An N-substituted urea compound of an o-phenylenediamine skeleton and a preparation method thereof

Abstract

The application discloses an N-substituted urea compound with an o-phenylenediamine skeleton and a preparation method thereof, and belongs to the field of organic chemistry. N N-substituted phenyl- N The method uses a carbodiimide derivative and The method has the advantages of mild conditions, simple operation, high yield, environmental friendliness and the like. The obtained compound can be used as an organic synthesis intermediate for constructing a complex heterocyclic structure, has wide biological activity and significant metal coordination capacity, and has important application prospects in the fields of agriculture, medicine and material science.

Description

Technical Field

[0001] This invention relates to organic compounds and their preparation methods, and particularly to an N-substituted urea compound with an o-phenylenediamine skeleton and its preparation method. Background Technology

[0002] Urea derivatives with o-phenylenediamine as their backbone are a class of highly valuable organic intermediates, widely used in pharmaceuticals, pesticides, functional materials, coordination chemistry, and other fields. In the pharmaceutical field, these compounds can serve as the core framework for kinase inhibitors, anti-inflammatory drugs, and antitumor drugs; in coordination chemistry, they can act as bidentate / multidentent ligands for constructing functional materials such as metal-organic frameworks (MOFs) and catalytic ligands.

[0003] at present, N Traditional synthetic methods for substituted urea compounds mainly include: addition reactions of isocyanates with amines, phosgene / triphosgene methods, urea exchange reactions, and chloroformate methods. J. Med. Chem., 2013, 56 , 2110-2124; Bioorg. Med. Chem. , 2017, 25 , 4701-4714; Res. Chem. Intermed. , 2012, 38 , 2479-2489; Synthesis , 2007, 22 (3497-3506). Existing methods for synthesizing urea compounds with o-phenylenediamine as the backbone generally suffer from the following problems: the isocyanate method relies on highly reactive and toxic isocyanate raw materials, resulting in high storage and operational risks; the phosgene method poses serious safety and environmental hazards; the urea exchange method has harsh reaction conditions, produces many byproducts, and is difficult to separate; the chloroformate method has redundant steps, high side reaction risks, and poor atom economy. Especially when the substrate contains multiple functional groups, traditional methods struggle to balance reaction efficiency with functional group compatibility.

[0004] Therefore, it is necessary to develop a mild, easy-to-operate, green, efficient, and widely applicable substrate-based method using o-phenylenediamine as the backbone. N A novel method for synthesizing substituted urea compounds has significant academic value and promising industrial applications. Summary of the Invention

[0005] Objective of the Invention: To overcome the shortcomings of existing technologies, this invention provides N-substituted urea compounds with an o-phenylenediamine skeleton and their preparation method. This method utilizes carbodiimide derivatives and N -Substituted phenyl- N Using hydroxyaryl amides as the starting material and zinc chloride as the catalyst, a highly efficient synthesis of an o-phenylenediamine-containing backbone was achieved. NA novel method for replacing urea compounds, this method offers advantages such as mild conditions, simple operation, high yield, and environmental friendliness. The o-phenylenediamine skeleton refers to the benzene ring having urea groups (-NR) at positions 1 and 2. 3 -C(O)-NHR 3 ) and amide group (-NH-C(O)-R 1 ) replace, form N,N -Disubstituted o-phenylenediamine core structural unit.

[0006] Technical solution: The present invention provides an N-substituted urea compound with the o-phenylenediamine skeleton, the structure of which is shown in general formula (Ⅰ).

[0007] (I) in, R 1 It is selected from phenyl, α-naphthyl, substituted phenyl, thiophene, C1-C4 alkyl, C3-C6 cycloalkyl or arylC1-C6 alkyl, wherein the substituent on the phenyl group is selected from halogen, C1-C4 alkyl or C1-C4 alkoxy; R 2 This indicates one or more substituents on the benzene ring, each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, or C1-C4 acyloxy. R 3 It is selected from C3-C6 cycloalkyl or C1-C4 alkyl.

[0008] The N-substituted urea compound with the o-phenylenediamine skeleton is any one of the following: , , , , , or .

[0009] The compounds of this invention are prepared according to the following reaction formulas: The formula shown in equation (Ⅱ) N -Substituted phenyl- N -hydroxyaryl amides and The carbodiimide derivative shown in formula (III) was reacted in an organic solvent at 20-35 °C under zinc chloride catalysis. After the reaction was completed, the product was extracted, dried, and the solvent was removed by vacuum distillation. Petroleum ether and ethyl acetate were used as eluents, and the product was separated by column chromatography to obtain the o-phenylenediamine skeleton of formula (I). N -Substituted urea compounds;

[0010] (ⅠⅠⅠ) (ⅠⅠ) (Ⅰ) Among them, R 1 Selected from phenyl, α-naphthyl, substituted phenyl, thiophene, C1-C4 alkyl, C3-C6 cycloalkyl, or arylC1-C6 alkyl, wherein the substituent on the phenyl group is selected from halogen, C1-C4 alkyl, or C1-C4 alkoxy; R 2 Represents one or more substituents on the benzene ring, each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, or C1-C4 acyloxy; R 3 Selected from C3-C6 cycloalkyl and C1-C4 alkyl.

[0011] Equation (II) is: R 2 -C6H5-N(OH)-C(O)-R 1 ; Equation (Ⅲ) is: R 3 -N=C=NR 3 ; The o-phenylenediamine skeleton refers to the benzene ring in formula (I) having urea (-NR) at positions 1 and 2 respectively. 3 -C(O)-NHR 3 ) and amide group (-NH-C(O)-R 1 ) replace, form N,N -Disubstituted o-phenylenediamine core structural unit.

[0012] Furthermore, R 1 It is phenyl, α-naphthyl, thiophene, tert-butyl, n-butyl, cyclohexyl, or benzyl; R 2 It has the following functional groups: hydrogen, fluorine, chlorine, bromine, methyl, methoxy, acetoxy; R 3 It is cyclohexyl, isopropyl, or tert-butyl.

[0013] Carbodiimide derivatives and N -Substituted phenyl- N The molar ratio of hydroxyaryl amide to zinc chloride is 1:1~1.5:0.1~0.3, preferably 1:1.2:0.2.

[0014] The reaction solvent is toluene, N,N At least one of dimethylformamide, acetone, chlorobenzene, 1,4-dioxane, tetrahydrofuran, and dimethyl sulfoxide, preferably toluene.

[0015] Compared with the prior art, the present invention has the following beneficial effects: Compared with existing chemical synthesis techniques, this invention provides for the first time a method using carbodiimide derivatives and... N -Substituted phenyl- NUsing hydroxyaryl amides as starting materials and zinc chloride as a catalyst, this method allows for the efficient synthesis of target compounds at room temperature without heating. It is a mild, simple, and environmentally friendly approach; it precisely constructs a dinitrogen functional group framework with o-phenylenediamine as the core, providing active sites for subsequent derivatization; and it has a wide substrate applicability, enabling the synthesis of compounds with different structures based on the o-phenylenediamine framework. N -Substituted urea compounds. Detailed Implementation

[0016] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions of the present invention will be further described below.

[0017] Example 1 N -(2-(1,3-dicyclohexylureido)phenyl)benzamide Under a nitrogen atmosphere, first add to a clean, dry 10 mL Schlenk reaction tube... N -phenyl- N 0.24 mmol of hydroxybenzamide and 0.04 mmol of zinc chloride were dissolved in 1 mL of toluene. Then, a solution of 0.2 mmol of dicyclohexylmethanediimide dissolved in 1 mL of toluene was added to the reaction tube. The reaction mixture was heated to 20–35 °C. o The reaction was continuously stirred at C. The reaction process was monitored in real time by thin-layer chromatography (TLC). After the starting material was completely consumed, the reaction system was quenched by slow dropwise addition of a saturated sodium bicarbonate aqueous solution. The aqueous phase was extracted with dichloromethane (15 mL x 3 times). The combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. Separation was performed by column chromatography (petroleum ether / ethyl acetate, V / V = 10:1–7:1) to give a white solid target compound in 90% yield.

[0018]

[0019] 1 H NMR (400 MHz, CDCl3) δ 8.64 (d, J = 8.0 Hz, 1H), 8.40 (s, 1H), 7.83(d, J = 8.0 2H), 7.58 (d, J = 8.0 Hz, 1H), 7.53 – 7.46 (m, 3H), 7.20 (d, J =4.0 Hz, 2H), 4.50 (t, J = 12.0 Hz, 1H), 3.97 (d, J= 8.0 Hz, 1H). 3.65 – 3.58(m, 1H), 2.03 (s, 1H), 1.77 – 1.65 (m, 5H) 1.57 – 1.47 (m, 4H), 1.37 – 1.22(m, 5H), 1.05 – 0.85 (m, 5H). 13 C NMR (100 MHz, CDCl3) δ 165.0, 155.8, 137.2,134.2, 132.1, 130.8, 129.6, 129.0, 127.2, 126.8, 124.4, 121.2, 55.8, 49.2,32.5, 31.1, 25.8, 25.3, 25.2, 24.7. Taking Example 1 as an example, the reaction mechanism of the present invention is as follows: Under the catalysis of zinc chloride (ZnCl2), the nitrogen atom in the carbodiimide structure of dicyclohexylmethanediimide (1a) coordinates with zinc ions to form activated intermediate I. Subsequently, N -phenyl- N In hydroxybenzamide (2a), the hydroxyl oxygen atom acts as a nucleophile, attacking the central carbon atom of intermediate I, undergoing a nucleophilic addition reaction, and simultaneously losing ZnCl2 to produce... N -Aryl- O -Imine intermediate II. Subsequently, this intermediate undergoes a [3,3]-σ-sigmatropic rearrangement to form rearranged intermediate III. Finally, intermediate III is transformed into the final stable target product (3a) through aromatization. N -(2-(1,3-dicyclohexylureido)phenyl)benzamide. The reaction process is as follows:

[0020] Intermediate I: Carbodiimide-ZnCl2 complex; Intermediate II: N -Aryl- O -Imine intermediate; Intermediate III: [3,3]-σ migration rearrangement product; Final product 3a: aromatized product N -(2-(1,3-dicyclohexylurea)phenyl)benzamide.

[0021] This invention discloses for the first time a zinc chloride-catalyzed... N -phenyl- NThe [3,3]-σ migration rearrangement reaction mechanism between hydroxybenzamide and carbodiimide provides strong support for the novelty and inventiveness of this invention. It should be noted that the above reaction mechanism is a theoretical conjecture proposed by the inventors based on experimental results, and the scope of protection of this invention does not depend on the correctness of this mechanism.

[0022] Example 2 N -(5-acetyl-2-(1,3-dicyclohexylureido)phenyl)benzamide Under a nitrogen atmosphere, first add to a clean, dry 10 mL Schlenk reaction tube... N -(3-acetylphenyl)- N 0.24 mmol of hydroxybenzamide and 0.04 mmol of zinc chloride were dissolved in 1 mL of toluene. Then, a solution of 0.2 mmol of dicyclohexylmethanediimide dissolved in 1 mL of toluene was added to the reaction tube. The reaction mixture was heated to 20–35 °C. o The reaction was continuously stirred at C. The reaction process was monitored in real time by thin-layer chromatography (TLC). After the starting material was completely consumed, the reaction system was quenched by slow dropwise addition of a saturated sodium bicarbonate aqueous solution. The aqueous phase was extracted with dichloromethane (15 mL x 3 times). The combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. Separation was performed by column chromatography (petroleum ether / ethyl acetate, V / V = 10:1–7:1) to give a white solid target compound in 74% yield.

[0023]

[0024] 1 H NMR (400 MHz, CDCl3) δ 8.79 (d, J = 8.0 Hz, 1H), 8.63 (s, 1H), 8.03(d, J = 8.0 Hz, 1H), 7.84 (d, J = 8.0 Hz, 3H), 7.61 (t, J = 8.0 Hz, 1H), 7.54(t, J = 8.0 Hz, 2H), 4.51 (t, J = 12.0 Hz, 1H), 4.03 (d, J = 8.0 Hz, 1H),3.70-3.53 (m, 1H), 2.62 (s, 3H), 2.12 (d, J= 24 Hz, 1H), 1.77 -0.91 (m,14H), 1.04 -0.91 (m, 5H). 13 C NMR (100 MHz, CDCl3) δ 197.2, 165.1, 155.2,137.7, 137.5, 133.7, 132.4, 131.6, 131.0, 129.0, 126.8, 123.6, 121.5, 56.26,49.4, 33.3, 29.4, 26.7, 25.7, 25.2, 25.0, 24.7. Example 3 N -(2-(1,3-dicyclohexylureido)-4-methylphenyl)benzamide Under a nitrogen atmosphere, first add to a clean, dry 10 mL Schlenk reaction tube... N -(p-Tolyl)- N 0.24 mmol of hydroxybenzamide and 0.04 mmol of zinc chloride were dissolved in 1 mL of toluene. Then, a solution of 0.2 mmol of dicyclohexylmethanediimide dissolved in 1 mL of toluene was added to the reaction tube. The reaction mixture was heated to 20–35 °C. o The reaction was continuously stirred at C. The reaction process was monitored in real time by thin-layer chromatography (TLC). After the starting material was completely consumed, the reaction system was quenched by slow dropwise addition of a saturated sodium bicarbonate aqueous solution. The aqueous phase was extracted with dichloromethane (15 mL x 3 times). The combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. Separation was performed by column chromatography (petroleum ether / ethyl acetate, V / V = 10:1–7:1) to give a white solid target compound in 78% yield.

[0025]

[0026] 1 H NMR (400 MHz, CDCl3) δ 8.48 (d, J = 8.0 Hz, 1H), 8.28 (s, 1H), 7.82(d, J = 4.0 Hz, 2H), 7.58 – 7.48 (m, 3H), 7.27 (d, J = 12.0 Hz, 2H), 6.98 (s,1H), 4.47 (t, J = 12.0 Hz, 1H), 4.00 (d, J= 8.0 Hz, 1H), 3.66 – 3.57 (m,1H), 2.38 (s, 3H), 2.04 – 1.93 (m, 1H), 1.57 – 1.47 (m, 9H), 1.37 – 1.22 (m,6H), 1.06 – 0.86 (m, 5H). 13 C NMR (100 MHz, CDCl3) δ 164.9, 155.9, 134.5,134.3, 132.0, 131.0, 130.2, 128.9, 127.3, 126.8, 121.2, 55.7, 49.2, 33.5,32.5, 25.8, 25.3, 25.1, 24.7, 20.8. Example 4 N -(2-(1,3-dicyclohexylureido)phenyl)-2-naphthylcarboxamide Under a nitrogen atmosphere, first add to a clean, dry 10 mL Schlenk reaction tube... N -phenyl- N Hydroxy-2-naphthylcarboxamide (0.24 mmol), zinc chloride (0.04 mmol), and 1 mL of toluene were added to dissolve them. Then, a solution of dicyclohexylmethanediimide (0.2 mmol) dissolved in 1 mL of toluene was added to the reaction tube. The reaction mixture was heated to 20-35°C. o The reaction was continuously stirred at C. The reaction process was monitored in real time by thin-layer chromatography (TLC). After the starting material was completely consumed, the reaction system was quenched by slow dropwise addition of a saturated sodium bicarbonate aqueous solution. The aqueous phase was extracted with dichloromethane (15 mL x 3 times). The combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. Separation was performed by column chromatography (petroleum ether / ethyl acetate, V / V = 10:1–7:1) to give a white solid target compound in 84% yield.

[0027]

[0028] 1 H NMR (400 MHz, CDCl3) δ 8.69 (d, J = 12.0 Hz, 1H), 8.57 (s, 1H), 8.38 (s, 1H), 7.97 (d, J = 12.0 Hz, 2H), 7.88 (q, J= 8.0 Hz, 2H), 7.62 -7.55 (m, 2H), 7.51 -7.46 (m, 1H), 7.22 - 7.18 (m, 2H), 4.51 (t, J = 12.0 Hz, 1H), 4.05 (d, J = 8.0 Hz, 1H), 3.69 – 3.62 (m, 1H), 2.06 (s, 1H), 1.78 – 1.63(m, 5H), 1.56 – 1.47 (m, 4H), 1.40 – 1.23 (m, 5H), 1.06 – 0.89 (m, 5H). 13 CNMR (100 MHz, CDCl3) δ 165.1, 155.8, 137.3, 134.8, 132.5, 131.4, 130.8,129.6, 129.1, 128.9, 128.0, 127.9, 127.7, 127.4, 126.9, 124.4, 122.9, 121.2,55.8, 49.2, 33.6, 32.5, 25.7, 25.2, 25.1, 24.7. Example 5 N -(2-(1,3-dicyclohexylureo)phenyl)thiophene-2-carboxamide Under a nitrogen atmosphere, first add to a clean, dry 10 mL Schlenk reaction tube... N -phenyl- N 2-hydroxythiophene-2-carboxamide (0.24 mmol) and zinc chloride (0.04 mmol) were dissolved in 1 mL of toluene. Then, a solution of dicyclohexylmethanediimide (0.2 mmol) dissolved in 1 mL of toluene was added to the reaction tube. The reaction mixture was kept at 20–35 °C. o The reaction was continuously stirred at C. The reaction process was monitored in real time by thin-layer chromatography (TLC). After the starting material was completely consumed, the reaction system was quenched by slow dropwise addition of a saturated sodium bicarbonate aqueous solution. The aqueous phase was extracted with dichloromethane (15 mL x 3 times). The combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. Separation was performed by column chromatography (petroleum ether / ethyl acetate, V / V = 10:1–7:1) to give a white solid target compound in 82% yield.

[0029]

[0030] 1 H NMR (400 MHz, CDCl3) δ 8.56 (d,J = 8.0 Hz, 1H), 8.24 (s, 1H), 7.56(q, J = 4.0 Hz, 2H), 7.46 - 7.42 (m, 1H), 7.19 (d, J = 4.0 Hz, 2H), 7.14 (t, J = 4.0 Hz, 1H), 4.55 – 4.47 (m, 1H), 3.97 (d, J = 8.0 Hz, 1H), 3.66 – 3.57(m, 1H), 2.09 – 1.73 (m, 6H), 1.58 – 1.47 (m, 4H), 1.42 – 1.26 (m, 5H), 1.02– 0.86 (m, 5H). 13 C NMR (100 MHz, CDCl3) δ 159.4, 155.7, 138.8, 136.9, 131.2,130.8, 129.6, 128.5, 128.0, 126.9, 124.3, 120.9, 55.7, 49.1, 33.4, 32.4,31.2, 25.7, 25.0, 24.6. Example 6 N -(2-(1,3-diisopropylurea)phenyl)benzamide Under a nitrogen atmosphere, first add to a clean, dry 10 mL Schlenk reaction tube... N -phenyl- N 0.24 mmol of hydroxybenzamide and 0.04 mmol of zinc chloride were dissolved in 1 mL of toluene. Then, a solution of 0.2 mmol of diisopropylmethanediimide dissolved in 1 mL of toluene was added to the reaction tube. The reaction mixture was heated to 20–35 °C. o The reaction was continuously stirred at C. The reaction process was monitored in real time by thin-layer chromatography (TLC). After the starting material was completely consumed, the reaction system was quenched by slow dropwise addition of a saturated sodium bicarbonate aqueous solution. The aqueous phase was extracted with dichloromethane (15 mL x 3 times). The combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. Separation was performed by column chromatography (petroleum ether / ethyl acetate, V / V = 10:1–7:1) to give a white solid target compound in 89% yield.

[0031]

[0032] 1H NMR (400 MHz, CDCl3) δ 8.64 (d, J = 8.0 Hz, 1H), 8.36 (s, 1H), 7.83(d, J = 8.0 Hz, 2H), 7.57 (t, J = 8.0 Hz, 1H), 7.52 -7.45 (m, 3H), 7.21 (d, J = 4.0 Hz, 2H), 4.93 - 4.86 (m, 1H), 4.00 - 3.93 (m, 2H), 1.26 (s, 3H), 0.98 (s, 9H). 13 C NMR (100 MHz, CDCl3) δ165.0, 155.9, 137.2, 134.1, 132.1, 130.5,129.7, 128.9, 126.9, 126.8, 124.5, 121.3, 47.7, 42.4, 23.6, 22.1. Example 7 N -(2-(1,3-di-tert-butylurea)phenyl)benzamide Under a nitrogen atmosphere, first add to a clean, dry 10 mL Schlenk reaction tube... N -phenyl- N 0.24 mmol of hydroxybenzamide and 0.04 mmol of zinc chloride were dissolved in 1 mL of toluene. Then, a solution of 0.2 mmol of di-tert-butylmethanediimide dissolved in 1 mL of toluene was added to the reaction tube. The reaction mixture was heated to 20–35 °C. o The reaction was continuously stirred at C. The reaction process was monitored in real time by thin-layer chromatography (TLC). After the starting material was completely consumed, the reaction system was quenched by slow dropwise addition of a saturated sodium bicarbonate aqueous solution. The aqueous phase was extracted with dichloromethane (15 mL x 3 times). The combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. Separation was performed by column chromatography (petroleum ether / ethyl acetate, V / V = 10:1–7:1) to give a white solid target compound in 90% yield.

[0033]

[0034] 1 H NMR (400 MHz, CDCl3) δ 8.68 (d, J = 8.0 Hz, 1H), 8.63 (s, 1H), 7.90(d, J= 8.0 Hz, 2H), 7.57 -7.49 (m, 3H), 7.43 (t, J = 8.0 Hz, 1H), 7.21 –7.14 (m, 2H), 3.93 (s, 1H), 1.43 (s, 9H), 1.17 (s, 9H). 13 C NMR (100 MHz, CDCl3) δ 164.9, 156.1, 137.1, 134.2, 132.2, 130.5 129.8, 129.5, 128.6, 126.8,124.2, 120.5, 57.8, 50.7, 29.9, 29.2. The above are merely preferred embodiments of the present invention and do not constitute any limitation on the present invention. Any equivalent substitutions or modifications made by those skilled in the art to the technical solutions and content disclosed in the present invention without departing from the scope of the present invention shall be deemed to have remained within the protection scope of the present invention.

Claims

1. An N-substituted urea compound with an o-phenylenediamine skeleton, the structure of which is shown in general formula (Ⅰ). ； （Ⅰ） in, R 1 It is selected from phenyl, α-naphthyl, substituted phenyl, thiophene, C1-C4 alkyl, C3-C6 cycloalkyl or arylC1-C6 alkyl, wherein the substituent on the phenyl group is selected from halogen, C1-C4 alkyl or C1-C4 alkoxy; R 2 This indicates one or more substituents on the benzene ring, each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, or C1-C4 acyloxy. R 3 It is selected from C3-C6 cycloalkyl or C1-C4 alkyl.

2. The N-substituted urea compound with an o-phenylenediamine skeleton according to claim 1, wherein the N-substituted urea compound is any one of the following: 、 、 、 , , or .

3. The o-phenylenediamine skeleton according to claim 1 or 2 N A method for preparing substituted urea compounds, characterized in that, Includes the following steps: Under inert gas protection, the formula (II) shown N -Substituted phenyl- N -hydroxyaryl amides and The carbodiimide derivative shown in formula (III) was reacted in an organic solvent at 20-35 °C under zinc chloride catalysis. After the reaction was completed, the product was extracted, dried, and the solvent was removed by vacuum distillation. Petroleum ether and ethyl acetate were used as eluents, and the product was separated by column chromatography to obtain the o-phenylenediamine skeleton of formula (I). N -Substituted urea compounds; ； （ⅠⅠⅠ） （ⅠⅠ） （Ⅰ） The structure of equation (Ⅰ) is as follows: ； （Ⅰ） Where R 1 Selected from phenyl, α-naphthyl, substituted phenyl, thiophene, C1-C4 alkyl, C3-C6 cycloalkyl, or arylC1-C6 alkyl, wherein the substituent on the phenyl group is selected from halogen, C1-C4 alkyl, or C1-C4 alkoxy; R 2 Represents one or more substituents on the benzene ring, each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, or C1-C4 acyloxy; R 3 Selected from C3-C6 cycloalkyl and C1-C4 alkyl groups. Equation (II) is: R 2 -C6H5-N(OH)-C(O)-R 1 ; Equation (Ⅲ) is: R 3 -N=C=NR 3 ; The o-phenylenediamine skeleton refers to the benzene ring in formula (I) having urea (-NR) at positions 1 and 2 respectively. 3 -C(O)-NHR 3 ) and amide group (-NH-C(O)-R 1 ) replace, form N,N -Disubstituted o-phenylenediamine core structural unit.

4. The method according to claim 3, characterized in that, R 1 It is phenyl, α-naphthyl, thiophene, tert-butyl, n-butyl, cyclohexyl, or benzyl; R 2 It has the following functional groups: hydrogen, fluorine, chlorine, bromine, methyl, methoxy, acetoxy; R 3 It is cyclohexyl, isopropyl, or tert-butyl.

5. The method according to claim 3, characterized in that, The reaction solvent is toluene. N,N - At least one of dimethylformamide, acetone, chlorobenzene, 1,4-dioxane, tetrahydrofuran, and dimethyl sulfoxide.

6. The method according to claim 5, characterized in that, The reaction solvent is toluene.

7. The method according to claim 3, characterized in that, The carbodiimide derivative and N -Substituted phenyl- N The molar ratio of hydroxyaryl amide to zinc chloride is 1:1~1.5:0.1~0.3.

Images