Sulfonylurea derivative and application thereof in thermosensitive color developing agent

Abstract

The invention discloses a sulfonylurea derivative and application of the sulfonylurea derivative in a thermosensitive color developing agent, and relates to the technical field of color developing agents. The invention discloses a sulfonylurea derivative which is # imgabs0 #. Through the electron donor characteristic of the sulfonylurea group and the synergistic effect of substituent groups (such as tertiary butyl and methoxyl), the color development activation temperature threshold value is greatly reduced, so that a heat-sensitive material realizes rapid color development under lower energy consumption, and the problem of thermal response lag of a traditional color developing agent is effectively solved. The temperature-sensitive color developing agent has the advantages that the performance and the safety are considered in component selection, harmful substances are avoided from the source, meanwhile, the wide activation temperature zone of 60-120 DEG C meets the requirements of diversified temperature-sensitive equipment, and a more reliable and sustainable solution is provided for modern office and data storage.

Description

Technical Field

[0001] The present invention relates to the technical field of color developers, and specifically relates to a sulfonylurea derivative and its application in thermosensitive color developers. Background Art

[0002] In the field of thermosensitive color development, with the continuous development of technology, the market demand for high-performance color developers is increasing day by day. Currently, thermosensitive color developers are mainly divided into two categories: colorless dye type and color developer type, and are widely used in fields such as fax machines and thermal printers.

[0003] Traditional thermosensitive color developers have certain limitations. On the one hand, the color development sensitivity of some color developers is poor, and a relatively high thermal stimulus is required to fully develop color, which not only reduces the printing efficiency but also may shorten the equipment life due to excessive wear of the thermal head; on the other hand, the color development stability is insufficient, and the printed documents are prone to fading or color change under light, high temperature or high humidity environments, affecting the reliability and durability of information storage. In addition, from the perspective of environmental protection and health and safety, some traditional color developers contain potential harmful substances, which may cause pollution to the environment or have an adverse impact on human health during the production, use or waste treatment process.

[0004] In this context, the development of new thermosensitive color developers has become the focus of the industry. Sulfonylurea compounds provide a new direction for the research and development of thermosensitive color developers due to their unique chemical structures and properties. The sulfonylurea group in its molecule can undergo an efficient thermal chemical reaction with thermosensitive materials to achieve rapid color development, and at the same time can be combined with other molecular groups to optimize the performance. If a sulfonylurea derivative can be successfully developed as a thermosensitive color developer, it is expected to make breakthroughs in improving color development sensitivity, stability and environmental performance, and meet the urgent needs of high-quality thermosensitive printing materials in modern office, data storage and other fields. Summary of the Invention

[0005] The object of the present invention is to provide a sulfonylurea derivative with high color development sensitivity, excellent color development stability, good environmental adaptability and environmental protection and safety in view of the problems existing in the prior art, aiming to overcome the deficiencies of traditional thermosensitive color developers in color development effect, durability and environmental performance.

[0006] To achieve the above object, the technical solution adopted by the present invention is: a sulfonylurea derivative, and the sulfonylurea derivative is a compound represented by Formula 1: Formula 1; R1 is selected from any one of: an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to C 15 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms; or R1 is selected from: a C6-C 15aryl.

[0007] Further, the C1-C5 alkyl group is selected from any one of methyl, ethyl, and tert-butyl.

[0008] Further, the C6-C 15 aryl is selected from phenyl.

[0009] Further, the C1-C5 alkoxy group is selected from methoxy or ethoxy.

[0010] Further, the C6-C aryl substituted by C1-C5 alkyl 15 is selected from methylphenyl or tert-butylphenyl.

[0011] Further, the C6-C aryl substituted by C1-C5 alkoxy 15 is selected from methoxyphenyl.

[0012] Further, the sulfonylurea derivative is selected from any one of the compounds represented by the following structures: .

[0013] Further, the preparation method of the sulfonylurea derivative: ; First step: Intermediate 1 is synthesized by Buchwald-Hartwig arylation reaction of Raw material 1 and Raw material 2; Second step: Intermediate 2 is synthesized by borylation reaction of Intermediate 1; Third step: The sulfonylurea derivative is synthesized by Suzuki reaction of Intermediate 2 and Raw material 3.

[0014] Further, the Raw material 1 is the compound represented by the following structure: , , , , , , , , .

[0015] Application of a sulfonylurea derivative in a thermosensitive chromogenic agent.

[0016] Further, the thermosensitive chromogenic agent contains a sulfonylurea derivative described in the present invention.

[0017] Furthermore, the sulfonylurea derivative is used as an electron donor in the thermosensitive chromogenic agent.

[0018] Furthermore, the thermosensitive chromogenic agent further comprises a chromogenic composition composed of a phenolic compound and an acidic substance.

[0019] Furthermore, the mass fraction of the sulfonylurea derivative in the thermosensitive chromogenic agent is 0.5 - 15 parts, and the activation temperature of the chromogenic reaction is 60 - 120 °C.

[0020] Furthermore, the phenolic compound is selected from at least one of bisphenol A, hydroquinone, resorcinol, and 4 - hydroxybenzoate.

[0021] Furthermore, the acidic substance is selected from at least one of stearic acid, salicylic acid, p - toluenesulfonic acid, and dodecylbenzenesulfonic acid.

[0022] Furthermore, the hot - melt filler is selected from at least one of paraffin wax, microcrystalline wax, and polyethylene wax.

[0023] Furthermore, the preparation method of the thermosensitive chromogenic agent is as follows: mix the sulfonylurea derivative, phenolic compound, acidic substance, and hot - melt filler according to the mass fraction, heat the mixture to 50 - 100 °C to melt and stir evenly, then cool to room temperature, and grind to obtain the thermosensitive chromogenic system. The thermosensitive chromogenic mechanism of the sulfonylurea derivative described in the present invention belongs to the electron - transfer type chromogenic mechanism. Its core lies in that the derivative, as an electron donor, undergoes an oxidation - reduction reaction with an electron acceptor under heat - activation conditions to generate a colored substance. The molecular structure of the sulfonylurea derivative described in the present invention endows it with electron - rich characteristics. In the chromogenic system, it serves as a precursor compound of the leuco form. Phenolic compounds (electron acceptors): such as bisphenol A, hydroquinone, resorcinol, etc. These compounds can accept electrons under specific conditions (such as an acidic environment) to form a quinoid structure. Acidic substances (chromogenic reaction promoters / fusion agents): such as stearic acid, salicylic acid, etc. Their functions are crucial: providing an acidic environment: protonating phenolic compounds (electron acceptors) to enhance their ability to accept electrons (electron - deficient property). Fusion effect: when heated to its melting point, the acidic substance first melts into a liquid state. Dissolution effect: the molten acidic substance dissolves the solid phenolic compound (electron acceptor) and the sulfonylurea derivative (electron donor), enabling them to come into full contact and mix.

[0024] When a specific area of a thermosensitive recording material (such as thermal paper) is heated by a thermal print head to a set activation temperature, the acidic substances in the system first melt. The molten acidic substances dissolve and mix the originally solid and physically isolated sulfonylurea derivatives (electron donors) and phenolic compounds (electron acceptors), while providing an acidic environment. In the molten acidic medium, the protonated phenolic compounds (strong electron acceptors) undergo a redox reaction (electron transfer) with the sulfonylurea derivatives (electron donors). The sulfonylurea derivatives lose electrons (are oxidized). The phenolic compounds gain electrons (are reduced), and their structures rearrange to form quinone-type chromophores (such as quinomethides, quinoneimines, etc.). The newly formed quinone-type chromophores have strong absorption in the visible light region, thus presenting colors (such as black, blue, etc.) in the heated area.

[0025] The thermosensitive color development mechanism of the sulfonylurea derivatives described in the present invention is a typical melt-mediated electron transfer reaction. Heating causes the acidic substances to melt and dissolve the reactants. In an acidic environment, the sulfonylurea derivatives (electron donors) transfer electrons to the phenolic compounds (electron acceptors), resulting in a structural change of the latter to form quinone-type colored substances. The hot-melt filler isolates the reactants at room temperature and melts to participate in the formation of the reaction medium at high temperatures. A sulfonylurea derivative, due to its excellent electron donor properties and designable molecular structure, is the key to achieving high sensitivity, high stability, and environmental friendliness.

[0026] Compared with the prior art, the beneficial effects of the present invention are: 1. Significantly improved color development sensitivity: Through the synergistic effect of the electron donor properties of the sulfonylurea group and substituents (such as tert-butyl, methoxy), the color development activation temperature threshold is greatly reduced, enabling the thermosensitive material to achieve rapid color development with lower energy consumption and effectively solving the problem of thermal response lag of traditional color developers.

[0027] 2. Overall enhanced color development stability: The steric hindrance groups (such as tert-butylphenyl) and electron regulation groups (such as methoxy) in the molecular structure significantly inhibit the environmental degradation of the quinone-type chromophores, maintaining the color development contrast under high temperature and high humidity conditions and overcoming the technical bottleneck of easy fading of traditional thermosensitive materials.

[0028] 3. Simultaneous optimization of environmental friendliness and applicability: The component selection takes into account both performance and safety, avoiding harmful substances at the source. At the same time, the wide activation temperature range of 60 - 120 °C adapts to the diverse requirements of thermosensitive devices, providing a more reliable and sustainable solution for modern office and data storage. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 For the sulfonylurea derivative 1 described in the present invention 1 HNMR spectrum.

[0030] Figure 2The invention relates to a method for synthesizing the sulfonylurea derivatives. DETAILED DESCRIPTION

[0031] The technical solution of the present invention will be described clearly and completely below in conjunction with the accompanying drawings of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example 1

[0032] Synthesis of sulfonylurea derivative 1: ;

[0033] Step 1: Under nitrogen protection, add 20g of raw material 1, 25.29g of raw material 2, 14.78g of sodium tert-butoxide, 2.11g of tri(dibenzylideneacetone)dipalladium, 0.15g of tri-tert-butylphosphine and 220g of toluene into the reaction system, stir evenly, heat to 20°C, and reflux for 12h; after the reaction is completed, lower the temperature slightly, filter with diatomaceous earth to remove salt and catalyst, cool the filtrate to room temperature, wash three times with water, retain the organic phase, and then extract the aqueous phase with ethyl acetate; after combining the organic phases, dry with anhydrous magnesium sulfate, spin dry, column chromatography, and use a mixture of petroleum ether and dichloromethane as an eluent to obtain 25.85g of intermediate 1.

[0034] Step 2: Under nitrogen protection, add 25.85 g of intermediate 1 and 300 g of ultra-dry tetrahydrofuran into the reaction system, cool to -70°C, add 3.84 g of n-butyl lithium dropwise, stir for 1 h after the addition is complete, add 16.09 g of triisopropyl borate dropwise, and naturally warm to room temperature after the addition is complete, react for 10 h, spin dry the solvent to obtain 18.82 g of intermediate 2.

[0035] Step 3: Under nitrogen protection, add 18.82 g of intermediate 2, 27.18 g of raw material 3, 12.44 g of anhydrous potassium carbonate, 1.56 g of tetrakis(triphenylphosphine)palladium and 200 g of a mixed solution of toluene, ethanol and water (volume ratio 2:1:1) into the reaction system, heat to 75°C for reflux reaction for 10 hours, turn off the heating, cool to room temperature, stand for separation, extract the aqueous phase twice with ethyl acetate, combine the organic phases, wash three times with water, spin dry, and column chromatography, using a mixture of petroleum ether and dichloromethane as an eluent to obtain 28.54 g of sulfonylurea derivative 1.

[0036] Product structure identification: MS [MS+1] of sulfonylurea derivative 1: 797; Sulfonylurea derivatives 1 1HNMR - Chloroform - d Figure 1 : δ8.37 (m, 1H), 8.11 (d, 1H), 7.89 - 7.77 (m, 3H), 7.72 - 7.61 (m, 2H), 7.60 - 7.48 (m, 2H), 7.48 - 7.42 (m, 1H), 7.46 - 7.24 (m, 10H), 7.09 (m, 1H), 7.00 (d, 1H), 5.76 (d, 2H), 5.30 (m, 1H), 5.17 (d, 1H), 5.07 (t, 2H), 3.21 (s, 3H), 2.49 (d, 3H), 2.39 (t, 3H), 1.58 (s, 3H).

[0037] Examples 2 - 9 In Examples 2 - 9, sulfonylurea derivatives 2 - 9 were successively synthesized. Referring to the synthesis method of Example 1, raw material 1 was replaced, and the rest was the same as in Example 1. The specific structures of raw material 1, sulfonylurea derivatives 2 - 9, and MS [MS + 1] data are shown in Table 1.

[0038] Table 1. Structures of raw material 1, sulfonylurea derivatives 2 - 9, and MS [MS + 1] data in Examples 2 - 9.

[0039]

[0040]

[0041] Performance Testing Preparation of thermosensitive color developer 1: Mix the following components by mass: the sulfonylurea derivative (sulfonylurea derivative 1 prepared in Example 1, 7 parts), phenolic compound (hydroquinone, 30 parts), acidic substance (salicylic acid, 30 parts), and heat - fusible filler (paraffin, 7 parts). Heat the mixture to 100 °C until it melts and stir evenly, then cool to room temperature and grind to obtain thermosensitive color developer 1.

[0042] For thermosensitive color developers 2 - 9, referring to the preparation method of thermosensitive color developer 1, one of the sulfonylurea derivatives was successively replaced with sulfonylurea derivatives 2 - 9 prepared in Examples 2 - 9, and the rest was the same as the preparation of thermosensitive color developer 1.

[0043] For thermosensitive color developer 10, referring to the preparation method of thermosensitive color developer 1, one of the sulfonylurea derivatives was replaced with comparative compound 1, and the rest was the same as the preparation of thermosensitive color developer 1.

[0044] Comparative Compound 1: .

[0045] Color reaction activation temperature and color contrast test: Thermosensitive color developers 1-10 were mixed with colorless substrate (thermosensitive paper) at a mass ratio of 1:5, and deionized water was added to make a slurry, which was evenly coated on the surface of the PET film (coating amount: 5g / m 2 ), dried at 50°C and cut into 10 mm × 50 mm test pieces for use. A controllable temperature thermal gradient plate (accuracy ±1°C) was used, and the temperature gradient was set to 50-150°C, with a temperature difference of 5°C in adjacent areas. Each temperature zone is 10 mm long, corresponding to different positions of the test piece. The test piece was flatly attached to the surface of the thermal gradient plate, pressurized at 0.5 MPa for 2 seconds, and then quickly peeled off. Immediately use a colorimeter (CIE-Lab mode) to measure the color contrast ΔE of each temperature zone 1 (relative to the unheated area). Definition ΔE 1 ≥15 is effective color development, and the lowest activation temperature of each sample (the first time ΔE 1 ≥15). Accelerate aging (85℃ / 85% RH environment, 24h) of the color-developed test piece and re-measure ΔE 1 The color difference retention rate was calculated based on the values, and the data are shown in Table 2.

[0046] Table 2. Color development reaction activation temperature and color development contrast test data of thermosensitive color developers 1-10.

[0047]

[0048] The sulfonylurea derivatives described in the present invention are used as thermosensitive colorants, and show a comprehensive performance trend compared with traditional comparative compounds: their minimum activation temperature is significantly reduced, indicating that the color sensitivity is greatly improved; they show a stronger color contrast under high-temperature color development conditions, proving that the color development reaction is more efficient; at the same time, the color stability is significantly enhanced after aging tests, highlighting the excellent ability to resist environmental degradation. More importantly, this type of derivative achieves the dual effects of low-temperature rapid color development and long-term stable storage through the synergistic effect of the sulfonylurea group and specific substituents (such as tert-butyl and methoxy) in the molecular structure, fundamentally overcoming the technical bottleneck of traditional thermosensitive materials that are difficult to balance sensitivity and durability.

[0049] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A sulfonylurea derivative, characterized in that, The sulfonylurea derivative is a compound represented by Formula 1: Formula 1; The R1 is selected from any one of: C1-C5 alkyl, C6-C 15 aryl, and C1-C5 alkoxy; or R1 is selected from: C6-C 15 aryl substituted by at least one C1-C5 alkyl or C1-C5 alkoxy group.

2. A sulfonylurea derivative according to claim 1, wherein The C1-C5 alkyl group is selected from any one of methyl, ethyl, and tert-butyl.

3. The sulfonylurea derivative according to claim 1, characterized in that, The C6-C 15 aryl is selected from: phenyl.

4. A sulfonylurea derivative according to claim 1, characterized in that, The C1-C5 alkoxy group is selected from methoxy or ethoxy.

5. A sulfonylurea derivative according to claim 1, characterized in that, The aryl group substituted by C1-C5 alkyl is selected from: methylphenyl or tert-butylphenyl. 15 The aryl group substituted by C1-C5 alkyl is selected from: methylphenyl or tert-butylphenyl.

6. A sulfonylurea derivative according to claim 1, wherein The C6-C aryl group substituted by an alkoxy group of C1-C5 15 is selected from: methoxyphenyl.

7. A sulfonylurea derivative according to claim 1, wherein The sulfonylurea derivative is selected from any one of the compounds represented by the following structures: 。 8. A sulfonylurea derivative according to claim 1, wherein, The preparation method of the sulfonylurea derivative: ； The first step: Intermediate 1 is synthesized by the Buchwald-Hartwig arylation reaction of Raw Material 1 and Raw Material 2; The second step: Intermediate 2 is synthesized by the borylation reaction of Intermediate 1; The third step: The sulfonylurea derivative is synthesized by the Suzuki reaction of Intermediate 2 and Raw Material 3.

9. A sulfonylurea derivative according to claim 8, characterized in that, The Raw Material 1 is a compound represented by the following structure: 、 、 、 、 、 、 、 、 。 10. Use of a sulfonylurea derivative according to any one of claims 1-9 in a thermosensitive color developer.

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