A preparation method of α-aryliminoaryl acetonitrile derivative

Abstract

The present invention discloses a method for preparing an α-arylimino aryl acetonitrile derivative, comprising the following steps: (1) using ethanol as a solvent, mixing an aromatic aldehyde and an aromatic amine to react to generate a Schiff base compound; (2) using cesium carbonate as a base, anhydrous N,N-dimethylformamide as a solvent, and malononitrile as a cyanogen source to mix with the Schiff base compound generated in step (1), heating to 90-100° C., and reacting for 7-8 hours to obtain an α-arylimino aryl acetonitrile derivative. The method synthesizes a target compound by reacting aromatic aldehyde, aromatic amine, and malononitrile under the action of cesium carbonate. The method has the advantages of simple reaction steps, using a green cyanogen source malononitrile, avoiding the use of highly toxic reagents such as potassium cyanide and trimethylsilyl cyanide, convenient post-processing, high product regioselectivity, and being able to effectively construct the basic skeleton of the α-arylimino aryl acetonitrile.

Description

Technical Field

[0001] The invention belongs to the field of chemical synthesis and relates to a method for preparing an α-aryliminoaryl acetonitrile derivative. Background Art

[0002] α-Arylimidoaryl acetonitrile is an important class of functionalized compounds that are widely found in many natural bioactive molecules. (Anbarasan, P.; Schareina, T.; Beller, M. Recent developments and perspectives in palladium-catalyzed cyanation of aryl halides: synthesis ofbenzonitriles, Chem. Soc. Rev. 2011, 40, 5049–5067; Enders, D.; Shilvock, JP Some recent applications of α-amino nitrile chemistry, Chem. Soc. Rev. 2000, 29, 359–373; Surmont, R.; De Corte, B.; De Kimpe, N. Regiospecific synthesis of α-chloro- and α-fluoro-1,2-diones, Tetrahedron Lett. 2009, 50,3877–3880).

[0003] α-Arylimidoaryl acetonitrile derivatives are also commonly used as important agricultural plant growth regulators to improve soybean growth. (The potential for increasing soybean yield with plant growth regulators, Peat, JR; Jeffcoat, B. Easter School in Agricultural Science, University of Nottingham, Proceedings, 1982, 33rd, 237-49)

[0004] In addition, α-aryliminoaryl acetonitrile compounds are also important synthons for the synthesis of various nitrogen-containing heterocycles and α-amino acids (De Corte, B.; Denis, JM; De Kimpe, N. A convenient synthesis of C-unsubstituted and C-monoalkylated ketene imines by dehydrocyanation ofimidoyl cyanides using vacuum gas-solid reactions, J. Org. Chem. 1987, 52,1147–1149; Ping, Y.; Ding, Q.; Peng, Y. Advances in C–CN Bond Formation via C–H Bond Activation, ACS Catal., 2016, 6, 5989–6005; Roychowdhury, A.; Kumar, VV; Bhaduri, A.P. Diarylimidoylcyanides, an Attractive Class of Intermediate: Novel Synthesis of α-Anilino-β-Nitroenamines, N, N′ -Disubstituted Amidines and Substituted Phenyl Glyoxate, Synth. Commun. 2006,36, 715–727).

[0005] In recent years, a palladium-catalyzed CH cyanation of arenes using α-aryliminoaryl acetonitrile as a new cyanating agent has been developed. This reaction system can obtain monocyanated aromatic hydrocarbons with high regioselectivity (α-Iminonitrile: a new cyanating agent for the palladium catalyzed CH cyanationof arenes, Chen, Z.-B.; Zhang, F.-L.; Yuan, Q.; Chen, H.-F.; Zhu, Y.-M.; Shen, J.-K., RSC Adv. 2016, 6(69), 64234-64238). Due to the important biological activities and special applications of α-aryliminoaryl acetonitrile in organic synthesis, the research on its preparation methods has attracted more and more attention. Typically, α-aryliminyl aryl acetonitrile compounds can be prepared by using Schiff base as a raw material, and then reacting bromine cyanide (BrCN) to obtain an N-bromo-α-cyanoamine intermediate, which is then removed by removing hydrogen bromide under the action of alkaline aluminum oxide to generate α-aryliminyl aryl acetonitrile compounds. Because bromine cyanide (BrCN) is an inorganic highly toxic substance, the use of this method is very limited (Reaction of cyanogen bromide with benzylideneanilines, Rai, M.; Krishan, K.; Singh, A. Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry (1976), 14B(5), 376-7).

[0006] The condensation of nitroso compounds and α-methylene nitriles is also an effective method for synthesizing α-aryliminoaryl acetonitrile, but the substrate nitroso compounds are difficult to obtain, which affects the practical application of this method (A convenient synthesis of α, β-disubstituted cinnamonitriles (1-anilino-2-cyano-1,2-diphenylethenes), Takahashi, K.; Kimura, S.; Ogawa, Y.; Yamada, K.; Iida, H.Synthesis (1978), (12), 892-3). In addition, α-aryliminoaryl acetonitrile compounds can also be effectively prepared by using a three-component Strecker reaction of aromatic aldehydes, aromatic amines and potassium cyanide to first generate α-cyanoamine intermediates, followed by oxidative dehydrogenation by various oxidants, such as activated manganese dioxide (MnO2) (A novel method for the oxidation of α-aminonitriles, Sandhu, Jagtar S.; Mohan, Suresh; Kapoor, Amrit L. Chem. Ind.(London, United Kingdom) 1971, (5), 152-3.), 2-iodobenzoic acid (IBX) (P. Fontaine,A. Chiaroni, G. Masson, J. Zhu, One-Pot Three-Component Synthesis of α-Iminonitriles by IBX / TBAB-Mediated Oxidative Strecker Reaction, Org. Lett.2008, 10, 1509–1512.), Potassium monopersulfate (Oxone) (Zhu, J.; Gualtierotti, JB; Schumacher, X.; Wang, Q. Synthesis of Iminonitriles by Oxone / TBAB-Mediated One-Pot Oxidative Three-Component Strecker Reaction, Synthesis 2013,45, 1380–1386), or natural porphyrin iron coordination compounds as oxidation catalysts.(Hemin-catalyzed controlled oxidative cyanation of secondary amine for the synthesis of α-aminonitriles and α-iminonitriles, Li, F.; Xu, Y.; Xu, Y.; Wang, C.; Ma, J.; Chen, P.; Wang, L. Molecular Catalysis (2022), 529, 112576). In 2013, a free radical pathway for the efficient synthesis of α-iminonitriles from methylimine and TMSN3 was studied via the cooperative catalysis of iodophenyldiacetic acid (PIDA) and sodium bromide (Chen, F.; Huang, X.; Cui, Y.; Jiao, N. Direct Transformation of MethylImines to α-Iminonitriles under Mild and Transition-Metal-Free Conditions, Chem. Eur. J. 2013, 19, 11199–11202).

[0007] Recently, a new strategy for the synthesis of α-iminonitriles was developed by using nitromethane as a cyanating agent through coumarin-catalyzed condensation of aromatic amines and aromatic aldehydes at 80°C (Satyanarayana, I.; Manjappa, KB; Yang, D. Nitromethane as a surrogate cyanating agent: 7-N,N-dimethylamino-4-hydroxycoumarin-catalyzed, metal-free synthesis of α-iminonitriles, GreenChem. 2020, 22, 8316–832221).

[0008] However, the application of these methods in the synthesis of α-imidonitriles is limited by the harsh reaction conditions, difficult-to-obtain substrates and toxic cyanide donors, efficient separation of isomers, or the use of noble metal catalysts. Summary of the Invention

[0009] The technical problem to be solved by the present invention is to provide a simple, environmentally friendly method for synthesizing α-iminonitrile with easily available raw materials and mild reaction conditions.

[0010] The technical solution of the present invention is: a method for preparing an α-aryliminoaryl acetonitrile derivative, comprising the following steps:

[0011] (1) Using ethanol as solvent, aromatic aldehyde and aromatic amine are mixed and reacted to form Schiff base compounds;

[0012] (2) Cesium carbonate is used as a base, anhydrous N,N-dimethylformamide is used as a solvent, and malononitrile is used as a cyanide source. The mixture is mixed with the Schiff base compound generated in step (1), heated to 90-100° C., and reacted for 7-8 hours to obtain an α-aryliminoaryl acetonitrile derivative.

[0013] Furthermore, the aromatic aldehyde is thiophene-3-carboxaldehyde or 1-naphthaldehyde or a compound represented by formula I.

[0014] In Formula I, R 1 is H or 4-Cl, 4-Br, 4-Me, 2-MeO, 3-MeO, 2-Cl, 3-Cl, 3 - PhO - 4 - F.

[0015] Furthermore, the structure of the aromatic amine is shown in Formula II,

[0016] In formula II, R 2 is H, 4-MeO, 4-Br, 4-Cl, 2-Me or 3-Me.

[0017] Furthermore, the molar ratio of the aromatic aldehyde to the aromatic amine is 1:1.

[0018] Furthermore, the molar ratio of the cesium carbonate to malononitrile is 1:1.

[0019] Furthermore, the molar ratio of the aromatic aldehyde to malononitrile is 4:5.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The method synthesizes the target compound by reacting aromatic aldehyde, aromatic amine and malononitrile under the action of cesium carbonate. The method has the advantages of simple reaction steps, using green cyanide source malononitrile, avoiding the use of highly toxic reagents such as potassium cyanide and trimethylsilyl cyanide, convenient post-processing, high product regioselectivity, and being able to effectively construct the basic skeleton of α-aryliminoaryl acetonitrile.

[0022] Compared to methods in the literature, this method uses a non-toxic cyanide source to synthesize the target compound, resulting in high yields and readily available raw materials. The reaction is highly stereoselective, produces a single product, and offers simplified post-processing. It avoids the use of highly toxic cyanide reagents and difficult-to-obtain substrates. Furthermore, this method eliminates the need for precious metal catalysts. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is the molecular structure diagram of compound 3a. DETAILED DESCRIPTION

[0024] The experimental methods in the following examples are conventional methods unless otherwise specified. The experimental materials used in the following examples are purchased from commercial channels unless otherwise specified.

[0025] 1. Optimization of reaction conditions and synthesis of derivatives

[0026] Typical experimental steps (taking the synthesis reaction of product 3a as an example)

[0027] Aromatic aldehyde 1a (4 mmol, 0.732 g) and aromatic amine 2a (4 mmol, 0.492 g) were added to a 50 mL round-bottom flask with ethanol (15 mL) as the solvent. The mixture was stirred at room temperature for 5 h, and the solid was removed. The removed solid was washed with ethanol and then dried. The yield was 95%. Subsequently, the solid removed from the previous step (4 mmol, 1.150 g) and malononitrile (5 mmol, 0.330 g) were added to a 50 mL round-bottom flask. Cesium carbonate (5 mmol, 1.301 g) was used as the base, and anhydrous N,N-dimethylformamide (DMF, 25 mL) was used as the solvent. The mixture was heated to 100°C and reacted for 8 h. After the reaction, N,N-dimethylformamide was removed under reduced pressure using an oil pump, followed by extraction with ethyl acetate (10 mL). The extract was concentrated and purified by column chromatography (dichloromethane:petroleum ether = 1:20). The resulting product 3a was recrystallized from dichloromethane and petroleum ether with a yield of 83%.

[0028] 1. Optimization of reaction conditions

[0029] Table 1 Optimization of alkaline reagent, temperature, and reaction time in the synthesis of typical product 3a

[0030]

[0031]

[0032] The results in Table 1 demonstrate that the choice of inorganic base significantly impacts the reaction (Catalogs 1-7, equivalent to malononitrile). Using cesium carbonate (Cs2CO3) or potassium carbonate (K2CO3) as the base reagent, the yields of target compound 3a were 83% and 81%, respectively, clearly demonstrating that cesium carbonate or potassium carbonate promotes the reaction to proceed fully. However, when the cesium carbonate dosage was reduced to 0.5 or 0.2 equivalents (Catalogs 8-9), the yield of target compound 3a decreased, indicating that the cesium carbonate base reagent was participating in the reaction in a single equivalent. Reaction temperature also significantly impacts the reaction (Catalogs 4, 10-12). Reaction temperatures below 90°C are clearly detrimental to the reaction, while the optimal reaction temperature is 90-100°C. In an oxygen atmosphere, the optimal reaction time for this reaction is 8 hours. Studies have shown that temperatures below 8 hours do not allow the reaction to proceed fully (Catalogs 4, 13-14). While nitrogen clearly inhibits the reaction, it is clear that both oxygen in the air and pure oxygen promote the reaction (Catalog 4, 13-15).

[0033] 2. Synthesis of α-aryliminoarylacetonitrile derivatives

[0034] The following table shows the synthesis results of α-aryliminoaryl acetonitrile derivatives:

[0035] Table 2 Synthesis of α-aryliminoaryl acetonitrile derivatives

[0036]

[0037]

[0038] 2. Experimental Data

[0039] The structures of the above 18 products were characterized by H NMR, C NMR, IR, mass spectrometry, and elemental analysis, and their stereochemical structures were determined by single crystal X-ray diffraction analysis. The molecular structures and experimental data are as follows:

[0040] Compound number: 3a

[0041] (Z)-α-(p-Anisimido)-4-bromophenylacetonitrile

[0042] (Z)-4-bromo-N-(4-methoxyphenyl)benzimidoyl cyanide (3a)

[0043]

[0044] Melting point 108.1-108.2 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ(ppm): 7.99 (d, 2H,J = 7.8 Hz), 7.66 (d, 2H, J = 8.4 Hz ), 7.36 (d, 2H, J =8.4 Hz), 6,99 (d, 2H, J = 8.4 Hz ), 3.87 (s, 3H); 13 C-NMR (CDCl3, 150 MHz) δ( ppm ): 159.91, 141.41, 135.24, 133.25, 132.23, 129.20, 127.19, 123.31,114.57, 111.47, 55.54; IR (KBr, cm -1 ): 2956, 2838, 2213, 1610, 1587, 1574,1503, 1260, 768; MS(EI) (m / z): 315.49 [(M+1) + ] (100%); Elemental analysis theoretical value C 15 H 11 BrN2O (%): C, 57.16; H, 3.52; N, 8.89; Found: C, C, 57.12; H, 3.48; N,8.92.

[0045] Compound number: 3b

[0046] (Z)-α-(p-Anisimido)-p-Tolueneacetonitrile

[0047] (Z)-N-(4-methoxyphenyl)-4-methylbenzimidoyl cyanide (3b)

[0048]

[0049] Melting point 93.7-93.8 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):7.94 (d, 2H, J = 7.2 Hz), 7.23 (t, 4H, J = 10.8 Hz), 6.92 (d, 2H, J = 7.2Hz), 3.79 (s, 3H), 2.37 (s, 3H); 13 C-NMR (CDCl3, 150 MHz) δ ( ppm): 158.25,142.19, 140.93, 136.05, 130.59, 128.67, 126.90, 121.88, 113.40, 110.68,54.50, 20.61; IR (KBr, cm -1 ): 2975, 2212, 1604, 1571, 1503, 1249, 1174, 839;MS (EI) (m / z): 251.42 [(M+1) + ] (100%); Elemental analysis theoretical value C 16 H 14 N2O (%): C, 76.78; H, 5.64; N, 11.19; Found: C, 76.78; H, 5.64; N, 11.19.

[0050] Compound number: 3c

[0051] (Z)-α-(p-Anisimido)-o-Anisylphenylacetonitrile

[0052] (Z)-2-methoxy-N-(4-methoxyphenyl)benzimidoyl cyanide (3c)

[0053]

[0054] Melting point 64.8-65.1 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):7.73 (d, 1H, J = 7.2 Hz), 7.42 (t, 1H, J = 7.2 Hz), 7.21 (d, 2H, J = 8.4 Hz),6.98 (t, 1H, J = 7.2 Hz), 6.96 (d, 1H, J = 9 Hz), 6.91 (d, 2H J = 8.4 Hz),3.89 (s, 3H), 3.78 (s, 3H); 13 C-NMR (CDCl3, 150 MHz) δ ( ppmIR (KBr, cm -1 ): 2964, 2835, 2214, 1602, 1575, 1503,1459, 1259, 839; MS(EI) (m / z): 267.34 [(M+1) + ] (100%); Elemental analysis theoretical value C 16 H 14 N2O2 (%): C, 72.17; H, 5.30; N, 10.52; Found: C, 72.15; H, 5.22; N,10.56.

[0055] Compound number: 3d

[0056] (Z)-α-(p-Anisimido)-m-Anisylacetonitrile

[0057] (Z)-3-methoxy-N-(4-methoxyphenyl)benzimidoyl cyanide (3d)

[0058]

[0059] Melting point 64.8-65.1 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):7.70 (d, 1H, J = 7.2 Hz), 7.67 (s, 1H), 7.42 (t, 1H, J = 8.4 Hz), 7.32 (d,2H, J = 7.8 Hz), 7.10 (d, 1H, J = 7.8 Hz), 6.99 (d, 2H J = 8.4 Hz), 3.89 (s,3H), 3.85 (s, 3H); 13 C-NMR (CDCl3, 150 MHz) δ ( ppmIR (KBr, cm -1 ): 2972, 2834, 2212, 1606, 1571, 1502, 1466, 1029,831; MS(EI) (m / z): 267.70 [(M+1) + ] (100%); Elemental analysis theoretical value C 16 H 14 N2O2 (%): C, 72.17; H, 5.30; N, 10.52; Found: C, 72.17; H, 5.30; N, 10.52.

[0060] Compound number: 3e

[0061] (Z)-α-(p-Anisimido)-3-Chlorophenylacetonitrile

[0062] (Z)-3-chloro-N-(4-methoxyphenyl)benzimidoyl cyanide (3e)

[0063]

[0064] Melting point 101.1-102 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):8.06 (s, 1H), 7.91 (d, 1H, J = 7.8 Hz ), 7.44 (d, 1H, J = 7.8 Hz), 7.37 (d,1H, J = 7.8 Hz), 7.30 (d, 2H, J = 7.8 Hz ), 6.92 (d, 2H, J = 7.8 Hz), 3.78(s, 3H); 13 C-NMR (CDCl3, 150 MHz) δ ( ppmIR (KBr, cm -1 ): 2941, 2838, 2216, 1603, 1562, 1501, 1468, 1248, 840; MS(EI)(m / z): 271.41[(M+1) + ] (100%); Elemental analysis theoretical value C 15 H 11 ClN2O (%): C, 66.55; H, 4.10; N, 10.35; Found: C, 66.58; H, 4.06; N, 10.38.

[0065] Compound number: 3f

[0066] (Z)-α-(p-Chlorophenylimino)-m-Chlorophenylacetonitrile

[0067] (Z)-3-chloro-N-(4-chlorophenyl)benzimidoyl cyanide (3f)

[0068]

[0069] Melting point 97.5-98.2 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):8.13 (s, 1H), 7.99 (d, 1H, J = 7.8 Hz), 7.56 (d, 1H, J = 7.8 Hz), 7.47 (t,1H, J = 7.8 Hz ), 7.44 (d, 2H, J = 8.4 Hz), 7.17 (d, 2H, J = 8.4 Hz); 13 C-NMR (CDCl3, 150 MHz) δ ( ppm ):146.89, 138.54, 135.51, 135.06, 133.62, 133.09,130.39, 129.61, 127.87, 126.71, 122.09, 110.51; IR (KBr, cm -1): 3079, 2216,1621, 1596, 1565, 1482, 1274, 1096, 835; MS(EI) (m / z): 275.24 [(M+1) + ] (12%); Elemental analysis theoretical value C 14 H8Cl2N2 (%): C, 61.12; H, 2.93; N, 10.18; Found: C, 61.10; H, 2.98; N, 10.24.

[0070] Compound number: 3g

[0071] (Z)-α-(p-Anisimido)phenylacetonitrile

[0072] (Z)-N-(4-methoxyphenyl)benzimidoyl cyanide (3g)

[0073]

[0074] Melting point 66-66.9 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):8.13 (d, 2H, J = 7.2 Hz), 7.55 (m, 1H), 7.51 (t, 2H, J = 7.2 Hz ), 7.33 (d,2H, J = 9 Hz), 6.98 (d, 2H, J = 8.4 Hz), 3.85 (s, 3H); 13 C-NMR (CDCl3, 150MHz) δ ( ppm ):159.55, 141.78, 136.87, 134.18, 132.37, 129.26, 128.98, 127.93,123.09, 114.50, 111.68, 55.55; IR (KBr, cm -1 ): 2959, 2855, 2214, 1603, 1500,1447, 1279, 1030, 825; MS(EI) (m / z): 237.61 [(M+1) + ] (100%); Elemental analysis theoretical value C 15 H 12N2O (%): C, 76.25; H, 5.12; N, 11.86; Found: C, 76.22; H, 5.08; N,11.90.

[0075] Compound number: 3h

[0076] (Z)-α-(p-Anisimido)-4-chlorophenylacetonitrile

[0077] (Z)-4-chloro-N-(4-methoxyphenyl)benzimidoyl cyanide (3h)

[0078]

[0079] Melting point 97.6-98.0 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):8.06 (d, J = 9 Hz, 2H), 7.49 (d, J = 10.2 Hz, 2H), 7.35 (d, J = 8.4 Hz, 2H),6.69 (d, J = 8.4 Hz, 2H), 3.86 (s, 3H); 13 C-NMR (CDCl3, 150 MHz) δ ( ppm ):159.83, 141.39, 138.67, 135.17, 132.75, 129.28, 129.09, 123.31, 114.53,111.53, 55.56; IR (KBr, cm -1 ): 2956, 2837, 2211, 1609, 1572, 1502, 1442, 1258,1095, 825; MS(EI) (m / z): 271.50 [(M+1) + ] (100%); Elemental analysis theoretical value C 15 H 11 ClN2O(%): C, 66.55; H, 4.10; N, 10.35; Found: C, 66.52; H, 4.05; N, 10.38.

[0080] Compound number: 3i

[0081] (Z)-α-(p-Anisimido)-3-phenoxy-4-fluorophenylacetonitrile

[0082] (Z)-4-fluoro-N-(4-methoxyphenyl)-3-phenoxybenzimidoyl cyanide (3i)

[0083]

[0084] Oily; 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ): 7.74 (m, 2H), 7.21 (t, 2H, J =7.8 Hz ), 7.18 (d, 2H, J = 9 Hz), 6.99 (t, 1H, J = 7.8 Hz ), 6.89 (d, 2H, J =8.4 Hz ), 6.83 (d, 2H, J = 9 Hz), 3.68 (s, 3H); 13 C-NMR (CDCl3, 150 MHz) δ( ppm ): 159.83, 156.90 (d, J = 257 Hz), 156.78, 144.70 (d, J = 12 Hz), 141.26,134.53 (d, J = 3 Hz), 131.44 (d, J = 3 Hz), 130.10, 129.99, 124.93 (d, J =7.5 Hz), 123.85, 123.34, 120.58 (d, J = 1.5 Hz), 117.58, 114.53, 111.50,55.52; IR (KBr, cm -1 ): 2967, 2883, 2212, 1603, 1589, 1506, 1488, 1250, 1028,835; MS(EI) (m / z): 347.48 [(M+1) + ] (100%); Elemental analysis theoretical value C 21 H 15 FN2O2 (%): C, 72.82; H, 4.37; N, 8.09; Found: C, 72.80; H, 4.32; N, 8.12.

[0085] Compound number: 3j

[0086] (Z)-α-(p-Anisimido)-3-thiopheneacetonitrile

[0087] (Z)-N-(4-methoxyphenyl)thiophene-3-carbimidoyl cyanide (3j)

[0088]

[0089] Melting point 70.9-71.6 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):8.00 (d, J = 1.8 Hz, 2H), 7.65 (d, J = 4.8 Hz, 2H), 7.34 (dd, J = 0.3 Hz, 5.4Hz, 1H), 7.22 (d, J = 9 Hz, 2H), 6.91 (d, J = 9 Hz, 2H), 3.78 (s, 3H); 13 C-NMR (CDCl3, 150 MHz) δ ( ppm ): 159.44, 141.65, 138.93, 131.75, 130.64, 127.47,125.73, 123.00, 114.50, 112.04, 55.54; IR (KBr, cm -1 ): 2925, 2831, 2212, 1606,1570, 1500, 1458, 1252, 1030, 832; MS(EI) (m / z): 243.41 [(M+1) + ] (100%) Elemental analysis theoretical value C 13 H 10 N2OS (%): C, 64.44; H, 4.16; N, 11.56; Found: C, 64.40; H,4.07; N, 11.58.

[0090] Compound number: 3k

[0091] (Z)-α-(p-Anisimido)-1-naphthylacetonitrile

[0092] (Z)-N-(4-methoxyphenyl)-1-naphthimidoyl cyanide (3k)

[0093]

[0094] Melting point 134.5-134.9 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ( ppm ): 9.12 (d, J = 8.4 Hz, 1H), 8.19 (d, J = 7.2 Hz, 1H), 8.01 (d, J = 8.4Hz, 1H), 7.91 (d, J = 8.4 Hz, 1H), 7.63 (t, 1H, J = 7.2 Hz ), 7.57 (dt, 2H, J = 7.2 Hz, J = 7.8 Hz), 7.37 (d, J = 9 Hz, 2H), 7.03 (d , J = 9 Hz, 2H), 3.84(s, 3H); 13 C-NMR (CDCl3, 150 MHz) δ ( ppm ):159.48, 142.17, 138.28, 134.19,133.15, 131.23, 130.50, 130.37, 128.93, 128.40, 126.86, 125.52, 124.84,122.75, 114.56, 112.37, 55.59; IR (KBr, cm -1 ): 2999, 2835, 2217, 1600, 1559,1499, 1468, 1249, 1022, 775; MS(EI) (m / z): 287.35 [(M+1) + ] (100%) Elemental analysis theoretical value C 19 H 14 N2O (%): C, 79.70; H, 4.93; N, 9.78; Found: C, 79.66; H, 4.90; N,9.82.

[0095] Compound number: 3l

[0096] (Z)-α-(p-Chlorophenylimino)-o-Chlorophenylacetonitrile

[0097] (Z)-2-chloro-N-(4-chlorophenyl)benzimidoyl cyanide(3l)

[0098]

[0099] Melting point 60.5-60.7 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):7.72 (d, J = 7.8 Hz, 1H), 7.46 (t, 1H, J = 7.2 Hz), 7.42(d, 1H, J = 6.6 Hz),7.39 (d, J = 8.4 Hz, 2H), 7.36 (t, 1H, J = 7.8 Hz), 7.12 (d, J = 8.4 Hz, 2H); 13 C-NMR (CDCl3, 150 MHz) δ ( ppm ): 145.79, 137.54, 132.59, 132.34, 131.81,130.21, 130.06, 128.55, 126.37, 121.43, 120.82, 109.83; IR (KBr, cm -1 ): 3070,2962, 2214, 1606, 1589, 1563, 1482, 1296, 1092, 1028, 833; MS(EI) (m / z):275.45 [(M+1) + ] (100%) Elemental analysis theoretical value C 14 H8Cl2N2 (%): C, 61.12; H, 2.93; N,10.18; Found: C, 61.16; H, 2.90; N, 10.20.

[0100] Compound number: 3m

[0101] (Z)-α-(p-Bromophenylimino)-p-Chlorophenylacetonitrile

[0102] (Z)-N-(4-bromophenyl)-4-chlorobenzimidoyl cyanide (3m)

[0103]

[0104] Melting point 117-118 o C (petroleum ether / dichloromethane); 1H-NMR (CDCl3, 600 MHz) δ ( ppm ):8.07 (d, J = 8.4 Hz, 2H), 7.59 (d, J = 8.4 Hz, 2H), 7.51 (d, J = 8.4 Hz, 2H),7.09 (d, J = 8.4 Hz, 2H); 13 C-NMR (CDCl3, 150 MHz) δ ( ppm ): 147.60, 139.67,138.84, 132.53, 131.94, 129.49, 122.24, 121.32, 110.51; IR (KBr, cm -1 ): 3087,2214, 1588, 1559, 1490, 1479, 1112, 1007, 833; MS(EI) (m / z): 320.92 [(M+1) + ](60%); Elemental analysis theoretical value C 14 H8BrClN2 (%): C, 52.62; H, 2.52; N, 8.77; Found: C, 52.60; H, 2.48; N, 8.82.

[0105] Compound number: 3n

[0106] (Z)-α-(m-toluimido)-p-tolueneacetonitrile

[0107] (Z)-4-methyl-N-(m-tolyl)benzimidoyl cyanide (3n)

[0108]

[0109] Melting point 61.1-62.0 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):7.95 (d, J = 8.4 Hz, 2H), 7.26 (t, 3H, J = 8.4 Hz), 7.03 (d, J = 7.2Hz, 1H),6.98 (d, 2H, J = 9.6 Hz), 2.37 (s, 3H), 2.33 (s, 3H); 13C-NMR (CDCl3, 150 MHz)δ ( ppm IR (KBr, cm -1 ): 2924, 2855,2213, 1592, 1566, 1506, 1480, 1283, 1010, 822; MS(EI) (m / z): 235.43 [(M+1) + ](100%); Elemental analysis theoretical value C 16 H 14 N2 (%): C, 82.02; H, 6.02; N, 11.96; Found: C,82.06; H, 6.04; N, 11.91.

[0110] Compound number: 3o

[0111] (Z)-α-(m-toluimido)-4-chlorophenylacetonitrile

[0112] (Z)-4-chloro-N-(m-tolyl)benzimidoyl cyanide (3o)

[0113]

[0114] Melting point 65.8-66.4 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):8.06 (d, J = 8.4 Hz, 2H), 7.48 (d, J = 8.4 Hz, 2H), 7.34 (t, J = 7.8 Hz, 1H),7.13 (d, J = 7.8 Hz, 1H), 6.99 (s, 2H), 2.40 (s, 3H); 13 C-NMR (CDCl3, 150 MHz)δ ( ppm): 148.86, 139.33, 139.22, 138.19, 132.24, 129.41, 129.38, 129.21,128.46, 121.15, 117.34, 110.75, 21.43; IR (KBr, cm -1 ): 2921, 2857, 2214, 1588,1561, 1485, 1380, 1111, 1006, 837; MS(EI) (m / z): 255.60 [(M+1) + ] (100%); Elemental analysis theoretical value C 15 H 11 ClN2 (%): C, 70.73; H, 4.35; N, 11.00; Found: C, 70.70; H,4.38; N, 11.06.

[0115] Compound number: 3p

[0116] (Z)-α-(m-toluimido)-m-chlorophenylacetonitrile

[0117] (Z)-3-chloro-N-(m-tolyl)benzimidoyl cyanide (3p)

[0118]

[0119] Melting point 56.0-56.2 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):8.06 (s, 1H), 7.92 (d, J = 7.8 Hz, 2H), 7.46 (d, J = 8.4 Hz, 1H), 7.38 (t, J = 7.8 Hz, 1H), 7.27 (t, J = 7.8 Hz, 1H), 7.06 (d, 1H), 6.93 (d, J = 7.8 Hz ,1H), 2.33 (s, 3H); 13 C-NMR (CDCl3, 150 MHz) δ ( ppm): 147.62, 138.30, 136.86,134.37, 134.34, 131.67, 129.22, 128.15, 127.58, 126.76, 125.50, 120.12,116.30, 109.62, 20.34; IR (KBr, cm -1 ): 2924, 2855, 2214, 1566, 1470, 1424,1253, 1094, 1027, 791; MS(EI) (m / z): 255.43 [(M+1) + ] (100%); Elemental analysis theoretical value C 15 H 11 ClN2 (%): C, 70.73; H, 4.35; N, 11.00; Found: C, 70.72; H, 4.35; N,11.08.

[0120] Compound number: 3q

[0121] (Z)-α-(m-toluimido)-o-chlorophenylacetonitrile

[0122] (Z)-2-chloro-N-(m-tolyl)benzimidoyl cyanide (3q)

[0123]

[0124] Melting point 76.4-77.2 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):7.76 (d, J = 7.2 Hz, 1H), 7.49 (d, 1H, J = 8.4 Hz), 7.45 (t, J = 7.8 Hz, 1H),7.39 (t, J = 7.2 Hz, 1H), 7.35 (t, 1H, J = 8.4 Hz), 7.14 (d, J = 7.2 Hz, 1H),7.031 (d, 2H, J = 5.4 Hz), 2.41 (s, 3H); 13 C-NMR (CDCl3, 150 MHz) δ ( ppm):148.61, 139.37, 137.99, 133.27, 133.22, 132.61, 131.23, 130.98, 129.23,128.65, 127.39, 120.94, 117.21, 111.11, 21.44; IR (KBr, cm -1 ): 3020, 2918,2214, 1591, 1480, 1431, 1296, 1067, 758; MS(EI) (m / z): 255.48 [(M+1) + ](100%); Elemental analysis theoretical value C 15 H 11 ClN2 (%): C, 70.73; H, 4.35; N, 11.00; Found: C, 70.74; H, 4.38; N, 11.02.

[0125] Compound number: 3r

[0126] (Z)-α-(o-Toluylimino)-4-chlorophenylacetonitrile

[0127] (Z)-4-chloro-N-(o-tolyl)benzimidoyl cyanide (3r)

[0128]

[0129] Melting point 101.0-101.6 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ( ppm ): 8.10 (s, 2H), 7.52 (s, 2H), 7.29 (s, 2H), 7.23 (s, 1H) 7.03 (s, 1H),2.27 (s, 3H); 13 C-NMR (CDCl3, 150 MHz) δ ( ppm IR (KBr, cm -1 ): 3016, 2907, 2213, 1591, 1561, 1487, 1402, 1270, 1094,837; MS(EI) (m / z): 255.38 [(M+1) +] (100%); Elemental analysis theoretical value C 15 H 11 ClN2 (%): C, 70.73; H, 4.35; N, 11.00; Found: C, 70.74; H, 4.36; N, 11.05.

[0130] Compound number: 3s

[0131] (Z)-α-(p-Anisimido)-2-chlorophenylacetonitrile

[0132] (Z)-2-chloro-N-(4-methoxyphenyl)benzimidoyl cyanide (3s)

[0133]

[0134] Melting point 66.0-66.9 o C (petroleum ether / dichloromethane); 1 H-NMR (CDCl3, 600 MHz) δ ( ppm ):7.76 (d, J = 7.2 Hz , 1H, ), 7.50 (s, J = 7.8 Hz, 1H), 7.46 (t, J = 7.8 Hz,1H), 7.41 (t, J = 7.8 Hz, 3H), 7.01 (d, J = 7.8 Hz, 2H), 3.87 (s, 3H); 13 C-NMR (CDCl3, 150 MHz) δ ( ppm IR (KBr, cm -1 ): 2931,2837, 2208, 1605, 1569, 1502, 1464, 1254, 1069, 833; MS(EI) (m / z): 271.40 [(M+1) + ] (100%); Elemental analysis theoretical value C 15 H 11 ClN2O (%): C, 66.55; H, 4.10; N, 10.35; Found: C, 66.52; H, 4.14; N, 10.38.

[0135] 3. Single crystal data of (Z)-α-(p-methoxyphenylimino)-p-bromophenylacetonitrile (3a)

[0136] The single crystal data of (Z)-α-(p-methoxyphenylimino)-p-bromophenylacetonitrile (3a) are as follows:

[0137] Compound 3a

[0138] Molecular formula C 15 H 11 BrN2O

[0139] Molecular weight 122.94

[0140] Test temperature 296(2) K

[0141] Wavelength 0.71073 A

[0142] Unit cell space group monoclinic, P2(1) / c

[0143] Unit cell three-dimensional a = 4.0093(9) A alpha = 90 deg.

[0144] b = 28.858(6) A beta = 98.450(3) deg.

[0145] c = 11.752(3) A gamma = 90 deg.

[0146] Unit cell volume 1344.9(5) A^3

[0147] Number of molecules in the unit cell, unit cell density 17, 2.580 Mg / m^3

[0148] Absorption coefficient 12.721 mm^-1

[0149] The number of electrons in the unit cell is 969

[0150] Crystal volume 0.35×0.33×0.30 mm

[0151] Data was collected over an angular range of 1.41 to 27.55 deg.

[0152] Diffraction index range: -5<=h<=5, -34<=k<=37, -15<=l<=14

[0153] Diffraction points collected 11826 / 3104 [R(int) = 0.0407]

[0154] Angular integrity = 27.55 99.9 %

[0155] Refinement method Full-matrix least-squares on F^2

[0156] Data Restriction Parameters 3104 / 0 / 173

[0157] GOOF value based on F2 is 1.035

[0158] The residual factor R value for the observable diffraction point is R1 = 0.0374, wR2 = 0.0848

[0159] The residual factor R value for all diffraction points is R1 = 0.0601, wR2 = 0.0929

[0160] The peak and valley values of the residual electron density after refinement are 0.358 and -0.376 eA^-3.

Claims

1. A method for preparing an α-aryliminoaryl acetonitrile derivative, characterized in that: The steps include: (1) Using ethanol as solvent, aromatic aldehyde and aromatic amine are mixed and reacted to form Schiff base compounds; (2) Cesium carbonate is used as a base, anhydrous N,N-dimethylformamide is used as a solvent, and malononitrile is used as a cyanide source. The mixture is mixed with the Schiff base compound generated in step (1), heated to 90-100° C., and reacted for 7-8 hours to obtain an α-aryliminoaryl acetonitrile derivative; The aromatic aldehyde is thiophene-3-carboxaldehyde or 1-naphthaldehyde or a compound represented by formula I, Ⅰ In Formula I, R 1 is H or 4-Cl, 4-Br, 4-Me, 2-MeO, 3-MeO, 2-Cl, 3-Cl, 3 - PhO - 4 - F; The structure of the aromatic amine is shown in Formula I, Ⅱ In formula II, R 2 is H, 4-MeO, 4-Br, 4-Cl, 2-Me or 3-Me.

2. The preparation method according to claim 1, characterized in that The molar ratio of the aromatic aldehyde to the aromatic amine is 1:

1.

3. The preparation method according to claim 1, characterized in that The molar ratio of the cesium carbonate to malononitrile is 1:

1.

4. The preparation method according to claim 1, characterized in that The molar ratio of the aromatic aldehyde to malononitrile is 4:5.

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