Preparation method of adiponitrile derivative with complex skeleton

Abstract

The invention discloses a preparation method of an adiponitrile derivative with a complex skeleton, which comprises the following steps: taking cheap and easily available terminal olefin, a safe and nontoxic cyano source azobisisobutyronitrile and a derivative thereof as initial raw materials, and carrying out cross-coupling reaction without a transition metal catalyst; an adiponitrile derivative with a complex skeleton and a plurality of all-carbon quaternary carbon centers is constructed in one step; the method is mild in condition, the reaction process is easy and convenient to operate, the substrate adaptability is wide, and the prepared adiponitrile derivative with the complex framework has the value as a functional material precursor.

Description

Technical Field

[0001] This invention relates to a method for preparing adiponitrile derivatives with complex skeletons, belonging to the field of pharmaceutical intermediates and organic synthesis technology. Background Technology

[0002] Adiponitrile, also known as 1,4-dicyanobutane, is an important organic chemical platform molecule and a key synthetic intermediate. Due to its unique dicyano structure, adiponitrile has wide applications in the textile industry, engineering materials, pharmaceuticals, food, and mineral flotation. However, industrial preparation methods for adiponitrile either involve environmental safety concerns or significant energy consumption. With the growing consensus in my country regarding environmental protection and energy security, research into green and simple processes is of great importance for the synthesis of adiponitrile.

[0003] Currently, the main industrial strategy for preparing the adiponitrile skeleton is the hydrocyanation reaction of butadiene, such as... Figure 1 As shown in (Seidel, WC, et al. Ann. NYAcad. Sci., 1983, 415, 201; Long, J., et al. Angew. Chem. Int. Ed., 2025, e202422337.). This strategy constructs the adiponitrile skeleton through the addition reaction of butadiene and hydrogen cyanide, but it involves the handling of highly toxic hydrogen cyanide, posing serious safety hazards and requiring stringent procedures. Meanwhile, laboratory strategies for preparing the adiponitrile skeleton include: acrylonitrile dimerization (Wang, Y., et al. ACS Appl. Mater. Interfaces, 2022, 14, 35534; Su, J., et al. Green Chem., 2024, 26, 8220; Xu, L., et al. Ind. Eng. Chem. Res., 2024, 63, 16009.), and other strategies such as cyclohexanone ring-opening and adipic acid amination. Figure 1 As shown in (Qiu, X., et al. Nature, 2021, 597, 64; Zhao, Z., et al. J. Am. Chem. Soc., 2025, 147, 1155.; Xu, X., et al. Catal. Sci. Technol., 2022, 12, 3947; Du, L., et al. Chem. Eng. Sci., 2024, 290, 119851.). Although strategies for preparing adiponitrile skeletons in the laboratory have provided a series of new methods, they can only construct simple adiponitrile skeletons without other substituents.

[0004] The cyano group, due to its unique structure, can participate in many types of reactions. Figure 1By derivatizing the cyano group, high-value-added downstream products can be easily constructed. For example, hexamethylenediamine and adipic acid can be prepared through reduction and hydrolysis reactions, respectively (Lv, Y., et al. J. Catal., 2019, 372, 330; Mukherjee, C. et al. Eur. J. Org. Chem., 2006, 5238.). The resulting products can be further converted into nylon-like products and used as high-performance materials in industrial production and machinery manufacturing. Simultaneously, azircycloheptane can also be prepared through cyclization reactions (Lv, Y., et al. Chemistry Select, 2018, 3, 3268.). In addition, adiponitrile is also used in textiles, chemical analysis, materials modification (Gong, B., et al. Ind. Eng. Chem. Res., 2023, 62, 1338.) and new energy vehicles (Cong, W., et al. Chem. Eng. Process., 2025, 213, 110325.).

[0005] Full-carbon and quaternary carbon centers are widely found in natural products and pharmaceutical active molecules, and are among the most common structural building blocks in complex compound molecules. The construction of full-carbon and quaternary carbon centers is an essential step in the synthesis of complex organic molecules. Introducing full-carbon and quaternary carbon centers into the adiponitrile skeleton can make its structure more diverse, thereby achieving structural complexity and property diversification of the adiponitrile skeleton.

[0006] In summary, significant progress has been made in the construction strategies of adiponitrile structural frameworks. However, traditional construction strategies face challenges that urgently need to be overcome: 1. They involve the use of highly toxic hydrogen cyanide; 2. They can only construct adiponitriles with simple structures, while constructing adiponitriles with complex frameworks is quite difficult. Therefore, a safe method needs to be developed to easily construct structurally complex adiponitrile derivatives without the use of highly toxic cyanide sources. Thus, we designed a method to construct adiponitrile derivatives with complex frameworks and multiple all-carbon and quaternary carbon centers in one step, starting from simple, readily available, safe, and stable starting materials. Summary of the Invention

[0007] To address the problems in existing methods for synthesizing complex adiponitrile derivatives, this invention provides a method for synthesizing adiponitrile derivatives with complex skeletons. This invention uses terminal olefins, azobisisobutyronitrile and their derivatives as raw materials, and achieves the dual-carbon functionalization of olefins under mild conditions without the need for transition metal catalysts, thereby synthesizing adiponitrile derivatives.

[0008] The structural formulas of adiponitrile derivatives with complex skeletons are as follows:

[0009]

[0010] Among them, R 1It is one of 2-biphenyl, 4-biphenyl, 4-tolyl, 4-chlorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-bromophenyl, 4-cyanophenyl, 4-nitrophenyl, 4-methoxyphenyl, phenyl, benzyl, phenethyl, and 2-naphthyl; R 2 It is one of methyl, ethyl, or isopropyl; R 3 It is one of hydrogen, methyl, or ethoxycarbonyl.

[0011] The complex adiponitrile derivative of this invention is prepared by adding terminal olefins, azobisisobutyronitrile and their derivatives into a reactor, reacting at 75-85°C for 12 hours under argon atmosphere and in the presence of solvent, removing the solvent by vacuum distillation, and then purifying by column chromatography. The molar ratio of terminal olefins to azobisisobutyronitrile and their derivatives is 1:2-3.

[0012] The terminal olefin has one of the following structural formulas:

[0013]

[0014] Among them, R 1 R is any position on the benzene ring. 1 It is one of phenyl, methyl, fluorine, chlorine, bromine, cyano, nitro, methoxy, and 2-naphthyl; R 2 It is one of hydrogen, methyl, or ethoxycarbonyl; R 3 It is one of phenyl or benzyl.

[0015] The structural formulas of the azobisisobutyronitrile and its derivatives are as follows:

[0016]

[0017] R is one of methyl, ethyl, or isopropyl.

[0018] The adiponitrile derivatives of this invention, with their complex skeletons, contain multi-substituted adiponitrile structures and two or three all-carbon quaternary carbon centers, and can be used as precursors for functional materials.

[0019] The beneficial effects of this invention are as follows:

[0020] This invention uses inexpensive and readily available terminal olefins, safe and non-toxic "cyano source" azobisisobutyronitrile and its derivatives as starting materials. Cross-coupling reactions can occur without transition metal catalysts to construct adiponitrile derivatives with complex skeletons and multiple all-carbon and quaternary carbon centers in one step. The method of this invention is mild, the reaction process is simple to operate, and it has a wide substrate adaptability. The prepared adiponitrile derivatives with complex skeletons have value as precursors for functional materials. Attached Figure Description

[0021] Figure 1 This is a schematic diagram illustrating the traditional synthesis methods and applications of adiponitrile. Detailed Implementation

[0022] The present invention will be further described in detail below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the content described herein. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased.

[0023] Example 1: The structural formula of the complex adiponitrile derivative 3-([1,1'-biphenyl]-4-yl)-2,2,3,5,5-pentamethyladiponitrile 3aa in this example is as follows:

[0024]

[0025] The synthetic method of 3-([1,1'-biphenyl]-4-yl)-2,2,3,5,5-pentamethylhexadionitrile 3aa is as follows:

[0026]

[0027] According to the molar ratio of 4-(1-propen-2-yl)biphenyl (1a), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 4-(1-propen-2-yl)biphenyl and 0.5 mmol of azobisisobutyronitrile were added to the reactor sequentially, and 0.76 mmol of ethylene glycol dimethyl ether was added to the reactor under argon atmosphere. After reacting at 80°C for 12 h, the solvent was removed by vacuum distillation at 45°C to obtain the crude product. The crude product was subjected to column chromatography (300 mesh silica gel) to obtain 49 mg of a complex adiponitrile derivative (3-([1,1'-biphenyl]-4-yl)-2,2,3,5,5-pentamethyladiponitrile 3aa), wherein the eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0028] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.63-7.60(m,4H),7.55-7.53(m,2H),7.46-7.43(m,2H),7.37-7.34(m,1H),2. 62-2.59(m,1H),2.33-2.30(m,1H),1.77(s,3H),1.49(s,3H),1.36(s,3H),1.10(s,3H),0.87(s,3H); 13C NMR (126MHz, CDCl3) δ140.36,140.22,140.15,128.95,128.13,127.66,127.03,126. 85,125.69,124.82,45.50,44.89,42.14,31.92,30.86,26.85,23.91,23.05,19.34.

[0029] In this example, the yield of 3-([1,1'-biphenyl]-4-yl)-2,2,3,5,5-pentamethylhexadionitrile 3aa was 74%.

[0030] Meanwhile, a gram-scale scale-up experiment was conducted on Example 1. 6.0 mmol of 4-(1-propen-2-yl)biphenyl and 15 mmol of azobisisobutyronitrile were added sequentially to the reactor, followed by the addition of 22.8 mmol of ethylene glycol dimethyl ether under argon atmosphere. The reaction was carried out at 80°C for 12 h. The solvent was removed by vacuum distillation at 45°C to obtain the crude product. The crude product was subjected to column chromatography (300-mesh silica gel) to obtain 1.41 g of a complex-structured adiponitrile derivative (3-([1,1'-biphenyl]-4-yl)-2,2,3,5,5-pentamethyladiponitrile 3aa). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40. The gram-scale scale-up experiment showed a yield of 71% for 3aa.

[0031] Example 2: The structural formula of the complex adiponitrile derivative 3-([1,1'-biphenyl]-4-yl)-2,5-diethyl-2,3,5-trimethyladiponitrile 3ab in this example is as follows:

[0032]

[0033] The synthesis method of 3-([1,1'-biphenyl]-4-yl)-2,5-diethyl-2,3,5-trimethyladiponitrile 3ab is as follows:

[0034]

[0035] According to the molar ratio of 4-(1-propen-2-yl)biphenyl (1a), azobisisovalerate (2b), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 4-(1-propen-2-yl)biphenyl, 0.5 mmol of azobisisovalerate, and 0.76 mmol of ethylene glycol dimethyl ether were added to the reactor in the presence of argon gas. The reaction was carried out at 80 °C for 12 h. The solvent was removed by vacuum distillation at 45 °C to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 47 mg of a complex adiponitrile derivative (3-([1,1'-biphenyl]-4-yl)-2,5-diethyl-2,3,5-trimethyladiponitrile 3ab), wherein the eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0036] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (600MHz, CDCl3) δ7.63-7.59(m,4H),7.55(m,2H),7.46-7.44(m,2H),7.37-7.34(m,1H),2.59-2.53(m,1H),2.40-2.35(m,1H) ,1.77-1.75(m,3H),1.64-1.60(m,2H),1.34(s,2H),1.26-1.25(m,3H),1.13-1.09(m,3H),1.01-0.94(m,3H),0.75-0.74(m,3H); 13 C NMR (126MHz, CDCl3) δ141.23,140.05,128.89,128.84,128.18,128.03,127.58,127.52,126 .96,126.93,126.79,126.71,47.62,45.33,37.13,35.63,27.74,26.95,23.48,9.52,9.02.

[0037] In this example, the yield of 3-([1,1'-biphenyl]-4-yl)-2,5-diethyl-2,3,5-trimethylhexadionitrile 3ab was 65%.

[0038] Example 3: The structural formula of the complex adiponitrile derivative 3-([1,1'-biphenyl]-4-yl)-2,5-diisobutyl-2,3,5-trimethyladiponitrile 3ac in this example is as follows:

[0039]

[0040] The synthetic method of 3-([1,1'-biphenyl]-4-yl)-2,5-diisobutyl-2,3,5-trimethyladiponitrile 3ac is as follows:

[0041]

[0042] According to the molar ratio of 4-(1-propen-2-yl)biphenyl (1a), azobisisopentanone (2c), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 4-(1-propen-2-yl)biphenyl and 0.5 mmol of azobisisopentanone were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80°C for 12 h. The solvent was removed by vacuum distillation at 45°C to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 49 mg of a complex adiponitrile derivative (3-([1,1'-biphenyl]-4-yl)-2,5-diisobutyl-2,3,5-trimethyladiponitrile 3ac), wherein the eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0043] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (600MHz, CDCl3) δ7.65-7.59(m,6H),7.46-7.44(m,2H),7.37-7.34(m,1H),2.57-2.53(m,1H),2.40-2.37(m,1H),1.75-1.74(m,3H),1.66-1 .62(m,3H),1.51-1.48(m,1H),1.40(s,1H),1.12-1.11(m,2H),1.07-1. 03(m,9H),0.97(d,J=6.7Hz,2H),0.89-0.85(m,3H),0.77-0.76(m,3H); 13 C NMR (126MHz, CDCl3) δ140.17,139.96,139.81,128.82,128.77,128.28,128.07,127.51,126.91,126.84,126.57, 60.28,52.69,45.97,45.89,45.72,45.33,34.34,34.02,26.06,25.99,25.46,25.00,24.67,24.48,24.24,23.99.

[0044] In this example, the yield of 3-([1,1'-biphenyl]-4-yl)-2,5-diisobutyl-2,3,5-trimethyladiponitrile 3ac was 60%.

[0045] Example 4: The structural formula of the complex adiponitrile derivative 2-([1,1'-biphenyl]-4-yl)-4-cyano-2-(2-cyanopropane-2-yl)-4-methylpentanoate ethyl ester 3ba in this example is as follows:

[0046]

[0047] The synthetic method of ethyl 2-([1,1'-biphenyl]-4-yl)-4-cyano-2-(2-cyanopropane-2-yl)-4-methylpentanoate 3ba is as follows:

[0048]

[0049] According to the molar ratio of ethyl 2-([1,1'-biphenyl]-4-yl)acrylate (1b), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of ethyl 2-([1,1'-biphenyl]-4-yl)acrylate, 0.5 mmol of azobisisobutyronitrile, and 0.76 mmol of ethylene glycol dimethyl ether were added to the reactor in the presence of argon gas. The reaction was carried out at 80°C for 12 h. The solvent was removed by vacuum distillation at 45°C to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 48 mg of a complex-structure adiponitrile derivative (ethyl 2-([1,1'-biphenyl]-4-yl)-4-cyano-2-(2-cyanopropane-2-yl)-4-methylpentanoate 3ba), wherein the eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0050] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.84-7.82(m,1H),7.58-7.54(m,5H),7.47-7.44(m,2H),7.40-7.36(m,1H),4.59-4.56( m,1H),4.28-4.16(m,2H),2.70-2.65(m,1H),1.99(s,3H),1.94(s,3H),1.56(s,3H),1.46(s,3H),1.27(s,3H); 13 C NMR (126MHz, CDCl3) δ173.68,142.15,141.33,139.33,137.26,131.80,130.09,128.96,128.33,128 .24,125.99,125.50,125.35,62.77,45.72,44.50,36.07,32.66,30.74,30.31,29.80,27.60,15.00.

[0051] In this example, the yield of ethyl 2-([1,1'-biphenyl]-4-yl)-4-cyano-2-(2-cyanopropane-2-yl)-4-methylpentanoate 3ba was 63%.

[0052] Example 5: The structural formula of the complex adiponitrile derivative 2,2,3,5,5-pentamethyl-3-(p-tolyl)adiponitrile 3ca in this example is as follows:

[0053]

[0054] The synthetic method of 2,2,3,5,5-pentamethyl-3-(p-tolyl)adiponitrile 3ca is as follows:

[0055]

[0056] According to the molar ratio of 1-methyl-4-(1-methylvinyl)benzene (1c), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 1-methyl-4-(1-methylvinyl)benzene, 0.5 mmol of azobisisobutyronitrile, and 0.76 mmol of ethylene glycol dimethyl ether were added to the reactor sequentially under argon atmosphere. The reaction was carried out at 80°C for 12 h. The solvent was removed by vacuum distillation at 45°C to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 48 mg of a complex-structured adiponitrile derivative (2,2,3,5,5-pentamethyl-3-(p-tolyl)adiponitrile 3ca). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0057] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.34-7.32(m,2H),7.16-7.16(m,2H),2.56-2.54(m,1H),2.33(s,3 H),2.26-2.23(m,1H),1.71(s,3H),1.46(s,3H),1.31(s,3H),1.05(s,3H),0.85(s,3H); 13 C NMR (126MHz, CDCl3) δ137.97,137.09,128.93,127.41,45.28,44.53,41.97,31.77,30.65,26.74,23.72,22.86,20.83,19.25.

[0058] In this example, the yield of 2,2,3,5,5-pentamethyl-3-(p-tolyl)adiponitrile 3ca was 53%.

[0059] Example 6: The structural formula of the complex adiponitrile derivative 3-(4-chlorophenyl)-2,2,3,5,5-pentamethyladiponitrile 3da in this example is as follows:

[0060]

[0061] The synthesis method of 3-(4-chlorophenyl)-2,2,3,5,5-pentamethylhexadionitrile 3da is as follows:

[0062]

[0063] According to the molar ratio of 1-chloro-4-(1-methylvinyl)benzene (1d), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 1-methyl-4-(1-chlorovinyl)benzene, 0.5 mmol of azobisisobutyronitrile, and 0.76 mmol of ethylene glycol dimethyl ether were added to the reactor sequentially under argon atmosphere. The reaction was carried out at 80°C for 12 h. The solvent was removed by vacuum distillation at 45°C to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 33 mg of a complex-structured adiponitrile derivative (3-(4-chlorophenyl)-2,2,3,5,5-pentamethyladiponitrile 3da). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0064] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.45-7.43(m,2H),7.38-7.36(m,2H),2.56-2.53(m,1H),2. 30-2.27(m,1H),1.74(s,3H),1.58(s,3H),1.36(s,3H),1.06(s,3H),0.89(s,3H); 13 C NMR (126MHz, CDCl3) δ139.88,133.62,128.93,128.47,125.27,124.38,45.28,44.66,41.85,31.68,30.57,26.98,23.67,22.79,19.13.

[0065] In this example, the yield of 3-(4-chlorophenyl)-2,2,3,5,5-pentamethylhexadionitrile 3da was 57%.

[0066] Example 7: The structural formula of the complex adiponitrile derivative 3-(4-benzonitrile)-2,2,3,5,5-pentamethyladiponitrile 3ea in this example is as follows:

[0067]

[0068] The synthesis method of 3-(4-benzonitrile)-2,2,3,5,5-pentamethyladiponitrile 3ea is as follows:

[0069]

[0070] According to the molar ratio of 1-cyano-4-(1-methylvinyl)benzene (1e), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 1-cyano-4-(1-methylvinyl)benzene, 0.5 mmol of azobisisobutyronitrile, and 0.76 mmol of ethylene glycol dimethyl ether were added to the reactor sequentially under argon atmosphere. The reaction was carried out at 80°C for 12 h. The solvent was removed by vacuum distillation at 45°C to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 24 mg of a complex-structured adiponitrile derivative (3-(4-benzonitrile)-2,2,3,5,5-pentamethyladiponitrile 3ea). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0071] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.70-7.68(m,2H),7.65-7.64(m,2H),2.60-2.57(m,1H),2.3 0-2.27(m,1H),1.75(s,3H),1.49(s,3H),1.37(s,3H),1.042(s,3H),0.89(s,3H); 13 C NMR (126MHz, CDCl3) δ147.08,132.10,128.52,124.95,124.03,118.33,111. 82,111.80,45.46,45.25,41.83,31.58,30.52,27.50,23.72,22.85,19.09.

[0072] In this example, the yield of 3-(4-benzonitrile)-2,2,3,5,5-pentamethylhexadionitrile 3ea was 42%.

[0073] Example 8: The structural formula of the complex adiponitrile derivative 3-(4-nitrophenyl)-2,2,3,5,5-pentamethyladiponitrile 3fa in this example is as follows:

[0074]

[0075] The synthesis method of 3-(4-nitrophenyl)-2,2,3,5,5-pentamethylhexadionitrile 3fa is as follows:

[0076]

[0077] According to the molar ratio of 1-nitro-4-(1-methylvinyl)benzene (1f), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 1-nitro-4-(1-methylvinyl)benzene, 0.5 mmol of azobisisobutyronitrile, and 0.76 mmol of ethylene glycol dimethyl ether were added to the reactor sequentially under argon atmosphere. The reaction was carried out at 80°C for 12 h. The solvent was removed by vacuum distillation at 45°C to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 30 mg of a complex-structure adiponitrile derivative (3-(4-nitrophenyl)-2,2,3,5,5-pentamethyladiponitrile 3fa), wherein the eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0078] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ8.25-8.23(m,2H),7.71-7.69(m,2H),2.63-2.60(m,1H),2. 32-2.29(m,1H),1.78(s,3H),1.50(s,3H),1.39(s,3H),1.05(s,3H),0.90(s,3H); 13 C NMR (126MHz, CDCl3) δ149.05,147.22,128.59,124.78,123.85,123.36,45.47,41.76,31.51,30.44,27.53,23.67,22.78,19.16.

[0079] In this example, the yield of 3-(4-nitrophenyl)-2,2,3,5,5-pentamethylhexadionitrile 3fa was 50%.

[0080] Example 9: The structural formula of the complex adiponitrile derivative 3-(4-methoxyphenyl)-2,2,3,5,5-pentamethyladiponitrile 3ga in this example is as follows:

[0081]

[0082] The synthesis method of 3-(4-methoxyphenyl)-2,2,3,5,5-pentamethylhexadionitrile 3ga is as follows:

[0083]

[0084] According to the molar ratio of 1-methoxy-4-(1-methylvinyl)benzene (1g), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 1-methoxy-4-(1-methylvinyl)benzene and 0.5 mmol of azobisisobutyronitrile were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80℃ for 12 h. The solvent was removed by vacuum distillation at 45℃ to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 35 mg of a complex-structured adiponitrile derivative (3-(4-methoxyphenyl)-2,2,3,5,5-pentamethyladiponitrile 3ga), wherein the eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0085] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.25-7.24(m,2H),6.89-6.87(m,2H),3.81(s,3H),2.75-2. 72(m,2H),2.22-2.14(m,3H),1.45(s,3H),1.36(s,3H),1.11(s,3H),1.00(s,3H); 13 C NMR (126MHz, CDCl3) δ159.48,131.22,124.44,124.36,114.25,55.34,50.83,42.56,37.41,32.84,28.39,27.11,26.89,25.21.

[0086] In this example, the yield of 3-(4-methoxyphenyl)-2,2,3,5,5-pentamethylhexadionitrile 3ga was 62%.

[0087] Example 10: The structural formula of 3ha of the complex adiponitrile derivative 4-cyano-2-(2-cyanopropan-2-yl)-4-methyl-2-phenylpentanoate is as follows:

[0088]

[0089] The synthesis method of 3ha of ethyl 4-cyano-2-(2-cyanopropan-2-yl)-4-methyl-2-phenylpentanoate is as follows:

[0090]

[0091] According to the molar ratio of ethyl 2-phenylacrylate (1h), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of ethyl 2-phenylacrylate and 0.5 mmol of azobisisobutyronitrile were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80℃ for 12h. The solvent was removed by vacuum distillation at 45℃ to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 40 mg of a complex structure adiponitrile derivative (ethyl 4-cyano-2-(2-cyanopropan-2-yl)-4-methyl-2-phenylpentanoate 3ha), wherein the eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0092] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.69-7.67(m,2H),7.39-7.34(m,3H),4.43-4.36(m,2H),2.80-2.77( m,1H),2.51-2.48(m,1H),1.47(s,3H),1.44(s,3H),1.41(m,3H),1.29(s,3H),0.84(s,3H); 13 C NMR (126MHz, CDCl3) δ170.21,134.99,129.61,128.20,128.03,61.73,58.57,44.47,40.98,31.37,30.85,28.63,25.43,23.95,13.77.

[0093] In this example, the yield of ethyl 4-cyano-2-(2-cyanopropane-2-yl)-4-methyl-2-phenylpentanoate 3ha was 64%.

[0094] Example 11: The structural formula of the complex adiponitrile derivative ethyl 2-benzyl-4-cyano-2-(2-cyanopropane-2-yl)-4-methylpentanoate 3ia in this example is as follows:

[0095]

[0096] The synthesis method of ethyl 2-benzyl-4-cyano-2-(2-cyanopropan-2-yl)-4-methylpentanoate 3ia is as follows:

[0097]

[0098] According to the molar ratio of ethyl 2-benzyl acrylate (1d), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of ethyl 2-benzyl acrylate and 0.5 mmol of azobisisobutyronitrile were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80℃ for 12 h. The solvent was removed by vacuum distillation at 45℃ to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 43 mg of a complex-structured adiponitrile derivative (ethyl 2-benzyl-4-cyano-2-(2-cyanopropane-2-yl)-4-methylpentanoate 3ia). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0099] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.55-7.53(m,2H),7.30-7.26(m,3H),4.36-4.25(m,2H),3.66-3.63(m,1H),3.22-3.19(m,1 H),2.37-2.34(m,1H),2.16-2.13(m,1H),1.45(s,3H),1.40(s,3H),1.378-1.36(m,3H),1.35(s,3H),1.32(s,3H); 13 CNMR(126MHz, CDCl3)δ172.04,136.70,132.02,128.18,127.15,124.66,124.08 ,61.78,54.72,45.85,40.37,40.05,30.38,30.36,28.31,25.22,23.95,13.88.

[0100] In this example, the yield of ethyl 2-benzyl-4-cyano-2-(2-cyanopropane-2-yl)-4-methylpentanoate 3ia was 66%.

[0101] Example 12: The structural formula of the complex adiponitrile derivative 2-phenylethyl-4-cyano-2-(2-cyanopropane-2-yl)-4-methylpentanoate ethyl ester 3ja in this example is as follows:

[0102]

[0103] The synthesis method of ethyl 2-phenylethyl-4-cyano-2-(2-cyanopropan-2-yl)-4-methylpentanoate 3ja is as follows:

[0104]

[0105] According to the molar ratio of ethyl 2-phenylethyl acrylate (1j), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of ethyl 2-phenylethyl acrylate and 0.5 mmol of azobisisobutyronitrile were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80℃ for 12 h. The solvent was removed by vacuum distillation at 45℃ to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 46 mg of a complex-structured adiponitrile derivative (ethyl 2-phenylethyl-4-cyano-2-(2-cyanopropane-2-yl)-4-methylpentanoate 3ja). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0106] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.33-7.28(m,4H),7.23-7.20(m,1H),4.28-4.23(m,2H),3.18-3.12(m,1H),2.92-2.86(m,1H),2.62-2.55(m,1H) ),2.45-2.42(m,1H),2.21-2.14(m,1H),2.11-2.08(m,1H),1.57(s,3H),1.53(s,3H),1.46(s,3H),1.43(s,3H),1.36(t,J=7.2Hz,3H); 13 C NMR (126MHz, CDCl3) δ171.92,141.16,128.62,128.16,126.28,124.46,123.74,61 .70,52.75,42.68,38.43,33.70,31.24,31.01,30.10,28.54,25.40,23.47,13.96.

[0107] In this example, the yield of 3-(4-chlorophenyl)-2,2,3,5,5-pentamethylhexadionitrile 3ja was 68%.

[0108] Example 13: The structural formula of the complex adiponitrile derivative 3-([1,1'-biphenyl]-4-yl)-2,2,5,5-tetramethyladiponitrile 3ka in this example is as follows:

[0109]

[0110] The synthetic method for 3-([1,1'-biphenyl]-4-yl)-2,2,5,5-tetramethyladiponitrile 3 kDa is as follows:

[0111]

[0112] According to the molar ratio of 4-bistyrene (1k), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 4-bistyrene and 0.5 mmol of azobisisobutyronitrile were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80℃ for 12 h. The solvent was removed by vacuum distillation at 45℃ to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 44 mg of a complex adiponitrile derivative (3-([1,1'-biphenyl]-4-yl)-2,2,5,5-tetramethyladiponitrile 3ka). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0113] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.63-7.61(m,4H),7.48-7.43(m,4H),7.39-7.36(m,1H),2.86- 2.84(m,1H),2.30-2.27(m,2H),1.53(s,3H),1.42(s,3H),1.18(s,3H),1.04(s,3H); 13 C NMR (126MHz, CDCl3) δ140.83,140.23,138.38,128.81,27.50,127.35,126.96,124.24,124.19,51.24,42.48,37.21,32.91,28.42,26.88,25.28.

[0114] In this example, the yield of 3-([1,1'-biphenyl]-4-yl)-2,2,5,5-tetramethyladiponitrile 3 kJ was 70%.

[0115] Example 14: The structural formula of the complex adiponitrile derivative 3-([1,1'-biphenyl]-4-yl)-2,5-diethyl-2,5-dimethyladiponitrile 3kb in this example is as follows:

[0116]

[0117] The synthesis method of 3-([1,1'-biphenyl]-4-yl)-2,5-diethyl-2,5-dimethyladiponitrile 3kb is as follows:

[0118]

[0119] According to the molar ratio of 4-bistyrene (1k), azobisisovalerate (2b), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 4-bistyrene and 0.5 mmol of azobisisovalerate were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80℃ for 12 h. The solvent was removed by vacuum distillation at 45℃ to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 46 mg of a complex-structured adiponitrile derivative (3-([1,1'-biphenyl]-4-yl)-2,5-diethyl-2,5-dimethyladiponitrile 3kb). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0120] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.61-7.58(m,5H),7.45-7.42(m,3H),7.36-7.33(m,1H),2.93-2.85(m,1H),2.39-2.34(m,1H),2.22-2. 18(m,1H),1.93-1.86(m,1H),1.57(s,1H),1.44(s,2H),1.31(s,3H),1.15-1.11(m,3H),1.02-0.98(m,3H),0.89-0.87(m,3H); 13 C NMR (126MHz, CDCl3) δ140.70,140.27,138.35,138.07,128.79,127.46,127.25,126.96,50.22,48.93 ,42.56,42.43,40.94,37.55,37.40,34.02,32.23,32.01,31.52,30.00,24.42,24.33,22.81,21.00.

[0121] In this example, the yield of 3-([1,1'-biphenyl]-4-yl)-2,5-diethyl-2,5-dimethylhexadionitrile 3kb was 67%.

[0122] Example 15: The structural formula of the complex adiponitrile derivative 3-([1,1'-biphenyl]-4-yl)-2,5-diisobutyl-2,5-dimethyladiponitrile 3kc in this example is as follows:

[0123]

[0124] The synthesis method of 3-([1,1'-biphenyl]-4-yl)-2,5-diisobutyl-2,5-dimethyladiponitrile 3kc is as follows:

[0125]

[0126] According to the molar ratio of 4-bistyrene (1k), azobisisoheptanenitrile (2c), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 4-bistyrene and 0.5 mmol of azobisisoheptanenitrile were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80℃ for 12 h. The solvent was removed by vacuum distillation at 45℃ to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 50 mg of a complex structure adiponitrile derivative (3-([1,1'-biphenyl]-4-yl)-2,5-diisobutyl-2,5-dimethyladiponitrile 3kc). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0127] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.63-7.58(m,4H),7.46-7.43(m,4H),7.37-7.34(m,1H),2.90-2.86(m,1H),2.39-2.36(m,1H),2.17-2.11(m,1H),1. 87-1.81(m,2H),1.56(s,1H),1.51(s,1H),1.46-1.38(m,2H),1.20-1 .18(m,1H),1.12-1.11(m,3H),1.12-0.97(m,9H),0.96-0.87(m,6H); 13 C NMR (126MHz, CDCl3) δ140.23,139.11,128.82,127.49,127.31,126.93,49. 66,45.80,40.77,40.44,36.65,36.58,25.62,25.10,24.73,24.03,23.69.

[0128] In this example, the yield of 3-([1,1'-biphenyl]-4-yl)-2,5-diisobutyl-2,5-dimethyladiponitrile 3kc was 62%.

[0129] Example 16: The structural formula of the complex adiponitrile derivative 3-([1,1'-biphenyl]-2-yl)-2,2,5,5-tetramethyladiponitrile 3la in this example is as follows:

[0130]

[0131] The synthetic method of 3-([1,1'-biphenyl]-2-yl)-2,2,5,5-tetramethyladiponitrile 3la is as follows:

[0132]

[0133] According to the molar ratio of 2-vinyl-1,1'-biphenyl (1l), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 2-vinyl-1,1'-biphenyl, 0.5 mmol of azobisisobutyronitrile, and 0.76 mmol of ethylene glycol dimethyl ether were added to the reactor in the presence of argon gas. The reaction was carried out at 80°C for 12 h. The solvent was removed by vacuum distillation at 45°C to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 35 mg of a complex adiponitrile derivative (3-([1,1'-biphenyl]-2-yl)-2,2,5,5-tetramethyladiponitrile 3la). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0134] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.67-7.65(m,1H),7.46-7.35(m,7H),7.28(m,1H),3.21-3.18(m,1H) ,2.45-2.40(m,1H),2.05-2.01(m,1H),1.31(s,3H),1.25(s,3H),1.21(s,3H),1.10(s,3H); 13 C NMR (126MHz, CDCl3) δ143.45,141.14,136.84,131.28,130.26,128.16,128.03,127.48,127. 33,126.34,124.33,123.75,43.97,43.78,38.07,31.52,28.11,27.19,26.99,25.07,23.42.

[0135] In this example, the yield of 3-([1,1'-biphenyl]-2-yl)-2,2,5,5-tetramethyladiponitrile 3la was 55%.

[0136] Example 17: The structural formula of the complex adiponitrile derivative 3-(4-fluorophenyl)-2,2,5,5-tetramethyladiponitrile 3ma in this example is as follows:

[0137]

[0138] The synthesis method of 3-(4-fluorophenyl)-2,2,5,5-tetramethyladiponitrile 3ma is as follows:

[0139]

[0140] According to the molar ratio of 1-fluoro-4-vinylbenzene (1m), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 1-fluoro-4-vinylbenzene and 0.5 mmol of azobisisobutyronitrile were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80℃ for 12 h. The solvent was removed by vacuum distillation at 45℃ to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 32 mg of a complex-structured adiponitrile derivative (3-(4-fluorophenyl)-2,2,5,5-tetramethyladiponitrile 3ma). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0141] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.34-7.61(m,2H),7.08-7.05(m,2H),2.79-2.76(m,1H),2.21- 2.19(m,1H),2.18-2.15(m,1H),1.47(s,3H),1.38(s,3H),1.10(s,3H),1.01(s,3H); 13 C NMR (126MHz, CDCl3) δ163.51,161.55,135.06,135.03,124.00,123.96,115. 91,115.74,50.82,42.58,37.17,32.62,29.70,28.17,27.14,26.78,25.24.

[0142] In this example, the yield of 3-(4-fluorophenyl)-2,2,5,5-tetramethyladiponitrile 3ma was 62%.

[0143] Example 18: The structural formula of the complex adiponitrile derivative 3-(4-chlorophenyl)-2,2,5,5-tetramethyladiponitrile 3na in this example is as follows:

[0144]

[0145] The synthesis method of 3-(4-chlorophenyl)-2,2,5,5-tetramethyladiponitrile 3na is as follows:

[0146]

[0147] According to the molar ratio of 1-chloro-4-vinylbenzene (1n), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 1-chloro-4-vinylbenzene and 0.5 mmol of azobisisobutyronitrile were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80°C for 12 h. The solvent was removed by vacuum distillation at 45°C to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 35 mg of a complex adiponitrile derivative (3-(4-chlorophenyl)-2,2,5,5-tetramethyladiponitrile 3na). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0148] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.35-7.34(m,2H),7.30-7.28(m,2H),2.77-2.75(m,1H),2.24- 2.21(m,1H),2.19-2.14(m,1H),1.47(s,3H),1.38(s,3H),1.10(s,3H),1.00(s,3H); 13 C NMR (126MHz, CDCl3) δ137.87,134.06,129.04,123.96,123.83,50.95,42.44,37.06,32.67,28.18,27.06,26.74,25.22.

[0149] In this example, the yield of 3-(4-chlorophenyl)-2,2,5,5-tetramethyladiponitrile 3na was 65%.

[0150] Example 19: The structural formula of the complex adiponitrile derivative 3-(3-chlorophenyl)-2,2,5,5-tetramethyladiponitrile 3oa in this example is as follows:

[0151]

[0152] The synthesis method of 3-(3-chlorophenyl)-2,2,5,5-tetramethyladiponitrile 3oa is as follows:

[0153]

[0154] According to the molar ratio of 1-chloro-3-vinylbenzene (1o), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 1-chloro-3-vinylbenzene and 0.5 mmol of azobisisobutyronitrile were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80°C for 12 h. The solvent was removed by vacuum distillation at 45°C to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 33 mg of a complex-structured adiponitrile derivative (3-(3-chlorophenyl)-2,2,5,5-tetramethyladiponitrile 3oa). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0155] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.34-7.31(m,4H),2.77-2.74(m,1H),2.22-2.19(m,2H),1.48(s,3H),1.38(s,3H),1.12(s,3H),1.03(s,3H); 13 C NMR (126MHz, CDCl3) δ141.46,134.74,130.11,128.39,123.91,123.75,51.15,42.43,37.04,32.65,28.10,27.04,26.81,25.18.

[0156] In this example, the yield of 3-(3-chlorophenyl)-2,2,5,5-tetramethyladiponitrile 3oa was 61%.

[0157] Example 20: The structural formula of the complex adiponitrile derivative 3-(4-bromophenyl)-2,2,5,5-tetramethyladiponitrile 3pa in this example is as follows:

[0158]

[0159] The synthesis method of 3-(4-bromophenyl)-2,2,5,5-tetramethyladiponitrile 3pa is as follows:

[0160]

[0161] According to the molar ratio of 1-bromo-4-vinylbenzene (1p), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 1-bromo-4-vinylbenzene and 0.5 mmol of azobisisobutyronitrile were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80°C for 12 h. The solvent was removed by vacuum distillation at 45°C to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 36 mg of a complex-structured adiponitrile derivative (3-(4-bromophenyl)-2,2,5,5-tetramethyladiponitrile 3pa). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0162] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.51-7.49(m,2H),7.24-7.23(m,2H),2.76-2.74(m,1H),2. 21(m,1H),2.18-2.13(m,1H),1.47(s,3H),1.38(s,3H),1.10(s,3H),1.00(s,3H); 13 C NMR (126MHz, CDCl3) δ833.65,827.23,819.17,819.00,817.36,746.22,737.59,732.15,727.86,723.38,722.19,721.90,720.39.

[0163] In this example, the yield of 3-(4-bromophenyl)-2,2,5,5-tetramethyladiponitrile 3pa was 57%.

[0164] Example 21: The structural formula of the complex adiponitrile derivative 3-(4-nitrophenyl)-2,2,5,5-tetramethyladiponitrile 3qa in this example is as follows:

[0165]

[0166] The synthetic method of 3-(4-nitrophenyl)-2,2,5,5-tetramethyladiponitrile 3qa is as follows:

[0167]

[0168] According to the molar ratio of 1-nitro-4-vinylbenzene (1q), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 1-methyl-4-(1-chlorovinyl)benzene, 0.5 mmol of azobisisobutyronitrile, and 0.76 mmol of ethylene glycol dimethyl ether were added to the reactor sequentially, and the reaction was carried out at 80℃ for 12 h. The solvent was removed by vacuum distillation at 45℃ to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 30 mg of a complex-structure adiponitrile derivative (3-(4-nitrophenyl)-2,2,5,5-tetramethyladiponitrile 3qa). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0169] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.33-7.31(m,2H),7.08-7.04(m,2H),2.78-2.76(m,1 H),2.20-2.17(m,2H),1.47(s,3H),1.37(s,3H),1.10(s,3H),1.01(s,3H); 13 C NMR (126MHz, CDCl3) δ163.48,161.52,135.03,135.00,123.97,123.93,115.88,115.71,50.79,42.55,37.14,32.59,28.14,27.11,26.75,25.21.

[0170] In this example, the yield of 3-(4-nitrophenyl)-2,2,5,5-tetramethylhexadionitrile 3qa was 52%.

[0171] Example 22: The structural formula of the complex adiponitrile derivative 2,2,5,5-tetramethyl-3-phenyladiponitrile 3ra in this example is as follows:

[0172]

[0173] The synthetic method of 2,2,5,5-tetramethyl-3-phenylhexadionitrile 3ra is as follows:

[0174]

[0175] According to the molar ratio of styrene (1r), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of styrene and 0.5 mmol of azobisisobutyronitrile were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80℃ for 12 h. The solvent was removed by vacuum distillation at 45℃ to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 34 mg of a complex-structured adiponitrile derivative (2,2,5,5-tetramethyl-3-phenyladiponitrile 3ra). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0176] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.36-7.33(m,5H),2.79-2.76(m,1H),2.24-2.23(m,2H),1.47(s,3H),1.37(s,3H),1.11(s,3H),0.99(s,3H); 13 C NMR (126MHz, CDCl3) δ139.28,128.79,128.08,124.18,124.15,51.49,42.47,37.13,32.74,28.24,26.92,26.90,25.16.

[0177] In this example, the yield of 2,2,5,5-tetramethyl-3-phenylhexadionitrile 3ra was 70%.

[0178] Example 23: The structural formula of the complex adiponitrile derivative 3-(4-methoxyphenyl)-2,2,5,5-tetramethyladiponitrile 3sa in this example is as follows:

[0179]

[0180] The synthesis method of 3-(4-methoxyphenyl)-2,2,5,5-tetramethyladiponitrile 3sa is as follows:

[0181]

[0182] According to the molar ratio of 4-methoxystyrene (1s), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 4-methoxystyrene and 0.5 mmol of azobisisobutyronitrile were added sequentially to the reactor, and 0.76 mmol of ethylene glycol dimethyl ether was added under argon atmosphere. The reaction was carried out at 80°C for 12 h. The solvent was removed by vacuum distillation at 45°C to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 34 mg of a complex adiponitrile derivative (3-(4-methoxyphenyl)-2,2,5,5-tetramethyladiponitrile 3sa). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0183] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.24-7.22(m,2H),6.88-6.86(m,2H),3.79(s,3H),2.74-2. 71(m,1H),2.19–2.16(m,2H),1.44(s,3H),1.35(s,3H),1.09(s,3H),0.99(s,3H); 13 C NMR (126MHz, CDCl3) δ159.34,131.07,124.28,124.20,114.10,55.19,55.18,50.68,42.41,37.26,32.69,28.23,26.96,26.73,25.05.

[0184] In this example, the yield of 3-(4-methoxyphenyl)-2,2,5,5-tetramethyladiponitrile 3sa was 64%.

[0185] Example 24: The structural formula of the complex adiponitrile derivative 2,2,5,5-tetramethyl-3-(naphth-2-yl)adiponitrile 3ta in this example is as follows:

[0186]

[0187] The synthetic method of 2,2,5,5-tetramethyl-3-(naphth-2-yl)adiponitrile 3ta is as follows:

[0188]

[0189] According to the molar ratio of 2-naphthylene (1t), azobisisobutyronitrile (2a), and ethylene glycol dimethyl ether of 1:2.5:3.8, 0.2 mmol of 2-naphthylene, 0.5 mmol of azobisisobutyronitrile, and 0.76 mmol of ethylene glycol dimethyl ether were added to the reactor sequentially, and the reaction was carried out at 80℃ for 12 h. The solvent was removed by vacuum distillation at 45℃ to obtain the crude product. The crude product was then subjected to column chromatography (300 mesh silica gel) to obtain 30 mg of a complex-structured adiponitrile derivative (2,2,5,5-tetramethyl-3-(naphth-2-yl)adiponitrile 3ta). The eluent for column chromatography was ethyl acetate:petroleum ether = 1:40.

[0190] The nuclear magnetic resonance (NMR) spectral characterization data of the product are as follows: 1 H NMR (500MHz, CDCl3) δ7.89-7.86(m,4H),7.54-7.51(m,3H),3.00-2.97(m,1 H),2.38-2.36(m,2H),1.56(s,3H),1.41(s,3H),1.15(s,3H),0.97(s,3H); 13 C NMR (126MHz, CDCl3) δ136.98,133.25,133.01,128.65,127.94,127.68,126.48,1 26.27,124.26,124.20,51.72,42.59,37.24,33.00,28.47,27.05,26.79,25.36.

[0191] In this example, the yield of 2,2,5,5-tetramethyl-3-(naphth-2-yl)adiponitrile 3ta was 51%.

Claims

1. A method for preparing a complex adiponitrile derivative, characterized in that: Terminal olefins, azobisisobutyronitrile and their derivatives were added to a reactor and reacted at 75-85℃ for 12 hours under argon atmosphere and in the presence of solvent. The solvent was removed by vacuum distillation and purified by column chromatography to obtain a complex adiponitrile derivative with the following structural formula. Among them, R 1 It is one of 2-biphenyl, 4-biphenyl, 4-tolyl, 3-chlorophenyl, 4-chlorophenyl, 4-fluorophenyl, 4-bromophenyl, 4-cyanophenyl, 4-nitrophenyl, 4-methoxyphenyl, phenyl, benzyl, phenethyl, and 2-naphthyl; R 2 It is one of methyl, ethyl, or isopropyl; R 3 It is one of hydrogen, methyl, or ethoxycarbonyl.

2. The method for preparing the complex adiponitrile derivative according to claim 1, characterized in that, The structural formula of the terminal olefin is as follows: Among them, R 1 R is any position on the benzene ring. 1 It is one of phenyl, methyl, fluorine, chlorine, bromine, cyano, nitro, methoxy, and 2-naphthyl; R 2 It is one of hydrogen, methyl, or ethoxycarbonyl; R 3 It is one of phenyl or benzyl.

3. The method for preparing the complex adiponitrile derivative according to claim 1, characterized in that, The structural formulas of azobisisobutyronitrile and its derivatives are as follows: R is one of methyl, ethyl, or isopropyl.

4. The method for preparing the complex adiponitrile derivative according to claim 1, characterized in that: The solvent is one of ethylene glycol dimethyl ether, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, acetonitrile, and diethylene glycol dimethyl ether.

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