(Z)-p-toluenesulfonyl hydrazone derivative and preparation method thereof

Abstract

The invention relates to the technical field of compound synthesis, in particular to (Z)-p-toluenesulfonyl hydrazone derivatives and a preparation method thereof. The (E)-p-toluenesulfonyl hydrazone derivative, a photosensitizer and a solvent are mixed and react under illumination to obtain the (Z)-p-toluenesulfonyl hydrazone derivative. The photosensitizer selected by the method is green and low in cost, free of heavy metal residues, wide in substrate application range, high in isomerization efficiency, short in reaction time and good in cis-product stability, the system is easy for amplified production, the high-purity hydrazone compound and the photoisomerization product thereof can be efficiently, mildly and greenly prepared, and the method is suitable for industrial production. The application potential in the fields of drug synthesis, precise drug delivery and functional materials is obviously improved.

Description

Technical Field

[0001] This invention relates to the field of compound synthesis technology, and more particularly to a ( Z )-p-Toluenesulfonylhydrazone derivatives and their preparation methods. Background Technology

[0002] The structural flexibility and potential bioactivity of aldehyde-derived hydrazones and their isomerization products make them highly promising for drug development and precision medicine, focusing on three main areas: First, the efficient synthesis of bioactive drug molecules. Through the mild conditions and high selectivity of visible light isomerization, hydrazone precursors for antitumor, anti-infective, and anti-inflammatory drugs can be precisely synthesized, overcoming the high toxicity and poor selectivity of traditional synthesis methods and enriching the drug molecule library. This application direction draws on the advantages of photocatalytic isomerization technology in organic synthesis and combines it with the bioactive potential of hydrazones. Second, the precise modification and optimization of drug molecules. Isomerization reactions can be used to perform directional conformational regulation or functional group modification of drug molecules, improving water solubility, targeting, bioavailability, and metabolic stability, reducing toxic side effects, and enhancing pharmacodynamic performance. Studies on the structural and activity differences between cis and trans isomers have confirmed that conformational regulation is an effective means of optimizing drug performance. Thirdly, the development of photoresponsive precision drug delivery systems, based on their visible light-driven energy conversion characteristics, involves constructing hydrazone-linked photoresponsive drug delivery carriers to achieve precise photocontrolled release and activation of drugs at lesion sites (such as tumor tissue), achieving "on-demand drug delivery," significantly improving treatment accuracy and reducing damage to normal tissues. The design of this system can draw on the photoresponsive regulation technology of UV-visible light-controlled isomerization polymers and refer to the targeted delivery strategies of photodynamic therapy. Future research should focus on in vitro and in vivo bioactivity screening, toxicological evaluation, and in vivo efficacy verification of isomerized products to promote their translation from basic research to clinical treatment scenarios.

[0003] Hydrazones, as an important class of organic intermediates containing a C=N-NH-R core skeleton, occupy an irreplaceable position in multiple fields such as drug synthesis, organocatalysis, and functional materials due to their unique chemical activity and structural tunability. In drug synthesis, hydrazone skeletons are widely found in bioactive molecules such as antibacterial, antitumor, and antituberculosis molecules. They are also the core building blocks for constructing key pharmacodynamic motifs such as chiral amines, aminophosphonates, and nitrogen-containing heterocycles. Their efficient synthesis directly affects the efficiency and cost of drug development. In organic synthesis methodology, hydrazones can serve as precursors for reactive intermediates such as nitrogen radicals and carbenes, participating in various important transformation reactions such as radical coupling, cycloaddition, and CH bond insertion. In the field of functional materials, the C=N double bond of hydrazones exhibits unique photoresponsive cis-trans isomerism, undergoing reversible configurational changes under visible / ultraviolet light irradiation. This isomerization process is accompanied by significant changes in molecular spatial arrangement, dipole moment, conjugated system, and chemical reactivity. It is the core foundation for the application of hydrazone compounds in fields such as smart drug delivery, photoresponsive functional materials, and regulation of organic synthesis intermediates. It is also an important precursor material for the preparation of photoresponsive materials such as azobenzene polymers.

[0004] Currently, there are two main technical approaches for the photocatalytic isomerization synthesis of hydrazones: One is the noble metal complex photosensitizer system, represented by Ru(bpy)3Cl2 and Ir(ppy)3, which achieves trans-cis isomerization via energy transfer under blue light irradiation, achieving a conversion rate of up to 55-60%. This approach boasts strong photostability and high energy transfer efficiency, but suffers from high cost and heavy metal residues. The other is the organic dye photosensitizer system, represented by Eosin Y and Rose Bengal, which drives isomerization via single-electron transfer under green light irradiation, achieving a conversion rate of approximately 40-50%. This approach is low-cost and free of heavy metal pollution, but suffers from poor solubility, easy aggregation and degradation, and spontaneous reversal of the cis product. Both approaches use DMF as a solvent, require 12-28 hours of continuous light irradiation, and are primarily suitable for simple aldehyde substrates.

[0005] Currently, photocatalytic synthesis systems for hydrazones face five major technical bottlenecks: First, it's difficult to balance cost and efficiency with photosensitizers—precious metals are expensive and leave heavy metal residues, while organic dyes are prone to aggregation and degradation. Second, reaction selectivity is poor; aldehydes are prone to self-condensation, and hydrazines are prone to coupling, resulting in yields of only 60%-75%. Third, substrate universality is narrow, with poor compatibility with aldehydes containing special functional groups, heterocycles, or large steric hindrances. Fourth, isomerization efficiency is low, with cis-products accounting for less than 60%, and the reaction requires 12-24 hours. Fifth, system scale-up is difficult, with problems such as uneven illumination, temperature runaway, and complex solvent recovery, hindering industrial application.

[0006] Given the aforementioned technical bottlenecks, developing efficient and green methods for synthesizing hydrazone compounds is of great significance for advancing organic synthesis technology and expanding the pathways for preparing functional molecules. Summary of the Invention

[0007] The purpose of this invention is to provide a ( Z This invention relates to p-toluenesulfonylhydrazone derivatives and their preparation methods, aiming to address the problems existing in the prior art.

[0008] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a ( Z The preparation method of p-toluenesulfonylhydrazone derivatives includes the following steps: Will( E A mixture of p-toluenesulfonylhydrazone derivatives, a photosensitizer, and a solvent is reacted under light to obtain ( Z )-p-Toluenesulfonylhydrazone derivatives.

[0009] Optionally, the ( E The structural formula of p-toluenesulfonylhydrazone derivatives is shown in Formula I: Formula I; R1 is selected from one of methyl, methoxy, methylthio, or hydrogen, R2 is nitro or hydrogen, and R3 is methyl or hydrogen.

[0010] Optionally, the photosensitizer is disodium eosin Y, rhodamine, 4,5,6,7-tetrafluorotetraiodofluorescein, or 4,4-di-tert-butyl.

[0011] Optionally, the solvent is one or more of N,N-dimethylformamide, acetonitrile, dichloromethane, and dimethyl sulfoxide.

[0012] Optionally, the wavelength of the illumination is 400~450 nm.

[0013] Optionally, the reaction temperature is 0~80℃ and the reaction time is 2~10h.

[0014] Optionally, the amount of photosensitizer used is ( E 2 mol of p-toluenesulfonylhydrazone derivatives.

[0015] The present invention also provides the above-mentioned ( Z The preparation method of p-toluenesulfonylhydrazone derivatives ( Z )-p-Toluenesulfonylhydrazone derivatives, having the structure shown in Formula II: Formula II; R1 is selected from one of methyl, methoxy, methylthio, or hydrogen, R2 is nitro or hydrogen, and R3 is methyl or hydrogen.

[0016] Compared with the prior art, the present invention has the following beneficial effects: This invention discloses a method for EZ isomerization of hydrazones under visible light conditions. No new substances are generated in the reaction, but it affects the stereoselectivity of subsequent reactions. The reaction utilizes the core structure of hydrazones, C=N-NH-Ts, with electrophilic groups attached to the aromatic ring or aliphatic chain. These groups, capable of reducing the molecular electron cloud density through inductive or conjugated reactions, significantly activate the N / N bonds of the hydrazone, modulating the reactivity of the C=N bond. They are key regulatory groups for photocatalytic denitrification, radical coupling, and carbene generation of hydrazones, generating isomers of the hydrazone and thus increasing its reactivity.

[0017] The photosensitizer selected in this invention is green and low-cost, with no heavy metal residues, has a wide range of substrate applications, high isomerization efficiency, short reaction time, good product stability, and the system is easy to scale up for production. It is driven by visible light and does not require high temperature and high pressure, which can efficiently, mildly and greenly prepare high-purity hydrazone compounds and their photoisomerization products, significantly enhancing their application potential in drug synthesis, precision drug delivery and functional materials. Attached Figure Description

[0018] Figure 1 The hydrogen spectrum of compound 1a in Example 1; Figure 2 The carbon spectrum of compound 1a in Example 1; Figure 3 The hydrogen spectrum of compound 2a in Example 1; Figure 4 The carbon spectrum of compound 2a in Example 1; Figure 5 The hydrogen spectrum of compound 1b in Example 2; Figure 6 The carbon spectrum of compound 1b in Example 2; Figure 7 The hydrogen spectrum of compound 2b in Example 2; Figure 8 The carbon spectrum of compound 2b in Example 2; Figure 9 The hydrogen spectrum of compound 1c in Example 3; Figure 10 The carbon spectrum of compound 1c in Example 3; Figure 11 The hydrogen spectrum of compound 2c in Example 3; Figure 12 The carbon spectrum of compound 2c in Example 3; Figure 13 The hydrogen spectrum of compound 1d in Example 4; Figure 14 The carbon spectrum of compound 1d in Example 4; Figure 15 The hydrogen spectrum of compound 2d in Example 4; Figure 16 The carbon spectrum of compound 2d in Example 4; Figure 17 The hydrogen spectrum of compound 1e in Example 5; Figure 18 The carbon spectrum of compound 1e in Example 5; Figure 19 The hydrogen spectrum of compound 2e in Example 5; Figure 20 This is the carbon spectrum of compound 2e from Example 5. Detailed Implementation

[0019] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0020] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0021] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0022] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be obvious to those skilled in the art. This application specification and embodiments are merely exemplary.

[0023] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0024] All raw materials used in this invention can be obtained commercially or prepared using existing technologies.

[0025] This invention provides a ( Z The preparation method of p-toluenesulfonylhydrazone derivatives includes the following steps: Will( E A mixture of p-toluenesulfonylhydrazone derivatives, a photosensitizer, and a solvent is reacted under light to obtain ( Z )-p-Toluenesulfonylhydrazone derivatives.

[0026] In some embodiments of the present invention, the reaction progress is monitored by thin-layer chromatography until the reaction is complete. Ethyl acetate and water are added for extraction and separation. The organic layers are combined, dried over anhydrous Na₂SO₄, concentrated, and recrystallized to obtain (… Z )-p-Toluenesulfonylhydrazone derivatives.

[0027] In this invention, preparation ( Z The equation for p-toluenesulfonylhydrazone derivatives is shown below: .

[0028] The volume ratio of ethyl acetate to water is 3:1.

[0029] In this invention, the ( E The structural formula of p-toluenesulfonylhydrazone derivatives is shown in Formula I: Formula I; Wherein, R1 is selected from one of methyl, methoxy, methylthio, or hydrogen; R2 is nitro or hydrogen; R3 is methyl or hydrogen; and -NHTs are... .

[0030] In this invention, the photosensitizer is disodium eosin Y, rhodamine, 4,5,6,7-tetrafluorotetraiodofluorescein, or 4,4-di-tert-butyl, preferably disodium eosin Y.

[0031] In this invention, the solvent is one or more of N,N-dimethylformamide, acetonitrile, dichloromethane, and dimethyl sulfoxide.

[0032] In this invention, the wavelength of the illumination is 400~450 nm, for example, it can be 400 nm, 425 nm or 450 nm.

[0033] In some embodiments of the present invention, the source of the illumination is an LED lamp.

[0034] In this invention, the reaction temperature is 0~80℃, for example, it can be 0℃, 10℃, 20℃, 25℃, 30℃, 40℃, 50℃, 60℃, 70℃ or 80℃, etc., and the reaction time is 2~10h, for example, it can be 2h, 4h, 6h, 8h or 10h, etc.

[0035] In this invention, the amount of photosensitizer used is ( E 2 mol of p-toluenesulfonylhydrazone derivatives.

[0036] The present invention also provides the above-mentioned ( Z The preparation method of p-toluenesulfonylhydrazone derivatives ( Z )-p-Toluenesulfonylhydrazone derivatives, having the structure shown in Formula II: Formula II; Wherein, R1 is selected from one of methyl, methoxy, methylthio, or hydrogen; R2 is nitro or hydrogen; R3 is methyl or hydrogen; and -NHTs are... .

[0037] The aldehyde p-toluenesulfonylhydrazone provided by this invention possesses a C=N-NH-Ts structural unit. Relying on the controllable NN bond breaking under photocatalysis and the generation of carbene or free radical intermediates, it serves as a multifunctional green building block in drug synthesis. It solves the pain points of using highly toxic reagents, cumbersome procedures, and low selectivity in the synthesis of analgesic drugs. Its core functions focus on three dimensions: key active skeleton construction, drug molecule modification, and efficient synthesis of important intermediates. It also meets the green, modular, and highly selective requirements of modern drug development and is widely used in the synthesis and optimization of various drugs, including antibacterial, antitumor, antituberculosis, and antihistamine drugs. On the one hand, the hydrazone skeleton is a special structure widely present in many bioactive molecules, playing a crucial role in various important transformations such as free radical reactions, cycloaddition, and transition metal catalytic reactions. On the other hand, the C=N photoresponsive isomerism and easily broken bond characteristics can significantly improve its reaction controllability, thus it is often used as a substrate or "photocontrolled protection-activation unit" in photocatalytic synthetic chemistry for the efficient construction of pharmacodynamic motifs such as chiral amines, nitrogen heterocycles, and azo chromophores. Therefore, integrating these two structural advantages into a single framework can yield hydrazone compounds with novel photoresponsive properties. These intermediates may have greater application value in drug synthesis and functional materials. However, systematic reports on photocatalytic directed synthesis methods for hydrazone compounds possessing both bioactive frameworks and photocontrolled reaction properties have not yet been found.

[0038] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0039] Example 1 Compound 1a (0.5 mmol), disodium eosin Y (2 mol%), N,N-dimethylformamide (5 mL), and a magnetic stir bar were added sequentially to a ground glass joint reaction tube, and the mixture was irradiated with a 425 nm LED lamp. The reaction was carried out at 25 °C for 2 h. The reaction progress was monitored by thin-layer chromatography until the reaction was complete. 60 mL of ethyl acetate and 20 mL of water were added for extraction and separation. The organic layers were combined, dried over anhydrous Na₂SO₄, concentrated, and recrystallized to give compound 2a in 78% yield. The reaction equation is as follows: The characterization of compound 1a is as follows: 1 H NMR (400 MHz, CDCl3): δ 8.28 (s, 1 H), 7.93-7.83 (m, 2 H), 7.72 (s, 1 H), 7.49-7.42 (m, 2 H), 7.35-7.27 (m, 2 H), 7.21-7.12 (m, 2 H), 2.46 (s, 3H), 2.39 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 147.63, 144.23, 141.91, 135.21,129.73, 129.66, 127.89, 127.62, 125.71, 21.55, 15.11. The characterization of compound 2a is as follows: 1 H NMR (400 MHz, CDCl3): δ 8.57 (s, 1 H), 7.86 (d, J = 8.3 Hz, 2 H), 7.73 (s, 1 H), 7.44 (d, J = 8.4 Hz, 2 H), 7.27 (d, J = 8.1 Hz, 2 H), 7.14 (d,J = 8.4 Hz, 2 H), 2.46 (s, 3 H), 2.37 (s, 3 H); 13 C NMR (101 MHz, CDCl3): δ147.68, 144.22, 141.87, 135.33, 129.87, 129.70, 127.93, 127.66, 125.75,21.59, 15.16. Example 2 Compound 1b (0.5 mmol), disodium eosin Y (2 mol%), N,N-dimethylformamide (5 mL), and a magnetic stir bar were added sequentially to a ground glass joint reaction tube, and the mixture was irradiated with a 425 nm LED lamp. The reaction was carried out at 25 °C for 2 h. The reaction progress was monitored by thin-layer chromatography until the reaction was complete. 60 mL of ethyl acetate and 20 mL of water were added for extraction and separation. The organic layers were combined, dried over anhydrous Na₂SO₄, concentrated, and recrystallized to give compound 2b in 70% yield. The reaction equation is as follows: The characterization of compound 1b is as follows: 1 H NMR (400 MHz, CDCl3): δ 8.08 (s, 1 H), 7.80 (d, J = 8.0 Hz, 2 H), 7.67 (s, 1 H), 7.39 (d, J = 7.8 Hz, 2 H), 7.22 (d, J = 7.9 Hz, 2 H), 7.07 (d,J = 7.8 Hz, 2 H), 2.32 (s, 3 H), 2.27 (s, 3 H); 13 C NMR (101 MHz, CDCl3): δ148.20, 144.18, 140.78, 135.21, 130.42, 129.65, 129.32, 127.90, 127.33,21.56, 21.46. The characterization of compound 2b is as follows: 1 H NMR (400 MHz, CDCl3): δ 8.23 ​​(s, 1 H), 7.75 (d, J = 8.0 Hz, 2 H), 7.48 (d, J = 8.0 Hz, 2 H), 7.20-7.12 (m, 5 H), 2.32 (s, 3 H), 2.29 (s, 3 H); 13 C NMR (101 MHz, CDCl3): δ 144.90, 143.66, 133.05, 129.64, 129.52, 128.89,128.49, 127.62, 127.22, 21.67, 21.57. Example 3 Compound 1c (0.5 mmol), disodium eosin Y (2 mol%), N,N-dimethylformamide (5 mL), and a magnetic stir bar were added sequentially to a ground glass joint reaction tube, and the mixture was irradiated with a 425 nm LED lamp. The reaction was carried out at 25 °C for 2 h. The reaction progress was monitored by thin-layer chromatography until the reaction was complete. 60 mL of ethyl acetate and 20 mL of water were added for extraction and separation. The organic layers were combined, dried over anhydrous Na₂SO₄, concentrated, and recrystallized to give compound 2c in 68% yield. The reaction equation is as follows: The characterization of compound 1c is as follows: 1 H NMR (400 MHz, CDCl3): δ 8.35 (s, 1 H), 8.25 (s, 1 H), 8.02 (ddd, J= 9.4, 8.1, 1.3 Hz, 2 H), 7.94-7.82 (m, 2 H), 7.64 (td, J = 7.7, 1.2 Hz, 1H), 7.52 (td, J = 7.8, 1.5 Hz, 1 H), 7.33 (d, J = 8.1 Hz, 2 H), 2.42 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 147.85, 144.57, 142.12, 135.17, 133.58, 130.51,129.81, 128.77, 128.22, 127.96, 124.77, 21.62. The characterization of compound 2c is as follows: 1 H NMR (400 MHz, CDCl3): δ 8.42 (s, 1 H), 8.36 (s, 1 H), 8.02 (dd, J =8.3, 1.4 Hz, 1 H), 7.95-7.92 (m, 1 H), 7.89-7.84 (m, 3 H), 7.63 (td, J = 7.7,1.3 Hz, 1 H), 7.52 (ddd, J = 8.8, 7.5, 1.5 Hz, 1 H), 7.33 (d, J = 8.1 Hz, 1H), 2.42 (s, 3 H); 13C NMR (101 MHz, CDCl3): δ 144.52, 142.16, 135.58, 134.25,133.65, 130.47, 129.79, 128.74, 127.92, 125.54, 124.73, 21.59. Example 4 Compound 1d (0.5 mmol), disodium eosin Y (2 mol%), N,N-dimethylformamide (5 mL), and a magnetic stir bar were added sequentially to a ground glass joint reaction tube, and the mixture was irradiated with a 425 nm LED lamp. The reaction was carried out at 25 °C for 2 h. The reaction progress was monitored by thin-layer chromatography until the reaction was complete. 60 mL of ethyl acetate and 20 mL of water were added for extraction and separation. The organic layers were combined, dried over anhydrous Na₂SO₄, concentrated, and recrystallized to give compound 2d in 75% yield. The reaction equation is as follows: The characterization of compound 1d is as follows: 1 H NMR (400 MHz, CDCl3): δ 8.52 (s, 1 H), 7.87 (d, J = 8.0 Hz, 2 H), 7.75 (s, 1 H), 7.48 (d, J = 8.4 Hz, 2 H), 7.27 (d, J = 7.9 Hz, 2 H), 6.82 (d,J = 8.3 Hz, 2 H), 3.78 (s, 3 H), 2.36 (s, 3 H); 13 C NMR (101 MHz, CDCl3): δ161.36, 148.35, 144.17, 135.25, 129.69, 128.99, 127.93, 125.99, 114.04,55.36, 21.61. The characterization of compound 2d is as follows: 1 H NMR (400 MHz, CDCl3): δ 8.63 (s, 1 H), 7.86-7.73 (m, 2 H), 7.67 (s,1 H), 7.43-7.31 (m, 2 H), 7.16 (d, J = 8.0 Hz, 2 H), 6.76-6.65 (m, 2 H), 3.67(s, 3 H), 2.25 (s, 3 H); 13C NMR (101 MHz, CDCl3): δ 161.21, 148.29, 143.99, 135.16, 129.55, 128.86, 127.79, 125.90, 113.89, 55.22, 21.46. Example 5 Compound 1e (0.5 mmol), disodium eosin Y (2 mol%), N,N-dimethylformamide (5 mL), and a magnetic stir bar were added sequentially to a ground glass joint reaction tube, and the mixture was irradiated with a 425 nm LED lamp. The reaction was carried out at 25 °C for 2 h. The reaction progress was monitored by thin-layer chromatography until the reaction was complete. 60 mL of ethyl acetate and 20 mL of water were added for extraction and separation. The organic layers were combined, dried over anhydrous Na₂SO₄, concentrated, and recrystallized to give compound 2e in 59% yield. The reaction equation is as follows: The characterization of compound 1e is as follows: 1 H NMR (400 MHz, CDCl3): δ 8.10 (s, 1 H), 7.93 (d, J = 8.0 Hz, 2 H), 7.72-7.57 (m, 2 H), 7.36-7.25 (m, 5 H), 2.40 (s, 3 H), 2.16 (s, 3 H); 13 C NMR (101 MHz, CDCl3): δ 152.60, 144.12, 137.21, 135.32, 129.56, 129.51, 128.26,128.08, 126.23, 21.58, 13.43. The characterization of compound 2e is as follows: 1 H NMR (400 MHz, CDCl3): δ 8.34 (s, 1 H), 7.94 (d, J = 7.9 Hz, 2 H), 7.63 (dd, J = 6.7, 3.0 Hz, 2 H), 7.39-7.20 (m, 5 H), 2.39 (s, 3 H), 2.16 (s,3 H); 13 C NMR (101 MHz, CDCl3): δ 152.63, 144.12, 137.21, 135.30, 129.57,129.50, 128.25, 128.06, 126.22, 21.58, 13.45. The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A kind of ( Z A method for preparing p-toluenesulfonylhydrazone derivatives, characterized in that, Includes the following steps: Will( E A mixture of p-toluenesulfonylhydrazone derivatives, a photosensitizer, and a solvent is reacted under light to obtain ( Z )-p-Toluenesulfonylhydrazone derivatives.

2. As described in claim 1 ( Z A method for preparing p-toluenesulfonylhydrazone derivatives, characterized in that, The ( E The structural formula of p-toluenesulfonylhydrazone derivatives is shown in Formula I: Formula I; R1 is selected from one of methyl, methoxy, methylthio, or hydrogen, R2 is nitro or hydrogen, and R3 is methyl or hydrogen.

3. As described in claim 1 ( Z A method for preparing p-toluenesulfonylhydrazone derivatives, characterized in that, The photosensitizer is disodium eosin Y, rhodamine, 4,5,6,7-tetrafluorotetraiodofluorescein, or 4,4-di-tert-butyl.

4. As described in claim 1 ( Z A method for preparing p-toluenesulfonylhydrazone derivatives, characterized in that, The solvent is one or more of N,N-dimethylformamide, acetonitrile, dichloromethane, and dimethyl sulfoxide.

5. As described in claim 1 ( Z A method for preparing p-toluenesulfonylhydrazone derivatives, characterized in that, The wavelength of the illumination is 400~450 nm.

6. As described in claim 1 ( Z A method for preparing p-toluenesulfonylhydrazone derivatives, characterized in that, The reaction temperature is 0~80℃, and the reaction time is 2~10 h.

7. As described in claim 1 ( Z A method for preparing p-toluenesulfonylhydrazone derivatives, characterized in that, The amount of photosensitizer used is ( E 2 mol of p-toluenesulfonylhydrazone derivatives.

8. The claim 1 to 7 ( Z The preparation method of p-toluenesulfonylhydrazone derivatives ( Z )-p-Toluenesulfonylhydrazone derivatives, characterized in that, It has the structure shown in Formula II: Formula II; Formula II; wherein R1 is selected from one of methyl, methoxy, methylthio or hydrogen, R2 is nitro or hydrogen, and R3 is methyl or hydrogen.

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