a hole transport material;

[0579] Reference device 1

[0580] The preparation process is the same as that of the hole transport material of the present invention. The structure of the hole transport material 2PACz used in the reference device 1 is as follows:

[0581] The performance testing method for the perovskite solar cells prepared in this embodiment of the invention is as follows:

[0582] The current-voltage characteristic curve (IV) of the solar cell was recorded using a Keithley 2400 digital source meter, with a xenon lamp (Osram XBO 450) simulating AM 1.5 sunlight at an intensity of 1000 W / m. 2 After calibration with silicon cells, the test temperature was 25℃. The JV data of the test cells are shown in Table 1 and Figures 2-32.

[0583] Table 1. Performance test results of perovskite solar cells prepared in Examples 1-35 of this invention.

[0584] As can be seen from Table 1 and Figures 1-32, the perovskite solar cells fabricated with the hole transport material synthesized in this invention show significantly improved fill factor and open-circuit voltage compared to the reference device 1 using commercially available hole transport materials. The fill factor of the 2PACz-based device is less than 80%, while the fill factor of the devices based on the hole transport material of this invention is mostly around 82%, and can even reach 84.4%. In addition, the open-circuit voltage of the devices based on the hole transport material of this invention can reach up to 1.170V, while the open-circuit voltage of the devices based on 2PACz can only reach 1.135V. The photoelectric conversion efficiency of the devices based on the hole transport material of this invention is mostly greater than 24%, and even exceeds 25%. The improved performance is due to two main reasons. First, the long axis of the hole transport material structure described in this invention can be more effectively conjugated, making the HOMO energy level of the material more compatible with the energy level of the active layer material, thus enhancing the hole extraction capability. Second, the introduction of short-axis functional groups into the hole transport material structure described in this invention can not only improve the crystallization of the perovskite film by delaying its growth, but also passivate interface defects, thereby improving the interface quality between the hole transport layer and the active layer.

[0585] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A compound, characterized in that, having the structure of Formula I: wherein is an anchoring group selected from carboxyl, sulfonic acid group or phosphoric acid group; R a selected from H, halogen or C1-C 10 straight-chain or branched alkyl; R b selected from halogen, CN, SH, OH, CO2R f wherein R f is selected from C1-C 10 straight-chain or branched alkyl; Ar1 and Ar2 are independently selected from C6 to C6. 16 Aryl or C4~C 18 Mixed aromatics; R c , R e independently selected from H, halogen, hydroxyl, amino, cyano, phenyl, C1-C4alkyl, C1-C4alkoxy, 5-6 membered heteroaryl; and 10 straight chain or branched alkyl, C1-C4alkoxy, 5-6 membered heteroaryl; and R d selected from H, C1-C6linear or branched alkyl, C1-C6linear or branched alkyl substituted with S or NH, C1-C6alkoxy, C6-C10aryl, C4-C10heteroaryl; and 10 linear or branched alkyl, C1-C6linear or branched alkyl substituted with S or NH, C1-C6alkoxy, C6-C10aryl, C4-C10heteroaryl; and 16 linear or branched alkyl, C1-C6linear or branched alkyl substituted with S or NH, C1-C6alkoxy, C6-C10aryl, C4-C10heteroaryl; and 18 linear or branched alkyl, C1-C6 or R c , R d and the atom on which it is located forms a fused ring 1 with Ar2, and R e , R d and the atom on which it is located forms a fused ring 2 with Ar1; or R c , R d and the atom they are attached to form a fused ring 1 with Ar2; or R e , R d and the atom they are attached to form a fused ring 2 with Ar1; The heteroatoms in fused ring 1 and fused ring 2 are independently selected from O, S, Se, N, one or more of N, O and S and contains at least N; y is selected from a single bond, O, S, Se, R g and R h Independently selected from H, C1~C 10 One or more of the following: straight-chain or branched alkyl, C1-C6 alkoxy, S- or NH-substituted carbon atom C1-C6 straight-chain or branched alkyl, and 5- or 6-membered heteroaryl.

2. The compound of claim 1, wherein said R a selected from H or C1-C4 linear or branched alkyl; said R b selected from halogen, CN, CO2R f wherein R f selected from C1-C4 linear or branched alkyl; Ar1 and Ar2 are independently selected from C6 to C6. 14 Aryl or C4~C 16 Mixed aromatics; R c , R e independently selected from one or more of H, chloro, bromo, hydroxyl, amino, cyano, phenyl, C1-C6 linear or branched alkyl, C1-C3 alkoxy, 5-6 membered heteroaryl; R d C1-C4 linear or branched alkyl substituted with a carbon atom selected from C1-C5 linear or branched alkyl, S or NH; 12 C1-C4 linear or branched alkyl substituted with a carbon atom selected from C1-C5 linear or branched alkyl, S or NH; 12 C1-C4 linear or branched alkyl substituted with a carbon atom selected from C1-C5 linear or branched alkyl, S or NH; or R c , R d and the atom on which they are located form a fused ring 1 with Ar2, and R e , R d and the atom on which they are located form a fused ring 2 with Ar1; or R c , R d and the atom they are attached to form a fused ring 1 with Ar2; or R e , R d and the atom they are attached to form a fused ring 2 with Ar1; the ring in which the heteroatom in the fused ring 1 and the fused ring 2 is independently selected from a six-membered heterocyclic ring containing N and O, or a six-membered heterocyclic ring containing N and S, or a five-membered heterocyclic ring containing only N; y is selected from a single bond, O, S, R g and R h is independently selected from one or more of C1-C6straight chain or branched chain alkyl.

3. The compound of claim 1 or 2, wherein The compound has a structure shown in formula I-1:

4. The compound of claim 3, wherein R c , R d and the atom on which they are located form a fused ring 1 with Ar2, and R e , R d and the atom on which they are located form a fused ring 2 with Ar1; or R c , R d and the atom they are attached to form a fused ring 1 with Ar2; or R e , R d and the atom they are attached to form a fused ring 2 with Ar1; the heteroatom in the fused ring 1 and the fused ring 2 is independently selected from one or more of O, S, N and contains at least N; the fused ring 1 and the fused ring 2 are independently selected from a 5-membered or 6-membered ring.

5. The compound according to any one of claims 1 to 4, wherein The C1~C 10 The linear or branched alkyl, C1-C4 linear or branched alkyl, C1-C6 linear or branched alkyl, C1-C5 linear or branched alkyl, and C1-C4 alkoxy groups further contain substituents selected from one or more of halogens, hydroxyl groups, amino groups, cyano groups, nitro groups, carboxyl groups, sulfonic acid groups, boric acid groups, ester groups, SiH3, and SMe. The C6~C 16 Aryl, C6~C 14 Aryl, C6~C 12 Aryl, C4~C 18 heteroaryl, C4~C 16 heteroaryl, C4~C 12 Heteroaryl groups and 5-6-membered heteroaryl groups further contain substituents selected from D, C1-C6 straight-chain or branched alkyl groups, S or NH-substituted carbon atoms of C1-C6 straight-chain or branched alkyl groups, C1-C4 alkoxy groups, C3-C6... 15 cycloalkyl, C4-C 16 heteroaryl, C6-C 16 Aryl, halogen, hydroxyl, mercapto, amino, cyano, nitro, carboxyl, sulfonic acid, boric acid, ester, SiH3, SMe, OR1', SR1', SeR1', TeR1' one or more of N, O and S and contains at least N; The the “-” in the formula (I) represents a connecting position; R1', R2', and R3' are independently selected from H, D, C1-C6 straight-chain or branched alkyl groups, C3-C6... 15 cycloalkyl, C6-C 16 Aryl, C4~C 18 Mixed aromatics; The C4~C 18 heteroaryl, 5-6 quinary heteroaryl, C4-C 16 heteroaryl, C4-C 12 The heteroatoms in the heteroaryl group are selected from one or more of Si, Ge, N, P, O, S, and Se, and the number of heteroatoms is independently selected from 1, 2, or 3.

6. The compound of claim 1, wherein said R a is selected from H, methyl or ethyl; said R b selected from F, CN, CO2CH3or CO2CH2CH3; Ar1and Ar2are independently selected from any of the following structures: R c , R e independently one or more selected from the group consisting of H, chloro, bromo, hydroxy, amino, cyano, methyl, trifluoromethyl, methoxy, benzyloxy, thienyl, pyridyl; R d selected from any one of the structures shown below: L1, L2are independently selected from the group consisting of H, D, C1-C6alkyl, C3-C6cycloalkyl, C4-C6alkenyl, C4-C6alkynyl, C6-C10aryl, C1-C6heteroalkyl, and heteroaryl; 20 straight-chain or branched alkyl, C1-C6 15 cycloalkyl, C6-C10 18 aryl, C4-C10 18 heteroaryl; or R c , R d and the atom on which they are located form a fused ring 1 with Ar2, and R e , R d and the atom on which they are located form a fused ring 2 with Ar1; the ring in which the heteroatom in the fused ring 1 and the fused ring 2 is independently selected from a six-membered heterocyclic ring containing N and O, or a six-membered heterocyclic ring containing N and S, or a five-membered heterocyclic ring containing only N; y is selected from a single bond, O, S, R g and R h Independently selected from one or more of methyl or ethyl.

7. The compound of claim 1, wherein The compounds have any one of the following structures:

8. An organic hole transport material, characterized by, the compound of any one of claims 1-7.

9. A perovskite solar cell, characterized by, The organic hole transport material of claim 8.

10. The perovskite solar cell according to claim 9, characterized in that, The perovskite solar cell comprises, in sequence, a conductive oxide substrate, an organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer and an electrode layer. Alternatively, the perovskite solar cell comprises, in sequence, a conductive oxide substrate, an inorganic p-type semiconductor hole transport layer, an organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer and an electrode layer. The organic hole transport layer comprises the organic hole transport material of claim 8.

Images