Universal substrate for pyridine amino ligand, preparation method of universal substrate and preparation method of pyridine amino ligand

Abstract

The invention provides a pyridine amino ligand universal substrate, a preparation method and a preparation method of a pyridine amino ligand, the structure of the pyridine amino ligand universal substrate is as shown in formula I # imgabs0 #, in the formula, X is halogen; r1, R2, R3, R4, R5, R6, R7, R10, R11 and R12 are independently selected from-H, C1-C40 alkyl, C1-C40 heteroalkyl, C6-C40 aryl, C6-C40 heteroaryl,-Si (RC) 3,-Ge (RC) 3,-P (RP) 2,-N (RN) 2,-ORC,-SRC,-NO2,-CN,-CF3, RCS (O)-, RCS (O) 2-, (RC) 2C = N-, RCC (O) O-, RCOC (O)-, RCC (O) N (R)-, (RC) 2NC (O)-or halogen; r1 is selected from alkyl of C1-C40, hetero-alkyl of C1-C40, aryl of C6-C40, hetero-aryl of C6-C40,-Si (RC) 3, and-Ge (RC) 3; R1 is selected from alkyl of C1-C40, hetero-alkyl of C1-C40, aryl of C6-C40, hetero-aryl of C6-C40; the reaction for preparing the pyridine amino ligand by taking the general substrate as the raw material is as follows: # imgabs 1 #, because the general substrate of the pyridine amino ligand can stably exist, the pyridine amino ligand can be prepared only through one step, so that the preparation difficulty of the pyridine amino ligand is greatly reduced, and the yield of the pyridine amino ligand is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to a general substrate of a pyridine amino ligand, a preparation method thereof, and a preparation method of the pyridine amino ligand. Background Art

[0002] Polyolefins have a wide range of applications in human life due to their abundant raw materials, low price, excellent performance, etc. They are everywhere, from daily necessities to national defense ordnance. China is the world's largest producer and consumer of polyolefins, but there is a serious problem of structural overcapacity in the domestic polyolefin industry. High-end polyolefin products rely on imports, and the self-sufficiency rate is only 44%. The core scientific problem of polyolefins lies in the catalyst, which directly determines the structure and performance of polyolefins. Therefore, the research and development of new catalysts is very important.

[0003] The polyolefin catalyst family is very large. Among them, non-metallocene catalysts have attracted much attention since their invention due to their easily available raw materials, simple synthesis, strong modifiability of ligand structures, and the ability to regulate the catalytic performance of catalysts through ligands, thereby better controlling the structure and performance of the resulting polymers.

[0004] In the past thirty years of development, countless new non-metallocene catalysts with different characteristics have emerged. Among them, the catalyst with a pyridine amino ligand framework developed by Union Carbide Corporation was further developed through a joint cooperation between Symyx Technologies and The Dow Chemical Company. This pyridine amino hafnium catalyst has excellent polymerization activity and stereoselectivity, and can be used for the synthesis of high isotactic polypropylene with high molecular weight. In addition, this catalyst family can also carry out reversible and efficient chain transfer reactions with some alkyl metal complexes (for example, ZnEt2), which is very suitable for the preparation of olefin block copolymers.

[0005] The pyridine amino hafnium catalyst has multiple adjustable substituents, which also provides a large design space for such catalysts. Starting from pyridine derivatives, pyridine amino ligands can be gradually constructed through reactions such as Suzuki coupling. By adjusting the substituents, catalysts with different catalytic activities, thermal stabilities, and monomer selectivities can be obtained, and the molecular weight, molecular weight distribution, and stereoregularity of the polymerized products can be regulated.

[0006] The core of polyolefins lies in the catalyst, and the core of the catalyst lies in ligand design. The synthesis steps of the naphthyl pyridine amino hafnium catalyst of The Dow Chemical Company are cumbersome, the functional group compatibility is poor, and the yield is relatively low. Therefore, developing a catalyst with a simple synthesis method, good group compatibility, and a high-yield preparation method provides a theoretical direction and application value for the development of new polyolefins.

[0007] In view of this, the present invention is hereby provided. Summary of the Invention

[0008] In view of one of the defects in the above-mentioned prior art, the present invention provides a general substrate for pyridylamino ligands. This general substrate can exist stably and is easy to store. When used as a raw material for preparing pyridylamino ligands, it can improve the yield of pyridylamino ligands, realizing the efficient preparation of pyridylamino ligands.

[0009] The present invention also provides a preparation method for the general substrate of pyridylamino ligands. The preparation process of this method is simple and can ensure a high yield of pyridylamino ligands.

[0010] The present invention also provides a preparation method for pyridylamino ligands. It can use the general substrate of pyridylamino ligands as the raw material to directly obtain pyridylamino ligands in one step. The preparation process is simple and reduces the generation amount of by-products. The obtained pyridylamino ligands can be designed according to actual usage requirements and show high catalytic activity for both the homopolymerization and copolymerization of olefins. Compared with the polymers prepared by naphthylpyridylamino catalysts, the molecular weight distribution of the polymers is narrower.

[0011] The object of the present invention is to provide a general substrate for pyridylamino ligands in view of the above problems in the prior art, which has the structure shown in Formula I,

[0012]

[0013] wherein X is a halogen; R1, R2, R3, R4, R5, R6, R7, R 10 , R 11 , R 12 are independently selected from -H, a C1-C 40 hydrocarbon group, a C1-C 40 heterohydrocarbon group, a C6-C 40 aryl group, a C6-C 40 heteroaryl group, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)- or a halogen.

[0014] It should be noted that in the above solution, R C and R P are unsubstituted C1-C 18 hydrocarbyl or -H, and R N is an unsubstituted C1-C 18 hydrocarbyl.

[0015] The term "heterohydrocarbyl" mentioned in the present invention refers to: a straight-chain or branched-chain hydrocarbon containing one or more heteroatoms in the chain skeleton, and the heteroatoms are elements other than carbon, including but not limited to nitrogen, oxygen, sulfur, silicon, etc.

[0016] Furthermore, R3, R4, R5, R6, R7, R 10 , R 11 , R 12 are independently selected from C 1- C 20 hydrocarbyl, C 1- C 20 heterohydrocarbyl, C 1- C 20 aryl, C 1- C 20 heteroaryl.

[0017] Preferably, R4, R5, and R6 are all -H.

[0018] Furthermore, R1 and R2 are different from each other. One is an aryl group which is unsubstituted or substituted by a hydrocarbyl group, a heteroaryl group which is unsubstituted or substituted by a hydrocarbyl group, a C1-C 40 hydrocarbyl or a C1-C 40 heterohydrocarbyl, and the other is -H.

[0019] Preferably, the substituents on the aryl group and the heteroaryl group are C1-C 20 hydrocarbyl.

[0020] More preferably, the substituents on the aryl group and the heteroaryl group are located at the 2-position, and the structure of the substituent is i-Pr.

[0021] Furthermore, R1 and R2 are the same and are selected from C1-C 20 hydrocarbyl.

[0022] Furthermore, using the substance having the structure shown in Formula IIa as a raw material, reacting with an organolithium compound or a Grignard reagent under an inert atmosphere and a preset temperature to obtain a general substrate of a pyridine amino ligand having the structure shown in Formula Ia, the preparation steps are as follows:

[0023]

[0024] Among them, X is a halogen or a pseudo-halogen; R3, R4, R5, R6, R7, R 10 , R 11 , R 12 are independently selected from -H, a C1-C 40 hydrocarbyl group, a C1-C 40 heterohydrocarbyl group, a C6-C 40 aryl group, a C6-C 40 heteroaryl group, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)- or a halogen;

[0025] R1 is selected from a C1-C 40 hydrocarbyl group, a C1-C 40 heterohydrocarbyl group, a C6-C 40 aryl group, a C6-C 40 heteroaryl group, -Si(R C )3, -Ge(R C )3.

[0026] Preferably, under an inert atmosphere, a substance having the structure shown in Formula IIa is mixed with Li-R1 to prepare a mixed solution, and the reaction is carried out in the solution, and the temperature is controlled between -78 °C and the boiling point of the solvent during the reaction; after the reaction is completed, a pyridine amino ligand general substrate having the structure shown in Formula Ia is obtained through post-treatment.

[0027] Preferably, the solvent of the mixed solution is at least one of benzene organic solvents and ether organic solvents.

[0028] More preferably, the benzene organic solvent is toluene, and the ether organic solvents include diethyl ether and tetrahydrofuran.

[0029] Preferably, the reaction time is 1 hour - 12 hours.

[0030] Further, the preparation process of the substance shown in Formula IIa is as follows:

[0031]

[0032] Preferably, the preparation process is as follows: Mix raw material I with the structure shown in Formula IVa, a catalyst, a solvent, and raw material II with the structure shown in Formula III, and continuously stir for reaction. During the reaction process, control the temperature between -78°C and the boiling point of the solvent to obtain a substance with the structure shown in Formula IIa.

[0033] Preferably, the reaction duration is 1 - 24 h.

[0034] Preferably, the solvent is at least one of benzene organic solvents and alcohol organic solvents.

[0035] More preferably, the benzene organic solvents include toluene and dichlorobenzene; the alcohol organic solvents include methanol and ethanol.

[0036] Preferably, the catalyst is selected from at least one of formic acid and p-toluenesulfonic acid.

[0037] Furthermore, using the substance with the structure shown in Formula IIb as a raw material, react with an organoaluminum compound under an inert atmosphere and a preset temperature to obtain a general substrate of a pyridine amino ligand with the structure shown in Formula Ib. The preparation steps are as follows:

[0038]

[0039] Wherein, X is a halogen; R3, R4, R5, R6, R7, R 10 , R 11 , R 12 are independently selected from -H, a C1-C 40 hydrocarbon group, a C1-C 40 heterohydrocarbon group, a C6-C 40 aryl group, a C6-C 40 heteroaryl group, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)- or a halogen;

[0040] R1 is selected from a C1-C 40 hydrocarbon group, a C1-C 40 heterohydrocarbon group, a C6-C40 aryl, C6-C 40 heteroaryl.

[0041] Preferably, under an inert atmosphere, a substance having the structure shown in Formula IIb is mixed with Al-(R1)3 to form a mixed solution, and the reaction is carried out in the solution. During the reaction, the temperature is controlled between -78°C and the boiling point of the solvent; after the reaction is completed, the pyridine amino ligand general substrate having the structure shown in Formula Ib is obtained through post-treatment.

[0042] Preferably, the solvent of the mixed solution is at least one of benzene organic solvents and ether organic solvents.

[0043] More preferably, the benzene organic solvent is toluene, and the ether organic solvents include diethyl ether and tetrahydrofuran.

[0044] Preferably, the reaction time is 1 hour - 12 hours.

[0045] Furthermore, the preparation process of the substance shown in Formula IIb is as follows:

[0046]

[0047] Preferably, the preparation process is: raw material I having the structure shown in Formula IVb, a catalyst, a solvent, and raw material II having the structure shown in Formula III are mixed and continuously stirred for reaction. During the reaction, the temperature is controlled between -78°C and the boiling point of the solvent to obtain a substance having the structure shown in Formula IIb.

[0048] Preferably, the reaction duration is 1 - 24 h.

[0049] Preferably, the solvent is at least one of benzene organic solvents and alcohol organic solvents.

[0050] More preferably, the benzene organic solvents include toluene and dichlorobenzene; the alcohol organic solvents include methanol and ethanol.

[0051] Preferably, the catalyst is selected from at least one of formic acid and p-toluenesulfonic acid.

[0052] The present invention also provides a preparation method of a pyridine amino ligand. Using the pyridine amino ligand general substrate prepared in the above scheme as a raw material, the structure of the pyridine amino ligand is shown in Formula V:

[0053]

[0054] Among them, R1, R2, R3, R4, R5, R6, R7, R 10 、R 11 、R 12 are each independently selected from -H, C1-C 40 hydrocarbon group, C1-C40 heteroalkyl group of C6-C 40 aryl group of C6-C 40 heteroaryl group of C6-C C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)- or halogen; R8 is selected from aryl or heteroaryl group of C6-C 20 ;

[0055] The preparation process is as follows:

[0056]

[0057] wherein, R8 is The structure of R8-R9 is R9 is a group containing B, Zn, Mg, Sn, Si or H; T is a hydrocarbon group of C1-C 40 heteroalkyl group of C1-C 40 aryl group of C6-C 40 heteroaryl group of C6-C 40 ;

[0058] Preferably, R9 is B(OH)2.

[0059] More preferably, T is Me, Et, Ph, OMe or t-Bu.

[0060] Under an inert atmosphere, the general substrate of the pyridine amino ligand shown in formula I, catalyst, ligand, solvent, base and the substance with the structure shown by R8-R9 are mixed to form a mixed solution for reaction, and the reaction temperature is between -78 °C and the boiling point of the solvent.

[0061] Preferably, the solvent includes at least one of benzene organic solvents and alcohol organic solvents.

[0062] More preferably, the benzene organic solvent is toluene; the alcohol organic solvents include methanol and ethanol.

[0063] Preferably, the reaction duration is 12 - 48 h.

[0064] Preferably, after the reaction, ethyl acetate extraction, brine washing, drying with anhydrous sodium sulfate, removal of the solvent using a rotary evaporator, and purification of the product by silica gel column chromatography are required.

[0065] Furthermore, during the preparation process, the catalyst includes a palladium catalyst in the 0-valent or 2-valent state.

[0066] Preferably, the catalyst is selected from at least one of: tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, and palladium acetate.

[0067] Preferably, the ligand includes a monodentate or bidentate ligand containing a P element.

[0068] Preferably, the ligand is selected from at least one of: DPPE, DPPP, DPPB, DPEphos, and Xantphos.

[0069] Preferably, the base includes a strong base-weak acid salt of a Group IA metal.

[0070] Preferably, the base is selected from at least one of: sodium carbonate, potassium carbonate, cesium carbonate, and potassium phosphate.

[0071] The advantages of the present invention are as follows:

[0072] 1. When preparing the pyridine amino ligand using the general substrate of the pyridine amino ligand of the present invention as a raw material, since the corresponding groups of organolithium compounds or organoaluminum compounds are connected to the general substrate in advance during the preparation of the general substrate, it will not affect the highly active groups introduced during the subsequent ligand preparation and catalyst preparation processes, ensuring the yield of the ligand.

[0073] 2. The general substrate of the pyridine amino ligand of the present invention can exist stably. Using it as a raw material, the preparation of the pyridine amino ligand can be achieved through only one-step reaction, simplifying the preparation process of the pyridine amino ligand. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] Figure 1 It is the nuclear magnetic resonance hydrogen spectrum of the general substrate of the pyridine amino ligand prepared in Example 1 of the present invention.

[0075] Figure 2 It is the nuclear magnetic resonance hydrogen spectrum of the general substrate of the pyridine amino ligand prepared in Example 2 of the present invention.

[0076] Figure 3 It is the nuclear magnetic resonance hydrogen spectrum of the catalyst prepared in Example 4 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0077] The exemplary embodiments of the present invention will be described in more detail with reference to the accompanying drawings. Those skilled in the art can understand that the following embodiments are only used to explain the technical principle of the present invention and are not intended to limit the protection scope of the present invention.

[0078] It should be noted in advance that the calculation of the yield in the present invention refers to the ratio between the mass of the product and the total mass of the raw materials, specifically, it refers to calculating the mass ratio between the product and the raw materials in each step, and then multiplying the mass ratios obtained in each step to obtain the total yield.

[0079] The present invention provides a general substrate for pyridine amino ligands, which has the structure shown in Formula I.

[0080]

[0081] Wherein, X is a halogen; R1, R2, R3, R4, R5, R6, R7, R 10 , R 11 , R 12 are independently selected from -H, a C1-C 40 hydrocarbyl group, a C1-C 40 heterohydrocarbyl group, a C6-C 40 aryl group, a C6-C 40 heteroaryl group, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)- or a halogen.

[0082] The general substrate for pyridine amino ligands having the above structure can be stably stored. Using this general substrate for pyridine amino ligands as a raw material, a pyridine amino ligand can be directly prepared through a one-step reaction.

[0083] By simply changing the raw materials during the preparation process, general substrates for pyridine amino ligands with different structures can be prepared, which are generally divided into the following two types:

[0084]

[0085] Among them, X is a halogen; R3, R4, R5, R6, R7, R 10 , R 11 , R 12 are independently selected from -H, a C1-C 40 hydrocarbyl group, a C1-C 40 heterohydrocarbyl group, a C6-C 40 aryl group, a C6-C 40 heteroaryl group, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)- or a halogen;

[0086] In formula A, R1 is selected from a C1-C 40 hydrocarbyl group, a C1-C 40 heterohydrocarbyl group, a C6-C 40 aryl group, a C6-C 40 heteroaryl group, -Si(R C )3, -Ge(R C )3.

[0087] In formula B, R1 is selected from a C1-C6 hydrocarbyl group or a C1-C 40 heterohydrocarbyl group.

[0088] The specific preparation process is as follows: Under an inert atmosphere, control the temperature in the reactor within the range of -78 °C to room temperature, add a substance having the structure shown in formula IIa / IIb, and then add Li-R1 / Al-(R1)3 to the reactor, and react for 1 to 12 hours, ensuring that the reaction temperature is within the range of -78 °C to room temperature during the reaction; after post-treatment, a general substrate of a pyridine amino ligand having the structure shown in formula Ia / Ib is obtained; wherein the post-treatment includes at least quenching, extraction, washing, drying, rotary evaporation and purification carried out in sequence.

[0089] By introducing an organolithium compound or an organoaluminum compound into the general substrate of the pyridine amino ligand in advance in the above preparation process, side reactions between the metal reagent and the group that may occur when introducing a sensitive group into the ligand structure are avoided, thereby effectively improving the yield of the pyridine amino ligand.

[0090] Next, the present invention will be further described with specific embodiments.

[0091] Example 1

[0092] As an embodiment of the present invention, this embodiment provides a general substrate of a pyridine amino ligand, and its structure is shown in Formula Ia1,

[0093]

[0094] It can be seen that in Formula Ia1, one of R1 and R2 is H, and the other is i-PrPh; both R3 and R7 are i-Pr; R4, R5, R6, R 10 , R 11 , R 12 are all H; X is Cl.

[0095] The preparation process of the general substrate of the pyridine amino ligand shown in Formula Ia1 is as follows:

[0096]

[0097] The specific preparation process is as follows:

[0098] Add the raw material (1.504 g, 5 mmol) with the structure shown in Formula IIa1 to the reactor, use a double-tube vacuum-nitrogen replacement more than three times to keep the nitrogen atmosphere in the reactor, then add ether (20 mL), and use an acetone-dry ice bath to adjust the temperature in the reactor to -78 °C. Then add the organolithium compound with the structure to the reactor and react for 6 hours. During the reaction, ensure that the reaction temperature is within the range of -78 °C to room temperature. After the reaction, quench with ammonium chloride, extract with ether, wash with brine, dry with anhydrous sodium sulfate, collect the extract and remove the solvent by rotary evaporation, and purify by column chromatography (PE:EA = 50:1) to obtain the general substrate of the pyridine amino ligand with the structure shown in Formula Ia1 (2.065 g, 98%).

[0099] Among them, the preparation process of the substance shown in Formula IIa1 is as follows:

[0100]

[0101] The specific preparation process is as follows:

[0102] Add raw material 1 (1.416 g, 10 mmol) with the structure shown in Formula Ⅳa1, TsOH (95 mg, 0.5 mmol), methanol (100 mL), and raw material 2 (1.773 g, 10 mmol) with the structure shown in Formula Ⅲ1 into a reactor with a stirring device in sequence, and continuously stir the reaction at room temperature for 8 hours. After the reaction is completed, remove the solvent by rotary evaporation, use neutral alumina to flash through a column with DCM as the eluent, collect the filtrate, remove the solvent by rotary evaporation, and recrystallize with pentane to obtain the substance shown in Formula IIa1 in the form of yellow crystals (2.41 g, 80.1%).

[0103] The nuclear magnetic resonance results of the prepared substance are as Figure 1 shown below:

[0104] 1 1H-NMR (600 MHz, ) δ 7.61 (d, J = 5.8 Hz, 2H), 7.53 (t, J = 7.7 Hz, 1H), 7.25–7.21 (m, 3H), 7.16 (d, J = 7.8 Hz, 1H), 7.12 (d, J = 7.6 Hz, 1H), 7.05–7.00 (m, 3H), 5.38 (s, 1H), 4.35 (s, 1H), 3.01 (dt, J = 13.5, 6.7 Hz, 1H), 2.94 (dt, J = 13.6, 6.8 Hz, 2H), 1.04 (d, J = 6.8 Hz, 6H), 1.01 (d, J = 6.8 Hz, 3H), 0.98 (d, J = 6.7 Hz, 6H), 0.89 (d, J = 6.8 Hz, 3H).

[0105] Example 2

[0106] As an embodiment of the present invention, this embodiment provides a general substrate of a pyridine amino ligand, and its structure is shown in Formula Ⅰb1,

[0107]

[0108] It can be seen that in Formula Ⅰb1, both R1 and R2 are Me; both R3 and R7 are i-Pr; R4, R5, R6, R 10 , R 11 , R 12 are all H; X is Br.

[0109] The preparation process of the general substrate of the pyridine amino ligand shown in Formula Ⅰb1 is as follows:

[0110]

[0111] The specific preparation process is as follows:

[0112] The raw material with the structure shown in Formula IIb1 (359 mg, 1 mmol) was added to the reactor. The reactor was evacuated and filled with nitrogen more than three times using a double-tube vacuum-nitrogen replacement to maintain a nitrogen atmosphere inside the reactor. Then, Tol (10 mL) was added. The temperature inside the reactor was adjusted to -78 °C using an acetone-dry ice bath. Then, the organoaluminum compound with the structure was added to the reactor (1.2 mL, 1 M in Hex). The reaction was heated under reflux for 4 hours, and the reaction temperature was ensured to be within the range of -78 °C to room temperature during the reaction. After the reaction was completed, the temperature inside the reactor was adjusted to 0 °C, and 3 M aqueous NaOH solution was slowly added dropwise for quenching. Ethyl acetate was added for extraction, followed by washing with brine. The organic phase was collected and dried over anhydrous sodium sulfate. The solvent was removed using a rotary evaporator, and the product was purified by column chromatography (PE:EA = 20:1) to obtain the pyridine amino ligand general substrate with the structure shown in Formula ⅠIb1 (372 mg, 99%).

[0113] Furthermore, the preparation process of the substance shown in Formula IIb1 is as follows:

[0114]

[0115] The specific preparation process is as follows:

[0116] Raw material 1 with the structure shown in Formula Ⅳb1 (200 mg, 1 mmol), HCOOH (2.3 mg, 0.05 mmol), methanol (80 mL), and raw material 2 with the structure shown in Formula Ⅲ1 (266 mg, 1.5 mmol) were successively added to the reactor equipped with a stirring device, and the reaction was continuously stirred at room temperature for 8 hours. After the reaction was completed, the solvent was removed using a rotary evaporator. Using DCM as the developing agent, flash column chromatography was carried out using neutral alumina, and the filtrate was collected. The solvent was removed using a rotary evaporator, and recrystallization was carried out using methanol to obtain the substance shown in Formula IIb1 as yellow crystals (298 mg, 83%).

[0117] The nuclear magnetic resonance results of the prepared substance are as shown in Figure 2 and are specifically as follows:

[0118] 1 1H-NMR (600 MHz) δ 7.53–7.47 (m, 2H), 7.34 (d, J = 7.2 Hz, 1H), 7.07–7.03 (m, 3H), 3.96 (s, 1H), 3.14 (dt, J = 13.7, 6.8 Hz, 2H), 1.57 (s, 3H), 1.43 (s, 6H), 1.07 (d, J = 6.8 Hz, 12H).

[0119] Example 3

[0120] As another embodiment of the present invention, this embodiment provides a pyridine amino ligand prepared from the pyridine amino ligand general substrate described in Embodiment 1. Its structure is shown in Formula V1, and the preparation process is as follows:

[0121]

[0122] The specific preparation process is as follows:

[0123] Add the pyridine amino ligand general substrate shown in Formula Ia1 (105 mg, 0.25 mmol), tetrakis(triphenylphosphine)palladium (14.4 mg, 0.0125 mmol), and DPPE (5.0 mg, 0.0125 mmol) into the reactor. Use a double-tube to evacuate and replace with nitrogen more than three times to keep the inside of the reactor under a nitrogen atmosphere. Then add toluene (1 mL) and potassium phosphate (0.25 mL, 2 M in H2O). Dissolve (45.7 mg, 0.375 mmol) with ethanol (1 mL) and add it to the reaction system. React at 100 °C for 12 hours. After the reaction is completed, extract three times with ethyl acetate (10 mL). Rotavaporize the extract to remove the solvent, and purify by column chromatography (PE:EA = 50:1) to obtain the pyridine amino ligand shown in Formula V1 (113 mg, 97%).

[0124] The NMR data of the pyridine amino ligand shown in Formula V1 are as follows:

[0125] 1 H-NMR (600 MHz,) δ 8.02 (d, J = 7.5 Hz, 2H), 7.77–7.71 (m, 1H), 7.23–7.16 (m, 4H), 7.15–7.10 (m, 6H), 7.05 (t, J = 7.7 Hz, 1H), 6.89 (d, J = 7.6 Hz, 1H), 5.68 (d, J = 7.4 Hz, 1H), 5.09 (d, J = 7.4 Hz, 1H), 3.41–3.29 (m, 3H), 1.11–1.08 (m, 9H), 1.06 (d, J = 6.8 Hz, 6H), 0.95 (d, J = 6.8 Hz, 3H).

[0126] Example 4

[0127] As another embodiment of the present invention, this embodiment provides a pyridine amino ligand prepared from the pyridine amino ligand general substrate described in Embodiment 1. Its structure is shown in Formula V2, and the preparation process is as follows:

[0128]

[0129] The specific preparation process is as follows:

[0130] Into the reactor, add the pyridine amino ligand general substrate shown in Formula Ⅰa1 (105 mg, 0.25 mmol), tetrakis(triphenylphosphine)palladium (14.4 mg, 0.0125 mmol), and DPEphos (6.7 mg, 0.0125 mmol) into the flask. Use a double manifold to evacuate and replace with nitrogen for more than three times to keep the inside of the reactor under a nitrogen atmosphere. Then add toluene (1 mL) and potassium phosphate (0.25 mL, 2 M in H2O). Dissolve (51 mg, 0.375 mmol) and add it to the reaction system. React at 100 °C for 12 hours. After the reaction is completed, extract with ethyl acetate (10 mL) three times. Remove the solvent from the extract by rotary evaporation and purify by column chromatography (PE:EA = 50:1) to obtain the pyridine amino ligand shown in Formula V2 (119 mg, 99%).

[0131] The nuclear magnetic resonance results of the pyridine amino ligand shown in Formula V2 are as Figure 3 shown, and the specific data are as follows:

[0132] 1 1H-NMR (600 MHz,) δ 7.74–7.70 (m, 1H), 7.40–7.37 (m, 1H), 7.15 (t, J = 3.1 Hz, 1H), 7.14–7.11 (m, 2H), 7.11–7.08 (m, 5H), 7.08–7.05 (m, 2H), 6.91 (m, J = 8.8, 7.8, 0.9 Hz, 2H), 5.65 (d, J = 8.0 Hz, 1H), 4.83 (d, J = 7.9 Hz, 1H), 3.33–3.17 (m, 3H), 2.24 (s, 3H), 1.07 (d, J = 6.8 Hz, 6H), 1.03 (d, J = 6.8 Hz, 6H), 1.01 (d, J = 6.8 Hz, 3H), 0.95 (d, J = 6.8 Hz, 3H).

[0133] Example 5

[0134] As another example of the present invention, this example provides a pyridine amino ligand prepared from the pyridine amino ligand general substrate described in Example 1. Its structure is shown in Formula V3, and the preparation process is as follows:

[0135]

[0136] The specific preparation process is as follows:

[0137] Into the reactor was added the pyridine amino ligand general substrate shown in Formula Ⅰa1 (105 mg, 0.25 mmol), palladium tetrakis(triphenylphosphine) (14.4 mg, 0.0125 mmol), and DPEphos (6.7 mg, 0.0125 mmol). The flask was charged, and the reactor was evacuated and backfilled with nitrogen more than three times to maintain a nitrogen atmosphere inside. Then, toluene (1 mL) was added, followed by potassium phosphate (0.25 mL, 2 M in H2O). (56.8 mg, 0.375 mmol) was dissolved and added to the reaction system. The reaction was carried out at 100 °C for 12 hours. After the reaction was completed, the mixture was extracted three times with ethyl acetate (10 mL). The extract was concentrated by rotary evaporation to remove the solvent, and then purified by column chromatography (PE:EA = 50:1) to obtain the pyridine amino ligand shown in Formula V3 (120 mg, 98%).

[0138] The NMR data of the pyridine amino ligand shown in Formula V3 are as follows:

[0139] 1 1H-NMR (600 MHz, ) δ 7.77–7.69 (m, 1H), 7.35 (d, J = 7.3 Hz, 1H), 7.21–7.17 (m, 4H), 7.15–7.07 (m, 6H), 6.96 (d, J = 7.9 Hz, 2H), 5.68 (d, J = 8.1 Hz, 1H), 4.80 (d, J = 8.1 Hz, 1H), 3.37–3.16 (m, 3H), 2.80–2.64 (m, 2H), 1.11 (d, J = 6.8 Hz, 6H), 1.07–1.01 (m, 12H), 0.98 (d, J = 6.8 Hz, 3H).

[0140] Example Six

[0141] As another example of the present invention, this example provides a pyridine amino ligand prepared from the pyridine amino ligand general substrate described in Example One, and its structure is shown in Formula V4. The preparation process is as follows:

[0142]

[0143] The specific preparation process is as follows:

[0144] Add the pyridine amino ligand general substrate shown in Formula Ia1 (105 mg, 0.25 mmol), tetrakis(triphenylphosphine)palladium (14.4 mg, 0.0125 mmol), and DPPE (4.8 mg, 0.0125 mmol) into the reactor. Use a double-tube to evacuate and replace with nitrogen for more than three times to keep the reactor under a nitrogen atmosphere. Then add toluene (1 mL) and potassium phosphate (0.25 mL, 2 M in H2O). Dissolve (63 mg, 0.375 mmol) with ethanol (1 mL) and add it to the reaction system. React at 100 °C for 12 hours. After the reaction, extract with ethyl acetate (10 mL) three times. Remove the solvent from the extract by rotary evaporation and purify by column chromatography (PE:EA = 50:1) to obtain the pyridine amino ligand shown in Formula V4 (116 mg, 92%).

[0145] The NMR data of the pyridine amino ligand shown in Formula V4 are as follows:

[0146] 1 1H-NMR (600 MHz, C6D6) δ 7.73–7.68 (m, 1H), 7.29 (dd, J = 10.2, 8.0 Hz, 2H), 7.21 (t, J = 7.6 Hz, 1H), 7.15–7.11 (m, 3H), 7.10–7.05 (m, 5H), 6.96–6.92 (m, 2H), 5.64 (d, J = 8.3 Hz, 1H), 4.73 (d, J = 8.3 Hz, 1H), 3.36 (dt, J = 13.7, 6.9 Hz, 1H), 3.25 (dt, J = 13.6, 6.8 Hz, 1H), 3.17 (dt, J = 13.7, 6.8 Hz, 2H), 1.15 (d, J = 6.9 Hz, 3H), 1.07 (d, J = 6.9 Hz, 9H), 1.03 (d, J = 6.8 Hz, 6H), 0.99 (d, J = 6.8 Hz, 3H), 0.95 (d, J = 6.8 Hz, 3H).

[0147] Example VII

[0148] As another example of the present invention, in this example, a catalyst with the structure shown in Formula VI1 is prepared using the pyridine amino ligand described in Example III as the raw material. The preparation process is as follows:

[0149]

[0150] The specific preparation process is as follows:

[0151] In the glove box, the pyridine amino ligand with the structure shown in Formula V1 (463 mg, 1 mmol) was added to a 50 mL Schlenk flask, 10 mL of toluene was added, and after the rubber stopper was inserted, it was taken out of the glove box. Then n-butyllithium (0.42 mL, 1.05 mmol, 2.5 mol in Hex) was added, and the reaction was carried out at room temperature for 1 hour. The solvent was dried under vacuum, and then it was transferred into the glove box. The flask was washed three times by the pentane decantation method. Then 10 mL of toluene was added, and hafnium tetrachloride (320 mg, 1 mmol) was added. After inserting the rubber stopper, it was taken out of the glove box and heated in an oil bath at 100 °C for 2 hours. The heating was stopped, and after cooling, methylmagnesium bromide (1.17 mL, 3.5 mmol, 3 mol / L in diethyl ether) was added. The reaction was carried out for 8 hours. The solvent was dried under vacuum, transferred into the glove box, dissolved in toluene, filtered, and the solvent was dried under vacuum again. The product was washed three times with pentane to obtain the catalyst with the structure shown in Formula VI1 (363 mg, 54%).

[0152] Example VIII

[0153] As another example of the present invention, in this example, the pyridine amino ligand described in Example IV was used as the raw material to prepare a catalyst with the structure shown in Formula VI2. The preparation process is as follows:

[0154]

[0155] The specific preparation process is as follows:

[0156] In the glove box, the pyridine amino ligand with the structure shown in Formula V2 (477 mg, 1 mmol) was added to a 50 mL Schlenk flask, 10 mL of toluene was added, and after the rubber stopper was inserted, it was taken out of the glove box. Then n-butyllithium (0.42 mL, 1.05 mmol, 2.5 mol in Hex) was added, and the reaction was carried out at room temperature for 1 hour. The solvent was dried under vacuum, and then it was transferred into the glove box. The flask was washed three times by the pentane decantation method. Then 10 mL of toluene was added, and hafnium tetrachloride (320 mg, 1 mmol) was added. After inserting the rubber stopper, it was taken out of the glove box and heated in an oil bath at 100 °C for 2 hours. The heating was stopped, and after cooling, methylmagnesium bromide (1.17 mL, 3.5 mmol, 3 mol / L in diethyl ether) was added. The reaction was carried out for 8 hours. The solvent was dried under vacuum, transferred into the glove box, dissolved in toluene, filtered, and the solvent was dried under vacuum again. The product was washed three times with pentane to obtain the catalyst product with the structure shown in Formula VI2 (438 mg, 64%).

[0157] The NMR data of the catalyst with the structure shown in Formula VI2 are as follows:

[0158] 11H-NMR (600 MHz), δ 8.39 (d, J = 5.8 Hz, 1H), 7.38 (t, J = 7.1 Hz, 1H), 7.30–7.27 (m, 1H), 7.18 (dd, J = 9.1, 7.2 Hz, 2H), 7.14 (t, J = 7.6 Hz, 1H), 7.09–7.06 (m, 2H), 7.03–6.98 (m, 3H), 6.83 (t, J = 7.9 Hz, 1H), 6.60 (s, 1H), 6.55 (d, J = 7.7 Hz, 1H), 3.83 (dt, 1H), 3.36 (dt, 1H), 2.90 (dt, J = 13.7, 6.8 Hz, 1H), 2.26 (s, 3H), 1.38 (dd, J = 6.8, 5.3 Hz, 6H), 1.17 (d, J = 6.9 Hz, 3H), 1.14 (d, J = 6.8 Hz, 3H), 0.94 (s, 3H), 0.69 (d, J = 6.7 Hz, 3H), 0.65 (s, 3H), 0.39 (d, J = 6.7 Hz, 3H).

[0159] Example IX

[0160] As another embodiment of the present invention, in this embodiment, a catalyst having the structure shown in Formula VI3 is prepared using the pyridine amino ligand described in Example V as a raw material. The preparation process is as follows:

[0161]

[0162] The specific preparation process is as follows:

[0163] In a glove box, add the pyridine amino ligand (491 mg, 1 mmol) with the structure shown in Formula V3 to a 50 mL Schlenk flask, add 10 mL of toluene, seal with a rubber stopper and take it out of the glove box. Add n-butyllithium (0.42 mL, 1.05 mmol, 2.5 mol / L in Hex), react at room temperature for 1 hour, use vacuum to dry the solvent, transfer it into the glove box, wash three times by pentane decantation, add 10 mL of toluene, add hafnium tetrachloride (320 mg, 1 mmol), seal with a rubber stopper and take it out of the glove box. Heat in an oil bath at 100 °C for 2 hours, stop heating, after cooling, add methylmagnesium bromide (1.17 mL, 3.5 mmol, 3 mol / L in diethylether), react for 8 hours, use vacuum to dry the solvent, transfer it into the glove box, dissolve in toluene, filter, use vacuum to dry the solvent, wash three times with pentane, and obtain a catalyst product with the structure shown in Formula VI3 (411 mg, 59%).

[0164] The NMR data of the catalyst with the structure shown in Formula VI3 are as follows:

[0165] 1H-NMR (600 MHz, ) δ 8.49 (dd, J = 6.8, 1.3 Hz, 1H), 7.40 (t, J = 7.2 Hz, 1H), 7.31–7.28 (m, 1H), 7.22 (s, 1H), 7.18–7.17 (m, 1H), 7.16–7.10 (m, 6H), 7.09–7.06 (m, 1H), 7.04–7.01 (m, 1H), 6.99–6.94 (m, 2H), 6.63 (d, J = 8.0 Hz, 1H), 6.56 (s, 1H), 6.48 (t, J = 7.9 Hz, 1H), 6.41 (d, J = 7.6 Hz, 1H), 3.83 (dt, 1H), 3.38 (dt, J = 13.6, 6.8 Hz, 1H), 2.83 (dt, J = 13.7, 6.9 Hz, 1H), 1.39 (d, J = 6.8 Hz, 3H), 1.35 (d, J = 6.8 Hz, 3H), 1.18 (d, J = 6.8 Hz, 3H), 1.09 (d, J = 6.9 Hz, 3H), 1.02 (s, 3H), 0.71 (s, 3H), 0.66 (d, J = 6.7 Hz, 3H), 0.39 (d, J = 6.7 Hz, 3H).

[0166] Example Ten

[0167] As another embodiment of the present invention, in this embodiment, a pyridine amino ligand as described in Example Six is used as a raw material to prepare a catalyst having the structure shown in Formula VI4. The preparation process is as follows:

[0168]

[0169] The specific preparation process is as follows:

[0170] In a glove box, add the pyridine amino ligand (505 mg, 1 mmol) with the structure shown in Formula V4 to a 50 mL Schlenk flask, add 10 mL of toluene, seal with a rubber stopper and transfer out of the glove box. Add n-butyllithium (0.42 mL, 1.05 mmol, 2.5 mol / L in Hex), react at room temperature for 1 hour, use vacuum to dry the solvent, transfer into the glove box, wash three times by pentane decantation method, add 10 mL of toluene, add hafnium tetrachloride (320 mg, 1 mmol), seal with a rubber stopper and transfer out of the glove box, heat in an oil bath at 100 °C for 2 hours, stop heating, after cooling, add methylmagnesium bromide (1.17 mL, 3.5 mmol, 3 mol / L in diethylether), react for 8 hours, use vacuum to dry the solvent, transfer into the glove box, dissolve in toluene, filter, use vacuum to dry the solvent, wash three times with pentane to obtain a catalyst product (299 mg, 42%) having the structure shown in Formula VI2.

[0171] The NMR data of the catalyst with the structure shown in Formula VI2 are as follows:

[0172] 1 1H-NMR (600 MHz, ) δ 8.38 (d, J = 6.6 Hz, 1H), 7.46 (t, 1H), 7.31 (d, J = 7.6 Hz, 1H), 7.27 (dd, J = 13.0, 7.9 Hz, 2H), 7.17 (d, J = 6.0 Hz, 1H), 7.14 (t, J = 7.6 Hz, 1H), 7.09–7.05 (m, 2H), 6.98 (dt, J = 14.8, 7.2 Hz, 2H), 6.88 (t, J = 7.9 Hz, 1H), 6.62–6.58 (m, 2H), 3.83 (dt, J = 13.6, 6.8 Hz, 1H), 3.39 (dtd, J = 20.5, 13.6, 6.8 Hz, 2H), 2.90 (dt, J = 13.6, 6.8 Hz, 1H), 1.37 (dd, J = 9.8, 6.9 Hz, 6H), 1.17 (d, J = 6.7 Hz, 6H), 1.14 (dd, J = 9.2, 6.8 Hz, 6H), 0.93 (s, 3H), 0.69 (d, J = 6.7 Hz, 3H), 0.65 (s, 3H), 0.39 (d, J = 6.7 Hz, 3H).

[0173] Comparative Example 1

[0174] As a comparative example of the present invention, this comparative example provides a pyridine ligand, and the preparation process is as follows:

[0175]

[0176] The specific processes of the above steps are as follows:

[0177] S1. Add 6-bromo-2-aldehyde pyridine (372 mg, 2 mmol) and bis(triphenylphosphine)palladium dichloride (70.19 mg, 0.1 mmol) into the reactor. Use a double-tube to evacuate and replace with nitrogen for more than three times to keep the reactor in a nitrogen atmosphere. Then add toluene (30 mL) and sodium carbonate (2 mL, 2 M in H2O). Dissolve 2-isopropylphenylboronic acid (423.96 mg, 4 mmol) with ethanol (30 mL) and add it to the reaction system. React at 85 °C with a stirring speed of 400 rpm for 10 hours. After the reaction is completed, extract with ethyl acetate (10 mL) three times. Remove the solvent from the extract by rotary evaporation and purify by column chromatography (PE:EA = 20:1) to obtain the substance with the structure shown in Figure 3 (yield: 46%).

[0178] S2. Add 130.67 mg (0.58 mmol) of the substance with the structure shown in Formula 3, TsOH (10.32 mg, 0.06 mmol), methanol (20 mL), and 2,6-diisopropylaniline (102.83 mg, 0.58 mmol) into the reactor with a stirring device in sequence, and continuously stir the reaction at room temperature for 24 hours. After the reaction is completed, remove the solvent by rotary evaporation. Use neutral alumina to flash column with DCM as the eluent, collect the filtrate, remove the solvent by rotary evaporation, and recrystallize with pentane to obtain the substance shown in Formula 5 as yellow crystals (yield: 71%).

[0179] S3. Add ether into the first reactor under nitrogen protection, then add isopropylphenyl bromide (78.84 mg, 0.396 mmol) and n-butyllithium (22.04 mg, 0.344 mmol), and ensure that the temperature in the reactor is -78 °C when adding butyllithium. After adding, remove it, and continuously react for 4 h. Then add the substance shown in Formula 5 (76.91 mg, 0.2 mmol) into the second reactor under nitrogen protection. Cool the two reactors to -78 °C, and use a double-headed needle to introduce the solution in the first reactor into the second reactor. After restoring to room temperature, react for 6 hours; then quench with NH4Cl, dilute with ether, wash twice with brine in a separatory funnel, filter, dry with Na2CO3, remove the solvent by rotary evaporation, and purify by column chromatography (PE:EA = 50:1) to obtain the white solid product shown in Formula 9, yield: 76%.

[0180] Comparative Example 2

[0181] This comparative example adopts the preparation method described in Comparative Example 1, the difference is that the selection of preparation raw materials is different from that of Comparative Example 1, and the preparation process is as follows:

[0182]

[0183] The specific processes of the above steps are as follows:

[0184] S1. Add 6-bromo-2-aldehyde pyridine and bis(triphenylphosphine)palladium dichloride into the reactor, use a double-row tube to vacuum-nitrogen displace more than three times to keep the reactor in a nitrogen atmosphere, then add toluene (30 mL), sodium carbonate, dissolve phenylboronic acid with ethanol (30 mL) and add it to the reaction system, and react at 90 °C and a stirring speed of 400 rpm for 24 hours. After the reaction is completed, extract three times with ethyl acetate, remove the solvent from the extract by rotary evaporation, and purify by column chromatography (PE:EA = 50:1) to obtain the pyridine amino ligand with the structure shown in 3, and the conversion rate is 88%.

[0185] S2. Add the pyridine amino ligand with the structure shown in Formula 3, TsOH, methanol, and 2,6 - diisopropylaniline into the reactor with a stirring device in sequence, and continuously stir and react at room temperature for 24 hours. After the reaction is completed, remove the solvent by rotary evaporation. Use neutral alumina to flash - column with DCM as the eluent, collect the filtrate, remove the solvent by rotary evaporation, and recrystallize with pentane to obtain the substance shown in Formula 5 in the form of yellow crystals, with a conversion rate of 86.51%.

[0186] S3. Add ether into the first reactor under nitrogen protection, then add bromoisopropylbenzene and n - butyllithium, and ensure that the temperature in the reactor is - 78 °C when adding n - butyllithium. After adding, remove it, and continuously react for 4 h. Then, under nitrogen protection, add the substance shown in Formula 5 into the second reactor. Cool the two reactors to - 78 °C, and use a double - headed needle to introduce the solution in the first reactor into the second reactor. After restoring to room temperature, react for 6 hours; then quench with NH4Cl, dilute with ether, wash twice with brine in a separatory funnel, filter, dry with Na2CO3, remove the solvent by rotary evaporation, and purify by column chromatography (PE:EA = 100:1) to obtain the catalyst in the form of a white solid shown in Formula 9, with a conversion rate of 89.60%.

[0187] The dosages of each substance are shown in the following table:

[0188] substance <![CDATA[M W (g / mol)]]> N n (mmol) m (g) / V (mL) 6-bromo-2-aldehyde pyridine 186.01 1 10 1.8601 phenylboronic acid 121.93 1.5 15 1.829 <![CDATA[Pd(PPh3)4]]> 1155.58 0.02 0.2 0.231 sodium carbonate 212.26 2 20 2.12 the substance shown in Formula 3 182.22 1 8 1.458 2,6-diisopropylaniline 177.29 1.2 9.6 1.702 p-toluenesulfonic acid 172.2 0.1 0.8 0.152 the substance shown in Formula 5 342.48 5 1 1712 1-bromo-6-isopropylbenzene 199.09 9.9 1.98 1.54 n-butyllithium 64.06 8.6 1.72 3.58 the substance shown in Formula 9 462.68

[0189] Comparative Example 3

[0190] This comparative example adopts the preparation method described in Comparative Example 1, with the difference that the selection of raw materials for preparation is different from that in Comparative Example 1. The preparation process is as follows:

[0191]

[0192]

[0193] The specific processes of the above - mentioned steps are as follows:

[0194] S1. Add 6 - bromo - 2 - pyridinecarboxaldehyde and bis(triphenylphosphine)palladium dichloride into the reactor. Use a double - row tube to vacuum - nitrogen displace more than three times to keep the reactor in a nitrogen atmosphere, then add toluene (30 mL), sodium carbonate. Dissolve phenylboronic acid with ethanol (30 mL) and add it to the reaction system. React at 100 °C and a stirring speed of 400 rpm for 12 hours. After the reaction is completed, extract three times with ethyl acetate, remove the solvent from the extract by rotary evaporation, and purify by column chromatography (PE:EA = 50:1) to obtain the pyridine amino ligand with the structure shown in Formula 3, with a conversion rate of 90%.

[0195] S2. Add the substance with the structure shown in Formula 3, TsOH, methanol, and 2,6 - diisopropylaniline into the reactor with a stirring device in sequence, and continuously stir and react at room temperature for 24 hours. After the reaction is completed, remove the solvent by rotary evaporation. Use neutral alumina for flash column chromatography with DCM as the eluent, collect the filtrate, remove the solvent by rotary evaporation, and recrystallize with pentane to obtain the substance shown in Formula 5 in the form of yellow crystals, with a conversion rate of 92%.

[0196] S3. Add diethyl ether into the first reactor under nitrogen protection, then add bromoisopropylbenzene and n - butyllithium, and ensure that the temperature in the reactor is - 78 °C when adding n - butyllithium. After adding, remove it, and continuously react for 4 h. Then, under nitrogen protection, add the substance shown in Formula 5 into the second reactor. Cool the two reactors to - 78 °C, and use a double - headed needle to introduce the solution in the first reactor into the second reactor. After restoring to room temperature, react for 6 hours; then quench with NH4Cl, dilute with diethyl ether, wash twice with brine in a separatory funnel, filter, dry with Na2CO3, remove the solvent by rotary evaporation, and purify by column chromatography (PE:EA = 100:1) to obtain the catalyst in the form of a white solid shown in Formula 9, with a conversion rate of 78%.

[0197] The dosages of each substance are shown in the following table:

[0198]

[0199]

[0200] Comparative Example 4

[0201] This comparative example adopts the preparation method described in Comparative Example 1, with the difference that the selection of raw materials for preparation is different from that in Comparative Example 1. The preparation process is as follows:

[0202]

[0203] The specific processes of the above steps are as follows:

[0204] S1. Add 6 - bromo - 2 - pyridinecarboxaldehyde and formic acid into the reactor, use a double - row tube to replace the vacuum with nitrogen more than three times to keep the reactor in a nitrogen atmosphere, then add ethanol, and then add 2,6 - diisopropylaniline into the reaction system. React at 80 °C for 3 hours. After the reaction is completed, extract three times with ethyl acetate. Remove the solvent from the extract by rotary evaporation, and purify by column chromatography (PE:EA = 50:1) to obtain the pyridine - amino ligand with the structure shown in Formula 3, with a conversion rate of 92%.

[0205] S2. Sequentially add the substance with the structure shown in Formula 3, TsOH, methanol, and 2-ethylphenylboronic acid into the reactor equipped with a stirring device, and continuously stir and react at a temperature of 100 °C for 12 hours. After the reaction is completed, remove the solvent by rotary evaporation. Using DCM as the eluent, perform flash column chromatography with neutral alumina, collect the filtrate, remove the solvent by rotary evaporation, and recrystallize with pentane to obtain the substance shown in Formula 5 in the form of yellow crystals, with a conversion rate of 81%.

[0206] S3. Add diethyl ether to the first reactor under nitrogen protection, then add bromoisopropylbenzene and n-butyllithium, and ensure that the temperature in the reactor is -78 °C when adding n-butyllithium. After adding, remove it, and continuously react for 4 h. Then, under nitrogen protection, add the substance shown in Formula 5 to the second reactor. Cool the two reactors to -78 °C, and use a double-headed needle to introduce the solution in the first reactor into the second reactor. After restoring to room temperature, react for 6 hours; then quench with NH4Cl, dilute with diethyl ether, wash twice with brine in a separatory funnel, filter, dry with Na2CO3, remove the solvent by rotary evaporation, and purify by column chromatography (PE:EA = 100:1) to obtain the white solid product shown in Formula 9, with a conversion rate of 87%.

[0207] The dosages of each substance are shown in the following table:

[0208]

[0209] Comparative Example 5

[0210] This comparative example provides a naphthylpyridine amino catalyst, and the preparation method is as follows:

[0211]

[0212] Specifically, in a glove box, add the naphthylpyridine amino ligand with the structure shown in Formula 1 (491 mg, 1 mmol) to a 50 mL Schlenk flask, add 10 mL of toluene, seal with a rubber stopper and take it out of the glove box, add n-butyllithium (0.42 mL, 1.05 mmol, 2.5 mol / L in Hex), react at room temperature for 1 hour, dry the solvent by vacuum pumping, transfer it into the glove box, wash three times by pentane pouring method, add 10 mL of toluene, add hafnium tetrachloride (320 mg, 1 mmol), seal with a rubber stopper and take it out of the glove box, heat in an oil bath at 110 °C for 1 hour, stop heating, after cooling, add methylmagnesium bromide (1.17 mL, 3.5 mmol, 3 mol / L in diethyl ether), react for 8 hours, dry the solvent by vacuum pumping, transfer it into the glove box, dissolve with toluene, filter, dry the solvent by vacuum pumping, and wash three times with pentane to obtain the catalyst product with the structure shown in Formula 2.

[0213] Experimental Example 1

[0214] As an experimental example of the present invention, pyridylamino ligands prepared from different general substrates of pyridylamino ligands were used as raw materials, and the catalytic performances of the obtained catalysts were compared. Specifically, the catalyst was used to catalyze the homopolymerization of 1-octene, and the polymerization conditions were as follows: 2 μmol of the catalyst, cocatalyst: Ph3C + B(C6F5)4 - 2.4 μmol, 10 mmol of octene, 16.4 mL of toluene. The comparison results are shown in the following table:

[0215]

[0216] Experimental Example Two

[0217] As an experimental example of the present invention, pyridylamino ligands prepared from different general substrates of pyridylamino ligands were used as raw materials, and the catalytic performances of the obtained catalysts were compared. Specifically, the catalyst was used to catalyze the homopolymerization of ethylene, and the polymerization conditions were as follows: 5 μmol of the catalyst, cocatalyst: Ph3C + B(C6F5)4 - 6 μmol, 40 mL of toluene, ethylene pressure of 1 atm, polymerization temperature of 40 °C. The comparison results are shown in the following table:

[0218]

[0219] It can be seen from Experimental Example One and Experimental Example Two that the catalysts prepared from the general substrate of pyridylamino ligands described in the present invention exhibit excellent catalytic performances for both olefin homopolymerization and copolymerization.

[0220] Experimental Example Three

[0221] As another experimental example of the present invention, the yields of pyridylamino ligands prepared by different preparation methods were counted and compared. The comparison results are shown in the following table:

[0222] It should be noted that in the yield part of the following table, general formula IIa / IIb / % refers to the yield of the step of preparing the substance with the structure shown in formula IIa / IIb; general substrate / % refers to the yield of the step of preparing the general substrate from the substance with the structure shown in formula IIa / IIb; ligand / % refers to the yield of the entire process from the preparation of the substance with the structure shown in formula IIa / IIb to the final ligand obtained.

[0223]

[0224] As can be seen from the above table: adopting the method of the present invention can ensure that the obtained general substrate has a very high yield, avoiding the increase in production cost caused by excessive by-products; at the same time, the yield of the ligand prepared from the general substrate is also significantly increased, which is conducive to the popularization of industrial production; while in the comparative example, the existing preparation method cannot avoid the appearance of by-products, resulting in a low proportion of the ligand in the product, and it needs to be purified before use. On the one hand, it significantly increases the production cost, and on the other hand, it makes the preparation process lengthy, affecting the production speed and being not conducive to industrial production.

[0225] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Although the present invention has been disclosed above with the preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art of this patent, without departing from the scope of the technical solution of the present invention, can make some changes or modifications to the above-mentioned technical content as equivalent embodiments of equivalent changes. The implementation schemes in the above embodiments can also be further combined or replaced. However, any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the present invention.

Claims

1. A general substrate of pyridine amino ligand, characterized in that, It has the structure shown in Formula I, Among them, X is a halogen; R1, R2, R3, R4, R5, R6, R7, R 10 , R 11 , R 12 are independently selected from -H, a C1-C 40 hydrocarbyl group, a C1-C 40 heterohydrocarbyl group, a C6-C 40 aryl group, a C6-C 40 heteroaryl group, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)- or a halogen.

2. The pyridine amino ligand general substrate according to claim 1, characterized in that, R3, R4, R5, R6, R7, R 10 , R 11 , R 12 each independently selected from C 1- C 20 hydrocarbyl, C 1- C 20 heterohydrocarbyl, C 1- C 20 aryl, C 1- C 20 heteroaryl; Preferably, R4, R5, and R6 are all -H.

3. The pyridine amino ligand general substrate according to claim 1 or 2, characterized in that, R1 and R2 are different from each other, one of which is an aryl group which is unsubstituted or substituted by a hydrocarbon group, a heteroaryl group which is unsubstituted or substituted by a hydrocarbon group, a C1-C 40 hydrocarbon group or a C1-C 40 heterohydrocarbon group, and the other is -H; Preferably, the substituents on the aryl and heteroaryl groups are C1-C6 hydrocarbon groups; More preferably, the substituents on the aryl and heteroaryl groups are located at the 2-position, and the structure of the substituent is i-Pr.

4. The pyridine amino ligand general substrate according to claim 1 or 2, characterized in that, R1 and R2 are the same and are selected from C1-C 20 hydrocarbyl groups.

5. A method for preparing a general substrate of a pyridine amino ligand according to any one of claims 1-4, characterized in that, Using the substance with the structure shown in Formula IIa as a raw material, reacting with an organolithium compound or a Grignard reagent under an inert atmosphere and a preset temperature to obtain a general substrate of a pyridine amino ligand with the structure shown in Formula Ia, and the preparation steps are as follows: Wherein, X is a halogen; R3, R4, R5, R6, R7, R 10 , R 11 , R 12 are each independently selected from -H, a C1-C 40 hydrocarbyl group, a C1-C 40 heterohydrocarbyl group, a C6-C 40 aryl group, a C6-C 40 heteroaryl group, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)- or a halogen; R1 is selected from a C1-C 40 hydrocarbyl group, a C1-C 40 heterohydrocarbyl group, a C6-C 40 aryl group, a C6-C 40 heteroaryl group, -Si(R C )3, -Ge(R C )3; Preferably, under an inert atmosphere, the substance with the structure shown in Formula IIa is mixed with Li-R1 to form a mixed solution, and the reaction is carried out in the solution. During the reaction process, the temperature is controlled between -78°C and the boiling point of the solvent; after the reaction is completed, the general substrate of the pyridine amino ligand with the structure shown in Formula Ia is obtained through post-treatment; Preferably, the solvent of the mixed solution is at least one of benzene organic solvents and ether organic solvents; More preferably, the benzene organic solvent is toluene, and the ether organic solvents include diethyl ether and tetrahydrofuran; Preferably, the reaction time is 1 hour - 12 hours.

6. The preparation method of the pyridine amino ligand general substrate according to claim 5, characterized in that, The preparation process of the substance shown in Formula IIa is as follows: Preferably, the preparation process is: mixing raw material one with the structure shown in Formula IVa, a catalyst, a solvent, and raw material two with the structure shown in Formula III, and continuously stirring for reaction. During the reaction process, the temperature is controlled between -78°C and the boiling point of the solvent to obtain the substance with the structure shown in Formula IIa; Preferably, the reaction duration is 1 - 24h; Preferably, the solvent is at least one of benzene organic solvents and alcohol organic solvents; More preferably, the benzene organic solvents include toluene and dichlorobenzene; the alcohol organic solvents include methanol and ethanol; Preferably, the catalyst is selected from at least one of formic acid and p-toluenesulfonic acid.

7. A method for preparing a general substrate of a pyridine amino ligand as described in claim 1 or 4, characterized in that, Using the substance with the structure shown in Formula IIb as a raw material, reacting with an organoaluminum compound under an inert atmosphere and a preset temperature to obtain a general substrate of a pyridine amino ligand with the structure shown in Formula Ib, and the preparation steps are as follows: wherein X is a halogen; R3, R4, R5, R6, R7, R 10 , R 11 , R 12 are each independently selected from -H, a C1-C 40 hydrocarbyl group, a C1-C 40 heterohydrocarbyl group, a C6-C 40 aryl group, a C6-C 40 heteroaryl group, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)- or a halogen; R1 and R2 are each independently selected from C1-C 40 hydrocarbyl groups, C1-C 40 heterohydrocarbyl groups, C6-C 40 aryl groups, C6-C 40 heteroaryl groups; Preferably, under an inert atmosphere, the substance with the structure shown in Formula IIb is mixed with Al-(R1)3 to form a mixed solution, and the reaction is carried out in the solution. During the reaction process, the temperature is controlled between -78°C and the boiling point of the solvent; after the reaction is completed, the general substrate of the pyridine amino ligand with the structure shown in Formula Ib is obtained through post-treatment; Preferably, the solvent of the mixed solution is at least one of benzene organic solvents and ether organic solvents; More preferably, the benzene organic solvent is toluene, and the ether organic solvents include diethyl ether and tetrahydrofuran; Preferably, the reaction time is 1 hour - 12 hours.

8. The preparation method of the pyridine amino ligand general substrate according to claim 7, characterized in that, The preparation process of the substance shown in Formula IIb is as follows: Preferably, the preparation process is: mixing raw material one with the structure shown in Formula IVb, a catalyst, a solvent, and raw material two with the structure shown in Formula III, and continuously stirring for reaction. During the reaction process, the temperature is controlled between -78°C and the boiling point of the solvent to obtain the substance with the structure shown in Formula IIb; Preferably, the reaction duration is 1 - 24h; Preferably, the solvent is at least one of benzene organic solvents and alcohol organic solvents; More preferably, the benzene organic solvents include toluene and dichlorobenzene; the alcohol organic solvents include methanol and ethanol; Preferably, the catalyst is selected from at least one of formic acid and p-toluenesulfonic acid.

9. A method for preparing a pyridine amino ligand, characterized in that, Prepared from the pyridine amino ligand general substrate according to any one of claims 1-8, the structure of the obtained pyridine amino ligand is shown in Formula V: Among them, R1, R2, R3, R4, R5, R6, R7, R 10 、R 11 、R 12 are each independently selected from -H, a C1-C 40 hydrocarbyl group, a C1-C 40 heterohydrocarbyl group, a C6-C 40 aryl group, a C6-C 40 heteroaryl group, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)- or a halogen; R8 is selected from a C6-C 20 aryl group; The preparation process is as follows: Among them, R8 is The structure of R8 - R9 is R9 is a group containing B, Zn, Mg, Sn, Si or H; T is a C1 - C 40 hydrocarbon group, a C1 - C 40 heterohydrocarbon group, a C6 - C 40 aryl group, a C6 - C 40 heteroaryl group; Preferably, R9 is B(OH)2; The specific preparation process is as follows: Under an inert atmosphere, the pyridine amino ligand general substrate shown in Formula I, the catalyst, the ligand, the solvent, the base and the substance having the structure shown in R8-R9 are mixed to form a mixed solution for reaction, and the reaction temperature is between -78 °C and the boiling point of the solvent; Preferably, the solvent includes at least one of benzene organic solvents and alcohol organic solvents; More preferably, the benzene organic solvent is toluene; the alcohol organic solvents include methanol and ethanol; Preferably, the reaction duration is 12-48 h; Preferably, after the reaction, it is also necessary to extract with ethyl acetate, wash with brine, dry with anhydrous sodium sulfate, remove the solvent with a rotary evaporator, and purify the product by silica gel column chromatography.

10. The preparation method of the pyridine amino ligand according to claim 9, wherein The catalyst includes a palladium catalyst of zero valence or divalent; Preferably, the catalyst is selected from at least one of tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, and palladium acetate; Preferably, the ligand includes a monodentate or bidentate ligand containing a P element; Preferably, the ligand is selected from at least one of DPPE, DPPP, DPPB, DPEphos, and Xantphos; Preferably, the base includes a strong base weak acid salt of Group IA metals; Preferably, the base is selected from at least one of sodium carbonate, potassium carbonate, cesium carbonate, and potassium phosphate.

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