Use of a catalyst and method for degradation of ester substances

Abstract

The application provides a use of a catalyst and a degradation method of an ester substance. In the technical scheme of the application, it is first proposed that the catalyst in the application can be used for degrading the ester substance, and the degradation of the ester substance is carried out in a reduction amination process, the reaction condition is mild, high-temperature and high-pressure conditions are not needed, the catalyst is cheap, the conversion rate is high, the functional group compatibility is high, the applicability is wide, and the product has certain commercial value.

Description

TECHNICAL FIELD

[0001] The present application relates to a new use of catalyst, in particular to a catalyst for degradation of ester and a degradation method thereof. BACKGROUND

[0002] Polyester is a polymer formed by polycondensation of polybasic acid and polyhydric alcohol, which also includes polymer obtained by condensation of lactone. Polyester has excellent properties such as high transparency, aging resistance, high elasticity, wear resistance, low temperature resistance, etc., and is widely used in textile industry, packaging industry, electronics and electrical appliances, medical treatment, construction and other fields. The types of polyester include polyethylene terephthalate (PET), polylactic acid (PLA), polybutylene succinate (PBS), polycaprolactone (PCL) and polyglycerol ester (PHA), etc. Among them, polyethylene terephthalate (PET) is the most widely used, which has accounted for 8% of the total plastic production, and is mainly used in food packaging, film, textile and synthetic fiber fields. In recent years, polylactic acid (PLA) has also been gradually valued, which can be obtained by fermentation of biomass such as straw, and has the characteristics of easy degradation, and is widely used in disposable plastic products. There are also many application examples of other polymers, such as polybutylene succinate can be made into degradable garbage bags, polycaprolactone is used as 3D printing material, and polyglycerol ester can be used in food processing industry. The largest demand here is PET, but it is difficult to be naturally degraded by microorganisms, and if it is directly discarded or incinerated, it will greatly damage the ecological environment. Therefore, it is particularly important to recycle and reuse polyester.

[0003] Currently, the main methods for PET degradation are physical method, biological degradation and chemical degradation. Compared with biological degradation, chemical degradation has the characteristics of high efficiency and high yield. Chemical degradation includes hydrolysis method, alcoholysis method, aminolysis method and reduction method. Hydrolysis method refers to the hydrolysis of PET into terephthalic acid and ethylene glycol in different acid or alkaline media. These two products are raw materials for synthesizing PET, so this method is increasingly valued. Hydrolysis method can be divided into acid hydrolysis method, alkaline hydrolysis method and neutral hydrolysis method. Acid hydrolysis and alkaline hydrolysis mainly use strong acid and strong base. Although the hydrolysis effect is excellent, the equipment is severely corroded, and it is difficult to realize commercialization. Neutral hydrolysis method degrades PET under water or steam conditions. Goje and his researchers use intermittent hydrolysis, but the required reaction conditions are relatively harsh, and further research is still needed. The alcoholysis method is relatively mature, and there are many commercial methods. DuPont Company in the United States developed a gas-phase low-pressure methanol depolymerization process. PET is made into powder by high temperature and grinding, and then methanol steam is used to depolymerize PET at normal pressure and 250-300 DEG C. Eastman Kodak Company announced a patent for a three-stage continuous low-pressure methanol depolymerization process of PET. The depolymerization is carried out at 240-260 DEG C and 0.2-0.6 MPa. The company has also developed a two-stage low-pressure methanol depolymerization process of PET. The method of degrading PET with ethylene glycol is also an important depolymerization method. Currently, companies such as Goodyear, DuPont and Hoechst have realized commercial device operation, and the process technology is increasingly mature. The method is usually carried out at 180-250 DEG C and 0.1-0.6 MPa, and a small amount of catalyst is usually added. Aminolysis method is to aminolyze PET to obtain terephthalic acid diamide and ethylene glycol. There is no report on its commercialization. Reduction method is to reduce PET with transition metal catalyst to obtain terephthalic alcohol and ethylene glycol products. The method has been concerned by researchers in the past decade. Cantat and his researchers use iridium as a catalyst and silicon hydride as a reducing agent to realize the selective reduction of PET and other polyesters into terephthalic alcohol or p-xylene.

[0004] Nowadays, the degradation of polyester is still a research hotspot for scientists, but the reaction type of degradation is still concentrated on the above several methods. How to realize the diversified degradation of polyester, enrich the diversity of polyester degradation products, and improve the recycling value of polyester is a very worthy content. SUMMARY

[0005] In view of the above-mentioned shortcomings of the prior art, the purpose of the present application is to provide a use of a catalyst and a degradation method of ester substances, which solves the problems of low degradation efficiency, high cost and poor economic benefit of ester substances in the prior art.

[0006] To achieve the above-mentioned purposes and other related purposes, the present application is realized by the following technical solutions.

[0007] The first aspect of the present application provides the use of one or more of the compounds of formula I and II as catalysts for the degradation of ester-containing substances,

[0008]

[0009] wherein R 1 , R 2 , R 3 , R 4 are independently selected from one of hydrogen, C1-C6 linear or branched alkyl; X and Y are independently selected from one of H, F, Cl, Br and trifluoromethylsulfonyl.

[0010] Preferably, the catalyst is used in the reductive amination reaction of an ester-containing substance with an amine compound.

[0011] Preferably, the ester-containing substance is an ester-containing compound or an ester-containing polymer.

[0012] More preferably, the ester-containing compound is one or more of an ester formed from a mono- or poly-carboxylic acid and a mono- or poly-alcohol, and a lactone.

[0013] More preferably, the mono- or poly-carboxylic acid is one or more of a C1-C20 alkyl carboxylic acid, a C6-C20 aryl carboxylic acid, a C3-C20 heterocyclic carboxylic acid. The poly-carboxylic acid includes one or more of a di-carboxylic acid and a tri-carboxylic acid. More preferably, the mono- or poly-alcohol is one or more of a C1-C20 alkyl alcohol, a C6-C20 aryl alcohol, a C3-C20 heterocyclic alcohol. The poly-alcohol includes one or more of a di-alcohol and a tri-alcohol.

[0014] More preferably, the lactone is one or more of a C3-C20 cyclic lactone.

[0015] More preferably, the ester-containing polymer is one or more of polylactic acid, polyglycolide, and a polyester formed from a poly-acid and a poly-alcohol.

[0016] Preferably, in the polyester formed from a poly-acid and a poly-alcohol, the poly-acid is one or both of terephthalic acid and succinic acid; and the poly-alcohol is one or more of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.

[0017] Most preferably, the ester-containing compound is one or more of a glyceride, a benzenepropanoate, a lactide, a succinate, an adipate, a valerolactone, a gamma-valerolactone, a benzoate, a terephthalate, a 2-furoate, and a furan-2,5-dicarboxylate.

[0018] Preferably, the amine compound has the following structure:

[0019] R 5 ,R 6 one or more selected from C1-C20 linear or branched alkyl, C1-C20 heteroatom-containing alkyl, C6-C20 aryl, R 7 one or more selected from C1-C20 alkyl, C1-C20 heteroatom-containing alkyl.

[0020] More preferably, the amine compound is one or more selected from tetrahydropyrrole, piperidine, N-methylbutylamine, diethylamine, morpholine, 4-[(methylamino)methyl]phenol, N-(4-methoxybenzyl)-N-methylamine, N-methyl-4-bromobenzylamine, 3-(methylamino)-1-propanol, N-(2-methoxyethyl)methylamine, N-methylpiperazine, 4-phenyl-1,2,3,6-tetrahydropyridine, 4-methylene-piperidine, 1,2,3,4-tetrahydroisoquinoline, N,N'-dimethyl-1,6-hexanediamine, n-propylamine, tryptamine, 2-(1-cyclohexenyl)ethylamine, 3-methoxypropylamine, N-(2-aminoethyl)morpholine, benzylamine, phenethylamine, 2-aminomethylpyridine, p-bromobenzylamine, p-hydroxybenzylamine, N-methyl-1,3-propanediamine, N,N'-dimethyl-1,4-butanediamine, and 3-aminobenzylamine.

[0021] Preferably, the catalyst is one or more selected from the following structural formulae:

[0022]

[0023]

[0024] The present application also discloses the use of one or more compounds of structural formulae I and II in combination with triflate as a catalyst system for degrading ester substances.

[0025] The second aspect of the present application also discloses a method for degrading ester substances, wherein the ester substances undergo a reductive amination reaction with an amine compound under the action of a main catalyst and a reducing agent; the reducing agent is a compound containing a silicon-hydrogen bond; the amine compound is a primary amine or a secondary amine; and the main catalyst is one or more selected from compounds of structural formulae I and II.

[0026]

[0027] wherein R 1 , R 2 , R 3 , R 4one of hydrogen, C1-C6 linear or branched alkyl; X and Y are independently selected from one of H, F, Cl, Br and trifluoromethylsulfonyl.

[0028] The fourth aspect of the present application further discloses a method for preparing an intermediate compound for synthesizing Lorcaserin, characterized in that, under the action of a main catalyst and a reducing agent, polylactic acid and 4-chlorobenzeneethanamine undergo a reductive amination reaction; the reducing agent is a compound containing a silicon-hydrogen bond; the main catalyst is one or more selected from compounds with structural formulae as shown in formula I and formula II.

[0029]

[0030] wherein, R 1 , R 2 , R 3 , R 4 is one of hydrogen, C1-C6 linear or branched alkyl; X and Y are independently selected from one of H, F, Cl, Br and trifluoromethylsulfonyl; and the synthetic route is as follows:

[0031]

[0032] Preferably, the reductive amination reaction also uses an organic solvent as a reaction medium, and the organic solvent is selected from cyclic ether solvents and benzene ring-containing solvents. More preferably, the cyclic ether solvent is one or more selected from dioxane, tetrahydrofuran and tetrahydropyran. More preferably, the benzene ring-containing solvent is one or more selected from toluene, chlorobenzene, fluorobenzene, trifluorotoluene, ethylbenzene, xylene and benzene.

[0033] Preferably, a catalytic amount of an activator is also used in the reaction, and the activator is selected from alkali metal salts of alcohols. More preferably, the alkali metal salt of alcohol is one or more selected from potassium methoxide, sodium methoxide and lithium methoxide.

[0034] Preferably, the ester substance is a compound containing an ester group or a polymer containing an ester group.

[0035] More preferably, the compound containing an ester group is one or more selected from esters formed by monohydric or polyhydric carboxylic acids and monohydric or polyhydric alcohols, and lactones.

[0036] More preferably, the monohydric or polyhydric carboxylic acid is one or more selected from C1-C20 alkyl carboxylic acids, C6-C20 aromatic carboxylic acids and C3-C20 heterocyclic carboxylic acids. The polybasic carboxylic acid includes one or more of dibasic carboxylic acids and tribasic carboxylic acids. More preferably, the monohydric or polyhydric alcohol is one or more selected from C1-C20 alkyl alcohols, C6-C20 aromatic alcohols and C3-C20 heterocyclic alcohols. The polyhydric alcohol includes one or more of dihydric and trihydric alcohols.

[0037] More preferably, the lactone is selected from one or more of C3-C20 cyclic lactones.

[0038] More preferably, the ester group-containing polymer is one or more selected from polylactic acid, polyglycolide, and a polyester formed by using a polybasic acid and a polyhydric alcohol as reaction monomers.

[0039] In the technical solution of the present application, theoretically, the above degradation route can degrade the ester group-containing polymer, but considering the use scenario, the influence of the molecular weight of the polymer on the degradation efficiency and other factors, preferably, the weight average molecular weight of the ester group-containing polymer is not more than 2 million, more preferably, the weight average molecular weight of the ester group-containing polymer is not more than 150W, such as 5W, 10W, 15W, 20W, 40W, 50W, 70W, 90W, 100W, 120W, 140W or 150W, etc.

[0040] Preferably, in the polyester formed by using a polybasic acid and a polyhydric alcohol as reaction monomers, the polybasic acid is selected from one or both of terephthalic acid and succinic acid; and the polyhydric alcohol is selected from one or more of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.

[0041] Most preferably, the ester group-containing compound is selected from one or more of glycerides, phenylpropionic acid esters, lactide, succinic acid esters, adipic acid esters, valerolactone, γ-valerolactone, benzoic acid esters, terephthalic acid esters, 2-furoic acid esters, and furan-2,5-dicarboxylic acid diesters.

[0042] Preferably, an auxiliary catalyst is also used in the reaction, and the auxiliary catalyst is a triflate salt. More preferably, the triflate salt is one or more of potassium triflate, sodium triflate, and lithium triflate.

[0043] Preferably, the silicon-hydrogen bond-containing compound is a silane compound. More preferably, the silane compound is one or more selected from phenylsilane, [CH3(CH2) n O]3SiH, and n is 0, 1, 2, 3 or 4.

[0044] Preferably, the amine compound is one or more of tetrahydropyrrole, piperidine, N-methylbutylamine, diethylamine, morpholine, 4-[(methylamino)methyl]phenol, N-(4-methoxybenzyl)-N-methylamine, N-methyl-4-bromobenzylamine, 3-(methylamino)-1-propanol, N-(2-methoxyethyl)methylamine, N-methylpiperazine, 4-phenyl-1,2,3,6-tetrahydropyridine, 4-methylene-piperidine, 1,2,3,4-tetrahydroisoquinoline, N,N'-dimethyl-1,6-hexanediamine, n-propylamine, tryptamine, 2-(1-cyclohexenyl)ethylamine, 3-methoxypropylamine, N-(2-aminoethyl)morpholine, benzylamine, phenethylamine, 2-aminomethylpyridine, p-bromobenzylamine, p-hydroxybenzylamine, N-methyl-1,3-propanediamine, N,N'-dimethyl-1,4-butanediamine, and 3-aminobenzylamine.

[0045] Preferably, the temperature of the reductive amination reaction is 100-150°C.

[0046] Preferably, the ratio of the moles of the ester groups in the ester substance to the moles of the amine groups in the amine compound is 1:(1-2).

[0047] Preferably, the ratio of the moles of the ester groups in the ester substance to the moles of the silicon-hydrogen bonds in the reducing agent is 1:(2-10).

[0048] Preferably, after the reductive amination reaction, the product is separated and purified.

[0049] In the reductive amination reaction of the present application, theoretically, 1 mol of the ester groups consumes 1 mol of the amine groups. Preferably, the ratio of the moles of the ester groups in the ester substance to the moles of the amine groups in the amine compound is 1:(1-2).

[0050] Preferably, the molar ratio of the main catalyst to the activating agent is 1:(0.5-1). Too much activating agent relative to the main catalyst is also not conducive to the degradation; too little activating agent relative to the main catalyst is not conducive to the activation of the catalyst and will also affect the degradation reaction.

[0051] Preferably, the molar ratio of the main catalyst to the auxiliary catalyst is 1:(0.1-5).

[0052] Preferably, the ratio of the moles of the ester groups in the ester substance to the moles of the silicon-hydrogen bonds in the reducing agent is 1:(2-10).

[0053] Preferably, after the reductive amination reaction, the product is separated and purified. The separation includes fractionation or adsorption.

[0054] Preferably, the catalyst is one or more of the following structural formulas:

[0055]

[0056] As described above, the use of the catalyst of the present application and the degradation method of ester substances and the synthesis method of pharmaceutical intermediates have the following beneficial effects:

[0057] In the technical solution of the present application, it is first proposed to use the catalyst as in the present application to degrade ester substances, and in the actual degradation of ester substances, the reduction amination process is also collected, which has mild reaction conditions, does not require high temperature and high pressure conditions, the catalyst is cheap, the conversion rate is high, the functional group compatibility is high, the applicability is wide; the product also has certain commercial value. DETAILED DESCRIPTION

[0058] The embodiments of the present application will be described in detail below with specific examples, and those skilled in the art can easily understand other advantages and effects of the present application from the content disclosed in the specification. The present application can also be implemented or applied by different specific embodiments, and the details in the specification can be modified or changed based on different views and applications without departing from the spirit of the present application.

[0059] Before further describing the specific embodiments of the present application, it should be understood that the protection scope of the present application is not limited to the following specific embodiments; it should also be understood that the terms used in the embodiments of the present application are for describing the specific embodiments, not for limiting the protection scope of the present application; in the specification and claims of the present application, the singular forms "one", "a" and "this" include the plural forms, unless otherwise explicitly stated in the text.

[0060] When the embodiments give numerical ranges, it should be understood that, unless otherwise stated by the present application, both endpoints of each numerical range and any number between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present application have the same meaning as generally understood by those skilled in the art. In addition to the specific methods, devices, materials used in the embodiments, any method, device and material of the prior art similar or equivalent to the methods, devices and materials described in the embodiments of the present application can also be used to implement the present application according to the master of the prior art by those skilled in the art and the description of the present application.

[0061] The term "contact" used in this text should be understood broadly, which can be any way that can make at least two reactants chemically react, for example, the two reactants can be mixed under appropriate conditions.

[0062] The selection of the polymers in the following examples of the embodiments is mainly to illustrate that the degradation method in the application can be used to degrade polymers containing ester groups, and to better and more intuitively show the effect of the technical scheme of the application. The selection of polymers in the examples is based on common polymers, such as polymers used for processing polyester beverage bottles and PLA straws. The applicant has confirmed through a large number of experiments that the degradation method in the application can effectively degrade ester polymers.

[0063] Example 1

[0064]

[0065] In a 8ml microwave tube, dichlorobis-zirconocene (29.1mg, 0.1mmol, 0.1eq) and potassium methoxide (3.5mg, 0.05mmol, 0.05eq) were added, and 1ml dioxane was stirred at room temperature for ten minutes, then triethoxysilane (1.48ml, 8mmol, 8eq) and polyethylene terephthalate (M W To 30000, 192mg, 1mmol, 1eq), potassium triflate (18.8mg, 0.1mmol, 0.1eq) and piperidine (247μl, 2.5mmol, 2.5eq) were added after stirring at room temperature for five minutes, and finally 1.5ml dioxane was added, and heated to 130°C with a sealed cap, and stirred for 16h. After the reaction was completed, it was cooled to room temperature, and the product could be obtained by silica gel purification, with a yield of 99% (actual mass of product / theoretical mass of product*100%).

[0066] The purified product was confirmed, and the specific test results were as follows:

[0067] 1 H-NMR (400MHz, CDCl3) δ (p.p.m.) 7.26 (s, 4H), 3.47 (s, 4H), 2.38 (s, 8H), 1.58 (p, J = 5.6 Hz, 8H), 1.43 (p, J = 6.0 Hz, 4H);

[0068] 13 C-NMR (100MHz, CDCl3) δ 137.1, 129.2, 63.7, 54.6, 26.0, 24.5;

[0069] IR (ATR): 3016, 2931, 2853, 2792, 2753, 2722, 2682, 1720, 1613, 1510, 1467, 1465, 1454, 1441, 1418, 1390, 1367, 1342, 1296, 1264, 1248, 1197, 1152, 1114, 1096, 1066, 1038, 1020, 994, 962, 944, 907, 862, 845, 809, 787, 774, 764, 735, 703;

[0070] HRMS (ESI) Calcd for [M+H]+: 273.2326 m / z, found: 273.2315 m / z.

[0071] Example 2

[0072]

[0073] In 8 ml microwave tube, add dichlorobis (ethylene) zirconium (29.1 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq), then add 1 ml dioxane, stir at room temperature for 10 minutes, then add triethoxysilane (1.48 ml, 8 mmol, 8 eq) and polyethylene terephthalate (M W In 8 ml microwave tube, add dichlorobis (ethylene) zirconium (29.1 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq), then add 1 ml dioxane, stir at room temperature for 10 minutes, then add triethoxysilane (1.48 ml, 8 mmol, 8 eq) and polyethylene terephthalate (M

[0074] H-NMR (400 MHz, CDC13) δ (p.p.m.) 8.26 (s, 2H), 7.75 (s, 4H), 3.57 (t, J = 7.0 Hz, 4H), 1.72 (h, J = 7.2 Hz, 4H), 0.94 (t, J = 7.4 Hz, 6H);

[0075] 13 C-NMR (100 MHz, CDC13) δ 160.3, 138.1, 128.2, 63.7, 24.1, 11.9;

[0076] IR (ATR): 2959, 2928, 2873, 2832, 1642, 1568, 1455, 1442, 1477, 1336, 1298, 1214, 1137, 1100, 1062, 1047, 1009, 967, 904, 884, 861, 825, 754;

[0077] HRMS (ESI) Calcd for [M+H]+: 217.1700 m / z, found: 217.1696 m / z.

[0078] Example 3

[0079]

[0080] In a 8 ml microwave tube, dichlorobis-ethylene zirconium (29.1 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq) were added, stirred at room temperature for ten minutes, then triethoxysilane (3.33 ml, 8 mmol, 18 eq) and glyceryl tristearate (891 mg, 1 mmol, 1 eq) were added, stirred at room temperature for five minutes, then potassium trifluoromethanesulfonate (18.8 mg, 0.1 mmol, 0.1 eq) and benzylamine (411 μl, 3.75 mmol, 3.75 eq) were added, finally 1.5 ml dioxane was added, sealed and heated to 130 °C, stirred for 16 h. After the reaction was completed, cooled to room temperature, the product can be purified by silica gel to obtain a yield of 89%.

[0081] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.26 (d, J = 8.5 Hz, 4H), 7.20 - 7.15 (m, 1H), 3.72 (s, 2H), 2.55 (t, J = 7.2 Hz, 2H), 1.92 (s, 1H), 1.18 (br, 32H), 0.81 (t, J = 6.6 Hz, 3H);

[0082] 13 C-NMR (100 MHz, CDC13) δ 140.2, 128.5, 128.3, 127.1, 54.1, 49.5, 32.1, 30.0, 29.8, 29.8, 29.7, 29.7, 29.5, 27.5, 22.8, 14.3;

[0083] IR (ATR): 3063, 3027, 2921, 2851, 1604, 1494, 1455, 1365, 1303, 1264, 1118, 1074, 1028, 907, 731;

[0084] HRMS (ESI) Calcd for [M+H]+: 360.3625 m / z, found: 360.3610 m / z.

[0085] Example 4

[0086]

[0087] In 8 ml microwave tube, add dichlorobis (ethylene) zirconium (29.1 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq), then add 1 ml dioxane, stir at room temperature for 10 minutes, then add triethoxysilane (1.48 ml, 8 mmol, 8 eq) and polybutylene succinate (M W In 8 ml microwave tube, add dichlorobis (ethylene) zirconium (29.1 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq), then add 1 ml dioxane, stir at room temperature for 10 minutes, then add triethoxysilane (1.48 ml, 8 mmol, 8 eq) and polybutylene succinate (M

[0088] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 6.71 (t, J = 2.1 Hz, 2H), 6.16 (t, J = 2.1 Hz, 2H), 4.02 (t, J = 6.9 Hz, 2H), 3.74 - 3.70 (m, 4H), 2.71 (t, J = 6.9 Hz, 2H), 2.50 - 2.44 (m, 4H);

[0089] 13 C-NMR (100 MHz, CDC13) δ 120.7, 108.1, 66.8, 59.6, 53.7, 47.1;

[0090] IR (ATR): 3050, 2963, 2940, 2923, 2895, 2858, 2813, 2691, 2242, 1680, 1549, 1499, 1453, 1359, 1301, 1282, 1266, 1139, 1115, 1089, 1071, 1009, 907, 868, 856, 721;

[0091] HRMS (ESI) Calcd for [M+H]+: 360.3625 m / z, found: 360.3610 m / z.

[0092] Example 5

[0093]

[0094] In a 8ml microwave tube, dichlorobis-methylcyclopentadienylzirconium (29.1mg, 0.1mmol, 0.1eq) and potassium methoxide (3.5mg, 0.05mmol, 0.05eq) were added, stirred at room temperature for 10 minutes, then triethoxysilane (1.48ml, 8mmol, 8eq) and polybutylene succinate (M W In a 8ml microwave tube, dichlorobis-methylcyclopentadienylzirconium (29.1mg, 0.1mmol, 0.1eq) and potassium methoxide (3.5mg, 0.05mmol, 0.05eq) were added, stirred at room temperature for 10 minutes, then triethoxysilane (1.48ml, 8mmol, 8eq) and polybutylene succinate (M

[0095] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 2.55 - 2.44 (m, 8H), 2.42 (t, J = 7.3 Hz, 4H), 1.72 (dq, J = 6.3, 3.2 Hz, 8H), 1.57 - 1.44 (m, 4H);

[0096] 13 C-NMR (100 MHz, CDC13) δ 56.2, 54.0, 26.8, 23.4;

[0097] IR (ATR): 2932, 2875, 2784, 2690, 1645, 1459, 1446, 1388, 1350, 1326, 1260, 1224, 1145, 1114, 1031, 986, 953, 927, 903, 876, 733, 700;

[0098] HRMS (ESI) Calcd for [M+H]+: 197.2013 m / z, found: 197.2005 m / z.

[0099] Example 6

[0100]

[0101] In a 8 ml microwave tube, dichlorobis(benzene)zirconium (29.1 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq) were added and stirred at room temperature for 10 min. Then triethoxysilane (1.11 ml, 6 mmol, 6 eq) and polyglycolic acid (M W In a 8 ml microwave tube, dichlorobis(benzene)zirconium (29.1 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq) were added and stirred at room temperature for 10 min. Then triethoxysilane (1.11 ml, 6 mmol, 6 eq) and polyglycolic acid (M

[0102] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.45 (d, J = 5.9 Hz, 2H), 7.36 - 7.29 (m, 3H), 5.30 (s, 2H), 4.02 (s, 2H), 3.80 - 3.70 (m, 2H), 2.95 - 2.81 (m, 2H);

[0103] 13 C-NMR (100 MHz, CDC13) δ 133.1, 129.8, 129.1, 128.9, 58.2, 51.8, 49.2; IR (ATR): 3085, 3061, 3029, 2924, 2851, 1738, 1633, 1603, 1495, 1359, 1264, 1202, 1159, 1050, 1029, 919, 860, 823, 733;

[0104] HRMS (ESI) Calcd for [M+H]+: 152.1070 m / z, found: 152.1069 m / z.

[0105] Example 7

[0106]

[0107] In a 8 ml microwave tube, dichlorobis(benzene)zirconium (29.1 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq) were added and stirred at room temperature for 10 min. Then triethoxysilane (1.11 ml, 6 mmol, 6 eq) and polyglycolic acid (M WFor 80000, 71 mg, 1 mmol, 1 eq), after stirring at room temperature for five minutes, potassium trifluoromethanesulfonate (18.8 mg, 0.1 mmol, 0.1 eq) and 4-chloro-phenethylamine (175 μl, 1.25 mmol, 1.25 eq) were added, finally 1.5 ml of dioxane was added, sealed and heated to 130 °C, stirring for 16 h. After the reaction was completed, it was cooled to room temperature and the product was purified by silica gel to obtain a yield of 68%. This product is an intermediate for the synthesis of Lorcaserin.

[0108] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.23 (d, J = 8.4 Hz, 2H), 7.10 (d, J = 8.5 Hz, 2H), 3.74 (dqd, J = 9.3, 6.3, 3.1 Hz, 1H), 2.91 - 2.73 (m, 4H), 2.66 (d, J = 9.0 Hz, 1H), 2.61 (s, 2H), 2.40 (dd, J = 12.1, 9.4 Hz, 1H), 1.11 (d, J = 6.2 Hz, 3H);

[0109] 13 C-NMR (100 MHz, CDC13) δ 138.3, 132.0, 130.1, 128.6, 65.5, 56.7, 50.7, 35.7, 20.7;

[0110] IR (ATR): 3051, 2968, 2835, 1731, 1492, 1455, 1407, 1373, 1264, 1090, 1046, 1015, 908, 835, 808, 729, 703;

[0111] HRMS (ESI) Calcd for [M+H]+: 214.0994 m / z, found: 214.0992 m / z.

[0112] Example 8

[0113]

[0114] In a 1000 ml two-necked reaction flask, dichlorobis-ethylene-zirconium (304 mg, 1 mmol, 0.01 eq) and potassium methoxide (36.5 mg, 0.5 mmol, 0.005 eq) were added, stirred at room temperature for ten minutes, then triethoxysilane (21.4 ml, 833 mmol, 8 eq) and polyethylene terephthalate (M WTo 1,4-bis(bromomethyl)benzene (30000, 20 g, 104 mmol, 1 eq) was added potassium trifluoromethanesulfonate (980 mg, 5.2 mmol, 0.05 eq) and tetrahydro-pyrrole (21.4 ml, 260 mmol, 2.5 eq) at room temperature. After stirring for 5 min, 240 ml of dioxane was added and the reaction mixture was heated to 130 °C for 24 h. After cooling to room temperature, the product was purified by silica gel to give a yield of 54%.

[0115] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.26 (s, 4H), 3.58 (s, 4H), 2.54-2.43 (m, 8H), 1.82-1.70 (m, J = 3.9 Hz, 8H);

[0116] 13 C-NMR (100 MHz, CDC13) δ 137.9, 129.0, 60.6, 54.2, 23.5;

[0117] IR (ATR): 2965, 2931, 2910, 2877, 2784, 2732, 2361, 1635, 1512, 1480, 1460, 1445, 1419, 1374, 1322, 1264, 1201, 1123, 1098, 1020, 996. 940, 880, 851, 825, 732, 702;

[0118] HRMS (ESI) Calcd for [M+H] + : 245.2013 m / z, found: 245.2014 m / z.

[0119] Example 9

[0120] The amine compound used was: tetrahydro-pyrrole.

[0121] Product: 1,4-bis(pyrrolidin-1-ylmethyl)benzene.

[0122]

[0123] Other synthesis method steps and parameters were the same as Example 1, 82% yield.

[0124] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.26 (s, 4H), 3.58 (s, 4H), 2.54-2.43 (m, 8H), 1.82-1.70 (m, J = 3.9 Hz, 8H);

[0125] 13 C-NMR (100 MHz, CDC13) δ 137.9, 129.0, 60.6, 54.2, 23.5;

[0126] IR (ATR): 2965, 2931, 2910, 2877, 2784, 2732, 2361, 1635, 1512, 1480, 1460, 1445, 1419, 1374, 1322, 1264, 1201, 1123, 1098, 1020, 996.940, 880, 851, 825, 732, 702;

[0127] HRMS (ESI) Calcd for [M+H] + : 245.2013 m / z, found: 245.2014 m / z.

[0128] Example 9

[0129] The amine compound used was: morpholine.

[0130] Product: 1,4-bis(morpholinomethyl)benzene.

[0131]

[0132] The other steps and parameters in the synthesis method were the same as in Example 1, 84% yield.

[0133] 1 H-NMR (400 MHz, CDC13) δ 7.26 (s, 4H), 3.69 (t, J = 4.6 Hz, 8H), 3.47 (s, 4H), 2.42 (t, J = 4.6 Hz, 8H);

[0134] 13 C-NMR (100 MHz, CDC13) δ 136.6, 129.2, 67.0, 63.2, 53.6;

[0135] IR (ATR): 3026, 3006, 2973, 2958, 2925, 2863, 1801, 2781, 2751, 2685, 2653, 1719, 1613, 1577, 1513, 1447, 1417, 1393, 1377, 1348, 1329, 1310, 1263, 1204, 1159, 1111, 1071, 1034, 1006, 969, 909, 863, 844, 791, 768, 733, 792;

[0136] HRMS (ESI) Calcd for [M+H] + : 277.1911 m / z, found: 277.1903 m / z.

[0137] Example 10

[0138] The amine compound used was: N-methylbutan-1-amine

[0139] Product: N,N'-(1,4-phenylenebis(methylene))bis(N-methylbutan-1-amine)

[0140]

[0141] The other steps and parameters in the synthesis method were the same as in Example 1, 90% yield.

[0142] 1 H-NMR (400 MHz, CDC13) δ 7.26 (s, 4H), 3.47 (s, 4H), 2.37 (t, J = 7.5 Hz, 4H), 2.19 (s, 6H), 1.55 - 1.47 (m, 4H), 1.38 - 1.28 (m, 4H), 0.91 (t, J = 7.4 Hz, 6H);

[0143] 13 C-NMR (100 MHz, CDC13) δ 137.8, 129.1, 62.1, 57.4, 42.3, 29.6, 20.7, 14.2;

[0144] IR (ATR): 3048, 3022, 2955, 2931, 2871, 2840, 2786, 1726, 1613, 1511, 1457, 1414, 1376, 1361, 1307, 1264, 1200, 1164, 1131, 1103, 1088, 1062, 1036, 1019, 970, 941, 895, 863, 822, 801, 769, 736, 704;

[0145] HRMS (ESI) Calcd for [M+H] + : 277.2639 m / z, found: 277.2631 m / z.

[0146] Example 11

[0147] The amine compound used was: diethylamine

[0148] Product: N,N'-(1,4-phenylenebis(methylene))bis(N-ethylethanamine)

[0149]

[0150] The other steps and parameters in the synthesis method were the same as in Example 1, 87% yield.

[0151] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.26 (s, 4H), 3.54 (s, 4H), 2.51 (q, J = 7.1 Hz, 8H), 1.04 (t, J = 7.2 Hz, 12H);

[0152] 13 C-NMR (100 MHz, CDC13) δ 138.3, 128.8, 57.3, 46.7, 11.8;

[0153] IR (ATR): 3048, 3012, 2967, 2933, 2873, 2797, 2723, 1510, 1454, 1418, 1383, 1361, 1290, 1264, 1199, 1098, 1059, 1020, 993, 970, 908, 849, 829, 805, 775, 737, 704;

[0154] HRMS (ESI) Calcd for [M+H] + : 249.2326 m / z, found: 249.2327 m / z.

[0155] Example 12

[0156] The amine compound used was: N-methylbenzylamine

[0157] Product: 1, 1 '-(1,4-phenylene)bis(N-benzyl-N-methylmethanamine)

[0158]

[0159] Other steps and parameters in the synthetic procedure were the same as in Example 1, 99% yield.

[0160] 1 H-NMR (400 MHz, CDC13) δ 7.32 - 7.23 (m, 12H), 7.19 - 7.14 (m, 2H), 3.45 (s, 4H), 3.44 (s, 4H), 2.12 (s, 6H);

[0161] 13 C-NMR (101 MHz, CDC13) δ 139.4, 138.0, 129.0, 128.9, 128.3, 127.0, 61.9, 61.7, 42.3;

[0162] IR (ATR): 3061, 3027, 2979, 2942, 2942, 2925, 2876, 2784, 2707, 1948, 1809, 1737, 1716, 1601, 1510, 1494, 1452, 1414, 1364, 1343, 1311, 1264, 1210, 1191, 1131, 1101, 1074, 1018, 977, 908, 870, 822, 801, 767, 733;

[0163] HRMS (ESI) Calcd for [M+H] + : 345.2326 m / z, found: 345.2316 m / z.

[0164] Example 13

[0165] The amine compound used was: N-(4-methoxybenzyl)-N-methylmethanamine

[0166] Product: 1,1'-(1,4-phenylene)bis(N-(4-methoxybenzyl)-N-methylmethanamine)

[0167]

[0168] Other steps and parameters in the synthetic procedure were the same as in Example 1, 88% yield.

[0169] 1H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.26 (s, 4H), 7.23 (d, J = 8.7 Hz, 4H), 6.82 (d, J = 8.6 Hz, 4H), 3.74 (s, 6H), 3.44 (s, 4H), 3.41 (s, 4H), 2.12 (s, 6H);

[0170] 13 C-NMR (100 MHz, CDC13) δ 158.7, 137.9, 131.3, 130.2, 128.9, 113.6, 61.5, 61.2, 55.3, 42.2;

[0171] IR (ATR): 2999.2978, 2947, 2909, 2881, 2785, 2707, 1734, 1611, 1564, 1509, 1456, 1442, 1415, 1364, 1300, 1264, 1244, 1171, 1130, 1103, 1033, 980, 908, 872, 811, 731, 703;

[0172] HRMS (ESI) Calcd for [M+H] + : 405.2537 m / z, found: 405.2543 m / z.

[0173] Example 14

[0174] The amine compound used was: N-methyl-4-bromobenzylamine

[0175] Product: 1,1'-(1,4-phenylene)bis(N-(4-bromobenzyl)-N-methylmethanamine)

[0176]

[0177] The other steps and parameters in the synthesis method were the same as in Example 1, 91% yield;

[0178] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.26 (s, 4H), 7.23 (d, J = 8.7 Hz, 4H), 6.82 (d, J = 8.6 Hz, 4H), 3.74 (s, 6H), 3.44 (s, 4H), 3.41 (s, 4H), 2.12 (s, 6H);

[0179] 13C-NMR (100 MHz, CDC13) δ 138.2, 137.7, 131.5, 130.8, 129.1, 120.9, 61.6, 61.1, 42.2;

[0180] IR (ATR): 3045, 3023 2978, 2943, 2924, 2878, 2785, 2705, 1900, 1735, 1699, 1591, 1510, 1455, 1402, 1362, 1305, 1263, 1239, 1191, 1131, 1098, 1069, 1029, 1010, 980, 940, 874, 834, 798, 736, 703;

[0181] HRMS (ESI) Calcd for [M+H] + : 503.0516 m / z, found: 503.0508 m / z.

[0182] Example 15

[0183] The amine compound used was: 4-[(methylamino)methyl]phenol

[0184] Product: 4,4'-(((l,4-phenylenebis(methylene))bis(methylazanediyl))bis(methylene))diphenol

[0185]

[0186] The triethoxysilane used was 12 equiv, and the other steps and parameters in the synthesis method were the same as in Example 1, 56% yield.

[0187] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.26 (s, 4H), 7.23 (d, J = 8.7 Hz, 4H), 6.82 (d, J = 8.7 Hz, 4H), 3.74 (s, 6H), 3.44 (s, 4H), 3.41 (s, 4H), 2.12 (s, 6H);

[0188] 13 C-NMR (100 MHz, CDC13) δ 158.7, 137.9, 131.3, 130.2, 128.9, 113.6, 61.5, 61.2, 55.3, 42.2;

[0189] IR (ATR): 3045, 3020, 2945, 2827, 2790, 2034, 1749, 1718, 1613, 1594, 1514, 1455, 1416, 1365, 1264, 1171, 1125, 1098, 1018, 984, 823, 734, 703;

[0190] HRMS (ESI) Calcd for [M+H] C32H32N2O4: 517.2350 m / z, found: 517.2346 m / z. + :377.2224 m / z, found:377.2210 m / z.

[0191] Example 16

[0192] The amine compound used was: 3-(methylamino)-1-propanol.

[0193] Product: 3,3'-((1,4-phenylenebis(methylene))bis(methylazanediyl))bis(propan-1-ol)

[0194]

[0195] The triethoxysilane used was 12 equiv, and the other steps and parameters in the synthesis method were the same as in Example 1, 88% yield.

[0196] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.26 (s, 4H), 4.39 (br, 2H), 3.75 (t, J = 5.3 Hz, 4H), 3.52 (s, 4H), 2.64 (t, J = 5.7 Hz, 4H), 2.23 (s, 6H), 1.76 - 1.71 (m, 4H);

[0197] 13 C-NMR (100 MHz, CDC13) δ 137.0, 129.4, 64.6, 62.6, 57.8, 42.1, 27.8;

[0198] IR (ATR): 3051, 2946, 2845, 2798, 1512, 1462, 1420, 1363, 1350, 1265, 1223, 1178, 1141, 1127, 1104, 1066, 1030, 943, 917, 894, 857, 821, 805, 732, 701;

[0199] HRMS (ESI) Calcd for [M+H] C32H32N2O4: 517.2350 m / z, found: 517.2346 m / z. +: 281.2224 m / z, found: 281.2211 m / z.

[0200] Example 17

[0201] The amine compound used was: N-(2-methoxyethyl)methylamine.

[0202] Product: N,N'-(l,4-phenylenebis(methylene))bis(2-methoxy-N-methylethan-l-amine)

[0203]

[0204] The other steps and parameters in the synthesis method were the same as in Example 1, 97% yield.

[0205] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.26 (s, 4H), 3.53 (s, 4H), 3.50 (t, J = 5.8 Hz, 4H), 3.32 (s, 6H), 2.59 (t, J = 5.8 Hz, 4H), 2.25 (s, 6H);

[0206] 13 C-NMR (100 MHz, CDC13) δ 137.1, 128.8, 70.5, 62.2, 58.5, 56.0, 42.4;

[0207] IR (ATR): 2981, 2929, 2877, 2840, 2812, 2789, 1511, 1455, 1417, 1364, 1265, 1192, 1116, 1066, 1041, 1018, 963, 909, 867, 839, 730, 702;

[0208] HRMS (ESI) Calcd for [M+H] + : 281.2224 m / z, found: 281.2218 m / z.

[0209] Example 18

[0210] The amine compound used was: N,4-dimethyl-N-(2-(methylamino)ethyl)benzenesulfonamide

[0211] Product: N,N'-(((1,4-phenylenebis(methylene))bis(methylazanediyl))bis(ethane- 2,1-diyl))bis(N,4-dimethylbenzenesulfonamide)

[0212]

[0213] The other steps and parameters in the synthetic procedure were the same as in Example 1, 87% yield.

[0214] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.64 (d, J = 8.2 Hz, 4H), 7.28 (d, J = 8.1 Hz, 4H), 7.21 (s, 4H), 3.49 (s, 4H), 3.12 (t, J = 6.8 Hz, 4H), 2.70 (s, 6H), 2.57 (t, J = 6.8 Hz, 4H), 2.39 (s, 6H), 2.21 (s, 6H);

[0215] 13 C-NMR (100 MHz, CDC13) δ 143.3, 137.4, 134.5, 129.7, 128.9, 127.4, 62.1, 55.1, 48.0, 42.2, 35.3, 21.5;

[0216] IR (ATR): 2949, 2924, 2849, 2794, 1720, 1598, 1494, 1456, 1421, 1337, 1305, 1287, 1265, 1157, 1103, 1089, 1031, 1018, 966, 896, 815, 731, 700;

[0217] HRMS (ESI) Calcd for [M+H] + : 587.2721 m / z, found: 587.2728 m / z.

[0218] Example 19

[0219] The amine compound used was: N-methylpiperazine;

[0220] Product: 1,4-bis((4-methylpiperazin-1-yl)methyl)benzene

[0221]

[0222] The other steps and parameters in the synthetic procedure were the same as in Example 1, 72% yield.

[0223] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.24 (s, 4H), 3.49 (s, 4H), 2.98 (br, 2H), 2.50 (br, 14H), 2.30 (s, 6H);

[0224] 13 C-NMR (100 MHz, CDC13) δ 136.8, 129.3, 62.7, 55.1, 52.8, 45.9;

[0225] IR (ATR): 3020, 2933, 2875, 2836, 2792, 2692, 2675, 1718, 1658, 1612, 1512, 1455, 1419, 1395, 1369, 1348, 1333, 1310, 1280, 1201, 1162, 1140, 1102, 1079, 1052, 1010, 984, 924, 855, 835, 811, 771, 757, 700;

[0226] HRMS (ESI) Calcd for [M+H] + : 303.2544 m / z, found: 303.2537 m / z.

[0227] Example 20

[0228] The amine compound used was: 4-phenyl-1,2,3,6-tetrahydropyridine

[0229] Product: 1,4-bis((4-phenyl-3,6-dihydropyridin-1(2H)-yl)methyl)benzene

[0230]

[0231] The other steps and parameters in the synthetic procedure were the same as in Example 1, 72% yield.

[0232] 1H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.39 (s, 4H), 7.38 (s, 4H), 7.31 (t, J = 7.5 Hz, 4H), 7.25 - 7.21 (m, 2H), 6.06 (tt, J = 3.5, 1.6 Hz, 2H), 3.70 (s, 4H), 3.23 (q, J = 3.0 Hz, 4H), 2.78 (t, J = 5.7 Hz, 4H), 2.61 (tt, J = 6.3, 2.8 Hz, 4H);

[0233] 13 C-NMR (100 MHz, CDC13) δ 140.8, 135.1, 129.6, 128.4, 127.2, 125.0, 121.4, 62.2, 53.1, 49.9, 27.8;

[0234] IR (ATR): 3002, 2943, 2912, 2793, 2304, 1660, 1636, 1598, 1575, 1557, 1494, 1445, 1423, 1392, 1361, 1336, 1264, 1154, 1124, 1104, 1073, 1046, 1022, 992, 966, 942, 896, 850, 824, 811, 732, 700;

[0235] HRMS (ESI) Calcd for [M+H] + : 421.2639 m / z, found: 421.2634 m / z.

[0236] Example 21

[0237] The amine compound used was: N-methyl-3-((methylamino)methyl)aniline.

[0238] Product: 3,3'-(((1,4-phenylenebis(methylene))bis(methylazanediyl))bis(methylene))-bis(N-methylaniline)

[0239]

[0240] The other steps and parameters in the synthesis method were the same as in Example 1, 53% yield.

[0241] 1H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.31 (s, 4H), 7.14 (t, J = 7.7 Hz, 2H), 6.71 (d, J = 7.5 Hz, 2H), 6.66 (t, J = 2.0 Hz, 2H), 6.51 (dd, J = 8.3, 2.4 Hz, 2H), 3.50 (s, 4H), 3.46 (s, 4H), 2.84 (s, 6H), 2.19 (s, 6H);

[0242] 13 C-NMR (100 MHz, CDC13) δ 149.5, 140.5, 138.0, 129.1, 129.0, 118.3, 118.2, 113.2, 113.2, 111.1, 62.3, 61.7, 42.5, 31.0;

[0243] IR (ATR): 3047, 2978, 2926, 2907, 2879, 2806, 2785, 2705, 1914, 1721, 1605, 1590, 1510, 1482, 1474, 1453, 1415, 1363, 1329, 1265, 1165, 1123, 1100, 1069, 1029, 1018, 991, 877, 865, 778, 735;

[0244] HRMS (ESI) Calcd for [M+H] + : 403.2857 m / z, found: 403.2840 m / z.

[0245] Example 22

[0246] The amine compound used was: 4-methylene piperidine.

[0247] Product: 1,4-bis((4-methylenepiperidin-1-yl)methyl)benzene

[0248]

[0249] The other steps and parameters in the synthesis method were the same as in Example 1, 67% yield.

[0250] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.27 (s, 4H), 4.65 (s, 4H), 3.51 (s, 4H), 2.46 (t, J = 5.7 Hz, 8H), 2.25 ((t, J = 5.7 Hz, 8H);

[0251] 13 C-NMR (100 MHz, CDC13) δ 146.7, 137.2, 129.2, 107.8, 62.8, 55.0, 34.6;

[0252] IR (ATR): 3024, 3011, 2981, 2947, 2933, 2905, 2885, 2813, 2775, 2754, 206, 2685, 2661, 2628, 1918, 1772, 1721, 1679, 1654, 1612, 1508, 1461, 1433, 1420, 1385, 1361, 1344, 1327, 1307, 1277, 1253, 1215, 1175, 1130, 1112, 1079, 1021, 1006, 990, 965, 909, 883, 849, 818, 806, 769, 736, 703;

[0253] HRMS (ESI) Calcd for [M+H] + : 297.2326 m / z, found: 297.2321 m / z.

[0254] Example 23

[0255] The amine compound used was: 1,2,3,4-tetrahydroisoquinoline.

[0256] Product: 1,4-bis((3,4-dihydroisoquinolin-2(1H)-yl)methyl)benzene

[0257]

[0258] The other steps and parameters in the synthesis method were the same as in Example 1, 83% yield.

[0259] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.26 (s, 4H), 7.01-6.97 (m, 6H), 6.86 (d, J = 7.6 Hz, 2H), 3.57 (s, 4H), 3.53 (s, 4H), 2.79 (t, J = 5.9 Hz, 4H), 2.64 (t, J = 5.9 Hz, 4H);

[0260] 13C-NMR (100 MHz, CDC13) δ 137.2, 134.9, 134.4, 129.1, 128.7, 126.7, 126.1, 125.6, 62.6, 56.2, 50.7, 29.2;

[0261] IR (ATR): 3022, 2916, 2795, 2720, 1909, 1668, 1606, 1584, 1511, 1497, 1463, 1453, 1425, 1390, 1365, 1338, 1310, 1264, 1234, 1192, 1130, 1088, 1056, 1020, 1009, 973, 933, 868, 839, 797, 733, 702;

[0262] HRMS (ESI) Calcd for [M+H] + : 369.2326 m / z, found: 369.2310 m / z.

[0263] Example 24

[0264] The amine compound used was: N,N'-dimethyl-1,6-hexanediamine.

[0265] Product: 3,10-dimethyl-3,10-diaza-1(1,4)-benzenacycloundecaphane

[0266]

[0267] The diamine was 1.25 equiv and the other steps and parameters in the synthesis procedure were the same as in Example 1, 50% yield.

[0268] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.23 (s, 4H), 3.44 (s, 4H), 2.34 (t, J = 7.6 Hz, 4H), 2.16 (s, 6H), 1.54-1.47 (m, 4H), 1.33 - 1.27 (m, 4H);

[0269] 13 C-NMR (100 MHz, CDC13) δ 137.2, 134.9, 134.4, 129.1, 128.7, 126.7, 126.1, 125.6, 62.6, 56.2, 50.7, 29.2;

[0270] IR (ATR): 2934, 2856, 2788, 1721, 1674, 1612, 1511, 1461, 1414, 1362, 1306, 1264, 1172, 1124, 1101, 1954, 1038, 1018, 983, 942, 894, 864, 802, 734, 703;

[0271] HRMS (ESI) Calcd for [M+H] + : 247.2169 m / z, found: 247.2164 m / z.

[0272] Example 25

[0273] The amine compound used was: 3-(2-[methylamino]ethyl)indole.

[0274] Product: 1,4-bis((S)-2-methyl-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indol-1-yl)benzene

[0275]

[0276] The other steps and parameters in the synthesis method were the same as in Example 1, 89% yield.

[0277] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.54 (h, J = 2.6 Hz, 2H), 7.34 (s, 2H), 7.31 (s, 1H), 7.30 (s, 2H), 7.27 (s, 1H), 7.19 - 7.05 (m, 6H), 4.33 (s, 2H), 3.24 (dtd, J = 11.5, 5.6, 2.5 Hz, 2H), 3.09 (dddd, J = 15.5, 10.4, 5.2, 2.5 Hz, 2H), 2.86 (ddt, J = 15.2, 4.1, 1.9 Hz, 2H), 2.76 (ddd, J = 14.8, 7.2, 3.8 Hz, 2H), 2.36 (s, 3H), 2.35 (s, 3H);

[0278] 13 C-NMR (100 MHz, CDC13) δ 141.0, 136.4, 134.63, 134.5, 129.5, 127.2, 121.7, 119.6, 118.5, 118.4, 111.0, 110.9, 109.2, 109.1, 66.9, 66.9, 53.1, 53.1, 43.7, 43.7, 21.6;

[0279] IR (ATR): 3202, 3053, 2944, 2911, 2845, 2789, 1689, 1621, 1608, 1541, 1503, 1487, 1466, 1451, 1418, 1366, 1337, 1306, 1263, 1236, 1215, 1182, 1157, 1123, 1106, 1057, 1036, 1010, 980, 921, 836, 815, 737, 702;

[0280] HRMS (ESI) Calcd for [M+H] + : 447.2544 m / z, found: 447.2526 m / z.

[0281] Example 26

[0282] The amine compound used was: N,N',N"-trimethyldiethylenetriamine.

[0283] Product: 3,6,9-trimethyl-3,6,9-triaza-1(1,4)-benzenacyclodecaphane

[0284]

[0285] The diamine was 1.25 equiv and the other steps and parameters in the synthesis method were the same as in Example 1, 41% yield.

[0286] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.22 (s, 4H), 3.44 (s, 4H), 2.54-2.43 (m, 8H), 2.18 (s, 9H);

[0287] 13 C-NMR (100 MHz, CDC13) δ 137.5, 129.1, 62.6, 56.0, 55.1, 42.6;

[0288] IR (ATR): 3049, 3022, 2977, 2874, 2834, 2787, 2708, 1910, 1650, 1632, 1573, 1511, 1455, 1414, 1363, 1263, 1249, 1225, 1163, 1249, 1225, 1163, 1132, 1100, 1030, 1017, 983, 943, 875, 830, 805, 735, 703;

[0289] HRMS (ESI) Calcd for [M+H] 248.2122 m / z, found: 248.2130 m / z. + :248.2122 m / z, found:248.2130 m / z.

[0290] Example 27

[0291] The amine compound used was: 2-(1-cyclohexenyl)ethylamine.

[0292] Product: (1E,1'E)-1,1'-(1,4-phenylene)bis(N-(2-(cyclohex-1-en-1-yl)ethyl)methanimine)

[0293]

[0294] The other steps and parameters in the synthesis method were the same as in Example 1, 52% yield.

[0295] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 8.25 (s, 2H), 7.75 (s, 4H), 5.46 (td, J = 3.5, 1.8 Hz, 2H), 3.72 - 3.67 (m, 4H), 2.31 (t, J = 7.5 Hz, 4H), 2.00 - 1.96 (m, 8H), 1.62 (tt, J = 5.4, 2.7 Hz, 4H), 1.54 (dq, J = 5.4, 2.9 Hz, 4H);

[0296] 13 C-NMR (100 MHz, CDC13) δ 160.6, 138.2, 135.6, 128.4, 122.9, 60.8, 39.5, 28.9, 25.4, 23.1, 22.6;

[0297] IR (ATR): 2994, 2925, 2835, 1701, 1641, 1567, 1437, 1369, 1346, 1298, 1264, 1216, 1153, 1135, 1088, 1032, 1016, 959, 919, 827, 802, 734, 703;

[0298] HRMS (ESI) Calcd for [M+H] 248.2122 m / z, found: 248.2130 m / z. + :248.2122 m / z, found:248.2130 m / z.

[0299] Example 28

[0300] The amine compound used was: N-(2-aminoethyl)morpholine

[0301] Product: (1E, 1'E)-1,1'-(1,4-phenylene)bis(N-(2-morpholinoethyl)methanimine)

[0302]

[0303] Other steps and parameters in the synthesis method were the same as in Example 1, 77% yield;

[0304] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 8.30 (s, 2H), 7.74 (s, 4H), 3.78 (t, J = 7.0 Hz, 4H), 3.72 - 3.69 (m, 8H), 2.71 (t, J = 7.0 Hz, 4H), 2.55 (t, J = 4.7 Hz, 8H);

[0305] 13 C-NMR (100 MHz, CDC13) δ 161.6, 138.1, 128.4, 67.0, 59.3, 59.1, 54.1;

[0306] IR (ATR): 2954, 2940, 2918, 2893, 2850, 2809, 2769, 2689, 1700, 1641, 1607, 1567, 1453, 1355, 1341, 1298, 1265, 1206, 1141, 1114, 1069, 1035, 1007, 914, 866, 828, 768, 731, 701;

[0307] HRMS (ESI) Calcd for [M+H] + : 359.2442 m / z, found: 359.2435 m / z.

[0308] Example 29

[0309] The amine compound used was: 3-methoxypropylamine

[0310] Product: (1E, 1'E)-1,1'-(1,4-phenylene)bis(N-(3-methoxypropyl)methanimine)

[0311]

[0312] The other steps and parameters in the synthetic procedure were the same as in Example 1, 73% yield.

[0313] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 8.32 (s, 2H), 7.78 (s, 4H), 3.72 (t, J = 6.9 Hz, 4H), 3.48 (t, J = 6.3 Hz, 4H), 3.35 (s, 6H), 1.99 (q, J = 6.6 Hz, 4H);

[0314] 13 C-NMR (100 MHz, CDC13) δ 160.9, 138.1, 128.3, 70.4, 58.6, 58.3, 30.8;

[0315] IR (ATR): 3026, 2978, 2923, 2869, 2842, 2752, 1700, 1642, 1607, 1568, 1479, 1450, 1384, 1337, 1299, 1216, 1185, 1158, 1116, 1087, 1055, 1016, 965, 915, 826, 752;

[0316] HRMS (ESI) Calcd for [M+H] + : 277.1911 m / z, found: 277.1906 m / z.

[0317] Example 30

[0318] The amine compound used was: tryptamine.

[0319] Product: (1E, 1'E)-1, 1'-(1, 4-phenylene)bis(N-(2-(1H-indol-3-yl)ethyl)methanimine)

[0320]

[0321] The other steps and parameters in the synthetic procedure were the same as in Example 2, 78% yield.

[0322] 1H-NMR (400 MHz, CD3SOCD3) δ (p.p.m.) 10.81 (s, 2H), 8.32 (s, 2H), 7.79 (s, 4H), 7.58 (d, J = 7.9 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H), 7.15 (d, J = 2.3 Hz, 2H), 7.06 (t, J = 6.9 Hz, 2H), 6.99 - 6.94 (m, 2H), 3.89 (t, J = 7.2 Hz, 4H), 3.05 (t, J = 7.3 Hz, 4H);

[0323] 13 C-NMR (100 MHz, CD3SOCD3) δ 160.4, 137.9, 136.2, 128.1, 127.3, 122.9, 120.9, 118.5, 118.2, 112.2, 111.3, 61.6, 26.7;

[0324] IR (ATR): 3354, 3177, 3106, 3071, 3047, 3015, 2923, 2905, 2876, 2848, 2831, 2227, 1636, 1618, 1584, 1488, 1456, 1430, 1376, 1356, 1339, 1299, 1264, 1232, 1147, 1128, 1100, 1076, 1065, 1009, 974, 923, 879, 853, 820, 735, 702;

[0325] HRMS (ESI) Calcd for [M+H] + : 419.2231 m / z, found: 419.2227 m / z.

[0326] Example 31

[0327] The amine compound used was: furanamine

[0328] Product: 1-(furan-2-ylmethyl)-1H-pyrrole

[0329]

[0330] The other steps and parameters in the synthetic method were the same as in Example 4, 78% yield.

[0331] 1H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.39 (dd, J = 1.9, 0.9 Hz, 1H), 6.73 (t, J = 2.1 Hz, 2H), 6.35 (dd, J = 3.2, 1.9 Hz, 1H), 6.27 (dd, J = 3.2, 0.9 Hz, 1H), 6.19 (t, J = 2.1 Hz, 2H), 5.04 (s, 2H);

[0332] 13 C-NMR (100 MHz, CDC13) δ 150.9, 142.8, 120.8, 110.5, 108.6, 108.2, 46.2;

[0333] IR (ATR): 3102, 3066, 3049, 2921, 2100, 1732, 1682, 1602, 1551, 1495, 1428, 1401, 1382, 1344, 1273, 1219, 1167, 1145, 1087, 1075, 1011, 967, 909, 885, 814, 760, 720, 700;

[0334] HRMS (ESI) Calcd for [M+H] + : 148.0757 m / z, found: 148.0752 m / z.

[0335] Example 32

[0336] The amine compound used was: benzylamine.

[0337] Product: 1-benzyl-1H-pyrrole

[0338]

[0339] The other steps and parameters in the synthesis method were the same as in Example 4, 76% yield.

[0340] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.39 (dd, J = 1.9, 0.9 Hz, 1H), 6.73 (t, J = 2.1 Hz, 2H), 6.35 (dd, J = 3.2, 1.9 Hz, 1H), 6.27 (dd, J = 3.2, 0.9 Hz, 1H), 6.19 (t, J = 2.1 Hz, 2H), 5.04 (s, 2H);

[0341] 13 C-NMR (100 MHz, CDC13) δ 150.9, 142.8, 120.8, 110.5, 108.6, 108.2, 46.2;

[0342] IR (ATR): 3064, 3030, 2921, 2852, 1736, 1606, 1549, 1496, 1454, 1439, 1396, 1355, 1278, 1267, 1190, 1156, 1087, 1067, 1029, 867, 909, 815, 718, 704;

[0343] HRMS (ESI) Calcd for [M+H] C26H25N4O2 433.1973 m / z, found: 433.1973 m / z. + :158.0965 m / z, found:158.0959 m / z.

[0344] Example 33

[0345] The amine compound used was: 2-aminomethylpyridine

[0346] Product: 2-((1H-pyrrol-1-yl)methyl)pyridine

[0347]

[0348] The other steps and parameters in the synthesis method were the same as in Example 4, 97% yield.

[0349] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 8.56 (d, J = 4.1 Hz, 1H), 7.60 (td, J = 7.7, 1.8 Hz, 1H), 7.18 (dd, J = 7.5, 6.0 Hz, 1H), 6.79 (d, J = 7.9 Hz, 1H), 6.75 (t, J = 2.1 Hz, 2H), 6.23 (t, J = 2.1 Hz, 2H), 5.21 (s, 2H);

[0350] 13 C-NMR (100 MHz, CDC13) δ 158.3, 149.1, 137.3, 122.5, 121.4, 120.9, 109.0, 55.1;

[0351] IR (ATR): 3049, 3012, 2977, 2928, 2851, 1713, 1681, 1593, 1571, 1497, 1474, 1427, 1348, 1289, 1281, 1266, 1248, 1149, 1087, 1067, 1049, 995, 968, 722;

[0352] HRMS (ESI) Calcd for [M+H]+ : 159.0917 m / z, found: 159.0916 m / z.

[0353] Example 34

[0354] The amine compound used was: p-bromobenzylamine

[0355] Product: 1-(4-bromobenzyl)-1H-pyrrole

[0356]

[0357] The other steps and parameters in the synthesis method were the same as in Example 4, 72% yield.

[0358] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.45 (d, J = 8.4 Hz, 2H), 6.98 (d, J = 8.4 Hz, 2H), 6.68 (t, J = 2.1 Hz, 2H), 6.21 (t, J = 2.1 Hz, 2H), 5.03 (s, 2H);

[0359] 13 C-NMR (100 MHz, CDC13) δ 137.4, 131.9, 128.7, 121.7, 121.2, 108.9, 52.8;

[0360] IR (ATR): 3100, 3046, 2923, 2857, 2784, 1893, 1679, 1594, 1551, 1496, 1488, 1436, 1406, 1349, 1287, 1265, 1189, 1109, 1086, 1010, 968, 843, 799, 721;

[0361] HRMS (ESI) Calcd for [M+H] + : 236.0070 m / z, found: 236.0060 m / z.

[0362] Example 35

[0363] The amine compound used was: p-hydroxybenzylamine

[0364] Product: 4-((1H-pyrrol-1-yl)methyl)phenol

[0365]

[0366] The other steps and parameters in the synthetic procedure were the same as in Example 4, 41% yield.

[0367] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.02 (d, J = 8.5 Hz, 2H), 6.77 (d, J = 8.5 Hz, 2H), 6.69 (t, J = 2.1 Hz, 2H), 6.19 (t, J = 1.9 Hz, 2H), 4.99 (s, 2H);

[0368] 13 C-NMR (100 MHz, CDC13) δ 155.2, 130.3, 128.8, 121.1, 115.6, 108.5, 52.9;

[0369] IR (ATR): 3100, 3048, 3023, 2953, 2923, 2854, 1614, 1598, 1514, 1497, 1397, 1352, 1264, 1225, 1202, 1171, 1109, 1086, 1066, 1014, 967, 821, 724, 701;

[0370] HRMS (ESI) Calcd for [M+H] + : 174.0914 m / z, found: 174.0913 m / z.

[0371] Example 36

[0372] The amine compound used was: 3-amino-1-propanol

[0373] Product: 3-(1H-pyrrol-1-yl)propan-1-ol

[0374]

[0375] The other steps and parameters in the synthetic procedure were the same as in Example 4, 51% yield.

[0376] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 6.68 (t, J = 2.1 Hz, 2H), 6.15 (t, J = 2.1 Hz, 2H), 4.03 (t, J = 6.8 Hz, 2H), 3.63 (t, J = 6.0 Hz, 2H), 2.03 - 1.96 (m, 2H), 1.60 (s, 1H);

[0377] 13C-NMR (100 MHz, CDC13) δ 120.7, 108.2, 59.8, 46.2, 34.1;

[0378] IR (ATR): 3101, 3050, 2928, 2881, 2240, 1774, 1682, 1549, 1500, 1499, 1399, 1374, 1354, 1280, 1166, 1088, 1052, 966, 943, 909, 722;

[0379] HRMS (ESI) Calcd for [M+H] + : 126.0914 m / z, found: 126.0913 m / z.

[0380] Example 37

[0381] The amine compound used was: 3-methylaminopropylamine.

[0382] Product: N-methyl-3-(1H-pyrrol-1-yl)propan-1-amine

[0383]

[0384] The other steps and parameters in the synthesis method were the same as in Example 4, 71% yield.

[0385] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 6.66 (t, J = 2.1 Hz, 2H), 6.14 (t, J = 2.1 Hz, 2H), 3.96 (t, J = 7.0 Hz, 2H), 2.58 (t, J = 7.0 Hz, 2H), 2.42 (s, 3H), 2.26 (s, 1H), 1.96 (t, J = 7.0 Hz, 2H);

[0386] 13 C-NMR (100 MHz, CDC13) δ 120.6, 108.1, 49.0, 47.5, 36.3, 31.4.

[0387] IR (ATR): 3098, 3047, 2933, 2875, 2850, 2794, 1643, 1547, 1500, 1472, 1448, 1379, 1280, 1131, 1112, 1088, 1060, 968, 815, 721;

[0388] HRMS (ESI) Calcd for [M+H]+ : 139.1230 m / z, found: 139.1229 m / z.

[0389] Example 38

[0390] The amine compound used was: 3-methoxypropylamine

[0391] Product: 1-(3-methoxypropyl)-1H-pyrrole

[0392]

[0393] The other steps and parameters in the synthesis method were the same as in Example 4, 63% yield.

[0394] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 6.66 (t, J = 2.1 Hz, 2H), 6.15 (t, J = 2.1 Hz, 2H), 3.99 (t, J = 6.9 Hz, 2H), 3.34 (s, 3H), 3.31 (d, J = 5.9 Hz, 2H), 2.00 (q, J = 6.4 Hz, 2H);

[0395] 13 C-NMR (100 MHz, CDC13) δ 120.8, 108.1, 69.2, 58.8, 46.3, 31.8;

[0396] IR (ATR): 3049, 2977, 2926, 2874, 2832, 2811, 2105, 1704, 1542, 1500, 1480, 1450, 1429, 1388, 1352, 1282, 1210, 1118, 1088, 1061, 1025, 964, 910, 853, 723, 700;

[0397] HRMS (ESI) Calcd for [M+H] + : 140.1070 m / z, found: 140.1065 m / z.

[0398] Example 39

[0399] The amine compound used was: 2-(1-cyclohexen-1-yl)ethylamine

[0400] Product: 1-(2-(cyclohex-1-en-1-yl)ethyl)-1H-pyrrole

[0401]

[0402] The other steps and parameters in the synthetic procedure were the same as in Example 4, 82% yield.

[0403] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 6.67 (t, J = 2.1 Hz, 2H), 6.15 (t, J = 2.1 Hz, 2H), 5.44 (tt, J = 3.7, 1.6 Hz, 1H), 3.98 - 3.94 (m, 2H), 2.42 - 2.37 (m, 2H), 2.03 - 1.98 (m, 2H), 1.96 - 1.92 (m, 2H), 1.69 - 1.63 (m, 2H), 1.57 (dp, J = 8.8, 2.7 Hz, 2H);

[0404] 13 C-NMR (100 MHz, CDC13) δ 134.4, 123.6, 120.6, 107.9, 48.7, 40.3, 28.4, 25.4, 23.0, 22.4;

[0405] IR (ATR): 3047, 2926, 2857, 2835, 1668, 1542, 1499, 1448, 1436, 1281, 1265, 1134, 1087, 1066, 1022, 969, 920, 801, 718;

[0406] HRMS (ESI) Calcd for [M+H] + : 176.1434 m / z, found: 176.1428 m / z.

[0407] Example 40

[0408] The amine compound used was: tryptamine

[0409] Product: 3-(2-(1H-pyrrol-1-yl)ethyl)-1H-indole

[0410]

[0411] The other steps and parameters in the synthetic procedure were the same as in Example 4, 68% yield.

[0412] 1H-NMR (400 MHz, CD3SOCD3) δ (p.p.m.) 10.83 (s, 1H), 7.55 (d, J = 7.9 Hz, 1H), 7.33 (dt, J = 8.1, 1.0 Hz, 1H), 7.09 - 7.05 (m, 1H), 7.03 (d, J = 2.4 Hz, 1H), 6.98 (td, J = 7.4, 1.1 Hz, 1H), 6.78 (t, J = 2.1 Hz, 2H), 5.96 (t, J = 2.1 Hz, 2H), 4.16 - 4.11 (m, 2H), 3.13 - 3.08 (m, 2H);

[0413] 13 C-NMR (100 MHz, CD3SOCD3) δ 136.1, 127.1, 122.9, 121.0, 120.5, 118.3, 111.4, 111.0, 107.4, 49.4, 27.5;

[0414] IR (ATR): 3120, 3096, 3054, 2926, 2873, 2849, 1619, 1592, 1554, 1499, 1456, 1422, 1365, 1339, 1282, 1226, 1133, 1088, 1063, 1011, 970, 850, 816, 727;

[0415] HRMS (ESI) Calcd for [M+H] + : 211.1230 m / z, found: 211.1221 m / z.

[0416] Example 41

[0417] The amine compound used was: 3-aminobenzylamine.

[0418] Product: 3-((1H-pyrrol-1-yl)methyl)aniline

[0419]

[0420] The other steps and parameters in the synthesis method were the same as in Example 4, 88% yield.

[0421] 1H-NMR (400 MHz, CDC13) δ (p.p.m.) 6.96 (t, J = 7.8 Hz, 1H), 6.56 (t, J = 2.1 Hz, 2H), 6.40 (dd, J = 7.8, 2.1 Hz, 2H), 6.20 (t, J = 2.0 Hz, 1H), 6.08 (t, J = 2.2 Hz, 2H), 4.81 (s, 2H), 3.36 (s, 2H).

[0422] 13 C-NMR (100 MHz, CDC13) δ 146.8, 139.4, 129.5, 121.2, 117.0, 114.2, 113.3, 108.3, 53.2;

[0423] IR (ATR): 3369, 3214, 3100, 3048, 2982, 2922, 1620, 1592, 1496, 1463, 1438, 1397, 1351, 1264, 1166, 1086, 996, 969, 866, 778, 724, 701;

[0424] HRMS (ESI) Calcd for [M+H] + : 173.1074 m / z, found: 173.1068 m / z.

[0425] Example 42

[0426] The amine compound used was: N-[3-(aminomethyl)phenyl]-2,2-dimethylpropanamide

[0427] Product: N-(3-((1H-pyrrol-1-yl)methyl)phenyl)pivalamide

[0428]

[0429] The other steps and parameters in the synthesis method were the same as in Example 4, 80% yield.

[0430] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.44 (d, J = 8.0 Hz, 1H), 7.39 (s, 1H), 7.33 (s, 1H), 7.26 (d, J = 7.9 Hz, 1H), 6.85 (d, J = 7.6 Hz, 1H), 6.70 (t, J = 2.1 Hz, 2H), 6.19 (s, 2H), 5.04 (s, 2H), 1.31 (s, 9H);

[0431] 13 C-NMR (100 MHz, CDC13) δ 176.8, 139.2, 138.5, 129.5, 123.0, 121.3, 119.4, 118.7, 108.7, 53.4, 39.8, 27.7;

[0432] IR (ATR): 3129, 3098, 3055, 2965, 2932, 2906, 2870, 1655, 1610, 1593, 1531, 1485, 1432, 1398, 1366, 1347, 1296, 1266, 1226, 1187, 1145, 1085, 1066, 1027, 1000, 971, 923, 886, 786, 761, 720;

[0433] HRMS (ESI) Calcd for [M+H] + : 257.1649 m / z, found: 257.1636 m / z.

[0434] Example 43

[0435] The amine compound used was: phenethylamine

[0436] Product: 1-phenethyl-1H-pyrrole

[0437]

[0438] The other steps and parameters in the synthesis method were the same as in Example 4, 67% yield.

[0439] 1 H-NMR (400 MHz, CDC13) δ (p.p.m.) 7.30 - 7.19 (m, 3H), 7.10 - 7.05 (m, 2H), 6.58 (s, 2H), 6.12 (s, 2H), 4.10 - 4.05 (m, 2H), 3.05 - 3.00 (m, 2H);

[0440] 13 C-NMR (100 MHz, CDC13) δ 138.5, 128.8, 128.6, 126.7, 120.6, 108.1, 51.2, 38.5;

[0441] IR (ATR): 3063, 3028, 2927, 2871, 1948, 1874, 1807, 1703, 1604, 1543, 1497, 1454, 1439, 1360, 1282, 1266, 1244, 1203, 1155, 1088, 1065, 1030, 969, 921, 894, 817, 719;

[0442] HRMS (ESI) Calcd for [M+H] C32H32N2O4S2: 570.1757 m / z, found: 570.1757 m / z. + : 172.1121 m / z, found: 172.1116 m / z.

[0443] Example 44

[0444]

[0445] In 8 ml microwave tube, bis(trifluoromethylsulfonic acid) zirconocene (52.0 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq) were added, and stirred at room temperature for 10 minutes, then added triethoxysilane (1.48 ml, 8 mmol, 8 eq) and polyethylene terephthalate (M W In 8 ml microwave tube, bis(trifluoromethylsulfonic acid) zirconocene (52.0 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq) were added, and stirred at room temperature for 10 minutes, then added triethoxysilane (1.48 ml, 8 mmol, 8 eq) and polyethylene terephthalate (M

[0446] The purified product was confirmed for product confirmation, and the specific test results were as follows: 1H-NMR (400 MHz, CDCI3) δ (p.p.m.) 7.26 (s, 4H), 3.47 (s, 4H), 2.38 (s, 8H), 1.58 (p, J = 5.6 Hz, 8H), 1.43 (p, J = 6.0 Hz, 4H);

[0447] 13C-NMR (100 MHz, CDCI3) δ 137.1, 129.2, 63.7, 54.6, 26.0, 24.5;

[0448] IR (ATR): = 3028, 3016, 2931, 2853, 2792, 2753, 2722, 2682, 1720, 1613, 1510, 1467, 1465, 1454, 1441, 1418, 1390, 1367, 1342, 1296, 1264, 1248, 1197, 1152, 1114, 1096, 1066, 1038, 1020, 994, 962, 944, 907, 862, 845, 809, 787, 774, 764, 735, 703;

[0449] HRMS (ESI) Calcd for [M+H]+: 273.2326 m / z, found: 273.2315 m / z.

[0450] Example 45

[0451]

[0452] In a 8 ml microwave tube, bis(n-butylcyclopentadienyl)zirconium dichloride (40.4 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq) were added and stirred for 10 minutes at room temperature, then triethoxysilane (1.48 ml, 8 mmol, 8 eq) and polyethylene terephthalate (M W In a 8 ml microwave tube, bis(n-butylcyclopentadienyl)zirconium dichloride (40.4 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq) were added and stirred for 10 minutes at room temperature, then triethoxysilane (1.48 ml, 8 mmol, 8 eq) and polyethylene terephthalate (M

[0453] The purified product was confirmed by1H-NMR (400 MHz, CDCI3) δ (p.p.m.) 7.26 (s, 4H), 3.47 (s, 4H), 2.38 (s, 8H), 1.58 (p, J = 5.6 Hz, 8H), 1.43 (p, J = 6.0 Hz, 4H);

[0454] 13C-NMR (100 MHz, CDCI3) δ 137.1, 129.2, 63.7, 54.6, 26.0, 24.5;

[0455] IR (ATR): = 3028, 3016, 2931, 2853, 2792, 2753, 2722, 2682, 1720, 1613, 1510, 1467, 1465, 1454, 1441, 1418, 1390, 1367, 1342, 1296, 1264, 1248, 1197, 1152, 1114, 1096, 1066, 1038, 1020, 994, 962, 944, 907, 862, 845, 809, 787, 774, 764, 735, 703;

[0456] HRMS (ESI) Calcd for [M+H]+: 273.2326 m / z, found: 273.2315 m / z.

[0457] Example 46

[0458]

[0459] In 8 ml microwave tube, dimethylsilyl bis(cyclopentadienyl) zirconium dichloride (34.8 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq) were added, and 1 ml dioxane was added and stirred at room temperature for 10 minutes, then triethoxysilane (1.48 ml, 8 mmol, 8 eq) and polyethylene terephthalate (M W In 8 ml microwave tube, dimethylsilyl bis(cyclopentadienyl) zirconium dichloride (34.8 mg, 0.1 mmol, 0.1 eq) and potassium methoxide (3.5 mg, 0.05 mmol, 0.05 eq) were added, and 1 ml dioxane was added and stirred at room temperature for 10 minutes, then triethoxysilane (1.48 ml, 8 mmol, 8 eq) and polyethylene terephthalate (M

[0460] The purified product was confirmed by product confirmation, and the specific test results were as follows: 1H-NMR (400 MHz, CDCI3) δ (p.p.m.) 7.26 (s, 4H), 3.47 (s, 4H), 2.38 (s, 8H), 1.58 (p, J = 5.6 Hz, 8H), 1.43 (p, J = 6.0 Hz, 4H);

[0461] 13C-NMR (100 MHz, CDCI3) δ 137.1, 129.2, 63.7, 54.6, 26.0, 24.5;

[0462] IR (ATR): = 3028, 3016, 2931, 2853, 2792, 2753, 2722, 2682, 1720, 1613, 1510, 1467, 1465, 1454, 1441, 1418, 1390, 1367, 1342, 1296, 1264, 1248, 1197, 1152, 1114, 1096, 1066, 1038, 1020, 994, 962, 944, 907, 862, 845, 809, 787, 774, 764, 735, 703;

[0463] HRMS (ESI) Calcd for [M+H]+: 273.2326 m / z, found: 273.2315 m / z.

[0464] The above examples are only illustrative of the principles of the application and their efficacy, and are not intended to limit the application. Any modifications or changes made by those skilled in the art without departing from the spirit and scope of the application should be covered by the claims of the application.

Claims

1. The use of one or more compounds of the structural formulas shown in Formula I and Formula II as a catalyst for the degradation of esters. in, R 1 R 2 R 3 R 4 The ester is independently selected from hydrogen, and a straight-chain or branched alkyl group of C1 to C6; X and Y are independently selected from H, F, Cl, Br and trifluoromethanesulfonyl; the ester is a compound containing an ester group or a polymer containing an ester group; the polymer containing an ester group is one or more selected from polylactic acid, polyglycolic acid, and polyesters formed with polyacids and polyols as reacting monomers; the compound containing an ester group is one or more selected from glycerol esters, succinate, adipate, terephthalate, and furan-2,5-dicarboxylate.

2. The use according to claim 1, characterized in that, The catalyst is used in the reductive transamination reaction of esters and amines; And / or, the structure of the amine compound is shown below: R 5 ,R 6 Selected from one or more of C1-C20 straight-chain or branched alkyl groups, C1-C20 heteroatom-containing alkyl groups, and C6-C20 aryl groups, R 7 It is selected from one of C1-C20 alkyl groups and C1-C20 alkyl groups containing heteroatoms.

3. The use according to claim 2, characterized in that, The amine compounds are selected from tetrahydropyrrole, piperidine, N-methylbutylamine, diethylamine, morpholine, 4-[(methylamino)methyl]phenol, N-(4-methoxybenzyl)-N-methylamine, N-methyl-4-bromobenzylamine, 3-(methylamino)-1-propanol, N-(2-methoxyethyl)methylamine, N-methylpiperazine, 4-phenyl-1,2,3,6-tetrahydropyridine, 4-methylenepiperidine, 1,2, One or more of the following: 3,4-tetrahydroisoquinoline, N,N'-dimethyl-1,6-hexanediamine, n-propylamine, tryptamine, 2-(1-cyclohexenyl)ethylamine, 3-methoxypropylamine, N-(2-aminoethyl)morpholine, benzylamine, phenethylamine, 2-aminomethylpyridine, p-bromobenzylamine, p-hydroxybenzylamine, N-methyl-1,3-propanediamine, N,N'-dimethyl-1,4-butanediamine, and 3-aminobenzylamine.

4. The use according to claim 3, characterized in that, And / or, in the polyester formed using polyacids and polyols as reactive monomers, the polyacid is selected from one or both of terephthalic acid and succinic acid; the polyol is selected from one or more of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.

5. The use according to claim 1, characterized in that, The catalyst is selected from one or more of the following structural formulas:

6. The use as described in any one of claims 1 to 5, characterized in that, One or more of the compounds with the structural formulas shown in Formula I and Formula II are used in combination with trifluoromethanesulfonate as a catalyst system for the degradation of esters.

7. A method for degrading esters, characterized in that, Under the action of a main catalyst and a reducing agent, esters and amines undergo a reductive-transamination reaction; the reducing agent is a compound containing silicon-hydrogen bonds; the amine is a primary or secondary amine; and the main catalyst is one or more compounds selected from those shown in Formula I and Formula II. Among them, R 1 R 2 R 3 R 4 Independently selected from hydrogen, and a straight-chain or branched alkyl group of C1 to C6; X and Y are independently selected from H, F, Cl, Br and trifluoromethanesulfonyl. The ester is a compound or polymer containing an ester group; the polymer containing an ester group is selected from one or more of polylactic acid, polyglycolic acid, and polyesters formed using polyacids and polyols as reacting monomers; the compound containing an ester group is selected from one or more of glycerol esters, succinate, adipate, terephthalate, and furan-2,5-dicarboxylate.

8. A method for preparing an intermediate compound for the synthesis of Lorcaserin, characterized in that, Under the action of a main catalyst and a reducing agent, polylactic acid undergoes a reductive transamination reaction with 4-chlorophenylethylamine; The reducing agent is a silicon-hydrogen bond compound; the main catalyst is one or more compounds selected from those with structural formulas as shown in Formula I and Formula II. Among them, R 1 R 2 R 3 R 4 Independently selected from hydrogen and one of C1-C6 straight-chain or branched alkyl groups; X and Y are independently selected from one of H, F, Cl, Br, and trifluoromethanesulfonyl groups; the synthetic route is as follows:

9. The method according to claim 7, characterized in that, Includes one or more of the following features: A) The reductive amination reaction also uses an organic solvent as a reaction medium, wherein the organic solvent is selected from cyclic ether solvents and solvents containing benzene rings; B) The reaction also employs an activator with a catalytic amount, the activator being selected from alkali metal salts of alcohols; C) An auxiliary catalyst is also used in the reaction, and the auxiliary catalyst is trifluoromethanesulfonate; D) The compound containing silane bonds is a silane compound; E) The structure of the amine compound is shown below: R 5 ,R 6 Selected from one or more of C1-C20 straight-chain or branched alkyl groups, C1-C20 heteroatom-containing alkyl groups, and C6-C20 aryl groups, R 7 Selected from C1-C20 alkyl groups and C1-C20 alkyl groups containing heteroatoms; F) The temperature for the reductive transamination reaction is 100–150 °C; G) The ratio of the number of moles of ester groups in the esters to the number of moles of amine groups in the amines is 1: (1～2)； H) The ratio of the number of moles of ester groups in the ester to the number of moles of silane bonds in the reducing agent is 1: (2～10)； I) After the reduction-transamination reaction is completed, the product is purified by separation.

10. The method according to claim 8, characterized in that, Includes one or more of the following features: A) The reductive amination reaction also uses an organic solvent as a reaction medium, wherein the organic solvent is selected from cyclic ether solvents and solvents containing benzene rings; B) The reaction also employs an activator with a catalytic amount, the activator being selected from alkali metal salts of alcohols; C) An auxiliary catalyst is also used in the reaction, and the auxiliary catalyst is trifluoromethanesulfonate; D) The compound containing silane bonds is a silane compound; E) The temperature of the reductive transamination reaction is 100–150 °C; F) The ratio of the number of moles of ester groups in the esters to the number of moles of amine groups in the amines is 1: (1～2)； G) The ratio of the number of moles of ester groups in the ester substance to the number of moles of silane bonds in the reducing agent is 1: (2～10)； After the reduction-transamination reaction described in H) is completed, the product is purified by separation.

11. The method according to claim 9 or 10, characterized in that: The cyclic ether solvent is selected from one or more of dioxane, tetrahydrofuran, and tetrahydropyran; And / or, the benzene ring-containing solvent is one or more selected from toluene, chlorobenzene, fluorobenzene, trifluorotoluene, ethylbenzene, xylene, and benzene; And / or, the alkali metal salt of the alcohol is one or more selected from potassium methoxide, sodium methoxide and lithium methoxide; and / or, the trifluoromethanesulfonate is one or more selected from potassium trifluoromethanesulfonate, sodium trifluoromethanesulfonate and lithium trifluoromethanesulfonate. And / or, the silane compound is selected from benzylsilane, [CH3(CH2)] n One or more of O]3SiH, where n is 0, 1, 2, 3 or 4; And / or, the amine compound is selected from tetrahydropyrrole, piperidine, N-methylbutylamine, diethylamine, morpholine, 4-[(methylamino)methyl]phenol, N-(4-methoxybenzyl)-N-methylamine, N-methyl-4-bromobenzylamine, 3-(methylamino)-1-propanol, N-(2-methoxyethyl)methylamine, N-methylpiperazine, 4-phenyl-1,2,3,6-tetrahydropyridine, 4-methylenepiperidine, 1, One or more of the following: 2,3,4-tetrahydroisoquinoline, N,N'-dimethyl-1,6-hexanediamine, n-propylamine, tryptophan, 2-(1-cyclohexenyl)ethylamine, 3-methoxypropylamine, N-(2-aminoethyl)morpholine, benzylamine, phenethylamine, 2-aminomethylpyridine, p-bromobenzylamine, p-hydroxybenzylamine, N-methyl-1,3-propanediamine, N,N'-dimethyl-1,4-butanediamine, and 3-aminobenzylamine; And / or, the molar ratio of the main catalyst to the activator is 1:(0.5~1); And / or, the molar ratio of the main catalyst to the auxiliary catalyst is 1:(0.1-5); And / or, the separation includes fractionation or adsorption; And / or, the polymer containing ester groups is selected from one or more of polylactic acid, polyglycolic acid, and polyesters formed using polyacids and polyols as reactive monomers; And / or, the weight-average molecular weight of the ester-containing polymer does not exceed 150W.

12. The method according to claim 11, characterized in that, In the polyester formed using polybasic acid and polyol as reactive monomers, the polybasic acid is selected from one or two of terephthalic acid and succinic acid; the polyol is selected from one or more of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. And / or, the weight-average molecular weight of the ester-containing polymer does not exceed 100W.

13. The method according to claim 8 or 9, characterized in that, The catalyst is selected from one or more of the following structural formulas:

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