Pyruvic acid (hetero)aryl thioester compounds for LED photopolymerization, preparation therefor and use thereof

Abstract

Disclosed in the present invention are pyruvic acid (hetero)aryl thioester compounds for LED photopolymerization, a preparation method therefor and the use thereof. The pyruvic acid (hetero)aryl thioester compounds disclosed by the invention can be used as LED photopolymerization initiators, have good absorption performance in a visible light region of 400 nm or above, and all particularly show good initiation property under LED light sources of 405 nm and 455 nm. Therefore, said compounds can effectively initiate photopolymerization reactions of photopolymerizable monomers, especially (meth)acrylate monomers. Additionally, the pyruvic acid (hetero)aryl thioester compounds have excellent biocompatibility and involve simple synthesis routes, thereby having extremely high practical value.

Description

Pyruvic acid (hetero)aryl thioester compounds for LED photopolymerization and their preparation and application Technical Field

[0001] The present invention belongs to the field of photopolymerization technology and relates to pyruvic acid (hetero)aryl thioester compounds. These compounds can be used as photoinitiators, particularly for LED photopolymerization. The present invention also relates to the preparation and application of pyruvic acid (hetero)aryl thioester compounds. Background Art

[0002] As photopolymerization technology has been widely used in traditional fields such as coatings, inks, microelectronics, printing, as well as new fields such as the preparation of laser video and three-dimensional components, and with the continuous research and development of LED photopolymerization technology, in order to meet the wide application needs of LED photopolymerization technology, it is necessary to develop photoinitiators suitable for LED light sources.

[0003] Several photoinitiators of this type already exist in the prior art. For example, CN104817653A discloses a coumarin aldoxime ester compound suitable for UV-LED curing, and CN102492059A discloses a substituted diphenyl sulfide ketoxime ester photoinitiator. However, to match the wavelength of the LED light source, these reported initiators typically require the introduction of large conjugated groups into the molecular structure, which significantly complicates the synthesis route of the initiator molecule. The use of expensive metal catalysts also increases the biotoxicity of the initiator molecule, creating inconveniences in practical production applications.

[0004] In view of this, the research and development of new photoinitiators that can be used as LED light sources, have simple structures and synthetic routes, and have good biocompatibility remains one of the core tasks in this field. In addition, photopolymers, especially poly(meth)acrylates, are widely used in fields such as biomedical materials due to their excellent mechanical properties, good reprocessability, and weather resistance. Therefore, the development of initiators that can effectively polymerize photopolymerizable monomers, especially (meth)acrylate monomers, is also urgently needed in the field of photopolymerization.

[0005] Summary of the Invention

[0006] To advance the development of LED photopolymerization technology, the present inventors have been dedicated to the promotion and application research of LED photopolymerization technology, particularly the continuous research and development of more photoinitiators suitable for LED photopolymerization. In light of the shortcomings of the existing technology, the present inventors have conducted extensive and in-depth research on photoinitiators suitable for LED photopolymerization, aiming to identify a novel, highly efficient initiator that can effectively initiate the photopolymerization of photopolymerizable monomers, particularly (meth)acrylate monomers, while also exhibiting excellent biocompatibility and a simple synthetic route.

[0007] The inventors surprisingly discovered that a novel class of highly efficient LED photoinitiators, pyruvic acid (hetero)arylthioesters, has been synthesized by reacting pyruvic acid with (hetero)arylthiophenols. The prepared initiator exhibits excellent absorption properties in the visible light region above 400 nm, effectively matching the wavelength of LED light sources. In particular, the photoinitiator exhibits excellent initiation performance under both 405 nm and 455 nm LED light sources, effectively initiating photopolymerization reactions of photopolymerizable monomers, particularly (meth)acrylate monomers. Furthermore, the initiator exhibits excellent biocompatibility and a simple synthetic route, resulting in extremely high practical value.

[0008] The purpose of the present invention is achieved based on the above findings.

[0009] Therefore, an object of the present invention is to provide a pyruvic acid (hetero)aryl thioester compound, which not only has an absorption wavelength suitable for LED light source polymerization, but also has good biocompatibility and low synthesis cost.

[0010] Another object of the present invention is to provide a method for preparing the pyruvic acid (hetero)aryl thioester compounds of the present invention.

[0011] Another object of the present invention is to provide the use of the pyruvic acid (hetero)aryl thioester compound of the present invention as a photoinitiator in LED photopolymerization.

[0012] The technical solutions for achieving the above-mentioned purpose of the present invention can be summarized as follows:

[0013] 1. A pyruvic acid (hetero)aryl thioester compound of general formula (I):

[0014] in:

[0015] M stands for C6-C 18 Aryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O, wherein C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 Alkarylthio or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O, wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 The alkarylthio group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino.

[0016] 2. The pyruvic acid (hetero)aryl thioester compound according to item 1, wherein:

[0017] M stands for C6-C 18 aryl or a 5- to 18-membered heteroaryl group containing one or more heteroatoms selected from N, S and O,

[0018] Among them, C6-C 18 Aryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxy,

[0019] -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio or C7-C 20 Alkaryl; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio or C7-C 20 The alkaryl group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate, or amino;

[0020] More preferably, C6-C 18 The 5-18 membered heteroaryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C6 alkyl ... 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0021] More preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkylthio, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy and C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0022] More preferably, C6-C 18The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, -CF3, -OCF3 or -OC6H5.

[0023] 3. The pyruvic acid (hetero)aryl thioester compound according to item 1 or 2, wherein:

[0024] M stands for C6-C 18 aryl or a 5- to 18-membered heteroaryl group containing one or more heteroatoms selected from N, S and O,

[0025] Among them, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of fluoro, methyl or methoxy.

[0026] 4. The pyruvic acid (hetero)aryl thioester compound according to any one of items 1 to 3, wherein:

[0027] M stands for

[0028] wherein R1 is selected from O, S or -NR 10 -;

[0029] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 Alkarylthio or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 Alkarylthio or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0030] R 10 represents hydrogen, C1-C 20 Alkyl, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 Alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein C1-C 20 Alkyl, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20The alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino.

[0031] 5. The pyruvic acid (hetero)aryl thioester compound according to item 4, wherein M represents wherein R2, R3, R4, R5, R6, R7, R8, and R9 are as defined in item 4.

[0032] 6. The pyruvic acid (hetero)aryl thioester compound according to item 4 or 5, wherein:

[0033] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 The arylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino; further preferably,

[0034] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkylthio, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy and C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0035] More preferably,

[0036] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, -CF3, -OCF3 or -OC6H5;

[0037] Most preferably,

[0038] R2, R3, R5, R6, R7, R8, and R9 are the same and are H; and R4 is selected from fluoro, methyl, or methoxy.

[0039] 7. The pyruvic acid (hetero)aryl thioester compound according to any one of items 1 to 6, wherein:

[0040] R 10 represents hydrogen, C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 Alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20The alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino.

[0041] 8. The pyruvic acid (hetero)aryl thioester compound according to any one of items 1 to 7, which is:

[0042] 9. A method for preparing a pyruvic acid (hetero)aryl thioester compound according to any one of items 1 to 8, comprising:

[0043] Make pyruvate and The reaction is carried out in the presence of a dehydrating agent and a catalyst to obtain a pyruvic acid (hetero)aryl thioester compound, namely:

[0044] wherein M is as defined in any one of items 1-8.

[0045] 10. The process according to item 9, wherein the reaction is carried out in the presence of one or more catalysts selected from the group consisting of 4-dimethylaminopyridine, piperidine, 3-methylpiperidine and triethylamine, preferably 4-dimethylaminopyridine; and / or the molar amount of the catalyst is 1-10%, preferably 5-10%, based on M-SH.

[0046] 11. The method according to item 9 or 10, wherein the reaction is carried out in the presence of one or more dehydrating agents selected from the group consisting of dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, preferably dicyclohexylcarbodiimide; and / or the molar amount of the dehydrating agent is 100-150%, preferably 120-140%, of M-SH.

[0047] 12. The method according to any one of items 9 to 11, wherein the molar ratio of M-SH to pyruvic acid is 1:1.1-1:3, preferably 1:1.1-1:2, more preferably 1:1.2-1:2.

[0048] 13. A photopolymerizable composition comprising:

[0049] (A) at least one monomeric or oligomeric ethylenically unsaturated photopolymerizable compound, and

[0050] (B) at least one pyruvic acid (hetero)arylthioester compound obtained according to any one of items 1 to 8 or any one of items 9 to 12.

[0051] 14. Use of the pyruvic acid (hetero)aryl thioester compound obtained according to any one of items 1 to 8 or the method of any one of items 9 to 12 as a photoinitiator in photopolymerization.

[0052] 15. Use of the pyruvic acid (hetero)aryl thioester compound obtained according to any one of items 1 to 8 or the method of any one of items 9 to 12 in the preparation of biopolymer materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] FIG1 is a diagram of the initiation mechanism of the photoinitiator provided by the present invention;

[0054] Figures 2 and 3 are UV-visible absorption spectra of the pyruvic acid (hetero)aryl thioester compounds of Examples 1-4;

[0055] FIG4 is a photopolymerization kinetic diagram of the polymerization of tripropylene glycol diacrylate (TPGDA) monomer initiated by the pyruvic acid (hetero)aryl thioester compounds of Examples 1-4 under a 405 nm LED light source;

[0056] FIG5 is a photopolymerization kinetic diagram of the polymerization of tripropylene glycol diacrylate (TPGDA) monomer initiated by the pyruvic acid (hetero)aryl thioester compounds of Examples 1-4 under a 455 nm LED light source;

[0057] 6 is a photopolymerization kinetic diagram of the polymerization of trimethylolpropane triacrylate (TMPTA) monomer initiated by the pyruvic acid (hetero)aryl thioester compounds of Examples 1-4 under a 405 nm LED light source;

[0058] 7 is a photopolymerization kinetic diagram of the polymerization of triethylene glycol dimethacrylate (TEGDMA) monomer initiated by the pyruvic acid (hetero)aryl thioester compounds of Examples 1-4 under a 405 nm LED light source;

[0059] FIG8 is a photopolymerization kinetic diagram of the pyruvic acid (hetero)aryl thioester compounds of Examples 1-4 initiating polymerization of methyl methacrylate (MMA) monomer under a 405 nm LED light source;

[0060] FIG9 is a graph showing the cell viability of human cervical cancer cells cultured in the pyruvic acid (hetero)aryl thioester compound MO-PTE of Example 2. DETAILED DESCRIPTION

[0061] The first aspect of the present invention provides a pyruvic acid (hetero)aryl thioester compound of the general formula (I):

[0062] in:

[0063] M stands for C6-C 18 Aryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O, wherein C6-C 18The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 Alkarylthio or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O, wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 The alkarylthio group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino.

[0064] In the present invention, the prefix "C n -C m " in each case means that the number of carbon atoms contained in the group is n to m.

[0065] "Halogen" refers to fluorine, chlorine, bromine and iodine and combinations thereof. In the present invention, preferably halogen includes F, Cl or a combination thereof.

[0066] The term "C n -C m "Alkyl" is a saturated hydrocarbon radical having n to m, for example 1 to 20, preferably 1 to 12, more preferably 1 to 8, particularly preferably 1 to 6 and especially preferably 1 to 4, carbon atoms, which may be branched or unbranched. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, in particular methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl and isomers thereof. C1- The C6 alkyl group may be methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, etc. The C1-C4 alkyl group may be methyl, ethyl, propyl, butyl and isomers thereof, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0067] The term "C3-C m "Cycloalkyl" refers to a saturated alicyclic monocyclic group having 3 to m, for example 3-10, preferably 3-8, more preferably 5-6, ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.

[0068] The term "C4-C m"Cycloalkylalkyl" means an alkyl group substituted by a cycloalkyl group and containing a total of 4 to m carbon atoms, for example 4-20 carbon atoms, preferably 4-12, more preferably 4-10, and most preferably 4-8 carbon atoms. The definitions of alkyl and cycloalkyl apply as described herein, and examples include cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, and the like.

[0069] The term "C4-C m "Alkylcycloalkyl" means a cycloalkyl group substituted by an alkyl group and containing a total of 4 to m carbon atoms, for example 4-20 carbon atoms, preferably 4-12, more preferably 4-10, and most preferably 4-8 carbon atoms. The definitions of alkyl and cycloalkyl apply as described herein, and examples include methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethylcyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, and the like.

[0070] The term "C6-C m "Aryl" refers to a monocyclic, bicyclic or tricyclic aromatic hydrocarbon group containing 6 to m carbon atoms, for example 6-18, preferably 6-10 carbon atoms. m As examples of the aryl group, there can be mentioned phenyl, azulenyl, cycloheptatrienyl, biphenyl, dicyclopentaphenyl, fluorenyl, phenanthrenyl, terphenyl, pyrenyl, naphthacene, yl, anthracenyl, indenyl, pentalenyl and naphthyl.

[0071] "5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O" is understood to mean a group having 5-18 ring members, such as 5-16, 5-14, 5-10 or 5-8, or 8-14, 9-14 or 9-13 ring members, wherein at least one ring atom is a heteroatom selected from N, O and S, more preferably N. The heteroaryl group preferably has 1 to 3, for example 1 or 2 heteroatoms. More preferably, the heteroaryl group is a ring system having two or three fused rings, which has 8-14, 9-14 or 9-13 ring members. Examples of heteroaryl groups include thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furanyl, dibenzofuranyl, benzofuranyl, chromenyl, xanthenyl, thioxanthenyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolinyl, quinolinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, phenanthridinyl, acridinyl, perylene, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isothiazolyl, isothiazin ... Azolyl, furazanyl, phenanthracene oxazinyl, 7-phenanthrenyl, anthraquinone-2-yl (= 9,10-dioxo-9,10-dihydroanthracen-2-yl), 3-benzo[b]thienyl, 5-benzo[b]thienyl, 2-benzo[b]thienyl, 4-dibenzofuranyl, 4-7-dibenzofuranyl, 4-methyl-7-dibenzofuranyl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, phenanthrenyl, Thiol, 2,7-phen Thiazole, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl-5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl, 1- Methyl-3-indazolyl, 2,7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 3-methoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridine -2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-pteridinyl, 6-pteridinyl, 7-pteridinyl, 6,7-dimethoxy-2-pteridinyl, 2-carbazolyl, 3-carbazolyl, 9-methyl-2-carbazolyl, 9 -methyl-3-carbazolyl, β-carbolin-3-yl, 1-methyl-β-carbolin-3-yl, 1-methyl-β-carbolin-6-yl, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl, 2-perylene-1, 1-methyl-5-perylene-1, 5-phenanthrolinyl, 6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isothiazolyl oxazolyl, 4-iso Azolyl, 5-iso Azolyl, 4-methyl-3-furazanyl, 2-phenanthracene Oxazine, 10-methyl-2-phenanthracene Azinyl, etc.

[0072] The term "C7-C m "Aralkyl" means an alkyl group substituted by an aryl group and containing 7 to m, for example 7-20, preferably 7-12 carbon atoms in total. Alkyl and aryl are as defined herein, examples include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and the like.

[0073] The term "C7-C m"Alkaryl" means an aryl group substituted by an alkyl group and containing 7 to m, such as 7-20, preferably 7-12 carbon atoms in total. The definitions of alkyl and aryl apply as herein, and examples include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, methylnaphthyl, ethylnaphthyl, and the like.

[0074] The term "C n -C m "Alkoxy" refers to n -C m Alkyl corresponding open chain C n -C m Any carbon atom of an alkane is bonded with an oxygen atom as a linker. n -C m Alkyl groups, such as C1-C 20 Alkoxy, preferably C1-C 12 Alkoxy, more preferably C1-C8 alkoxy, particularly preferably C1-C6 alkoxy. Examples include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy and isomers thereof, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy and isomers thereof. C1-C4 alkoxy may be methoxy, ethoxy, propoxy, butoxy and isomers thereof, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and the like.

[0075] The term "C4-C m "Cycloalkylalkoxy" refers to an alkoxy group substituted by a cycloalkyl group and containing a total of 4 to m carbon atoms, for example 4-20, preferably 4-12 carbon atoms, more preferably 4-10 carbon atoms. The definition of cycloalkyl applies herein. Examples include cyclopropylmethoxy, cyclopropylethoxy, cyclopropylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy, cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentylethoxy, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclohexylethoxy, cyclohexylpropoxy, cyclohexylbutoxy and the like.

[0076] The term "C6-C m "Aryloxy" refers to a C6-C m The C6-C m Any aromatic carbon atom in an aromatic hydrocarbon is bonded to an oxygen atom as a linker. m Aryl groups, such as phenoxy, tolyloxy, naphthoxy and the like.

[0077] The term "C7-C m "Aralkyloxy" refers to a C7-Cm The alkyl carbon atom corresponding to the aralkyl group is bonded with an oxygen atom as a linking group. m Aralkyl groups include benzyloxy, phenethoxy, naphthylmethoxy, naphthylethoxy and the like.

[0078] The term "C7-C m "Alkaryloxy" refers to a C7-C m The aryl carbon atom corresponding to the alkaryl group is bonded with an oxygen atom as a linking group. m Alkaryl groups, examples include methylphenoxy, dimethylphenoxy, trimethylphenoxy, ethylphenoxy, diethylphenoxy, triethylphenoxy, methylnaphthyloxy, ethylnaphthyloxy and the like.

[0079] The term "C n -C m "Alkylthio" refers to a C n -C m Alkyl corresponding open chain C n -C m Any carbon atom of an alkane is bonded with a sulfur atom as a linker. n -C m Alkyl groups, such as C1-C 20 Alkylthio, preferably C1-C 12 Alkylthio, more preferably C1-C8 alkylthio, particularly preferably C1-C6 alkylthio. Examples include methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, isooctylthio and isomers thereof. C1-C4 alkylthio may include methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio and the like.

[0080] The term "C4-C m The term "cycloalkylalkylthio" refers to an alkylthio group substituted by a cycloalkyl group and containing 4 to m carbon atoms, for example 4-20, preferably 4-12 carbon atoms, more preferably 4-10 carbon atoms in total. The definitions of cycloalkyl and alkylthio apply herein. Examples include cyclopropylmethylthio, cyclopropylethylthio, cyclopropylpropylthio, cyclopropylbutylthio, cyclobutylmethylthio, cyclobutylethylthio, cyclobutylpropylthio, cyclobutylbutylthio, cyclopentylmethylthio, cyclopentylethylthio, cyclopentylpropylthio, cyclopentylbutylthio, cyclohexylmethylthio, cyclohexylethylthio, cyclohexylpropylthio, cyclohexylbutylthio and the like.

[0081] The term "C6-C m "Arylthio" refers to a C6-C m The C6-C mAny aromatic carbon atom in an aromatic hydrocarbon is bonded to a sulfur atom as a linker. m Aryl groups, such as phenylthio, tolylthio, naphthylthio and the like.

[0082] The term "C7-C m "Aralkylthio" refers to a C7-C m The alkyl carbon atom corresponding to the aralkyl group is bonded with a sulfur atom as a linking group. m Aralkyl groups include benzylthio, phenethylthio, naphthylmethylthio, naphthylethylthio and the like.

[0083] The term "C7-C m "Alkarylthio" refers to a C7-C m The aryl carbon atom corresponding to the alkaryl group is bonded with a sulfur atom as a linking group. m Alkaryl groups, examples include methylphenylthio, dimethylphenylthio, trimethylphenylthio, ethylphenylthio, diethylphenylthio, triethylphenylthio, methylnaphthylthio, ethylnaphthylthio and the like.

[0084] “C1-C 20 "Haloalkyl" includes C1-C 12 Halogenated alkyl, C1-C8 haloalkyl, C1-C6 haloalkyl, C1-C4 haloalkyl. The halogen and alkyl in the haloalkyl are as defined herein.

[0085] “C1-C 20 "Haloalkoxy" includes C1-C 12 Halogenated alkoxy, C1-C8 haloalkoxy, C1-C6 haloalkoxy, C1-C4 haloalkoxy. The halogen and alkoxy in the haloalkoxy are as defined herein for halogen and alkoxy.

[0086] “C1-C 20 "Haloalkylthio" includes C1-C 12 Halogenated alkylthio, C1-C8 haloalkylthio, C1-C6 haloalkylthio, C1-C4 haloalkylthio. The halogen and alkylthio in the haloalkylthio are as defined herein for halogen and alkoxy.

[0087] In a preferred embodiment of the present invention,

[0088] M stands for C6-C 18 aryl or a 5- to 18-membered heteroaryl group containing one or more heteroatoms selected from N, S and O,

[0089] Among them, C6-C 18The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio or C7-C 20 Alkaryl; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio or C7-C 20 The alkaryl group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate, or amino;

[0090] More preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0091] More preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkylthio, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy and C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0092] More preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, -CF3, -OCF3 or -OC6H5;

[0093] Most preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of fluoro, methyl or methoxy.

[0094] In a preferred embodiment of the present invention,

[0095] M stands for

[0096] wherein R1 is selected from O, S or -NR 10 -;

[0097] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20Alkarylthio or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 The alkarylthio group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0098] R 10 represents hydrogen, C1-C 20 Alkyl, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 Alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein C1-C 20 Alkyl, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 The alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino.

[0099] In a preferred embodiment of the present invention,

[0100] M stands for in:

[0101] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 Alkarylthio or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20The alkarylthio group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino.

[0102] In a more preferred embodiment of the present invention,

[0103] M stands for in:

[0104] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0105] More preferably,

[0106] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20Alkoxy, C1-C 20 Halogenated alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkylthio, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy and C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0107] More preferably,

[0108] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, -CF3, -OCF3 or -OC6H5;

[0109] Most preferably,

[0110] R2, R3, R5, R6, R7, R8, and R9 are the same and are H; and R4 is selected from fluoro, methyl, or methoxy.

[0111] In a preferred embodiment of the present invention, R 10 represents hydrogen, C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 Alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 The alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino.

[0112] In a preferred embodiment of the present invention, M is wherein R2, R3, R5 and R6 are the same and are H; and R4 is selected from fluoro, methyl or methoxy.

[0113] In another preferred embodiment of the present invention, M is wherein R2, R3, R5, R6, R7, R8, and R9 are the same and are H.

[0114] As specific examples of pyruvic acid (hetero)arylthioester compounds of the general formula (I), there can be mentioned:

[0115] The second aspect of the present invention relates to a method for preparing a pyruvic acid (hetero)aryl thioester compound of the general formula (I) of the present invention, comprising reacting pyruvic acid with M-SH to obtain a pyruvic acid (hetero)aryl thioester compound. The specific reaction scheme is shown below:

[0116] Wherein M is as defined above.

[0117] The above reaction is usually carried out in a solvent, preferably an organic solvent. There are no particular restrictions on the choice of solvent type, as long as it can dissolve the reactants, dehydrating agent, and catalyst and is chemically inert to the reaction, i.e., does not participate in the reaction. Examples of solvents commonly used include dichloromethane, ethyl acetate, tetrahydrofuran, and N,N-dimethylformamide. Preferably, the reaction is carried out in dichloromethane.

[0118] The reaction is carried out in a solvent in the presence of a dehydrating agent and a catalyst. Suitable dehydrating agents are, for example, dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide; suitable catalysts are, for example, 4-dimethylaminopyridine (DMAP), piperidine, 3-methylpiperidine or triethylamine. The molar amount of the catalyst may be 1-10% of M-SH, preferably 5-10%. The molar amount of the dehydrating agent is 100-150% of M-SH, preferably 120-140%. The molar ratio of M-SH to pyruvic acid is 1:1.1-1:3, preferably 1:1.1-1:2, more preferably 1:1.2-1:2. The reaction may be carried out at -20°C to 40°C, preferably -10°C to 30°C, and the reaction time may be 0.5-10 hours, preferably 1-8 hours.

[0119] In a specific embodiment of the present invention, the reaction can be carried out by adding a solution of a dehydrating agent dropwise to a solution of pyruvic acid, M-SH and a catalyst. Preferably, pyruvic acid, M-SH and a catalyst are dissolved in a solvent and added to a reaction vessel, and then the dehydrating agent is dissolved in the same solvent and transferred to a dropping funnel, and then dropped into the above-mentioned reaction vessel, and the stirring reaction is continued. Then, the solvent is removed by distillation under reduced pressure to obtain a crude product, and a chromatographic column is used to separate the final product.

[0120] The pyruvic acid (hetero)aryl thioester compounds of the general formula (I) of the present invention are used as initiators for LED photopolymerization. They exhibit excellent absorption properties in the visible light region above 400 nm, effectively matching the wavelength of LED light sources. In particular, the photoinitiators of the present invention exhibit excellent initiation performance under both 405 nm and 455 nm LED light sources, effectively initiating photopolymerization reactions of photopolymerizable monomers, particularly (meth)acrylate monomers. Furthermore, they exhibit excellent biocompatibility and a simple synthetic route, thus possessing extremely high practical value.

[0121] Therefore, according to a third aspect of the present invention, there is provided a photopolymerizable composition comprising:

[0122] (A) at least one monomeric or oligomeric ethylenically unsaturated photopolymerizable compound, and

[0123] (B) at least one pyruvic acid (hetero)arylthioester compound of the general formula (I) as defined above.

[0124] The amount of the pyruvic acid (hetero)aryl thioester compound of formula (I) of the present invention is usually 0.01-10 wt %, preferably 0.05-6 wt %, such as 0.1-5 wt %, based on the total weight of the photopolymerizable composition.

[0125] The unsaturated compounds (A) may contain, for example, one or more ethylenically unsaturated double bonds and have a low molecular weight (monomers) or a relatively high molecular weight (oligomers).

[0126] Suitable oligomers may be epoxy (meth)acrylate resins, polyurethane (meth)acrylate resins, polyester (meth)acrylate resins, polyether (meth)acrylate resins or acrylated poly (meth)acrylate resins.

[0127] Suitable monomers may be the following monofunctional compounds: (meth)acrylic acid and its salts; (meth)acrylic acid esters, for example alkyl esters such as methyl, ethyl, 2-chloroethyl, N,N-dimethylaminoethyl, n-butyl, isobutyl, pentyl, hexyl esters, hydroxyalkyl esters such as 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl esters, epoxyalkyl esters such as glycidyl, 2,3-epoxybutyl, 3,4-epoxybutyl, 2,3-epoxycyclohexyl, 10,11-epoxyundecyl esters; (meth)acrylamide, N-substituted (meth)acrylamide, for example N- Methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-cyclohexylmethacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide, N-ethyl-N-phenylmethacrylamide, N-(4-hydroxyphenyl)acrylamide unsaturated acid anhydrides such as itaconic anhydride, maleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride; unsaturated esters such as maleic esters; styrenes such as methylstyrene, chloromethylstyrene and o-, m- and p-hydroxystyrene, divinylbenzene; vinyl ethers such as isobutyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether and phenylvinyl ether vinyl ethers, such as vinyl acetate, vinyl acrylate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate, divinyl succinate, diallyl phthalate, triallyl phosphate, vinyl chloride and vinylidene chloride; isocyanurates, such as triallyl isocyanurate and tris(2-acryloylethyl)isocyanurate; N-vinyl heterocyclic compounds, such as N-vinylpyrrolidone or substituted N-vinylpyrrolidone, N-vinylcaprolactam or substituted N-vinylcaprolactam, N-vinylcarbazole or N-vinylpyridine.

[0128] Suitable monomers may also be difunctional or higher-functional compounds, for example diacrylates, such as 1,6-hexanediol diacrylate (HDDA), ethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate (TPGDA), neopentyl glycol diacrylate, hexamethylene glycol diacrylate and bisphenol A diacrylate; trimethylolpropane triacrylate (TMPTA), trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate; tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate (TEGDMA), tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol acrylate. Hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol triitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethyl Acrylates, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol-modified triacrylates, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates and methacrylates, glycerol di- and triacrylates, 1,4-cyclohexane diacrylate, diacrylates and dimethacrylates of polyethylene glycol having a molecular weight of 200-1500; or mixtures thereof.

[0129] In particular, the pyruvic acid (hetero)aryl thioester compounds of the general formula (I) of the present invention are suitable for photopolymerization of (meth) acrylic compounds, preferably epoxy (meth) acrylic resins, polyurethane (meth) acrylic resins, polyester (meth) acrylic resins, polyether (meth) acrylic resins, acrylated poly (meth) acrylic resins, or monofunctional, difunctional or higher functionality (meth) acrylates as defined above.

[0130] In addition to the photoinitiator, the photopolymerizable composition may contain various additives. Examples are thermal inhibitors intended to prevent premature polymerization, such as 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl and its derivatives; antistatic agents; flow improvers and adhesion promoters; photopolymerization accelerators, such as amines, especially tertiary amines, such as tributylamine, triethanolamine, ethyl p-dimethylaminobenzoate, Michler's ketone, N-methyldiethanolamine, N,N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine, diazabicyclooctane (triethylenediamine), 18-diazabicyclo[5. 4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and salts thereof; chain transfer agents; photosensitizers for changing or broadening the spectral sensitivity, for example aromatic carbonyl compounds, for example benzophenone derivatives, thioxanthone derivatives, including in particular isopropylthioxanthone, anthraquinone derivatives and 3-acylcoumarin derivatives, terphenyls, styryl ketones and 3-(aroylmethylene)thiazolines, camphorquinones as well as eosin, rhodamine and erythrosine dyes; fillers; or pigments.

[0131] The photopolymerizable compositions according to the invention can be used for various purposes, for example as printing inks (e.g. screen printing inks, offset or flexographic printing inks, inkjet inks, sheet-fed printing inks, electrophotographic inks, gravure inks), as clear, white or pigmented coatings, in photocopying processes, in holographic recording materials, in image recording processes or for producing printing plates that can be developed with organic solvents or with aqueous alkaline media, for producing masks for screen printing, as dental filling compounds, as adhesives, as pressure-sensitive adhesives, as laminating resins, as etch resists or permanent resists, as photostructurable dielectrics and as solder masks for electronic circuits, as resists for producing color filters for display screens of any type or for generating structures during the production of plasma and electroluminescent displays, for producing optical switches, gratings, for producing three-dimensional articles by bulk polymerization or according to stereolithography, for producing composite materials of gel coatings and thick-layer compositions, for coating or sealing electronic components or as coatings for optical fibers. The compositions are also suitable for producing optical lenses, such as contact lenses or Fresnel lenses, and for the manufacture of medical devices, aids or implants.

[0132] In another aspect of the present invention, there is provided use of the pyruvic acid (hetero)aryl thioester compound of the general formula (I) of the present invention as a photoinitiator in photopolymerization.

[0133] The pyruvic acid (hetero)aryl thioester compounds of the general formula (I) of the present invention have excellent biocompatibility and are therefore suitable for the preparation of biopolymer materials. Suitable biopolymer materials can be polymer materials obtained from the photopolymerizable composition described above.

[0134] Therefore, in another aspect of the present invention, there is provided use of the pyruvic acid (hetero)aryl thioester compounds of the general formula (I) of the present invention in the preparation of biopolymer materials.

[0135] The present invention has the beneficial effect of better matching the wavelength of LED light sources with the pyruvic acid (hetero)aryl thioester compounds of general formula (I) compared to conventional photoinitiators. In particular, the photoinitiators of the present invention exhibit excellent initiation performance under both 405nm and 455nm LED light sources, effectively initiating the photopolymerization of photopolymerizable monomers, particularly (meth)acrylate monomers. Furthermore, they exhibit excellent biocompatibility and a simple synthetic route, resulting in extremely high practical value.

[0136] Example

[0137] The present invention will be further described below with reference to specific embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0138] Example 1: Synthesis of photoinitiator Me-PTE

[0139] The synthetic route of Me-PTE is as follows:

[0140] 4-Methylthiophenol (1.24 g, 10 mmol), pyruvic acid (1.056 g, 12 mmol), and 4-dimethylaminopyridine (DMAP) (0.12 g, 1 mmol) were added to a 100 mL single-necked flask, and then 30 mL of anhydrous dichloromethane was added to the flask to dissolve them. Dicyclohexylcarbodiimide (DCC) (2.47 g, 12 mmol) was dissolved in 20 mL of anhydrous dichloromethane and added to a normal pressure dropping funnel. The dichloromethane solution of DCC was then added dropwise to the single-necked flask at a rate of 1-2 drops per second. After the addition was completed, the reaction system was stirred at 25°C for 6 hours. After the reaction was completed, the white solid impurities were filtered out and the solution was retained. The reaction system was then separated and purified using a silica gel column chromatography to obtain the product, obtaining Me-PTE as a yellow oily liquid.

[0141] 1H NMR (400 MHz, CHLOROFORM-d) δ 7.34-7.24 (m, 4H), 2.46 (s, 3H), 2.42 (s, 3H).

[0142] 13C NMR (100 MHz, chloroform-d) δ 193.50, 189.75, 140.24, 134.31, 130.32, 122.69, 24.05, 21.38.

[0143] Example 2: Synthesis of photoinitiator MO-PTE

[0144] The synthetic route of MO-PTE is as follows:

[0145] 4-Methoxythiophenol (1.40 g, 10 mmol), pyruvic acid (1.056 g, 12 mmol), and DMAP (0.12 g, 1 mmol) were added to a 100 mL single-necked flask, followed by the addition of 30 mL of anhydrous dichloromethane to dissolve the mixture. DCC (2.47 g, 12 mmol) was dissolved in 20 mL of anhydrous dichloromethane and added to a normal pressure dropping funnel. The dichloromethane solution was then added dropwise to the single-necked flask at a rate of 1-2 drops per second. After the addition was complete, the reaction system was stirred at 25°C for 6 h. After the reaction was complete, the white solid impurities were filtered out and the solution was retained. The reaction system was then separated and purified using a silica gel column chromatography to obtain the product, MO-PTE, as a yellow oily liquid.

[0146] 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.34 (dd, 2H), 7.00 (dd, J=8.5, 1.7 Hz, 2H), 3.86 (s, 3H), 2.46 (s, 3H).

[0147] 13 C NMR (100 MHz, chloroform-d) δ 193.59, 190.15, 161.03, 135.92, 116.64, 115.20, 55.40, 24.07.

[0148] Example 3: Synthesis of Photoinitiator F-PTE

[0149] The synthetic route of F-PTE is as follows:

[0150] 4-Fluorobenzenethiol (1.28 g, 10 mmol), pyruvic acid (1.056 g, 12 mmol), and DMAP (0.12 g, 1 mmol) were added to a 100 mL single-necked flask, and 30 mL of anhydrous dichloromethane was subsequently added to the flask to dissolve them. DCC (2.47 g, 12 mmol) was dissolved in 20 mL of anhydrous dichloromethane and added to a normal pressure dropping funnel. The dichloromethane solution of DCC was then added dropwise to the single-necked flask at a rate of 1-2 drops per second. After the addition was complete, the reaction system was stirred and reacted at 25° C. for 6 h. After the reaction was complete, the white solid impurities were filtered out and the solution was retained. The reaction system was then separated and purified using a silica gel column chromatography to obtain the product, obtaining F-PTE as a yellow oily liquid.

[0151] 1H NMR (400 MHz, CHLOROFORM-d) δ 7.45-7.36 (m, 2H), 7.22-7.12 (m, 2H), 2.46 (s, 3H).

[0152] 13 C NMR (100 MHz, chloroform-d) δ 193.13, 189.31, 165.01, 162.52, 136.53, 136.44, 121.63, 121.60, 116.93, 116.71, 23.97.

[0153] Example 4: Synthesis of Photoinitiator Nap-PTE

[0154] The synthetic route of Nap-PTE is as follows:

[0155] 2-naphthol (1.60 g, 10 mmol), pyruvic acid (1.056 g, 12 mmol) and DMAP (0.12 g, 1 mmol) were added to a 100 mL single-necked flask, and then 30 mL of anhydrous dichloromethane was added to the flask to dissolve it. DCC (2.47 g, 12 mmol) was dissolved in 20 mL of anhydrous dichloromethane and added to a normal pressure dropping funnel. The dichloromethane solution of DCC was then added dropwise to the single-necked flask at a rate of 1-2 drops per second. After the addition was completed, the reaction system was stirred and reacted at 25 ° C for 6 hours. After the reaction was completed, the white solid impurities were filtered out and the solution was retained. The reaction system was then separated and purified using a silica gel column chromatography to obtain the product, obtaining Nap-PTE as a yellow oily liquid.

[0156] 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.03-7.83 (m, 4H), 7.65-7.40 (m, 3H), 2.50 (s, 3H).

[0157] 13 C NMR (100 MHz, chloroform-d) δ 193.40, 189.55, 134.56, 133.61, 133.54, 130.44, 129.16, 127.97, 127.89, 127.44, 126.78, 123.58, 24.04.

[0158] Example 5:

[0159] The purpose of Example 5 is to illustrate the light absorption performance of the pyruvic acid (hetero)aryl thioester photoinitiators of Examples 1-4.

[0160] The photoinitiators of Examples 1-4 were prepared to a concentration of 1×10 -4 mol L-1 The UV-visible absorption curves of the anhydrous acetonitrile solutions of the four photoinitiators in the wavelength range of 200-500 nm were tested using a UV spectrophotometer.

[0161] The UV-visible absorption spectra of the four photoinitiators are shown in Figures 2 and 3. It can be seen that the four photoinitiators PTEs have a certain absorption capacity in the visible light region above 400 nm (see the values ​​shown in Table 1 below) and are suitable for LED light sources.

[0162] Table 1

[0163] Examples 6-9:

[0164] The purpose of Examples 6-9 is to illustrate that the pyruvic acid (hetero)aryl thioester photoinitiators of Examples 1-4 can effectively initiate the photopolymerization reaction of acrylate monomers under the irradiation of LED light source.

[0165] 1. Prepare photosensitive resin

[0166] Four monomers, tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), triethylene glycol dimethacrylate (TEGDMA) and methyl methacrylate (MMA), and the pyruvic acid (hetero)aryl thioester photoinitiator prepared in Examples 1-4 were selected, and a photosensitive solution was prepared according to the following proportions:

[0167] Example 6:

[0168] Appropriate amounts of monomer tripropylene glycol diacrylate (TPGDA) and the photoinitiator of Example 1-4 were weighed respectively to prepare a photosensitive solution, with the mass ratio of photoinitiator to monomer being photoinitiator:TPGDA=1:100.

[0169] Example 7:

[0170] Appropriate amounts of monomer trimethylolpropane triacrylate (TMPTA) and the photoinitiator of Examples 1-4 were weighed respectively to prepare a uniform photosensitive solution, with the mass ratio of photoinitiator to monomer being photoinitiator:TMPTA=1:100.

[0171] Example 8:

[0172] Appropriate amounts of monomer triethylene glycol dimethacrylate (TEGDMA) and the photoinitiator of Example 1-4 were weighed respectively to prepare a photosensitive solution, with the mass ratio of photoinitiator to monomer being photoinitiator:TEGDMA=1:100.

[0173] Example 9: Appropriate amounts of monomer methyl methacrylate (MMA) and the photoinitiator of Example 1-4 were weighed respectively to prepare a photosensitive solution, with the mass ratio of photoinitiator to monomer being photoinitiator:MMA=1:100.

[0174] 2. Photopolymerization performance test

[0175] Appropriate amounts of the prepared photosensitive solutions in Examples 6-9 were taken with a capillary tube and evenly coated onto a KBr salt sheet to a thickness of approximately 30 μm. The salt sheet was then covered with another layer of salt to minimize the effects of oxygen in the air on polymerization. Photopolymerization kinetics were measured using a real-time infrared spectrometer (Nicolet 5700, Thermo Fisher Scientific, USA) with a light source having an emission wavelength of 405 nm or 455 nm (the light intensity reaching the photosensitive solution was set to 60 mW / cm 2 ).

[0176] Figures 4 and 5 show the double bond conversion curves of TPGDA initiated by the photoinitiators of Examples 1-4 under 405nm and 455nm LED illumination, respectively. Figure 6 shows the double bond conversion curves of TMPTA initiated by the photoinitiators of Examples 1-4 under 405nm LED illumination. Figures 7 and 8 show the double bond conversion curves of TEGDMA and MMA initiated by the photoinitiators of Examples 1-4 under 405nm LED illumination, respectively. Thus, the (hetero)aryl thiopyruvate photoinitiators of the present invention can effectively initiate the photopolymerization reaction of (meth)acrylate monomers under 405nm and 455nm LED illumination, demonstrating that the photoinitiators of the present invention have excellent initiation performance and applicability in LED photopolymerization systems.

[0177] Example 10:

[0178] The purpose of Example 10 is to illustrate that the pyruvic acid (hetero)aryl thioester photoinitiator MO-PTE used in Example 2 has good biocompatibility.

[0179] 1. Cytotoxicity test

[0180] MO-PTE was dissolved in dimethyl sulfoxide and added to the culture medium of cervical cancer cells (Hela) at different concentrations. The cells were cultured at 25°C for 24 hours, and the absorbance at a specific wavelength was measured using a microplate reader to detect cell survival.

[0181] Figure 9 shows the cell viability of cells cultured in medium supplemented with MO-PTE. L represents the illumination of the MO-PTE-containing dimethyl sulfoxide solution with a 405 nm LED for 30 seconds before culturing the cells. Figure 9 demonstrates that HeLa cells maintained high viability after incubation with medium supplemented with MO-PTE at varying concentrations, demonstrating the good biocompatibility of the photoinitiator MO-PTE.

Claims

1. A pyruvic acid (hetero)aryl thioester compound of general formula (I): in: M stands for C6-C 18 aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O, wherein C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkyl, C7-C 20 Alkaryloxy, C7-C 20 alkylthio or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O, wherein the mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkyl, C7-C 20 Alkaryloxy, C7-C 20 The alkarylthio group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino.

2. The pyruvic acid (hetero)aryl thioester compound according to claim 1, wherein: M stands for C6-C 18 aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O, Among them, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio or C7-C 20 Alkaryl; mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio or C7-C 20 The alkaryl group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino; More preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 The arylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino; More preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkylthio, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy and C6-C 18 The arylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, A mercapto group, a carboxyl group, a sulfonic acid group, a carboxylate group or an amino group; More preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, -CF3, -OCF3 or -OC6H5.

3. The pyruvic acid (hetero)aryl thioester compound according to claim 1 or 2, wherein: M stands for C6-C 18 aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O, Among them, C6-C 18 The aryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of fluoro, methyl or methoxy.

4. The pyruvic acid (hetero)aryl thioester compound according to any one of claims 1 to 3, wherein: M stands for Wherein R1 is selected from O, S or -NR 10 -; R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkyl, C7-C 20 Alkaryloxy, C7-C 20 alkylthio or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Fang Alkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkyl, C7-C 20 Alkaryloxy, C7-C 20 The alkarylthio group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino; R 10 Represents hydrogen, C1-C 20 Alkyl, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 an alkylaryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O; wherein C1-C 20 Alkyl, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 The alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino.

5. The pyruvic acid (hetero)aryl thioester compound according to claim 4, wherein M represents wherein R2, R3, R4, R5, R6, R7, R8, and R9 are as defined in claim 4.

6. The pyruvic acid (hetero)aryl thioester compound according to claim 4 or 5, wherein: R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 The arylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, thiol, carboxyl, sulfonic acid, carboxylate or amino; further preferably, R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkylthio, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy and C6-C 18 The arylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino; More preferably, R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, -CF3, -OCF3 or -OC6H5; Most preferably, R2, R3, R5, R6, R7, R8, R9 are the same and are H; R4 is selected from fluoro, methyl or methoxy.

7. The pyruvic acid (hetero)aryl thioester compound according to any one of claims 1 to 6, wherein: R 10 Represents hydrogen, C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 an alkylaryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O; wherein C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 The alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino.

8. The pyruvic acid (hetero)aryl thioester compound according to any one of claims 1 to 7, which is:

9. A method for preparing a pyruvic acid (hetero)aryl thioester compound according to any one of claims 1 to 8, comprising: Make pyruvate and The reaction is carried out in the presence of a dehydrating agent and a catalyst to obtain a pyruvic acid (hetero)aryl thioester compound, namely: wherein M is as defined in any one of claims 1-8.

10. The process according to claim 9, wherein the reaction is carried out in the presence of one or more catalysts selected from the group consisting of 4-dimethylaminopyridine, piperidine, 3-methylpiperidine and triethylamine, preferably 4-dimethylaminopyridine; and / or the molar amount of the catalyst is 1-10%, preferably 5-10%, of M-SH.

11. The method according to claim 9 or 10, wherein the reaction is carried out in the presence of one or more dehydrating agents selected from the group consisting of dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, preferably dicyclohexylcarbodiimide; and / or the molar amount of the dehydrating agent is 100-150%, preferably 120-140%, of M-SH.

12. The method according to any one of claims 9 to 11, wherein the molar ratio of M-SH to pyruvic acid is 1:1.1-1:3, preferably 1:1.1-1:2, more preferably 1:1.2-1:

2.

13. A photopolymerizable composition comprising: (A) at least one monomeric or oligomeric ethylenically unsaturated photopolymerizable compound, and (B) at least one pyruvic acid (hetero)aryl thioester compound obtained according to any one of claims 1 to 8 or according to any one of claims 9 to 12.

14. Use of the pyruvic acid (hetero)aryl thioester compound obtained according to any one of claims 1 to 8 or the method according to any one of claims 9 to 12 as a photoinitiator in photopolymerization.

15. Use of the pyruvic acid (hetero)aryl thioester compound obtained according to the method of any one of claims 1 to 8 or any one of claims 9 to 12 in the preparation of biopolymer materials.

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