Thickened aza derivative as well as preparation and application thereof

Abstract

The invention provides a fused aza derivative as well as preparation and application thereof. The absorption intensity of the fused aza derivative in a near-infrared region is higher, and the maximum molar absorption coefficient in a solution state exceeds 1.0 * 10 < 5 > L.M <-1 >. Cm <-1 >; the light stability and the light fastness of the dye are obviously superior to those of methine dyes, and the European wool light fastness third-level standard is met. The structure of the fused aza derivative is shown as a formula (I),

Description

Technical Field

[0001] This invention relates to the field of chemical engineering, and more specifically, to a condensed azirmono derivative and its preparation and application. Background Technology

[0002] UV-curable inks are high-performance ink systems that achieve instant curing through UV light irradiation. They are characterized by rapid curing and high adhesion, and are virtually free of volatile organic compounds (VOCs), making them very environmentally friendly. Therefore, UV-curable inks have experienced rapid development in recent years and have been widely used in printing, coating, and electronics manufacturing. However, the development of UV-curable ink technology with near-infrared absorption response has been slow. Currently, the market still lacks UV-curable inks that exhibit strong absorption in the near-infrared region while maintaining stable ink properties.

[0003] Organic dye-based inks are characterized by simple formulation, low processing cost, and stable ink properties, making them a promising ink formulation option. Currently available infrared organic dyes exhibit strong absorption in the near-infrared region; however, their photostability is poor, and the infrared characteristics of printed patterns quickly disappear, making them unsuitable for developing infrared-absorbing inks for high-end applications. Furthermore, various universities and research institutions have reported many types of infrared organic dyes with strong near-infrared absorption capabilities; however, these materials generally exhibit strong aggregation, limiting their solubility in ink solutions, hindering dispersion, and causing agglomeration, thus preventing their application as dyes in ink formulation. Currently, there is a lack of near-infrared absorbing organic dyes on the market that simultaneously meet the requirements of good photostability and excellent solubility in common photocurable ink monomers. Summary of the Invention

[0004] The technical problem to be solved by this invention is to provide a near-infrared absorbing organic dye for UV-curable inks and its preparation method. This organic dye has significant advantages in several aspects: it has efficient near-infrared absorption capability, exhibiting strong absorption in the near-infrared region of 760-950 nm; it has excellent solubility, maintaining good dispersion in a variety of common ink systems; it has good photostability, maintaining stable optical performance under long-term UV irradiation; and the organic dye utilizes a convergent synthesis strategy, with simple synthesis steps and engineering feasibility.

[0005] One object of the present invention is to provide a fused azirmono derivative or a stereoisomer thereof.

[0006] Another object of the present invention is to provide a method for preparing the aforementioned fused aza derivative or its stereoisomer.

[0007] Another object of the present invention is to provide an organic dye.

[0008] Another object of the present invention is to provide a UV-curable ink.

[0009] To achieve the above objectives, in one respect, the present invention provides a fused azirconium derivative or its stereoisomer, wherein the structure of the fused azirconium derivative is as shown in formula (I):

[0010]

[0011] X is selected from S, O, or Se;

[0012] Y is selected from halogen, cyano, amino, carboxyl, nitro, hydroxyl, substituted or unsubstituted aryl, substituted or unsubstituted alkynyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy.

[0013] R1, R2, R3, R4, and R5 are each independently selected from H, hydroxyl, amino, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, -Si(R 11 (R) 12 )R 13 substituted or unsubstituted aryl, substituted or unsubstituted alkynyl, substituted or unsubstituted alkenyl, -N(R) 14 )R 15 Alternatively, it may replace or oligomerize the side chains of ethylene glycol;

[0014] R 11 R 12 R 13 Each is independently selected from H or substituted or unsubstituted alkyl groups;

[0015] R 14 and R 15 Each is independently selected from H or substituted or unsubstituted alkyl groups;

[0016] Choose any 0, 1, 2, 3, or 4 of R1, R2, R3, R4, and R5 to be H (R1, R2, R3, R4, and R5 cannot all be H at the same time).

[0017] According to some specific embodiments of the present invention, the number of oxygen atoms in the oligoethylene glycol is 2-10.

[0018] According to some specific embodiments of the present invention, wherein,

[0019] X is selected from S, O, or Se;

[0020] Y is selected from F, Cl, Br, I, cyano, amino, carboxyl, nitro, hydroxyl, tert- to 18-membered aryl, C 1-20 Alkyl, C 1-20 alkynyl group, C1-20 Alkoxy or tetra- to octadecyl aryloxy; optionally, the alkyl, alkynyl, alkoxy, aryl, and aryloxy groups are selected from F, Cl, Br, I, C. 1-10 Alkyl, C 1-10 Substituted by alkoxy, cyano, amino, carboxyl, nitro, or hydroxyl groups;

[0021] R1, R2, R3, R4, and R5 are each independently selected from H, hydroxyl, amino, C, and C, respectively. 1-110 Alkoxy, C 1-110 Alkylthio, tetra- to octadecyloxy, -Si(R) 11 (R) 12 )R 13 4- to 18-aryl aryl, C 1-20 alkynyl group, C 1-20 alkenyl, -N(R) 14 )R 15 Or oligoethylene glycol side chains; optionally, the alkynyl, alkenyl, alkoxy, alkylthio, aryl, aryloxy, or oligoethylene glycol side chains are selected from F, Cl, Br, I, C. 1-10 Alkyl, C 1-10 Substituted by alkoxy, cyano, amino, carboxyl, nitro, or hydroxyl groups;

[0022] R 11 R 12 R 13 Each independently selected from H or C 1-110 Alkyl; optionally, the alkyl group is selected from F, Cl, Br, I, C. 1-10 Substituted by alkyl, cyano, amino, carboxyl, nitro, or hydroxyl substituents;

[0023] R 14 and R 15 Each was independently selected from H and C. 1-110 Alkyl; optionally, the alkyl group is selected from F, Cl, Br, I, C. 1-10 It is substituted by substituents of alkyl, cyano, amino, carboxyl, nitro or hydroxyl groups.

[0024] According to some specific embodiments of the present invention, wherein,

[0025] X is selected from S, O, or Se;

[0026] Y is selected from F, Cl, Br, I, cyano, amino, carboxyl, nitro, hydroxyl, hexa-membered, deca-membered, thirteen-membered or fourteen-membered aryl, C 1-20 Alkyl, C 1-20 alkynyl group, C 1-15Alkoxy or hexa-, deca-, thirteen-membered; optionally, the alkyl, alkynyl, alkoxy, aryl, and aryloxy groups are selected from F, Cl, Br, I, C. 1-10 Substituted by alkyl, cyano, amino, carboxyl, nitro, or hydroxyl substituents;

[0027] R1, R2, R3, R4, and R5 are each independently selected from H, hydroxyl, amino, C, and C, respectively. 1-110 Alkoxy, hexa-, deca-, thirteen-, or fourteen-membered aryloxy, C 1-110 Alkylthio, -Si(R) 11 (R) 12 )R 13 6-yuan, 10-yuan, 13-yuan or 14-yuan aryl, C 1-20 alkynyl group, C 1-20 alkenyl, -N(R) 14 )R 15 Or oligoethylene glycol side chains; optionally, the alkynyl, alkenyl, alkoxy, alkylthio, aryl, aryloxy, or oligoethylene glycol side chains are selected from F, Cl, Br, I, C. 1-10 Alkyl, C 1-10 Substituted by alkoxy, cyano, amino, carboxyl, nitro, or hydroxyl groups;

[0028] R 11 R 12 R 13 Each independently selected from H or C 1-110 Alkyl; optionally, the alkyl group is selected from F, Cl, Br, I, C. 1-10 Substituted by alkyl, cyano, amino, carboxyl, nitro, or hydroxyl substituents;

[0029] R 14 and R 15 Each was independently selected from H and C. 1-110 Alkyl; optionally, the alkyl group is selected from F, Cl, Br, I, C. 1-10 It is substituted by substituents of alkyl, cyano, amino, carboxyl, nitro or hydroxyl groups.

[0030] According to some specific embodiments of the present invention, wherein,

[0031] X is selected from S, O, or Se;

[0032] Y is selected from F, Cl, Br, I, cyano, amino, carboxyl, nitro, hydroxyl, C 1-20 Alkyl, C 1-15 Alkoxy, Optionally, the alkyl, alkynyl, or alkoxy group is selected from F, Cl, Br, I, or C. 1-10 Substituents of alkyl groups;

[0033] R1, R2, R3, R4, and R5 are each independently selected from H, hydroxyl, amino, hexa-membered, deca-membered, thirteen-membered or fourteen-membered aryloxy, hexa-membered, deca-membered, thirteen-membered or fourteen-membered aryl, C, etc. 1-20 alkynyl group, C 1-20 alkenyl,

[0034]

[0035] R6 is selected from F, Cl, Br, I, and C. 1-20 Alkyl or C 1-20 Alkoxy;

[0036] Optionally, the alkynyl, alkenyl, alkylamino, alkylene, alkoxy, alkylthio, aryl, and aryloxy groups in R1, R2, R3, R4, and R5 are selected from F, Cl, Br, I, and C. 1-10 Alkyl, C 1-10 Substituted by alkoxy, cyano, amino, carboxyl, nitro, or hydroxyl groups;

[0037] m is 0, 1, 2, 3, 4 or 5; n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12;

[0038] Each x, y, and z is an independent integer selected from 0 to 30.

[0039] According to some specific embodiments of the present invention, wherein,

[0040] X is selected from S, O, or Se;

[0041] Y is selected from F, Cl, Br, I, cyano, amino, carboxyl, nitro, hydroxyl, C 1-10 Alkyl, C 1-10 Alkoxy, Optionally, the alkyl, alkynyl, or alkoxy group is selected from F, Cl, Br, I, or C. 1-5 Substituents of alkyl groups;

[0042] R1, R2, R3, R4, and R5 are each independently selected from H, hydroxyl, amino, hexa-membered, deca-membered, thirteen-membered or fourteen-membered aryloxy, hexa-membered, deca-membered, thirteen-membered or fourteen-membered aryl, C, etc. 1-10 alkynyl group, C 1-10 alkenyl,

[0043]

[0044] R6 is selected from F, Cl, Br, I, and C. 1-10 Alkyl or C 1-10 Alkoxy;

[0045] Optionally, the alkynyl, alkenyl, alkylamino, alkylene, alkoxy, alkylthio, aryl, and aryloxy groups in R1, R2, R3, R4, and R5 are selected from F, Cl, Br, I, and C. 1-5 Alkyl, C 1-5 Substituted by alkoxy, cyano, amino, carboxyl, nitro, or hydroxyl groups;

[0046] m is 0, 1, 2, 3, 4 or 5; n is 0, 1, 2, 3, 4 or 5;

[0047] Each x, y, and z is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

[0048] According to some specific embodiments of the present invention, wherein,

[0049] X is selected from S or O;

[0050] Y is selected from F, Cl, Br, I, cyano, Optionally, the alkynyl group is replaced by a substituent selected from F, Cl, Br or I;

[0051] R1, R2, R3, R4, and R5 are each independently selected from H,

[0052] R6 is selected from F, Cl, Br, I, and C. 1-6 Alkyl or C 1-6 Alkoxy;

[0053] Optionally, the alkylene, alkylamino, alkoxy, and alkylthio groups in R1, R2, R3, R4, and R5 are replaced by substituents selected from F, Cl, Br, or I;

[0054] m is 0, 1, 2, 3, 4 or 5; n is 0, 1, 2, 3, 4 or 5;

[0055] Each x, y, and z is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

[0056] According to some specific embodiments of the present invention, wherein,

[0057] X is selected from S or O;

[0058] Y is selected from F, Cl, Br, I, or

[0059] R1, R2, R3, R4, and R5 are each independently selected from H,

[0060] R6 is selected from F, Cl, Br, or I;

[0061] Optionally, the alkylamino, alkoxy, and alkylthio groups in R1, R2, R3, R4, and R5 are replaced by substituents selected from F, Cl, Br, or I;

[0062] m is 0, 1, 2, or 3; n is 0, 1, or 2;

[0063] Each x, y, and z is independently selected from 0, 1, 2, 3, 4, 5, 6, or 7.

[0064] It is understood that when x, y, or z in this invention is selected from 0, it indicates that an alkyl group is not present at that position, i.e., the position is -H; for example, when When x is 0, it represents -C at that point. x H 2x+1 It does not exist; the structure is

[0065] According to some specific embodiments of the present invention, the fused aza derivative is selected from one of the following structures:

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072] On the other hand, the present invention also provides a method for preparing the fused aza derivative or its stereoisomer according to any one of the present invention, wherein the method comprises preparing the fused aza derivative or its stereoisomer of formula (I) using a compound of formula (II) and a boron-containing compound as raw materials:

[0073]

[0074] According to some specific embodiments of the present invention, the boron-containing compound is boron trifluoride diethyl ether.

[0075] According to some specific embodiments of the present invention, the compound of formula (II) and the boron-containing compound are reacted at 30-100°C to obtain the fused aza derivative of formula (I) or its stereoisomer.

[0076] According to some specific embodiments of the present invention, the compound of formula (II) and the boron-containing compound are reacted at 40-90°C to obtain the fused aza derivative of formula (I) or its stereoisomer.

[0077] According to some specific embodiments of the present invention, the reaction time of the compound of formula (II) and the boron-containing compound is 15 min to 24 h.

[0078] According to some specific embodiments of the present invention, the reaction time of the compound of formula (II) and the boron-containing compound is 30 min to 12 h.

[0079] According to some specific embodiments of the present invention, the molar ratio of the compound of formula (II) and the boron-containing compound is 1:(2-8); preferably 1:(3-6); more preferably 1:(4-5).

[0080] According to some specific embodiments of the present invention, the compound of formula (II) and the boron-containing compound are reacted in the presence of an organic base to obtain the fused aza derivative of formula (I) or its stereoisomer.

[0081] According to some specific embodiments of the present invention, the organic base is selected from triethylamine or diisopropylethylamine.

[0082] According to some specific embodiments of the present invention, the molar ratio of the compound of formula (II) and the organic base is 1:(1-4); preferably 1:(2-3).

[0083] According to some specific embodiments of the present invention, the compound of formula (II) and the boron-containing compound are reacted in a solvent to obtain the fused azirconium derivative of formula (I) or its stereoisomer.

[0084] According to some specific embodiments of the present invention, the solvent is a non-polar solvent.

[0085] According to some specific embodiments of the present invention, the solvent is selected from one or more of toluene, dichloroethane and dichloromethane, or a mixture thereof.

[0086] According to some specific embodiments of the present invention, the method further includes preparing the compound shown in formula (II) using the compound of formula (III) and sodium nitrite as raw materials:

[0087]

[0088] According to some specific embodiments of the present invention, the compound of formula (I) and sodium nitrite are reacted at 50-100°C to obtain the compound of formula (II).

[0089] According to some specific embodiments of the present invention, the compound of formula (I) and sodium nitrite are reacted at 60-90°C to obtain the compound of formula (II).

[0090] According to some specific embodiments of the present invention, the compound of formula (I) and sodium nitrite are reacted for 15 min-24 h to obtain the compound of formula (II).

[0091] According to some specific embodiments of the present invention, the compound of formula (I) and sodium nitrite are reacted for 30 min to 12 h to obtain the compound of formula (II).

[0092] According to some specific embodiments of the present invention, the compound of formula (I) and sodium nitrite are first reacted at low temperature, and then reacted at 50-100°C to obtain the compound of formula (II).

[0093] According to some specific embodiments of the present invention, the compound of formula (I) and sodium nitrite are first reacted at 0-5°C, and then reacted at 60-90°C to obtain the compound of formula (II).

[0094] According to some specific embodiments of the present invention, the compound of formula (I) and sodium nitrite are first reacted at low temperature for 15 min-6 h, and then reacted at 50-100 °C for 15 min-24 h to obtain the compound of formula (II).

[0095] According to some specific embodiments of the present invention, the compound of formula (I) and sodium nitrite are first reacted at 0-5°C for 30 min-2 h, and then reacted at 60-90°C for 30 min-12 h to obtain the compound of formula (II).

[0096] According to some specific embodiments of the present invention, the molar ratio of the compound of formula (I) and sodium nitrite is 1:(0.5-1); preferably 1:0.5.

[0097] According to some specific embodiments of the present invention, the compound of formula (I) and sodium nitrite are reacted in an organic acid and an anhydride to obtain a fused aza derivative of formula (I) or a stereoisomer thereof.

[0098] According to some specific embodiments of the present invention, the organic acid is selected from acetic acid or dilute hydrochloric acid; preferably acetic acid.

[0099] According to some specific embodiments of the present invention, the mass concentration of the dilute hydrochloric acid is 0.5-20%.

[0100] According to some specific embodiments of the present invention, the acid anhydride is acetic anhydride or propionic anhydride; preferably acetic anhydride.

[0101] According to some specific embodiments of the present invention, the molar ratio of the compound of formula (I) to the organic acid is 1:(175-350); preferably 1:(175-200).

[0102] According to some specific embodiments of the present invention, the molar ratio of the compound of formula (I) to the acid anhydride is 1:(70-140); preferably 1:(70-100).

[0103] According to some specific embodiments of the present invention, the compound of formula (I) and sodium nitrite are reacted under an inert gas atmosphere.

[0104] According to some specific embodiments of the present invention, the compound of formula (I) and sodium nitrite are reacted under light-protected conditions.

[0105] According to some specific embodiments of the present invention, the method further includes preparing the compound of formula (III) from the compound of formula (IV):

[0106]

[0107] According to some specific embodiments of the present invention, the compound of formula (IV) is prepared under alkaline conditions to obtain the compound of formula (III).

[0108] According to some specific embodiments of the present invention, the compound of formula (IV) is prepared in the presence of a base to obtain the compound of formula (III).

[0109] According to some specific embodiments of the present invention, the alkali is selected from potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, or sodium bicarbonate.

[0110] According to some specific embodiments of the present invention, the molar ratio of the compound of formula (IV) to the base is 1:(5-20); preferably 1:(10-15).

[0111] According to some specific embodiments of the present invention, the compound of formula (IV) is prepared in a solvent to obtain the compound of formula (III).

[0112] According to some specific embodiments of the present invention, the solvent is selected from ethylene glycol or propylene glycol.

[0113] According to some specific embodiments of the present invention, the compound of formula (IV) is reacted at 100°C-150°C to prepare the compound of formula (III).

[0114] According to some specific embodiments of the present invention, the compound of formula (IV) is reacted at 100°C-130°C to prepare the compound of formula (III).

[0115] According to some specific embodiments of the present invention, compound (IV) is reacted for 2-4 hours to prepare compound (III).

[0116] According to some specific embodiments of the present invention, compound (IV) is reacted for 3-4 hours to prepare compound (III).

[0117] According to some specific embodiments of the present invention, the method further includes preparing compound (IV) from compounds of formula (V) and formula (VI):

[0118]

[0119] According to some specific embodiments of the present invention, the compounds of formula (V) and (VI) are prepared in the presence of a catalyst to obtain the compound of formula (IV).

[0120] According to some specific embodiments of the present invention, the catalyst is an organometallic palladium complex or a mixture of an organometallic palladium complex and tris(o-methylphenyl)phosphine.

[0121] According to some specific embodiments of the present invention, the organometallic palladium complex is selected from one or more of tetra(triphenylphosphine)palladium, dichlorodi(triphenylphosphine)palladium, dichlorodi(1,1'-diphenylphosphinoferrocene)palladium and tri(dibenzylideneacetone)palladium.

[0122] According to some specific embodiments of the present invention, the catalyst is tetrakis(triphenylphosphine)palladium, dichlorodi(triphenylphosphine)palladium, dichlorodi(1,1'-diphenylphosphinoferrocene)palladium, or a mixture of tris(dibenzylideneacetone)dipalladium and tris(o-methylphenyl)phosphine.

[0123] According to some specific embodiments of the present invention, the catalyst is a mixture of tris(dibenzylacetone)palladium and tris(o-methylphenyl)phosphine.

[0124] According to some specific embodiments of the present invention, the molar ratio of the compound of formula (V) and tris(dibenzylacetone)dipalladium and tris(o-methylphenyl)phosphine is 1:(0.05-0.2):(0.2-0.8); preferably 1:(0.05-0.1):(0.2-0.4).

[0125] According to some specific embodiments of the present invention, the compounds of formula (V) and (VI) are prepared in the presence of a base to obtain the compound of formula (IV).

[0126] According to some specific embodiments of the present invention, the alkali is selected from potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, or sodium bicarbonate.

[0127] According to some specific embodiments of the present invention, the molar ratio of the compound of formula (V) to the base is 1:(5-20); preferably 1:10.

[0128] According to some specific embodiments of the present invention, compounds of formula (V) and (VI) are prepared to obtain compound (IV) in the presence of a catalyst and a base; said catalyst is a mixture of tris(dibenzylacetone)dipalladium and tris(o-methylphenyl)phosphine.

[0129] According to some specific embodiments of the present invention, the molar ratio of the compound of formula (V), tris(dibenzylacetone)dipalladium, tris(o-methylphenyl)phosphine and the base is 1:(0.05-0.2):(0.2-0.8):(5-20); preferably 1:0.05:0.2:10.

[0130] According to some specific embodiments of the present invention, the compounds of formula (V) and formula (VI) are prepared in a solvent to obtain the compound of formula (IV).

[0131] According to some specific embodiments of the present invention, the solvent is selected from one or more of toluene, 1,4-dioxane and N,N-dimethylformamide, or a mixture thereof.

[0132] According to some specific embodiments of the present invention, compound (V) and compound (VI) are reacted at 100°C-150°C to prepare compound (IV).

[0133] According to some specific embodiments of the present invention, compound (V) and compound (VI) are reacted at 110°C-130°C to prepare compound (IV).

[0134] According to some specific embodiments of the present invention, compound (IV) is prepared by reacting compound (V) and compound (VI) for 3-7 hours.

[0135] According to some specific embodiments of the present invention, compound (IV) is prepared by reacting compound (V) and compound (VI) for 5-6 hours.

[0136] According to some specific embodiments of the present invention, the method further includes preparing the compound of formula (V) using the compound of formula (VII) and NBS as raw materials:

[0137]

[0138] According to some specific embodiments of the present invention, the compound of formula (VII) and NBS are prepared in a solvent to obtain the compound of formula (V).

[0139] According to some specific embodiments of the present invention, the solvent is selected from one or more of dichloromethane, trichloromethane, 1,2-dichloroethane, tetrahydrofuran, and acetonitrile.

[0140] According to some specific embodiments of the present invention, compound (VII) and NBS are reacted at 15°C-40°C to prepare compound (V).

[0141] According to some specific embodiments of the present invention, compound (VII) and NBS are reacted at 20°C-30°C to prepare compound (V).

[0142] According to some specific embodiments of the present invention, compound (VII) is prepared by reacting compound (VII) with NBS for 2-4 hours.

[0143] According to some specific embodiments of the present invention, compound (VII) is prepared by reacting compound (VII) with NBS for 3-4 hours.

[0144] In another aspect, the present invention also provides an organic dye, wherein the organic dye contains any of the condensed aza derivatives or stereoisomers thereof described in any one of the present invention.

[0145] In another aspect, the present invention also provides an ultraviolet curable ink, wherein the ink contains any of the condensed azirmono derivatives or stereoisomers thereof described in any one of the present invention.

[0146] In summary, this invention provides a fused diazo derivative, its preparation, and its application. The technical solution of this invention has the following advantages:

[0147] This invention provides an organic dye for UV-curable inks, which has high near-infrared absorption capacity (strong absorption within 760-950nm), excellent dispersibility and solubility, outstanding photostability and lightfastness, and a simple and efficient synthesis process, and has the potential for large-scale industrial production.

[0148] Compared with commonly available methine-based organic infrared dyes, this invention has the following advantages:

[0149] (1) The absorption intensity is higher in the near-infrared region, and the maximum molar absorptivity in solution exceeds 1.0 × 10⁻⁶. 5 L·M -1 ·cm -1 ;

[0150] (2) It is also significantly better than methyl dyes in terms of light stability and light resistance, reaching the European wool light resistance level three standard (methyl dyes are about level one). Attached Figure Description

[0151] Figure 1 For intermediate S2 1 H NMR spectrum.

[0152] Figure 2 For intermediate S3 1 H NMR spectrum.

[0153] Figure 3 For intermediate S4 1 H NMR spectrum.

[0154] Figure 4 For compound A1 1 H NMR spectrum.

[0155] Figure 5 The image shows the UV-Vis-IR absorption spectrum of compound A1 in chloroform solution.

[0156] Figure 6 The image shows the UV-Vis-IR absorption spectrum of compound A1 in the film state.

[0157] Figure 7 For intermediate S5 1 H NMR spectrum.

[0158] Figure 8 For intermediate S6 1 H NMR spectrum.

[0159] Figure 9 For compound A2 1 H NMR spectrum.

[0160] Figure 10 The image shows the UV-Vis-IR absorption spectrum of compound A2 in chloroform solution.

[0161] Figure 11 This is the UV-Vis-IR absorption spectrum of compound A2 in the film state. Detailed Implementation

[0162] The following detailed embodiments illustrate the implementation process and beneficial effects of the present invention, aiming to help readers better understand the essence and characteristics of the present invention, and are not intended to limit the scope of implementation of this case.

[0163] Synthesis of Example A1:

[0164]

[0165] Synthesis of intermediate S2:

[0166] S1 (2 g, 10.24 mmol) was dissolved in 50 mL of dichloromethane. NBS (3.65 g, 20.48 mmol) was added to the reaction system, and the reaction was carried out at room temperature for 3 h. The mixture was extracted three times with dichloromethane, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The organic phase was recrystallized from 40 mL of ethanol and 200 mL of water to give product S2 (3.54 g, 98%). The obtained product S2 was analyzed by NMR (nuclear magnetic resonance). Figure 1 ) and mass spectrometry analysis, the results are as follows:

[0167] NMR analysis: 1 H NMR (500MHz, CDCl3) δ9.12 (s, 1H), 7.03 (s, 1H), 4.47-4.33 (m, 2H), 1.42 (dt, J = 8.5, 7.1Hz, 3H).

[0168] Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 353.03; experimental value 353.03.

[0169] Synthesis of intermediate S3:

[0170] Under an argon atmosphere, S2 (1 g, 2.83 mmol), 2,5-dimethoxyphenylboronic acid (1.55 g, 8.49 mmol), tris(dibenzylacetone)dipalladium (0.26 g, 0.28 mmol), and tris(o-methylphenyl)phosphine (0.46 g, 1.13 mmol) were added to a 100 mL round-bottom flask, along with 21 mL of toluene, 7 mL of 2 M K2CO3 aqueous solution, and 50 mg of phase transfer catalyst Aliquat 336. The reaction was refluxed at 110 °C for 5 h. The organic phases were extracted three times with dichloromethane, combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was subjected to silica gel column chromatography using dichloromethane:ethanol = 100:1 as eluent to obtain product S3 (1.19 g, 90%). The obtained product S3 was analyzed by NMR (Negative Nuclear Magnetic Resonance Analysis). Figure 2 ) and mass spectrometry analysis, the results are as follows:

[0171] NMR analysis: 1 H NMR (500MHz, CDCl3) δ9.08 (s, 1H), 7.45 (s, 1H), 7.17 (d, J = 3.1Hz, 1H), 7.09 (d, J = 2.7Hz, 1H), 6.95-6.87 (m, 3H), 6.81 (dd ,J=9.0,3.0Hz,1H),4.25(q,J=7.1Hz,2H),3.90-3.86(m,3H),3.81(d,J=4.0Hz,6H),3.78(s,3H),1.21(t,J=7.1Hz,3H).

[0172] Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 467.54; experimental value 467.54.

[0173] Synthesis of intermediate S4:

[0174] Under an argon atmosphere, S3 (1.19 g, 2.55 mmol) and KOH (1.43 g, 25.5 mmol) were added to a 100 mL round-bottom flask. 40 mL of ethylene glycol was added, and the reaction was carried out at 130 °C for 3 h. After the reaction, the mixture was extracted three times with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was subjected to silica gel column chromatography using dichloromethane as the eluent to obtain product S4 (0.81 g, 80%). NMR analysis of product S4 was performed. Figure 3 ) and mass spectrometry analysis, the results are as follows:

[0175] NMR analysis: 1 H NMR (500MHz, CDCl3) δ8.35(s,1H),7.64(s,1H),7.52(s,1H),7.29(d,J=3.0Hz,1H),7.23(d,J=3.0Hz,1 H),6.92(dd,J=8.9,1.1Hz,2H),6.83-6.73(m,2H),3.91(s,3H),3.89(s,3H),3.87(s,3H),3.84(s,3H).

[0176] Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 395.47; experimental value 395.47.

[0177] Synthesis of A1:

[0178] Under argon protection, a mixed solvent of acetic acid / acetic anhydride (5 mL / 2 mL) was added to a reaction flask containing S4 (0.395 g, 1.0 mmol). The mixture was stirred at 0 °C for 15 min, followed by the addition of NaNO2 (34.5 mg, 0.5 mmol), and stirring at 0 °C for 30 min. The temperature was then raised to 80 °C and stirred for 30 min. After the reaction was complete, crushed ice was added to the cooled reaction mixture, and the mixture was filtered, retaining the filter cake. The filter cake was dried, dissolved in dichloromethane, filtered through an alumina filter, and washed with dichloromethane. The solvent was removed under vacuum, and the residue was dissolved in dry 1,2-dichloroethane. 1.2 mL of triethylamine was added, followed by the slow addition of 1.2 mL of boron trifluoride diethyl ether at room temperature with stirring. The mixture was stirred for 0.5 h, then heated in an oil bath at 80 °C for 0.5 h, and cooled. The mixture was extracted three times with dichloromethane, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was subjected to silica gel column chromatography using dichloromethane as eluent to obtain product A1 (0.212 g, 50%). The obtained product A1 was analyzed by NMR (nuclear magnetic resonance). Figure 4 ) and mass spectrometry analysis, the results are as follows:

[0179] NMR analysis: 1 H NMR (500MHz, CDCl3) δ7.66 (d, J=2.8Hz, 2H), 7.58 (s, 2H), 7.31 (dd, J=2.4, 1.0Hz, 2H), 6.98-6.95 (m, 4H), 6.94 (d, J = 2.9Hz, 2H), 6.91 (d, J = 9.0Hz, 2H), 3.95 (d, J = 4.2Hz, 12H), 3.86 (s, 6H), 3.44 (s, 6H).

[0180] Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 849.73; experimental value 849.73.

[0181] The photophysical properties of Example A1 were characterized using a UV-Vis spectrophotometer. In dilute chloroform solution, the maximum absorption peak of the dimer was located at 792 nm, with a molar absorptivity of 1.135 × 10⁻⁶. 5 M -1. cm -1 ( Figure 5 In the film state, the maximum absorption peak red-shifts to 870 nm. Figure 6 ).

[0182] Synthesis of Example A2:

[0183]

[0184] Synthesis of intermediate S2:

[0185] Intermediate S2 was prepared by synthesis according to Example A1.

[0186] Synthesis of intermediate S5:

[0187] Under an argon atmosphere, S2 (1 g, 2.83 mmol), 2,5-dimethoxyphenylboronic acid (2.02 g, 8.49 mmol), tris(dibenzylacetone)dipalladium (0.26 g, 0.28 mmol), and tris(o-methylphenyl)phosphine (0.46 g, 1.13 mmol) were added to a 100 mL round-bottom flask, along with 21 mL of toluene, 7 mL of 2 M K2CO3 aqueous solution, and a small amount of Aliquat 336 phase transfer catalyst. The reaction was refluxed at 110 °C for 5 h. The organic phases were extracted three times with dichloromethane, combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was subjected to silica gel column chromatography using dichloromethane:ethanol = 100:1 as eluent to obtain product S5 (1.39 g, 85%). The obtained product S5 was analyzed by NMR (Negative Nuclear Magnetic Resonance Analysis). Figure 7 ) and mass spectrometry analysis, the results are as follows:

[0188] NMR analysis: 1 H NMR (500MHz, CDCl3) δ9.02 (s, 1H), 7.49 (s, 1H), 7.18 (d, J = 2.9Hz, 1H), 7.05 (d, J=3.0Hz,1H),6.90(dd,J=8.9,1.6Hz,2H),6.83(dd,J=8.9,3.0Hz,1H),6.78(dd ,J=8.9,2.9Hz,1H),4.54(hept,J=6.1Hz,1H),4.46(pd,J=6.1,2.4Hz,2H),4.28 -4.14(m,3H),1.42-1.29(m,18H),1.19(t,J=7.1Hz,3H),1.13(d,J=6.0Hz,6H).

[0189] Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 579.75; experimental value 579.75.

[0190] Synthesis of intermediate S6:

[0191] Under an argon atmosphere, S5 (1.39 g, 2.40 mmol) and KOH (1.35 g, 24.0 mmol) were added to a 100 mL round-bottom flask. 40 mL of ethylene glycol was added, and the reaction was carried out at 130 °C for 3 h. After the reaction, the mixture was extracted three times with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was subjected to silica gel column chromatography using dichloromethane as eluent to obtain product S6 (0.95 g, 78%). NMR analysis of product S6 was performed. Figure 8 ) and mass spectrometry analysis, the results are as follows:

[0192] NMR analysis: 1 H NMR (500MHz, CDCl3) δ8.31(s,1H),7.77(d,J=2.5Hz,1H),7.50(s,1H),7.34(d,J=3.0Hz,1H),7.24(d,J=3.0Hz,1H),6.91(d,J=8.9Hz,2H),6 .73(ddd,J=14.1,8.8,2.9Hz,2H), 4.55(dddt,J=24.2,22.7,12.1,6.0Hz,6H), 1.37(dd,J=16.8,6.0Hz,24H), 1.23(dd,J=13.8,6.9Hz,3H).

[0193] Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 507.69; experimental value 507.69.

[0194] Synthesis of A2:

[0195] Under argon protection, a mixed solvent of acetic acid / acetic anhydride (5 mL / 2 mL) was added to a reaction flask containing S6 (0.507 g, 1.0 mmol). The mixture was stirred at 0 °C for 15 min, followed by the addition of NaNO2 (34.5 mg, 0.5 mmol), and stirring at 0 °C for 30 min. The mixture was then heated to 80 °C and stirred for 30 min. After the reaction was complete, crushed ice was added to the cooled reaction mixture, and the mixture was filtered, retaining the filter cake. The filter cake was dried, dissolved in dichloromethane, filtered through an alumina filter, and washed with dichloromethane. The solvent was removed under vacuum, and the residue was dissolved in dry 1,2-dichloroethane. 1.2 mL of triethylamine was added, followed by the slow addition of 1.2 mL of boron trifluoride diethyl ether at room temperature with stirring. The mixture was stirred for 0.5 h, then heated in an oil bath at 80 °C for 0.5 h, and cooled. The mixture was extracted three times with dichloromethane, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was subjected to silica gel column chromatography using dichloromethane as eluent to obtain product A2 (0.462 g, 43%). The obtained product A2 was analyzed by NMR (nuclear magnetic resonance). Figure 9) and mass spectrometry analysis, the results are as follows:

[0196] NMR analysis: 1 H NMR (500MHz, CDCl3) δ7.58 (s, 2H), 7.34 (dd, J=7.9, 2.8Hz, 4H), 6.99-6.88 (m, 6H), 6.83 (dd, J=8.9, 3.0Hz, 2H), 4.65 (p, J= 6.1Hz,2H),4.53(m,4H),4.01-3.92(m,2H),1.44(d,J=6.1Hz,12H),1.36(dd,J=6.1,3.8Hz,24H),1.01(d,J=6.0Hz,12H).

[0197] Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1074.16; experimental value 1074.16.

[0198] The photophysical properties of Example A2 were characterized using a UV-Vis spectrophotometer. The obtained UV-Vis absorption spectra are shown in the attached figure. In dilute chloroform solution, the maximum absorption peak of the dimer is located at 793 nm. Figure 10 The molar absorption coefficient is 1.012 × 10⁻⁶. 5 M -1. cm -1 In the film state, the maximum absorption peak red-shifts to 848 nm. Figure 11 ).

[0199] Synthesis of Examples A3 to A21:

[0200] The preparation methods for A3 to A21 are the same as those for Examples A1 and A2, except that the boric acid substrate in the second step is replaced with other substituted substrates. The synthesis results and corresponding material characterization data are listed in the table below.

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208] Synthesis of Example B1:

[0209]

[0210] Under argon atmosphere, Al (0.09 g, 0.10 mmol) was dissolved in ultradry dichloromethane (20 mL), followed by the slow dropwise addition of tin tetrachloride (SnCl4, 12.0 μL, 0.10 mmol) and trimethylsilyl cyanide (TMSCN, 0.28 mL, 2.04 mmol) using a syringe. The reaction mixture was stirred at 25 °C for 3 hours, quenched with water, and extracted with dichloromethane. The combined organic phases were washed successively with saturated sodium bicarbonate solution and distilled water, and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the crude product was separated by silica gel column chromatography to obtain product B1 (0.07 g, 82%).

[0211] The prepared compound B1 was analyzed by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF): theoretical value 863.77; experimental value 863.77.

[0212] Elemental analysis of the prepared compound B1 was performed, and the results are as follows: calculated values: C, 63.96; H, 4.43; N, 8.11; O, 14.82; S, 7.42. Experimental values: C, 63.92; H, 4.41; N, 8.08; O, 14.79; S, 7.45.

[0213] Synthesis of Example B2:

[0214]

[0215] Under argon atmosphere, A2 (0.11 g, 0.1 mmol) was dissolved in ultradry dichloromethane (20 mL), followed by the slow dropwise addition of tin tetrachloride (SnCl4, 12.0 μL, 0.1 mmol) and trimethylsilyl cyanide (TMSCN, 0.28 mL, 2.04 mmol) using a syringe. The reaction mixture was stirred at 25 °C for 3 hours, quenched with water, and extracted with dichloromethane. The combined organic phases were washed successively with saturated sodium bicarbonate solution and distilled water, and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the crude product was separated by silica gel column chromatography to obtain product B2 (0.09 g, 80%).

[0216] The prepared B2 compound was analyzed by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF): theoretical value 1088.20; experimental value 1088.20.

[0217] Elemental analysis of the prepared compound B2 was performed, and the results are as follows: calculated values: C, 68.43; H, 6.48; N, 6.44; O, 11.76; S, 5.89. Experimental values: C, 68.46; H, 6.45; N, 6.42; O, 11.76; S, 5.91.

[0218] Synthesis of Examples B3 to B21:

[0219] The preparation methods for B3 to B21 are the same as those for Examples B1 and B2, except that the substituents of the reaction substrates are different. The synthesis results and corresponding material characterization data are listed in the table below.

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226] Synthesis of Example C1:

[0227]

[0228] Under argon atmosphere, 0.083 g (0.10 mmol) of a five-membered aromatic heterocyclic benzo[a]BODIPY compound A1 was weighed and placed in a 50 mL two-necked flask. 10 mL of dry dichloromethane was added, and the flask was placed in an ice-water bath with stirring. 0.23 mL of freshly prepared phenyl Grignard reagent was slowly added dropwise to the reaction system. After the addition was complete, the reaction was maintained at 0 °C for 5 hours. After the reaction was complete, the reaction solution was poured into a saturated ammonium chloride aqueous solution and stirred. The aqueous phase was extracted three times with dichloromethane. The combined organic phases were washed successively with ultrapure water and saturated brine, then dried over anhydrous sodium sulfate, and the organic phase was concentrated. The crude product was separated by silica gel column chromatography to obtain product C1 (0.06 g, 58%).

[0229] The prepared C1 compound was analyzed by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF): theoretical value 965.94; experimental value 965.94.

[0230] Elemental analysis of the prepared C1 compound yielded the following results: Calculated values: C, 69.63; H, 5.01; N, 4.35; O, 13.25; S, 6.64. Experimental values: C, 69.62; H, 5.04; N, 4.35; O, 13.23; S, 6.65.

[0231] Synthesis of Example C2:

[0232]

[0233] Under argon atmosphere, 0.11 g (0.10 mmol) of a five-membered aromatic heterocyclic compound of the BODIPY class A2 was weighed and placed in a 50 mL two-necked flask. 10 mL of dry dichloromethane was added, and the flask was placed in an ice-water bath with stirring. 0.23 mL of freshly prepared phenyl Grignard reagent was slowly added dropwise to the reaction system. After the addition was complete, the reaction was maintained at 0 °C for 5 hours. After the reaction was complete, the reaction solution was poured into a saturated ammonium chloride aqueous solution and stirred. The aqueous phase was extracted three times with dichloromethane. The combined organic phases were washed successively with ultrapure water and saturated brine, then dried over anhydrous sodium sulfate, and the organic phase was concentrated. The crude product was separated by silica gel column chromatography to obtain product C2 (0.07 g, 53%).

[0234] The prepared C2 compound was analyzed by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF): theoretical value 1190.38; experimental value 1190.38.

[0235] Elemental analysis of the prepared C2 compound yielded the following results: Calculated values: C, 72.65; H, 6.77; N, 3.53; O, 10.75; S, 5.39. Experimental values: C, 72.62; H, 6.76; N, 3.55; O, 10.75; S, 5.38.

[0236] Synthesis of Examples C3 to C21:

[0237] The preparation methods for C3 to C21 are the same as those for Examples C1 and C2, except that the substituents of the reaction substrates are different. The synthesis results and corresponding material characterization data are listed in the table below.

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244] Synthesis of Examples D1 to D21:

[0245] The preparation methods for D1 to D21 are the same as those for Examples A1 to A21, except that the reaction substrate S1 is different, and the sulfur atom (S) in X in Formula I is replaced with an oxygen atom (O). The synthesis results and corresponding material characterization data are listed in the table below.

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252] Synthesis of Examples E1 to E21:

[0253] The preparation methods for E1 to E21 are the same as those for Examples B1 to B21, except that the reaction substrate is different, and the sulfur atom (S) in Formula I is replaced with an oxygen atom (O). The synthesis results and corresponding material characterization data are listed in the table below.

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260] Synthesis of Examples F1 to F21:

[0261] The preparation methods for F1 to F21 are the same as those for Examples C1 to C21, except that the substituents of the reaction substrates are different, and the sulfur atom (S) in X of Formula I is replaced with an oxygen atom (O). The synthesis results and corresponding material characterization data are listed in the table below.

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268] Test example:

[0269] The structures of Comparative Examples 1, 2, 3, and 4 in the table above are shown below:

[0270]

[0271] Compared with BODIPY compounds reported in existing literature, such as Comparative Examples 1 and 2 in Org. Lett. 2014, 16, 748-751, and representative structures in related invention patents (e.g., Pub. No.: US2021 / 0130373 A1) (Comparative Examples 3 and 4), the solubility of the BODIPY compounds in inks of the present invention is significantly improved. In various UV-curable ink systems, the solubility can reach 5% by mass, an improvement that significantly enhances their performance in practical applications. For example, isobornyl acrylate (IBOA) and hydroxyethyl methacrylate (HEMA) are common UV-curable ink monomers with crosslinking properties. The compounds of the present invention exhibit excellent solubility and stability in both monomers, showing a clear advantage over Comparative Examples 1-4. Solubility test: The compound was added to IBOA or HEMA at a concentration of 5% by mass, sonicated for 20 minutes to ensure thorough mixing. Good solubility was indicated by a clear solution without particles or precipitates. Stability test: Well-dissolved ink samples were sealed and stored at room temperature, and observed daily for any particle or precipitate formation. The results are shown in the table below (where "—" indicates poor solubility and stability time cannot be provided):

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

Claims

1. A fused aza derivative or its stereoisomer, wherein, The structure of the fused aza derivative is shown in formula (I): X is selected from S, O, or Se; Y is selected from halogen, cyano, amino, carboxyl, nitro, hydroxyl, substituted or unsubstituted aryl, substituted or unsubstituted alkynyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy. R1, R2, R3, R4, and R5 are each independently selected from H, hydroxyl, amino, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, -Si(R 11 (R) 12 )R 13 substituted or unsubstituted aryl, substituted or unsubstituted alkynyl, substituted or unsubstituted alkenyl, -N(R) 14 )R 15 Or oligoethylene glycol side chain (preferably the number of oxygen atoms in the oligoethylene glycol is 2-10); R 11 R 12 R 13 Each is independently selected from H or substituted or unsubstituted alkyl groups; R 14 and R 15 Each is independently selected from H or substituted or unsubstituted alkyl groups; H can be any 0, 1, 2, 3, or 4 of R1, R2, R3, R4, and R5.

2. The fused aza derivative or its stereoisomer according to claim 1, wherein, X is selected from S, O, or Se; Y is selected from F, Cl, Br, I, cyano, amino, carboxyl, nitro, hydroxyl, tert- to 18-membered aryl, C 1-20 Alkyl, C 1-20 alkynyl group, C 1-20 Alkoxy or tetra- to octadecyl aryloxy; optionally, the alkyl, alkynyl, alkoxy, aryl, and aryloxy groups are selected from F, Cl, Br, I, C. 1-10 Alkyl, C 1-10 Substituted by alkoxy, cyano, amino, carboxyl, nitro, or hydroxyl groups; R1, R2, R3, R4, and R5 are each independently selected from H, hydroxyl, amino, C, and C, respectively. 1-110 Alkoxy, C 1-110 Alkylthio, tetra- to octadecyloxy, -Si(R) 11 (R) 12 )R 13 4- to 18-aryl aryl, C 1-20 alkynyl group, C 1-20 alkenyl, -N(R) 14 )R 15 The polyethylene glycol side chain; optionally, the alkynyl, alkenyl, alkoxy, alkylthio, aryl, aryloxy, or oligoethylene glycol side chain is selected from F, Cl, Br, I, C. 1-10 Alkyl, C 1-10 Substituted by alkoxy, cyano, amino, carboxyl, nitro, or hydroxyl groups; R 11 R 12 R 13 Each independently selected from H or C 1-110 Alkyl; optionally, the alkyl group is selected from F, Cl, Br, I, C. 1-10 Substituted by alkyl, cyano, amino, carboxyl, nitro, or hydroxyl substituents; R 14 and R 15 Each was independently selected from H and C. 1-110 Alkyl; optionally, the alkyl group is selected from F, Cl, Br, I, C. 1-10 It is substituted by substituents of alkyl, cyano, amino, carboxyl, nitro or hydroxyl groups.

3. The fused aza derivative or its stereoisomer according to any one of claims 1 to 2, wherein, X is selected from S, O, or Se; Y is selected from F, Cl, Br, I, cyano, amino, carboxyl, nitro, hydroxyl, hexa-membered, deca-membered, thirteen-membered or fourteen-membered aryl, C 1-20 Alkyl, C 1-20 alkynyl group, C 1-15 Alkoxy or hexa-, deca-, thirteen-membered; optionally, the alkyl, alkynyl, alkoxy, aryl, and aryloxy groups are selected from F, Cl, Br, I, C. 1-10 Substituted by alkyl, cyano, amino, carboxyl, nitro, or hydroxyl substituents; R1, R2, R3, R4, and R5 are each independently selected from H, hydroxyl, amino, C, and C, respectively. 1-110 Alkoxy, hexa-, deca-, thirteen-, or fourteen-membered aryloxy, C 1-110 Alkylthio, -Si(R) 11 (R) 12 )R 13 6-yuan, 10-yuan, 13-yuan or 14-yuan aryl, C 1-20 alkynyl group, C 1-20 alkenyl, -N(R) 14 )R 15 Or oligoethylene glycol side chains; optionally, the alkynyl, alkenyl, alkoxy, alkylthio, aryl, aryloxy, or oligoethylene glycol side chains are selected from F, Cl, Br, I, C. 1-10 Alkyl, C 1-10 Substituted by alkoxy, cyano, amino, carboxyl, nitro, or hydroxyl groups; R 11 R 12 R 13 Each independently selected from H or C 1-110 Alkyl; optionally, the alkyl group is selected from F, Cl, Br, I, C. 1-10 Substituted by alkyl, cyano, amino, carboxyl, nitro, or hydroxyl substituents; R 14 and R 15 Each was independently selected from H and C. 1-110 Alkyl; optionally, the alkyl group is selected from F, Cl, Br, I, C. 1-10 It is substituted by substituents of alkyl, cyano, amino, carboxyl, nitro or hydroxyl groups.

4. The fused aza derivative or its stereoisomer according to any one of claims 1 to 3, wherein, X is selected from S, O, or Se; Y is selected from F, Cl, Br, I, cyano, amino, carboxyl, nitro, hydroxyl, C 1-20 Alkyl, C 1-15 Alkoxy, Optionally, the alkyl, alkynyl, or alkoxy group is selected from F, Cl, Br, I, or C. 1-10 Substituents of alkyl groups; R1, R2, R3, R4, and R5 are each independently selected from H, hydroxyl, amino, hexa-membered, deca-membered, thirteen-membered or fourteen-membered aryloxy, hexa-membered, deca-membered, thirteen-membered or fourteen-membered aryl, C, etc. 1-20 alkynyl group, C 1-20 alkenyl, R6 is selected from F, Cl, Br, I, and C. 1-20 Alkyl or C 1-20 Alkoxy; Optionally, the alkynyl, alkenyl, alkylamino, alkylene, alkoxy, alkylthio, aryl, and aryloxy groups in R1, R2, R3, R4, and R5 are selected from F, Cl, Br, I, and C. 1-10 Alkyl, C 1-10 Substituted by alkoxy, cyano, amino, carboxyl, nitro, or hydroxyl groups; m is 0, 1, 2, 3, 4 or 5; n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; Each x, y, and z is an independent integer selected from 0 to 30.

5. The fused aza derivative or its stereoisomer according to any one of claims 1 to 4, wherein, X is selected from S, O, or Se; Y is selected from F, Cl, Br, I, cyano, amino, carboxyl, nitro, hydroxyl, C 1-10 Alkyl, C 1-10 Alkoxy, Optionally, the alkyl, alkynyl, or alkoxy group is selected from F, Cl, Br, I, or C. 1-5 Substituents of alkyl groups; R1, R2, R3, R4, and R5 are each independently selected from H, hydroxyl, amino, hexa-membered, deca-membered, thirteen-membered or fourteen-membered aryloxy, hexa-membered, deca-membered, thirteen-membered or fourteen-membered aryl, C, etc. 1-10 alkynyl group, C 1-10 alkenyl, R6 is selected from F, Cl, Br, I, and C. 1-10 Alkyl or C 1-10 Alkoxy; Optionally, the alkynyl, alkenyl, alkylamino, alkylene, alkoxy, alkylthio, aryl, and aryloxy groups in R1, R2, R3, R4, and R5 are selected from F, Cl, Br, I, and C. 1-5 Alkyl, C 1-5 Substituted by alkoxy, cyano, amino, carboxyl, nitro, or hydroxyl groups; m is 0, 1, 2, 3, 4 or 5; n is 0, 1, 2, 3, 4 or 5; Each x, y, and z is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

6. The fused aza derivative or its stereoisomer according to any one of claims 1 to 5, wherein, X is selected from S or O; Y is selected from F, Cl, Br, I, cyano, Optionally, the alkynyl group is replaced by a substituent selected from F, Cl, Br or I; R1, R2, R3, R4, and R5 are each independently selected from H, R6 is selected from F, Cl, Br, I, and C. 1-6 Alkyl or C 1-6 Alkoxy; Optionally, the alkylene, alkylamino, alkoxy, and alkylthio groups in R1, R2, R3, R4, and R5 are replaced by substituents selected from F, Cl, Br, or I; m is 0, 1, 2, 3, 4 or 5; n is 0, 1, 2, 3, 4 or 5; Each x, y, and z is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

7. The fused aza derivative or its stereoisomer according to any one of claims 1 to 6, wherein, X is selected from S or O; Y is selected from F, Cl, Br, I, or R1, R2, R3, R4, and R5 are each independently selected from H, R6 is selected from F, Cl, Br, or I; Optionally, the alkylamino, alkoxy, and alkylthio groups in R1, R2, R3, R4, and R5 are replaced by substituents selected from F, Cl, Br, or I; m is 0, 1, 2, or 3; n is 0, 1, or 2; Each x, y, and z is independently selected from 0, 1, 2, 3, 4, 5, 6, or 7.

8. The fused aza derivative or its stereoisomer according to any one of claims 1 to 7, wherein, The fused aza derivative is selected from one of the following structures:

9. A method for preparing the fused aza derivative or its stereoisomer according to any one of claims 1 to 8, wherein, The method comprises preparing a fused aza derivative of formula (I) or its stereoisomer from a compound of formula (II) and a boron-containing compound (preferably selected from boron trifluoride diethyl ether) as raw materials:

10. The preparation method according to claim 9, wherein, The method also includes preparing the compound shown in formula (II) using the compound of formula (III) and sodium nitrite as raw materials:

11. The preparation method according to claim 10, wherein, The method also includes preparing the compound of formula (III) from the compound of formula (IV):

12. The preparation method according to claim 11, wherein, The method further includes preparing compound (IV) from compounds of formula (V) and formula (VI):

13. The preparation method according to claim 11, wherein, The method also includes preparing the compound of formula (V) using the compound of formula (VII) and NBS as raw materials:

14. An organic dye, wherein, The organic dye contains the condensed aza derivative or its stereoisomer as described in any one of claims 1 to 8; preferably, the weight content of the condensed aza derivative or its stereoisomer in the organic dye is 0.5-5%.

15. A UV-curable ink, wherein, The ink contains the condensed azirconium derivative or its stereoisomer as described in any one of claims 1 to 8; preferably, the weight content of the condensed azirconium derivative or its stereoisomer in the ink is 0.5-5%.

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