CN107163169B - A kind of cumarin and carbazole type oxime ester compound and its preparation method and application - Google Patents

Abstract

The present invention relates to new material organic chemicals technical fields, it is related to a kind of cumarin and carbazole type oxime ester compound and its preparation method and application, more particularly to the new compound of structure shown in formula (I) or (II), its chemical preparating process technology, its purposes as radiation curing photoinitiator, and its photocureable coating or ink that can be excited in radiation curable formulation product, especially UV Vis LED, wait the application of many occasions.

Description

A class of coumarinocarbazole-type oxime ester compounds and its preparation method and application

【Technical field】

The present invention relates to the technical field of new material organic chemicals, in particular to a new class of coumarin-based oxime ester-type compounds, their chemical preparation technology, their use as radiation-curing photoinitiators, and their use in radiation-curing formulations. Products, especially in UV-Vis-LED excitable light-curable coatings or inks, and many other applications.

【Background technique】

Photoinitiator compounds are an important class of fine organic chemical materials. In the field of radiation curing technology using ultraviolet light or visible (UV) light or LED (i.e. Light-Emitting Diode) as light source, the photoinitiator compound that can generate free radical active species under light irradiation conditions is to induce ethylenically unsaturated It is a key species for efficient photopolymerization in the system, so it is one of the important components of radiation curing formulations. Photocuring has many advantages such as energy saving and environmental protection, high efficiency and speed, and time-space controllability. It has been widely used in traditional fields such as coating inks and adhesives, as well as high-tech products such as 3D printing. Compared with traditional UV curing, LED light curing using light-emitting diodes (LEDs) as a light source has significant advantages such as high energy utilization rate, small thermal effect, and no ozone generation. Photosensitive resin formulations for photocuring usually contain photoinitiators, reactive diluents, oligomers and various additives, among which photoinitiators are the key components of photocuring formulations, and their activity directly affects the photocuring rate and degree of curing and end product performance. Traditional photoinitiators are mainly used for UV curing with shorter wavelengths, which are difficult to match with LED light sources. Therefore, through reasonable molecular design and systematic research on the relationship between molecular structure design and performance, an efficient LED photoinitiator has been developed. It has great application prospect.

Coumarin derivatives have also been widely studied and used as visible light sensitizers or visible light initiators in the field of photopolymerization. Coumarin is a kind of heterocyclic compound, which widely exists in plants such as tonka bean and orchid, and its molecular structure is shown in Figure 1. As a chromophore with excellent performance, coumarin has been widely used in many fields, such as laser dyes and fluorescent probes. However, the absorption spectrum of coumarin itself is in the ultraviolet region (λ=310nm; ε=5170L mol ^{- 1} cm ^-1 ), which cannot meet the research needs of visible light initiators. Therefore, some auxochromes are usually introduced into the coumarin molecule or the length of its conjugated chain is extended, so that the position of the absorption peak is red-shifted to reach the near ultraviolet region or the visible region.

The molecular structure of coumarin

In the field of photocuring, photoinitiators with high photosensitivity, high stability, and easy preparation are still the first choice for the development of this field. With the continuous improvement of people's various requirements for environmental protection, production safety awareness, and labor insurance, As well as the continuous development of photopolymerization technology, low energy consumption, high safety and environmental protection exposure light sources such as LED and LDI have become a trend of technology application and development in this field.

【Content of invention】

The purpose of the present invention is to prepare a new type of coumarinocarbazolyl oxime ester compound, which can be used as a radiation-curable photoinitiator, and involves applications in many occasions such as photocurable coatings or inks that can be excited by UV-LEDs.

Technical scheme of the present invention is:

1. This application discloses a novel coumarinocarbazolyl oxime ester compound represented by the following general formula (I) or (II):

In the above-mentioned general formula (I) and (II) compound structure:

(1) R ₁ and R ₂ are each independently selected from C ₁ -C ₂₀ straight chain or branched chain alkyl, C ₃ -C ₁₂ cycloalkyl, cycloalkylalkyl, cycloheteroalkylalkyl;

(2) R ₃ and R ₄ are aryl groups substituted by Y, R ₅ , R ₆ , R ₇ , R ₈ , R ₉ (as shown in the general formula above), or R ₁₀ , R ₁₁ , R ₁₂ substituted tertiary alkyl group,

wherein R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ are independently hydrogen, halogen atom, R, OR, SR, NRR', CH ₂ OH, CH ₂ OR, or CH ₂ NRR', wherein R or R'independent of each other is a linear or branched alkyl or -C ₆ -C ₁₂ aryl group containing 1-24 carbon atoms (marked as -C ₁ -C ₂₄ , the same below), R or R' structure can contain 1-6 discontinuous oxygen, nitrogen, or sulfur elements, and R and R' can also form a 3-6-membered ring structure when they exist at the same time.

R ₁₀ , R ₁₁ , and R ₁₂ are independently R, and any two of them can also form a 3-6-membered carbocyclic structure. Y is a linking group, preferably -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH(OH)CH ₂ -, -CH ₂ CH(OR)CH ₂ -, -CH ₂ CH(OC(O)R)CH ₂ -, and the like. R ₃ preferably, CH ₃ , CH ₂ CH ₃ , CH ₂ CH(CH ₃ ) ₂ , CH ₂ Ph, or Y=CH ₂ or a vacancy (that is, directly connected to the benzene ring), R ₅ =R ₆ =R ₈ = R ₉ ＝H, R ₇ ＝CH ₃ , or alkylcycloalkyl, cycloheteroalkylalkyl structures;

The cycloalkylalkyl has the following structure:

Among them x=1～5, y=1～6;

The cycloheteroalkylalkyl has the following structure:

Wherein x=1～5, y=1～6, z represents S, O, N;

(3) A is C=O (that is, the compound of formula I or II is a carboxylate structure), or A is O=S=O (that is, the compound of formula I or II is a sulfonate structure).

Two, prepare the coumarinocarbazolyl oxime ester compound shown in some general formulas (I) and (II), its preparation method can realize the method by following technical scheme:

Step 1, the starting materials shown in the figure are reacted under the action of _BiCl3 to obtain compound (1) or (2), the reaction conditions are 100 ° C, _N2 protection, 72h, _BiCl3 can be replaced by _ZnCl2

Step 2, step 1 gained product (1) or (2) and material shown in (b) among the figure react to obtain (3) or (4) under the situation that potassium iodide and 18-crown-6 make catalyst, reaction condition is DMF, 100°C, 24h, DMF can be replaced by heating to reflux with acetone;

Step 3, the product (3) or (4) obtained in step 2 reacts with the substance shown in (c) in the figure under the action of _AlCl3 to obtain (5) or (6), the reaction condition is anhydrous CH ₂ Cl ₂ , 0 ℃, _N2 protection, 2h;

Step 4, the product (5) or (6) obtained in step 3 is reacted with isoamyl nitrite to obtain oxime, (7) or (8), and the reaction conditions are THF, room temperature, concentrated HCl, 5h;

Step 5, the product (7) or (8) obtained in step 4 reacts with an acid anhydride or acyl halide under the action of triethylamine to obtain the target product (I) or (II), the reaction conditions are CH ₂ Cl ₂ , room temperature, N ₂ Protection, protected from light, 2h; wherein, X shown in the figure is a halogen atom, and R ₄ AX is the corresponding acid halide or sulfonyl halide compound.

In the present invention, the use of heterocyclic oxime ester compounds represented by general formulas (I) and (II) as photoinitiators or other functional additive components in photocuring formulation systems, and as intermediates or raw materials in chemical synthesis or reagent use.

3. The present invention further discloses a mixture containing the compounds of the above general formula (I) and (II) that can be cured by light (ultraviolet or visible light or LED light or equivalent light source).

The characteristics of this type of light radiation curing formula system are:

(1) Containing at least one compound described by general formula (I) or (II) as one of photoinitiator or photoinitiator components;

(2) Contains at least one ethylenically (C=C) unsaturated compound.

Calculated per 100 parts by weight of the total amount of ethylenically unsaturated components in the system, the appropriate amount of the compound of general formula (I) contained is 0.01-30 parts by weight, preferably 0.5-10 parts by weight. Suitable radiation-curing systems comprise polymerizable ethylenically unsaturated components which are compounds or mixtures which can be crosslinked by free-radical polymerization of the double bond, such ethylenically unsaturated components being monomers, Oligomers or prepolymers, or mixtures or copolymers thereof, or aqueous dispersions of the aforementioned components.

The specific steps are as follows: (1) According to the mass ratio of monomer:photoinitiator:auxiliary agent: 100:0.5～1:0～4.5 ratio of raw materials; (2) Stir to fully dissolve; The light source of light intensity irradiates the polymerization system; (4) researches the polymerization conversion rate by the change of its characteristic peak with the method of online infrared; Wherein: the light source in the step (3) can be LED (high pressure, middle pressure and low pressure), and emission LEDs with a wavelength of 365-425nm, LDI light source.

The radiation curing system described above can contain inorganic or organic fillers and/or colorants (such as pigments or dyes, etc.) added according to actual needs, and other additives (such as ultraviolet absorbers, light stabilizers, flame retardants, etc.) , leveling agent, or defoamer, etc.) and solvents and other arbitrary components.

Suitable radical polymerizable monomers are for example ethylenically polymerizable monomers including but not limited to (meth)acrylates, acrolein, olefins, conjugated dienes, styrene, maleic anhydride, fumaric anhydride, Vinyl acetate, vinylpyrrolidone, vinylimidazole, (meth)acrylic acid, (meth)acrylic acid derivatives such as (meth)acrylamide, vinyl halides, vinylidene halides, and the like.

Suitable ethylenically-containing prepolymers and oligomers include, but are not limited to, (meth)acryl functional (meth)acrylic copolymers, urethane (meth)acrylates, polyester (meth) Acrylates, unsaturated polyesters, polyether (meth)acrylates, silicone (meth)acrylates, epoxy (meth)acrylates, etc., and water-soluble or water-dispersible analogs of the above things.

Whether the above-mentioned alkene-containing monomers or oligomers, prepolymers, or copolymers are well known to those skilled in the art, there is no special limitation.

For the gist of the present invention, we will further illustrate in conjunction with the following series of embodiments.

【Description of drawings】

Fig. 1 is the ultraviolet-visible absorption spectrogram of compound (1)

Figure 2 is the polymerization curve of compound (1) photopolymerized TMPTA

Figure 3 is the polymerization curve of compound (1) photopolymerized HDDA

【Detailed ways】

Embodiment one:

1. Preparation and characterization of compound (1)

The initial substance is 4-hydroxycarbazole, and the product is obtained through acylation, esterification, etc. and reaction. The used synthetic route of this preparation method is expressed as follows:

The specific process is as follows:

Step 1, the synthesis of compound (A). Under the protection of _N2 , 6.96g (0.038mol) of 4-hydroxycarbazole, 9.6mL (0.076mol) of ethyl acetoacetate, 1.19g (0.0038mol) of _BiCl3 were added to a 100mL round-bottomed flask, and the After reacting in an oil bath at 100°C for 72 hours, 500 mL of absolute ethanol was added to the reaction mixture, ultrasonically dispersed, filtered, and the filter cake was washed several times with ethanol to obtain an off-white solid, which was vacuum-dried at room temperature to obtain 5.84 g of product (1). Rate: 61.7%. The product can be directly used in the next reaction.

Step 2, the synthesis of compound (B). In a 250mL round bottom flask, add 3.54g (14.20mmol) compound (A), 2.74g (14.20mmol) bromoisoctane and 3.92g (28.40mmol) potassium carbonate and a small amount of potassium iodide and 18-crown-6 As catalyst and 100mL DMF as solvent. Under stirring conditions, react in an oil bath at 100°C for 24 hours. After TLC detects that there is no raw material point, the reaction is terminated, the inorganic salt is filtered off, the filtrate is poured into 1000 ml of sodium chloride aqueous solution, and the solid is separated by suction filtration. Chromatographic purification, the eluent is PE/EA=2:1, to obtain 2.25g of light yellow solid compound, the yield is 43.8%

The structure of the product was confirmed by nuclear magnetic resonance spectroscopy, and the specific characterization results are as follows:

¹ H NMR (400MHz, CDCl ₃ ) δ8.56(d, J=7.7Hz, 1H), 7.54(d, J=8.7Hz, 1H), 7.48–7.41(m, 1H), 7.36(d, J= 8.2Hz, 1H), 7.27(dt, J＝13.5, 3.2Hz, 1H), 7.19(d, J＝1.5Hz, 1H), 6.13(d, J＝1.1Hz, 1H), 4.18–4.04(m, 2H), 2.43(d, J＝1.0Hz, 3H), 1.37–1.13(m, 9H), 0.81(m, J＝21.6, 7.3Hz, 6H). ¹³ C NMR (101MHz, CDCl ₃ ) δ160.49, 152.88 ,149.35,142.24,139.50,125.04,122.80,120.54,120.02,119.43,110.52,109.68,109.23,108.15,104.77,46.66,38.45,29.93,27.74,23.332,128.9,21.9

Step 3, the synthesis of compound (C). Under the protection of N ₂ , 0.62 g (1.7 mmol) (B), 0.43 g AlCl ₃ (3.2 mmol) and 15 mL of anhydrous dichloromethane were successively added into a 250 mL three-necked flask as solvents. Cool in an ice-water bath, and when the temperature drops to 0°C, slowly add dropwise a solution of 0.32g (3.0mmol) n-butyryl chloride dissolved in 5mL of dichloromethane, keep the temperature below 10°C, complete the addition in about 1.5h, and continue stirring for 2h. The reaction solution was poured into dilute hydrochloric acid prepared by 200 g of ice and 30 ml of concentrated hydrochloric acid, extracted with dichloromethane, and washed with water until the pH value was neutral. Collect the organic layer, dry it with anhydrous sodium sulfate, and remove the organic solvent by rotary evaporation under reduced pressure. Pour the crude product into petroleum ether, and the precipitate precipitated by suction filtration is the pure product as a yellow powdery solid. Dry in a vacuum oven at 50°C After 24 hours, 0.62 g of the product was obtained, yield: 84.9%.

The structure of the product was confirmed by nuclear magnetic resonance spectroscopy, and the specific characterization results are as follows:

¹ H NMR (400MHz, DMSO) δ8.87(s, 1H), 8.17(dd, J=8.7, 1.3Hz, 1H), 7.82(d, J=8.7Hz, 1H), 7.71(d, J=8.7 Hz,1H),7.58(d,J=8.7Hz,1H),6.33(s,1H),4.32(d,J=7.3Hz,2H),3.11(t,J=7.1Hz,2H),2.51( d, J=1.8Hz, 3H), 1.73(h, J=7.3Hz, 2H), 1.37–1.11(m, 9H), 1.00(t, J=7.4Hz, 3H), 0.80(dt, J=14.1 ,7.3Hz,6H) ^.13 C NMR(101MHz,CDCl ₃ )δ199.00,159.86,152.58,149.23,142.78,142.05,129.31,125.22,123.60,121.27,119.50,111.28,110.42,1108.57 39.26, 38.47, 29.88, 27.69, 23.29, 21.92, 18.34, 17.01, 12.99, 12.95, 9.83.

Step 4, the synthesis of compound (D). Put 0.62g (1.44mmol) of (C), 10mL tetrahydrofuran, 0.6mL (7.2mmol) concentrated hydrochloric acid, 0.25g (2.1mmol) isoamyl nitrite into a 250ml three-neck flask, and stir at room temperature for 5h. The reactant was poured into 100ml of water, extracted with dichloromethane, and dried over anhydrous MgSO ₄ . Evaporate to dryness to obtain a viscous product and add petroleum ether to precipitate a solid. Suction filtration obtains 0.48 g of a yellow product with a yield of 73.2%. It can be directly used in the next reaction.

Step five, synthesis of target product (1). In a dark room, under the protection of _N2 gas, 0.18g (0.40mmol) of compound (D) and 10ml of dichloromethane were successively put into a three-necked flask, and after stirring at room temperature for 5min, 0.3mL of triethylamine was added, and 0.10g of triethylamine was added dropwise. Acetic anhydride (0.97mmol) was added dropwise in about 30 minutes, and stirring was continued for 2 hours. Add 50 ml of deionized water to the reaction system, extract with dichloromethane, wash with 2M HCl and 5% NaHCO ₃ aqueous solution, adjust the pH to neutral; dry over anhydrous NaSO ₄ , remove the solvent by distillation under reduced pressure; Chromatographic purification, the polarity of the eluent is PE/EA=2:1, and finally a yellow solid compound is obtained. 0.14 g of the product was obtained with a yield of 70.1%.

The structure of the product was confirmed by nuclear magnetic resonance spectroscopy, and the specific characterization results are as follows:

¹ H NMR (400MHz, CDCl ₃ ) δ9.14 (d, J=1.4Hz, 1H), 8.18 (dd, J=8.7, 1.5Hz, 1H), 7.57 (d, J=8.7Hz, 1H), 7.35 (d, J=8.7Hz, 1H), 7.23(d, J=8.7Hz, 1H), 6.14(s, 1H), 4.09(d, J=7.5Hz, 2H), 2.82(q, J=7.6Hz ,2H),2.42(s,3H),2.29(s,3H),1.24–1.10(m,11H),0.80(dt,J＝13.9,7.2Hz,7H). ¹³ C NMR(101MHz,CDCl3)δ188 .46,167.89,164.76,159.56,152.32,149.23,142.85,142.76,127.49,127.12,126.96,121.60,119.80,111.55,110.71,109.63,108.25,105.23,46.91,38.48,29.85,27.71,23.24,21.93,20.28,18.77 ,18.31,12.96,9.82,9.56.

2. UV-visible absorption spectrum test of compound (1)

Test method: Accurately weigh 0.001g of the product of compound (1) into a 100ml volumetric flask, then add acetonitrile to the 100ml scale in the volumetric flask to make a solution with a concentration of 10 ^-5 g/ml, and use a spectrophotometer for ultraviolet absorption Test, the test curve is shown in Figure 1. It can be seen from the figure that the maximum absorption wavelength λ _max of this molecule is at 375nm, which has a longer wavelength of ultraviolet absorption than traditional photoinitiators, and is easier to match with long-wavelength light sources.

3. Photopolymerization experiments on compound (1)

Test method (1): Use a single trimethylolpropane triacrylate (TMPTA) as a monomer and a single photoinitiator to mix it uniformly and then expose it, trimethylolpropane triacrylate: compound (1) = 100:1 ; Coating film thickness 100 μm; use FTIR online infrared to measure its light wavelength as 365nm, 385nm LED as excitation light source, light intensity is 30mW/ ^cm To test the photosensitive activity, the double bond conversion rate measured by real-time infrared is the maximum conversion rate within 1 min. As shown in Figure 2. TMPTA has high viscosity, high crosslinking density, and a conversion rate exceeding 50% has a good curing effect. It can be seen that this type of photoinitiator of the present invention has excellent photosensitive performance.

Test method (2): Use a single 1,6-Hexanediol diacrylate (1,6-Hexanedioldiacrylate, HDDA) as a monomer and mix it uniformly with a single photoinitiator before exposing, HDDA: compound (1) = 100: 1; film thickness 100 μm; use FTIR online infrared to measure its light wavelength at 365nm, 385nm and 405nm LED as exposure light source, light intensity is 30mW/cm ² (test photoinitiator by the change of monomer double bond in infrared spectrum Efficiency) to test photosensitive activity, the double bond conversion rate measured by real-time infrared is the maximum conversion rate within 1min. As shown in Figure 3. HDDA is rapidly cured under 385nm LED excitation, the conversion rate is close to 90%, and the surface is in good condition. The conversion rate also exceeds 80% under the excitation of 365nm LED, and the 405nm LED is at the band edge of absorption, and the conversion rate is not high. This is because HDDA has a low viscosity compared with TMPTA, and the conversion rate can be greatly improved under the same exposure conditions. It can be seen that this type of photoinitiator of the present invention can produce different photopolymerization effects according to different formulations in different photopolymerization systems. But generally have excellent photosensitivity.

In summary, the application performance of the coumarin-carbazole oxime ester photoinitiator described in this example is excellent, and it has very high photosensitivity, especially in a class of low-energy consumption and long-wavelength photoinitiators where LED is the light source. In the case of curing, it shows high light curing performance and has a wide range of applications.

Embodiment two: preparation and characterization of compound (2)

Compound (2) was prepared by the same preparation method as in the above-mentioned Example 1, the only difference being that p-isovaleryl chloride was used instead of n-butyryl chloride as the raw material. The yield of the target molecule in this example was 66.3%.

The structure of the product was confirmed by nuclear magnetic resonance spectroscopy, and the specific characterization results are as follows:

¹ H NMR (400MHz, CDCl ₃ ) δ8.83(s, 1H), 7.95(t, J=8.0Hz, 1H), 7.52(dd, J=8.6, 2.7Hz, 1H), 7.28(d, J= 8.7Hz, 1H), 7.16(s, 1H), 6.07(s, 1H), 4.05(t, J＝7.4Hz, 2H), 2.38(s, 3H), 1.92–1.79(m, 3H), 1.34– 1.11(m,15H),0.79(dt,J=13.5,7.0Hz,7H). ¹³ C NMR(101MHz,CDCl ₃ )δ188.82,159.34,152.29,149.02,143.13,142.86,142.73,127.37,126.63,125.57, 124.25, 121.82, 119.98, 111.50, 110.62, 109.23, 108.29, 105.25, 46.84, 38.46, 35.88, 29.83, 27.66, 23.24, 22.51, 21.91, 18.26, 16.11, 12.94, 9.79.

Embodiment three: preparation and characterization of compound (3)

Compound (3) was prepared by the same preparation method as in the above-mentioned Example 1, the only difference being that benzoic anhydride was used instead of acetic anhydride as the raw material. The productive rate of present embodiment target molecule is 80.2%,

The structure of the product was confirmed by mass spectrometry, and the specific characterization results are as follows:

HRMS (M+H) for C32H25F3NO3S4: 656.0624 (calculated), 656.0619 (experimental); (M+Na) for C32H24NaF3NO3S4: 678.0443 (calculated), 678.0449 (experimental).

Example 4: Preparation and characterization of compound (4).

Compound (4) was prepared by the same preparation method as in Example 3 above, except that p-isovaleryl chloride was used instead of n-butyryl chloride as the raw material. The productive rate of present embodiment target molecule is 70.8%

The structure of the product was confirmed by mass spectrometry, and the specific characterization results are as follows:

HRMS (M+H) for C32H25F3NO3S4: 656.0624 (calculated), 656.0619 (experimental); (M+Na) for C32H24NaF3NO3S4: 678.0443 (calculated), 678.0449 (experimental).

Embodiment five: preparation and characterization of compound (5)

Compound (5) was prepared by the same preparation method as in Example 1 above, except that p-isovaleryl chloride was used as a raw material instead of n-butyryl chloride, and p-toluenesulfonyl chloride was used as a raw material instead of acetic anhydride. The yield of the target molecule in this example was 75.8%.

The structure of the product was confirmed by mass spectrometry, and the specific characterization results are as follows:

HRMS (M+H) for C ₃₆ H ₄₁ N ₂ O ₆ S: 629.2624 (calculated), 629.2619 (experimental); (M+Na) for C ₃₆ H ₄₀ NaN ₂ O ₆ S: 651.2643 (calculated), 651.2649 ( experimental).

Embodiment six: preparation and characterization of compound (6)

Compound (6) was prepared by the same preparation method as in Example 3 above, except that p-isovaleryl chloride was used as a raw material instead of n-butyryl chloride, and methanesulfonyl chloride was used as a raw material instead of acetic anhydride. The yield of the target molecule in this example was 79.8%.

The structure of the product was confirmed by mass spectrometry, and the specific characterization results are as follows:

HRMS (M+H) for C ₃₀ H ₃₇ N ₂ O ₆ S: 553.2308 (calculated), 553.2309 (experimental); (M+Na) for C ₃₀ H ₃₆ NaN ₂ O ₆ S: 575.2313 (calculated), 575.2309 ( experimental).

Embodiment 7: Preparation and characterization of compound (7)

Compound (7) was prepared by the same preparation method as in Example 1 above, except that p-trifluoromethylbenzenesulfonyl chloride was used instead of acetic anhydride as the raw material. The yield of the target molecule in this example was 81.8%.

The structure of the product was confirmed by mass spectrometry, and the specific characterization results are as follows:

HRMS (M+H) for C ₃₅ H ₃₆ F ₃ N ₂ O ₆ S: 669.2234 (calculated), 669.2229 (experimental); (M+Na) for C ₃₅ H ₃₅ NaF ₃ N ₂ O ₆ S: 691.2243 (calculated ), 691.2249 (experimental).

Embodiment Eight: Preparation and Characterization of Compound (8)

Compound (8) was prepared by the same preparation method as in Example 1 above, except that 2,4-difluorobenzenesulfonyl chloride was used instead of acetic anhydride as the raw material. The yield of the target molecule in this example was 81.8%.

The structure of the product was confirmed by mass spectrometry, and the specific characterization results are as follows:

HRMS (M+H) for C ₃₄ H ₃₅ F ₂ N ₂ O ₆ S: 637.2114 (calculated), 637.2119 (experimental); (M+Na) for C ₃₄ H ₃₄ NaF ₂ N ₂ O ₆ S: 659.2123 (calculated ), 659.2121 (experimental).

(9) Preparation and characterization of compound (9)

Compound (9) was prepared by the same preparation method as in Example 1 above, except that 2-hydroxycarbazole was used instead of 4-hydroxycarbazole, and benzoic anhydride was used instead of acetic anhydride as raw materials. The yield of the target molecule in this example was 77.6%.

The structure of the product was confirmed by mass spectrometry, and the specific characterization results are as follows:

HRMS (M+H) for C ₃₅ H ₃₇ N ₂ O ₅ : 565.2624 (calculated), 565.2619 (experimental); (M+Na) for C ₃₅ H ₃₆ NaN ₂ O ₅ : 587.2743 (calculated), 587.2749 (experimental) .

Embodiment 10: Preparation and characterization of compound (10)

Compound (10) was obtained by the same preparation method as in the above-mentioned Example 1, the only difference being that 2-hydroxycarbazole was used instead of 4-hydroxycarbazole as a raw material, and p-trifluoromethylbenzenesulfonyl chloride was used instead of acetic anhydride as a raw material . The yield of the target molecule in this example was 79.8%.

The structure of the product was confirmed by mass spectrometry, and the specific characterization results are as follows:

HRMS (M+H) for C ₃₅ H ₃₆ F ₃ N ₂ O ₆ S: 669.2234 (calculated), 669.2229 (experimental); (M+Na) for C ₃₅ H ₃₅ NaF ₃ N ₂ O ₆ S: 691.2243 (calculated ), 691.2249 (experimental).

It should be emphasized that the examples listed above are only some exemplary experiments and should not be regarded as limiting experiments or conditions. The scope of innovation covered by the application for the present invention should be determined by the claims.

Claims (8)

1. a kind of coumarin and carbazolyl oxime ester compound shown in general formula (I) or (II), it is characterized in that, its structural formula is: In the above-mentioned general formula (I) or (II) compound structure: (1) R ₁ and R ₂ are each independently selected from C ₁ -C ₂₀ straight chain or branched chain alkyl, C ₃ -C ₁₂ cycloalkyl, cycloalkylalkyl, cycloheteroalkylalkyl; (2) R ₃ and R ₄ are aryl groups substituted by Y, R ₅ , R ₆ , R ₇ , R ₈ , R ₉ or tertiary alkyl groups substituted by R ₁₀ , R ₁₁ , R ₁₂ (as represented by the above general formula Show), Wherein, Y is a linking group, R ₅ , R ₆ , R ₇ , R ₈ , R ₉ are independently hydrogen, halogen atom, R, OR, SR, NRR', CH ₂ OH, CH ₂ OR, or CH ₂ NRR'; said R or R' are independently a linear or branched alkyl group or -C ₆ -C ₁₂ containing 1-24 carbon atoms (marked as -C ₁ -C ₂₄ , the same below) Aryl group, R or R' structure contains 1-6 discontinuous oxygen, nitrogen, or sulfur elements, when R and R' exist at the same time, a 3-6-membered ring structure is formed between them; R ₁₀ , R ₁₁ , R ₁₂ are independently R, and any two of the three form a 3-6 membered carbocyclic structure; (3) A is C=O (that is, the compound of formula I or II is a carboxylate structure), or O=S=O (that is, the compound of formula I or II is a sulfonate structure). 2. The compound according to claim 1, wherein Y in (2) is -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH(OH)CH ₂ -, -CH ₂ CH( OR) _CH2- , _-CH2CH (OC(O)R) _CH2- . 3. compound as claimed in claim 1, is characterized in that, described cycloalkylalkyl has following structure: Among them x=1～5, y=1～6; The cycloheteroalkylalkyl has the following structure: Wherein x=1～5, y=1～6, z represents S, O, N. 4. a method for preparing the coumarin and carbazolyl oxime ester compound shown in general formula (I) and (II) as claimed in claim 1, is characterized in that, preparation process is as follows: Step 1, 2-hydroxycarbazole or 4-hydroxycarbazole reacts under the action of a catalyst represented by _BiCl3 to obtain compound (1) or (2); Step 2, step one gained product (1) or (2) and material shown in (b) among the figure, i.e. bromoalkane, under the situation that potassium iodide and 18-crown-6 are made catalyst, react and obtain (3) or ( 4), the solvent is DMF; Step 3, the product (3) or (4) obtained in step 2 reacts with the substance shown in (c) in the figure, i.e. acid chloride, under the action of AlCl to obtain ( ₅ ) or (6); Step 4, the product (5) or (6) obtained in step 3 reacts with the substance (d) in the figure, i.e. isoamyl nitrite, under the action of concentrated hydrochloric acid to obtain oxime (7) or (8); Step 5, the product (7) or (8) obtained in step 4 and the substance (e) shown in the figure, that is, acid anhydride or the corresponding acid halide, react under the action of triethylamine to the target product (I) or (II ), wherein X shown in the figure is a halogen atom, and R ₄ AX is the corresponding acid halide or sulfonyl halide compound. 5. the preparation method of the coumarinocarbazolyl oxime ester compound shown in general formula (I) or (II) as claimed in claim 4, it is characterized in that, BiCl in step 1 ₃ Adopt ZnCl ₂ to replace. 6. The preparation method of the coumarinocarbazolyl oxime ester compound represented by general formula (I) or (II) as claimed in claim 4, wherein the solvent in step 2 is acetone. 7. the preparation method of the coumarin and carbazolyl oxime ester compound shown in general formula (I) or (II) as claimed in claim 4, is characterized in that, in step 4, product oxime is to replace nitrous acid with hydroxylamine hydrochloride Prepared by the reaction of isoamyl ester. At this time, hydroxylamine hydrochloride directly reacts with a carbonyl group to generate an oxime. The target molecular structure lacks a carbonyl group. At this time, the oxime is directly connected to the aromatic ring, that is, C=O in general formulas (I) and (II) base does not exist. 8. an application of the coumarin and carbazolyl oxime ester compound shown in general formula (I) or (II) as claimed in claim 1, is characterized in that, as the photoinitiator in the light radiation curing system or One of the photoinitiator components The characteristics of this type of light radiation curing formula system are: (1) Containing at least one compound described by general formula (I) as one of photoinitiator or photoinitiator components; (2) Containing at least one ethylenically bonded (C=C) unsaturated compound; Calculated per 100 parts by weight of the total amount of ethylenically unsaturated components in the system, the appropriate amount of the compound of general formula (I) contained is 0.5-10 parts by weight; Radiation-curable systems contain polymerizable ethylenically unsaturated components which are compounds or mixtures which are crosslinked by free radical polymerization of the double bond, such ethylenically unsaturated components being monomers, oligomers or Prepolymers, or mixtures or copolymers thereof, or aqueous dispersions of the aforementioned components.