Preparation method of N ortho-alkyl substituted 1, 10-phenanthroline compound and catalyst prepared by same

Abstract

The invention provides application of cyclobutanone compounds in preparation of N ortho-alkyl substituted 1, 10-phenanthroline compounds, and relates to the technical field of organic catalysts. The invention also provides a preparation method of the N ortho-alkyl substituted 1, 10-phenanthroline compound and the N ortho-alkyl substituted 1, 10-phenanthroline compound prepared by the preparation method. The preparation method takes 8-aminoquinoline and the cyclobutanone compound as shown in the formula (I) as reaction raw materials, and has the advantages of few synthesis steps, simple process, low raw material cost, avoidance of using highly toxic substances to participate in the reaction and the like. The N, N ortho-alkyl substituted 1, 10-phenanthroline compound can be used as a catalyst to participate in ethylene oligomerization reaction, and has a good industrial application prospect.

Description

[0001] The present invention relates to the technical field of organic catalysts, and in particular to the use of cyclobutanone compounds in the preparation of N-ortho-alkyl-substituted 1,10-phenanthroline compounds, a preparation method of N-ortho-alkyl-substituted 1,10-phenanthroline compounds and a catalyst prepared thereby. Background Art

[0002] Ethylene oligomerization is one of the most important reactions in the olefin polymerization industry. Through oligomerization, cheap small molecule olefins can be converted into products with high added value. The product of ethylene oligomerization, linear α-olefins (LAO), is an important organic chemical raw material. For example, C4-C 30 LAO can be used to prepare daily detergents, flotation agents, emulsifiers, lubricating components of refrigerators and drilling fluids, plasticizers, various additives, low-viscosity synthetic oils, polymers and copolymers, petroleum and petroleum product additives, higher alkylamines, higher organoaluminum compounds, higher alkylaryl hydrocarbons, higher fatty alcohols and fatty acids, epoxides and heat carrier additives, etc. 20 -C 30 Adhesives, sealants and coatings can also be synthesized based on LAO. In recent years, with the continuous development of the polyolefin industry, the demand for α-olefins has grown rapidly worldwide. Most of the α-olefins are prepared by ethylene polymerization.

[0003] The catalysts used in the ethylene oligomerization method mainly include nickel, chromium, zirconium and aluminum. In recent years, the Brookhart group (Brookhart, M et al., J. Am. Chem. Soc., 1998, 120, 7143-7144; WO99 / 02472, 1999) and the Gibson group (Gibson, VC et al., Chem. Commun., 1998, 849-850; Chem. Eur. J., 2000, 2221-2231) have found that some tridentate pyridine imine complexes of Fe (II) and Co (II) can catalyze ethylene oligomerization. Not only are the catalytic activity of the catalysts very high, but the selectivity of α-olefins is also very high. Therefore, this type of complex has a strong prospect for industrial application. For this type of Fe (II) and Co (II) complex catalyst, the key is the synthesis of the ligand, and whether this type of complex can be obtained and the cost depends on the synthesis method of the ligand.

[0004] Sun Wenhua's group at the Institute of Chemistry, Chinese Academy of Sciences (Sun Wenhua et al., Organometallics 2006, 25, 666-677) first used 1,10-phenanthroline imine compounds to coordinate with Fe (II) to obtain tridentate nitrogen imine complexes to catalyze ethylene polymerization. The catalytic activity and selectivity of this type of catalyst are very high. However, the disadvantage of the catalyst preparation method is that there are too many steps in the synthesis of the ligand, and highly toxic potassium cyanide is required to participate in the reaction to obtain 2-acyl-1,10-phenanthroline. In addition, CN101823996A discloses a method for preparing 2,8-position acyl-substituted quinoline, the essence of which is to use selenium dioxide to perform an oxidation reaction to generate an acyl group at the 2-position of quinoline; this method can also be used to generate 2-acyl-1,10-phenanthroline. However, in this method, selenium dioxide itself is a highly toxic chemical, which is expensive and difficult to purchase.

[0005] In addition, another route for preparing 1,10-phenanthroline compounds is to use the Skraup ring-closing synthesis method to react 8-aminoquinoline with an aldehyde compound to obtain 1,10-phenanthroline compounds. The main disadvantage of this route is that there is a large amount of tar in the reaction product, which makes it difficult to separate the reaction product.

[0006] Therefore, researchers attach great importance to developing a method for preparing ethylene polymerization catalysts with fewer synthesis steps, simple process, low raw material cost and avoiding the use of highly toxic substances to participate in the reaction. Summary of the invention

[0007] In view of the problems existing in the above prior art, one of the purposes of the present invention is to provide an application of cyclobutanone compounds in the preparation of N-ortho alkyl-substituted 1,10-phenanthroline compounds. The cyclobutanone compounds can be used as raw materials to synthesize N-ortho alkyl-substituted 1,10-phenanthroline compounds.

[0008] The second object of the present invention is to provide a method for preparing an N-ortho-alkyl-substituted 1,10-phenanthroline compound. The preparation method uses 8-aminoquinoline and a cyclobutanone compound represented by formula (I) as reaction raw materials, and has the advantages of fewer synthesis steps, simple process, low raw material cost, and avoidance of using highly toxic substances to participate in the reaction.

[0009] The third object of the present invention is to provide a 1,10-phenanthroline compound substituted with an N-ortho alkyl group. The 1,10-phenanthroline compound substituted with an N-ortho alkyl group can be used as a catalyst to participate in the polymerization reaction of ethylene, and has good industrial application prospects.

[0010] A fourth object of the present invention is to provide a catalyst for olefin polymerization.

[0011] To achieve one of the above purposes, the technical solution adopted by the present invention is as follows:

[0012] A use of a cyclobutanone compound in the preparation of an N-ortho-alkyl-substituted 1,10-phenanthroline compound, wherein the cyclobutanone compound has a structural formula as shown in formula (I),

[0013]

[0014] In formula (I), R is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, C1-C6 alkoxy and nitro.

[0015] In some preferred embodiments of the present invention, in formula (I), R is selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, halogen, C1-C4 alkoxy and nitro.

[0016] In some preferred embodiments of the present invention, in formula (I), R is selected from hydrogen, methyl, ethyl, propyl, butyl, ethylene, propylene, butene, acetylene, propyne, butyne, fluorine, chlorine, bromine, iodine, methoxy, ethoxy, propoxy, butoxy and nitro.

[0017] In some preferred embodiments of the present invention, the cyclobutanone compound is selected from at least one of 3-ethoxy-2-methylcyclobutanone, 3-ethoxy-2-ethylcyclobutanone and 3-ethoxy-2-propylcyclobutanone, 3-ethoxy-2-vinylcyclobutanone, 3-ethoxy-2-propylenecyclobutanone, 3-ethoxy-2-ethynylcyclobutanone, 3-ethoxy-2-propynylcyclobutanone, 3-ethoxy-2-fluorocyclobutanone, 3-ethoxy-2-chlorocyclobutanone, 3-ethoxy-2-bromocyclobutanone, 3-ethoxy-2-methoxycyclobutanone, 2,3-diethoxycyclobutanone, 3-ethoxy-2-propoxycyclobutanone and 3-ethoxy-2-nitrocyclobutanone.

[0018] According to the present invention, all of the above-listed substances can be used for the preparation of N-ortho-alkyl-substituted 1,10-phenanthroline compounds. In specific implementation, the type of cyclobutanone compound to be used is determined by the desired N-ortho-alkyl-substituted 1,10-phenanthroline compound.

[0019] In some preferred embodiments of the present invention, the method for preparing the cyclobutanone compound comprises: contacting vinyl ethyl ether and an acyl chloride compound in the presence of an organic amine to generate the cyclobutanone compound.

[0020] In some preferred embodiments of the present invention, the contacting conditions include: temperature of 50-150°C, preferably 75°C-100°C, time of 0.1-5h, preferably 1.5-3h; preferably, the contacting is carried out under reflux conditions.

[0021] In some preferred embodiments of the present invention, the organic amine is selected from C1-C6 fatty amines, C1-C6 alkyl groups, C1-C4 alkoxy groups, halogens and aniline substituted with nitro groups as substituents.

[0022] In some preferred embodiments of the present invention, the organic amine is selected from diisopropylethylamine, triethylamine, trimethylamine, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,4,6-trimethylaniline, 4-bromo-2,6-dimethylaniline, 2-ethylaniline, 2-ethyl-6-methylaniline, 2-isopropylaniline, 2,6-diethylaniline, 2,6-diisopropylaniline, 2-fluoroaniline, 2-fluoro-4-methylaniline, 2-fluoro-5-methylaniline, 2,4-difluoroaniline, 2,5-difluoroaniline, 2,6-difluoroaniline, 3,4-difluoroaniline, 2,3 ,4-trifluoroaniline, 2,4,5-trifluoroaniline, 2,4,6-trifluoroaniline, 2,3,4,5,6-pentafluoroaniline, 3-chloroaniline, 2,6-dichloroaniline, 2,3,4-trichloroaniline, 2,4,5-trichloroaniline, 2,4,6-trichloroaniline, 2-bromoaniline, 2-bromo-4-methylaniline, 2-bromo-4-fluoroaniline, 4-bromo-2-fluoroaniline, One or more of 2,6-dibromoaniline, 2,6-dibromo-4-methylaniline, 2,6-dibromo-4-chloroaniline, 2,4,6-tribromoaniline, 2-bromo-6-chloro-4-fluoroaniline, 2-bromo-4-chloro-6-fluoroaniline, 2-bromo-4,6-difluoroaniline, 3-nitroaniline, 4-methoxyaniline, 2-methyl-4-methoxyaniline and 4-ethoxyaniline.

[0023] According to the present invention, the embodiments are only used as examples. Although they are not exhaustive, those skilled in the art will know that the above-mentioned organic amines can be used for the preparation of cyclobutanone compounds and obtain comparable technical effects.

[0024] In some preferred embodiments of the present invention, the acyl chloride compound is selected from at least one of propionyl chloride, butyryl chloride and valeryl chloride.

[0025] In some preferred embodiments of the present invention, the molar ratio of the acyl chloride compound to the vinyl ethyl ether is 1:(5-15), preferably 1:(8-12); the molar ratio of the acyl chloride compound to the organic amine is 1:(1-5), preferably 1:(1-3.5).

[0026] In some specific embodiments of the present invention, the application conditions include:

[0027] Allowing 8-aminoquinoline to react with a cyclobutanone compound represented by formula (I) in an organic solvent to generate an N-ortho-alkyl-substituted 1,10-phenanthroline compound represented by formula (II);

[0028]

[0029] In formula (I) and formula (II), R has the same definition and is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, C1-C6 alkoxy or nitro;

[0030] Preferably, R is selected from hydrogen, methyl, ethyl, propyl, butyl, ethylene, propylene, butene, acetylene, propyne, butyne, fluorine, chlorine, bromine, iodine, methoxy, ethoxy, propoxy, butoxy and nitro.

[0031] According to the present invention, the organic solvent is selected from C1-C 10 Alkanes, C3-C 10 Cycloalkanes, C6-C 10 Aromatics, C1-C 10 Alcohol, C1-C 10 Ether and C3-C 10 At least one of the cyclic ethers, the substituent is selected from halogen, preferably chlorine.

[0032] According to the present invention, the organic solvent is one or more of dichloromethane, cyclohexane, benzene, toluene, xylene, chlorobenzene, ethanol, ether and tetrahydrofuran.

[0033] According to the present invention, the amount of the organic solvent used is 1.5-10 mL, preferably 2-5 mL, per gram of the 8-aminoquinoline.

[0034] According to the present invention, the reaction is carried out in the presence of a catalyst, which includes boron trifluoride etherate.

[0035] According to the present invention, the molar ratio of the cyclobutanone compound to the 8-aminoquinoline is (1-5):1, preferably (1.5-3.5):1; the molar ratio of the cyclobutanone compound to the catalyst is (1-5):1, preferably (1.5-3.5):1.

[0036] According to the present invention, the reaction conditions include: reaction temperature of 15-45°C, preferably 20-35°C; reaction time of 30-96h, preferably 42-72h.

[0037] According to the present invention, the reaction is carried out in the presence of a molecular sieve; the molecular sieve is Molecular sieve. According to the present invention, the amount of the molecular sieve is not limited, as long as the reaction can proceed smoothly.

[0038] To achieve the second purpose above, the technical solution adopted by the present invention is as follows:

[0039] A method for preparing an N-ortho-alkyl-substituted 1,10-phenanthroline compound comprises the following steps: reacting 8-aminoquinoline with a cyclobutanone compound represented by formula (I) in an organic solvent to generate an N-ortho-alkyl-substituted 1,10-phenanthroline compound represented by formula (II);

[0040]

[0041] In formula (I) and formula (II), R has the same definition and is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, C1-C6 alkoxy or nitro.

[0042] In some preferred embodiments of the present invention, in formula (I), R is selected from hydrogen, methyl, ethyl, propyl, butyl, ethylene, propylene, butene, acetylene, propyne, butyne, fluorine, chlorine, bromine, iodine, methoxy, ethoxy, propoxy, butoxy and nitro.

[0043] In some preferred embodiments of the present invention, the organic solvent is selected from C1-C 10 Alkanes, C3-C 10 Cycloalkanes, C6-C 10 Aromatics, C1-C 10 Alcohol, C1-C 10 Ether and C3-C 10 At least one of the cyclic ethers.

[0044] In some preferred embodiments of the present invention, the substituent is selected from halogen, preferably chlorine.

[0045] In some preferred embodiments of the present invention, the organic solvent is one or more of dichloromethane, cyclohexane, benzene, toluene, xylene, chlorobenzene, ethanol, diethyl ether and tetrahydrofuran.

[0046] In some preferred embodiments of the present invention, the amount of the organic solvent used is 1.5-10 mL, preferably 2-5 mL, per gram of the 8-aminoquinoline.

[0047] In some preferred embodiments of the present invention, the reaction is carried out in the presence of a catalyst, which includes boron trifluoride etherate.

[0048] In some preferred embodiments of the present invention, the molar ratio of the cyclobutanone compound to the 8-aminoquinoline is (1-5):1, preferably (1.5-3.5):1.

[0049] In some preferred embodiments of the present invention, the molar ratio of the cyclobutanone compound to the catalyst is (1-5):1, preferably (1.5-3.5):1.

[0050] In some preferred embodiments of the present invention, the reaction conditions include: reaction temperature of 15-45°C, preferably 20-35°C; reaction time of 30-96h, preferably 42-72h.

[0051] In some preferred embodiments of the present invention, the reaction is carried out in the presence of a molecular sieve; the molecular sieve is Molecular sieve, the usage of the molecular sieve is 10-20% of the mass of the solvent.

[0052] In some preferred embodiments of the present invention, Molecular sieves are commercially available.

[0053] To achieve the third purpose above, the technical solution adopted by the present invention is as follows:

[0054] An N-ortho-alkyl-substituted 1,10-phenanthroline compound prepared by the above preparation method.

[0055] To achieve the fourth objective above, the technical solution adopted by the present invention is as follows:

[0056] A catalyst for olefin polymerization is prepared by using the above-mentioned 1,10-phenanthroline compound substituted with an N-ortho alkyl group as a raw material.

[0057] The beneficial effects of the present invention are at least in the following aspects:

[0058] 1. The present invention provides a cyclobutanone compound for use in the preparation of an N-ortho-alkyl-substituted 1,10-phenanthroline compound. The cyclobutanone compound can be used as a raw material to synthesize an N-ortho-alkyl-substituted 1,10-phenanthroline compound, and the cyclobutanone compound in the present invention is obtained by reacting vinyl ethyl ether with an acyl chloride compound, and the synthesis steps are few, the raw material cost is low, and no highly toxic substances are involved in the reaction.

[0059] 2. The present invention provides a method for preparing an N-ortho-alkyl-substituted 1,10-phenanthroline compound, which uses 8-aminoquinoline and a cyclobutanone compound represented by formula (I) as reaction raw materials, and has the advantages of fewer synthesis steps, simple process, low raw material cost, and avoidance of using highly toxic substances to participate in the reaction.

[0060] 3. The present invention provides an N-ortho-alkyl-substituted 1,10-phenanthroline compound. The N-ortho-alkyl-substituted 1,10-phenanthroline compound can be used as a catalyst to participate in the ethylene polymerization reaction and has good industrial application prospects. DETAILED DESCRIPTION

[0061] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0062] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments may be combined with each other. The present invention will be described in detail below with reference to specific embodiments.

[0063] In the following embodiments, the yield is calculated based on the amount of propionyl chloride, and the amount of the obtained product is divided by the theoretical amount of the product.

[0064] Example 1

[0065] The synthesis of step A, 3-ethoxy-2-methylcyclobutanone, comprises the following steps:

[0066]

[0067] In a dry 350 mL pressure tube, 97.3 g of vinyl ethyl ether (129 mL, 1.35 mol, 10 equiv), 20.9 g of diisopropylethylamine (26.8 mL, 162 mmol, 1.2 equiv), and 12.4 g of propionyl chloride (135 mmol, 1.0 equiv) were added in sequence and vigorously stirred at 90 °C for 2 h.

[0068] After the reaction was completed, the reaction solution was filtered, the filtrate was collected, and the crude product was distilled under reduced pressure. The fraction at 42-48° C. was collected at 2 mmHg to obtain 12.0 g of light yellow liquid with lemon fragrance, with a yield of 70%.

[0069] Mass spectrum MS-EI:128.

[0070] Trans: 1 HNMR (400MHz, CDCl3) δ (ppm): 3.91 (dt, J=6.4,

[0071] 5.2Hz, 1H), 3.51 (dq, J=7.2, 1.6Hz, 2H), 3.19-3.26 (m, 1H), 3.11 (ddd, J=17.6, 6.8, 2.0Hz, 1H), 2. 98 (ddd, J=17.6, 5.2, 4.4Hz, 1H), 1.38-1.50 (m, 2H), 1.25 (t, J=6.8Hz, 3H), 0.92 (d, J=7.2Hz, 3H).

[0072] Cis: 1 HNMR (400MHz, CDCl3) δ (ppm): 4.26 (ddd, J=7.2,

[0073] 6.8, 3.6Hz, 1H), 3.43-3.51 (m, 1H), 3.34-3.43 (m, 1H), 3.24-3.23 (m, 1H), 3.17 (ddd, J=17.2, 6.0, 5.2Hz, 1H), 2.92 (ddd, J=17.6, 3.6, 2.0Hz, 1H), 1.54-1.62 (m, 2H), 1.25 (t, J=6.8Hz, 3H), 0.92 (d, J=7.2Hz, 3H).

[0074] Step B, the synthesis of 2-ethyl-1,10-phenanthroline, the steps are as follows:

[0075]

[0076] 14.4 g 8-aminoquinoline (10 mmol, 1.0 equiv) and Molecular sieves (commercially available) were added to a dry 100 mL round-bottom flask, replaced with nitrogen three times, 50 mL of redistilled (dried) dichloromethane (DCM) solution was added, and then 2.56 g of 3-ethoxy-2-methylcyclobutanone (2 mmol, 2.0 equiv) and 1.42 g of BF3.OEt2 (1.26 mL, 1 mmol, 1.0 equiv) were added. The reaction solution was stirred at room temperature for 48 h and then detected by thin layer chromatography (TLC).

[0077] The reaction solution was quenched with 1 mL of triethylamine and filtered to remove Molecular sieves, washed with 50 mL saturated NaHCO3 solution, extracted with DCM (50 mL × 3), the organic phase was dried over anhydrous Na2SO4, concentrated under reduced pressure, and finally the crude product was purified by silica gel column chromatography (first eluted with PE / EtOAc, 2:1, then with DCM / MeOH, 100:1), to obtain 1.02 g of reddish brown viscous liquid, with a yield of 50%.

[0078] Mass spectrum MS-EI:208.

[0079] NMR analysis: 1 HNMR (400MHz, CDCl3): δ9.25 (dd, J=2.96, 1H); 8.66 (d, J=8.36, 1H); 8.33 (d, J=8.36, 1H); 8. 28 (dd, J=7.84, 1H); 7.85 (dd, J=9.02, 2H); 7.65 (dd, J=4.36, 1H); 7.15 (d, J=7.52, 2H); 7.06 ( t, J=7.04, 1H); 3.01 (t, J=7.84, -CNCH2CH2CH3, 2H); 2.40 (m, J=7.52, phCH2CH3, 2H); 1.58 (m, J=7.44, CH3CH2CH2-, 2H); 1.20 (t, J=7.30, phCH2CH3, 6H); 0.90 (t, J=7.32, CH3CH2CH2-, 3H).

[0080] Example 2

[0081] This embodiment is basically the same as Embodiment 1, except that:

[0082] 1. In step A, valeryl chloride was used instead of propionyl chloride, with a yield of 68%;

[0083] The mass spectrometry results are as follows:

[0084] Mass spectrum MS-EI:156.

[0085] Trans: 1 HNMR (400MHz, CDCl3) δ (ppm): 3.91 (dt, J=6.4, 5.2Hz, 1H), 3.51 (dq, J=7.2, 1.6Hz, 2H), 3.19-3.26 (m, 1H), 3.11 (ddd, J=17.6, 6.8, 2.0Hz, 1H), 2.98 (ddd, J=17.6, 5.2, 4.4Hz, 1H), 1.60-1.70 (m, 2H), 1.38-1.50 (m, 2H), 1.25 (t, J=6.8Hz, 3H), 0.92 (t, J=7.2Hz, 3H).

[0086] Cis: 1HNMR (400MHz, CDCl3) δ (ppm): 4.26 (ddd, J=7.2, 6.8, 3.6Hz, 1H), 3.43-3.51 (m, 1H), 3.34-3.43 (m, 1H), 3.24-3.23 (m, 1H), 3.17 (ddd, J=17 .2, 6.0, 5.2Hz, 1H), 2.92 (ddd, J=17.6, 3.6, 2.0Hz, 1H), 1.54-1.62 (m, 2H), 1.28-1.44 (m, 2H), 1.22 (t, J=7.2Hz, 3H), 0.92 (t, J=7.2Hz, 3H).

[0087] 2. In step B, 3-ethoxy-2-propylcyclobutanone was used instead of 3-ethoxy-2-methylcyclobutanone to obtain 2-n-butyl-1,10-phenanthroline in a yield of 65%.

[0088] The mass spectrometry results are as follows:

[0089] Mass spectrum MS-EI: 236.

[0090] Trans: 1 HNMR (400MHz, CDCl3) δ (ppm): 9.23 (d, J=4.4

[0091] Hz, 1H), 8.23 ​​(d, J=8.0Hz, 1H), 8.15 (d, J=8.4Hz, 1H), 7.77 (d, J=8.8Hz, 1H), 7.72 (d, J=8.8Hz, 1H), 7.60 (dd, J=8.0, 4.4Hz, 1 H), 7.54 (d, J=8.0Hz, 1H), 3.22 (t, J=8.0Hz, 2H), 1.87 (quint, J=8.0Hz, 2H), 1.50 (sext, J=7.6Hz, 2H), 0.98 (t, J=7.6Hz, 3H);

[0092] 13 CNMR (101MHz, CDCl3) δ (ppm): 163.8, 150.3, 146.2, 145.8, 136.2, 136.0, 128.8, 126.9, 126.5, 125.5, 122.8, 122.7, 39.4, 32.7, 22.9, 14.1.

[0093] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. Use of a cyclobutanone compound in the preparation of an N-ortho-alkyl-substituted 1,10-phenanthroline compound, wherein: The structural formula of the cyclobutanone compound is shown in formula (I), In formula (I), R is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, C1-C6 alkoxy and nitro. Preferably, R is selected from hydrogen, methyl, ethyl, propyl, butyl, ethylene, propylene, butene, acetylene, propyne, butyne, fluorine, chlorine, bromine, iodine, methoxy, ethoxy, propoxy, butoxy and nitro. More preferably, the cyclobutanone compound is selected from 3-ethoxy-2-methylcyclobutanone, 3-ethoxy-2-ethylcyclobutanone and 3-ethoxy -2-propylcyclobutanone, 3-ethoxy-2-vinylcyclobutanone, 3-ethoxy-2-propylenecyclobutanone, 3-ethoxy-2-ethynylcyclobutanone, 3-ethoxy-2-propynylcyclobutanone, 3-ethoxy-2-fluorocyclobutanone, 3-ethoxy-2-chlorocyclobutanone, 3-ethoxy-2-bromocyclobutanone, 3-ethoxy-2-methoxycyclobutanone, 2,3-diethoxycyclobutanone, 3-ethoxy-2-propoxycyclobutanone and at least one of 3-ethoxy-2-nitrocyclobutanone.

2. The use according to claim 1, characterized in that: The preparation method of the cyclobutanone compound comprises: contacting vinyl ethyl ether with an acyl chloride compound in the presence of an organic amine to generate the cyclobutanone compound; Preferably, the contacting conditions include: a temperature of 50-150°C, preferably 75°C-100°C, and a time of 0.1-5h, preferably 1.5-3h; preferably, the contacting is carried out under reflux conditions.

3. The use according to claim 1 or 2, characterized in that: The organic amine is selected from C1-C6 fatty amines, C1-C6 alkyls, C1-C4 alkoxys, halogens and nitro-substituted anilines. Preferably, the organic amine is selected from diisopropylethylamine, triethylamine, trimethylamine, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4 -Dimethylaniline, 3,5-dimethylaniline, 2,4,6-trimethylaniline, 4-bromo-2,6-dimethylaniline, 2-ethylaniline, 2-ethyl-6-methylaniline, 2-isopropylaniline, 2,6-diethylaniline, 2,6-diisopropylaniline, 2-fluoroaniline, 2-fluoro-4-methylaniline, 2-fluoro-5-methylaniline, 2,4-difluoroaniline, 2,5-difluoroaniline, 2,6- Difluoroaniline, 3,4-difluoroaniline, 2,3,4-trifluoroaniline, 2,4,5-trifluoroaniline, 2,4,6-trifluoroaniline, 2,3,4,5,6-pentafluoroaniline, 3-chloroaniline, 2,6-dichloroaniline, 2,3,4-trichloroaniline, 2,4,5-trichloroaniline, 2,4,6-trichloroaniline, 2-bromoaniline, 2-bromo-4-methylaniline, 2-bromo-4-fluoroaniline, 4-bromo -2-fluoroaniline, 2,6-dibromoaniline, 2,6-dibromo-4-methylaniline, 2,6-dibromo-4-chloroaniline, 2,4,6-tribromoaniline, 2-bromo-6-chloro-4-fluoroaniline, 2-bromo-4-chloro-6-fluoroaniline, 2-bromo-4,6-difluoroaniline, 3-nitroaniline, 4-methoxyaniline, 2-methyl-4-methoxyaniline and 4-ethoxyaniline; and / or The acyl chloride compound is selected from at least one of propionyl chloride, butyryl chloride and valeryl chloride; Preferably, the molar ratio of the acyl chloride compound to the vinyl ethyl ether is 1:(5-15), preferably 1:(8-12); the molar ratio of the acyl chloride compound to the organic amine is 1:(1-5), preferably 1:(1-3.5).

4. A method for preparing an N-ortho-alkyl-substituted 1,10-phenanthroline compound, characterized in that: The method comprises the following steps: reacting 8-aminoquinoline with a cyclobutanone compound represented by formula (I) in an organic solvent to generate an N-ortho-alkyl-substituted 1,10-phenanthroline compound represented by formula (II); In formula (I) and formula (II), R has the same definition and is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, C1-C6 alkoxy or nitro; Preferably, R is selected from hydrogen, methyl, ethyl, propyl, butyl, ethylene, propylene, butene, acetylene, propyne, butyne, fluorine, chlorine, bromine, iodine, methoxy, ethoxy, propoxy, butoxy and nitro.

5. The preparation method according to claim 4, characterized in that: The organic solvent is selected from C1-C 10 Alkanes, C3-C 10 Cycloalkanes, C6-C 10 Aromatics, C1-C 10 Alcohol, C1-C 10 Ether and C3-C 10 At least one of the cyclic ethers, the substituent being selected from halogen, preferably chlorine; Preferably, the organic solvent is one or more of dichloromethane, cyclohexane, benzene, toluene, xylene, chlorobenzene, ethanol, ether and tetrahydrofuran; Preferably, the amount of the organic solvent used is 1.5-10 mL, preferably 2-5 mL, per gram of the 8-aminoquinoline.

6. The preparation method according to claim 4 or 5, characterized in that: The reaction is carried out in the presence of a catalyst, which includes boron trifluoride etherate.

7. The preparation method according to any one of claims 4 to 6, characterized in that: The molar ratio of the cyclobutanone compound to the 8-aminoquinoline is (1-5):1, preferably (1.5-3.5):1; the molar ratio of the cyclobutanone compound to the catalyst is (1-5):1, preferably (1.5-3.5):

1.

8. The preparation method according to any one of claims 4 to 7, characterized in that: The reaction conditions include: reaction temperature of 15-45°C, preferably 20-35°C; reaction time of 30-96h, preferably 42-72h.

9. The method for preparing the N-ortho-alkyl-substituted 1,10-phenanthroline compound according to any one of claims 4 to 8, characterized in that: The reaction is carried out in the presence of a molecular sieve; The molecular sieve is Molecular sieve, the usage of the molecular sieve is 0-20wt% of the mass of the solvent.

10. An N-ortho-alkyl-substituted 1,10-phenanthroline compound obtained by the preparation method according to any one of claims 4 to 9.

11. The N-ortho-alkyl-substituted 1,10-phenanthroline compound according to claim 10, characterized in that: The yield of the compound was greater than 80%.

12. A catalyst for olefin polymerization, characterized in that: The invention is prepared by using the 1,10-phenanthroline compound substituted with an N-ortho alkyl group as claimed in claim 10 or 11 as a raw material.

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