Organosilicon macromolecular azide coupling agent and preparation method thereof

Abstract

The invention discloses an organic silicon macromolecular azide coupling agent and a preparation method thereof. The organic silicon macromolecular azide coupling agent comprises three main chain structures: a linear single-chain structure, a trapezoidal double-chain structure and a three-chain structure. The organic silicon-containing azide coupling agent disclosed by the invention is easy to break and recombine under the condition of ultraviolet irradiation, so that the crosslinking of materials is realized.

Description

Technical Field

[0001] The present invention relates to an organosilicon macromolecular azide coupling agent and a preparation method thereof, and more specifically to a macromolecular photocoupler containing an organosilicon structure and an azide functional group, and specifically to an organosilicon macromolecular azide coupling agent with a linear single chain, a ladder double chain and a triple chain structure and a preparation method thereof. The technology is mainly used in photosensitive materials, photoresists, UV-CTP plates and OLED displays, and belongs to the field of organosilicon functional materials. Background Art

[0002] Small molecule photocrosslinkers are a class of compounds that can generate highly active intermediates under irradiation with light of a specific wavelength and form covalent bonds with the active sites of their receptors. These crosslinkers are widely used in photoresists, photosensitive coatings, and biological research due to their unique photosensitivity. According to the different active intermediates generated under light irradiation, small molecule photocrosslinkers can be divided into the following four categories: The first category is nitrenes, which mainly release nitrogen gas under light through the azide group on the aromatic ring to form highly active nitrene intermediates. Nitrene intermediates can be singlet states or form triplet states through intersystem crossing, and their singlet states can be inserted into CH bonds or XH bonds (X=N, O, S) to form stable covalent bonds. This mechanism gives nitrene photocrosslinkers efficient crosslinking properties. The second category is carbenes, including diazo compounds and diaziridine compounds. Diazo compounds release nitrogen gas under ultraviolet light to form carbene intermediates, which then react with adjacent CH bonds to form new covalent bonds. Diaziridine compounds also generate carbene intermediates through a similar process and react chemically with the matrix to complete cross-linking. The third category is carbocations, represented by aromatic diazonium salts. These compounds generate aromatic cation intermediates under the action of ultraviolet light and react with adjacent CH bonds or other heteroatom-hydrogen bonds to form a stable cross-linked structure. The fourth category is free radicals. This type of photocrosslinker generates free radicals under light irradiation and triggers cross-linking reactions between molecules to form a network structure.

[0003] Among the above types, azide small molecule photocrosslinkers occupy an important position in many applications due to their unique advantages. Their main advantages include: (1) Chemical stability: they can withstand ordinary chemical environments without decomposition. (2) Light stability: they have good stability in natural light and darkness and are not prone to spontaneous decomposition. (3) Rapid photolysis: they can be rapidly photolyzed under ultraviolet light to generate highly active nitrene intermediates. (4) High reactivity: the generated intermediates can react with nucleophilic functional groups (such as XH bonds, X=N, O, S) and can also be inserted into CH bonds to form covalent bonds.

[0004] Although azide-based small molecule photocrosslinkers have many advantages, they also have some disadvantages that cannot be ignored. For example, in some cases, this type of crosslinker may cause non-specific crosslinking. If the active site of the substrate lacks nucleophilic functional groups, the active intermediates may migrate to areas far away from the target, resulting in non-ideal crosslinking. In addition, the small molecular weight of small molecule azide compounds leads to uneven distribution in the material, which may affect the final crosslinking effect and material performance consistency.

[0005] Silicone materials have become an important component of modern polymer materials due to their unique properties. Their thermal stability, chemical inertness and excellent mechanical properties make them irreplaceable in many fields. The high bond energy of silicon-oxygen bonds gives silicone materials excellent thermal stability and weather resistance; their flexible molecular main chain gives the material excellent processing performance and elasticity. More importantly, silicone materials can achieve structural design through a variety of chemical pathways, such as linear single chain, ladder double chain and triple chain structures, etc., to meet the functional and structural needs of different fields. Summary of the invention

[0006] In order to overcome these disadvantages, we tried to introduce azide functional groups into the organosilicon macromolecular structure. Through this design, we can retain the photosensitivity of azide photocrosslinkers while improving their storage stability and crosslinking uniformity by utilizing the macromolecular structure.

[0007] The present invention introduces azide functional groups into organosilicon macromolecules, which not only inherits the high efficiency of azide group photocrosslinking, but also significantly improves the stability and processing performance of the material. This innovative design uses organosilicon macromolecules as carriers to evenly distribute azide groups on the main chain, avoiding the problem of uncontrollable crosslinking density in traditional small molecule azide coupling agents, while significantly reducing toxicity and explosion risks.

[0008] The purpose of the present invention is to provide an organosilicon macromolecular azide coupling agent with excellent performance.

[0009] The organosilicon macromolecular azide coupling agent provided by the present invention comprises three main chain structures:

[0010] (1) Linear single chain structure, the structural formula of which is shown in formula (1); it has good flexibility and easy processing, and is suitable for materials with low cross-linking density;

[0011] (2) Ladder double-chain structure, the structural formula of which is shown in formula (2); it improves the spatial stability and intermolecular force of the material and is suitable for high-strength applications;

[0012] (3) a three-chain structure, the structural formula of which is shown in formula (3); while increasing the cross-linking density, it also gives the material higher thermal stability and mechanical strength;

[0013]

[0014] In formula (1), formula (2) and formula (3), R 1 , R 2 , R 3 , R 4 Each independently represents a hydrogen atom, C 1 -C 10 Straight or branched alkyl (specifically C 1 -C 6 Straight-chain or branched alkyl groups, such as methyl and ethyl), mercapto groups, substituted or unsubstituted aromatic groups (such as phenyl), C 2 -C 10 Alkenyl (specifically C 2 -C 6 alkenyl, such as vinyl, propenyl), ( Represents C 1 -C 6 Straight or branched chain alkylene or n=an integer of 1-3, specifically one of 1), and R 1 , R 2 , R 3 , R 4 At least one of

[0015] x, y represent any value between 1 and 10;

[0016] R 5 It represents a capping group, which can be any of the following groups obtained by removing chlorine from the capping agents trimethylchlorosilane, dimethylvinylchlorosilane, and dimethylphenylchlorosilane.

[0017] The present invention also provides a method for preparing the above-mentioned organosilicon macromolecular azide coupling agent, wherein R 1 for The preparation method of the compound represented by formula (1) is as follows: the compound represented by formula (4) is dissolved in an acid solution, cooled to the reaction temperature, and sodium nitrite aqueous solution and sodium azide aqueous solution are added in sequence. After the reaction is completed, the solution is filtered and washed with water, and recrystallized with acetone to obtain the compound represented by formula (1).

[0018]

[0019] In formula (4), R 2 , R 3 , R 4 , R 5 , x, y are defined as R in formula (1) 2 , R 3 , R 4 , R 5, the definition of x, y;

[0020] In the above method, the acid is selected from at least one of hydrochloric acid, sulfuric acid, and nitric acid;

[0021] The molar ratio of the compound represented by formula (4) to sodium nitrite and sodium azide can be: 1:1-2:1-2;

[0022] The reaction temperature is 0-10°C, preferably 0-4°C;

[0023] The reaction time can be 0.2-3h.

[0024] The compound represented by the above formula (4) is prepared by a method comprising the following steps:

[0025] The compound represented by formula (5) and the compound represented by formula (6) are dissolved in an organic solvent, a palladium catalyst, a ligand, and a base are added, and a Heck reaction is performed to obtain a compound represented by formula (4);

[0026]

[0027] In formula (5), R 2 , R 3 , R 4 , R 5 , x, y are defined as R in formula (1) 2 , R 3 , R 4 , R 5 , definitions of x, y.

[0028] In the above method, the palladium catalyst is Pd(OAc) 2 or Pd(PPh 3 ) 4 ;

[0029] The ligand may specifically be tri(o-tolyl)phosphine;

[0030] The base is selected from at least one of potassium carbonate, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium bicarbonate, and triethylamine;

[0031] The temperature of the Heck reaction can be 60-120° C., and the time can be 0.2-5 h.

[0032] The compound represented by the above formula (5) is prepared by a method comprising the following steps: dissolving the compound represented by the formula (7) and the compound represented by the formula (8) to undergo hydrolysis condensation reaction, and adding a capping agent R 5 -Cl, to obtain a compound represented by formula (5);

[0033]

[0034] In formula (7), R 2 , x is defined the same as R in formula (1) 2 , the definition of x;

[0035] In formula (8), R 3 , R 4 , y is defined the same as R in formula (1) 3 , R 4 , definition of y;

[0036] R 5 -R in Cl 5 The definition of is the same as R in formula (1) 5 Definition of .

[0037] The compound represented by formula (7) can be prepared by hydrolysis and condensation of the compound represented by formula (9), and the compound represented by formula (8) can be prepared by hydrolysis and condensation of the compound represented by formula (10);

[0038]

[0039] R 1 for The preparation method of the compound represented by formula (2) is as follows: dissolving the compound represented by formula (11) in an acid solution, cooling to the reaction temperature, sequentially adding a sodium nitrite aqueous solution and a sodium azide aqueous solution, filtering and washing with water after the reaction is completed, and recrystallizing with acetone to obtain the compound represented by formula (2).

[0040]

[0041] In formula (11), R 2 , R 3 , R 4 , R 5 , x, y are defined the same as R in formula (2) 2 , R 3 , R 4 , R 5 , the definition of x, y;

[0042] In the above method, the acid is selected from at least one of hydrochloric acid, sulfuric acid, and nitric acid;

[0043] The molar ratio of the compound represented by formula (11) to sodium nitrite and sodium azide can be: 1:1-2:1-2;

[0044] The reaction temperature is 0-10°C, preferably 0-4°C;

[0045] The reaction time can be 0.2-3h.

[0046] The compound represented by the above formula (11) is prepared by a method comprising the following steps:

[0047] The compound represented by formula (12) and the compound represented by formula (6) are dissolved in an organic solvent, a palladium catalyst, a ligand, and a base are added, and a Heck reaction is performed to obtain a compound represented by formula (11);

[0048]

[0049] In formula (12), R 2 , R 3 , R 4 , R 5 , x, y are defined the same as R in formula (2) 2 , R 3 , R 4 , R 5 , x, y definitions

[0050] In the above method, the palladium catalyst is Pd(OAc) 2 or Pd(PPh 3 ) 4 ;

[0051] The ligand may specifically be tri(o-tolyl)phosphine;

[0052] The base is selected from at least one of potassium carbonate, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium bicarbonate, and triethylamine;

[0053] The temperature of the Heck reaction can be 60-120° C., and the time can be 0.2-5 h.

[0054] The compound represented by the above formula (12) is prepared by a method comprising the following steps: dissolving the compounds represented by the formula (13) and the formula (14), subjecting them to hydrolysis and condensation reaction, and adding a capping agent R 5 -Cl, to obtain a compound represented by formula (12);

[0055]

[0056] In formula (13), R 2 , x is defined the same as R in formula (2) 2 , the definition of x;

[0057] In formula (14), R 3 , R 4 , y is defined the same as R in formula (2) 3 , R 4 , definition of y;

[0058] Wherein, the compound represented by formula (13) is prepared by dissolving the compound represented by formula (15) and the compound represented by formula (16) and subjecting them to a hydrolysis condensation reaction;

[0059]

[0060] In formula (16), R 2 The definition of is the same as R in formula (2) 2 Definition of;

[0061] The compound represented by formula (14) is prepared by dissolving the compound represented by formula (17) and the compound represented by formula (18) and subjecting them to a hydrolysis condensation reaction;

[0062]

[0063] In formula (17), R 3 The definition of is the same as R in formula (2) 3 Definition of;

[0064] In formula (18), R 4 The definition of is the same as R in formula (2) 4 Definition of .

[0065] R 1 for The preparation method of the compound represented by formula (3) is as follows: dissolving the compound represented by formula (19) in an acid solution, cooling to the reaction temperature, sequentially adding a sodium nitrite aqueous solution and a sodium azide aqueous solution, filtering and washing with water after the reaction is completed, and recrystallizing with acetone to obtain the compound represented by formula (3);

[0066]

[0067] In formula (19), R 2 , R 3 , R 4 , R 5 , x, y are defined the same as R in formula (3) 2 , R 3 , R 4 , R 5 , the definition of x, y;

[0068] In the above method, the acid is selected from at least one of hydrochloric acid, sulfuric acid, and nitric acid;

[0069] The molar ratio of the compound represented by formula (19) to sodium nitrite and sodium azide can be: 1:1-2:1-2;

[0070] The reaction temperature is 0-10°C, preferably 0-4°C;

[0071] The reaction time can be 0.2-3h.

[0072] The compound represented by the above formula (19) is prepared by a method comprising the following steps:

[0073] The compound represented by formula (20) and the compound represented by formula (6) are dissolved in an organic solvent, a palladium catalyst, a ligand, and a base are added, and a Heck reaction is performed to obtain a compound represented by formula (19);

[0074]

[0075] In formula (20), R 2 , R 3 , R 4 , R 5 , x, y are defined the same as R in formula (3) 2 , R 3 , R 4 , R 5 , the definition of x, y;

[0076] In the above method, the palladium catalyst is Pd(OAc) 2 or Pd(PPh 3 ) 4 ;

[0077] The ligand may specifically be tri(o-tolyl)phosphine;

[0078] The base is selected from at least one of potassium carbonate, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium bicarbonate, and triethylamine;

[0079] The temperature of the Heck reaction can be 60-120° C., and the time can be 0.2-5 h.

[0080] The compound represented by the above formula (20) is prepared by a method comprising the following steps: dissolving the compound represented by the formula (21) and the compound represented by the formula (22), subjecting them to hydrolysis and condensation reaction, and adding a capping agent R 5 -Cl, to obtain a compound represented by formula (20):

[0081]

[0082] In formula (21), R 2 , x is defined the same as R in formula (3) 2 , the definition of x;

[0083] In formula (22), R 3 , R 4 , y is defined the same as R in formula (3) 3 , R 4 , definition of y;

[0084] R 5 -R in Cl 5 The definition of is the same as R in formula (3) 5 Definition

[0085] Wherein, the compound represented by formula (21) is prepared by hydrolyzing and condensing the compounds represented by formula (15), formula (16), and formula (23);

[0086]

[0087] The compound represented by formula (22) is prepared by hydrolyzing and condensing the compounds represented by formula (17), formula (18) and formula (23).

[0088] The above-mentioned organosilicon macromolecular azide coupling agent is used as a photocrosslinking agent in the preparation of photocrosslinking materials (such as photoresists, liquid crystal displays and biological imaging).

[0089] The above-mentioned organosilicon macromolecular azide coupling agent is prone to breakage and recombination reactions under ultraviolet light irradiation conditions, thereby achieving cross-linking of the material.

[0090] The above-mentioned organosilicon macromolecular azide coupling agent needs to be stored at low temperature and away from light.

[0091] The organic silicon macromolecular azide coupling agent can be used in photoresist and can also be used in other photo-crosslinked materials.

[0092] The present invention develops a macromolecular azide coupling agent with excellent performance by combining a variety of organosilicon structures such as linear single chains, ladder double chains and triple chains through molecular design. The coupling agent of the present invention can efficiently decompose and realize cross-linking of materials under ultraviolet light irradiation, showing the following advantages: (1) Efficient cross-linking: The uniform distribution of azide groups improves the uniformity and density of cross-linking. (2) Safety and stability: The macromolecular structure significantly improves the storage stability of the material and reduces toxicity and explosion risks. (3) Multifunctional adaptation: The structural flexibility makes it suitable for multiple fields such as photoresists, liquid crystal displays and biological imaging, showing broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0093] Figure 1 This is a diagram showing the effect of exposure and development in Example 10 of the present invention. DETAILED DESCRIPTION

[0094] The present invention is further described in detail below in conjunction with specific embodiments, and the examples provided are only for illustrating the present invention, rather than for limiting the scope of the present invention. The examples provided below can be used as a guide for further improvements by those of ordinary skill in the art, and do not constitute a limitation of the present invention in any way.

[0095] The experimental methods in the following examples, unless otherwise specified, are all conventional methods, and are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. The materials, reagents, etc. used in the following examples, unless otherwise specified, can all be obtained from commercial channels.

[0096] The present invention aims to develop an organosilicon macromolecular azide coupling agent with excellent performance, which is unique in that it contains three main chain structures:

[0097] (1) Linear single chain structure: has good flexibility and easy processing, suitable for materials with low cross-linking density;

[0098] (2) Ladder double-chain structure: improves the spatial stability and intermolecular force of the material, suitable for high-strength applications;

[0099] (3) Triple-chain structure: While increasing the cross-linking density, it also gives the material higher thermal stability and mechanical strength. Including but not limited to an organosilicon macromolecular azide coupling agent and its preparation method.

[0100] The organosilicon macromolecular azide coupling agent is mainly a compound represented by the following three structures:

[0101]

[0102] In formula (1), formula (2) and formula (3), R 1 , R 2 , R 3 , R 4 Each independently represents a hydrogen atom, C 1 -C 10 Straight or branched alkyl (specifically C 1 -C 6 Straight-chain or branched alkyl groups, such as methyl and ethyl), mercapto groups, substituted or unsubstituted aromatic groups (such as phenyl), C 2 -C 10 Alkenyl (specifically C 2 -C 6 alkenyl, such as vinyl, propenyl), ( Represents C 1 -C 6 Straight or branched chain alkylene or n=an integer of 1-3, specifically one of 1), and R 1 , R 2 , R 3 , R 4 At least one of

[0103] x, y represent any value between 1 and 10;

[0104] R 5 It represents the end-capping group, which can be any of the following groups obtained by removing chlorine from the end-capping agents trimethylchlorosilane, dimethylvinylchlorosilane, and dimethylphenylchlorosilane

[0105] In some embodiments, taking x=3 and y=3 as an example, the typical structure represented by formula (1) includes:

[0106]

[0107] In some embodiments, taking x=3 and y=3 as an example, the typical structure represented by formula (2) includes:

[0108]

[0109] In some embodiments, taking x=3 and y=3 as an example, the typical structure represented by formula (3) includes:

[0110]

[0111] Example 1. Synthesis of the compound of formula 1a

[0112] Synthesis of compound of formula 26:

[0113]

[0114] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2 g, stirred for 10 min, added 40 g of dry THF, stirred for another 30 min, then added the compound shown in formula 28 (4.8 g, 0.04 mol) dropwise through a syringe at normal pressure, and stirred at room temperature for 36 h. Extracted three times with dichloromethane (15 mL), collected the upper organic layer, and precipitated it in MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 10.0 g of the compound represented by formula 26 with a yield of 93%.

[0115] Synthesis of compound of formula 25:

[0116]

[0117] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2 g, stirred for 10 min, added 40 g of dry THF, stirred for another 30 min, then added the compound shown in formula 27 (5.28 g, 0.04 mol) dropwise through a syringe at normal pressure, and stirred at room temperature for 36 h. Extracted three times with dichloromethane (15 mL), collected the upper organic layer, and precipitated it in MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 10.8 g of the compound represented by formula 25 with a yield of 93%.

[0118] Synthesis of compound of formula 24:

[0119]

[0120] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2g, stirred for 10min, added 40g dry THF, stirred for another 30min, then added the compounds shown in formula 25 (5.82g, 0.02mol) and formula 26 (5.34g, 0.02mol) dropwise through a syringe at normal pressure, stirred at room temperature for 36h. Finally, 4.34g (0.08mol) of trimethylsilyl chloride was added for end-capping, extracted three times with dichloromethane (15mL), and the upper organic layer was collected and precipitated on MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 12.09 g of the compound represented by formula 24 with a yield of 94%.

[0121] Synthesis of compound of formula 1a-1:

[0122]

[0123] Take 6.43g (0.01mol) of the compound shown in Formula 24, add 1.72g of the compound shown in Formula 6, add 100ml of acetonitrile, add 0.3g of triethylamine, add to a three-necked flask, replace the air with nitrogen bubbling, add to an ice-water bath, and add Pd(OAc) 2 0.2 g of tri(o-tolyl)phosphine was added and the mixture was heated to reflux with stirring for 1 h. After the reaction was completed, the mixture was filtered and distilled to obtain 7.66 g of the compound shown in 1a-1 with a yield of 83.5%.

[0124] Synthesis of compound of formula 1a:

[0125]

[0126] Take 9.17 g (0.01 mol) of the compound represented by formula 1a-1 and add it into a 200 ml beaker. Stir mechanically, add 10 ml of concentrated hydrochloric acid to dissolve it, then cool the reaction temperature to 0-4 ° C, and add 1.38 g of sodium nitrite dissolved in 5 ml of water to prepare a sodium nitrite aqueous solution, and 1.56 g of sodium azide dissolved in 5 ml of water to prepare a sodium azide solution. React for 1.5 hours. After the reaction is completed, filter and wash with water, and recrystallize with acetone to obtain 8.46 g of the compound represented by formula 1a, with a yield of 85%.

[0127] Example 2: Synthesis of the compound represented by formula 1b

[0128] Synthesis of compound of formula 29:

[0129]

[0130] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2 g, stirred for 10 min, added 40 g of dry THF, stirred for another 30 min, then added the compound shown in formula 31 (5.37 g, 0.04 mol) dropwise through a syringe at normal pressure, and stirred at room temperature for 36 h. Extracted three times with dichloromethane (15 mL), collected the upper organic layer, and precipitated it in MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 11.18 g of the compound represented by formula 29 with a yield of 90%.

[0131] Synthesis of the compound shown in formula 28:

[0132]

[0133] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2 g, stirred for 10 min, added 40 g of dry THF, stirred for another 30 min, then added the compound shown in formula 30 (5.77 g, 0.04 mol) dropwise through a syringe at normal pressure, and stirred at room temperature for 36 h. Extracted three times with dichloromethane (15 mL), collected the upper organic layer, and precipitated it in MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 12.02 g of the compound represented by formula 28 with a yield of 92%.

[0134] Synthesis of compound of formula 27:

[0135]

[0136] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2g, stirred for 10min, added 40g dry THF, stirred for another 30min, then added the compound shown in formula 28 (6.5g, 0.02mol) and formula 29 (6.2g, 0.02mol) dropwise through a syringe at normal pressure, stirred at room temperature for 36h. Finally, 4.34g (0.08mol) of trimethylsilyl chloride was added for end-capping, extracted with dichloromethane (15mL) three times, and the upper organic layer was collected and precipitated on MgSO 4 The solution was filtered to remove MgSO 4The solvent was removed by rotary evaporation to obtain 11.0 g of the compound represented by formula 27 with a yield of 93%.

[0137] Synthesis of compound of formula 1b-1:

[0138]

[0139] Take 7.21g (0.01mol) of the compound shown in Formula 27, add 3.44g of the compound shown in Formula 6, add 100ml of acetonitrile, add 0.3g of triethylamine, add to a three-necked flask, replace the air with nitrogen bubbling, add to an ice-water bath, and add Pd(OAc) 2 0.2 g of tri(o-tolyl)phosphine was added and the mixture was heated to reflux with stirring for 1 h. After the reaction was completed, the mixture was filtered and distilled to obtain 17.52 g of the compound of formula 1b-1 with a yield of 83%.

[0140] Synthesis of the compound shown in Formula 1b:

[0141]

[0142] Take 17.49 g (0.01 mol) of the compound represented by formula 1b-1 and add it into a 200 ml beaker. Stir mechanically, add 10 ml of concentrated hydrochloric acid to dissolve it, then cool the reaction temperature to 0-4 ° C, add 2.76 g of sodium nitrite dissolved in 10 ml of water, and 3.12 g of sodium azide dissolved in 10 ml of water in turn, and react for 1.5 hours. After the reaction is completed, filter and wash with water, and recrystallize with acetone to obtain 16.0 g of the compound represented by formula 1b with a yield of 84%.

[0143] Example 3: Synthesis of the compound of formula 1c

[0144] Synthesis of compound of formula 32:

[0145]

[0146] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2g, stirred for 10min, added 40g dry THF, stirred for another 30min, then added 7.92g (0.06mol) of the compound shown in formula 33 dropwise through a syringe at normal pressure, stirred at room temperature for 36h. Finally, 4.34g (0.08mol) of trimethylsilyl chloride was added for end-capping, extracted three times with dichloromethane (15mL), and the upper organic layer was collected and concentrated in MgSO 4 The solution was filtered to remove MgSO 4 Most of the solvent was removed by rotary evaporator to obtain 6.37 g of the compound represented by formula 32 with a yield of 94%.

[0147] Synthesis of compound of formula 1c-1:

[0148]

[0149] Take 6.79g (0.01mol) of the compound shown in formula 32, add 3.44g of the compound shown in formula 6, add 100ml of acetonitrile, add 0.3g of triethylamine, add to a three-necked flask, replace the air with nitrogen bubbling, add to an ice-water bath, and add Pd(OAc) 2 0.2 g of tri(o-tolyl)phosphine was added and the mixture was heated to reflux with stirring for 1 h. After the reaction was completed, the mixture was filtered and distilled to obtain 10.42 g of the compound of formula 1c-1 with a yield of 85%.

[0150] Synthesis of compound of formula 1c:

[0151]

[0152] Take 12.25g (0.01mol) of the compound shown in formula 1c-1 and add it into a 200ml beaker. Stir mechanically, add 10ml of concentrated hydrochloric acid to dissolve it, then cool the reaction temperature to 0-4°C, then add a solution prepared by dissolving 2.76g of sodium nitrite in 10ml of water and a solution prepared by dissolving 3.12g of sodium azide in 10ml of water in sequence, react for 1.5h, filter and wash with water after the reaction is completed, and recrystallize from acetone to obtain 11.19g of the compound shown in formula 1c with a yield of 81%.

[0153] Example 4: Synthesis of the compound represented by formula 2a

[0154] Synthesis of the compound shown in formula 35:

[0155]

[0156] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2g, stirred for 10min, added 40g dry THF, stirred for another 30min, then added 8.88g, 0.06mol of the compound shown in formula 37 and 8.16g, 0.06mol of the compound shown in formula 38 dropwise through a syringe at normal pressure, stirred at room temperature for 36h. Extracted three times with dichloromethane (15mL), collected the upper organic layer and precipitated it in MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 4.89 g of the compound represented by formula 35 with a yield of 92%.

[0157] Synthesis of the compound represented by formula 36

[0158]

[0159] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2 g, stirred for 10 min, added 40 g of dry THF, stirred for another 30 min, then added 8.16 g, 0.06 mol of the compound shown in formula 38 dropwise through a syringe at normal pressure, and stirred at room temperature for 36 h. Extracted three times with dichloromethane (15 mL), collected the upper organic layer, and precipitated it in MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 4.60 g of the compound represented by formula 36 with a yield of 93%.

[0160] Synthesis of the compound shown in formula 34:

[0161]

[0162] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2 g, stirred for 10 min, added 40 g of dry THF, stirred for another 30 min, then added 5.31 g (0.01 mol) of the compound shown in formula 35 and 4.95 g (0.01 mol) of the compound shown in formula 36 dropwise through a syringe at normal pressure, stirred at room temperature for 36 h, and finally added 4.34 g (0.04 mol) of trimethylsilyl chloride for end-capping, extracted three times with dichloromethane (15 mL), collected the upper organic layer, and precipitated it in MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 7.63 g of the compound represented by formula 34 with a yield of 87%.

[0163] Synthesis of the compound shown in formula 2a-1:

[0164]

[0165] Take 11.66g (0.01mol) of the compound shown in Formula 34, add 1.72g of the compound shown in Formula 6, add 100ml of acetonitrile, add 0.3g of triethylamine, add to a three-necked flask, replace the air with nitrogen bubbling, add to an ice-water bath, and add Pd(OAc) 2 0.2 g of tri(o-tolyl)phosphine was added and the mixture was heated under reflux with stirring for 1 h. After the reaction was completed, the mixture was filtered and distilled to obtain 11.95 g of the compound of formula 2a-1 with a yield of 83%.

[0166] Synthesis of compound of formula 2a:

[0167]

[0168] Take 14.37g (0.01mol) of the compound represented by formula 2a-1 and add it into a 200ml beaker. Stir mechanically, add 10ml of concentrated hydrochloric acid to dissolve it, then cool the reaction temperature to 0-4°C, and add 1.38g of sodium nitrite dissolved in 5ml of water to prepare a sodium nitrite solution, and 1.56g of sodium azide dissolved in 5ml of water to prepare a sodium azide solution. React for 1.5h. After the reaction is completed, filter and wash with water, and recrystallize with acetone to obtain 12.58g of the compound represented by formula 2a, with a yield of 83%.

[0169] Example 5. Synthesis of the compound represented by formula 2b

[0170] Synthesis of the compound shown in formula 40:

[0171]

[0172] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2 g, stirred for 10 min, added 40 g of dry THF, stirred for another 30 min, then added 8.88 g, 0.06 mol, of the compound shown in formula 37 dropwise through a syringe at normal pressure, and stirred at room temperature for 36 h. Extracted three times with dichloromethane (15 mL), collected the upper organic layer, and precipitated it in MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 5.05 g of the compound represented by formula 40 with a yield of 89%.

[0173] Synthesis of compound of formula 41:

[0174]

[0175] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2g, stirred for 10min, added dry THF 40g, stirred for another 30min, then added dropwise 8.61g, 0.06mol of the compound shown in formula 38 through a syringe under normal pressure, and stirred at room temperature for 36h. Extracted three times with dichloromethane (15mL), the upper organic layer was collected and dried over MgSO4 overnight. The solution was filtered to remove MgSO4, and the solvent was removed by rotary evaporator to obtain 4.26g of the compound shown in formula 41, with a yield of 86%.

[0176] Synthesis of the compound shown in formula 39:

[0177]

[0178] In a 500 ml round bottom flask, add 24 g of deionized water and K2 CO 3 0.2 g, stirred for 10 min, added 40 g of dry THF, stirred for another 30 min, then added 5.67 g (0.01 mol) of the compound shown in formula 40 and 4.95 g (0.01 mol) of the compound shown in formula 41 dropwise at normal pressure through a syringe, and stirred at room temperature for 36 h. Finally, 4.34 g (0.04 mol) of trimethylsilyl chloride was added for end-capping, extracted three times with dichloromethane (15 mL), and the upper organic layer was collected and precipitated on MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 9.98 g of the compound represented by formula 39 with a yield of 83%.

[0179] Synthesis of the compound shown in formula 2b-1:

[0180]

[0181] Take 12.02g (0.01mol) of the compound shown in Formula 39, add 3.44g of the compound shown in Formula 6, add 100ml of acetonitrile, add 0.3g of triethylamine, add to a three-necked flask, replace the air with nitrogen bubbling, add to an ice-water bath, and add Pd(OAc) 2 0.2 g of tri(o-tolyl)phosphine was added and the mixture was heated under reflux with stirring for 1 h. After the reaction was completed, the mixture was filtered and distilled to obtain 13.82 g of the compound of formula 2b-1 with a yield of 79%.

[0182] Synthesis of the compound shown in formula 2b:

[0183]

[0184] Take 17.49 g (0.01 mol) of the compound represented by formula 2b-1 and add it into a 200 ml beaker. Stir mechanically, add 10 ml of concentrated hydrochloric acid to dissolve it, then cool the reaction temperature to 0-4 ° C, add 2.76 g of sodium nitrite dissolved in 10 ml of water, and 3.12 g of sodium azide dissolved in 10 ml of water in turn, and react for 1.5 hours. After the reaction is completed, filter and wash with water, and recrystallize with acetone to obtain 17.34 g of the compound represented by formula 2b with a yield of 91%.

[0185] Example 6: Synthesis of the compound represented by formula 2c

[0186] Synthesis of the compound shown in formula 42:

[0187]

[0188] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 30.2g, stirred for 10min, added 40g dry THF, stirred for another 30min, then added 10.06g (0.02mol) of the compound shown in formula 35 dropwise through a syringe at normal pressure, stirred at room temperature for 36h. Finally, 4.34g (0.04mol) of trimethylsilyl chloride was added for end-capping, extracted three times with dichloromethane (15mL), and the upper organic layer was collected and precipitated on MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 9.26 g of the compound represented by formula 42 with a yield of 77%.

[0189] Synthesis of compound of formula 2c-1:

[0190]

[0191] Take 12.02g (0.01mol) of the compound shown in Formula 42, add 3.44g of the compound shown in Formula 6, add 100ml of acetonitrile, add 0.3g of triethylamine, add to a three-necked flask, replace the air with nitrogen bubbling, add to an ice-water bath, and add Pd(OAc) 2 0.2 g of tri(o-tolyl)phosphine was added and the mixture was heated under reflux with stirring for 1 h. After the reaction was completed, the mixture was filtered and distilled to obtain 13.29 g of the compound shown in 2c-1 with a yield of 76%.

[0192] Synthesis of the compound shown in formula 2c:

[0193]

[0194] Take 17.49 g (0.01 mol) of the compound shown in the structural formula 2c-1 and add it into a 200 ml beaker. Stir mechanically, add 10 ml of concentrated hydrochloric acid to dissolve it, then cool the reaction temperature to 0-4 ° C, add 2.76 g of sodium nitrite dissolved in 10 ml of water, and 3.12 g of sodium azide dissolved in 10 ml of water in turn, and react for 1.5 hours. After the reaction is completed, filter and wash with water, and recrystallize with acetone to obtain 15.62 g of the compound shown in the formula 2c with a yield of 82%.

[0195] Example 7: Synthesis of the compound represented by formula 3a

[0196] Synthesis of compound of formula 44:

[0197]

[0198] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 30.2g, stirred for 10min, added 40g dry THF, stirred for another 30min, then added 1.48g, 0.01mol of the compound shown in formula 37, 1.52g, 0.01mol of the compound shown in formula 46, and 1.36g, 0.01mol of the compound shown in formula 38 dropwise through a syringe at normal pressure, and stirred at room temperature for 36h. Extracted three times with dichloromethane (15mL), the upper organic layer was collected and precipitated in MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 6.59 g of the compound represented by formula 44 with a yield of 87%.

[0199] Synthesis of compound of formula 45:

[0200]

[0201] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2g, stirred for 10min, added 40g dry THF, stirred for another 30min, then added 1.52g, 0.01mol of the compound shown in formula 46 and 2.72g, 0.02mol of the compound shown in formula 38 dropwise through a syringe at normal pressure, stirred at room temperature for 36h. Extracted three times with dichloromethane (15mL), collected the upper organic layer and precipitated it in MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 5.77 g of the compound represented by formula 45 with a yield of 85%.

[0202] Synthesis of compound of formula 43:

[0203]

[0204] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2g, stirred for 10min, added 40g of dry THF, stirred for another 30min, then added 11.54g of the compound shown in formula 45, 0.02mol of the compound shown in formula 44, 13.58g, 0.02mol, under normal pressure, through a syringe, and stirred at room temperature for 36h. Finally, 12.96g (0.12mol) of trimethylsilyl chloride was added for end-capping, extracted three times with dichloromethane (15mL), and the upper organic layer was collected and precipitated on MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 15.54 g of the compound represented by formula 43 with a yield of 92%.

[0205] Synthesis of compound of formula 3a-1

[0206]

[0207] Take 16.89g (0.01mol) of the compound shown in Formula 43, add 1.72g of the compound shown in Formula 6, add 100ml of acetonitrile, add 0.3g of triethylamine, add to a three-necked flask, replace the air with nitrogen bubbling, add to an ice-water bath, and add Pd(OAc) 2 0.2 g of tri(o-tolyl)phosphine was added and the mixture was heated under reflux with stirring for 1 h. After the reaction was completed, the mixture was filtered and distilled to obtain 16.20 g of the compound shown in 3a-1 with a yield of 82.6%.

[0208] Synthesis of the compound shown in formula 3a:

[0209]

[0210] Take 19.62g (0.01mol) of the compound represented by formula 3a-1 and add it into a 200ml beaker. Stir mechanically, add 10ml of concentrated hydrochloric acid to dissolve it, then cool the reaction temperature to 0-4°C, and add 1.38g of sodium nitrite dissolved in 5ml of water to prepare a sodium nitrite solution, and 1.56g of sodium azide dissolved in 5ml of water to prepare a sodium azide solution. React for 3h. After the reaction is completed, filter and wash with water, and recrystallize with acetone to obtain 17.15g of the compound represented by formula 3a, with a yield of 84%.

[0211] Example 8: Synthesis of the compound represented by formula 3b

[0212] Synthesis of the compound represented by formula 48

[0213]

[0214] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2g, stirred for 10min, added 40g dry THF, stirred for another 30min, then added 8.88g, 8.88mol of the compound shown in formula 37 and 4.56g, 0.03mol of the compound shown in formula 46 dropwise at normal pressure through a syringe, and stirred at room temperature for 36h. Extracted three times with dichloromethane (15mL), collected the upper organic layer, and precipitated it in MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 10.8 g of the compound represented by formula 35 with a yield of 84%.

[0215] Synthesis of compound of formula 47

[0216]

[0217] In a 500 ml round bottom flask, add 24 g of deionized water and K 2 CO 3 0.2g, stirred for 10min, added 40g dry THF, stirred for another 30min, then added 7.93g (0.01mol) of the compound shown in formula 48 and 7.21g (0.01mol) of the compound shown in formula 38 dropwise through a syringe at normal pressure, stirred at room temperature for 36h. Finally, 6.48g (0.6mol) of trimethylsilyl chloride was added for end-capping, extracted three times with dichloromethane (15mL), and the upper organic layer was collected and precipitated on MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 14.66 g of the compound represented by formula 47 with a yield of 85%.

[0218] Synthesis of the compound represented by formula 3b-1

[0219]

[0220] Take 17.25g (0.01mol) of the compound shown in Formula 47, add 3.44g of the compound shown in Formula 6, add 100ml of acetonitrile, add 0.3g of triethylamine, add to a three-necked flask, replace the air with nitrogen bubbling, add to an ice-water bath, and add Pd(OAc) 2 0.2 g of tri(o-tolyl)phosphine was added and the mixture was heated to reflux with stirring for 1 h. After the reaction was completed, the mixture was filtered and distilled to obtain 18.4 g of the compound of formula 3b-1 with a yield of 81%.

[0221] Synthesis of the compound represented by formula 3b

[0222]

[0223] Take 22.72 g (0.01 mol) of the compound shown in formula 3b-1 and add it into a 200 ml beaker. Stir mechanically, add 10 ml of concentrated hydrochloric acid to dissolve it, then cool the reaction temperature to 0-4 ° C, add 2.76 g of sodium nitrite dissolved in 10 ml of water, and 3.12 g of sodium azide dissolved in 10 ml of water in turn, react for 2 hours, filter and wash with water after the reaction is completed, and recrystallize with acetone to obtain 20.88 g of the compound shown in formula 3b with a yield of 86%.

[0224] Example 9: Synthesis of the compound represented by formula 3C

[0225] Synthesis of the compound shown in formula 49:

[0226]

[0227] In a 500 ml round bottom flask, add 24 g of deionized water and K2 CO 3 0.2g, stirred for 10min, added 40g dry THF, stirred for another 30min, then added 15.14g (0.02mol) of the compound shown in formula 44 dropwise through a syringe at normal pressure, stirred at room temperature for 36h. Finally, 6.48g (0.06mol) of trimethylsilyl chloride was added for end-capping, extracted three times with dichloromethane (15mL), and the upper organic layer was collected and concentrated in MgSO 4 The solution was filtered to remove MgSO 4 The solvent was removed by rotary evaporation to obtain 11.21 g of the compound represented by formula 49 with a yield of 65%.

[0228] Synthesis of the compound represented by formula 3C-1:

[0229]

[0230] Take 17.25g (0.01mol) of the compound shown in Formula 49, add 3.44g of the compound shown in Formula 6, add 100ml of acetonitrile, add 0.3g of triethylamine, add to a three-necked flask, replace the air with nitrogen bubbling, add to an ice-water bath, and add Pd(OAc) 2 0.2 g of tri(o-tolyl)phosphine was added and the mixture was heated to reflux with stirring for 1 h. After the reaction was completed, the mixture was filtered and distilled to obtain 17.95 g of the compound of formula 3C-1 with a yield of 79%.

[0231] Synthesis of the compound shown in formula 3C:

[0232]

[0233] Take 22.72 g (0.01 mol) of the compound represented by formula 3C-1 and add it into a 200 ml beaker. Stir mechanically, add 10 ml of concentrated hydrochloric acid to dissolve it, then cool the reaction temperature to 0-4 ° C, add a solution prepared by dissolving 2.76 g of sodium nitrite in 10 ml of water, and a solution prepared by dissolving 3.12 g of sodium azide in 10 ml of water in sequence, and react for 2 hours. After the reaction is completed, filter and wash with water, and recrystallize with acetone to obtain 20.64 g of the compound represented by formula 3C with a yield of 85%.

[0234] Example 10: Application of the compound represented by Formula 1C as a photosensitizer

[0235] The compound shown in Formula 1C is dissolved in dichloromethane, added to the benzocyclobutene resin solution, and stirred evenly to obtain a negative photosensitive benzocyclobutene resin (the mass ratio of the compound shown in Formula 1C to the benzocyclobutene resin is 5:95). The prepared solution is spin-coated on a silicon wafer, and after soft drying, it is exposed using a mask in a photolithography machine. The effect after exposure and development is as follows: Figure 1 As shown, the resolution can reach 13 microns.

[0236] The present invention has been described in detail above. For those skilled in the art, without departing from the purpose and scope of the present invention, and without the need to carry out unnecessary experimental conditions, the present invention can be implemented in a wide range under equivalent parameters, concentrations and conditions. Although the present invention provides specific embodiments, it should be understood that the present invention can be further improved. In a word, according to the principles of the present invention, the application is intended to include any changes, uses or improvements to the present invention, including departure from the disclosed scope in the application, and changes made with conventional techniques known in the art.

Claims

1. A compound represented by formula (1), formula (2) or formula (3): In formula (1), formula (2) and formula (3), R1, R2, R3 and R4 each independently represent a hydrogen atom, a C1-C 10 Straight-chain or branched alkyl, mercapto, substituted or unsubstituted aromatic, C2-C 10 Alkenyl, ( represents a C1-C6 straight or branched alkylene group or n=1-3 integer) and at least one of R1, R2, R3, R4 is x, y represent any value between 1 and 10; R5 represents a capping group, which is any one of the groups obtained by removing chlorine from the following capping agents: trimethylchlorosilane, dimethylvinylchlorosilane, and dimethylphenylchlorosilane.

2. The compound according to claim 1, characterized in that R1, R2, R3, and R4 each independently represent a hydrogen atom, a C1-C6 straight or branched alkyl group, a mercapto group, a phenyl group, a C2-C6 alkenyl group, ( represents a C1-C6 straight or branched alkylene group or n=1-3 integer) and at least one of R1, R2, R3, R4 is 3. A method for preparing the compound of formula (1) according to claim 1, wherein: R1 is The method comprises the following steps: dissolving the compound represented by formula (4) in an acid solution, cooling the solution to the reaction temperature, sequentially adding a sodium nitrite aqueous solution and a sodium azide aqueous solution, filtering and washing with water after the reaction is completed, and recrystallizing with acetone to obtain a compound represented by formula (1). In formula (4), R2, R3, R4, R5, x, and y have the same definitions as R2, R3, R4, R5, x, and y in formula (1).

4. The method according to claim 3, characterized in that The acid is selected from at least one of hydrochloric acid, sulfuric acid and nitric acid; The molar ratio of the compound represented by formula (4) to sodium nitrite and sodium azide is: 1:1-2:1-2; The reaction temperature is 0-10°C; The reaction time is 0.2-3h.

5. The method according to claim 3, characterized in that: The compound represented by formula (4) is prepared by a method comprising the following steps: The compound represented by formula (5) and the compound represented by formula (6) are dissolved in an organic solvent, a palladium catalyst, a ligand, and a base are added, and a Heck reaction is performed to obtain a compound represented by formula (4); In formula (5), R2, R3, R4, R5, x, and y have the same definitions as R2, R3, R4, R5, x, and y in formula (1).

6. The method according to claim 5, characterized in that The palladium catalyst is Pd(OAc)2 or Pd(PPh3)4; The base is selected from at least one of potassium carbonate, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium bicarbonate, and triethylamine; The ligand is tri(o-tolyl)phosphine; The temperature of the Heck reaction is 60-120° C., and the time is 0.2-5 h.

7. A method for preparing the compound of formula (2) according to claim 1, wherein: R1 is The method comprises the following steps: dissolving the compound represented by formula (11) in an acid solution, lowering the reaction temperature, sequentially adding a sodium nitrite aqueous solution and a sodium azide aqueous solution, filtering and washing with water after the reaction is completed, and recrystallizing with acetone to obtain a compound represented by formula (2). The definitions of R2, R3, R4, R5, x, and y in formula (11) are the same as those of R2, R3, R4, R5, x, and y in formula (2).

8. A method for preparing the compound of formula (3) according to claim 1, wherein R1 is The steps include: The compound represented by formula (19) is dissolved in an acid solution, cooled to the reaction temperature, and sodium nitrite aqueous solution and sodium azide aqueous solution are added in sequence. After the reaction is completed, the solution is filtered and washed with water, and recrystallized with acetone to obtain the compound represented by formula (3); In formula (19), R2, R3, R4, R5, x, and y have the same definitions as R2, R3, R4, R5, x, and y in formula (3).

9. Use of the compound represented by formula (1), formula (2) or formula (3) in claim 1 as a photocrosslinking agent in the preparation of a photocrosslinking material.

Images