WO2012122854A1 - Asymmetric (α-diimine) nickel complex catalyst and preparation method and use thereof - Google Patents

Abstract

Disclosed in the present invention are an asymmetric (α-diimine) nickel complex catalyst and preparation method and use thereof. The complex is as shown in formula I, wherein R^l is a diphenylmethyl, R² is methyl or diphenylmethyl, R³ is methyl, ethyl, isopropyl, diphenylmethyl or halogen, R⁴ is an alkyl with a total carbon atom number of 1-3, R⁵ is hydrogen or an alkyl with a total carbon atom number with 1-3, and X is chlorine or bromine. The preparation method is: under oxygen free conditions, reacting a ligand with (DME)NiBr₂ or NiCl₂·4H₂0 to obtain the product. The present invention synthesizes an asymmetric α-diimine ligand and metal nickel complex; the complex can catalyse ethylene polymerization well to obtain a high molecular weight polymer under the action of cocatalysts diethylaluminium chloride, methylaluminoxane or modified methylaluminoxane, and at the same time, its activity is very high: the highest activity can be l0⁷g·mol^-1(M)·h^-1. Thus it is likely to have a wide application in industry.

Description

 Asymmetric PC diimine nickel complex catalyst and preparation method and application thereof

 The invention relates to an asymmetric α-diimine nickel complex catalyst and a preparation method and application thereof.

Background technique

 As the fastest growing, most productive, and versatile synthetic resin, polyethylene is widely used in many fields such as industrial, agricultural, military, medical, and daily life. Currently, industrialized polyethylene catalysts are Ziegler-Natta type catalysts (DE Pat 889229 (1953); IT Pat 536899 (1955) Wo P IT Pat 545332 (1956); Chem. Rev., 2000, 100, 1169 and related to this special edition. Literature, Phillips type catalysts (Belg. Pat. 530617 (1955); Chem. Rev. 1996, 96, 3327) and metallocene-type catalysts (W. Kaminsky, Metalorganic Catalysts for Synthesis and Polymerization, Berlin: Springer, 1999), and A highly efficient ethylene oligomerization and polymerization catalyst for the late transition metal complex type developed in recent years.

 Nickel complex catalyzed ethylene oligomerization (SHOP process) is a epoch-making contribution to the transition metal catalyzed ethylene reaction in the 1980s. Based on the large-scale production of α-olefins, the development of the chemical industry has been greatly promoted. Its structure is shown in the following figure (Angew. Chem., Int. Ed. Engl. 1978, 17, 466-467; Angew. Chem., Int. Ed. Engl. 1983, 22, 503; J. Chem. Soc, Chem Commun. 1994, 2203-2204):

 In 1995, Brookhart's research group reported the polymerization of ethylene catalyzed by α-imine complexed nickel and palladium complexes (J. Am. Chem. Soc, 1995, 117, 6414) to obtain high molecular weight, highly branched polyethylene. The structure is as follows:

2

 In the past few years, our group has been working on ethylene oligomerization and polymerization catalysts and catalytic processes, and has researched and developed ethylene oligomerization catalysts for many types of nickel complexes.

Among them, 4,5-diazepine-9-one benzoyl hydrazide nickel compound can better catalyze ethylene oligomerization and polymerization (Applied Catalysis A: General. 2003, 246, 11).

R ¹ = R ² = H, N0 ₂

 In the case of the designed and synthesized mononuclear and dinuclear pyridoimine nickel complexes, branched polyethylene was obtained by ethylene polymerization catalysis, and the nuclear chain study confirmed that the branched chain was a butyl group (J. Organomet. Chem., 2005, 690, 1570 and J. Organo 1739),

In addition, we designed and synthesized the 2-benzimidazole-1, 10-phenanthroline nickel complex to catalyze the oligomerization of ethylene to U x lo mol - ¹ '!!- ¹ (Eur. J. Inorg. Chem. 2007 , 3816).

R ¹ =H, Me X=CI, Br

R ² =H, Me, Et, /-Pr, Bn

 In the past few years, the inventors have developed a number of patents for nickel complex catalysts in the study of ethylene oligomerization and polymerization catalysts and catalytic processes: Chinese patent ZL 00 1 21033.5, application date July 17, 2000, authorization notice Japanese 2003.1.8; Chinese Patent Application No. 01118455.8, Application Date May 31, 2001; Chinese Patent ZL 01 1 20214.9, Application Date: July 6, 2001, Authorized Announcement Date 2004.7.7; Chinese Patent Application No. 01120554.7, Application date July 20, 2001; Chinese patent ZL 02 1 18523.9, application date April 26, 2002, authorization announcement date 2004.12.22; Chinese patent ZL 02 1 23213.X, application date June 12, 2002 Authorization Announcement Date 2003.11.19; Chinese Patent Application No. 03137727.0, Application Date June 23, 2003; Chinese Patent Application No. 03148378.X, Application Date July 2, 2003; Chinese Patent Application No. 03154463.0, Application Date October 2003 8th; Chinese patent application number

200410086284.7 Application Date October 29, 2004; Chinese Patent Application No. 200410081711.2 Application Date December 30, 2004; Chinese Patent Application No. 200710119281.2 Application Date July 19, 2007. The results of the late transition metal olefin polymerization catalysts over the past decade have shown many advantages over metallocene catalysts (simplified synthesis, low cost, and good stability), and their structures are also easily modified to regulate the product ( Polymers and oligomers) Structure and molecular weight. Therefore, the design of a large sterically hindered catalyst and the use of the catalyst to synthesize a polyolefin material with new properties are instructive for the industrialization of the catalyst.

Invention disclosure

 The object of the present invention is to provide an asymmetric α-diimine nickel complex catalyst and a preparation method and application thereof. The asymmetry provided by the present invention is as shown in Formula I:

In the formula I, R ¹ is a diphenylmethyl group, R ² is a methyl group or a diphenylmethyl group, R ³ is a methyl group, an ethyl group, an isopropyl group, a diphenylmethyl group or a halogen, and R ⁴ is a carbon atom. A total of 1-3 alkyl groups, R ⁵ is hydrogen or an alkyl group having a total of 1-3 carbon atoms, and X is chlorine or bromine.

Specifically, the R ¹ dibenzyl group; R ² is a diphenylmethyl group; R ³ is a methyl group, an isopropyl group, a diphenylmethyl group or a halogen, specifically a methyl group; R ⁴ is a methyl group, B Or isopropyl; R ⁵ is methyl or hydrogen; X is bromine.

 More specifically, the asymmetric alpha diimine nickel complex of the above formula I is selected from any of the following C1-C19 complexes:

CI : R = R ² = CHPh ₂ ; R ³ = Me; R ⁴ = Me; R ⁵ = H; X is Br.

C2: R = R ² = CHPh ₂ ; R ³ = Me; R ⁴ = Et; R ⁵ = H; X is Br.

C3: R = R ² = CHPh ₂ ; R ³ = Me; R ⁴ = / -Pr; R ⁵ = H; X is Br.

C4: R = R ² = CHPh ₂ ; R ³ = Me; R ⁴ = Me; R ⁵ = Me _; X is Br.

C5: R = R ² = CHPh ₂ ; ³ = Me; R ⁴ = Et; R ⁵ = Me; X is Br.

C6: R = R ³ = CHPh ₂ ; R ² = Me; R ⁴ = Me; R ⁵ = H; X is Br.

C7: R = R ³ = CHPh ₂ ; R ² = Me; R ⁴ = Et; R ⁵ = H; X is Br.

C8: R = R ³ = CHPh ₂ ; R ² = Me; R ⁴ = / -Pr; R ⁵ = H _; X is Br.

C9: R = R ³ = CHPh ₂ ; R ² = Me; R ⁴ = Me; R ⁵ = Me _; X is Br.

CIO: R ¹ = R = CHPh ₂ ; R ⁴ = Me ; R ^4: = Et; R ⁵ = Me; X is Br.

Cl l : R ¹ = R ³ = CHPh ₂ ; R ² = Me ; R = Me; R ⁵ = H; X is Cl.

C12: R ¹ = R ³ = CHPh ₂ ; ² = Me ; R = Et; R ⁵ = H; X is Cl.

C13: R ¹ = R ³ = CHPh ₂ ; R ² = Me ; R = / -Pr; R ⁵ = H _; X is Cl.

C14: R ¹ = R ³ = CHPh ₂ ; R ² = Me ; R = Me; R ⁵ = Me _; X is Cl.

C15: R ^L = R ³ = = CHPh ₂ ; R ⁴ = Me: , R ⁴ = = Et; R ⁵ = Me; X is Cl.

C16: R ¹ = CHPh ₂ ; R ² = R ³ = Me; R ^4: = Et; R ⁵ = H; X is Br.

C17: R ¹ = CHPh ₂ ; R ² = R ³ = Me; R ⁴ = Et; R ⁵ = H; X is Cl. C18: R = R ² = CHPh ₂ ; R ³ = / -Pr; R ⁴ = Me; R ⁵ = H; X is Br.

C19: R = R ² = CHPh ₂ ; R ³ = /-Pr; R ⁴ = Me; R ⁵ = H; X is Cl.

The method for preparing the above complex provided by the present invention comprises the steps of: reacting a compound of the formula V with (DME) ^^81~ ₂ or ^3⁄4 1 ₂ 413⁄40 in a solvent under an inert atmosphere, the reaction The complex shown in Formula I is obtained.

In this method, the molar ratio of the compound of the formula V to (DME) MBr ₂ or MC1 ₂ 4H ₂ 0 is 1: 1-1.1, specifically 1:1; the solvent is selected from the group consisting of dichloromethane, ethanol and methanol. At least one, specifically dichloromethane; the amount of the solvent is based on the total dissolved reactant; in the reaction step, the temperature is 10-30 ° C, specifically 20 ° C, the time is 8-12 hours, Specifically, it is 8 hours; the inert atmosphere is a nitrogen atmosphere. (DME) In MBr ₂ , DME is ethylene glycol dimethyl ether, and the Chinese name of (DME) MBr ₂ is dimethyl ethane ether bromide, which is commercially available from various publicly available sources.

 The ligand compound provided by the present invention,

 (Formula V)

In the formula V, R ¹ is a diphenylmethyl group, R ² is a methyl group or a diphenylmethyl group, R ³ is a methyl group, an ethyl group, an isopropyl group, a diphenylmethyl group or a halogen, and R ⁴ is a carbon atom. A total of 1-3 alkyl groups, and R ⁵ is hydrogen or an alkyl group having a total of 1-3 carbon atoms.

Specifically, in the formula V, R ¹ is a dibenzyl group; R ² is a diphenylmethyl group; and R ³ is a methyl group, an ethyl group, an isopropyl group, a diphenylmethyl group or a halogen, specifically a methyl group. ; R ⁴ is a methyl group; and R ⁵ is a methyl group.

 The process for the preparation of the compound of the formula V provided by the present invention comprises the steps of: the 2-imine fluorenone of the formula III and the alkyl group having a total of 1-3 carbon atoms represented by the formula IV in the presence of a catalyst. The substituted aniline is subjected to a reflux reaction in a solvent, and the reaction is completed to obtain the compound of the formula V;

(Formula III) R ¹ is a diphenylmethyl group, R ² is a methyl group or a diphenylmethyl group; and R ³ is a methyl group, an ethyl group, an isopropyl group or a diphenylmethyl halide;

(Formula IV)

R ⁴ is an alkyl group having a total of 1 to 3 carbon atoms; and R ⁵ is hydrogen or an alkyl group having a total of 1 to 3 carbon atoms.

 In the step 2) of the above method, the alkyl-substituted aniline having a total of 1 to 3 carbon atoms represented by the formula IV is at least one selected from the group consisting of methyl, ethyl and isopropyl, specifically methyl; The solvent is selected from at least one of toluene, absolute ethanol and acetic acid, specifically toluene; the catalyst is selected from at least one of p-toluenesulfonic acid and acetic acid, specifically p-toluenesulfonic acid; the catalyst, formula III The ratio of the 2-imine fluorenone, the alkyl substituted aniline having a total of 1-3 carbon atoms represented by the formula IV to the solvent is 0.4-0.6 mmol: l-1.2 mmol: l. l-1.4 mmol: 30-60 ml, specifically 0.5-0.6 mmol: 1.1-1.2 mmol: 1.1-1.3 mmol: 50-60 ml, 0.5-0.6 mmol: 1.1-1.2 mmol: 1.2-1.3 mmol: 50-60 ml, 0.5-0.6 mmol: 1.1 -1.2 mmol: 1.1-1.3 mmol: 53-58 mK 0.5-0.6 mmol: 1.1-1.2 mmol: 1.2-1.3 mmol: 53-58 ml, specifically 0.5 mmol: lmmol: l.lmol: 50 ml; in the reaction step, The time is 8-10 hours, specifically 8 hours.

 The above process for preparing the compound of the formula V further comprises the steps of: dissolving the product after completion of the reaction in methylene chloride, and performing column chromatography on a basic alumina or silica gel column to have a volume ratio of 15: A mixed solvent of petroleum ether and ethyl acetate was eluted as a eluent, and the eluted fraction was detected by thin layer chromatography, and the third fraction was collected, and the solvent was removed to obtain a purified compound of the formula V.

 Further, in the above method, the 2-imine fluorenone of the formula III can be obtained by the following method: in the presence of a catalyst, the anthraquinone is reacted with the compound of the formula II in a solvent, and the reaction is carried out. Finishing to obtain 2-imine fluorenone of formula III;

 (Formula II)

In the formula II, R ¹ is a diphenylmethyl group, R ² is a methyl group or a diphenylmethyl group, specifically a diphenylmethyl group; and R ³ is a methyl group, an ethyl group, an isopropyl group, a diphenylmethyl group or a halogen, specifically a methyl group; the solvent is selected from at least one of toluene, absolute ethanol and acetic acid, specifically toluene; the catalyst is selected from at least one of p-toluenesulfonic acid and acetic acid, specifically p-toluene a sulfonic acid; a catalyst, an anthracenedione, a compound of the formula II and the solvent The ratio is 0.1-0.12mmol: l-1.2mmol: l. l-1.4mmol: 30-60ml, specifically O. lmmol: lmmol: l. lmmol: 50ml; in the reaction step, the time is 2-4 hours , specifically for 2 hours. In order to obtain the purified 2-imine fluorenone of the formula III, the following treatment can also be carried out: the product after completion of the reaction is dissolved in dichloromethane and subjected to column chromatography on a silica gel column to have a volume ratio of 10:1. A mixed solvent of petroleum ether and ethyl acetate is eluted as a eluent, and the eluted fraction is detected by thin layer chromatography, and the second fraction is collected, and the solvent is removed to obtain a purified 2-imine oxime represented by Formula III. ketone.

 The catalyst composition for catalyzing ethylene polymerization provided by the present invention comprises: a complex represented by Formula I as a main catalyst and a cocatalyst; wherein the cocatalyst is selected from the group consisting of aluminoxane, alkyl aluminum and alkyl chloride At least one of aluminum.

 In the above catalyst composition, the aluminoxane is methylaluminoxane (MAO), modified methyl aluminoxane

(MMAO), ethylaluminoxane or isobutylaluminoxane; the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum or tri-n-octyl aluminum; The alkyl aluminum chloride is diethyl aluminum chloride, sesquichlorodiethylaluminum or ethyl aluminum dichloride;

 The molar ratio of the metal aluminum in the aluminoxane to the metal nickel in the main catalyst is 1000-4000: 1, specifically 2000-3000: 1, specifically 1000-3000: 1, 1000-2000: 1 , 2000-4000: 1 or

 3000-4000: 1 , more specifically 3000: 1; the molar ratio of the metal aluminum in the aluminum alkyl to the metal nickel in the main catalyst is 100-600: 1, specifically 200: 1; The molar ratio of the metal aluminum in the alkyl aluminum to the metal nickel in the main catalyst is 200-1000: 1, specifically 200-800: 1, 200-600: 1, 200-400: 1, 400- 1000: 1, 400-800: 1, 400-600: 1, 600-1000: 1, 600-800: 1 or 800-1000: 1, specifically 500-700: 1, more specifically 600: 1.

 The method for producing polyethylene provided by the present invention comprises the steps of: catalyzing the polymerization of ethylene under the conditions of using the complex of the formula I or the catalyst composition as a catalyst, and the reaction is completed to obtain the polyethylene.

 In the method, in the polymerization step, the temperature is 20-60 ° C, specifically 20-40 ° C or 40-60 ° C, specifically 20 ° C, the pressure is 0.1-10 MPa, specifically 1-3 MPa, the time is 5-120 minutes, specifically 5-60 minutes, 5-20 minutes, 5-30 minutes, 10-60 minutes, 10-30 minutes, 10-20 minutes, 20-60 minutes or 20-30 Minutes, specifically 30 minutes; the solvent is selected from at least one of toluene, dichloromethane and hexane, specifically toluene.

 The reaction scheme for preparing the complex represented by the formula I and the ligand represented by the formula V provided by the above invention is shown in Fig. 1.

DRAWINGS

 Figure 1 is a reaction flow diagram for preparing the complexes and ligands of the present invention;

 2 is a schematic view showing the crystal structure of the complex C4;

 Figure 3 is a schematic view showing the crystal structure of the complex C5;

 Figure 4 is a schematic view showing the crystal structure of the complex C8;

 Figure 5 is a schematic view showing the crystal structure of the complex C10;

Figure 6 is a schematic view showing the crystal structure of the complex C14; The best way to implement the invention

 The invention is further illustrated by the following specific examples, but the invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The materials are commercially available from the public unless otherwise stated. The modified methylaluminoxane MMAO used in the following examples was purchased from AKZO NOBOBEL, a 1.93 mol/L heptane solution. The molecular weight of the product polyethylene obtained in the ethylene polymerization example was measured by a conventional GPC method. Polymerization activity = polymer yield / catalyst amount · time.

The 2-(2,6-diphenylmethyl-4-methylanilino)fluorenone used in the following examples can be obtained by the following method: 2,6-diphenylmethyl-4-methyl A solution of p-toluenesulfonic acid (0.30 g, 1.74 mmol) in p-toluenesulfonic acid was added to a solution of aniline (7.5 g, 17.1 mmol) and oxadione (3.0 g, 16.5 mmol) in toluene (150 mL). The solvent was removed, and the residue was subjected to silica gel column chromatography using a mixed solvent of dichloromethane and petroleum ether in a volume ratio of 1.5:1. The eluted fraction was measured by a thin layer of silica gel plate, and the developing solvent was a volume of petroleum ether and ethyl acetate. The mixture was collected in a ratio of 10:1, and the third fraction was collected, and the solvent was removed to give an orange-yellow solid. Yield: 26%. Melting point: 222-223 °C. The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3025.9 (w), 1722.6 (m), 1649.9 (m), 1595.3 (m), 1491.5 (m), 1446.6 (m), 1274.4 (w) , 1026.4 (m), 694.7 (vs). 1H MR (400 MHz, CDC1 ₃ , TMS): δ 8.02 (t, J=6.56, 2H), 7.71 (m, 2H), 7.26-7.22 (m, 4H) , 7.18(d, J=6.98, 2H), 7.05(d, 5H), 6.86(d, 4H), 6.79(s, 2H), 6.60(t, 4H), 6.43(t, 2H), 6.14(d , J=7.08, 1H), 5.43(s, 2H), 2.26(s, 3H). ¹³ C NMR (100 MHz, CDC1 ₃ , TMS): δ 189.91, 162.5, 146.08, 143.11, 142.61, 141.91, 133.36, 131.94, 131.89, 129.83, 129.59, 128.84, 128.54, 128.29, 127.93, 127.13, 126.33, 125.64, 124.06, 121.67, 52.29, 21.67. Elemental analysis: C ₄₅ H ₃₃ NO (603.75) Theoretical value: C 89.52, H 5.51, N 2.32. Experimental values: C 89.22, H 5.77, N 1.99.

The 2-(l-(2,4-diphenylmethyl-6-methylanilino)fluorenone used can be prepared as follows: in 2,4-diphenylmethyl-6-methylaniline ( 1.30 g, 2.96 mmol) and anthraquinone (0.53 g, 2.91 mmol) in toluene (100 mL) were added to a solution of (0.1 g, 0.29 mmol) of p-toluenesulfonic acid, and refluxed for 3 h. The mixture was subjected to silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 10:1, and the eluted fraction was detected by a thin layer of silica gel plate. The developing solvent was 10:1, and the second fraction was collected to remove the solvent. Yield: 47%. Melting point: 98-99 ° C. The structure confirmed data is as follows: FT-IR (; KBr, cm" ¹ ): 3056.2 (w) _: 3023.6 (w), 1728.3 (s ), 1651.9(m), 1596.5(m), 1492.3 (m), 1443.3 (m), 1274.2(m), 1223.5(m), 1073.6(m), 1025.9(s), 909.5(m), 829. l (m), 805.0(s), 740.9(s), 696.3(vs). 1H NMR (400 MHz, CDC1 ₃ , TMS): 58.06 (t, J = 6.81, 2H), 7.85 (d, J = 8.34, 1H), 7.74(t, J=7.54, 1H), 7.32-7.17(m, 7H), 7.13-7.07(m, 7H), 6.95(d, J=7.42, 2H), 6.91(s, 1H), 6.77(d, J=7.63, 2H), 6.68(s, 1H), 6.4 l(t, J =6.36, 3H), 6.19(t, J=7.39, 1H), 5.54(s, 1H), 5.50(s, 1H), 1.98(s, 3H) ¹³ C NMR (100 MHz, CDC1 ₃ , TMS): δ 189.84, 161.59, 146.75, 144.28, 142.95, 142.69, 141.74, 139.68, 132.95, 131.94, 130.51, 130.44, 129.82, 129.49, 129.42, 129.09, 128.96, 128.31, 128.02, 127.54, 126.31, 126.08, 125.14, 124.59, 122.93 , 121.77, 56.42, 52.57, 17.82. Elemental analysis: C ₄₅ H ₃₃ NO (603.75) Theoretical value: C 89.52, H 5.51, N 2.32. Found: C 89.77, H 5.61, N 2.04.

The 2-(2-diphenylmethyl-4,6-dimethylanilino)fluorenone used can be prepared as follows: in 2-diphenylmethyl-4,6-dimethylaniline (1.64 g, 5.71 mmol) and anthraquinone (1.00 g, 5.49 mmol) in toluene (100 mL) A catalytic amount (0.11 g, 0.64 mmol) of p-toluenesulfonic acid was added to the solution, and the reaction was refluxed for 2 h. The solvent was removed, and the residue was subjected to silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1. The eluted fraction was detected by a thin layer of silica gel plate, the third fraction was collected, and the solvent was removed to obtain an orange. Red solid. Yield: 61%. Melting point: 185-186. C. The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3028.9 (w), 2912. l(w), 1718.7 (vs), 1644.8 (s), 1596.7 (s), 1488.4 (m), 1445.8 ( m), 1273.8 (s), 1214.6 (m), 1150.6 (m), 1072.5 (m), 1023.5 (s), 906.5 (m), 829.0 (s), 773.5 (vs), 741.7 (s), 693.0 ( 1H NMR (400 MHz, CDCls, TMS): 58.06 (d, J = 3.81, IH), 8.05 (s, IH), 7.83 (d, J = 8.36, IH), 7.23 (t, J = 7.64) , lH), 7.24(m, 3H), 7.17(t, J=6.61, lH), 7.09(d, J=7.55, 2H), 6.99(s, IH), 6.86(d, J=7.61, 2H) ), 6.70(s, IH), 6.46(m, 3H), 6.20(t, J=7.39, IH), 5.58(s, IH), 2.31(s, 3H), 2.00(s, 3H). ¹³ C NMR (100 MHz, CDC1 ₃ , TMS): 5190.01, 161.40, 145.78, 143.20,

142.71, 141.99, 133.60, 133.00, 131.94, 129.88, 129.70, 129.44, 128.90, 128.19, 128.08, 127.90, 127.58, 126.20, 125.15, 124.44, 123.02, 121.71, 52.68, 21.35, 17.68. Elemental analysis: C ₃₃ H ₂₅ NO (451.56) Theoretical value: C 87.77, H 5.58, N 3.10. Found: C 87.94, H 5.73, N 2.94. 2-(2,6-diphenylmethyl-4-isopropylaniline) fluorenone It can be prepared as follows: a solution of 2,6-diphenylmethyl-4-isopropylaniline (2.61 g, 5.6 mmol) and anthraquinone (1.0 g, 5.5 mmol) in toluene (150 mL) A catalytic amount (0.11 g) of p-toluenesulfonic acid was added thereto, and reflux reaction was carried out for 2 hours. The solvent was removed, and the residue was subjected to silica gel column chromatography using a mixed solvent of dichloromethane and petroleum ether in a volume ratio of 5:1. The elution fraction was measured by a thin layer of silica gel plate, and the developing solvent was a volume of petroleum ether and ethyl acetate. The mixture was collected in a ratio of 10:1, and the third fraction was collected, and the solvent was removed to give an orange-yellow solid. Yield: 51%. The structural confirmation data is as follows: 1H MR (400 MHz, CDCI3, TMS): δ 8.02 (t, J=6.55, 2H), 7.70 (t, J=6.40, 2H), 7.23 (t, J=7.28, 4H), 7.05-7.96 (m, 5H), 6.84 (d, 6H), 6.59 (t, J=7.45, 4H), 6.42 (t, J=7.29, 2H), 6.02 (d, J=7.10, IH), 5.44 ( s, 2H) , 2.79 (m, IH) , 1.13 (d, J = 6.84, 6H) . ¹³ C NMR (100 MHz, CDC1 ₃ , TMS): 5189.74, 162.33, 146.16, 144.27, 142.98, 142.36, 141.75 , 131.70, 131.43, 129.59, 129.33, 128.25, 127.99, 127.68, 127.43, 127.15, 126.07, 125.95, 125.37, 123.76, 121.42, 52.19, 33.48, 24.07.

 Example 1. Preparation of 1-(2,6-dimethylaniline; )-2-(2,6-diphenylbenzyl-4-methylaniline;)苊[LI] 2-(2,6- Catalyst amount (0.048) in a solution of diphenylmethyl-4-methylanilinone (0.34 g, 0.56 mmol) and 2,6-dimethylaniline (0.075 g, 0.62 mmol) in toluene (30 mL) g, 0.28 mmol) of p-toluenesulfonic acid, heated to reflux for 10 h. The solvent toluene was removed, and the residue was subjected to silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 8:1. The eluted fraction was detected by a thin layer of silica gel plate, and the second fraction was collected, and the solvent was removed to obtain an orange-yellow solid, which was 1-(2,6-dimethylaniline)-2-(2,6-diphenylbenzene). Base 4-methylaniline) 苊 [Ll]. Yield: 38%. Melting point: 211-212 ° C.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3024.6 (w), 2915.6 (w), 1735.0 (m), 1664.5 (m), 1592.7 (m), 1493.8 (s), 1441.4 (s) , 1233.3 (s), 1034.0 (s), 921.0 (m),

831.8 (m), 763.8 (vs ), 739.8 (s) 1H NMR (400 MHz, CDC1 3, TMS): δ 7.72 (d, J = 8.20, IH); 7.58 (d, J = 8.25, IH);. 7.26-7.23 (m, 5H); 7.17 (m, 4H); 7.12-7.06 (m, 5H); 6.99 (t, J=7.80, IH); 6.94 (d, J=7.49, 4H); 6.79 (s , 2H); 6.60 (t, J=7.38, 4H); 6.53 (d, J=7.12, IH); 6.42 (t, J=7.33, 2H); 6.10 (d, J=7.08, IH); 5.30 ( s, 2H); 2.27 (s, 3H), 2.21 (s, 6H). ¹³ C NMR (100 MHz, CDCI3, TMS): δ 163.58, 161.52, 149.46, 146.88, 143.43, 142.04, 140.09, 132.75, 132.38, 129.99, 129.71, 128.91, 128.81, 128.45, 128.26, 127.84, 127.60, 127.01, 126.22, 125.57, 124.96, 124.34, 123.82, 121.84, 52.40, 21.69, 18.29. Elemental analysis: C ₅₃ H ₄₂ N ₂ (706.91). Found: C, 89.77; H, 5.68; N, 4.21.

 From the above, the compound is structurally correct and is the target compound.

 Example 2 Preparation of 1-(2,6-diethylaniline; )-2-(2,6-diphenylbenzyl-4-methylaniline;)苊[L2] 2-(2,6- Catalyst amount (0.15) of diphenylmethyl-4-methylanilinone (1.06 g, 1.75 mmol) and 2,6-diethylaniline (0.29 g: 1.93 mmol) in toluene (85 mL) g, 0.87 mmol) of p-toluenesulfonic acid, heated to reflux for 10 h. The solvent toluene was removed, and the residue was subjected to silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 8:1. The eluted fraction was detected by a thin layer of silica gel plate, and the second fraction was collected, and the solvent was removed to obtain an orange-yellow solid, which was 1-(2,6-diethylaniline)-2-(2,6-diphenylbenzene). Base 4-methylaniline) 苊 [L2]. Yield: 33%. Melting point: 214-215 ° C.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3025.5 (w), 2928.4 (w), 1739.3 (m), 1672.5 (m), 1593.8 (m), 1494.0 (s), 1441.7 (vs) , 1235.0 (vs), 1036.4 (s), 920.6 (m), 831.0 (m), 762.1 (vs), 739.3 (s). 1H MR (400 MHz, CDC1 ₃ , TMS): δ 7.70 (d, J= 8.20, IH), 7.55 (d, J=8.23, IH), 7.28-7.17 (m, 10H), 7.13 (d, J=7.36, 4H), 7.95 (d, J=7.16, 5H): 6.82 (s , 2H), 6.60 (t, J=7.31, 4H), 6.53 (d, J=7.06, IH), 6.42 (t, J=7.22, 2H), 6.03 (d, J=7.04, IH), 5.66 ( s, 2H), 2.70 (m, 2H), 5.54 (m, 2H), 2.29 (s, 3H), 1.18 (t, J=7.47, 6H). ¹³ C NMR (100 MHz, CDC1 ₃ , TMS): δ 163.65, 161.81, 148.52, 146.97, 143.65, 141.95, 140.10, 132.74, 132.38, 130.82, 129.94, 129.72, 128.99, 128.71, 128.22, 127.87, 127.34, 127.02, 126.27, 126.21, 125.60, 124.40, 124.18, 122.40, 52.34 , 24.60, 21.69, 14.54. Elemental analysis: C ₅₅ H ₄₆ N ₂ (734.97) Theory: C, 89.88; H, 6.31; N, 3.81. Found: C, 89.44; H, 6.17; N, 4.03.

 From the above, the compound is structurally correct and is the target compound.

 Example 3 Preparation of 1-(2,6-diisopropylaniline)-2-(2,6-diphenylbenzyl-4-methylaniline)oxime [L3] 2-(2,6-di Catalyst amount (0.1) of a solution of diphenylmethyl-4-methylanilinone (0.80 g, 1.33 mmol) and 2,6-diisopropylaniline (0.25 g, 1.41 mmol) in toluene (70 mL) Lg, 0.64 mmol) of p-toluenesulfonic acid, heated to reflux for 8 h. The solvent toluene was removed, and the residue was subjected to silica gel column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 8:1. The eluted fraction was detected by a thin layer of silica gel plate, and the third fraction was collected, and the solvent was removed to give a pale-yellow solid, which was 1- 6-diisopropylaniline)-2-(2,6-didiphenylmethyl- 4-methylaniline) 苊 [L3]. Yield: 34%. Melting point: 228-229 °C.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3025.6 (w), 2958.4 (m), 1737.6 (s), 1650.8 (m), 1592.4 (s), 1493.0 (s), 1442.5 (s) , 1238.8 (vs), 1039.0 (s), 927.1 (m), 829.6 (m), 764.1 (s), 744.1 (s). 1H NMR (400 MHz, CDC1 ₃ , TMS): δ 7.67 (d, J= 8.22, IH), 7.51 (d, J=8.25, IH), 7.29-7.24 (m, 7H), 7.22-7.17 (m, 3H), 7.12 (d, J=7.45, 4H), 6.94-6.88 (m , 5,,,,,, (m, 2H), 2.28 (s, 3H), 1.29 (d, J=7.05, 6H), 1.02 (d, J=6.78, 6H). ¹³ C NMR (100 MHz, CDCI3, TMS): δ 163.78, 162.22, 147.28, 147.01, 143.77, 141.85, 140.13, 135.86, 132.75, 132.44, 129.90, 129.72, 129.02, 128.72, 128.18, 127.91, 127.16, 129.79, 126.17, 125.61, . 124.61, 124.46, 123.70, 123.01, 52.27, 28.63, 24.39, 23.87, 21.67 elemental _{analysis: C 57 H 5 oN 2 (} 763.02) theory: C, 89.72; H, 6.60 ; N, 3.67 Found:. C, 89.33; H, 6.80; N, 3.44.

 From the above, the compound is structurally correct and is the target compound.

 Example 4 Preparation of 1-(2,4,6-trimethylaniline)-2-(2,6-diphenylmethyl-4-methylaniline)oxime [L4] 2-(2,6- Amount of catalyst added to a solution of diphenylmethyl-4-methylanilinone (0.62 g, 1.03 mmol) and 2,4,6-trimethylaniline (0.15 g, 1.11 mmol) in toluene (50 mL) (0.09 g, 0.52 mmol) of p-toluenesulfonic acid, heated to reflux for 8 h. The solvent toluene was removed, and the residue was subjected to silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 8:1. The eluted fraction was detected by a thin layer of silica gel plate, and the third fraction was collected, and the solvent was removed to obtain a pale yellow solid, which was 1-(2,4,6-trimethylaniline)-2-(2,6-di. Benzyl-4-methylaniline)苊[L4]. Yield: 30%. Melting point: 231-232 °C.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3025.9 (w), 2914.7 (m), 1737.3 (s), 1664.7 (m), 1594.4 (m), 1493.2 (s), 1441.4 (s) , 1235.2 (vs), 1036.8 (s), 918.6 (m), 837.0 (m), 765.8 (s), 738.8 (s). 1H MR (400 MHz, CDC1 ₃ , TMS): δ 7.71 (d, J= 8.22, IH), 7.57 (d, J=8.20, IH), 7.29-7.22 (m, 5H), 7.19-7.15 (m, 2H), 7.11 (d, J=7.46, 4H), 6.99 (m, 3H) ), 6.93 (d, J=7.55, 4H), 6.79 (s, 2H), 6.60 (m, 5H), 6.42 (t, J=7.22, 2H), 6.10 (d, J=7.13, IH), 5.61 (s, 2H), 2.38 (s, 3H), 2.27 (s, 3H), 2.17 (s, 6H). ¹³ C NMR (100 MHz, CDC1 ₃ , TMS): δ 163.58, 161.63, 146.88, 143.38, 142.01 , 140.02, 132.96, 132.64, 132.35,

129.95, 129.67, 129.11, 128.84, 128.63, 128.21, 128.05, 127.79, 127.54, 126.92, 126.16, 125.50, 124.67, 124.23, 121.81, 52.33, 21.65, 21.05, 18.17. Elemental analysis: C ₅₄ H ₄₄ N ₂ (720.94) Theoretical values: C, 89.96; H, 6.15; N, 3.89. Found: C, 89.55; H, 5.98; N, 4.11.

 From the above, the compound is structurally correct and is the target compound.

 Example 5 Preparation of 1-(2,6-diethyl-4-methylaniline)-2-(2,6-diphenylmethyl-4-methylaniline)

[L5]

 2-(2,6-Diphenylmethyl-4-methylaniline)fluorenone (1.09 g, 1.81 mmol) and P 2,6-diethyl-4-methylaniline (0.32 g, 1.96 mmol) A solution of the catalyst (0.16 g, 0.93 mmol) of p-toluenesulfonic acid was added to a solution of toluene (90 mL) and heated to reflux for 8 h. The solvent toluene was removed, and the residue was subjected to silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 8:1. The eluted fraction was detected by a thin layer of silica gel plate, and the third fraction was collected, and the solvent was removed to obtain an orange-yellow solid, which was 1- 6-diethyl-4-methylaniline -2-(2,6-di-di) Benzyl-4-methylaniline) 苊 [L5]. Yield: 31%. Melting point: 218-219 °C.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3024.2 (w), 2912.9 (w), 1738.3 (m), 1660.2 (m), 1594.5 (m), 1493.84 (s), 1442.0 (vs) , 1234.9 (vs), 1035.6 (s), 917.9 (m), 834.1 (m), 767.2 (s), 740.9 (s). 1H NMR (400 MHz, CDC1 ₃ , TMS): δ 7.69 (d, J= 8.25,

IH), 7.53 (d, J=8.28, IH), 7.26-7.33 (m, 5H), 7.17 (m, 2H), 7.11 (d, J=7.56, 4H), 7.02 (s, 2H), 6.93 ( m, 5H), 6.80 (s, 2H), 6.58 (t, 5H), 6.40 (t, J=7.35, 2H), 6.01 (d, J=7.16, IH), 5.62 (s, 2H), 2.64 ( m, 2H), 2.49 (m, 2H), 2.43 (s, 3H), 2.27 (s, 3H), 1.15 (t, J=7.52, 6H). "C MR (100 MHz, CDC1 ₃ , TMS): δ 163.70, 161.96, 147.00, 145.96, 143.64, 141.95, 140.06, 133.30, 132.66, 132.39, 130.63, 129.93, 129.71, 128.95, 128.57, 128.19, 127.85, 127.30, 127.04, 126.96, 126.18, 125.56, 124.33, 122.41, 52.31, 24.57, 21.67, 21.39, 14.65. Elemental analysis: C ₅₆ H ₄₈ N ₂ (748.99) Theoretical value: C, 89.80; H, 6.46; N, 3.74. Value: C, 89.67; H, 6.33; N, 3.92.

 From the above, the compound is structurally correct and is the target compound.

 Example 6 Preparation of [1-(2,6-dimethylanilin)-2-(2,6-diphenylmethyl-4-methylaniline) hydrazine] nickel bromide (II) [complex C1]

An equimolar amount of (DME) MBr ₂ dichloromethane solution was added dropwise to the 1-(2,6-dimethylanilino)-2-(2,6-diphenylmethyl)-prepared in Example 1 at room temperature. 4-Methylaniline) in methylene chloride solution, stirred under nitrogen for 12 h, added diethyl ether, a red solid precipitated, filtered, washed with diethyl ether and dried to give a red solid, which is [1-(2,6- Dimethylaniline)-2-(2,6-diphenylmethyl-4-methylaniline) oxime] Nickel(II) bromide [complex Cl]. Yield: 83.3%.

The structural confirmation data is as follows: FT-IR(KBr, cm" ¹ ): 3025.7 (w), 2964.3 (w), 1645.1 (w), 1601.3 (m), 1580.9 (s), 1494.2 (m), 1444.1 (s) , 1292.9 (m), 1187.7 (w), 1082.2 (m), 1031.5 (m), 826.6 (m), 772.2 (vs), 747.8 (s). Elemental analysis: C ₅₃ H ₄₂ Br ₂ N ₂ M (925.42 Theoretical value: C, 68.79; H, 4.57; N, 3.03. Found: C, 68.40; H, 4.76; N, 3.31.

 From the above, the compound is structurally correct and is the target compound.

 Example 7 Preparation of [1-(2,6-diethylaniline)-2-(2,6-diphenylmethyl-4-methylaniline) oxime] nickel bromide (II) [complex C2]

An equimolar amount of (DME) MBr ₂ dichloromethane solution was added dropwise to the 1-(2,6-diethylaniline)-2-(2,6-diphenylmethyl)-prepared in Example 2 at room temperature. 4-Methylaniline) in methylene chloride solution, stirred under nitrogen for 12 h, added diethyl ether, a red solid precipitated, filtered, washed with diethyl ether and dried to give a red solid, which is [1-(2,6- Diethylaniline)-2-(2,6-diphenylbenzyl-4-methylaniline) hydrazine] nickel (II) bromide [complex C2]. Yield: 86.8%.

The structural confirmation data is as follows: FT-IR(KBr, cm" ¹ ): 3028.8 (w), 2967.9 (w), 1649.0 (w), 1629.6 (m), 1582.5 (s), 1492.7 (s), 1442.9 (s) , 1287.9 (m), 1178.6 (m), 1075.5 (m), 1029.4 (m), 827.4 (m), 768.7 (vs), 744.4 (s). Elemental analysis: C ₅₅ H ₄₆ Br ₂ N ₂ M (953.47 Theoretical value: C, 69.28; H, 4.86; N, 2.94. Experimental value: C, 68.89; H, 4.59; N, 3.13

 From the above, the compound is structurally correct and is the target compound.

 Example 8 Preparation of [1-(2,6-diisopropylaniline)-2-(2,6-diphenylmethyl-4-methylaniline) oxime] nickel bromide (II) [Mixed Object C3]

An equimolar amount of (DME) MBr ₂ dichloromethane solution was added dropwise to the 1-(2,6-diisopropylaniline)-2-(2,6-diphenylmethyl) group obtained in Example 3 at room temperature. The solution of -4-methylaniline) in methylene chloride was stirred under nitrogen for 8 h, then diethyl ether was evaporated to dryness, filtered, washed with diethyl ether and dried to give a red solid, which was [1-(2,6) -Diisopropylaniline)-2-(2,6-diphenylmethyl-4-methylaniline) oxime] Nickel(II) bromide [complex C3]. Yield: 85.9%.

The structure confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3024.0 (w), 2967.9 (m), 1646.0 (w), 1619.9 (m), 1581.6 (s), 1493.4 (s), 1444.3 (s), 1290.0 (m), 1179.9 (m), 1078.6 (w), 1036.9 (m), 828.8 (m), 769.9 (vs), 745.3 (s). Elemental analysis: C ₅₇ H ₅₀ Br ₂ N ₂ M (981.52): C, 69.75; H, 5.13; N, 2.85. Found: C, 69.57; H, 5.03; N, 3.22.

 From the above, the compound is structurally correct and is the target compound.

 Example 9 Preparation of [1-(2,4,6-trimethylaniline)-2-(2,6-diphenylbenzyl-4-methylaniline) hydrazine] nickel (II) bromide [ Complex C4]

An equimolar amount of (DME) MBr ₂ dichloromethane solution was added dropwise to the 1-(2,4,6-trimethylaniline)-2-(2,6-diphenylbenzene) obtained in Example 4 at room temperature. The solution of benzyl 4-methylaniline hydrazine in methylene chloride was stirred under nitrogen for 8 h, and diethyl ether was added to precipitated as a red solid, which was filtered, washed with diethyl ether and dried to give a red solid, which was [1-(2, 4,6-trimethylaniline)-2-(2,6-diphenylmethyl-4-methylaniline) hydrazine] nickel (II) bromide [complex C4]. Yield: 82.4%.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3025.5 (w), 2973.0 (w), 1645.4 (w), 1602.1 (m), 1585.1 (s), 1493.6 (s), 1444.1 (s) , 1294.1 (m), 1198.9 (w), 1074.9 (w), 1031.5 (m), 825.3 (m), 767.3 (vs), 742.9 (s). Elemental analysis: C ₅₄ H ₄₄ Br ₂ N ₂ M (939.44 Theoretical value: C, 69.04; H, 4.72; N, 2.98. Experimental value: C, 69.31; H, 4.51; N, 3.16.

 From the above, the compound is structurally correct and is the target compound.

 A schematic diagram of the crystal structure of the complex is shown in Fig. 2. It can be seen from the figure that the coordination structure is very similar, and the central nickel atom is N-N coordinated to form a twisted tetrahedral structure.

 Example 10 Preparation of [1-(2,6-diethyl-4-methylaniline)-2-(2,6-diphenylbenzyl-4-methylaniline) oxime] Nickel bromide ( II) [Complex C5]

An equimolar amount of (DME) MBr ₂ dichloromethane solution was added dropwise to the 1-(2,6-diethyl-4-methylaniline)-2-(2,6-di) obtained in Example 5 at room temperature. The solution of diphenylmethyl-4-methylaniline) in methylene chloride was stirred under a nitrogen atmosphere for 8 h, and diethyl ether was added to precipitated as a red solid, which was filtered, washed with diethyl ether and dried to give a red solid. (2,6-Diethyl-4-methylaniline)-2-(2,6-diphenylmethyl-4-methylaniline) oxime] Nickel(II) bromide [complex C5]. Yield: 75.0%.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3022.7 (w), 2968.4 (w), 1652.3 (m), 1621.9 (s), 1583.3 (s), 1493.8 (s), 1445.0 (s) , 1290.4 (m), 1182.4 (w), 1075.8 (w), 1030.8 (m), 829.1 (m), 770.0 (vs), 742.1 (s). Elemental analysis: C ₅₆ H ₄₈ Br ₂ N ₂ M (967.5 Theoretical value: C, 69.52; H 5.00; N, 2.90. Experimental value: C, 69.18; H, 5.14; N, 3.10.

 From the above, the compound is structurally correct and is the target compound.

 A schematic diagram of the crystal structure of the complex is shown in FIG. It can be seen from the figure that the coordination structure is very similar, and the central nickel atom is N-N coordinated to form a twisted tetrahedral structure.

Example 11 Preparation of 1-(2,6-dimethylaniline; )-2-(2,4-diphenylmethyl-6-methylaniline;)苊[L6] 2-(2,4- Catalyst (0.09 g) of diphenylmethyl-6-methylanilinone (0.68 g, 1.13 mmol) and 2,6-dimethylaniline (0.16 g, 1.32 mmol) in toluene (60 mL) g, 0.52 mmol) of p-toluenesulfonic acid, heated to reflux for 8 h. The solvent toluene was removed, and the residue was subjected to alumina column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 15:1. The eluted fraction was detected by a thin layer of silica gel plate, and the third fraction was taken, and the solvent was removed to obtain a yellow solid, which was 1- 6-dimethylaniline)-2-(2,4-diphenylmethyl-6- Methyl aniline) 苊 [L6]. Production £1

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66Z000/ZT0ZN3/X3d 1^8ΖΖΐ Z OAV The sulfonic acid was heated to reflux for 8 h. The solvent toluene was removed, and the residue was subjected to silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 15:1. The eluted fraction was detected by a thin layer of silica gel plate, and the third fraction was collected, and the solvent was removed to obtain a yellow solid, which was 1-(2,6-diisopropylaniline)-2-(2,4-diphenylene). Keto-6-methylaniline) 苊 [L8]. Yield: 27%. Melting point: 243-244 °C

The structural confirmation data is as follows: FT-IR (KBr, cm- ¹ ): 3022.7(w), 29563.0(m), 1678.7(m),

1653.4(m), 1596.7 (m), 1492.8(m), 1439.0 (m), 1277.67(w), 1248. l(m), 1187.5(w), 1078.7(w), 1032. l(m), 925.6 (m), 833. l(m), 741.3(s), 6967.7(vs). 1H MR (400 MHz, CDCls, TMS): 57.75 (d, J=8.25, IH), 7.70 (d, J=8.23 , IH), 7.35-7.19 (m, 10H),

7.16-7.05 (m, 8H), 7.00 (d, J=7.31, 2H), 6.92 (s, IH), 6.89(d, ]=7.52, 2H), 6.71(s, IH), 6.52 (d, J =7.12, IH), 6.46(t, J=7.44, 2H), 6.32 (d, J=7.16, IH), 6.24 (t, J=7.31, IH), 5.75 (s, IH), 5.52 (s, IH), 2.21 (m, IH), 2.91 (m, IH), 2.04 (s, 3H), 1.33 (d, J=6.72, 3H), 1.20 (d, J=6.76, 3H), 1.13 (d, J = 6.80, 3H), 0.86 (d, J = 6.76, 3H). ¹³ C NMR (100 MHz, CDC1 ₃ TMS): 5162.62, 161.59, 147.63, 147.33, 144.52, 143.60, 141.79, 140.43, 139.00, 135.72 _: 135.54, 133.34, 130.45, 129.97, 129.56, 129.49, 129.11, 128.75, 128.51, 128.29, 127.97, 127,56, 127.50, 126.26, 125.98, 125.26, 124.92, 124.48, 123.70, 123.46, 123.08, 123.01, 56.46, 52.55, . 28.70, 28.62, 23.91, 23.69, 23.50, 23.20, 17.70 elemental _{analysis: C "H 50 N 2 (} 763.02) theory: C, 89.72; H, 6.60 ; N, 3.67 Found:. C, 89.87; H, 6.96; N, 3.30.

 From the above, the compound is structurally correct and is the target compound.

 Example 14 Preparation of 1-(2,4,6-trimethyl-aniline)-2-(2,4-diphenylmethyl-6-methylaniline)oxime [L9] 2-(2,4 -Dibiphenylmethyl-6-methylaniline)indolone (1.03 g, 1.71 mmol) and 2,4,6-trimethylaniline

A solution of (0.25 g, 0.87 mmol) of p-toluenesulfonic acid (0.24 g, 1.78 mmol) in toluene (85 mL) was evaporated. The solvent toluene was removed, and the residue was subjected to silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 15:1. The eluted fraction was detected by a thin layer of silica gel plate, and the third fraction was collected, and the solvent was removed to obtain an orange-yellow solid, which was 1-(2,4,6-trimethyl-aniline)-2-(2,4- Dibiphenylmethyl-6-methylaniline) 苊 [L9]. Yield: 32%. Melting point: 164-165. C

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3023.5(w), 2967.6(w), 1667.4(m), 1640.8(m), 1596.7 (m), 1493.2 (m), 1441.8 (m) , 12778.4 (w), 1232.7(m), 1207.3(mw), 1075.8(m), 1032.2(m), 922.4(m), 829.6(m), 738.4(s), 696.5(vs). 1H NMR (400 MHz, CDCI3, TMS): 57.77 (d, J=8.25, IH), 7.71 (d, J=8.24, IH), 7.32-7.26 (m, 4H), 7.24-7.19 (m, 3H), 7.17-7.07 (m, 8H), 6.99 (d, J=6.69, 3H), 6.95 (s, IH), 6.89 (d, J=8.46, 3H), 6.70 (s, IH), 6.65 (d, J=7.10, IH), 6.45 (t, J=7.41, 2H), 6.37 (d, J=7.14, IH), 6.23 (t, J=7.28, IH), 5.73 (s, IH), 5.51 (s, IH), 2.38 (s, 3H), 2.24 (s, 3H), 2.04 (s, 6H). ¹³ C NMR (100 MHz, CDCI3, TMS): 5162.64, 161.46, 147.58, 146.85, 144.54, 143.50, 141.84, 140.31, 138.96 , 133.30, 132.99, 130.46, 130.04, 129.56, 129.49, 129.33, 129.16, 129.10, 129.03, 128.71, 128.51, 128.30, 127.98, 127.91, 127.46, 126.26, 125.98, 125.18, 124.97, 124.84, 124.60, 123.02, 122.13, 56.46 , 52.62, 21.05, 18.24, 17.77. Elemental analysis: C ₅₄ H ₄₄ N ₂ (720.94) Theoretical values: C, 89.96; H, 6.15; N, 3.89 . Experimental values: C, 90.11; H, 6.54; N, 2.62.

From the above, the compound is structurally correct and is the target compound. Example 15. Preparation of 1-(2,6-diethyl-4-methylaniline)-2-(2,4-diphenylmethyl-6-methylaniline) oxime [L10]

 2-(2,4-Diphenylmethyl-6-methylaniline)fluorenone (1.0 g, 1.66 mmol) and P 2,6-diethyl-4-methylaniline (0.28 g, 1.72) A solution of the catalyst (0.14 g, 0.81 mmol) of p-toluenesulfonic acid was added to a solution of toluene (80 mL). The solvent toluene was removed, and the residue was subjected to silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 15:1. The third fraction was collected by a thin layer of silica gel plate to detect the elution fraction, and the solvent was removed to obtain an orange-yellow solid, which was 1- 6-diethyl-4-methylaniline)-2-(2,4-diphenylbenzene) Methyl-6-methylaniline) 苊 [L10]. Yield: 40%. Melting point: 192-193. C

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3022.7 (w), 2967.5 (w), 1674.4 (m), 1649.3 (m), 1597.4 (m), 1492.5 (m), 1442.3 (m) , 1277.9 (w), 1233. l(w), 1205. l(w), 1076.3(m), 1030.4(m), 922.8(m), 833.3(m), 745.4(s), 697.6(vs). 1H MR (400 MHz, CDCls, TMS): 57.75 (d, J=8.17, 1H), 7.70 (d, J=8.16, 1H), 7.30-7.26 (m, 5H), 7.24-7.20 (m, 2H) , 7.18-7.09 (m, 8H), 7.04 (s, 1H), 7.00 (d, J=6.43, 3H), 6.90 (d, J=8.81, 3H), 6.71 (s, 1H), 6.63 (d, J=6.99, 1H), 6.46 (t, J=7.20, 2H), 6.34 (d, J=7.01, 1H), 6.25 (t, J=7.07, 1H), 5.75 (s, 1H), 5.51 (s , 1H), 2.70(m, 1H), 2.58-2.45 (m, 2H), 2.42 (s, 3H), 2.32 (m, 1H), 2.03 (s, 3H ), 1.23(t, J=7.40, 3H ), 1.03(t, J=7.36, 3H). ¹³ C MR (100 MHz, CDCI3, TMS): 5162.67, 161.52, 147.67, 146.05, 144.54, 143.61, 141.84, 140.34, 138.96, 133.34, 133.28, 130.84, 130.54 , 130.44, 130.00, 129.58, 129.50, 129.35, 129.11, 128.63, 128.49, 128.31, 127.98, 127.74, 127.54, 127.44, 127.31, 127.18, 126.27, 125.98, 125.23, 124.95, 123.02, 122.62, 56.48, 52.57, 24.90, 24.66 , 21.3 4, 17.74, 14.70, 13.96 Elemental _{analysis: C 56 H 48 N 2 (} 748.99) Theory: C, 89.80; H, 6.46 ; N, 3.74 Found:. C, 89.67; H, 6.33; N, 3.69.

 From the above, the compound is structurally correct and is the target compound.

 Example 16: Preparation of [1-(2,6-dimethylanilin)-2-(2,4-diphenylmethyl-6-methylaniline) oxime] nickel bromide CII) [complex C6 ]

An equimolar amount of (DME) MBr ₂ dichloromethane solution was added dropwise to the 1-(2,6-dimethylanilino)-2-(2,4-di-diphenylmethyl)-prepared in Example 11 at room temperature. 6-Methylaniline) in methylene chloride solution, stirred under nitrogen for 8 h, added diethyl ether and a red solid precipitated, filtered, washed with diethyl ether and dried to give a red solid, which is [1-(2,6- Dimethylaniline)-2-(2,4-dibiphenylmethyl-6-methylaniline)oxime] Nickel(II) bromide [complex C6]. Yield: 81.1%.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3026.0 (w), 2974.7 (w), 1643.6 (w), 1598.6 (m), 1577.5 (m), 1491.0 (m), 1447.6 (m) , 1293.4 (m), 1191.6 (m), 1032.4 (m), 826.6 (m), 776.7 (s), 744. l(s), 700.9 (vs). Elemental analysis: C ₅₃ H ₄₂ Br ₂ N ₂ M (925.42) Theoretical value: C, 68.79; H, 4.57; N, 3.03. Found: C, 68.55; H, 4.21; N, 3.27.

 From the above, the compound is structurally correct and is the target compound.

 Example 17, Preparation of [1-(2,6-diethylaniline)-2-(2,4-diphenylmethyl-6-methylaniline) oxime] nickel(II) bromide [complex C7]

An equimolar amount of (DME) MBr ₂ dichloromethane solution was added dropwise to the preparation of Example 12 at room temperature. L-(2,6-Diethylaniline)-2-(2,4-dibiphenylmethyl-6-methylaniline) in methylene chloride solution, stirred under nitrogen for 8 h, added diethyl ether A red solid precipitated, filtered, washed with diethyl ether and dried to give a red solid. Yield: 83.7%.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3023.9 (w), 2969.5 (w), 1646.0 (w), 1620.2 (m), 1580.2 (m), 1492.7 (m), 1444.3 (m) , 1294.6 (m), 1184.5 (w), 1030.9(w), 825.0(m), 774.9(s), 745.9(s), 699.5(vs). Elemental analysis: C ₅₅ H ₄₆ Br ₂ N ₂ M (953.47 Theoretical value: C, 69.28; H, 4.86; N, 2.94. Experimental value: C, 69.46; H, 4.93; N, 2.58.

 From the above, the compound is structurally correct and is the target compound.

 Example 18 Preparation of [1-(2,6-diisopropylaniline)-2-(2,4-diphenylmethyl-6-methylaniline) oxime] nickel bromide (II) [Mixed Object C8]

An equimolar amount of (DME) MBr ₂ dichloromethane solution was added dropwise to the 1-(2,6-diisopropylaniline)-2-(2,4-dibiphenylmethyl) obtained in Example 13 at room temperature. -6-Methylaniline) in methylene chloride solution, stirred under nitrogen for 8 h, added diethyl ether to precipitate a red solid, filtered, washed with diethyl ether and dried to give a red solid, which is [1-(2,6) -Diisopropylaniline)-2-(2,4-diphenylmethyl-6-methylaniline) oxime] Nickel(II) bromide [complex C8]. Yield: 85.8%.

The structure confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3023.0 (w), 2963.9 (w), 1651.0 (w), 1622.4 (m), 1581.3 (s), 1493.7 (s), 1442.0 (s) , 1293.2 (m), 1181.0 (m), 1030.7 (m), 831.9 (m), 776.2 (s), 741.8 (s), 696.5 (vs). Elemental analysis: C ₅₇ H ₅ .Br ₂ N ₂ M ( 981.52) Theoretical value: C, 69.75; H, 5.13; N, 2.85. Experimental value: C, 69.66; H, 5.21; N, 2.60.

 From the above, the compound is structurally correct and is the target compound.

 A schematic diagram of the crystal structure of the complex is shown in FIG. It can be seen from the figure that the coordination structure is very similar, and the central nickel atom is N-N coordinated to form a twisted tetrahedral structure.

 Example 19 Preparation of [1-(2,4,6-trimethylaniline)-2-(2,4-diphenylmethyl-6-methylaniline) hydrazine] nickel (II) bromide [ Complex C9]

Equimolar (DME) MBr ₂ dichloromethane solution was added dropwise to the preparation of Example 14 at room temperature.

1-(2,4,6-trimethylaniline)-2-(2,4-dibiphenylmethyl-6-methylaniline) in dichloromethane, stirred under nitrogen for 8 h, added The ether was precipitated as a red solid, filtered, washed with diethyl ether and dried to give a red solid, which was [1-(2,4,6-trimethylaniline)-2-(2,4-diphenylmethyl-6) -Methylaniline) 苊] combined with nickel (II) bromide [complex C9]. Yield: 77.9%.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3023.3 (w), 2968.6 (w), 1644.7 (w), 1619.7

(m), 1579.4(s), 1492.8 (s), 1446.4 (s), 1294.1 (m), 1200.9 (m), 1030.7 (m), 827.7 (m), 773.5 (s), 743.8 (s), 699.8 (vs). Elemental analysis: C ₅₄ H ₄₄ Br ₂ N ₂ M (939.44) Theory: C, 69.04; H, 4.72; N, 2.98. Found: C, 69.33; H, 4.87; N, 2.75

 From the above, the compound is structurally correct and is the target compound.

 Example 20 Preparation of [1-(2,6-diethyl-4-methylaniline)-2-(2,4-diphenylmethyl-6-methylaniline) oxime] Nickel bromide ( II) [Complex C10]

An equimolar amount of (DME) MBr ₂ dichloromethane solution was added dropwise to the 1-(2,6-diethyl-4-methylaniline)-2-(2,4-di) obtained in Example 15 at room temperature. Diphenylmethyl-6-methylaniline) in methylene chloride solution, in Stir under nitrogen for 8 h, add diethyl ether to precipitate a red solid, which is filtered, washed with diethyl ether and dried to give a red solid, which is [1-(2,6-diethyl-4-methylaniline)-2-(2) , 4-diphenylmethyl-6-methylaniline) 苊] nickel (II) bromide [complex C10]. Yield: 79.5%.

The structural confirmation data is as follows: FT-IR(KBr, cm" ¹ ): 3024.1 (w), 2968. l(w), 1644.7 (m), 1620.2 (m), 1580.0(s), 1492.6(s), 1451.4 ( s), 1293.4 (m), 1200.5 (m), 1030.9 (m), 827.6 (m), 774.7 (s), 744.0 (s), 699.0 (vs). Elemental analysis: C ₅₆ H ₄₈ Br ₂ N ₂ M (967.5) Theoretical value: C, 69.52; H, 5.00; N, 2.90. Experimental value: C, 69.62; H, 5.20; N, 2.67.

 From the above, the compound is structurally correct and is the target compound.

 A schematic diagram of the crystal structure of the complex is shown in FIG. It can be seen from the figure that the coordination structure is very similar, and the central nickel atom is N-N coordinated to form a twisted tetrahedral structure.

 Example 21 Preparation of [1-(2,6-dimethylanilin)-2-(2,4-diphenylmethyl-6-methylaniline) hydrazine] nickel chloride (II) [complex C1 1]

An equimolar amount of MC1 ₂ _6H ₂ dichloromethane solution was added dropwise to the 1-(2,6-dimethylanilino)-2-(2,4-di-diphenylmethyl) obtained in Example 11 at room temperature. -6-Methylaniline) in methylene chloride solution, stirred under nitrogen for 8 h, added diethyl ether as a red solid precipitated, filtered, washed with diethyl ether and dried to give a red solid, which is [1-(2,6) - dimethylaniline) -2-(2,4-dibiphenylmethyl-6-methylaniline;) hydrazine] nickel chloride (II) [complex Cl l]. Yield: 82.8%.

The structural confirmation data is as follows: FT-IR(KBr, cm" ¹ ): 3024.6 (w), 2964.8(w), 1657.6 (w), 1626.5 (m), 1578.2(s), 1493.4 (s), 1444.0 (m) , 1289.9 (m), 1 190.3 (m), 1032.9 (s), 829.4 (m), 772.7 (s), 741. l(s), 697.6 (vs). Elemental analysis: C ₅₃ H ₄₂ C1 ₂ N ₂ M (836.51) Theoretical value: C, 76.10; H, 5.06; N, 3.35. Found: C, 76.27; H, 5.22; N, 3.19.

 From the above, the compound is structurally correct and is the target compound.

 Example 22 Preparation of [1-(2,6-diethylaniline)-2-(2,4-diphenylmethyl-6-methylaniline) hydrazine] nickel chloride (II) [complex C12]

An equimolar amount of MC1 ₂ _6H ₂ dichloromethane solution was added dropwise to the 1-(2,6-diethylaniline)-2-(2,4-di-diphenylmethyl)-prepared in Example 12 at room temperature. 6-Methylaniline) in methylene chloride solution, stirred under nitrogen for 8 h, added diethyl ether to precipitate a red solid, filtered, washed with diethyl ether and dried to give a red solid, which is [1-(2,6- Diethylaniline)-2-(2,4-dibiphenylmethyl-6-methylaniline) oxime] nickel chloride (II) [complex C12]. Yield: 86.0%.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3025.9 (w), 2965.7 (w), 1659.8 (w), 1627.9

(m), 1592.3(s), 1492.9(s), 1444.8(s), 1288.8 (m), 1 184.9 (m), 1035. l(s), 827. l(m), 772.6(s), 740.4 (s), 698.0(vs). Elemental analysis: C ₅₅ H ₄₆ C1 ₂ N ₂ M (864.57) Theory: C, 76.41; H, 5.36; N, 3.24. Experimental value: C, 76.53; H, 5.59; N, 3.1 1.

 From the above, the compound is structurally correct and is the target compound.

 Example 23 Preparation of [1-(2,6-isopropylaniline)-2-(2,4-diphenylmethyl-6-methylaniline) oxime] nickel chloride (II) [complex C13]

Equimolar MC1 ₂ _6H _{2 2} dichloromethane solution was added dropwise to 1-(2,6-isopropylaniline)-2-(2,4-diphenylmethyl-6-methylaniline at room temperature In a dichloromethane solution of hydrazine, stirred under nitrogen for 8 h, added diethyl ether The red solid precipitated, filtered, washed with diethyl ether and dried to give a red solid, which was [1-(2,6-isopropylaniline)-2-(2,4-diphenylmethyl-6-methylaniline ) 苊] nickel chloride (II) [complex C13]. Yield: 72.7%. The structure confirms the data as follows: FT-IR (KBr, cm" ¹ ): 3025.1 (w), 2963.4(w), 1653.7 (w), 1624.0 (m), 1585.4(s), 1493.4 (s ), 1442.5 (s), 1289.8 (m), 1182.8 (m), 1032.3 (s), 829.8 (m), 777.3 (s), 741.9 (s), 697.4 (vs). Elemental analysis: C ₅₇ H ₅₀ Cl ₂ N ₂ Ni (892.62) Theoretical value: C, 76.70; H, 5.65; N, 3.14. Found: C, 76.88; H, 5.72; N, 3.01.

 From the above, the compound is structurally correct and is the target compound.

 Example 24 Preparation of [1-(2,4,6-trimethylaniline)-2-(2,4-diphenylmethyl-6-methylaniline) hydrazine] nickel chloride (II) [ Complex C14]

An equimolar amount of MC1 ₂ .6H ₂ dichloromethane solution was added dropwise to 1-(2,4,6-trimethylaniline)-2-(2,4-diphenylmethyl-6- at room temperature. Methylaniline) in methylene chloride solution, stirred under nitrogen for 8 h, added diethyl ether, a red solid precipitated, filtered, washed with diethyl ether and dried to give a red solid, which is [1-(2,4,6- Trimethylaniline; )-2-(2,4-dibiphenylmethyl-6-methylaniline;) hydrazine] nickel chloride (II) [complex C14]. Yield: 80.3%.

The structure confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3025.0 (w), 2967.2w), 1655.7 (w),

1626.6(m), 1583.3(s), 1493.9(m), 1444.8 (m), 1290.6(m), 1193.4 (w), 1031.8(m), 830.0(m), 775.0(s), 740.8(s), Elemental analysis: C ₅₄ H ₄₄ C1 ₂ N ₂ M (850.54) Theoretical value: C, 76.25; H, 5.21; N, 3.29. Found: C, 76.44; H, 5.37; N, 2.91.

 From the above, the compound is structurally correct and is the target compound.

 A schematic diagram of the crystal structure of the complex is shown in Fig. 6. It can be seen from the figure that the coordination structure is very similar, and the central nickel atom is N-N coordinated to form a twisted tetrahedral structure.

 Example 25 Preparation of [1-(2,6-diethyl-4-methylaniline)-2-(2,4-diphenylmethyl-6-methylaniline) hydrazine] II) [Complex C 15]

An equimolar amount of MC1 ₂ _6H ₂ dichloromethane solution was added dropwise to the 1-(2,6-diethyl-4-methylaniline)-2-(2,4-di) obtained in Example 15 at room temperature. To a solution of diphenylmethyl-6-methylanilinium in methylene chloride, stirred under nitrogen for 8 h, added diethyl ether and a red solid precipitated, filtered, washed with diethyl ether and dried to give a red solid. (2,6-Diethyl-4-methylaniline)-2-(2,4-dibiphenylmethyl-6-methylaniline) hydrazine] Nickel chloride (II) [complex C15]. Yield: 77.8%.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3024.3 (w), 2963.6 (w), 1654.1 (w), 1624.4 (m), 1586.9 (m), 1490.8 (m), 1445.7 (m) , 1288.9 (m), 1200.4 (m), 1031.7 (m), 829.6 (m), 774.9 (s), 740.4 (s), 679.7 (vs). Elemental analysis: C ₅₆ H ₄₈ C1 ₂ N ₂ M (878.59 Theoretical value: C, 76.55; H, 5.51; N, 3.19. Found: C, 76.77; H, 5.87; N, 2.92.

 From the above, the compound is structurally correct and is the target compound.

 Example 26 Preparation of 1-(2,6-diethylaniline; )-2-(2-diphenylmethyl-4,6-dimethylaniline;) 苊[L11] 2-(2-diphenyl Methyl-4,6-dimethylanilinone oxime (1.30 g, 2.88 mmol) and 2,6-diethylaniline

A solution of (0.44 g, 1.39 mmol) of p-toluenesulfonic acid was added (0.44 g, 2.95 mmol) in toluene (150 mL). The solvent toluene was removed, and the residue was subjected to silica gel column chromatography using a solvent mixture of petroleum ether and ethyl acetate in a volume ratio of 20:1. The eluted fraction was detected by a thin layer of silica gel plate, and the third fraction was collected and removed. The solvent gave a yellow solid which was 1-(2,6-diethylaniline;)-2-(2-diphenylmethyl-4,6-dimethylaniline;) 苊 [Ll l]. Yield: 22%. Melting point: 197-198. C.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3016.1 (w), 2963.7 (m), 1664.0 (s), 1641.4 (m), 1591.5 (s), 1489.5 (m), 1440. l ( Vs), 1274.9 (m), 1235.5(s), 1148. l(w), 1081.9 (w), 1035.0 (m), 924.0(m), 832.9(m), 782.3(s), 740. l(s ), 695.4(vs). 1H MR (400 MHz, CDCls, TMS): δ 7.76 (d, J = 8.24, 1H), 7.71 (d, J = 8.12, 1H), 7.30-7.24 (m, 4H),

7.20-7.12(m, 6H), 6.68(d, J=8.44, 3H), 6.73(s, 1H), 6.56(d, J=7.04, 1H), 6.50(t, J=7.31, 2H), 6.39 (d, J=7.25, 1H), 6.26(d, J=7.27, 1H), 5.77(s, 1H), 2.74(m, 1H), 2.62-2.50(m, 2H), 2.36(m, 1H) , 2.33(s, 3H), 2.07(s, 3H), 1.25(t, J=7.40, 3H), 1.05(t, J=7.45, 3H). ¹³ C NMR (100 MHz, CDC1 ₃ , TMS): δ 162.26, 161.32, 148.47, 146.51, 143.68, 141.94,

140.23, 133.14, 132.75, 130.92, 130.57, 130.30, 129.91, 129.64, 129.38, 129.16, 128.58, 128.29, 128.00, 127.92, 127.56, 127.42, 126.36, 126.26, 125.96, 125.09, 124.65, 123.96, 122.97, 122.40, 52.54, 24.76, 24.49, 21.25, 17.46, 14.44, 13.70. Elemental analysis: C ₄₃ H ₃₈ N ₂ (582.78) Theory: C 88.62, H 6.57, N 4.81. Found: C 88.78, H 6.68, N 4.74.

 From the above, the compound is structurally correct and is the target compound.

 Example 27 Preparation of [1-(2,6-diethylaniline)-2-(2-diphenylmethyl-4,6-dimethylanilinium) ruthenium bromide (II) [complex C16]

An equimolar amount of (DME) MBr ₂ dichloromethane solution was added dropwise to the 1-(2,6-diethylaniline)-2-(2-diphenylmethyl-4,6 obtained in Example 26 at room temperature. - dimethylaniline) in methylene chloride solution, stirred under nitrogen for 8 h, added diethyl ether, a red solid precipitated, filtered, washed with diethyl ether and dried to give a red solid, which is [1-(2,6- Diethylaniline)-2-(2-diphenylmethyl-4,6-dimethylaniline) oxime] nickel (II) bromide [complex C16]. Yield: 84.3%.

The structural confirmation data is as follows: FT-IR(KBr, cm" ¹ ): 3021.2 (w), 2968.8(w), 1652.5 (w), 1621.8 (s), 1582.0(m), 1490.7 (m), 1440.6 (s) , 1291. l(s), 1183.8 (m), 1038.8(m), 828.9(m), 773.2(s), 739.2(s), 699.4(vs). Elemental analysis: C ₄₃ H ₃₈ Br ₂ N ₂ M (801.28): Theoretical value: C 64.45, H 4.78, N 3.50. Experimental value: C 64.70, H 4.87, N 3.33.

 From the above, the compound is structurally correct and is the target compound.

 Example 28 Preparation of [1-(2,6-diethylaniline)-2-(2-diphenylmethyl-4,6-dimethylaniline) oxime] nickel chloride (II) [complex C17]

An equimolar amount of MC1 ₂ _6H ₂ dichloromethane solution was added dropwise to the 1-(2,6-diethylaniline)-2-(2-diphenylmethyl-4,6 obtained in Example 26 at room temperature. - dimethylaniline) in methylene chloride solution, stirred under nitrogen for 8 h, added diethyl ether to precipitate a red solid, filtered, washed with diethyl ether and dried to give a red solid, which is [1-(2,6- Diethylaniline)-2-(2-diphenylmethyl-4,6-dimethylaniline) oxime] nickel chloride (II) [complex C17]. Yield: 79.2%.

The structural confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3027.2 (w), 2964.8 (w), 1656.0 (w), 1625.8

(m), 1584.9(s), 1490.7 (m), 1442.8(s), 1289.7 (m), 1185.0 (m), 1034.8(s), 828.8(m), 773.8(s), 742.7(s), 699.9 (vs). Elemental analysis: C ₄₃ H ₃₈ Cl ₂ N ₂ Ni (712.37) Theory: C 72.50, H 5.38, N 3.93. Found: C 72.66, H 5.63, N 3.76. From the above, the compound is structurally correct and is the target compound.

 Example 29 Preparation of 1-(2,4,6-trimethylaniline)-2-(2,6-dibiphenylmethyl-4-isopropylaniline) oxime [L12]

2-(2,6-Diphenylmethyl-4-isopropylaniline) fluorenone (1.00 g, 1.58 mmol) and 2,4,6-trimethylaniline (0.23 g, 1.70 mmol) A catalyst amount (0.14 g, 0.81 mmol) of p-toluenesulfonic acid was added to a solution of toluene (80 mL) and heated to reflux for 8 h. The solvent toluene was removed, and the residue was subjected to silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 15:1. The eluted fraction was detected by a thin layer of silica gel plate, and the second fraction was collected, and the solvent was removed to obtain an orange-yellow solid, which was 1-(2,4,6-trimethylaniline)-2-(2,6-di-di) Benzyl-4-isopropylaniline) hydrazine [L12] ₀ Yield: 46%.

The structural confirmation data are as follows: 1H MR (400 MHz, CDC1 ₃ , TMS): 57.70 (d, J=8.23, 1H), 7.56 (d, J=8.25, 1H), 7.28-7.21 (m, 5H), 7.16 ( t, J=7.00, 2H), 7.09 (d, J=7.46, 4H), 6.98-6.91 (m, 7H), 6.83 ( s, 2H), 6.58 ( s, 5H), 6.40 (t, J=7.35 , 2H) , 5.96 (d, J=7.16, 1H) , 5.62 ( s, 2H) , 2.81 (m, 1H) , 2.38 ( s, 3H) , 2.18 ( s, 6H), 1.14 (d, J=6.88 , 6H) . ¹³ C MR (100 MHz, CDC1 ₃ , TMS): 5163.53, 161.50, 147.08, 146.76, 143.71, 143.37, 141.91, 139.86, 132.80, 131.97, 129.79, 129.50, 128.96, 128.47, 127.98, 127.85, 127.61 , 127.37, 126.81, 125.99, 125.31, 124.55, 124.02, 121.63, 52.31, 50.88, 33.52, 24.18, 20.92, 18.04.

 From the above, the compound is structurally correct and is the target compound.

Example 30 Preparation of [1-(2,4,6-trimethylaniline)-2-(2,6-dibenzoyl-4-isopropylaniline) oxime] nickel bromide (II) [complex C1 ⁸ ]

Equimolar (DME) MBr ₂ in dichloromethane was added dropwise to the preparation of Example 29 at room temperature.

1-(2,4,6-trimethylaniline)-2-(2,6-didiphenylmethyl-4-isopropylaniline) in dichloromethane, stirred under nitrogen for 8 h. Add diethyl ether to precipitate a red solid, which is filtered, washed with diethyl ether and dried to give a red solid, which is [1-(2,4,6-trimethylaniline)-2-(2,6-diphenylmethyl)- 4-isopropylaniline) 苊] combined with nickel (II) bromide [complex C18]. Yield: 82.1%.

The structure confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3024.0 (w), 2973.3 (w), 1641.6 (w), 1592.6

(m), 1574.5(m), 1492.0 (m), 1447.8 (m), 1294.3 (m), 1192.2 (m), 1032.4(m), 826.6(m), 776.7(s), 744. l(s) Elemental analysis: C ₅₆ H ₄₈ Br ₂ N ₂ Ni (967.5 ) Theory: C, 69.52; H, 5.00; N, 2.90; calc.: C, 69.55; H, 4.71; N, 3.27 As can be seen from the above, the compound is structurally correct and is the target compound.

 Example 31, Preparation of [1-(2,4,6-trimethylaniline)-2-(2,6-diphenylbenzyl-4-isopropylaniline) oxime] nickel chloride (II) [complex C19]

An equimolar solution of MC1 ₂ _6H ₂ in dichloromethane was added dropwise to the 1-(2,4,6-trimethylaniline)-2-(2,6-dibibenzene) obtained in Example 29 at room temperature. Methyl-4-isopropylaniline oxime in methylene chloride solution, stirred under nitrogen for 8 h, added diethyl ether, a red solid precipitated, filtered, washed with diethyl ether and dried to give a red solid. 2,4,6-trimethylaniline; )-2-(2,6-diphenylbenzyl-4-isopropylaniline) oxime] nickel chloride (II) [complex C19]. Yield: 78.9%.

The structure confirmation data is as follows: FT-IR (KBr, cm" ¹ ): 3024.0 (w), 2970.7 (w), 1643.6 (w), 1597.6 (m), 1577.5 (m), 1491.0 (m), 1447.6 (m) , 1291.4 (m), 1190.6 (m), 1030.4(m), 826.6(m), 776.7 (s), 744. l ( s), 700.9 (vs) Elemental _{analysis: C 53 H 42 C1 2 N} 2 M (878.59) Theory: C, 76.55; H, 5.51 ; N, 3.19; Found: C, 76.35; H, 5.21; N, 3.27. From the above, the compound is structurally correct and is the target compound.

Example 32: Ethylene polymerization under the combined catalytic pressure of the obtained complex C4 and diethylaluminum chloride Et ₂ AlCl prepared by using Example 9:

a) Ethylene polymerization under pressure uses a 300 ml stainless steel polymer kettle equipped with mechanical stirring paddles and temperature control. The polymerization vessel was evacuated and heated to 100 ° C for a period of two hours. The polymerization vessel was slowly cooled to the desired polymerization temperature (20 ° C;) under pre-replacement of nitrogen in the kettle with ethylene. The kettle was rinsed three times with toluene, and then 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C4), 0.44 mL of a cocatalyst (Et ₂ AlCl, 0.68 mol/L of a toluene solution), and the remaining toluene were added. The total amount of toluene is 100 ml;). The polymerization vessel was closed, ethylene was passed and the pressure of ethylene was kept constant (10 MPa). After the polymerization reaction reached a predetermined time (30 min), the ethylene pressure in the autoclave was released, and 100 mL of ethanol was added to the mixture to examine whether or not polyethylene was formed. If polyethylene is formed, it is filtered and washed and dried in an oven at 60 ° C to a constant weight, and the polymerization activity is calculated from the yield of the polymer. Polymerization activity: 6.08 X 10 ⁶ g-mol-l(Ni)-hl , polymer M _w = 1043 kg 'mor ¹ , M _w /M _n =2.8.

b) In the same way as a), replace only as follows: 50 mL of toluene, 20 mL of toluene solution containing 1.5 μιηο1 catalyst CC4), 0.88 mL of cocatalyst CEt ₂ AlCl were added to the reactor. , 0.68 mol/L toluene solution), residual toluene (to make the total amount of toluene 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 9.28 X 10 ⁶ g-mol-l(Ni)-hl, polymer M _w = 543 kg-mol" ¹ , MM _n = 2.4.

c) In the same way as a), replace only as follows: Add 50 mL of toluene, 20 mL of toluene solution containing 1.5 μιηο1 catalyst CC4) to the reactor, 1.32 mL of cocatalyst CEt ₂ AlCl , 0.68 mol/L in toluene), and the remaining toluene (so that the total amount of toluene is 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 10.8 X 10 ⁶ g'mol-lCM) 'hl, polymer M _w = 597 kg 'mol - ¹ , M _w / M _n = 2.2.

d) In the same way as a), replace only as follows: 50 mL of toluene, 20 mL of toluene solution containing 1.5 μιηο1 catalyst CC4), 1.76 mL of cocatalyst CEt ₂ AlCl were added to the reactor. , 0.68 mol/L in toluene), and the remaining toluene (so that the total amount of toluene is 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 9.88 X 10 mol-l CM) 'hl, polymer M _w = 674 kg 'mol - ¹ , M _w / M _n = 2.6.

e) In the same way as a), replace only as follows: Add 50 mL of toluene to the reactor, 20 mL of toluene solution with 1.5 μιηο1 catalyst (^4;), 2.20 mL of cocatalyst CEt ₂ AlCl, 0.68 mol/L in toluene), and residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 9.83 X 10 mol-l CM) 'hl, polymer M _w = 743 kg 'mol - ¹ , M _w / M _n = 2.5.

f) In the same way as a), replace only as follows: 1. Slowly cool the polymerization vessel to the envisaged polymerization temperature (40 °C) under pre-replacement of nitrogen in the kettle with ethylene; 2. Add 50 mL of toluene to the reaction kettle in turn, 20 mL of toluene solution containing 1.5 μιηο1 catalyst (C4), 1.32 mL of catalytic (Et ₂ AlCl, 0.68 mol/L in toluene), and residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 6.36 X 10 ⁶ g'mol-l (;M) 'hl, polymer M _w =462 kg-mol" ¹ , M _w /M _n = 2.3.

g) In the same way as a), replace only as follows: 1. Slowly cool the polymerization vessel to the envisaged polymerization temperature (60 °C) under pre-replacement of nitrogen in the kettle with ethylene; 2. Add 50 mL of toluene to the reactor, 20 mL of toluene solution containing 1.5 μm ηο1 catalyst (C4), 1.32 mL of cocatalyst (Et ₂ AlCl, 0.68 mol/L in toluene), and residual toluene (to make total toluene) The amount is 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 4.48 X 10 ⁶ g'mol-l(M)'hl, polymer M _w =298 kg-mol" ¹ , M _w /M _n = 2.2.

h) In the same way as a), replace only as follows: 1. Add 50 mL of toluene to the reactor, 20 mL of toluene solution containing 1.5 μιηο1 catalyst (C4), 1.32 mL of cocatalyst (Et ₂ AlCl, 0.68 mol/L toluene solution), residual toluene (to make the total amount of toluene 100 ml); 2) The polymerization reaction reached a preset time of 5 min. Polymerization activity: 13.0 Χ 10 ·ιηο1-1 (Μ)·1ι-1, polymer M _w = 563 kg-mol" ¹ , M _w /M _n = 2.2.

i) In the same way as a), replace only as follows: 1. Add 50 mL of toluene to the reactor, 20 mL of toluene solution containing 1.5 μιηο1 catalyst (^4;), 1.32 mL. Cocatalyst CEt ₂ AlCl _: 0.68 mol/L toluene solution), residual toluene (total 100 ml of toluene); 2) Polymerization reached a preset time of 10 min. Polymerization activity: 11.8 X 10 ⁶ g'mol-l (M hl, polymer M _w = 569 kg-mol" ¹ , M _w /M _n = 2.3.

j) In the same way as a), replace only as follows: 1. Add 50 mL of toluene to the reactor, 20 mL of toluene solution containing 1.5 μιηο1 catalyst (^4;), 1.32 mL. Cocatalyst CEt ₂ AlCl _: 0.68 mol/L toluene solution), residual toluene (to make 100 toluene total); 2) Polymerization reached a preset time of 20 min. Polymerization activity: 10.9 X 10 ⁶ g'mol-l (M hl, polymer M _w =581 kg-mol" ¹ , M _w /M _n = 2.4.

k) In exactly the same way as a), replace only as follows: 1. Add 50 mL of toluene to the reactor, 20 mL of toluene solution containing 1.5 μιηο1 catalyst (C4), 1.32 mL of cocatalyst (Et ₂ AlCl, 0.68 mol/L toluene solution), residual toluene (to make the total amount of toluene 100 ml); 2) The polymerization reaction reached a preset time of 60 min. Polymerization activity: 6.65 X 10 ⁶ g_mol-l CM; Hi-l, polymer M _w = 5795 kg-mol" ¹ , M _w / M _n = 2.7.

Example 33, using the obtained complex C1 and Et ₂ AlCl prepared in Example 6 to carry out ethylene polymerization under catalytic pressure

In the same manner as in a) in Example 32, the replacement was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C1), and 1.32 mL of a cocatalyst were sequentially added to the reaction vessel. (Et ₂ AlCl, 0.68 mol/L in toluene), residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 9.95 X 10 ⁶ g'mol-l (;M) 'hl, polymer M _w = 472 kg-mol" ¹ , M _w /M _n = 2.4.

Example 34, using the obtained complex C2 and Et ₂ AlCl prepared in Example 7 to carry out ethylene polymerization under catalytic pressure In the same manner as in a) in Example 32, the substitution was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C2), and 1.32 mL of a cocatalyst were sequentially added to the reaction vessel. (Et ₂ AlCl, 0.68 mol/L in toluene), residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 6.88 Χ 10 ⁶ _§ ·ιηο1-1 (;Μ)·1ι-1, polymer M _w =687 kg-ιηοΓ ¹ , M _w /M _n = 2.3.

Example 35, using the obtained complex C3 and Et ₂ AlCl prepared in Example 8 to carry out ethylene polymerization under catalytic pressure

In the same manner as a) in Example 32, the substitution was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C3), and 1.32 mL of a cocatalyst were sequentially added to the reaction vessel. (Et ₂ AlCl, 0.68 mol/L in toluene), residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 10.9 X 10 ⁶ g_mol-l (;M)_h-l, polymer M _w =942 kg-mol" ¹ , M _w /M _n = 2.7.

Example 36, using the obtained complex C5 and Et ₂ AlCl prepared in Example 10 to carry out ethylene polymerization under catalytic pressure

In the same manner as a) in Example 32, the substitution was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C5), and 1.32 mL of a cocatalyst were sequentially added to the reaction vessel. (Et ₂ AlCl, 0.68 mol/L in toluene), residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 8.53 Χ 10 ⁶ _§ ·ιηο1-1 (;Μ)·1ι-1, polymer M _w =774 kg-mol" ¹ , M _w /M _n = 2.4.

 Example 37. Preparation of the obtained complex by using Example 9 C4 and MAO combined with catalytically pressurized ethylene n:

1) Ethylene polymerization under pressure uses a 300 ml stainless steel polymerization vessel equipped with mechanical stirring paddles and temperature control. The polymerization vessel was evacuated and heated to 100 ° C for a period of two hours. The polymerization vessel was slowly cooled to the desired polymerization temperature (20 ° C) under the condition that the nitrogen in the autoclave was previously replaced with ethylene. The kettle was rinsed three times with toluene, followed by 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C4), 1.02 mL of a cocatalyst (MAO, 1.46 mol/L in toluene), and the remaining toluene (total toluene) For 100 ml;). The kettle was closed, ethylene was passed and the pressure of ethylene was kept constant (10 MPa). After the polymerization reaction reached a predetermined time (30 min), the ethylene pressure in the autoclave was released, and 100 mL of ethanol was added to the mixture to examine whether or not polyethylene was formed. If polyethylene is formed, it is filtered and washed and dried in an oven at 60 ° C to a constant weight, and the polymerization activity is calculated from the yield of the polymer. Polymerization activity: 3.30 X 10 ⁶ g_mol-l(M)_h-l, polymer M _w = 1278 kg-mol" ¹ , M _w /M _n = 21.

2) In the same way as 1), replace only as follows: Add 50 mL of toluene to the reactor, 20 mL of toluene solution with 1.5 μιηο1 catalyst (^4;), 2.04 mL of cocatalyst (MAO, 1.46 mol/L in toluene), residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 7.21 Χ 10 ⁶ _§ ·ιηο1-1 (Μ)·1ι-1.

3) In the same way as 1), replace only as follows: Add 50 mL of toluene to the reactor, 20 mL of toluene solution with 1.5 μιηο1 catalyst (^4;), 3.06 mL of cocatalyst (MAO, 1.46 mol/L in toluene), residual toluene (total 100 ml of toluene). According to the yield of the polymer Calculate the polymerization activity. Polymerization activity: 9.32 X 10 ⁶ g-mol-l(Ni)-hl, polymer M _w = 699 kg-mol" ¹ , M _w / M _n = 2.5.

4) In the same way as in 1), replace only as follows: Add 50 mL of toluene to the reactor, 20 mL of toluene solution with 1.5 μιηο1 catalyst (C4), 4.08 mL of cocatalyst (MAO) , 1.46 mol/L toluene solution), residual toluene (to make the total amount of toluene 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 4.08 X 10 ⁶ g'mol-l (M) 'hl, polymer M _w = 813 kg-mol" ¹ , MM _n = 3.1.

5) In the same way as 1), replace only as follows: 1. Slowly cool the polymerization vessel to the envisaged polymerization temperature (40 ° C) under pre-replacement of nitrogen in the kettle with ethylene; 2. Add 50 mL of toluene to the reaction kettle, 20 mL of toluene solution containing 1.5 μm ηο1 catalyst (C4), 3.06 mL of cocatalyst (MAO, 1.46 mol/L of toluene solution), and residual toluene (to make the total amount of toluene 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 5.41 Χ 10 ⁶ _§ ·ιηο1-1 (;Μ)·1ι-1, polymer M _w =563 kg-mol" ¹ , M _w /M _n = 2.4.

6) In the same way as 1), replace only as follows: 1. Slowly cool the polymerization vessel to the envisaged polymerization temperature (60 °C) under pre-replacement of nitrogen in the kettle with ethylene; 2. Add 50 mL of toluene to the reaction kettle, 20 mL of toluene solution containing 1.5 μm ηο1 catalyst (C4), 3.06 mL of cocatalyst (MAO, 1.46 mol/L of toluene solution), and residual toluene (to make the total amount of toluene 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 4.37 Χ 10 ⁶ _§ ·ιηο1-1 (;Μ)·1ι-1, polymer M _w =367 kg-mol" ¹ , M _w /M _n = 2.2.

7) In exactly the same way as 1), replace only as follows: 1. Add 50 mL of toluene to the reactor, 20 mL of toluene solution with 1.5 μιηο1 catalyst (C4), 3.06 mL of cocatalyst. (MAO, 1.46 mol/L in toluene), residual toluene (total 100 ml of toluene); 2) Polymerization reached a preset time of 5 min. Polymerization activity: 10.6 X 10 ⁶ g-mol-l(Ni)-hl, polymer M _w =576 kg-mol" ¹ , M _w /M _n = 2.5.

8) In exactly the same way as 1), replace only as follows: 1. Add 50 mL of toluene to the reactor, 20 mL of toluene solution with 1.5 μιηο1 catalyst (C4), 3.06 mL of cocatalyst. (MAO, 1.46 mol/L toluene solution), residual toluene (to make 100 ml of total toluene); 2) The polymerization reaction reached a preset time of 10 min. Polymerization activity: 10.2 X 10 ⁶ g'mol-l (M; Hi-1, polymer _Mw = 584 kg-mol ^-1 , M _w /M _n = 2.5).

9) In exactly the same way as 1), replace only as follows: 1. Add 50 mL of toluene to the reactor, 20 mL of toluene solution with 1.5 μιηο1 catalyst (C4), 3.06 mL of cocatalyst. (MAO, 1.46 mol/L toluene solution), residual toluene (to make the total amount of toluene 100 ml); 2) The polymerization reaction reached a preset time of 20 min. Polymerization activity: 9.60 X 10 ⁶ g'mol-l (M; Hi-l, polymer M _w = 602 kg-mol" ¹ , M _w / M _n = 2.6.

10) In the same way as 1), replace only as follows: 1. Add 50 mL of toluene to the reactor, 20 mL of toluene solution containing 1.5 μm ηοΐ catalyst (C4), 3.06 mL of cocatalyst. (MAO, 1.46 mol/L toluene solution), residual toluene (to make the total amount of toluene 100 ml); 2) The polymerization reaction reached a preset time of 60 min. Polymerization activity: 6.10 X 10 ⁶ g'mol-l (M; Hi-l, polymer M _w = 885 13⁄4 M _w /M _n = 3.3

Example 38. The obtained complexes C1 and MAO prepared in Example 6 were combined with catalytically pressurized ethylene according to the same procedure as in Example 37, except that the substitution was carried out as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C1), 3.06 mL of a cocatalyst (MAO, 1.46 mol/L of a toluene solution), and residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 9.23 X 10 ⁶ g'mol-l(M)'hl, polymer M _w =674 kg-mol" ¹ , M _w /M _n = 2.5

 Example 39. Preparation of the obtained complex by using Example 7 Ethylene polymerization under combined catalytic pressure of C2 and MAO

In the same manner as in 1) of Example 37, the replacement was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C2), and 3.06 mL of a cocatalyst were sequentially added to the reaction vessel. (MAO, 1.46 mol/L in toluene), residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 7.73 X 10 ⁶ g_mol-l (;M)_h-l, polymer M _w =677 kg 'mol ^-1 , M _w /M _n = 2.6

Example 40, using the obtained complex C3 and MAO prepared in Example 8 in combination with catalytically pressurized ethylene, in exactly the same manner as in Example 37, except that the substitution was carried out as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C3), 3.06 mL of a cocatalyst (MAO, 1.46 mol/L of a toluene solution), and residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 9.39 X 10 ⁶ g'mol-l (;M)'hl, polymer M _w =745 kg-mol" ¹ , M _w /M _n = 2.5

Example 41, using the obtained complex C5 and MAO prepared in Example 10 in combination with catalytically pressurized ethylene, in the same manner as in Example 37, 1), was replaced only as follows: sequentially added to the reaction vessel 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C5), 3.06 mL of a cocatalyst (MAO, 1.46 mol/L of a toluene solution), and residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 1.89 X 10 ⁶ g'mol-l(;M)'hl, polymer M _w =744 kg-mol" ¹ , M _w /M _n = 2.7

 Example 42. Preparation of the obtained complex by the use of Example 20 C10 and MMAO in combination with catalytic polymerization of ethylene:

A) Ethylene polymerization under pressure uses a 300 ml stainless steel polymerization vessel equipped with a mechanical stirring paddle and a temperature control device. The polymerization vessel was evacuated and heated to 100 ° C for a period of two hours. The polymerization vessel was slowly cooled to the desired polymerization temperature (20 ° C;) under pre-replacement of nitrogen in the kettle with ethylene. The kettle was rinsed three times with toluene, followed by 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μιηο1 catalyst (C10), 0.78 mL of cocatalyst (MMAO, 1.93 mol/L heptane solution), and residual toluene (toluene) The total amount is 100 ml;). The polymerization vessel was closed, ethylene was passed and the pressure of ethylene was kept constant (10 MPa). After the polymerization reaction reaches a preset time (30 min), the ethylene pressure in the autoclave is released, and 100 mL is added to the mixture. Ethanol, check if polyethylene is formed. If polyethylene is formed, it is filtered and washed and dried in an oven at 60 ° C to a constant weight, and the polymerization activity is calculated from the yield of the polymer. Polymerization activity: 7.67 X 10 ⁶ g-mol-l(Ni)-hl _o

B) In the same way as A), replace only as follows: Add 50 mL of toluene, 20 mL of toluene solution containing 1.5 μιηο1 catalyst CCIO), 1.56 mL of cocatalyst (MMAO, in sequence) to the reactor. 1.93 mol/L heptane solution), residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 7.96 X 10 ⁶ g_mol-l (;M)_h-l.

C) In the same way as Α), replace only as follows: Add 50 mL of toluene, 20 mL of toluene solution containing 1.5 μιηο1 catalyst CCIO), 2.34 mL of cocatalyst (MMAO, in order) to the reactor. 1.93 mol/L heptane solution), and the remaining toluene (so that the total amount of toluene is 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 8.25 Χ 10 ⁶ _§ ·ιηο1-1 (;Μ)·1ι-1.

D) In the same way as Α), replace only as follows: Add 50 mL of toluene, 20 mL of toluene solution containing 1.5 μιηο1 catalyst CC10), 3.12 mL of cocatalyst (MMAO, in order). 1.93 mol/L heptane solution), and the remaining toluene (so that the total amount of toluene is 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 7.19 Χ 10 ⁶ _§ ·ιη _Ο 1-1(Μ)·1 -1.

Ε) In the same way as Α), replace only as follows: 1. Slowly cool the polymerization vessel to the envisaged polymerization temperature (40 °C) under pre-replacement of nitrogen in the kettle with ethylene; 2. Add 50 mL of toluene to the reactor, 20 mL of toluene solution containing 1.5 μm ηο1 catalyst (C10), 2.34 mL of cocatalyst (MMAO, 1.93 mol/L heptane solution), and residual toluene (total amount of toluene) For 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 6.89 Χ 10 ⁶ _§ ·ιη _Ο 1-1(Μ)·1 -1.

F) In the same way as Α), replace only as follows: 1. Slowly cool the polymerization vessel to the envisaged polymerization temperature (60 °C) under pre-replacement of nitrogen in the kettle with ethylene; 2. Add 50 mL of toluene to the reactor, 20 mL of toluene solution containing 1.5 μm ηο1 catalyst (C10), 2.34 mL of cocatalyst (MMAO, 1.93 mol/L heptane solution), and residual toluene (total amount of toluene) For 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 6.12 Χ 10 ⁶ _§ ·ιη _Ο 1-1(Μ)·1 -1.

G) In the same way as Α), only replace as follows: 1. Slowly cool the polymerization vessel to the envisaged polymerization temperature (80 °C) under pre-replacement of nitrogen in the kettle with ethylene; 2. Add 50 mL of toluene to the reactor, 20 mL of toluene solution containing 1.5 μm ηο1 catalyst (C10), 2.34 mL of cocatalyst (MMAO, 1.93 mol/L heptane solution), and residual toluene (total amount of toluene) For 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 3.25 Χ 10 ⁶ _§ ·ιη _Ο 1-1(Μ)·1 -1.

 Example 43. Preparation of the obtained complex by the use of Example 16 C6 and MMAO combined with ethylene polymerization under catalytic pressure

In the same manner as in A) of Example 42, the replacement was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C6), and 2.34 mL of a cocatalyst were sequentially added to the reaction vessel. (MMAO, 1.93 mol/L heptane solution), residual toluene (to make the total amount of toluene 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 4.21 Χ 10 ⁶ _§ ·ιηο1-1 (;Μ)·1ι-1.

 Example 44. Preparation of the obtained complex by using Example 17 C7 and MMAO combined with ethylene polymerization under catalytic pressure

In the same manner as in A) of Example 42, the replacement was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C7), 2.34 mL of a cocatalyst (MMAO, 1.93 mol/L of heptane solution), and residual toluene (total amount of toluene of 100 ml) were sequentially added. The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 8.95 Χ 10 ⁶ _§ ·ιη _Ο 1-1(Μ)·1 -1.

 Example 45. Preparation of the obtained complex by the use of Example 18 C8 and MMAO combined with ethylene polymerization under catalytic pressure

In the same manner as in A) of Example 42, the replacement was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C8), and 2.34 mL of a cocatalyst were sequentially added to the reaction vessel. (MMAO, 1.93 mol/L heptane solution), residual toluene (to make the total amount of toluene 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 7.44 Χ 10 ⁶ _§ ·ιη _Ο 1-1(Νί)

 Example 46. Preparation of the obtained complex by using Example 19 Polymerization of ethylene under combined catalytic pressure of C9 and MMAO

In the same manner as in A) of Example 42, the replacement was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C9), and 2.34 mL of a cocatalyst were sequentially added to the reaction vessel. (MMAO, 1.93 mol/L heptane solution), residual toluene (to make the total amount of toluene 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 7.72 X 10 ⁶ g_mol-l (Ni)

 Example 47, Preparation of the obtained complex by using Example 27 Ethylene polymerization under combined catalytic pressure of C16 and MMAO

In the same manner as in A) of Example 42, the replacement was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C16), and 2.34 mL of a cocatalyst were sequentially added to the reaction vessel. (MMAO, 1.93 mol/L heptane solution), residual toluene (to make the total amount of toluene 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 7.91 Χ 10 ⁶ _§ ·ιη _Ο 1-1(Νί)

 Example 48. Preparation of the obtained complex by the use of Example 24 C14 and MMAO in combination with catalytic polymerization of ethylene:

a) Ethylene polymerization under pressure uses a 300 ml stainless steel polymerization vessel equipped with a mechanical stirring paddle and a temperature control device. The polymerization vessel was evacuated and heated to 100 ° C for a period of two hours. The polymerization vessel was slowly cooled to the desired polymerization temperature (20 ° C;) under pre-replacement of nitrogen in the kettle with ethylene. The kettle was rinsed three times with toluene, followed by 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C14), 0.78 mL of a cocatalyst (MMAO, 1.93 mol/L of heptane), and the remaining toluene (toluene). The total amount is 100 ml;). The polymerization vessel was closed, ethylene was passed and the pressure of ethylene was kept constant (10 MPa). After the polymerization reaction reached a predetermined time (30 min), the ethylene pressure in the autoclave was released, and 100 mL of ethanol was added to the mixture to examine whether or not polyethylene was formed. If polyethylene is formed, it is filtered and washed and dried in an oven at 60 ° C to a constant weight, and the polymerization activity is calculated from the yield of the polymer. Polymerization activity: T^SX lo mol-KNi)-!!- ¹ .

b) In the same way as a), replace only as follows: Add 50 mL of toluene to the reactor, 20 mL of 1.5 μιηο1 catalyst (CI toluene solution, 1.56 mL of cocatalyst (MMAO, 1.93 mol/L heptane solution), residual toluene (to make a total amount of toluene 100 ml). Calculate the polymerization activity according to the yield of the polymer. Polymerization activity: 8.68 X 10 ⁶ g_mol-lCNi)_h—

3) In the same way as in 1), replace only as follows: Add 50 mL of toluene to the reactor, 20 mL of toluene solution with 1.5 μιηο1 catalyst (C 14;), 2.34 mL of cocatalyst (MMAO, 1.93 mol/L heptane solution), residual toluene (to make the total amount of toluene 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 8.47 X 10 ⁶ g_mol-lCNi)_h—

4) In exactly the same way as in 1), replace only as follows: Add 50 mL of toluene, 20 mL of toluene solution containing 1.5 μιηο1 catalyst CC14), 3.12 mL of cocatalyst (MMAO, to the reactor). 1.93 mol/L heptane solution), residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 6.87 X 10 ⁶ g_mol-lCNi)_h—

5) In the same way as in 1), replace only as follows: 1. Slowly cool the polymerization vessel to the envisaged polymerization temperature (40 °C) under pre-replacement of nitrogen in the kettle with ethylene; 2. Add 50 mL of toluene to the reaction kettle in turn, 20 mL of 1.5 μιηο1 catalyzed [J(C14) toluene solution, 1.56 mL of cocatalyst (MMAO, 1.93 mol/L heptane solution), and residual toluene (making The total amount of toluene is 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 7.56 Χ 10 ⁶ _§ ·ιη _Ο 1-1(Νί)

6) In the same way as in 1), replace only as follows: 1. Slowly cool the polymerization vessel to the envisaged polymerization temperature (60 °C) under pre-replacement of nitrogen in the kettle with ethylene; 2. Add 50 mL of toluene to the reaction kettle in turn, 20 mL of 1.5 μιηο1 catalyzed [J(C14) toluene solution, 1.56 mL of cocatalyst (MMAO, 1.93 mol/L heptane solution), and residual toluene (making The total amount of toluene is 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 5.33 Χ 10 ⁶ _§ ·ιη _Ο 1-1(Νί)

VII) In the same way as in 1), replace only as follows: 1. Slowly cool the polymerization vessel to the envisaged polymerization temperature (80 °C) under pre-replacement of nitrogen in the kettle with ethylene; 2. Add 50 mL of toluene to the reaction kettle in turn, 20 mL of 1.5 μιηο1 catalyzed [J(C14) toluene solution, 1.56 mL of cocatalyst (MMAO, 1.93 mol/L heptane solution), and residual toluene (making The total amount of toluene is 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 3.55 Χ 10 ⁶ _§ ·ιη _Ο 1-1(Νί)

Λ) In the same way as in 1), replace only as follows: 1. Add 50 mL of toluene, 20 mL of toluene solution containing 1.5 μιηο1 catalyst CC14), and 1.56 mL of cocatalyst to the reactor. MMAO, 1.93 mol/L heptane solution), residual toluene (to make the total amount of toluene 100 ml); 2) The polymerization reaction reached a preset time of 5 min. Polymerization activity: 14.6 X 10 ⁶ _§ ·ιηο1-1 (;Μ)

IX) In accordance with the same method as in 1), replace only as follows: 1. Add 50 mL of toluene, 20 mL of toluene solution containing 1.5 μιηο1 catalyst CC14), and 1.56 mL of cocatalyst to the reactor. MMAO, 1.93 mol/L heptane solution), residual toluene (to make the total amount of toluene 100 ml); 2) The polymerization reaction reached a preset time of 10 min. Polymerization activity: 17.5 X 10 ⁶ g_mol-lCNi; Hi-

X) In the same way as in 1), replace only as follows: 1. Add 50 mL of toluene to the reactor, 20 mL of toluene solution containing 1.5 μm ηοΐ catalyst (C14), 1.56 mL of cocatalyst. (MMAO, 1.93 mol/L heptane solution), residual toluene (to make the total amount of toluene 100 ml); 2) The polymerization reaction reached a preset time of 60 min. Polymerization activity: 5.81 X 10 ⁶ g_mol-lCNi; Hi-

 Example 49. Preparation of the obtained complex by using Example 21 C11 and MMAO combined with ethylene polymerization under catalytic pressure

In the same manner as in a) in Example 48, the replacement was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C11), and 1.56 mL of a cocatalyst were sequentially added to the reaction vessel. (MMAO, 1.93 mol/L heptane solution), residual toluene (to make the total amount of toluene 100 ml). Root The polymerization activity was calculated from the yield of the polymer. Polymerization _{^{activity: 8.77 Χ 10 6 § · ιη}} Ο 1-1 (Νί) Example 50 Example 22 was prepared using the resulting complex and MMAO C12 joint under pressure ethylene polymerization catalyst embodiment

In the same manner as in a) in Example 48, the substitution was carried out only as follows: 50 mL of toluene was sequentially added to the reaction vessel, and 20 mL of 1.5 μιηο1 catalyzed [J(C12) toluene solution, 1.56 was dissolved. mL cocatalyst (MMAO, 1.93 mol/L heptane solution), residual toluene (total 100 ml of toluene). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 7.67 Χ 10 ⁶ _§ ·ιη _Ο 1-1(Νί)

 Example 51. Preparation of the obtained complex by using Example 23 C13 and MMAO combined with ethylene polymerization under catalytic pressure

In the same manner as in a) in Example 48, the replacement was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C13), and 1.56 mL of a cocatalyst were sequentially added to the reaction vessel. (MMAO, 1.93 mol/L heptane solution), residual toluene (to make the total amount of toluene 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 9.39 Χ 10 ⁶ _§ ·ιη _Ο 1-1(Νί)

 Example 52. Preparation of the obtained complex by using Example 25 Ethylene polymerization under combined catalytic pressure of C15 and MMAO

In the same manner as in a) in Example 48, the replacement was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C15), and 1.56 mL of a cocatalyst were sequentially added to the reaction vessel. (MMAO, 1.93 mol/L heptane solution), residual toluene (to make the total amount of toluene 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 9.49 Χ 10 ·ιη _Ο 1-1 (Μ)

 Example 53. Preparation of the obtained complex by using Example 28 Ethylene polymerization under combined catalytic pressure of C17 and MMAO

In the same manner as in a) in Example 48, the replacement was carried out only as follows: 50 mL of toluene, 20 mL of a toluene solution containing 1.5 μm of the catalyst (C17), and 1.56 mL of a cocatalyst were sequentially added to the reaction vessel. (MMAO, 1.93 mol/L heptane solution), residual toluene (to make the total amount of toluene 100 ml). The polymerization activity was calculated from the yield of the polymer. Polymerization activity: 6.68 Χ 10 ⁶ _§ ·ιη _Ο 1-1(Νί)

Industrial application

The present invention is designed and synthesized an asymmetric ligand and a diimine nickel complexes containing ^Ν Λ Ν ligand, all compounds of formula V are ligands by NMR, IR and elemental analysis was confirmed, Formula I The complexes C1-C17 were characterized by elemental analysis and infrared spectroscopy; in addition, the crystal structures of the complexes C4, C5, C8, C10 and C14 were tested by X-ray single crystal diffraction. The asymmetric α-imine nickel metal complex provided by the invention exhibits high catalytic activity for catalyzing ethylene polymerization, and the obtained high molecular weight polymer can reach K^g or^N^h- ¹ ; Broad industrial application prospects.

Claims

Rights request

1, the formula II shows the alpha two

 (Formula I)

In the formula I, R ¹ is a diphenylmethyl group, R ² is a methyl group or a diphenylmethyl group, R ³ is a methyl group, an ethyl group, an isopropyl group, a diphenylmethyl group or a halogen, and R ⁴ is a carbon atom. A total of 1-3 alkyl groups, R ⁵ is hydrogen or an alkyl group having a total of 1-3 carbon atoms, and X is chlorine or bromine.

The complex according to claim 1, wherein: R ¹ -benyl; R ² is a benzhydryl group; and R ³ is a methyl group, an isopropyl group, a diphenylmethyl group or a halogen. Specifically, methyl; R ⁴ is methyl, ethyl or isopropyl; R ⁵ is methyl or hydrogen; and X is bromine.

 The complex according to claim 1, wherein the α-diimine nickel complex represented by the formula I is produced by the method according to any one of claims 4 or 5.

A method of preparing the complex according to any one of claims 1 or 2, comprising the steps of: reacting the compound according to any one of claims 6-8 with (DME) ^^81~ ₂ under an inert atmosphere Or ^3⁄4 1 ₂ 413⁄40 is reacted in a solvent, and the reaction is completed to obtain the complex according to any one of claims 1 or 2.

The method according to claim 4, wherein the molar ratio of the compound according to any one of claims 6-8 to (DME) MBr ₂ or MC1 ₂ 4H ₂ 0 is 1: 1-1.1, specifically The solvent is selected from at least one of dichloromethane, methanol and ethanol, specifically dichloromethane; in the reaction step, the temperature is 10-30 ° C, specifically 20 ° C, time It is 8-12 hours, specifically 8 hours; the inert atmosphere is a nitrogen atmosphere.

 6. A compound of the formula V,

 (Formula V)

R ¹ is a diphenylmethyl group, R ² is a methyl group or a diphenylmethyl group, R ³ is a methyl group, an ethyl group, an isopropyl group, a diphenylmethyl group or a halogen, and R ⁴ is a total of 1-3 carbon atoms. Alkyl, R ⁵ is hydrogen or an alkyl group having a total of 1-3 carbon atoms.

7. The compound according to claim 6, wherein: R ¹ is a dibenzyl group; R ² is a diphenylmethyl group; and R ³ is a methyl group, an ethyl group, an isopropyl group, a diphenylmethyl group or a halogen. , specifically methyl; R ⁴ is methyl; R ⁵ is A

The compound according to claim 6 or 7, wherein the compound of the formula V is produced by the method according to any one of claims 9-11.

 9. A process for the preparation of a compound according to any one of claims 7 or 8 which comprises the steps of: in the presence of a catalyst, the total number of carbon atoms represented by the formula II is 2 -3 of an alkyl-substituted aniline is refluxed in a solvent to obtain a compound of any of 7 or 8;

 (式ΙΠ)

R ¹ is a diphenylmethyl group, R ² is a methyl group or a diphenylmethyl group; R ³ is a methyl group, an ethyl group, an isopropyl group, a diphenylmethyl group or

 (Formula IV)

R ⁴ is an alkyl group having a total of 1 to 3 carbon atoms; and R ⁵ is hydrogen or an alkyl group having a total of 1 to 3 carbon atoms.

10. The method according to claim 9, wherein: R ² is a diphenylmethyl group, and R ³ is a methyl group; and the alkyl substituted aniline having a total of 1 to 3 carbon atoms represented by the formula IV is selected from the group consisting of At least one of a group, an ethyl group and an isopropyl group, specifically a methyl group; the solvent is selected from at least one of toluene, absolute ethanol and acetic acid, specifically toluene; the catalyst is selected from the group consisting of p-toluenesulfonic acid And at least one of acetic acid, specifically p-toluenesulfonic acid; said catalyst, 2-imine fluorenone of formula III, alkyl substituted aniline having a total of 1-3 carbon atoms represented by formula IV, and said solvent The dosage ratio is 0.4-0.6mmol: l-1.2mmol: l. l-1.4mmol: 30-60ml, specifically 0.5mmol: lmmol: l. lmol: 50ml; in the reaction step, the time is 8-10 hours , specifically for 8 hours.

 The method according to claim 9 or 10, wherein the method of preparing the compound according to any one of claims 7 or 8 further comprises the step of dissolving the product after completion of the reaction in dichloromethane. Column chromatography on a basic alumina or silica gel column, eluting with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 15:1 as a leaching agent, and eluting fractions by thin layer chromatography The third fraction is collected and the solvent is removed to obtain the purified compound of claim 7 or 8.

 A catalyst composition for catalyzing the polymerization of ethylene, comprising: the complex and the cocatalyst according to any one of claims 1 to 3 as a main catalyst; wherein the cocatalyst is selected from the group consisting of aluminoxane and aluminum alkyl And at least one of alkyl aluminum chlorides.

13. The catalyst composition according to claim 12, wherein: the aluminoxane is methyl aluminoxane, modified methyl aluminoxane, ethyl aluminoxane or isobutyl aluminoxane; The aluminum alkyl is trimethyl aluminum, Triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum or tri-n-octyl aluminum; the alkyl aluminum chloride is diethyl aluminum chloride, sesquichlorodiethyl aluminum or dichloride Base aluminum

 The molar ratio of the metal aluminum in the aluminoxane to the metal nickel in the main catalyst is 1000-4000:1, specifically 2000-3000: 1, more specifically 3000:1; The molar ratio of the metal aluminum to the metal nickel in the main catalyst is 100-600: 1, specifically 200:1; the molar ratio of the metal aluminum in the alkyl aluminum chloride to the metal nickel in the main catalyst 200-1000: 1, specifically 500-700: 1, more specifically 600: 1.

 A method for producing a polyethylene, comprising the steps of: catalyzing the polymerization of ethylene under the conditions of using the complex according to any one of claims 1-3 or the catalyst composition according to any one of claims 12 or 13 as a catalyst; The reaction is completed to obtain the polyethylene.

 The method according to claim 14, wherein: in the polymerization step, the temperature is 20-60 ° C, specifically 20 ° C, the pressure is 0.1-10 MPa, specifically 1-3 MPa, time. It is 5-120 minutes, specifically 30 minutes; the solvent is selected from at least one of toluene, dichloromethane and hexane, specifically toluene.