Iron catalyst for 1,2 / 3,4 selective polymerization of conjugated dienes and its application

Abstract

An iron catalyst for the 1,2 / 3,4 selective polymerization of conjugated dienes, characterized in that it is an iron complex having the general formula of the following formula 1 or formula 2: #imgabs0# wherein R1 is one of H, ‑CH3, ‑CH2CH3, ‑CH(CH3)2, ‑CH(CH3)CH2CH3, ‑CH2CH(CH3)2, ‑C(CH3)3, ‑C6H5, ‑(2‑CH3)C6H5, ‑(2‑CH2CH3)C6H5, ‑(2‑CH(CH3)2)C6H5, ‑(2‑CH2CH(CH3)2)C6H5, and ‑(2‑C(CH3)3)C6H5; R2 is ‑SCH3, ‑SCH2CH3, ‑SCH(CH3)2, ‑SCH2CH(CH3)2, ‑SCH2CH2CH2CH3, ‑SC(CH3)3, ‑SC6H5, ‑OCH3, ‑OCH2CH3, ‑OCH(CH3)2, ‑OCH2CH(CH3)2, ‑OCH2CH2CH2CH3, ‑OC(CH3)3, ‑O C6H5,‑P(CH3)2,‑P(CH2CH3)2,‑P(CH(CH3)2)2,‑P(CH(CH3)2)2,‑P(C(CH3)3)2,‑P(C6H5 )2, ‑P(=O)(CH3)2, ‑P(=O)(CH2CH3)2, ‑P(=O)(CH(CH3)2)2, ‑P(=O)(C(CH3)3)2, ‑P=(O)(C6H5)2, ‑N(CH3)2, ‑N(CH2CH3)2, ‑N(CH(CH3)2)2, ‑N(C(CH3)3)2, ‑N(C6H5)2; X is chlorine or bromine. The invention also relates to the use of the iron catalyst for the syndiotactic 1,2 / 3,4-selective polymerization of conjugated dienes in the preparation of syndiotactic 1,2 / 3,4-polyconjugated dienes.

Description

Technical Field

[0001] The present invention relates to the polymerization of conjugated dienes, in particular to an iron catalyst for the selective polymerization of syndiotactic 1,2 / 3,4 conjugated dienes, and also to the use of the iron catalyst for the selective polymerization of syndiotactic 1,2 / 3,4 conjugated dienes in the preparation of syndiotactic 1,2 / 3,4 polyconjugated dienes. Background Art

[0002] 1,2 / 3,4-polyconjugated dienes can be classified into three isomers based on their microstructure: atactic, syndiotactic, and isotactic. Syndiotactic 1,2 / 3,4-polyconjugated dienes are crystalline polymers used in thermoplastic elastomers and polyolefin modification. Highly crystalline polymers can be used to manufacture staple fibers for rubber fillers and carbon fibers. Due to their crystallinity, their mechanical strength significantly surpasses that of rubber materials. Syndiotactic 1,2 / 3,4-polyconjugated dienes are typically synthesized by the selective polymerization of conjugated diene monomers in the presence of a catalyst. Common catalysts for the selective polymerization of conjugated diene monomers in the presence of a catalyst include molybdenum-based (CN2006100833608), iron-based (CN1554682A, CN1557847A), and cobalt-based (US4182813) catalyst systems consisting of corresponding metal compounds, aluminum alkyls, and electron donors.

[0003] Taking iron-based catalyst systems as an example, patents US6620760, US6284702, and US6407026 use iron-based catalyst systems to prepare syndiotactic 1,2-polybutadiene with a melting point of approximately 160°C-180°C. These catalysts are composed of a metal compound, an aluminum alkyl, and an electron donor. The metal compound and electron donor form active centers under the action of the aluminum alkyl. The electron donor easily reacts with the co-catalyst to produce side reactions, so the electron donor is often used in excess of the metal compound. Furthermore, the catalyst activity and selectivity vary significantly with the amount of electron donor used, resulting in a lack of stability.

[0004] Patents WO2015068094(A1)-2015-05-14 and WO2015068095(A1)-2015-05-14, as well as documents Coord. Chem. Rev. 2010, 254, 661-676 and Macromolecules 2021, 54, 5879-5914, describe the use of iron catalysts with pyridine-2-imine ligands for the syndiotactic 1,2 / 3,4-selective polymerization of butadiene and isoprene. References such as Journal of Molecular Catalysis, 17(1982), 65-76, and Acta Polymerica Sinica, 1988, 145-148 report the use of o-phenanthroline as an electron donor in a three-way catalyst for the 1,2-selective polymerization of butadiene and the 3,4-selective polymerization of isoprene. Among them, the iron catalyst with pyridine-2-imine as the ligand is easily affected by alkyl aluminum, temperature, etc. due to the imine bond, while the catalyst with o-phenanthroline as the electron donor has small steric hindrance of o-phenanthroline and insufficient protection of the catalyst active center. As a result, the high-temperature stability of these two iron catalysts is insufficient, which in turn causes the activity of the iron catalyst to decrease. Moreover, due to stability and steric hindrance issues, the regio- and stereoselectivity of the 1,2 / 3,4 catalysts of these two iron catalysts are not high, and some polymers are still amorphous and not crystalline, which affects the material properties. Summary of the Invention

[0005] The first technical problem to be solved by the present invention is to provide an iron catalyst for the syndiotactic 1,2 / 3,4 selective polymerization of conjugated dienes with a clear structure, high thermal stability, high catalytic activity, and high regio- and syndiotactic stereoselectivity in response to the above-mentioned technical status.

[0006] The second technical problem to be solved by the present invention is to provide an application of the above-mentioned iron catalyst for the selective 1,2 / 3,4 polymerization of conjugated dienes in response to the above-mentioned technical status.

[0007] The technical solution adopted by the present invention to solve the first technical problem mentioned above is: an iron catalyst for the 1,2 / 3,4 selective polymerization of conjugated dienes, characterized in that it is an iron complex, and the general formula of the iron complex is the following formula 1 or formula 2:

[0008]

[0009] wherein R1 is one of H, -CH3, -CH2CH3, -CH(CH3)2, -CH(CH3)CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -C6H5, -(2-CH3)C6H5, -(2-CH2CH3)C6H5, -(2-CH(CH3)2)C6H5, -(2-CH2CH(CH3)2)C6H5, and -(2-C(CH3)3)C6H5;

[0010] R2 is a substituent containing a heteroatom, which is -SCH3, -SCH2CH3, -SCH(CH3)2, -SCH2CH(CH3)2, -SCH2CH2CH2CH3, -SC(CH3)3, -SC6H5, -OCH3, -OCH2CH3, -OCH(CH3)2, -OCH2CH(CH3)2, -OCH2CH2CH2CH3, -OC(CH3)3, -OC6H5, -P(CH3)2, -P(CH2CH3)2, -P(CH( One of -P(CH(CH3)2)2, -P(C(CH3)3)2, -P(C6H5)2, -P(=O)(CH3)2, -P(=O)(CH2CH3)2, -P(=O)(CH(CH3)2)2, -P(=O)(C(CH3)3)2, -P=(O)(C6H5)2, -N(CH3)2, -N(CH2CH3)2, -N(CH(CH3)2)2, -N(C(CH3)3)2, -N(C6H5)2;

[0011] X is chlorine or bromine.

[0012] It is further designed that the iron complex is prepared by reacting an asymmetric ligand with a tetrahydrofuran complex of ferrous chloride or a tetrahydrofuran complex of ferrous bromide.

[0013] And if the general formula of the iron complex is Formula 1, then the asymmetric ligand is 6-R1-6'-R2-2,2'-bipyridine;

[0014] If the general formula of the iron complex is Formula 2, the asymmetric ligand is 2-R1-9-R2-1,10-phenanthroline.

[0015] It is further designed that the volume ratio of the amount of the asymmetric ligand, the amount of ferrous chloride or ferrous bromide, and tetrahydrofuran is 1.03-1.2:1:334-180, the reaction time is 8-12 hours, and the temperature is 25-61°C.

[0016] It is further designed that the preparation method of the asymmetric ligand comprises the following steps in sequence:

[0017] Step 1: preparing a monobromo compound by a palladium-catalyzed coupling reaction of a dibromo compound;

[0018] Step 2: preparing the asymmetric ligand by subjecting a monobromo compound to a copper-catalyzed coupling reaction;

[0019] If the asymmetric ligand is 6-R1-6'-R2-2,2'-bipyridine, the dibromo compound is 6,6'-dibromo-2,2'-bipyridine, and the monobromo compound is 6-R1-6'-bromo-2,2'-bipyridine;

[0020] If the asymmetric ligand is 2-R1-9-R2-1,10-phenanthroline, the dibromo compound is 2,9-dibromo-1,10-phenanthroline, and the monobromo compound is 2-R1-9-bromo-1,10-phenanthroline.

[0021] It is further designed that the specific process of the palladium-catalyzed coupling reaction is: dissolving the dibromo compound and R1OB(OH)2 in an organic solvent A, then adding a mixed solution of the Pd compound and potassium carbonate, stirring at 80-122°C for 14-37 hours, collecting the resulting solid, and separating it by column chromatography to obtain the monobromo compound; wherein the molar ratio of the dibromo compound, R1OB(OH)2, Pd compound and potassium carbonate is 1:1.0-1.5:0.005-0.015:0.03-0.11.

[0022] In a further design, the Pd compound is one of palladium chloride, palladium acetate, tris(dibenzylideneacetone)palladium, tetrakistriphenylphosphine palladium, and bis(triphenylphosphine)palladium dichloride.

[0023] It is further designed that the specific process of the copper-catalyzed coupling reaction is: dissolving a monobromo compound and R2H in an organic solvent A, adding cuprous iodide, potassium carbonate and proline in sequence, and reacting in an oxygen-free environment of 85-130°C for 5-36 hours, collecting the resulting solid, and separating it by column chromatography to obtain the asymmetric ligand; wherein the molar ratio of the monobromo compound, R2H, cuprous iodide, proline and potassium carbonate is 1:1.5-25:0.005-0.012:0.0025-0.02:0.0012-0.1.

[0024] The organic solvent A is at least one of N,N-dimethylformamide, dimethyl sulfoxide, and dioxane, and the organic solvent A involved in the palladium-catalyzed coupling reaction and the copper-catalyzed coupling reaction can be the same or different.

[0025] The preparation process of the iron complex is as follows:

[0026]

[0027] The technical solution adopted by the present invention to solve the second technical problem is: the use of an iron catalyst for the 1,2 / 3,4 selective polymerization of conjugated dienes as described above, characterized in that it comprises the following steps in sequence:

[0028] Step 1: After the polymerization bottle is treated in an anhydrous and oxygen-free environment at high temperature, the iron catalyst, conjugated diene solution, and co-catalyst as described above are added, and polymerization is carried out in an anhydrous and oxygen-free environment at 30-150° C. for 1-12 hours. The solvent of the conjugated diene solution is an organic solvent B; the organic solvent B is at least one of n-butane, n-pentane, n-hexane, n-heptane, n-octane, isooctane, cyclopentane, cyclohexane, benzene, toluene, xylene, hydrogenated gasoline, dodecane, and paraffin oil. Preferably, n-hexane, hydrogenated gasoline, cyclohexane, and toluene are selected.

[0029] Step 2: terminate the polymerization reaction and precipitate the polymer, followed by filtering, washing, and drying to obtain the syndiotactic 1,2 / 3,4 polyconjugated diene.

[0030] In order to increase the yield of syndiotactic 1,2 / 3,4 polyconjugated diene, the molar ratio of the conjugated diene, iron catalyst and co-catalyst is 667-80000:1:13-458, and the total volume of organic solvent B and conjugated diene monomer is 20 mL-1.8 L.

[0031] In a further design, the conjugated diene is at least one of butadiene, isoprene, myrcene, farnesene, and ocimene; and the co-catalyst is at least one of diisobutylaluminum hydride, diethylaluminum hydride, triisobutylaluminum, tri-n-butylaluminum, trimethylaluminum, triethylaluminum, trioctylaluminum, methylaluminoxane (MAO), triisobutylaluminum-modified methylaluminoxane (MMAO), diethylmagnesium, dibutylmagnesium, and diethylzinc.

[0032] Preferably, the co-catalyst is at least one of MAO, MMAO, triisobutylaluminum, tri-n-butylaluminum, triethylaluminum, and trioctylaluminum.

[0033] In step 2, the polymerization reaction is terminated using a mixed solution C comprising methanol, hydrochloric acid, and an antioxidant. The volume of the hydrochloric acid is 1-3% of the volume of the methanol, and the weight of the antioxidant is 2-4% of the volume of the methanol. The antioxidant can make the syndiotactic 1,2 / 3,4-polyconjugated diene more stable during storage, and the hydrochloric acid can remove residual iron ions in the polymer.

[0034] Compared with the prior art, the advantages of the present invention are: based on the polymerization mechanism of conjugated dienes, in the iron catalyst for the syndiotactic 1,2 / 3,4 selective polymerization of conjugated dienes, the introduction of an asymmetric ligand can guide the conjugated diene monomer and the growing polymer chain to be arranged in an exo-exo configuration, which is beneficial to the syndiotactic stereoselective polymerization; the heteroatoms N, P, S, and O on one side of the ligand can produce a weak coordination effect with the active center, which is beneficial to stabilizing the configuration of the active center of the catalyst, especially the stability of the catalyst under high temperature conditions, and thus has a positive effect on both selectivity and activity; the introduction of steric hindering groups R1 and R2 on both sides of the ligand also helps to improve the 1,2 / 3,4 region and syndiotactic stereoselectivity of the catalyst for the polymerization of conjugated dienes. These characteristics of the ligand give the iron catalyst a clear structure, high catalytic activity, high regio- and syndiotactic stereoselectivity, and high thermal stability. It can selectively polymerize conjugated dienes at 150°C, and the catalytic activity and 1,2 / 3,4 regio- and syndiotactic selectivity are basically unaffected by temperature. The application of the aforementioned iron catalyst for the syndiotactic 1,2 / 3,4-selective polymerization of conjugated dienes in the preparation of syndiotactic 1,2 / 3,4-polyconjugated dienes does not require the addition of excessive electron donors, so that the iron catalyst for the syndiotactic 1,2 / 3,4-selective polymerization of conjugated dienes can form catalytic active centers only under the action of a co-catalyst, thereby being able to catalyze the highly syndiotactic 1,2-selective polymerization of butadiene and the highly syndiotactic 3,4-selective polymerization of isoprene, myrcene, farnesene, and ocimene at 30 to 150°C with high activity, and the prepared syndiotactic 1,2 / 3,4-polyconjugated dienes are all crystalline. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is the infrared test spectrum of some iron catalysts in the examples of the present invention. DETAILED DESCRIPTION

[0036] The embodiments of the present invention are described in further detail below.

[0037] 1. Iron Catalyst

[0038] Example 1

[0039] Preparation and analysis of FeBr2-BP-Me-SEt:

[0040] Step 1, 0.04 mol of 6,6'-dibromo-2,2'-bipyridine and 0.044 mol of methyl borate were dissolved in 51 mL of N,N-dimethylformamide, and 0.37 mmol of tetrakistriphenylphosphine palladium, 4.4 mmol of potassium carbonate and 8 mL of water were added in sequence, and stirred at 83 ° C for 25 hours; 250 mL of water and 250 mL of dichloromethane were added to the reaction solution, the dichloromethane phase was collected and dried, and the obtained solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 2:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peak appeared at 2.76 ppm, the corresponding group was Ar-CH3, and the product was identified as 6-methyl-6'-bromo-2,2'-bipyridine, and the yield of the 6-methyl-6'-bromo-2,2'-bipyridine was 75.3%.

[0041] Step 2: 0.02 mol of 6-methyl-6'-bromo-2,2'-bipyridine and 0.05 mol of ethanethiol were dissolved in 50 mL of N,N-dimethylformamide, and 1.0 mmol of potassium carbonate, 0.2 mmol of cuprous iodide and 0.2 mmol of proline were added in sequence. After nitrogen bubbling in the reaction flask to drive out oxygen, the mixture was stirred at 119 ° C for 30 h; the reaction was stopped, the solvent was removed, 120 mL of water and 120 mL of dichloromethane were added to the reaction flask, the dichloromethane phase was collected and dried, and the obtained solid was purified by column chromatography. Chromatographic separation was performed, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 3:1; the separated product was then subjected to nuclear magnetic resonance spectroscopy analysis. Since characteristic peaks appeared at 1.31 ppm and 3.00 ppm, the corresponding group was Ar-SCH2CH3, and the product was identified as 6-methyl-6'-ethylthio-2,2'-bipyridine (BP-Me-SEt), and the yield of 6-methyl-6'-ethylthio-2,2'-bipyridine (BP-Me-SEt) was 88.6%.

[0042] Step 3: Dissolve 0.022 mol of 6-methyl-6'-ethylthio-2,2'-bipyridine (BP-Me-SEt) and 0.02 mol of FeBr2(THF)2 in 10 mL of tetrahydrofuran, stir and react at 35°C for 10 h, let stand and stratify, and filter to obtain a solid, which is the iron catalyst FeBr2-BP-Me-SEt; wash the obtained iron catalyst FeBr2-BP-Me-SEt three times with ether, dry and weigh, and the yield is 93.5%; the characteristic peak of the iron catalyst FeBr2-BP-Me-SEt infrared test appears at 1623 cm -1 、1582cm -1 、1526cm -1 、1479cm -1The results of mass spectrometry and elemental analysis showed that C 13 H 14 Br2FeN2S, M / Z: 445.86, C, 61.45; H, 5.55; Fe, 21.98; N, 11.02.

[0043] Example 2

[0044] Preparation and analysis of FeBr2-Phen-Ph-OPh:

[0045] Step 1, 0.03 mol of 2,9-dibromo-1,10-o-phenanthroline and 0.033 mol of phenyl borate were dissolved in 58 mL of dimethyl sulfoxide, 0.3 mmol of palladium acetate, 3.0 mmol of potassium carbonate and 6 mL of water were added in sequence, and the mixture was stirred at 88° C. for 36 hours; 150 mL of water and 250 mL of dichloromethane were added to the reaction solution, the organic phase was collected and dried, and the obtained solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 5:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis, and since the characteristic peak appeared at 7.49-8.23 ppm, the corresponding group was Ar-H, and the product was identified as 2-phenyl-9-bromo-1,10-o-phenanthroline, and the yield of the 2-phenyl-9-bromo-1,10-o-phenanthroline was 81.2%.

[0046] Step 2: 0.02 mol of 2-phenyl-9-bromo-1,10-o-phenanthroline and 0.04 mol of phenol were dissolved in 48 mL of dioxane, and 1.0 mmol of potassium carbonate, 0.15 mmol of cuprous iodide, and 0.17 mmol of proline were added in sequence. After nitrogen bubbling was carried out to drive out oxygen in the reaction flask, the mixture was stirred at 109 ° C. for 36 hours; the solvent was dried, 100 mL of water was added to the residual solid for washing, and 100 mL of dichloromethane was extracted. The solid obtained by drying the dichloromethane was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 7:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peak appeared at 6.91-7.29 ppm, the corresponding group was Ar-H, and the product was identified as 2-phenyl-9-phenoloxy-1,10-o-phenanthroline (Phen-Ph-OPh).

[0047] Step 3: Dissolve 0.011 mol of 2-phenyl-9-phenoloxy-1,10-phenanthroline and 0.01 mol of FeBr2(THF)2 in 8 mL of dichloromethane, stir and react at 25°C for 12 hours, let the suspension stand and separate, then filter to obtain a solid iron catalyst FeBr2-Phen-Ph-OPh; wash the obtained iron catalyst FeBr2-Phen-Ph-OPh three times with n-hexane, dry and weigh, and calculate the yield to be 78.2%. The characteristic peak of the iron catalyst FeBr2-Phen-Ph-OPh in infrared test appears at 1611 cm -1 、1584cm -1 、1520cm -1 、1482cm -1 The results of mass spectrometry and elemental analysis showed that C 24 H 16 Br2FeN2O, M / Z: 563.89, C, 74.25; H, 4.15; Fe, 14.38; N, 7.22.

[0048] Example 3

[0049] Preparation and analysis of FeBr2-Phen-Ph-SMe:

[0050] Step 1, 0.02 mol of 2,9-dibromo-1,10-o-phenanthroline and 0.02 mol of phenyl borate were dissolved in 48 mL of dioxane, and 0.2 mmol of tris(dibenzylideneacetone)palladium, 2.0 mmol of potassium carbonate and 5 mL of water were added in sequence, and stirred at 86° C. for 32 h; the reaction was stopped, the solvent was dried, 140 mL of water was added for washing, 100 mL of ethyl acetate was extracted, the ethyl acetate phase was collected and dried, and the obtained solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 10:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis, and since the characteristic peak appeared at 7.49-8.23 ppm, the corresponding group was Ar-H, and the product was identified as 2-phenyl-9-bromo-1,10-o-phenanthroline, and the yield of the 2-phenyl-9-bromo-1,10-o-phenanthroline was 85.5%.

[0051] Step 2: 0.02 mol of 2-phenyl-9-bromo-1,10-phenanthroline and 0.04 mol of methyl mercaptan were dissolved in 48 mL of dioxane, and 0.5 mmol of potassium carbonate, 0.16 mmol of cuprous iodide and 0.30 mmol of proline were added in sequence. After nitrogen bubbling in the reaction flask to remove oxygen, the reaction was incubated at 98 ° C for 30 h; the volatile components were removed, and the mixture was washed and extracted with 120 mL of water and 100 mL of dichloromethane, respectively. The dichloromethane was spin-dried, and the solid was separated by column chromatography. The gradient elution solvent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 11:2 to 11:1; the separated product was then subjected to H-NMR analysis. Since the characteristic peak appeared at 2.54 ppm, the corresponding group was Ar-SCH3, and the product was identified as 2-phenyl-9-methylthio-1,10-o-phenanthroline (Phen-Ph-SMe), and the yield of 2-phenyl-9-methylthio-1,10-o-phenanthroline (Phen-Ph-SMe) was 67.7%.

[0052] Step 3: Dissolve 0.011 mol of 2-phenyl-9-methylthio-1,10-phenanthroline and 0.01 mol of FeBr2(THF)2 in 10 mL of ethanol and react at 58°C for 8 hours; remove the ethanol by spin drying to obtain a solid catalyst FeBr2-Phen-Ph-SMe; wash the obtained iron catalyst FeBr2-Phen-Ph-SMe three times with ether, dry and weigh, and calculate the yield to be 80.8%. Figure 1 As shown in the spectrum in Figure a, the characteristic peak of the iron catalyst FeBr2-Phen-Ph-SMe infrared test appears at 1625 cm -1 、1584cm -1 、1540cm -1 、1472cm -1 The results of mass spectrometry and elemental analysis showed that C 19 H14Br2FeN2S, M / Z: 517.86, C, 69.96; H, 4.33; Fe, 17.12; N, 8.59.

[0053] Example 4

[0054] FeCl2-BP- t Preparation and analysis of Bu-OMe:

[0055] Step 1. Dissolve 0.05 mol of 6,6'-dibromo-2,2'-bipyridine and 0.056 mol of tert-butyl borate in 40 mL of dimethyl sulfoxide, add 0.5 mmol of bis(triphenylphosphine)palladium dichloride, 5.0 mmol of potassium carbonate and 15 mL of water in sequence, and react at 91°C for 27 hours; add 100 mL of water and 300 mL of ethyl acetate to the reaction solution, collect the organic phase and spin dry, and separate the solid by column chromatography, wherein the eluent is a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane is 4:1; then perform nuclear magnetic hydrogen spectrum analysis on the separated product. Since the characteristic peak appears at 1.29 ppm, the corresponding group is Ar-C-(CH3)3, and the product is identified as 6-tert-butyl-6'-bromo-2,2'-bipyridine, and the yield of 6-tert-butyl-6'-bromo-2,2'-bipyridine is 88.6%.

[0056] Step 2: 0.01 mol of 6-tert-butyl-6'-bromo-2,2'-bipyridine and 0.05 mol of methanol were dissolved in 45 mL of N,N-dimethylformamide, and 0.08 mmol of cuprous iodide, 0.27 mmol of potassium carbonate and 0.17 mmol of proline were added in sequence. After nitrogen was bubbled through the reaction flask to remove oxygen, the reaction was carried out in a reactor at 85°C for 28 hours. 40 mL of water and 80 mL of ethyl acetate were added to the reaction solution, the organic matter was collected and dried, and the solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 4:1. The separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peak appeared at 4.06 ppm, the corresponding group was Ar-OCH3, and the product was identified as 6-tert-butyl-6'-methoxy-2,2'-bipyridine (BP- t Bu-OMe), the 6-tert-butyl-6'-methoxy-2,2'-bipyridine (BP- t The yield of Bu-OMe) was 90.6%.

[0057] Step 3: Dissolve 0.033 mol of 6-tert-butyl-6'-methoxy-2,2'-bipyridine and 0.03 mol of FeCl2(THF)2 in 15 mL of dichloromethane, stir at 35 ° C for 10 h, let the suspension stand and stratify, and filter to obtain a solid iron catalyst FeCl2-BP- t Bu-OMe; the obtained iron catalyst FeCl2-BP- t Bu-OMe was washed three times with ether, dried and weighed to give a yield of 84.5%. Figure 1 As shown in Figure b, the iron catalyst FeCl2-BP- t The characteristic peak of Bu-OMe infrared test appears at 1610 cm -1 、1584cm-1 、1528cm -1 、1485cm -1 The results of mass spectrometry and elemental analysis showed that C 15 H 18 Cl2FeN2O, M / Z: 368.01, C, 63.85; H, 6.43; Fe, 19.79; N, 9.93.

[0058] Example 5

[0059] FeCl2-BP- i Preparation and analysis of Pr-P(CH3)2:

[0060] Step 1: Dissolve 0.025 mol of 6,6'-dibromo-2,2'-bipyridine and 0.025 mol of isopropyl borate in 60 mL of dioxane, add 0.25 mmol of bis(triphenylphosphine)palladium dichloride, 2.5 mmol of potassium carbonate and 20 mL of water in sequence, and stir at 97 ° C for 14 h; spin dry the solvent, add 40 mL of water to the solid for washing and extract with 55 mL of dichloromethane, spin dry the dichloromethane, and the solid is purified by column chromatography Separation was performed, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 7:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peaks appeared at 1.31ppm and 3.44ppm, the corresponding group was Ar-CH(CH3)2, and the product was identified as 6-isopropyl-6'-bromo-2,2'-bipyridine, and the yield of 6-isopropyl-6'-bromo-2,2'-bipyridine was 85.9%.

[0061] Step 2: 0.02 mol of 6-isopropyl-6'-bromo-2,2'-bipyridine and 0.04 mol of dimethylphosphine were dissolved in 80 mL of anhydrous and oxygen-free dimethyl sulfoxide, and 0.19 mmol of cuprous iodide, 0.024 mmol of potassium carbonate and 0.05 mmol of proline were added in sequence. After nitrogen bubbling was carried out to drive out oxygen in the reaction flask, the mixture was stirred at 129 ° C for 35 h; 100 mL of water and 200 mL of ethyl acetate were added to the reaction solution, the organic phase was collected, and the solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 2:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peak appeared at 0.98 ppm, the corresponding group was Ar-P(CH3)2, and the product was identified as 6-isopropyl-6'-dimethylphosphine-2,2'-bipyridine (BP- i Pr-P(CH3)2), the 6-isopropyl-6'-dimethylphosphine-2,2'-bipyridine (BP- i The yield of Pr-P(CH3)2) was 82.7%.

[0062] Step 3: Dissolve 0.023 mol of 6-isopropyl-6'-dimethylphosphine-2,2'-bipyridine and 0.02 mol of FeCl2(THF)2 in 10 mL of tetrahydrofuran, stir and react at 27 ° C for 10 h, concentrate, add ether, let stand and filter, and the obtained solid is the iron catalyst FeCl2-BP- i Pr-P(CH3)2; the obtained iron catalyst FeCl2-BP- i Pr-P(CH3)2 was washed three times with ether, dried and weighed to calculate the yield to be 86.5%; Figure 1 As shown in the spectrum in Figure c, the iron catalyst FeCl2-BP- i The characteristic peak of Pr-P(CH3)2 infrared test appears at 1614 cm -1 、1582cm -1 、1538cm -1 、1480cm -1 The results of mass spectrometry and elemental analysis showed that C 15 H 19 Cl2FeN2P, M / Z: 384.00, C, 63.62; H, 6.76; Fe, 19.72; N, 9.89.

[0063] Example 6

[0064] Preparation and analysis of FeCl2-Phen-Et-N(CH3)2:

[0065] Step 1: 0.01 mol of 2,9-dibromo-1,10-phenanthroline and 0.015 mol of ethyl borate were dissolved in 48 mL of anhydrous and oxygen-free dimethyl sulfoxide, and 0.1 mmol of tris(dibenzylideneacetone)palladium, 1.0 mmol of potassium carbonate and 2 mL of water were added in sequence, and stirred at 122 ° C for 24 h; the solvent was removed under reduced pressure, 100 mL of water was added to the solid for washing, and 65 mL of dichloromethane was used for extraction. The dichloromethane was collected and dried, and the solid was dried with Column chromatography separation was performed, wherein the gradient elution solvent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 6:1 to 3:1; the separated product was then subjected to nuclear magnetic resonance spectroscopy analysis. Since characteristic peaks appeared at 1.30 ppm and 3.40 ppm, the corresponding group was Ar-CH2CH3, and the product was identified as 2-ethyl-9-bromo-1,10-o-phenanthroline, and the yield of 2-ethyl-9-bromo-1,10-o-phenanthroline was 92.5%.

[0066] Step 2: 0.01 mol of 2-ethyl-9-bromo-1,10-phenanthroline and 0.09 mol of dimethylamine were dissolved in 60 mL of dimethyl sulfoxide, and 0.1 mmol of cuprous iodide, 0.5 mmol of potassium carbonate and 0.1 mmol of proline were added in sequence. After nitrogen was bubbled through the reactor to drive out oxygen, the reaction was stirred in the reactor at 110 ° C for 35 h to stop the reaction; the solvent was removed, 80 mL of water was added to the solid for washing, and 80 mL of dichloromethane was used for extraction. The solid was separated by column chromatography, wherein the eluent was a mixture of dichloromethane and methanol, and The volume ratio of dichloromethane and methanol is 15:1; the separated product is then subjected to H-NMR analysis. Since the characteristic peak appears at 3.15 ppm, the corresponding group is Ar-H, and the product is identified as 2-ethyl-9-(N,N'-dimethylamino)-1,10-o-phenanthroline (Phen-Et-N(CH3)2), and the yield of 2-ethyl-9-(N,N'-dimethylamino)-1,10-o-phenanthroline (Phen-Et-N(CH3)2) is 89.9%, H-NMR spectrum: (Ar-N(CH3)2).

[0067] Step 3: Dissolve 0.021 mol of 2-ethyl-9-(N,N'-dimethylamino)-1,10-phenanthroline and 0.02 mol of FeCl2(THF)2 in 12 mL of ethanol, stir at 25°C for 10 h, remove ethanol, and the resulting solid is an iron catalyst FeCl2-Phen-Et-N(CH3)2; wash the obtained iron catalyst FeCl2-Phen-Et-N(CH3)2 three times with ether, dry and weigh, and the yield is 94.5%; the characteristic peak of the iron catalyst FeCl2-Phen-Et-N(CH3)2 infrared test appears at 1608 cm -1 、1582cm -1 、1521cm -1 、1485cm -1 The results of mass spectrometry and elemental analysis showed that C 16 H 17 Cl2FeN3, M / Z: 377.01, C, 65.55; H, 5.85; Fe, 19.05; N, 9.56.

[0068] Example 7

[0069] Preparation and analysis of FeBr2-Phen-Ph-OMe:

[0070] Step 1, 0.01 mol of 2,9-dibromo-1,10-o-phenanthroline and 0.01 mol of phenyl borate were dissolved in 45 mL of N,N-dimethylformamide, and 0.1 mmol of palladium acetate, 0.4 mmol of potassium carbonate and 4 mL of water were added in sequence, and stirred in a reactor at 121° C. for 28 hours; 90 mL of water and 90 mL of dichloromethane were added to the reaction solution for washing and extraction, respectively, the dichloromethane phase was collected and dried, and separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 5:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis, and since the characteristic peak appeared at 3.44-8.23 ppm, the corresponding group was Ar-H, and the product was identified as 2-phenyl-9-bromo-1,10-o-phenanthroline, and the yield of the 2-phenyl-9-bromo-1,10-o-phenanthroline was 84.6%.

[0071] Step 2: 0.01 mol of 2-phenyl-9-bromo-1,10-phenanthroline and 0.10 mol of methanol were dissolved in 40 mL of dioxane, and 0.11 mmol of cuprous iodide, 0.5 mmol of potassium carbonate and 0.19 mmol of proline were added in sequence. After nitrogen bubbling was carried out to drive out oxygen in the reaction flask, the mixture was stirred in a reactor at 107 ° C for 24 h; after the dioxane was dried, 120 mL of water and 120 mL of dichloromethane were added to the solid for washing and extraction, and the solid was separated by column chromatography. The product was separated by 1% ethyl acetate and 1% n-hexane, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 6:1; the separated product was then subjected to H-NMR analysis, and since the characteristic peak appeared at 4.06 ppm, the corresponding group was Ar-OCH3, and the product was identified as 2-phenyl-9-methoxy-1,10-o-phenanthroline (Phen-Ph-OMe), and the yield of 2-phenyl-9-methoxy-1,10-o-phenanthroline (Phen-Ph-OMe) was 75.4%.

[0072] Step 3: Dissolve 0.022 mol of 2-phenyl-9-methoxy-1,10-phenanthroline and 0.02 mol of FeBr2(THF)2 in 12 mL of dichloromethane, react at 30°C for 9 hours, concentrate, let stand in a refrigerator, and freeze to precipitate a solid. The resulting solid is the iron catalyst FeBr2-Phen-Ph-OMe; wash the resulting iron catalyst FeBr2-Phen-Ph-OMe three times with ether, dry and weigh, and the yield is calculated to be 82.1%. Figure 1 As shown in the spectrum in Figure d, the characteristic peak of the iron catalyst FeBr2-Phen-Ph-OMe infrared test appears at 1614 cm -1 、1581cm -1 、1524cm -1 、1483cm -1The results of mass spectrometry and elemental analysis showed that C 19 H 14 Br2FeN2O, M / Z: 501.99, C, 69.96; H, 4.33; Fe, 17.12; N, 8.59.

[0073] Example 8

[0074] Preparation and analysis of FeBr2-Phen-Me-OPh:

[0075] Step 1, 0.05 mol of 2,9-dibromo-1,10-o-phenanthroline and 0.059 mol of methyl borate were dissolved in 60 mL of dimethyl sulfoxide, and 0.45 mmol of palladium chloride, 4.9 mmol of potassium carbonate and 10 mL of water were added in sequence, stirred at 97 ° C, and the reaction was stopped after 21 hours; the dimethyl sulfoxide was removed under reduced pressure, and 50 mL of water and 50 mL of ethyl acetate were added to the solid for washing and extraction, and the ethyl acetate was collected and dried. The obtained solid was separated by column chromatography, wherein the eluent was a mixture of dichloromethane and n-hexane, and the volume ratio of dichloromethane to n-hexane was 1:10; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peak appeared at 2.51 ppm, the corresponding group was Ar-CH3, and the product was identified as 2-methyl-9-bromo-1,10-o-phenanthroline, and the yield of the 2-methyl-9-bromo-1,10-o-phenanthroline was 65.9%.

[0076] Step 2: Dissolve 0.04 mol of 2-methyl-9-bromo-1,10-phenanthroline and 0.06 mol of phenol in 50 mL of N,N-dimethylformamide and 2.0 mmol of potassium carbonate, and add 0.35 mmol of cuprous iodide and 0.39 mmol of proline in sequence. After nitrogen bubbling in the reaction flask to drive out oxygen, stir at 121 ° C. and track the reaction with a plate. Stop the reaction for 22 hours; remove part of the solvent under reduced pressure, add 53 mL of water and 81 mL of dichloromethane to the reaction solution, collect the dichloromethane and spin dry it The solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 5:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peak appeared at 6.91-7.29 ppm, the corresponding group was Ar-H, and the product was identified as 2-methyl-9-phenoloxy-1,10-o-phenanthroline (Phen-Me-OPh). The yield of 2-methyl-9-phenoloxy-1,10-o-phenanthroline (Phen-Me-OPh) was 67.9%.

[0077] Step 3: Dissolve 0.031 mol of 2-methyl-9-phenoloxy-1,10-phenanthroline and 0.03 mol of FeBr2(THF)2 in 15 mL of tetrahydrofuran, react at 61°C under a nitrogen atmosphere for 8 hours, cool and allow to stand for stratification before filtering. The resulting solid is the iron catalyst FeBr2-Phen-Me-OPh; wash the resulting iron catalyst FeBr2-Phen-Me-OPh three times with ether, dry and weigh, and calculate the yield to be 86.4%. The characteristic peak of the iron catalyst FeBr2-Phen-Me-OPh in infrared testing appears at 1615 cm -1 、1582cm -1 、1528cm -1 、1483cm -1 The results of mass spectrometry and elemental analysis showed that C 19 H 14 Br2FeN2O, M / Z: 501.88, C, 69.96; H, 4.33; Fe, 17.12; N, 8.59.

[0078] Example 9

[0079] Preparation and analysis of FeCl2-BP-Me-P(=O)(CH3)2:

[0080] Step 1: Dissolve 0.02 mol of 6,6'-dibromo-2,2'-bipyridine and 0.02 mol of methyl borate in 50 mL of N,N-dimethylformamide, add 0.2 mmol of tetrakistriphenylphosphine palladium, 2.0 mmol of potassium carbonate and 15 mL of water in sequence, and stir at 107°C for 34 hours to stop the reaction; remove N,N-dimethylformamide, add 180 mL of water and 180 mL of dichloromethane to the solid, spin-dry the organic phase, and separate the solid by column chromatography, wherein the eluent is a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane is 6:1; then perform nuclear magnetic hydrogen spectrum analysis on the separated product. Since the characteristic peak appears at 2.51 ppm, the corresponding group is Ar-CH3, and the product is identified as 6-methyl-6'-bromo-2,2'-bipyridine, and the yield of the 6-methyl-6'-bromo-2,2'-bipyridine is 76.8%.

[0081] Step 2: 0.02 mol of 6-methyl-6'-bromo-2,2'-bipyridine and 0.04 mol of dimethylphosphine oxide were dissolved in 60 mL of anhydrous and oxygen-free dimethyl sulfoxide, and 0.17 mmol of cuprous iodide, 1.5 mmol of potassium carbonate and 0.2 mmol of proline were added in sequence. After nitrogen bubbling in the reaction flask to remove oxygen, the mixture was stirred at 130 ° C for 24 h; dimethyl sulfoxide was dried, 110 mL of water was added to the solid for washing, and 110 mL of ethyl acetate was used for extraction, and the organic phase was dried, wherein the gradient eluent was dichloromethane and methanol. The invention relates to a method for preparing a mixture of 6-methyl-6'-(dimethylphosphoryl)-2,2'-bipyridine (BP-Me-P(=O)(CH3)2) and a mixture of dichloromethane and methanol, and the volume ratio of dichloromethane to methanol is 10:1 to 7:1; the separated product is then subjected to nuclear magnetic hydrogen spectrum analysis, and since the characteristic peak appears at 2.06 ppm, the corresponding group is Ar-P(=O)(CH3)2, and the product is identified as 6-methyl-6'-(dimethylphosphoryl)-2,2'-bipyridine (BP-Me-P(=O)(CH3)2), and the yield of 6-methyl-6'-(dimethylphosphoryl)-2,2'-bipyridine (BP-Me-P(=O)(CH3)2) is 76.2%.

[0082] Step 3: Dissolve 0.011 mol of 6-methyl-6'-(dimethylphosphoryl)-2,2'-bipyridine and 0.01 mol of FeCl2(THF)2 in 8 mL of dichloromethane, stir at 40°C for 8.5 h, cool at low temperature to precipitate a solid, and the obtained solid is an iron catalyst FeCl2-BP-Me-P(=O)(CH3)2; wash the obtained iron catalyst FeCl2-BP-Me-P(=O)(CH3)2 three times with n-hexane, dry and weigh to calculate the yield of 75.6%; the characteristic peak of the iron catalyst FeCl2-BP-Me-P(=O)(CH3)2 infrared test appears at 1612 cm -1 、1585cm -1 、1545cm -1 、1487cm -1 The results of mass spectrometry and elemental analysis showed that C 13 H 15 Cl2FeN2OP, M / Z: 371.96, C, 61.20; H, 5.93; Fe, 21.89; N, 10.98.

[0083] Example 10

[0084] Preparation and analysis of FeCl2-BP-Mt-OPh:

[0085] Step 1, 0.04 mol of 6,6'-dibromo-2,2'-bipyridine and 0.04 mol of ethyl borate were dissolved in 60 mL of dimethyl sulfoxide, and 0.4 mmol of palladium acetate, 4.0 mmol of potassium carbonate and 12 mL of water were added in sequence, and the reaction was stirred at 91 ° C for 32 hours to stop the reaction; the solvent was removed, 80 mL of water and 80 mL of dichloromethane were added to the solid, the organic phase was spin-dried to obtain a solid, and the obtained solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 8:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peaks appeared at 1.30 ppm and 3.40 ppm, the corresponding groups were Ar-CH2CH3, and the product was identified as 6-ethyl-6'-bromo-2,2'-bipyridine, and the yield of the 6-ethyl-6'-bromo-2,2'-bipyridine was 78.9%.

[0086] Step 2: 0.01 mol of 6-ethyl-6'-bromo-2,2'-bipyridine and 0.02 mol of phenol were dissolved in 54 mL of N,N-dimethylformamide, and 0.1 mmol of cuprous iodide, 0.8 mmol of potassium carbonate and 0.2 mmol of proline were added in sequence. After nitrogen bubbling in the reaction flask to remove oxygen, the mixture was stirred at 117 ° C for 24 h; the reaction was stopped, the solvent was removed, 90 mL of water and 90 mL of dichloromethane were added to the reaction flask, and the dichloromethane was collected to obtain a solid. The product was separated by column chromatography using a mixture of ethyl acetate and n-hexane as the eluent, with the volume ratio of ethyl acetate to n-hexane being 5:1. The separated product was then subjected to H-NMR analysis. Since a characteristic peak appeared at 6.91-7.29 ppm, the corresponding group was Ar-H. The product was identified as 6-ethyl-6'-phenoloxy-2,2'-bipyridine (BP-Et-OPh), and the yield of 6-ethyl-6'-phenoloxy-2,2'-bipyridine (BP-Et-OPh) was 88.1%.

[0087] Step 3: Dissolve 0.01 mol of 6-ethyl-6'-phenoloxy-2,2'-bipyridine (BP-Et-OPh) and 0.01 mol of FeBr2(THF)2 in 8 mL of dichloromethane, stir and react at 26°C for 10 hours, place in a refrigerator and let stand to precipitate a solid. The resulting solid is the iron catalyst FeCl2-BP-Mt-OPh; wash the obtained iron catalyst FeCl2-BP-Mt-OPh three times with ether, dry and weigh, and the yield is 80.3%; the characteristic peak of the iron catalyst FeCl2-BP-Mt-OPh infrared test appears at 1618 cm -1 、1587cm -1 、1526cm -1 、1485cm -1The results of mass spectrometry and elemental analysis showed that C 18 H 16 Cl2FeN2O, M / Z: 402.00, C, 68.38; H, 5.10; Fe, 17.66; N, 8.86.

[0088] Example 11

[0089] FeBr2-BP- i Preparation and analysis of Bu-SMe:

[0090] Step 1, 0.03 mol of 6,6'-dibromo-2,2'-bipyridine and 0.035 mol of isobutyl borate were dissolved in 60 mL of dimethyl sulfoxide, and 0.22 mmol of tetrakistriphenylphosphine palladium, 2.0 mmol of potassium carbonate and 7 mL of water were added in sequence, and stirred at 110°C for 37 hours; the solvent was removed, 45 mL of water was added for washing, 57 mL of dichloromethane was added for extraction, and the solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 9:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peaks appeared at 0.88 ppm, 1.82 ppm, and 2.80 ppm, the corresponding group was Ar-CH2CH(CH3)2, and the product was identified as 6-isobutyl-6'-bromo-2,2'-bipyridine, and the yield of 6-isobutyl-6'-bromo-2,2'-bipyridine was 87.6%.

[0091] Step 2: 0.01 mol of 6-isobutyl-6'-bromo-2,2'-bipyridine and 0.02 mol of methyl mercaptan were dissolved in 45 mL of N,N-dimethylformamide and 1.0 mmol of potassium carbonate, and 0.05 mmol of cuprous iodide and 0.1 mmol of proline were added in sequence. After nitrogen bubbling in the reaction flask to drive out oxygen, the mixture was stirred at 110 ° C for 23 h; the solvent was dried under reduced pressure, washed with 7 mL of water, extracted with 60 mL of dichloromethane, and the solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 3:1; the separated product was subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peak appeared at 2.54 ppm, the corresponding group was Ar-SCH3, and the product was identified as 6-isobutyl-6'-methylthio-2,2'-bipyridine (BP- i Bu-SMe), and the 6-isobutyl-6'-methylthio-2,2'-bipyridine (BP- i The yield of Bu-SMe) was 74.3%.

[0092] Step 3: Dissolve 0.011 mol of 6-isobutyl-6'-methylthio-2,2'-bipyridine and 0.01 mol of FeBr2(THF)2 in 18 mL of dichloromethane and stir at 25°C for 9 h. After filtering the suspension, the obtained solid is the iron catalyst FeBr2-BP- i The obtained iron catalyst FeBr2-BP- i Bu-SMe was washed three times with n-hexane and dried and weighed to obtain a yield of 86.8%. i The characteristic peak of Bu-SMe infrared test appears at 1610 cm -1 、1588cm -1 、1530cm -1 、1480cm -1 The results of mass spectrometry and elemental analysis showed that C 15 H 18 Br2FeN2S, M / Z: 473.89, C, 63.85; H, 6.43; Fe, 19.79; N, 9.93.

[0093] Example 12

[0094] FeBr2-BP- s Preparation and analysis of Bu-SPh:

[0095] Step 1. Dissolve 0.02 mol of 6,6'-dibromo-2,2'-bipyridine and 0.025 mol of sec-butyl borate in 64 mL of dimethyl sulfoxide, add 0.11 mmol of tris(dibenzylideneacetone)palladium, 1.1 mmol of potassium carbonate and 8 mL of water in sequence, and stir at 93°C for 25 hours; spin dry the solvent and extract with dichloromethane, and separate the solid by column chromatography, wherein the eluent is a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane is 11:1; then perform nuclear magnetic hydrogen spectrum analysis on the separated product, since the characteristic peaks appear at 0.76, 1.20, 1.52, and 2.78 ppm, the corresponding group is Ar-CH(CH3)CH2CH3, and the product is identified as 6-sec-butyl-6'-bromo-2,2'-bipyridine, and the yield of 6-sec-butyl-6'-bromo-2,2'-bipyridine is 62.3%.

[0096] Step 2: 0.02 mol of 6-sec-butyl-6'-bromo-2,2'-bipyridine and 0.04 mol of thiophenol were dissolved in 40 mL of dioxane and 0.9 mmol of potassium carbonate, and 0.18 mmol of cuprous iodide and 0.23 mmol of proline were added in sequence. After nitrogen bubbling was used to drive out oxygen from the reaction flask, the mixture was stirred at 107 ° C for 31 h; the volatile components were dried, washed with 40 mL of water, extracted with 40 mL of dichloromethane, and the solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 3:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peak appeared at 7.38-7.48 ppm, the corresponding group was Ar-H, and the product was identified as 6-sec-butyl-6'-phenolthio-2,2'-bipyridine (BP- s Bu-SPh), the 6-sec-butyl-6'-phenolthio-2,2'-bipyridine (BP- s The yield of Bu-SPh) was 78.6%.

[0097] Step 3: Dissolve 0.012 mol of 6-sec-butyl-6'-phenolthio-2,2'-bipyridine and 0.01 mol of FeBr2(THF)2 in 8 mL of tetrahydrofuran, and stir at 35°C for 11 h; let the suspension stand for stratification and filter to obtain a solid iron catalyst FeBr2-BP- s Bu-SPh; the obtained iron catalyst FeBr2-BP- s Bu-SPh was washed three times with n-hexane, dried and weighed, and the yield was calculated to be 87.7%. s The characteristic peak of Bu-SPh infrared test appears at 1625 cm -1 、1584cm -1 、1523cm -1 、1480cm -1 The results of mass spectrometry and elemental analysis showed that C 20 H 20 Br2FeN2S, M / Z: 535.90, C, 69.78; H, 5.86; Fe, 16.22; N, 8.14.

[0098] Example 13

[0099] FeCl2-Phen- t Bu-OEt preparation and analysis:

[0100] Step 1. Dissolve 0.03 mol of 2,9-dibromo-1,10-o-phenanthroline and 0.033 mol of tert-butyl borate in 39 mL of N,N-dimethylformamide, add 0.15 mmol of tetrakistriphenylphosphine palladium, 1.2 mmol of potassium carbonate and 5 mL of water in sequence, and stir at 98°C for 22 hours; spin dry the solvent, add 40 mL of water for washing, extract with 50 mL of dichloromethane, and separate the solid by column chromatography, wherein the eluent is a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane is 11:1; then perform nuclear magnetic hydrogen spectrum analysis on the separated product. Since the characteristic peak appears at 1.29 ppm, the corresponding group is Ar-C(CH3)3, and the product is identified as 2-tert-butyl-9-bromo-1,10-o-phenanthroline, and the yield of 2-tert-butyl-9-bromo-1,10-o-phenanthroline is 75.9%.

[0101] Step 2: 0.01 mol of 2-tert-butyl-9-bromo-1,10-o-phenanthroline and 0.25 mol of ethanol were dissolved in 60 mL of dimethyl sulfoxide, and 0.1 mmol of cuprous iodide, 0.8 mmol of potassium carbonate and 0.2 mmol of proline were added in sequence. After nitrogen bubbling in the reactor to drive out oxygen, the mixture was stirred at 91 ° C for 18 hours; after removing the solvent, 30 mL of dichloromethane was added and extracted three times. The dichloromethane was combined and dried, and the solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 3:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peaks appeared at 1.36 and 4.39 ppm, the corresponding groups were Ar-OCH2CH3, and the product was identified as 2-tert-butyl-9-ethoxy-1,10-o-phenanthroline (Phen- t Bu-OEt), the 2-tert-butyl-9-ethoxy-1,10-phenanthroline (Phen- t The yield of Bu-OEt) was 67.1%.

[0102] Step 3: Dissolve 0.012 mol of 2-tert-butyl-9-ethoxy-1,10-phenanthroline and 0.01 mol of FeCl2(THF)2 in 10 mL of anhydrous and oxygen-free tetrahydrofuran, react at room temperature for 8 h, and filter to obtain a solid iron catalyst FeCl2-Phen- t The obtained iron catalyst FeCl2-Phen- t The solid was washed three times with ether and dried and weighed to obtain a yield of 72.9%. t The characteristic peak of Bu-OEt infrared test appears at 1615 cm -1 、1584cm -1 、1522cm-1 、1489cm -1 The results of mass spectrometry and elemental analysis showed that C 18 H 20 Cl2FeN2O, M / Z: 406.03, C, 67.52; H, 6.30; Fe, 17.44; N, 8.75.

[0103] Example 14

[0104] FeCl2-Phen- i Preparation and analysis of Pr-P(CH3)2:

[0105] Step 1. Dissolve 0.01 mol of 2,9-dibromo-1,10-o-phenanthroline and 0.01 mol of isopropyl borate in 48 mL of dimethyl sulfoxide, add 0.05 mmol of tetrakistriphenylphosphine palladium, 0.3 mmol of potassium carbonate and 5 mL of water in sequence, and stir at 101 ° C for 35 hours to stop the reaction; remove the solvent, add 75 mL of water for washing, and extract with 60 mL of ethyl acetate. The obtained solid is separated by column chromatography, wherein the eluent is a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane is 7:1; the separated product is then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peaks appear at 1.31 ppm and 3.44 ppm, the corresponding groups are Ar-CH(CH3)2, and the product is identified as 2-isopropyl-9-bromo-1,10-o-phenanthroline, and the yield of 2-isopropyl-9-bromo-1,10-o-phenanthroline is 77.4%.

[0106] Step 2: Dissolve 0.01 mol of 2-isopropyl-9-bromo-1,10-o-phenanthroline and 0.022 mol of dimethylphosphine in 40 mL of anhydrous and oxygen-free dioxane, and add 0.12 mmol of cuprous iodide, 1.0 mmol of potassium carbonate and 0.2 mmol of proline in sequence. After nitrogen bubbling in the reaction flask to drive out oxygen, stir at 109 ° C for 18 hours; remove the solvent, add 80 mL of water for washing, extract with 90 mL of dichloromethane, and separate by column chromatography, wherein the eluent is a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane is 5:1; then perform nuclear magnetic hydrogen spectrum analysis on the separated product. Since the characteristic peak appears at 0.98 ppm, the corresponding group is Ar-P(CH3)2, and the product is identified as 2-isopropyl-9-dimethylphosphine-1,10-o-phenanthroline (Phen- i Pr-P(CH3)2), the 2-isopropyl-9-dimethylphosphino-1,10-phenanthroline (Phen- i The yield of Pr-P(CH3)2) was 73.7%.

[0107] Step 3: Dissolve 0.011 mol of 2-isopropyl-9-dimethylphosphino-1,10-phenanthroline and 0.01 mol of FeCl2(THF)2 in 5 mL of tetrahydrofuran, stir and react at 25 ° C for 10 h under nitrogen protection, let the suspension stand and filter, and the obtained solid is the iron catalyst FeCl2-Phen- i Pr-P(CH3)2; the obtained iron catalyst FeCl2-Phen- i Pr-P(CH3)2 was washed three times with ether and dried and weighed to obtain a yield of 85.1%. i The characteristic peak of Pr-P(CH3)2 infrared test appears at 1614 cm -1 、1585cm -1 、1527cm -1 、1480cm -1 The results of mass spectrometry and elemental analysis showed that C 17 H 19 Cl2FeN2P, M / Z: 408.00, C, 66.47; H, 6.23; Fe, 18.18; N, 9.12.

[0108] Example 15

[0109] Preparation and analysis of FeCl2-Phen-Et-SMe:

[0110] Step 1, 0.02 mol of 2,9-dibromo-1,10-o-phenanthroline and 0.02 mol of ethyl borate were dissolved in 65 mL of dimethyl sulfoxide, and 0.3 mmol of tris(dibenzylideneacetone)palladium, 1.5 mmol of potassium carbonate and 6 mL of water were added in sequence, and the reaction was stirred at 80°C for 36 hours to stop the reaction; 170 mL of water and 170 mL of dichloromethane were added to the reaction solution, the dichloromethane was collected and dried, and the obtained solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 3:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis, and since the characteristic peaks appeared at 1.30 and 3.40 ppm, the corresponding groups were Ar-CH2CH3, and the product was identified as 2-ethyl-9-bromo-1,10-o-phenanthroline, and the yield of the 2-ethyl-9-bromo-1,10-o-phenanthroline was 81.2%.

[0111] Step 2: 0.02 mol of 2-ethyl-9-bromo-1,10-phenanthroline and 0.04 mol of methyl mercaptan were dissolved in 50 mL of dioxane, and 0.2 mmol of cuprous iodide, 2.0 mmol of potassium carbonate and 0.4 mmol of proline were added in sequence. After nitrogen was bubbled through the reaction flask to remove oxygen, the reaction was stirred at 88 ° C for 22 h to stop the reaction; 120 mL of water and 120 mL of dichloromethane were added to the reaction solution, the dichloromethane was collected and dried, and the obtained solid was separated by column chromatography. , wherein the eluent is a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane is 4:1; the separated product is then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peak appears at 2.54ppm, the corresponding group is Ar-SCH3, and the product is identified as 2-ethyl-9-methylthio-1,10-o-phenanthroline (Phen-Et-SMe). The yield of 2-ethyl-9-methylthio-1,10-o-phenanthroline (Phen-Et-SMe) is 75.9%.

[0112] Step 3: Dissolve 0.02 mol of 2-ethyl-9-methylthio-1,10-phenanthroline and 0.02 mol of FeCl2(THF)2 in 10 mL of tetrahydrofuran, stir and react at 30°C for 8 hours, let stand and stratify, and filter to obtain a solid iron catalyst FeCl2-Phen-Et-SMe; wash the obtained iron catalyst FeCl2-Phen-Et-SMe three times with ether, dry and weigh, and the yield is 65.9%; the characteristic peak of the iron catalyst FeCl2-Phen-Et-SMe infrared test appears at 1612 cm -1 、1580cm -1 、1525cm -1 、1485cm -1 The results of mass spectrometry and elemental analysis showed that C 15 H 14 Cl2FeN2S, m / e: 379.96 (100.0%), C, 64.78; H, 5.07; Fe, 20.08; N, 10.07.

[0113] Example 16

[0114] Preparation and analysis of FeCl2-Phen-Et-OEt:

[0115] Step 1, 0.01 mol of 2,9-dibromo-1,10-o-phenanthroline and 0.01 mol of ethyl borate were dissolved in 35 mL of dioxane, and 0.07 mmol of palladium chloride, 0.4 mmol of potassium carbonate and 5 mL of water were added in sequence, and the mixture was reacted at 95° C. for 21 h; the solvent was spin-dried, washed with 40 mL of water, extracted with 55 mL of dichloromethane, and the solid was separated by column chromatography, wherein the gradient elution was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 15:1 to 10:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peaks appeared at 1.30 ppm and 3.40 ppm, the corresponding groups were Ar-CH2CH3, and the product was identified as 2-ethyl-9-bromo-1,10-o-phenanthroline, and the yield of 2-ethyl-9-bromo-1,10-o-phenanthroline was 68.2%.

[0116] Step 2: 0.01 mol of 2-ethyl-9-bromo-1,10-phenanthroline and 0.25 mol of ethanol were dissolved in 30 mL of dimethyl sulfoxide, and 0.07 mmol of cuprous iodide, 0.5 mmol of potassium carbonate and 0.15 mmol of proline were added in sequence. After nitrogen bubbling in the reactor to remove oxygen, the mixture was stirred at 117 ° C for 7 h; the solvent was drained, washed with 80 mL of water, extracted with 80 mL of dichloromethane, and the resulting solid was separated by column chromatography, wherein the eluent was ethyl acetate. The product was prepared by hydrogen nuclear magnetic spectrum analysis. Since the characteristic peaks appeared at 1.36 ppm and 4.39 ppm, the corresponding groups were Ar-OCH2CH3. The product was identified as 2-ethyl-9-ethoxy-1,10-o-phenanthroline (Phen-Et-OEt). The yield of 2-ethyl-9-ethoxy-1,10-o-phenanthroline (Phen-Et-OEt) was 68.3%.

[0117] Step 3: Dissolve 0.022 mol of 2-ethyl-9-ethoxy-1,10-phenanthroline and 0.02 mol of FeCl2(THF)2 in 10 mL of tetrahydrofuran, and stir at 47°C for 8 h; filter the reaction solution to obtain a solid iron catalyst FeCl2-Phen-Et-OEt; wash the obtained iron catalyst FeCl2-Phen-Et-OEt three times with ether, dry and weigh, and calculate the yield to be 69.6%; the characteristic peak of the iron catalyst FeCl2-Phen-Et-OEt infrared test appears at 1611 cm -1 、1581cm -1 、1524cm -1 、1489cm -1 The results of mass spectrometry and elemental analysis showed that C 16 H 16Cl2FeN2O, M / Z: 378.00, C, 65.78; H, 5.52; Fe, 19.11; N, 9.59.

[0118] Example 17

[0119] FeCl2-Phen- t Preparation and analysis of Bu-OMe:

[0120] Step 1. Dissolve 0.02 mol of 2,9-dibromo-1,10-phenanthroline and 0.023 mol of tert-butyl borate in 50 mL of dimethyl sulfoxide, add 0.15 mmol of palladium acetate, 1.0 mmol of potassium carbonate and 5 mL of water in sequence, and stir at 108°C for 27 hours; remove the solvent, wash with 110 mL of water, extract with 110 mL of dichloromethane, and separate by column chromatography, wherein the eluent is a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane is 15:1; then perform nuclear magnetic hydrogen spectrum analysis on the separated product. Since the characteristic peak appears at 1.29 ppm, the corresponding group is Ar-C(CH3)3, and the product is identified as 2-tert-butyl-9-bromo-1,10-phenanthroline, and the yield of 2-tert-butyl-9-bromo-1,10-phenanthroline is 75.1%.

[0121] Step 2: 0.02 mol of 2-tert-butyl-9-bromo-1,10-o-phenanthroline and 0.44 mol of methanol were dissolved in 54 mL of N,N-dimethylformamide, and 0.12 mmol of cuprous iodide, 1.0 mmol of potassium carbonate and 0.27 mmol of proline were added in sequence. After nitrogen bubbling in the reactor to drive out oxygen, the mixture was stirred at 100 ° C for 13 h; after reduced pressure distillation, 100 mL of water was added to dissolve the mixture, and 100 mL of dichloromethane was used for extraction and column chromatography separation, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 3:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peak appeared at 4.06 ppm, the corresponding group was Ar-OCH3, and the product was identified as 2-tert-butyl-9-methoxy-1,10-o-phenanthroline (Phen- t Bu-OMe), and the 2-tert-butyl-9-methoxy-1,10-phenanthroline (Phen- t The yield of Bu-OMe) was 68.6%.

[0122] Step 3: Dissolve 0.021 mol of 2-tert-butyl-9-methoxy-1,10-phenanthroline and 0.02 mol of FeCl2(THF)2 in 10 mL of tetrahydrofuran, stir at 43 ° C for 11 h, and filter the suspension to obtain a solid iron catalyst FeCl2-Phen- tBu-OMe; the obtained iron catalyst FeCl2-Phen- t Bu-OMe was washed three times with ether and dried and weighed to give a yield of 65.9%. t The characteristic peak of Bu-OMe infrared test appears at 1614 cm -1 、1586cm -1 、1520cm -1 、1483cm -1 The results of mass spectrometry and elemental analysis showed that C 17 H 18 Cl2FeN2O, M / Z: 392.01, C, 66.69; H, 5.93; Fe, 18.24; N, 9.15.

[0123] Example 18

[0124] Preparation and analysis of FeBr2-BP-Et-OMe:

[0125] Step 1, 0.02 mol of 6,6'-dibromo-2,2'-bipyridine and 0.02 mol of ethyl borate were dissolved in 55 mL of dioxane, and 0.1 mmol of bis(triphenylphosphine)palladium dichloride, 1.0 mmol of potassium carbonate and 5 mL of water were added in sequence, and stirred at 85°C under a nitrogen atmosphere for 14 hours; the dioxane was removed, washed with 60 mL of water, extracted with 72 mL of ethyl acetate, and the solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 8:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peaks appeared at 1.30 ppm and 3.40 ppm, the corresponding groups were Ar-CH2CH3, and the product was identified as 6-ethyl-6'-bromo-2,2'-bipyridine, and the yield of the 6-ethyl-6'-bromo-2,2'-bipyridine was 67.0%.

[0126] Step 2: Dissolve 0.02 mol of 6-ethyl-6'-bromo-2,2'-bipyridine and 0.20 mol of methanol in 60 mL of dioxane, and add 0.2 mmol of cuprous iodide, 1.0 mmol of potassium carbonate and 0.2 mmol of proline in sequence. After nitrogen bubbling in the reaction kettle to drive out oxygen, stir at 95 ° C for 5 h; remove the solvent, wash with 45 mL of water, extract with 50 mL of dichloromethane, and separate by column chromatography, wherein the eluent is a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane is 3:1; the separated product is then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peak appears at 4.06 ppm, the corresponding group is Ar-OCH3, and the product is identified as 6-ethyl-6'-methoxy-2,2'-bipyridine (BP-Et-OMe), and the 6-ethyl-6'-methoxy-2,2'-bipyridine (BP-Et-OMe) is 53.2%.

[0127] Step 3: Dissolve 0.02 mol of 6-ethyl-6'-methoxy-2,2'-bipyridine and 0.02 mol of FeBr2(THF)2 in 10 mL of tetrahydrofuran, stir and react at 28°C for 11 hours, let stand and stratify, and filter to obtain a solid iron catalyst FeBr2-BP-Et-OMe; wash the obtained iron catalyst FeBr2-BP-Et-OMe three times with ether, dry and weigh, and calculate the yield to be 87.9%. The characteristic peak of the iron catalyst FeBr2-BP-Et-OMe infrared test appears at 1601 cm -1 、1586cm -1 、1522cm -1 、1486cm -1 The results of mass spectrometry and elemental analysis showed that C 13 H 14 Br2FeN2O, M / Z: 429.88, C, 61.45; H, 5.55; Fe, 21.98; N, 11.02.

[0128] Example 19

[0129] Preparation and analysis of FeBr2-BP-Ph-SEt:

[0130] Step 1, 0.03 mol of 6,6'-dibromo-2,2'-bipyridine and 0.03 mol of phenyl borate were dissolved in 60 mL of dimethyl sulfoxide, and 0.22 mmol of tetrakistriphenylphosphine palladium, 2.5 mmol of potassium carbonate and 4 mL of water were added in sequence, and the reaction was stirred at 87°C for 14 hours to stop the reaction; the solvent was removed, 50 mL of water and 50 mL of dichloromethane were added for extraction, and column chromatography was performed, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 5:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peak appeared at 7.49-8.23 ppm, the corresponding group was Ar-H, and the product was identified as 6-phenyl-6'-bromo-2,2'-bipyridine, and the yield of the 6-phenyl-6'-bromo-2,2'-bipyridine was 78.3%.

[0131] Step 2: 0.02 mol of 6-phenyl-6'-bromo-2,2'-bipyridine and 0.04 mol of ethanethiol were dissolved in 60 mL of dioxane and 2.0 mmol of potassium carbonate, and 0.1 mmol of cuprous iodide and 0.2 mmol of proline were added in sequence, and stirred at 90 ° C in a nitrogen atmosphere for 27 h; the solvent was dried, washed with 50 mL of water, extracted with 47 mL of dichloromethane, and separated by column chromatography, wherein the eluent was ethyl acetate and n-hexane. The product was prepared by mixing the raw materials with the raw materials in a mixture of ethyl acetate and n-hexane in a volume ratio of 10:1. The isolated product was then subjected to H-NMR analysis. Characteristic peaks appeared at 1.31 ppm and 3.00 ppm, corresponding to the group Ar-SCH2CH3. The product, 6-phenyl-6'-ethylthio-2,2'-bipyridine (BP-Ph-SEt), was identified. The yield of 6-phenyl-6'-ethylthio-2,2'-bipyridine (BP-Ph-SEt) was 76.4%.

[0132] Step 3: Dissolve 0.031 mol of 6-phenyl-6'-ethylthio-2,2'-bipyridine and 0.03 mol of FeBr2(THF)2 in 10 mL of dichloromethane, react at 28°C for 12 hours, filter the suspension, and obtain a solid iron catalyst FeBr2-BP-Ph-SEt; wash the obtained iron catalyst FeBr2-BP-Ph-SEt three times with n-hexane, dry and weigh, and calculate the yield to be 84.8%. The characteristic peak of the iron catalyst FeBr2-BP-Ph-SEt infrared test appears at 1615 cm -1 、1588cm -1 、1524cm -1 、1486cm -1 The results of mass spectrometry and elemental analysis showed that C 18 H 16Br2FeN2S, M / E: 507.87, C, 42.55; H, 3.17; Br, 31.45; Fe, 10.99; N, 5.51; S, 6.31.

[0133] Example 20

[0134] Preparation and analysis of FeBr2-BP-Ph-N(CH3)2:

[0135] Step 1: 0.02 mol of 6,6'-dibromo-2,2'-bipyridine and 0.022 mol of phenyl borate were dissolved in 62 mL of N,N-dimethylformamide, and 0.1 mmol of tris(dibenzylideneacetone)palladium, 1.1 mmol of potassium carbonate, and 8 mL of water were added in sequence. The reaction was stirred at 80°C under a nitrogen atmosphere for 30 h to stop the reaction. The solvent was removed, 50 mL of water and 40 mL of dichloromethane were added to the reaction solution, the dichloromethane phase was collected and dried, and the solid was separated by column chromatography, wherein the eluent was a mixture of ethyl acetate and n-hexane, and the volume ratio of ethyl acetate to n-hexane was 3:1; the separated product was then subjected to nuclear magnetic hydrogen spectrum analysis. Since the characteristic peak appeared at 7.49-8.23 ppm, the corresponding group was Ar-H, and the product was identified as 6-phenyl-6'-bromo-2,2'-bipyridine, and the yield of the 6-phenyl-6'-bromo-2,2'-bipyridine was 68.8%.

[0136] Step 2: 0.03 mol of 6-phenyl-6'-bromo-2,2'-bipyridine and 0.32 mol of dimethylamine were dissolved in 60 mL of dioxane, and 0.21 mmol of cuprous iodide, 2.1 mmol of potassium carbonate and 0.4 mmol of proline were added in sequence. After nitrogen was bubbled through the reaction flask to remove oxygen, the reaction was stirred at 85 ° C for 35 h to stop the reaction; the solvent was removed, 40 mL of water was added for washing, 40 mL of dichloromethane was extracted and dried, and the mixture was separated by column chromatography, wherein the eluent was ethyl acetate and n-hexane. The product was purified by hydrogen nuclear magnetic spectrum analysis. Since the characteristic peak appeared at 3.15 ppm, the corresponding group was Ar-N(CH3)2. The product was identified as 6-phenyl-6'-(N,N'-dimethyl)-2,2'-bipyridine (BP-Ph-N(CH3)2). The yield of 6-phenyl-6'-(N,N'-dimethyl)-2,2'-bipyridine (BP-Ph-N(CH3)2) was 68.3%.

[0137] Step 3: Dissolve 0.021 mol of 6-phenyl-6'-(N,N'-dimethyl)-2,2'-bipyridine and 0.02 mol of FeBr2(THF)2 in 10 mL of tetrahydrofuran, stir and react at 35°C for 12 hours, let stand and separate, and filter. The resulting solid is the iron catalyst FeBr2-BP-Ph-N(CH3)2; wash the obtained iron catalyst FeBr2-BP-Ph-N(CH3)2 three times with ether, dry and weigh, and the yield is 74.7%. Figure 1 As shown in the spectrum in Figure d, the characteristic peak of the iron catalyst FeBr2-BP-Ph-N(CH3)2 infrared test appears at 1612 cm -1 、1584cm -1 、1528cm -1 、1486cm -1 The results of mass spectrometry and elemental analysis showed that C 18 H 17 Br2FeN3, M / E: 490.91, C, 68.16; H, 5.40; Fe, 17.61; N, 8.83.

[0138] 2. Syndiotactic 1,2 / 3,4 Polyconjugated Diolefins

[0139] Example 21

[0140] Preparation and analysis of syndiotactic 3,4-polyisoprene:

[0141] After anhydrous and oxygen-free treatment of a 50 mL polymerization flask, 0.01 mmol of FeCl2-Phen-Et-SMe was added under a dry nitrogen atmosphere. 20 mL of a hexane solution containing 20 mmol of isoprene (16.0% isoprene mass concentration) was added to the polymerization flask, and 0.30 mmol of triisobutylaluminum was added to initiate polymerization. The entire operation was carried out under a nitrogen atmosphere and the reaction temperature was maintained at 30°C. After 12 hours of reaction, mixed solution C was added to terminate the reaction and the polymer was precipitated. The polymer was then filtered and dried in a vacuum oven at 30°C for 12 hours to obtain syndiotactic 3,4-polyisoprene. Mixed solution C contained methanol, hydrochloric acid, and 2,6-di-tert-butyl-4-methylphenol. The mass of 2,6-di-tert-butyl-4-methylphenol was 3% of the volume of methanol, and the volume of hydrochloric acid was 2% of the volume of methanol.

[0142] Example 22

[0143] Preparation of syndiotactic 3,4-polyisoprene:

[0144] After anhydrous and oxygen-free treatment in a 50 mL polymerization flask, 0.02 mmol of FeBr2-Phen-Ph-OPh was added under a dry nitrogen atmosphere. 25 mL of a toluene solution containing 50 mmol of isoprene (22.0% mass concentration) was added to the flask, along with 0.80 mmol of MAO. The reaction was carried out at 60°C. After 3 hours, mixed solution C was added to terminate the reaction and the polymer was precipitated. The polymer was then filtered and dried in a vacuum oven at 30°C for 12 hours to obtain syndiotactic 3,4-polyisoprene. Mixed solution C contained methanol, hydrochloric acid, and antioxidant 264, with the weight of antioxidant 264 being 3% of the volume of methanol and the volume of hydrochloric acid being 2% of the volume of methanol.

[0145] Example 23

[0146] Preparation of syndiotactic 3,4-polymyrcene:

[0147] After the 50 mL polymerization bottle was treated to be anhydrous and oxygen-free, 0.01 mmol of FeCl2-BP- t Bu-OMe, 35 mL of a hexane solution containing 60 mmol of myrcene was added to a polymerization flask, followed by 0.13 mmol of MAO and polymerization at 90°C. After 1.5 hours, mixed solution C was added to terminate the reaction and the polymer was precipitated. The polymer was then filtered and dried in a vacuum oven at 30°C for 12 hours to obtain syndiotactic 3,4-polymyrcene. Mixed solution C contained methanol, hydrochloric acid, and 2,6-di-tert-butyl-4-methylphenol. The mass of 2,6-di-tert-butyl-4-methylphenol was 3% by volume of methanol, and the volume of hydrochloric acid was 2% by volume of methanol.

[0148] Example 24

[0149] Preparation of syndiotactic 3,4-polymyrcene:

[0150] After anhydrous and oxygen-free treatment, a 100 mL polymerization flask was dehydrated and oxygen-free. 0.01 mmol of FeBr2-Phen-Ph-SMe was added under a dry nitrogen atmosphere. 60 mL of a heptane solution containing 100 mmol of myrcene was added to the flask, followed by 1.0 mmol of MMAO. The mixture was allowed to react at 58°C for 7 hours. Mixed solution C was added to terminate the reaction, and the polymer was precipitated. The mixture was then filtered and dried in a vacuum oven at 30°C for 12 hours to obtain syndiotactic 3,4-polymyrcene. Mixed solution C contained methanol, hydrochloric acid, and 2,6-di-tert-butyl-4-methylphenol, with the mass of 2,6-di-tert-butyl-4-methylphenol being 3% by volume of methanol and the volume of hydrochloric acid being 2% by volume of methanol.

[0151] Example 25

[0152] Preparation of syndiotactic 3,4-polyfarnesene:

[0153] After anhydrous and oxygen-free treatment, a 500 mL polymerization flask was added to a dry nitrogen atmosphere. 0.015 mmol of FeBr2-BP-Ph-SEt was then added. A 150 mL toluene solution containing 0.15 mol of farnesene was then added. 0.30 mmol of MMAO was then added and the reaction was carried out at 105°C for 10 hours. Mixed Solution C was added to terminate the reaction, and the polymer was precipitated. The resulting product was filtered and dried in a vacuum oven at 30°C for 12 hours. The resulting product was syndiotactic 3,4-polyfarnesene. Mixed Solution C contained methanol, hydrochloric acid, and 2,6-di-tert-butyl-4-methylphenol. The mass of 2,6-di-tert-butyl-4-methylphenol was 3% by volume of methanol, and the volume of hydrochloric acid was 2% by volume of methanol.

[0154] Example 26

[0155] Preparation of syndiotactic 3,4-polyocimene:

[0156] After the 200 mL polymerization bottle was treated to be anhydrous and oxygen-free, 0.1 mmol of FeCl2-Phen- t Bu-OEt, 80 mL of a polyocimene-n-hexane solution containing 0.40 mol was added to a polymerization flask, and 3.0 mmol of triisobutylaluminum was added to initiate polymerization at 65°C. After 3 hours, mixed solution C was added to terminate the reaction and the polymer was precipitated. Subsequently, the polymer was filtered and dried in a vacuum oven at 30°C for 12 hours to obtain syndiotactic 3,4-polyocimene. Mixed solution C contained methanol, hydrochloric acid, and 1010 antioxidant, with the mass of 1010 antioxidant accounting for 4% of the volume of methanol and the volume of hydrochloric acid accounting for 2% of the volume of methanol.

[0157] Example 27

[0158] Preparation of syndiotactic 3,4-polyocimene:

[0159] After the 1000 mL polymerization bottle was treated to be anhydrous and oxygen-free, 0.01 mmol of FeBr2-BP- s Bu-SPh, 500 mL of a toluene solution containing 0.12 mol of polyocimene was added to a polymerization flask, followed by 1.00 mmol of MAO, and polymerization was initiated at 85°C for 2 hours. Mixed solution C was added to terminate the reaction and the polymer was precipitated. The polymer was then filtered and dried in a vacuum oven at 30°C for 12 hours to obtain syndiotactic 3,4-polyocimene. Mixed solution C contained methanol, hydrochloric acid, and 2,6-di-tert-butyl-4-methylphenol, with the mass of 2,6-di-tert-butyl-4-methylphenol being 3% by volume of methanol and the volume of hydrochloric acid being 2% by volume of methanol.

[0160] Example 28

[0161] Preparation of syndiotactic 1,2-polybutadiene:

[0162] After the 500 mL polymerization bottle was treated to be anhydrous and oxygen-free, 0.01 mmol of FeCl2-BP- i Pr-P(CH3)2: 200 mL of a toluene solution containing 0.8 mol of butadiene was added to a polymerization flask, followed by 0.40 mmol of triisobutylaluminum. The polymerization was carried out at 120°C for 1 hour. Mixed Solution C was added to terminate the reaction and the polymer was precipitated. The product was then filtered and dried in a vacuum oven at 30°C for 12 hours to obtain syndiotactic 1,2-polybutadiene. Mixed Solution C contained methanol, hydrochloric acid, and 2,6-di-tert-butyl-4-methylphenol. The mass of 2,6-di-tert-butyl-4-methylphenol was 3% by volume of methanol, and the volume of hydrochloric acid was 2% by volume of methanol.

[0163] Example 29:

[0164] Preparation of syndiotactic-1,2-butadiene: After anhydrous and oxygen-free treatment, a 500 mL polymerization flask was added under a dry nitrogen atmosphere. 0.05 mmol of FeBr2-Phen-Me-OPh was then added. 200 mL of an isooctane solution containing 400 mmol of butadiene was then added to the flask. Subsequently, 0.60 mmol of MAO was added sequentially. The reaction temperature was maintained at 60°C under a nitrogen atmosphere throughout the entire process. After 6 hours of reaction, mixed solution C was added to terminate the reaction and the polymer was precipitated. The polymer was then filtered and dried in a vacuum oven at 45°C for 12 hours to obtain syndiotactic-1,2-butadiene. Mixed solution C contained methanol, hydrochloric acid, and 2,6-di-tert-butyl-4-methylphenol. The mass of 2,6-di-tert-butyl-4-methylphenol was 3% by volume of methanol, and the volume of hydrochloric acid was 2% by volume of methanol.

[0165] Example 30:

[0166] Preparation of syndiotactic-3,4-isoprene: After anhydrous and oxygen-free treatment in a 2-L reactor, 0.1 mmol of FeBr2-BP-Me-SEt was added under a dry nitrogen atmosphere. 800 mL of a xylene solution containing 1.5 mol of isoprene was added to the reactor, followed by 50.0 mmol of triisobutylaluminum. The reaction temperature was maintained at 130°C under a nitrogen atmosphere throughout the entire process. After 12 hours of reaction, mixed solution C was added to terminate the reaction and the polymer was precipitated. The polymer was then filtered and dried in a vacuum oven at 30°C for 12 hours to obtain syndiotactic-3,4-isoprene. Mixed solution C contained methanol, hydrochloric acid, and 2,6-di-tert-butyl-4-methylphenol. The mass of 2,6-di-tert-butyl-4-methylphenol was 3% by volume of methanol, and the volume of hydrochloric acid was 2% by volume of methanol.

[0167] Example 31

[0168] Preparation of syndiotactic-1,2-butadiene: After anhydrous and oxygen-free treatment of a 5L reactor, 0.3mmol of FeCl2-Phen-Et-N(CH3)2 was added under a dry nitrogen atmosphere. 1.8L of a cyclohexane solution containing 3.6mol of butadiene was added to the polymerization flask, followed by 20mmol of tri-n-butylaluminum. The entire operation was performed under a nitrogen atmosphere and the reaction temperature was maintained at 10°C. After 8 hours, mixed solution C was added to terminate the reaction and the polymer was precipitated. The polymer was then filtered and dried in a vacuum oven at 30°C for 12 hours to obtain syndiotactic-1,2-butadiene. Mixed solution C contained methanol, hydrochloric acid, and 1010 antioxidant, with the mass of 1010 antioxidant being 3% of the volume of methanol and the volume of hydrochloric acid being 2% of the volume of methanol.

[0169] Example 32:

[0170] Preparation of syndiotactic 3,4-ocimene: After anhydrous and oxygen-free treatment of a 2L reactor, 0.1mmol of FeBr2-Phen-Ph-OMe was added in a dry nitrogen atmosphere. 800mL of a hydrogenated gasoline solution containing 0.6mol of ocimene was added to a polymerization bottle. 45.80mmol of MAO was added, and polymerization was carried out at 120°C in a nitrogen atmosphere. After 9 hours, mixed solution C was added to terminate the reaction and the polymer was precipitated. Subsequently, it was filtered and dried in a vacuum oven at 30°C for 12 hours to obtain syndiotactic 3,4-ocimene. Mixed solution C contains methanol, hydrochloric acid, and 2,6-di-tert-butyl-4-methylphenol. The mass of 2,6-di-tert-butyl-4-methylphenol is 3% by volume of methanol, and the volume of hydrochloric acid is 2% by volume of methanol.

[0171] Example 33

[0172] Preparation of syndiotactic 3,4-myrcene: In a dry nitrogen atmosphere, 0.2 mmol of FeBr2-BP- i Bu-SMe was added sequentially to a 1L heptane solution containing 2.0 mol of myrcene. Polymerization was initiated with 12 mmol of MMAO at 80°C for 5 hours. Mixed solution C was added to terminate the reaction and the polymer was precipitated. The polymer was then filtered and dried in a vacuum oven at 30°C for 12 hours to obtain syndiotactic 1,2-butadiene. Mixed solution C contained methanol, hydrochloric acid, and 1010 antioxidant, with the mass of 1010 antioxidant accounting for 3% of the volume of methanol and the volume of hydrochloric acid accounting for 2% of the volume of methanol.

[0173] 3. Example Analysis of Syndiotactic 1,2 / 3,4 Polyconjugated Diolefins

[0174] The polyconjugated diene samples of Examples 21 to 33 were tested, and the relevant test results are shown in Table 1 below:

[0175] Table 1 Performance analysis of examples of syndiotactic 1,2 / 3,4 polyconjugated dienes

[0176]

[0177] In summary, the iron catalysts in the examples catalyze the selective syndiotactic-1,2 polymerization of butadiene and the selective syndiotactic-3,4 polymerization of isoprene, myrcene, farnesene, and ocimene at 20-150° C. with high activity. The resulting polymers are crystalline, and each iron catalyst has good stability even at relatively high temperatures.

Claims

1. An iron catalyst for the 1,2 / 3,4 selective polymerization of conjugated dienes, characterized in that: It is an iron complex, and the general formula of the iron complex is the following formula 1 or formula 2: wherein R1 is one of -CH3, -CH2CH3, -CH(CH3)2, -CH(CH3)CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -C6H5, -(2-CH3)C6H5, -(2-CH2CH3)C6H5, -(2-CH(CH3)2)C6H5, -(2-CH2CH(CH3)2)C6H5, and -(2-C(CH3)3)C6H5; R2 is -SCH3, -SCH2CH3, -SCH(CH3)2, -SCH2CH(CH3)2, -SCH2CH2CH2CH3, -SC(CH3)3, -SC6H5, -OCH3, -OCH2 CH3, -OCH(CH3)2, -OCH2CH(CH3)2, -OCH2CH2CH2CH3, -OC(CH3)3, -OC6H5, -P(CH3)2, -P(CH2CH3)2, -P(C One of -H(CH3)2)2, -P(C(CH3)3)2, -P(C6H5)2, -P(=O)(CH3)2, -P(=O)(CH2CH3)2, -P(=O)(CH(CH3)2)2, -P(=O)(C(CH3)3)2, -P=(O)(C6H5)2, -N(CH3)2, -N(CH2CH3)2, -N(CH(CH3)2)2, -N(C(CH3)3)2, -N(C6H5)2; X is chlorine or bromine.

2. The iron catalyst according to claim 1, characterized in that The iron complex is prepared by reacting an asymmetric ligand with a tetrahydrofuran complex of ferrous chloride or a tetrahydrofuran complex of ferrous bromide. And if the general formula of the iron complex is Formula 1, then the asymmetric ligand is 6-R1-6'-R2-2,2'-bipyridine; If the general formula of the iron complex is Formula 2, the asymmetric ligand is 2-R1-9-R2-1,10-phenanthroline.

3. The iron catalyst according to claim 2, characterized in that The volume ratio of the amount of the asymmetric ligand, the amount of ferrous chloride or ferrous bromide, and tetrahydrofuran is 1.03-1.2:1:334-180, the reaction time is 8-12 hours, and the temperature is 25-61°C.

4. The iron catalyst according to claim 2, characterized in that The preparation method of the asymmetric ligand comprises the following steps in sequence: Step 1: preparing a monobromo compound by a palladium-catalyzed coupling reaction of a dibromo compound; Step 2: preparing the asymmetric ligand by subjecting a monobromo compound to a copper-catalyzed coupling reaction; If the asymmetric ligand is 6-R1-6'-R2-2,2'-bipyridine, the dibromo compound is 6,6'-dibromo-2,2'-bipyridine, and the monobromo compound is 6-R1-6'-bromo-2,2'-bipyridine; If the asymmetric ligand is 2-R1-9-R2-1,10-phenanthroline, the dibromo compound is 2,9-dibromo-1,10-phenanthroline, and the monobromo compound is 2-R1-9-bromo-1,10-phenanthroline.

5. The iron catalyst according to claim 4, characterized in that The specific process of the palladium-catalyzed coupling reaction is: dissolving the dibromo compound and R1OB(OH)2 in an organic solvent A, then adding a mixed solution of a Pd compound and potassium carbonate, stirring at 80-122°C for 14-37 hours, collecting the resulting solid, and separating it by column chromatography to obtain the monobromo compound; wherein the molar ratio of the dibromo compound, R1OB(OH)2, Pd compound, and potassium carbonate is 1:1.0-1.5:0.005-0.015:0.03-0.

11.

6. The iron catalyst according to claim 5, characterized in that The Pd compound is one of palladium chloride, palladium acetate, tris(dibenzylideneacetone)dipalladium, tetrakistriphenylphosphine palladium, and bis(triphenylphosphine)palladium dichloride.

7. The iron catalyst according to claim 4, characterized in that The specific process of the copper-catalyzed coupling reaction is as follows: dissolving a monobromo compound and R2H in an organic solvent A, sequentially adding cuprous iodide, potassium carbonate, and proline, and reacting in an oxygen-free environment at 85 to 130° C. for 5 to 36 hours, collecting the resulting solid, and separating it by column chromatography to obtain the asymmetric ligand; wherein the molar ratio of the monobromo compound, R2H, cuprous iodide, proline, and potassium carbonate is 1:1.5-25:0.005-0.012:0.0025-0.02:0.0012-0.

1.

8. Use of the iron catalyst for 1,2 / 3,4 selective polymerization of conjugated dienes according to any one of claims 1 to 7, characterized in that: The steps are as follows: Step 1: After the polymerization bottle is treated in anhydrous and oxygen-free conditions at high temperature, the iron catalyst according to any one of claims 1 to 7, the conjugated diene solution, and the co-catalyst are added, and the polymerization is carried out in anhydrous and oxygen-free conditions at 30 to 150° C. for 1 to 12 hours, wherein the solvent of the conjugated diene solution is an organic solvent B; Step 2: terminating the polymerization reaction and precipitating the polymer, followed by filtering, washing, and drying to obtain a syndiotactic 1,2 / 3,4-polyconjugated diene; The conjugated diene is at least one of butadiene, isoprene, myrcene, farnesene, and ocimene; and the co-catalyst is at least one of diisobutylaluminum hydride, diethylaluminum hydride, triisobutylaluminum, tri-n-butylaluminum, trimethylaluminum, triethylaluminum, trioctylaluminum, methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, diethylmagnesium, dibutylmagnesium, and diethylzinc.

9. The use according to claim 8, characterized in that Calculated by mole fraction, the molar ratio of the conjugated diene, the iron catalyst and the co-catalyst is 667-80000:1:13-458, and the total volume of the organic solvent B and the conjugated diene is 20 mL-1.8 L.

10. The use according to claim 8, characterized in that In step 2, the polymerization reaction is terminated by using a mixed solution C, which contains methanol, hydrochloric acid and an antioxidant, wherein the volume of the hydrochloric acid is 1-3% of the volume of the methanol, and the mass of the antioxidant is 2-4% of the volume of the methanol.

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